JP5223087B2 - Method for producing foam suppressor and plasticizer, and foam suppressor and plasticizer - Google Patents

Description

  The present invention relates to a chemical substance modifying agent (compound) and use thereof, and in particular, a chemical substance modifying agent (compound) for modifying physical properties of a compound having a linear alkyl chain or a composition containing the same, The present invention relates to a modified compound and a modified composition manufacturing method using the compound, and a modified compound and a modified composition obtained by the modified composition manufacturing method.

  The present invention provides a novel dicarboxylic acid diester compound as an example of the modifying compound.

  Conventionally, as a method of controlling the cohesive force of a substance having a linear alkyl chain and thereby changing the melting point, flexibility, etc. of the substance, a method of changing the chain length of the linear alkyl chain, A method of introducing a side chain such as a group or an unsaturated bond, a method of mixing an alkyl chain having a different chain length, and the like are known.

  In any of these methods, the cohesive force of a linear alkyl chain is controlled using steric hindrance that depends on the shape of the molecule. That is, the cohesive force of the linear alkyl chain is essentially van der Waals force, and when the molecules are attracted and contacted by van der Waals force, repulsive force appears due to steric hindrance, and the linear alkyl chain The collective state is determined. As described above, the melting point, flexibility, and the like are changed by controlling the cohesive force of the linear alkyl chain by steric hindrance.

By the way, as a report regarding the oxaalkyl chain in which an oxygen atom is contained in the alkyl chain, oxaalkanedicarboxylic acid HOOC (CH ₂ ) _m O (CH ₂ ) _n COOH, alkyl / oligooxyethylene / alkyl triblock compound H (CH ₂ ) There are reports on _m (OCH ₂ CH ₂ ) _n O (CH ₂ ) ₁ H and the like (see, for example, Non-Patent Documents 1 to 10 and Patent Documents 1 to 3).

  Patent Documents 1 and 2 and Non-Patent Document 1 disclose a method for synthesizing oxaalkanedicarboxylic acid. Non-Patent Document 1 describes that the melting point of oxaalkanedicarboxylic acid is lower than that of the same chain length alkanedicarboxylic acid. Patent Document 3 and Non-Patent Document 2 disclose the synthesis of polymers using oxaalkanedicarboxylic acid as a raw material. Patent Document 3 describes that polymerization using oxaalkanedicarboxylic acid improves the dyeability and strength of the resulting polyetherester fiber, but does not cause a significant decrease in melting point. In contrast, Non-Patent Document 2 describes that the melting point of the polyamide obtained by polymerization using oxaalkanedicarboxylic acid corresponds to the raw material oxaalkanedicarboxylic acid. Non-patent document 3 reports the physical properties of some symmetric alkyl ethers.

  Non-patent documents 4 to 9 are reports on basic research on physical properties of alkyl / oligooxyethylene / alkyl triblock compounds as model compounds of block polymers. In these documents, synthesis methods and physical properties of alkyl / oligooxyethylene / alkyl triblock compounds are disclosed. Non-Patent Documents 4 and 5 describe that the melting point of alkyl / oligooxyethylene / alkyl triblock compounds is lower than that of alkanes having a similar number of skeleton atoms.

Non-Patent Document 10 discloses a synthesis method of alkyl / oligooxyethylene / alkyl triblock compound nonionic surfactant H (CH ₂ ) _n (OCH ₂ CH ₂ ) _m O (CH ₂ ) _n H. .
Japanese Examined Patent Publication No. 45-01944 (published July 3, 1970) Japanese Patent Publication No.42-024566 (published on November 25, 1967) British Patent No. 1105571 Saotome, K .; Sato, K., Bull. Chem. Soc. Jpn. 1966, 39, 485-489 Saotome, K .; Sato, K., J. Polym. Sci., Polym. Chem. Ed. 1966, 4, 1303-1309 Tyagi, OS; Bisht, HS; Chatterjee, AK, J.Phys.Chem.B2004,108,3010-3016 Fukuhara, K.; Mizawa, T.; Inoue, T.; Kumamoto, H.; Terai, Y.; Matsuura, H.; Viras, K., Phys.Chem.Chem.Phys.2005,7,1457-1463 Fukuhara, K.; Mizawa, T.; Inoue, T.; Kumamoto, H .; Matsuura, H., J.Phys.Chem.B2004,108,515-522 Chen, Y.; Olson, KL; Baker, GL, Macromolecules2002,35,3914-3920 Chen, Y.; Baker, GL; Ding, Y.; Rabolt, JF, J.Am.Chem.Soc.1999,121,6962-6963 Domszy, RC; Booth, C., Makromol.Chem. 1982,183,1051-1070 Teo, HH; Swales, TGE; Domszy, RC; Heatley, F .; Booth, C., Makromol. Chem. 1983, 184, 861-877 Chen, Y .; Baker, GL, J. Org. Chem. 1999, 64, 6870-6873

  However, any of the conventional methods for changing the melting point, flexibility, etc. of the substance having a linear alkyl chain is a method for controlling the cohesive force of the linear alkyl chain using steric hindrance. When side chains such as methyl groups or unsaturated bonds are introduced into the chain, there is a problem in that the shape of the molecular aggregate itself is affected. Further, when the cohesive force of a substance is controlled using steric hindrance, there is a problem that the effect of the control is not sufficient.

  Further, glycol compounds such as ethylene glycol are often used for the purpose of lowering the freezing point, but glycol systems are basically hydrophilic and have high viscosity.

  There are reports that the melting points of oxaalkanedicarboxylic acids and alkyl / oligooxyethylene / alkyl triblock compounds are lower than those of alkanes having a similar number of skeletal atoms, but the melting points of polymers using these do not decrease. Cases and cases where it falls are reported, and the effect of introducing such a molecular structure into the molecule is unclear. Further, it is unclear what kind of oxaalkanedicarboxylic acid and alkyl / oligooxyethylene / alkyltriblock compound have a lower melting point than alkanes having a similar number of skeleton atoms.

  The present invention has been made in view of the above problems, and its purpose is to sufficiently control the cohesive force of a substance having a linear alkyl chain without affecting the shape of the molecular aggregate itself. A chemical substance modifier (compound) for modifying the physical properties of a compound having a linear alkyl chain or a composition containing the same, a method for producing a modified compound or a modified composition using the same, and An object of the present invention is to provide a modified compound or a modified composition produced by using this.

In order to solve the above problems, the chemical substance modifier according to the present invention has the following general formula (1):
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a halogen atom, an acryloyloxy group, a carboxyl group, an amino group, a cyano group, or a vinyl group, i and l are each independently an integer of 2 to 20, j is an integer of 2 to 12, k is an integer of 0 to 7, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is characterized by being a compound having a structure represented by

  According to said structure, instead of the raw material which has the said linear alkyl chain used when manufacturing the compound which has a linear alkyl chain, the said compound is used using the said chemical substance modifier (compound) as a raw material. By synthesizing, a modified compound in which the physical properties of the compound having a linear alkyl chain are modified can be produced. In the present specification, the term “substance modifying agent” may be used as a synonym for “chemical substance modifying agent (compound)”. The term “denaturation” or “modification” can also be used as a synonym for “modification”.

  A modified composition in which the physical properties of a compound having a linear alkyl chain are modified by mixing a compound having a linear alkyl chain or a composition containing the compound with the chemical substance modifier (compound). Can be manufactured. In the present specification, the term “modified composition” may be used as a synonym for “modified composition”.

  Further, according to the above configuration, when the oxaalkyl chain of the modified compound and the modified composition produced using the chemical substance modifier (compound) is to be crystallized, Similarly, it is considered that there is a tendency to pack in a lamellar shape with a planar zigzag structure as a stable structure. Here, in the isotropic liquid state, the oxaalkyl chain has a molecular chain that is flexible and takes disordered orientation, and repulsion between oxygen atoms between the chains is avoided. It is almost the same. However, in the oxaalkyl chain, repulsion of oxygen atoms between the chains inhibits crystallization compared to the corresponding linear alkyl chain. Therefore, the modified compound or modified composition having an oxaalkyl chain has properties similar to those of a compound or composition having a linear alkyl chain in the liquid state, and has a lowering or disappearance of the melting point, glass. It becomes possible to perform significant modification of physical properties such as a transition point, a crystal / liquid crystal transition temperature, a foaming property, and a pour point.

  Moreover, according to the said structure, since the three-dimensional structure of a linear alkyl chain and an oxaalkyl chain hardly changes, it has little influence on the shape itself as a molecular assembly. Therefore, it is advantageous in designing and controlling the three-dimensional structure as compared with a physical property modification method by introducing a side chain or an unsaturated bond into a linear alkyl chain that is necessarily accompanied by a three-dimensional structure change.

  Moreover, according to the said structure, since the said oxaalkyl chain is fundamentally hydrophobic and does not have hydrogen bonding property, it is low-viscosity. Therefore, it can be used for the purpose of lowering the freezing point or the like in place of or in addition to the hydrophilic, high-viscosity glycol compound basically.

  Moreover, according to the said structure, it becomes possible to control material properties in a wide range by adjusting the chain length of the oxaalkyl chain and the positions of oxygen atoms and oxyalkylene groups in the oxaalkyl chain.

  Moreover, according to the said structure, the chemical property of the linear alkyl ether type compound like the said oxaalkyl chain is similar to a linear alkyl compound, and its toxicity is low. The ether bond is chemically and thermally stable. Moreover, even if it decomposes | disassembles, when the carbon number of the adjacent alkyl chain is an even number, a decomposition product will be easily biodegraded and a final product will also be water and a carbon dioxide. Therefore, there is an effect that the load on the environment is very small.

  Moreover, according to the said structure, in the synthesis | combination of the chemical substance modifier (compound) which has the said oxaalkyl chain, and manufacture of the modification | reformation compound using this, it is not necessary to use a special method, and almost existing methods are used. It is possible to apply.

  Moreover, according to the said structure, there exists an effect that the physical property of the compound which has a linear alkyl chain can be continuously controlled by mixing and using several said oxaalkyl chains. Furthermore, when a mixture of several types of the above oxaalkyl chains is used, the mixed state of homologues is considered to be close to ideal mixing, which is advantageous in predicting and designing physical properties.

Moreover, in the method for producing a chemical substance modifier (compound) compound according to the present invention, the physical properties of a compound having a linear alkyl chain are modified using the modifier as a raw material in order to solve the above problems. A method for producing a modifying compound comprising:
In the modified compound, the linear alkyl chain of the compound having a linear alkyl chain is represented by the following general formula (2):
_{- (CH 2) i -O -} [(CH 2) j -O] k - (CH 2) l - (2)
(In the general formula (2), i and l are each independently an integer of 2 to 20, j is an integer of 2 to 12, k is an integer of 0 to 7, (A) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. )
It is characterized by being an oxaalkyl chain having a structure represented by:

In other words, the method for producing a modified compound according to the present invention is a modified compound in which the physical properties of a compound having a linear alkyl chain are modified in order to solve the above problems, The alkyl chain is represented by the following general formula (2)
_{- (CH 2) i -O -} [(CH 2) j -O] k - (CH 2) l - (2)
(In the general formula (2), i and l are each independently an integer of 2 to 20, j is an integer of 2 to 12, k is an integer of 0 to 7, (A) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. ), Wherein the modified compound is synthesized using the compound as a raw material.

  In the method for producing a modifying compound according to the present invention, the modifying compound is preferably a plasticizer, a surfactant, a liquid crystal molecule, an elastomer, or a synthetic resin.

  According to said structure, it becomes possible to extend the chain length of the alkyl chain part of plasticizers, such as a phthalate ester, without raising melting | fusing point, and there exists an effect that a plasticizer with little transferability can be provided. .

  Moreover, according to said structure, the presence area | region in a liquid state becomes large by the effect of the cloud point rise of a surfactant, melting | fusing point fall, gel area | region reduction, etc., and the area | region of usable temperature and usable density | concentration expands. There is an effect. In addition, it is possible to provide a surfactant having a low foaming property and a very strong foam breaking property.

  Moreover, according to said structure, there exists an effect that the crystal / liquid crystal transition temperature of a liquid crystal molecule can be reduced and a liquid crystal expression area | region can be expanded.

  Moreover, according to said structure, there exists an effect that the elastomer which lowers | hangs the glass transition point of an elastomer and maintains a softness | flexibility and rubber elasticity at lower temperature can be provided.

  In addition, the pressure-sensitive adhesive containing such an elastomer provides a pressure-sensitive adhesive that can be used even in a cold region because the tendency to pack lamellar oxaalkyl chains is inhibited and crystallization is inhibited during solidification. It becomes possible.

  Moreover, according to said structure, there exists an effect that a flexible material can be produced, without adding a plasticizer to a synthetic resin.

  The modifying compound according to the present invention is characterized by being produced by the method for producing the modifying compound.

  The method for producing a modified composition according to the present invention is a method for producing a modified composition in which physical properties of a compound having a linear alkyl chain or a composition containing the compound are modified, the compound or A method of mixing the composition and the chemical substance modifier (compound) may be used.

  According to said structure, the physical property of the compound which has a linear alkyl chain, or the composition containing the said compound is easily changed only by mixing the said compound or composition, and the said chemical substance modifier (compound). be able to.

  In the method for producing a modified composition according to the present invention, the modified composition is preferably a plasticizer, a surfactant, a liquid crystal molecule, an elastomer, or a synthetic resin.

  The modified composition according to the present invention is characterized by being produced by the method for producing the modified composition.

Moreover, in order to solve the said subject, the foam suppressor or foam suppressor modifier which concerns on this invention is represented by following General formula (1).
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom, R ² represents a hydroxyl group or a carboxyl group, i and l are each independently an integer of 2 or more and 20 or less, and j is 2 or more and 12 or less. K is an integer of 0 to 7, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is characterized by including the compound which has a structure represented by this.

  In the foam suppressor according to the present invention, since the compound represented by the general formula (1) has the oxaalkyl chain, the tendency of packing the oxaalkyl chains into a lamellar shape during the molecular assembly formation is inhibited. The Therefore, the foam or emulsion film structure becomes unstable. Thereby, foaming property is suppressed and foam breaking property is excellent, and foams and emulsions can be effectively destroyed. In addition, there is an effect that it is possible to develop an antifoaming agent that is less expensive and less environmentally friendly than a silicon-based antifoaming agent.

Moreover, in order to solve the said subject, the lubricating oil or lubricating oil modifier which concerns on this invention is the following general formula (1).
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a halogen atom, R ² represents a hydrogen atom or a halogen atom, i and l are each independently an integer of 2 to 20, and j is 2 Is an integer of 12 or less, k is an integer of 0 or more and 7 or less, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is characterized by including the compound which has a structure represented by this.

  In the lubricating oil according to the present invention, the compound represented by the above general formula (1) is excellent in the characteristics that the temperature dependency of the low temperature fluidity and fluidity is small, so that it can be used alone as a lubricating oil. It can also be used as a modifier in conventional lubricating oils.

  Since the lubricating oil or lubricating oil modifier of the present invention is excellent in low-low-temperature fluidity and low temperature dependency of fluidity, it has particularly low-temperature characteristics such as aircraft or cold district specification automobiles or power engines. Excellent as a required lubricant.

  According to said structure, since the said lubricating oil has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a lubricating oil having a low pour point.

Moreover, in order to solve the said subject, the hydraulic fluid or hydraulic fluid modifier which concerns on this invention is the following general formula (1).
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a halogen atom, R ² represents a hydrogen atom or a halogen atom, i and l are each independently an integer of 2 to 20, and j is 2 Is an integer of 12 or less, k is an integer of 0 or more and 7 or less, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is characterized by including the compound which has a structure represented by this.

  The hydraulic oil according to the present invention is excellent in the characteristics that the compound represented by the general formula (1) has low temperature fluidity and low temperature dependence of the fluidity, so that it can be used alone as hydraulic oil. It can be used as a modifier in conventional hydraulic oils.

  According to said structure, since the said hydraulic oil has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide hydraulic oil having a low pour point.

Moreover, in order to solve the said subject, the viscosity index regulator which concerns on this invention is the following general formula (1).
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a halogen atom, R ² represents a hydrogen atom or a halogen atom, i and l are each independently an integer of 2 to 20, and j is 2 Is an integer of 12 or less, k is an integer of 0 or more and 7 or less, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is characterized by including the compound which has a structure represented by this.

  The viscosity index adjusting agent according to the present invention is excellent in the characteristics that the compound represented by the general formula (1) has low temperature fluidity and small temperature dependence of the fluidity, and this is used alone as a viscosity index adjusting agent. It can also be used as a modifier in a conventional viscosity index adjuster.

  According to said structure, since the said viscosity index regulator has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a viscosity index modifier having a low pour point.

  Since the viscosity index modifier of the present invention is excellent in low temperature fluidity and low temperature dependency of fluidity, the viscosity of various oils that require low temperature physical properties such as aircraft and cold region specification automobile engines, etc. Excellent index adjuster.

Moreover, in order to solve the said subject, the coating compounding agent which concerns on this invention has the following general formula (1).
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a halogen atom, R ² represents a hydrogen atom or a halogen atom, i and l are each independently an integer of 2 to 20, and j is 2 Is an integer of 12 or less, k is an integer of 0 or more and 7 or less, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is characterized by including the compound which has a structure represented by this.

  Since the coating compounding agent according to the present invention is excellent in the characteristics that the compound represented by the general formula (1) has low temperature fluidity and small temperature dependence of fluidity, it is used alone as a coating compounding agent. Moreover, it has the characteristic that it can mix | blend and use as a modifier with the conventional coating compounding agent.

  According to said structure, since the said coating compounding agent has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a paint compounding agent having a low pour point.

  The paint compounding agent of the present invention is excellent as a paint compounding agent that requires low-temperature properties such as a paint for cold districts because it is excellent in low temperature fluidity and low temperature dependency of fluidity. . In the past, adjusting the viscosity of paints for cold districts has required maintenance of elevated temperatures, adding extra solvents, and cumbersome operations, but recently the use of solvents has been drastically reduced. Therefore, none of these methods are appropriate.

  Specifically, the paint compounding agent of the present invention can be used for a paint compounding agent such as a thixotropic agent or a leveling agent.

Moreover, in order to solve the said subject, surfactant or surfactant modifier which concerns on this invention is the following general formula (3).
R ³ -Hydrophilic group (3)
In the surfactant or surfactant modifier having the structure represented by:
R ³ is the following general formula (4)
_{H- (CH 2) i -O -} [(CH 2) j -O] k - (CH 2) l - (4)
(In general formula (4), i and l are each independently an integer of 2 or more, 20 or less, j is an integer of 2 or more and 12 or less, k is an integer of 0 or more and 7 or less, and (A) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is characterized by using the compound which has a structure represented by this.

In the surfactant or surfactant modifier according to the present invention, the hydrophilic group may be —COONa, —COOK, or — (OCH ₂ CH ₂ ) _n OH in the general formula (3). Good. Here, n is preferably 3 or more and 40 or less. Moreover, the antifoaming agent or antifoaming agent modifier which concerns on this invention may contain the said surfactant.

  The surfactant according to the present invention is excellent in the feature that the compound represented by the general formula (3) has low temperature fluidity and small temperature dependence of fluidity, and therefore this is used alone as a surfactant. It can also be used, and it can be used by blending it with a conventional surfactant as a modifier.

  According to said structure, since the said surfactant has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a surfactant having a low pour point.

  Since the surfactant of the present invention is excellent in low temperature fluidity and low temperature dependence of fluidity, it is particularly required to have low temperature physical properties such as low temperature specifications or cold district specifications. Excellent as an agent.

The plasticizer or plasticizer modifier according to the present invention is represented by the following general formula (1).
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a halogen atom, R ² represents a hydrogen atom or a halogen atom, i and l are each independently an integer of 2 to 20, and j is 2 Is an integer of 12 or less, k is an integer of 0 or more and 7 or less, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. )
It contains the chemical substance modifier which has the structure represented by these.

  In the plasticizer according to the present invention, the compound represented by the general formula (1) is excellent in the characteristics that the temperature dependency of the low temperature fluidity and the fluidity is small. It can also be used as a modifier in conventional plasticizers.

  According to said structure, since the said plasticizer has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a plasticizer having a low pour point.

  Since the plasticizer of the present invention is excellent in low temperature fluidity and low temperature dependency of fluidity, it is particularly excellent as a plasticizer requiring low temperature properties such as a plasticizer for low temperature specifications or cold district specifications. ing.

Further, the novel dicarboxylic acid diester compound according to the present invention is:
A dicarboxylic acid diester compound represented by the following general formula (5),

R ⁴ in the general formula (5) is the following general formula (6).
_{- (CH 2) a - (} 6)
(In general formula (6), a is an integer of 1-12).
The following general formula (7)

The following general formula (8)

Or the following general formula (9)

(R ^{7 to} R ¹⁰ in the general formulas (7) to (9) are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, and one or more in the alkyl group) The carbon atom of which may be substituted with an oxygen atom, or an oxaalkyl group ) ,
R ⁵ and R ⁶ in the general formula (5) are represented by the following general formula (10)
_{^{R 7 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l - (10)
(In the general formula (10), R ⁷ represents a hydrogen atom, a hydroxyl group, a halogen atom or a carboxyl group, i and l are each independently an integer of 2 to 20, and j is an integer of 2 to 12. And k is an integer of 0 to 7, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. R ⁵ and R ⁶ may be the same or different from each other. )
It is the group represented by these.

  The present invention provides a plasticizer or plasticizer modifier, a foam suppressor or a foam suppressor modifier, a lubricating oil or a lubricant modifier, a hydraulic oil or a hydraulic fluid modifier containing the novel dicarboxylic acid diester compound. Also included are viscosity index modifiers, paint formulation agents, surfactants or surfactant modifiers.

  The dicarboxylic acid diester compound is a novel compound that has not been found so far. The dicarboxylic acid ester compound is a compound having an oxaalkyl chain. Therefore, as described above, the novel dicarboxylic acid ester compound has properties similar to those of a compound having a linear alkyl chain in the liquid state, while lowering or disappearing the melting point, lowering the glass transition point, crystal / liquid crystal transition temperature. The physical properties have been drastically altered, such as a decrease in foaming, suppression of foaming properties, and a decrease in pour point. Therefore, the dicarboxylic acid diester compound is a plasticizer or a plasticizer modifier, a foam suppressor or a foam suppressor modifier, a lubricating oil or a lubricating oil modifier, a hydraulic oil or a hydraulic oil modifier, a viscosity index. It can be suitably used as a regulator, a paint compounding agent, a surfactant or a surfactant modifier.

  In the plasticizer according to the present invention, the novel dicarboxylic acid diester compound represented by the above general formula (5) is excellent in the characteristics that the temperature dependency of the low temperature fluidity and the fluidity is small, so that it is used alone. It can also be used as a modifier in conventional plasticizers.

  According to said structure, since the said plasticizer has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a plasticizer having a low pour point.

Since the plasticizer of the present invention is excellent in low temperature fluidity and low temperature dependency of fluidity, it is particularly excellent as a plasticizer requiring low temperature properties such as a plasticizer for low temperature specifications or cold district specifications. In the foam suppressor according to the present invention, since the novel dicarboxylic acid diester compound represented by the general formula (5) has the oxaalkyl chain, a lamellar shape of the oxaalkyl chains is formed during the formation of the molecular assembly. The tendency to packing is impeded. Therefore, the foam or emulsion film structure becomes unstable. Thereby, foaming property is suppressed and foam breaking property is excellent, and foams and emulsions can be effectively destroyed. In addition, there is an effect that it is possible to develop an antifoaming agent that is less expensive and less environmentally friendly than a silicon-based antifoaming agent.

  In the lubricating oil according to the present invention, the novel dicarboxylic acid diester compound represented by the above general formula (5) is excellent in low temperature fluidity and small temperature dependence of fluidity, so that it should be used alone. It can also be used as a modifier in conventional lubricating oils.

  Since the lubricating oil or lubricating oil modifier of the present invention is excellent in low temperature fluidity and low temperature dependency of temperature, low temperature physical properties such as aircraft or cold region specification automobiles or power engines are particularly required. Excellent as a lubricating oil.

  According to said structure, since the said lubricating oil has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a lubricating oil having a low pour point.

  In the hydraulic oil according to the present invention, the novel dicarboxylic acid diester compound represented by the general formula (5) is excellent in the characteristics that low temperature fluidity and temperature dependence of fluidity are small. It can also be used as a modifier and can be used as a modifier in conventional lubricating oils.

According to said structure, since the said hydraulic oil has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide hydraulic oil having a low pour point.
Since the viscosity index modifier of the present invention is excellent in low temperature fluidity and low temperature dependency of fluidity, the viscosity of various oils that require low temperature physical properties such as aircraft and cold region specification automobile engines, etc. Excellent index adjuster.

  The viscosity index modifier according to the present invention is excellent in the characteristics that the novel dicarboxylic acid diester compound represented by the above general formula (5) has low temperature fluidity and small temperature dependence of fluidity. It can be used as an index adjusting agent, and can be used as a modifier in a conventional viscosity index adjusting agent.

  According to said structure, since the said viscosity index regulator has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a viscosity index modifier having a low pour point.

  Since the viscosity index modifier of the present invention is excellent in low-temperature fluidity and low temperature dependence of fluidity, it is particularly useful for various oils that require low-temperature properties such as aircraft and cold region specification automobile engines. Excellent as a viscosity index modifier.

  In the coating compounding agent according to the present invention, the novel dicarboxylic acid diester compound represented by the general formula (5) is excellent in the low temperature fluidity and the small temperature dependence of the fluidity. It can be used as an agent, and can be used as a modifier in a conventional paint compounding agent.

  According to said structure, since the said coating compounding agent has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a paint compounding agent having a low pour point.

  The paint compounding agent of the present invention is excellent as a paint compounding agent that requires low-temperature properties such as a paint for cold districts because it is excellent in low temperature fluidity and low temperature dependency of fluidity. .

  Specifically, the paint compounding agent of the present invention can be used for a paint compounding agent such as a thixotropic agent or a leveling agent.

  As the surfactant according to the present invention, the novel dicarboxylic acid diester compound represented by the above general formula (5) is excellent in the characteristics that the temperature dependency of low temperature fluidity and fluidity is small. It can also be used, and it can be used by blending it with a conventional surfactant as a modifier.

  According to said structure, since the said surfactant has the said oxaalkyl chain, in the case of solidification, the tendency to pack in the lamellar shape of this oxaalkyl chain is inhibited, and crystallization is inhibited. Therefore, it is possible to provide a surfactant having a low pour point.

  Since the surfactant of the present invention is excellent in low temperature fluidity and low temperature dependence of fluidity, it is particularly required to have low temperature physical properties such as low temperature specifications or cold district specifications. Excellent as an agent.

As described above, the chemical substance modifier (compound) according to the present invention is represented by the following general formula (1).
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a halogen atom, an acryloyloxy group, a carboxyl group, an amino group, a cyano group, or a vinyl group, i and l are each independently an integer of 2 to 20, j is an integer of 2 to 12, k is an integer of 0 to 7, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. ) In the modified compound and the modified composition produced using the above compound, the oxaalkyl chain in the isotropic liquid state has a flexible molecular chain and takes disordered orientation. Since repulsion of oxygen atoms between chains is avoided, the cohesive force in the liquid is almost the same as that of a linear alkyl chain. However, in the oxaalkyl chain, repulsion of oxygen atoms between the chains inhibits crystallization compared to the corresponding linear alkyl chain. Therefore, in the liquid state, it exhibits physical properties similar to those of a straight chain alkyl chain, and the above oxaalkyl chain has a lower melting point / disappearance, a lower glass transition point, a lower crystal / liquid crystal transition temperature, and a reduced foaming property. It is possible to make significant changes in physical properties such as lowering the pour point.

  According to the present invention, a plasticizer or plasticizer modifier, a foam suppressor or foam suppressor modifier, a lubricating oil or lubricating oil modifier, a hydraulic oil or hydraulic fluid modifier, a viscosity index modifier, a paint It is possible to provide a novel dicarboxylic acid diester compound that can be suitably used as a compounding agent, a surfactant, a surfactant modifier, or the like.

  An embodiment of the present invention will be described as follows. As a result of intensive studies in view of the above problems, the present inventors have found that a modified compound in which a linear alkyl chain of a compound having a linear alkyl chain is replaced with an oxaalkyl chain having a certain structure is an oxaalkyl Surprisingly, a wide variety of physical properties such as melting point, cloud point, gel region, foaming properties, etc. that seem to be unrelated to each other compared to compounds in which the chain part is a linear alkyl chain It was also found that it was remarkably modified. And using the compound having such an oxaalkyl chain, for example, if it is a surfactant, reacting the compound with a hydrophilic group, a compound to be modified with the compound, or a composition containing the compound It has been found that the physical properties of the compound having a linear alkyl chain and the composition can be greatly modified by mixing, and the present invention has been completed.

  Hereinafter, the present invention includes (I) a chemical substance modifying agent (compound), (II) a modifying compound and a method for producing a modifying composition, and (III) a modifying compound and other chemical substance modifying agent (compound). And (IV) a novel dicyanrubonic acid diester compound.

(I) Chemical substance modifier (compound)
(I-1) The compound The compound according to the present invention has the following general formula (1):
^{_{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a halogen atom, an acryloyloxy group, a carboxyl group, an amino group, a cyano group, or a vinyl group, i and l are each independently an integer of 2 to 20, j is an integer of 2 to 12, k is an integer of 0 to 7, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. Any compound may be used as long as it has a structure represented by:

  The compound of the present invention includes, for example, i) a method for producing a modified compound in which a portion of the linear alkyl chain of the compound having a linear alkyl chain is an oxaalkyl chain, ii) has a linear alkyl chain It can be used to modify the physical properties of a compound having a linear alkyl chain or a composition containing the compound by a method of producing a modified composition by mixing with a compound or a composition containing the compound.

  Here, the “compound having a linear alkyl chain” is not particularly limited as long as it is a compound having a linear alkyl chain having 7 to 135 carbon atoms, but more preferably 7 carbon atoms. It is a compound having a linear alkyl group of 40 to 40, more preferably 9 to 30 and particularly preferably 9 to 24. Such a compound may be a low molecular compound or a high molecular compound. Moreover, you may have a linear alkyl chain in a principal chain, and you may have in a side chain.

  In addition, the modified compound with modified physical properties includes a compound modified to lower the melting point, a compound modified to lose the melting point, a compound modified to lower the glass transition point, It refers to a compound modified so that the liquid crystal transition temperature is lowered, a compound modified so that foaming property is suppressed, a compound modified so that the pour point is lowered, and the like. The modified composition with modified physical properties is a composition modified so that the melting point is lowered, a composition modified so that the melting point disappears, or a composition modified so that the glass transition point is lowered. Product, a composition modified so that the crystal / liquid crystal transition temperature is lowered, a composition modified so that foamability is suppressed, a composition modified so that the pour point is lowered, and the like.

Here, the reason why the melting point is lowered or disappeared, the glass transition point is lowered, the crystal / liquid crystal transition temperature is lowered, the pour point is lowered, and the foaming property is suppressed is considered as follows. The oxaalkyl chain included in the structure represented by the general formula (1) has a planar zigzag structure as long as i, j, k, and l are satisfied. That is, in the case of —OCH ₂ —CH ₂ CH ₂ — or —OCH ₂ —CH ₂ O—, it is stable that the CH ₂ —CH ₂ single bond takes a Gauche configuration, but the adjacent alkyl chain is constant. If it is longer than this length, it is stable to take a trans configuration in the crystalline state due to the cohesive strength of the alkyl chain. That is, although the oxaalkyl chain contains an oxyalkylene group, as long as the above i, j, k, and l are satisfied, the entire chain is in a crystalline state due to the cohesive strength of the alkyl group. A planar zigzag structure is adopted to stabilize the shape.

  Thus, it is considered that the oxaalkyl chain having a planar zigzag structure tends to be packed in a lamellar shape with a planar zigzag structure as a stable structure, similar to a linear alkyl chain, when attempting to crystallize. However, unlike the case of a linear alkyl chain, when the oxaalkyl chain is packed in a lamellar shape, oxygen is electrostatically repelled between molecules as shown in FIG. It is thought to inhibit the conversion. As described above, in the oxaalkyl chain, crystallization is inhibited by electrostatic repulsion between oxygen, as compared with the corresponding linear alkyl chain, so that the melting point is lowered or disappeared, the glass transition point is lowered, the crystal / liquid crystal transition. Various physical property changes such as a decrease in temperature and a decrease in pour point are considered to occur.

  In addition, since the tendency of packing oxaalkyl chains into a lamellar shape is hindered, the foam and emulsion film structure become unstable. Thereby, it is thought that foaming property is suppressed and foam breaking property is excellent, and foams and emulsions can be effectively destroyed.

In the above oxaalkyl chain, _i -O sandwiched alkylene group at both ends _{- [(CH 2) j -O} ] k - moieties, and more preferably located at the center of the oxaalkyl chain. Thereby, since an oxaalkyl chain tends to take a stable planar zigzag structure, it can be used suitably by this invention. The present inventors _{have, (CH 2) i -O -} [(CH 2) 2 -O] 4 - (CH 2) In _12-i, infrared absorption and DSC (differential scanning oxaalkyl chain varying i Analysis using a calorimeter). As a result, it has been found that the ratio i / l of the lengths of alkylene groups at both ends is very suitable, for example, in the range of 0.35 to 2.7.

  In the oxaalkyl chain, i, j and l are more preferably even numbers. Thus, since i, j, and l are even numbers, the biodegradability of the obtained substance is improved, so the burden on the environment can be reduced.

In the present invention, using the above compound as a raw material having an oxaalkyl chain instead of the raw material having a linear alkyl chain used for producing a compound having a linear alkyl chain, the above compound is used. By synthesizing the compound, a modified compound in which the physical properties of the compound having a linear alkyl chain are modified can be produced. In such a case, the compound having at least one reactive functional group is used as the compound. That is, in the general formula (1), at least one of R ¹ and R ² is a hydroxyl group, mercapto group, halogen atom, acryloyloxy group, carboxyl group, amino group, cyano group, or vinyl group Is used. Thereby, it can be made to react with the other raw material for synthesize | combining the target modified compound.

In the present invention, a compound having a linear alkyl chain or a composition containing the compound is mixed with the above compound to produce a modified composition in which the physical properties of the compound having a linear alkyl chain are modified. be able to. In this case, as the above compound, in the general formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a mercapto group, a halogen atom, an acryloyloxy group, a carboxyl group, an amino group, a cyano group, Alternatively, the above compound which is a vinyl group may be used.

Furthermore, in the present invention, a modified compound with modified physical properties can be produced by introducing the above compound into the target compound. The target compound may be a low molecular compound or a high molecular compound. The target compound may or may not have a linear alkyl chain. In addition, when the above compound is introduced into the above target compound, the melting point is lowered / disappeared, the glass transition point is lowered, the crystal / liquid crystal transition temperature is lowered, and the foaming property is suppressed, compared with the case where a linear alkyl chain is introduced. In addition, a decrease in pour point is more remarkable. In such a case, a compound having at least one reactive functional group is used as the compound. That is, in the general formula (1), at least one of R ¹ and R ² is a hydroxyl group, mercapto group, halogen atom, acryloyloxy group, carboxyl group, amino group, cyano group, or vinyl group Is used. Thereby, the said compound can be introduce | transduced into a compound.

(I-2) Manufacturing method of chemical substance modifier (compound) The manufacturing method of the said compound is not specifically limited, It can manufacture suitably using a conventionally well-known method.

  Although an example of the manufacturing method of the said compound is shown below, the manufacturing method of the said compound is not limited to this.

In the general formula (1), the above compound in the case where k = 0, for example, H— (CH ₂ ) _i —O— (CH ₂ ) ₁ —H, is represented by the following reaction formula (11):

Can be synthesized. That is, an alkyl halide such as RCl (or RBr) and an alcohol R′OH are reacted in an aqueous sodium hydroxide solution in the presence of a phase transfer catalyst (eg, tetrabutylammonium hydrogensulfate: TBAH (tetrabutylammonium hydrogensulfate)). Just do it.

For example, H— (CH ₂ ) _i —O— (CH ₂ ) ₁ —OH is represented by the following reaction formula (12):

In the reaction formula (12), C ₅ Cl is exemplified. In the reaction formula (12), C ₅ and C ₆ represent a hydrogen atom, for example, RCl (or RBr). In the following description, the hydrogen atom may be omitted) and alkylene glycol HOR′OH (in the reaction formula (12), HOC ₆ OH is May be reacted in a sodium hydroxide aqueous solution in the presence of a phase transfer catalyst (for example, tetrabutylammonium hydrogen sulfate). At this time, alkylene glycol HOR′OH is used in a large excess with respect to the alkyl halide.

In the above general formula (1), the above compound in the case of k ≧ 1, for example, H— (CH ₂ ) _i —O — [(CH ₂ ) _j —O] _k — (CH ₂ ) ₁ —OH For example, the following reaction formula (13)

As shown in the above, the terminal OH group of H— (CH ₂ ) _i —O— (CH ₂ ) ₁ —OH prepared by the above-described method is substituted with a halogen atom with thionyl chloride or the like, and the above reaction formula (12) An oxyalkylene group may be introduced by the same method as described above. Further, the chain can be extended by the same method.
The said compound manufactured by the said method can be refine | purified to high purity of 99.5% or more, for example.

  In addition, the manufacturing method of the said compound is not limited to this, For example, the method of using toluenesulfonic acid ester instead of alkyl halide, the method of ring-opening polymerization of cyclic ether to an alkyl chain, etc. may be used. Good.

(II) Method for Producing Modified Compound and Modified Composition (II-1) Method for Producing Modified Compound In the method for producing a modified compound according to the present invention, the physical properties of a compound having a linear alkyl chain are modified. It is a manufacturing method of a modified compound.

In the present invention, in order to produce a modified compound in which the physical properties of a compound having a linear alkyl chain are modified, the linear alkyl chain of the compound having a linear alkyl chain is represented by the following general formula (2).
_{- (CH 2) i -O -} [(CH 2) j -O] k - (CH 2) l - (2)
(In the general formula (2), i and l are each independently an integer of 2 to 20, j is an integer of 2 to 12, k is an integer of 0 to 7, (A) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. )
A modified compound having an oxaalkyl chain having a structure represented by the above is produced by synthesizing the compound as a raw material. In other words, instead of the raw material having a linear alkyl chain in the production of the compound having a linear alkyl chain, the modified compound is synthesized using the compound as the raw material having the oxaalkyl chain.

  Here, synthesizing the modified compound using the compound as the raw material having the oxaalkyl chain instead of the raw material having the linear alkyl chain in the production of the compound having a linear alkyl chain means that the linear alkyl It is not limited to the case where the compound as the raw material having the oxaalkyl chain is used in place of all of the raw materials having a chain, but the compound as the raw material having the oxaalkyl chain in addition to the raw material having a linear alkyl chain The case where is used is also included.

  If a raw material having a linear alkyl chain and a compound having the oxaalkyl chain are used as a raw material for the modified compound, a compound having a linear alkyl chain and a modified compound having the oxaalkyl chain A mixture can be obtained. Thereby, modification of physical properties can be adjusted. Further, when the modifying compound is a polymer compound, if a raw material having a linear alkyl chain and a compound as a raw material having an oxaalkyl chain are used, the compound having a plurality of alkyl chains is partially An oxaalkyl chain can be introduced. Thereby, the modification of physical properties can be adjusted.

  Moreover, the compound as a raw material which has the said oxaalkyl chain may be used individually by 1 type, and may be used in combination of several types. By using a plurality of types of compounds in combination, the physical properties of the compound having a linear alkyl chain can be continuously controlled. Furthermore, when a plurality of types of compounds are used in combination, the mixed state of homologues is considered to be close to ideal mixing, which is advantageous in predicting and designing physical properties.

  The method of synthesizing the modified compound using the raw material having the oxaalkyl chain instead of the raw material having a linear alkyl chain is not particularly limited. For example, the surfactant is described as an example. Then, as a raw material, instead of linear alkyl halide, linear primary alcohol, alkylamine, etc., oxygen-containing linear alkyl halide having the above oxaalkyl chain, primary alcohol having the above oxaalkyl chain A surfactant may be synthesized according to a conventional method using the amine having an oxaalkyl chain.

  The modifying compound is not particularly limited, but is preferably a plasticizer, a surfactant, a liquid crystal molecule, an elastomer, a synthetic resin, or the like.

  The linear alkyl chain is, for example, a lipophilic group (hydrophobic group) in the surfactant, a soft segment in the liquid crystal molecule, a soft block in the elastomer, and a main chain in the synthetic resin. Or it exists as a side chain.

  When the modifying compound is a plasticizer, the modifying compound can be produced by reacting the compound with, for example, phthalic acid.

  Further, when the modifying compound is a surfactant, a hydrophilic group is introduced by the method of sulfating the compound with concentrated sulfuric acid or the like, or the method of addition polymerization of ethylene oxide to the compound, and the modification. Quality compounds can be produced.

  When the modifying compound is a liquid crystal molecule, the modifying compound can be produced by reacting the compound with, for example, 4-cyano-4'-hydroxybiphenyl.

  Further, when the modifying compound is an elastomer, the compound is used as a monomer, and if necessary, other monomers such as terephthalic acid, aliphatic diisocyanate, alicyclic diisocyanate are added and polymerized. By making it, the said modification | reformation compound can be manufactured.

  When the modifying compound is a synthetic resin, the compound is used as a monomer, and if necessary, other monomers such as aliphatic diisocyanate and alicyclic diisocyanate are added and polymerized. Thus, the modified compound can be produced.

  In addition, the method for producing a modifying compound according to the present invention may be a method for introducing the above compound into a target compound. The target compound may be a low molecular compound or a high molecular compound. The target compound may or may not have a linear alkyl chain. As such an example, for example, a case where an oxaalkyl chain is introduced as a side chain into a polymer compound can be exemplified. Thereby, the modification of physical properties can be adjusted.

  Also in this case, the compound having the oxaalkyl chain may be used alone or in combination of a plurality of types. By using a plurality of types of compounds in combination, the physical properties of the compound having a linear alkyl chain can be continuously controlled.

(II-2) Method for Producing Modified Composition A method for producing a modified composition according to the present invention comprises a modified composition in which the physical properties of a compound having a linear alkyl chain or a composition containing the compound are modified. It is a manufacturing method.

  In the present invention, in order to produce a modified composition in which the physical properties of a compound having a linear alkyl chain or a composition containing the compound are modified, the compound or the composition and the compound are mixed.

  This increases the proportion of oxaalkyl groups in which repulsion of oxygen atoms between chains inhibits crystallization in a compound having a linear alkyl chain or a composition containing the compound, so that the melting point is lowered or eliminated, glass It becomes possible to modify physical properties such as a transition point, a crystal / liquid crystal transition temperature, a foaming property, and a pour point.

  Moreover, the compound which has the said oxaalkyl chain may be used individually by 1 type, and may be used combining several types. By using a plurality of types of compounds in combination, the physical properties of the compound having a linear alkyl chain can be continuously controlled. Furthermore, when a plurality of types of compounds are used in combination, the mixed state of homologues is considered to be close to ideal mixing, which is advantageous in predicting and designing physical properties.

  The modified composition is not particularly limited, but is preferably a plasticizer, a surfactant, a liquid crystal molecule, an elastomer, a synthetic resin, or the like.

(II-3) Antifoaming agent The above compound can also be used as an antifoaming agent. Therefore, such an antifoaming agent is also included in the present invention. The antifoaming agent according to the present invention only needs to contain the above compound. Thereby, since the said compound has the said oxaalkyl chain, in the case of molecular assembly formation, the tendency to pack in the lamellar shape of oxaalkyl chains is inhibited. Therefore, the foam or emulsion film structure becomes unstable. Thereby, foaming property is suppressed and foam breaking property is excellent, and foams and emulsions can be effectively destroyed. In addition, it is possible to develop a foam suppressor that is less expensive and less environmentally friendly than silicon foam suppressors.

The foam suppressor according to the present invention is not particularly limited as long as it comprises the above compound, but preferably, in the general formula (1), R ¹ is a hydrogen atom, and R ² is It preferably contains a compound that is a hydroxyl group or a carboxyl group. That is, the foam suppressor according to the present invention has the following general formula (1):
_{^{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom, R ² represents a hydroxyl group or a carboxyl group, i and l are each independently an integer of 2 or more and 20 or less, and j is 2 or more and 12 or less. K is an integer of 0 to 7, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. It is preferable that the compound which has a structure represented by this is included. Moreover, the foam suppressant concerning this invention may contain the said surfactant.

(III) Modified Compound and Other Uses of Compound As described above, the modified compound obtained by the method for producing a modified compound according to the present invention has a lower melting point, lower glass transition point, and suppression of foaming properties. Etc., it has very good physical properties. Therefore, the present invention also includes a modified compound obtained by the method for producing a modified compound according to the present invention. Hereinafter, the modified compound and other uses of the compound will be described.

(III-1) Surfactant In the surfactant according to the present invention, the linear alkyl chain in the surfactant molecule is replaced with the oxaalkyl chain. As a result, due to effects such as an increase in the cloud point of the surfactant, a lowering of the melting point, and a reduction in the gel region, the existence region in the liquid state is widened, and the usable temperature and usable concentration regions can be expanded. Further, it is possible to provide a surfactant having a low foaming property and a very strong foam breaking property.

  The surfactant having a linear alkyl chain is not particularly limited, and examples thereof include linear alkyl polyoxyethylene ether, S-alkyl polyoxyethylene ether, alkylphenyl polyoxyethylene ether, N, N′— Nonionic surfactants such as di (alkanol) alkanamides and amine oxides; soap, alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid methyl, alkyl sulfate, alkyl sulfate (poly Oxyethylene) salts, phosphoric acid alkyl salts, N-acyl amino acid salts, ionic surfactants such as dialkyldimethylammonium chloride and monoalkyltrimethylammonium chloride; amphoteric surfactants such as sulfobetaine and betaine. More specifically, examples of the surfactant according to the present invention include surfactants in which the alkyl chain of these surfactants is the oxaalkyl group.

Moreover, this surfactant is the following general formula (3), for example.
R ³ -Hydrophilic group (3)
In the surfactant having the structure represented by
R ³ is the following general formula (4)
_{H- (CH 2) i -O -} [(CH 2) j -O] k - (CH 2) l - (4)
(In general formula (4), i and l are each independently an integer of 2 or more, 20 or less, j is an integer of 2 or more and 12 or less, k is an integer of 0 or more and 7 or less, and (A) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. ) May be used.

For example, nonionic surfactants are used in a very wide range of detergents, but since they often gel in a slightly high concentration region around 50% by weight, various measures have been taken to prevent gelation. Yes. With a nonionic surfactant having a hydrophobic group as the oxaalkyl group, the gelation problem can be solved very effectively. The nonionic surfactant is not particularly limited. For example, in the general formula (3), a linear alkylpolyoxy having a structure in which the hydrophilic group is — (OCH ₂ CH ₂ ) _n OH. Mention may be made of ethylene ether. Here, n is preferably 3 or more and 40 or less, more preferably 6 or more and 25 or less in terms of the degree of polymerization or average degree of polymerization of oxyethylene.

As described above, since the nonionic surfactant often gels in a slightly high concentration region around 50% by weight, it is necessary to prevent gelation. The present inventor found that when the hydrophobic group of the nonionic surfactant was changed to the oxaalkyl group, surprisingly, the liquid region was remarkably expanded as compared with the conventional nonionic surfactant. I found it. FIG. 2 shows a two-component phase diagram of a nonionic surfactant and water. The left side of FIG. 2 (the figure with “C ₁₂ E ₆ / water system” attached) is a two-component phase diagram of a nonionic surfactant having a linear alkyl chain as a hydrophobic group and water, and the right side of FIG. “C ₅ OC ₆ E ₆ / water system” is a two-component phase diagram of the nonionic surfactant of the present invention having the oxaalkyl chain as a hydrophobic group and water. In FIG. 2, a portion indicated by L is a liquid region, a portion indicated by S is a solid phase region, a portion indicated by H ₁ , V ₁ , and L _α in the center is indicated by a gel phase (lyotropic liquid crystal phase) and 2φ. This region corresponds to a two-phase separation region between water and a surfactant phase. In the case of such a nonionic surfactant, the surfactant obtained by synthesis is obtained as a substantially pure substance, and therefore, it is necessary to dilute it when used as a product.

  In the case of a nonionic surfactant having a linear alkyl chain as a hydrophobic group, the melting point is about 26 ° C., and it may solidify in winter. Moreover, if this is diluted with water at room temperature, it will gel in the area | region of about 40 to 85 weight% (wt%), and mechanical stirring will become impossible. In order to avoid this, it is necessary to dilute while heating to about 60 ° C. to avoid the gelation region, resulting in an extra energy loss.

On the other hand, in the nonionic surfactant of the present invention having an oxaalkyl chain as a hydrophobic group, as shown in the right side of FIG. 2 (the figure attached with “C ₅ OC ₆ E ₆ / water system”), the solid phase region However, due to a decrease in melting point (melting point of pure nonionic surfactant is -2.4 ° C.), it moves to a low temperature range. Moreover, it turns out that the gel phase area | region has decreased surprisingly compared with the case where it has a linear alkyl chain as a hydrophobic group. Moreover, it turns out that the two-phase separation area | region of water and surfactant phase shown by 2phi in FIG. 2 has also moved to the high temperature range. Due to these effects, the liquid phase region is remarkably expanded. Moreover, since the melting point of the pure substance is −2.4 ° C., there is no concern about solidification when diluted with water. Furthermore, since it becomes a liquid phase area | region in any density | concentration near room temperature, it turns out that it can dilute to arbitrary density | concentration without gelatinizing and it turns out that a heating is not required.

  Even in the nonionic surfactant of the present invention having an oxaalkyl chain as a hydrophobic group, the critical micelle concentration is the same as that of the nonionic surfactant having a linear alkyl chain, and there is no influence by oxaalkylation.

In addition, as shown in the results of the comparison of foam breaking properties performed in Examples described later (FIG. 3), in the nonionic surfactant of the present invention having an oxaalkyl chain as a hydrophobic group, a linear alkyl chain as a hydrophobic group Compared to the case of having a strong foam breaking property. In FIG. 3, C ₅ OC ₆ E ₆ represents a nonionic surfactant of the present invention having an oxaalkyl chain, and C ₁₂ E ₆ represents a nonionic surfactant having a linear alkyl chain as a hydrophobic group.

  The method for producing the surfactant of the present invention is not particularly limited, and can be produced by a conventionally known method.

  Hereinafter, an example of the method for producing the surfactant will be described by taking the nonionic surfactant as an example, but the method for producing the surfactant is not limited thereto. Moreover, although the nonionic surfactant of the specific structure is illustrated in the following method, when the value of i, j, l, and k differs, it can manufacture with the same method.

First, the synthesis of the hydrophobic oxaalkyl chain moiety H— (CH ₂ ) _i —O — [(CH ₂ ) _j —O] _k — (CH ₂ ) ₁ — represented by the above general formula (4) is described below. Reaction formula (14)

Do by. Since this reaction is the same as the reaction of the reaction formula (12) described in the above (I-2), the description is omitted here.

Next, in order to introduce a hydrophilic group (oligooxyethylene chain) into the obtained oxaalkyl chain part, as shown in the following reaction formula (15), the obtained H— (CH ₂ ) _i —O— The terminal OH group of (CH ₂ ) ₁ —OH is halogenated with thionyl chloride or the like.

  Subsequently, an oxaalkyl chain having a halogenated terminal is added to the following reaction formula (16).

As shown in FIG. 2, a hydrophilic group is introduced by a two-step synthesis method.

  Here, a two-step synthesis method is used to obtain a high-purity monodisperse sample. However, the method is not limited to this as long as a hydrophilic group can be introduced. For example, an ethylene oxide addition polymerization method is used. It may be used.

Further, as another example of the surfactant according to the present invention, for example, the following general formula (3)
R ³ -Hydrophilic group (3)
(In the general formula (3), the hydrophilic group is —COONa or —COOK.)
In the surfactant having the structure represented by
R ³ is the following general formula (4)
_{H- (CH 2) i -O -} [(CH 2) j -O] k - (CH 2) l - (4)
(In general formula (4), i and l are each independently an integer of 2 or more, 20 or less, j is an integer of 2 or more and 12 or less, k is an integer of 0 or more and 7 or less, and (A) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. ) Can be mentioned.

(III-2) Liquid Crystal Molecule In the liquid crystal molecule according to the present invention, the linear alkyl chain portion of the liquid crystal molecule having a linear alkyl chain is the oxaalkyl chain. Thereby, the crystal / liquid crystal transition temperature of the liquid crystal molecules can be lowered, and the liquid crystal expression region can be expanded.

  Here, the liquid crystal molecule having a linear alkyl chain is not particularly limited, and examples thereof include alkylcyanobiphenyl, alkoxycyanobiphenyl, dialkoxybiphenyl and the like. More specifically, examples of the liquid crystal molecules according to the present invention include liquid crystal molecules in which the alkyl chain of these liquid crystal molecules is the oxaalkyl group. Note that the number of carbon atoms in the alkyl chain of the liquid crystal molecule having a linear alkyl chain is preferably 7 or more and 40 or less, and more preferably 7 or more and 16 or less.

(III-3) Elastomer In the elastomer according to the present invention, the linear alkyl chain portion of the elastomer having a linear alkyl chain is the oxaalkyl chain. Thereby, the glass transition point of an elastomer can be lowered | hung and the elastomer which maintains a softness | flexibility and rubber elasticity at lower temperature can be provided. Therefore, for example, an elastomer that is hard and cannot be used in a cold region can be modified by the method of the present invention so that it can be used even in a cold region.

  Here, the elastomer having a linear alkyl chain is not particularly limited, and examples thereof include a styrene alkylene elastomer, a polyurethane elastomer, and a polyamide elastomer. More specifically, examples of the elastomer according to the present invention include elastomers in which the alkyl chain of these elastomers is the oxaalkyl group. In addition, it is preferable that carbon number of the alkyl chain of the elastomer which has the said linear alkyl chain is 7-40, More preferably, it is 7-12.

(III-4) Synthetic Resin In the synthetic resin according to the present invention, the linear alkyl chain portion of the synthetic resin having a linear alkyl chain is the oxaalkyl chain. Thereby, a flexible material can be produced without adding a plasticizer to the synthetic resin.

  Here, the synthetic resin having a linear alkyl chain is not particularly limited, and examples thereof include an acrylic graft polymer. More specifically, examples of the synthetic resin according to the present invention include synthetic resins in which the alkyl chain of these synthetic resins is the oxaalkyl group. In addition, it is preferable that carbon number of the alkyl chain of the synthetic resin which has the said linear alkyl chain is 7 or more and 40 or less, and it is more preferable that it is 7 or more and 12 or less.

(III-5) Adhesive The adhesive according to the present invention contains the above synthetic resin or elastomer whose physical properties have been modified.

  Since the synthetic resin or elastomer has the oxaalkyl chain, the tendency to pack the oxaalkyl chains into a lamellar shape during solidification is inhibited, and crystallization is inhibited. Therefore, it is possible to provide an adhesive that can be used even in cold regions.

  Here, as said synthetic resin or elastomer contained in the adhesive of this invention, an acrylic ester polymer, a methacrylic ester polymer, etc. can be mentioned, for example. More specifically, examples of the pressure-sensitive adhesive according to the present invention include a pressure-sensitive adhesive containing a synthetic resin or elastomer in which the alkyl chain of the synthetic resin or elastomer is the oxaalkyl group.

(III-6) Lubricating oil In addition, among the above compounds, the compound in which R ¹ and R ² are each independently a hydrogen atom or a halogen atom in the above general formula (1) is itself an oxalate compound during solidification. It is useful as a lubricating oil having a low pour point, in which the tendency of packing alkyl chains into a lamellar shape is inhibited and crystallization is inhibited.

That is, the lubricating oil according to the present invention preferably contains a compound in which R ¹ is a hydrogen atom or a halogen atom and R ² is a hydrogen atom or a halogen atom in the general formula (1). That is, the lubricating oil according to the present invention has the following general formula (1):
_{^{R 1 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l -R 2 (1)
(In General Formula (1), R ¹ represents a hydrogen atom or a halogen atom, R ² represents a hydrogen atom or a halogen atom, i and l are each independently an integer of 2 to 20, and j is 2 Is an integer of 12 or less, k is an integer of 0 or more and 7 or less, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. )
It is preferable that the compound which has a structure represented by these is included. The lubricating oil is also used as a brake oil, an organic solvent, an organic heat medium or the like.
(IV) Novel dicarboxylic acid diester compound The novel dicarboxylic acid diester compound according to the present invention is:
A dicarboxylic acid diester compound represented by the following general formula (5),

R ⁴ in the general formula (5) is the following general formula (6).
_{- (CH 2) a - (} 6)
(In general formula (6), a is an integer of 1-12).
The following general formula (7)

The following general formula (8)

Or the following general formula (9)

(R ^{7 to} R ¹⁰ in the general formulas (7) to (9) are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, and one or more in the alkyl group) The carbon atom of which may be substituted with an oxygen atom, or an oxaalkyl group ) ,
R ⁵ and R ⁶ in the general formula (5) are represented by the following general formula (10)
_{^{R 7 - (CH 2) i}} -O - [(CH 2) j -O] k - (CH 2) l - (10)
(In the general formula (10), R ⁷ represents a hydrogen atom, a hydroxyl group, a halogen atom or a carboxyl group, i and l are each independently an integer of 2 to 20, and j is an integer of 2 to 12. And k is an integer of 0 to 7, and the following (a) to (h)
(A) k = 0 and i + l ≧ 6
(B) j = 2 or 3, k = 1, and i + l ≧ 8
(C) j = 2 or 3, k = 2, and i + l ≧ 10
(D) j = 2 or 3, k = 3, and i + l ≧ 12
(E) j = 2 or 3, k ≧ 4, and i + l ≧ 3k
(F) j = 4, k = 1, and i + l ≧ 6
(G) j = 4, k ≧ 2, and i + l ≧ 8
(H) j> 5, i ≧ 2, and l ≧ 2.
Satisfy any relationship. R ⁵ and R ⁶ may be the same or different from each other. )
It is the group represented by these.

  The dicarboxylic acid diester compound includes an oxaalkyl chain in which an alkylene group included in a linear alkyl chain is replaced with an ether oxygen atom. The physical properties of the compound having such a structure are as described above.

  Regarding I, j, k, and l in the general formula (10), the descriptions of the general formulas (1), (2), and (4) are incorporated.

  Although it does not specifically limit as said novel dicarboxylic acid diester compound, Dicarboxylic acid dialkyl ester (compound A, B, C, D, E) typically represented in FIG. 4, and phthalic acid dialkanol ester (Compounds F and G). In FIG. 4, the description of carbon atoms and hydrogen atoms is omitted.

4 is a compound represented by CH ₂ (COOC ₆ H ₁₂ OC ₆ H ₁₃ ) ₂ , and Compound B is a compound represented by C ₄ H ₈ (COOC ₆ H ₁₂ OC ₆ H ₁₃ ) ₂ . Compound C is a compound represented by C ₆ H ₁₂ (COOC ₆ H ₁₂ OC ₆ H ₁₃ ) ₂ and Compound D is represented by C ₈ H ₁₆ (COOC ₆ H ₁₂ OC ₆ H ₁₃ ) ₂ Compound E is a compound represented by CH ₂ (COOC ₄ H ₈ OC ₂ H ₄ OC ₄ H ₉ ) ₂ . 4 is a compound represented by Pht (COOC ₆ H ₁₂ OC ₆ H ₁₂ OH) ₂ (where “Pht” represents a phenylene group, the same shall apply hereinafter), and compound G in FIG. (COOC ₄ H ₈ OC ₂ H ₄ OC ₄ H ₈ OH) A compound represented by ₂ .

  The compounds A to E shown in FIG. 4 are merely examples of the dicarboxylic acid dialkyl ester according to the present invention, and the chain length between two carbonyl groups in the dicarboxylic acid dialkyl ester according to the present invention is not particularly limited. Further, as in Compound E, each oxaalkyl chain not sandwiched between two carbonyl groups may contain two or more ether oxygen atoms. Further, the two oxaalkyl chains not sandwiched between the two carbonyl groups in the dicarboxylic acid dialkyl ester according to the present invention may have the same structure or different structures.

  The compounds F and G shown in FIG. 4 are merely examples of phthalic acid dialkanol esters, and the chain length of the oxaalkyl chain contained in the phthalic acid dialkanol esters according to the present invention is not particularly limited. Further, as in compound H, each of the two oxaalkyl chains contained in the phthalic acid dialkanol ester may contain two or more ether oxygen atoms. Further, the two oxaalkyl chains in the dialkanol phthalate according to the present invention may have the same structure or different structures.

The compounds A to D shown in FIG. 4 can be produced, for example, as follows (Reaction Formula (17)). That is, after adding a few drops of concentrated sulfuric acid to a reaction solution containing C _n (COOH) ₂ and C ₆ OC ₆ OH, compounds A to D can be produced by refluxing under reduced pressure. Incidentally, C _n and C ₆ in the reaction formula (17) has a described omitting the hydrogen atoms.

4 is produced using, for example, C ₄ OC ₂ OC ₄ OH obtained by the above-described reaction formula (13) instead of C ₆ OC ₆ OH in the above reaction formula (17). do it.

Moreover, the compounds F and G shown in FIG. 4 can be manufactured as follows, for example (reaction formula (18)). That is, Compound G can be produced by adding a few drops of concentrated sulfuric acid to a reaction solution containing Pht (CO) ₂ O and C ₆ OC ₆ OH and then heating under reflux under reduced pressure, whereby Pht (CO) ₂ O and C Compound H can be produced by adding a few drops of concentrated sulfuric acid to a reaction solution containing ₄ OC ₂ OC ₄ OH and heating to reflux under reduced pressure. In the reaction formula (18), C ₂ , C _4, and C ₆ are described without a hydrogen atom.

  The dicarboxylic acid ester compound is a compound having an oxaalkyl chain. Therefore, as described above, the novel dicarboxylic acid ester compound has properties similar to those of a compound having a linear alkyl chain in the liquid state, while lowering or disappearing the melting point, lowering the glass transition point, crystal / liquid crystal transition temperature. The physical properties have been drastically altered, such as a decrease in foaming, suppression of foaming properties, and a decrease in pour point. Therefore, the dicarboxylic acid diester compound is a plasticizer or a plasticizer modifier, a foam suppressor or a foam suppressor modifier, a lubricating oil or a lubricating oil modifier, a hydraulic oil or a hydraulic oil modifier, a viscosity index. It can be suitably used for a regulator, a paint compounding agent, a surfactant or a surfactant modifier.

  As shown in the examples described later, the plasticizer having an oxaalkyl chain of the present invention is particularly excellent in thermophysical properties. However, the plasticizer having an oxaalkyl chain of the present invention not only has thermophysical properties but also has the potential to outperform other ready-made products. For example, (1) reduction of environmental load, (2) expansion of usable polymer, (3) low odor plasticizer, (4) low bleed property, etc. may be mentioned.

  Regarding the reduction of environmental load in (1) above, the use of a linear oxaalkyl chain with high biodegradability instead of a branched alkyl chain reduces the environmental load while maintaining heat and chemical stability. It can be said that.

  Regarding the expansion of the above (2) usable polymer, the following may be considered. Since the basic skeleton of most conventional plasticizers was an alkyl chain, it was difficult to adjust the polarity of the molecule. However, plasticizers having an oxaalkyl chain had an ether oxygen atom in the alkyl chain, It is possible to adjust the polarity more widely than ever. Therefore, compatibility with more types of polymers can be increased, and application to various polymers becomes possible.

  The following may be considered for the above (3) low odor plasticizer. Low melting point substances, not limited to plasticizers, generally have a drawback in that the boiling point is lowered and the vapor pressure is increased and odor is generated. However, the characteristics of the physical property improvement method developed by the present inventors by the oxaalkylation method (i.e., the method for producing the modified compound according to the present invention) is that the physical properties in the liquid state are greatly different from the compounds having a corresponding alkyl chain However, it is characterized in that only the solid state stability can be lowered and the melting point and glass transition point can be lowered due to the crystallization inhibition effect of the oxaalkyl chain. Therefore, it is possible to reduce the odor by increasing the molecular weight and lowering the vapor pressure and to keep the melting point low at the same time. That is, the plasticizer having an oxaalkyl chain has a reduced odor while maintaining a thermodynamic function equivalent to that of a conventional plasticizer.

  (4) Regarding the low bleed property, the following can be considered. The low melting point plasticizer basically has a low molecular weight, so that the bleeding property which oozes out from the polymer body when used for a long time has been a problem. In contrast, a plasticizer having an oxaalkyl chain can maintain a low melting point even if the length of the oxaalkyl chain is increased, and therefore has a low self-diffusibility and an entanglement effect with the polymer. The oozing rate can be reduced. Accordingly, the plasticizer having an oxaalkyl chain is expected to be a plasticizer having low bleeding properties.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by an Example.

Example 1: Preparation of compound
Using the methods of the above reaction formulas (11) to (18), the compounds shown in Table 1 below were produced. The obtained compound was identified by infrared spectrum, gas chromatography and the like, and the melting point was measured using DSC (manufactured by Shimadzu Corporation, DSC-50). Tables 1 and 2 below show the compounds obtained and their melting points, and the melting point reduction compared to the melting point when the oxaalkyl chain is a straight chain alkyl having the same number of skeletal atoms. In the chemical formulas shown in Tables 1 and 2, (CH ₂ ) is omitted, and the numbers in the formulas indicate the number of —CH ₂ —. Moreover, the thing without description of the terminal group has shown that the terminal is a hydrogen atom. For example, 8O2O2O8 _{is, H- (CH 2) 8 -O-} (CH 2) 2 -O- (CH 2) 2 -O- (CH 2) illustrating the 8 -H.

<Production of H— (CH ₂ ) ₇ —O— (CH ₂ ) ₄ —Br>
H (CH ₂ ) ₇ OH (47 g) and Br (CH ₂ ) ₄ Br (162 g) were reacted in a 50% aqueous sodium hydroxide solution (45 g) at 75 ° C. for 14 hours in the presence of TBAH (catalytic amount). To produce H— (CH ₂ ) ₇ —O— (CH ₂ ) ₄ —Br.

_{<H- (CH 2) 7 -O-} (CH 2) 4 -SH manufacturing>
(NH ₂ ) ₂ C═S (15 g) was heated to 75 ° C. in triethylene glycol (solvent; 30 g), and H (CH ₂ ) ₇ O (CH ₂ ) ₄ Br (47 g) was added dropwise. Stir for minutes. After completion of dropping, tetraethylenepentamine (38 g) was added dropwise and stirred at 75 ° C. for 15 minutes. By reacting 12 hours returned to room _{temperature, H- (CH 2) 7 -O-} (CH 2) was produced ₄ -SH.

<Production of H— (CH ₂ ) ₅ —O— (CH ₂ ) ₆ —OH>
H (CH ₂ ) ₅ Cl (20 g) and HO (CH ₂ ) ₆ OH (140 g) in diethylene glycol dimethyl ether (solvent; 150 g) in the presence of Na (3.5 g) at 90 ° C. for 24 hours. by reacting, H- and _{(CH 2) 5 -O- (CH} 2) to produce a ₆ -OH.

_{<H- (CH 2) 7 -O-} (CH 2) 4 -OH manufacturing>
By reacting H (CH ₂ ) ₇ Cl (25 g) with HO (CH ₂ ) ₄ OH (112 g) in the presence of Na (3.6 g) at 90 ° C. for 24 hours, H— (CH ₂ ) ₇ -O- (CH ₂₎ was produced ₄ -OH.

_{<H- (CH 2) 7 -O-} (CH 2) a ₆ -OH production>
H (CH ₂ ) ₇ Cl (28 g) was reacted with HO (CH ₂ ) ₆ OH (135 g) in the presence of Na (3.3 g) in diethylene glycol dimethyl ether (solvent; 150 g) at 90 ° C. for 18 hours. To produce H— (CH ₂ ) ₇ —O— (CH ₂ ) ₆ —OH.

_{<H- (CH 2) 8 -O-} (CH 2) 5 -OH manufacturing>
H (CH ₂ ) ₈ Cl (25 g) and HO (CH ₂ ) ₅ OH (120 g) were reacted in diethylene glycol dimethyl ether (solvent: 150 g) in the presence of Na (3.2 g) at 90 ° C. for 18 hours. To produce H— (CH ₂ ) ₈ —O— (CH ₂ ) ₅ —OH.

_{<H- (CH 2) 8 -O-} (CH 2) 6 -H of production>
H (CH ₂ ) ₈ Cl (89 g) and H (CH ₂ ) ₆ OH (51 g) were reacted in 50% aqueous sodium hydroxide solution (120 g) at 80 ° C. for 12 hours in the presence of TBAH (catalytic amount). To produce H— (CH ₂ ) ₈ —O— (CH ₂ ) ₆ —H.

_{<H- (CH 2) 9 -O-} (CH 2) 5 -H of production>
H (CH ₂ ) ₉ Cl (98 g) and H (CH ₂ ) ₅ OH (44 g) in 50% aqueous sodium hydroxide solution (120 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 12 hours. By reacting, H— (CH ₂ ) ₉ —O— (CH ₂ ) ₅ —H was produced.

_{<H- (CH 2) 10 -O-} (CH 2) 4 -H of production>
H (CH ₂ ) ₁₀ Cl (106 g) and H (CH ₂ ) ₄ OH (37 g) in 50% aqueous sodium hydroxide solution (120 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 12 hours. By reacting, H— (CH ₂ ) ₁₀ —O— (CH ₂ ) ₄ —H was produced.

_{<H- (CH 2) 11 -O-} (CH 2) 3 -H manufacturing>
H (CH ₂ ) ₁₁ Cl (57 g) and H (CH ₂ ) ₃ OH (15 g) in 50% aqueous sodium hydroxide solution (60 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 12 hours. By reacting, H— (CH ₂ ) ₁₁ —O— (CH ₂ ) ₃ —H was produced.

_{<H- (CH 2) 12 -O-} (CH 2) 2 -H manufacturing>
H (CH ₂ ) ₁₂ Cl (123 g) and H (CH ₂ ) ₂ OH (23 g) in 50% aqueous sodium hydroxide (120 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 12 hours By reacting, H— (CH ₂ ) ₁₂ —O— (CH ₂ ) ₂ —H was produced.

_{<H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) 4 -Br manufacturing>
H (CH ₂ ) ₄ O (CH ₂ ) ₂ OH (44 g) and Br (CH ₂ ) ₄ Br (158 g) in 50% aqueous sodium hydroxide (40 g) in the presence of TBAH (catalytic amount) H- (CH ₂ ) ₄ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₄ —Br was produced by reacting at 75 ° C. for 14 hours.

_{<H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) 4 -SH manufacturing>
(NH ₂ ) ₂ C═S (16 g) is warmed to 75 ° C. in triethylene glycol (solvent; 28 g) and H (CH ₂ ) ₄ O (CH ₂ ) ₂ O (CH ₂ ) ₄ Br ( 48 g) was added dropwise and stirred for 15 minutes. After completion of dropping, tetraethylenepentamine (38 g) was added dropwise and stirred at 75 ° C. for 15 minutes. By reacting 12 hours returned to room _{temperature, H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) was produced ₄ -SH.

_{<H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) 4 -OH manufacturing>
By reacting H (CH ₂ ) ₄ O (CH ₂ ) ₂ Cl (82 g) with HO (CH ₂ ) ₄ OH (360 g) in the presence of Na (11 g) at 90 ° C. for 24 hours, _{H- (CH 2) 4 -O- (} CH 2) 2 -O- (CH 2) was produced ₄ -OH.

_{<H- (CH 2) 5 -O-} (CH 2) 2 -O- (CH 2) 3 -OH manufacturing>
H (CH ₂ ) ₅ O (CH ₂ ) ₂ Cl (90 g) and HO (CH ₂ ) ₃ OH (300 g) were reacted in the presence of Na (10 g) at 90 ° C. for 24 hours to produce H _{- (CH 2) 5 -O- (} CH 2) 2 -O- (CH 2) 3 was prepared -OH.

_{<H- (CH 2) 5 -O-} (CH 2) 2 -O- (CH 2) 5 -H of production>
H (CH ₂ ) ₅ Cl (42 g) and HO (CH ₂ ) ₂ OH (6 g) in 50% aqueous sodium hydroxide solution (20 g) in the presence of TBAH (catalytic amount) at 65 ° C. for 18 hours. by reacting, to prepare a _{H- (CH 2) 5 -O- (} CH 2) 2 -O- (CH 2) 5 -H.

_{<H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) a ₆ -OH production>
H (CH ₂ ) ₄ O (CH ₂ ) ₂ Cl (41 g) and HO (CH ₂ ) ₆ OH (236 g) in the presence of Na (5.7 g) in diethylene glycol dimethyl ether (solvent; 250 g) By reacting at 90 ° C. for 24 hours, H— (CH ₂ ) ₄ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₆ —OH was produced.

_{<H- (CH 2) 6 -O-} (CH 2) 2 -O- (CH 2) 4 -OH manufacturing>
By reacting H (CH ₂ ) ₆ O (CH ₂ ) ₂ Cl (49 g) and HO (CH ₂ ) ₄ OH (180 g) in the presence of Na (6 g) at 90 ° C. for 24 hours, - and _{(CH 2) 6 -O- (CH} 2) 2 -O- (CH 2) to produce a ₄ -OH.

_{<H- (CH 2) 8 -O-} (CH 2) 2 -O- (CH 2) 2 -OH manufacturing>
By reacting H (CH ₂ ) ₈ Cl (109 g) with HO (CH ₂ ) ₂ O (CH ₂ ) ₂ OH (500 g) in the presence of Na (13.6 g) at 85 ° C. for 18 hours. _{, H- (CH 2) 8 -O-} (CH 2) 2 -O- (CH 2) was prepared ₂ -OH.

_{<H- (CH 2) 6 -O-} (CH 2) 2 -O- (CH 2) a ₆ -H production>
H (CH ₂ ) ₆ Cl (48 g) and HO (CH ₂ ) ₂ OH (6 g) in a 50% aqueous sodium hydroxide solution (20 g) in the presence of TBAH (catalytic amount) at 65 ° C. for 24 hours by reacting, H- and _{(CH 2) 6 -O- (CH} 2) 2 -O- (CH 2) to produce a ₆ -H.

_{<H- (CH 2) 7 -O-} (CH 2) 2 -O- (CH 2) 7 -H of production>
H (CH ₂ ) ₇ Cl (47 g) and HO (CH ₂ ) ₂ OH (7 g) were mixed in 50% aqueous sodium hydroxide solution (23 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 12 hours. By reacting, H— (CH ₂ ) ₇ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₇ —H was produced.

_{<H- (CH 2) 8 -O-} (CH 2) 2 -O- (CH 2) 8 -H of production>
H (CH ₂ ) ₈ Cl (89 g) and HO (CH ₂ ) ₂ OH (12 g) were mixed in 50% aqueous sodium hydroxide (40 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 12 hours. By reacting, H— (CH ₂ ) ₈ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₈ —H was produced.

_{<H- (CH 2) 5 -O-} (CH 2) 6 -O- (CH 2) 5 -H of production>
H (CH ₂ ) ₅ OH (132 g) and Br (CH ₂ ) ₆ Br (283 g) were mixed in 50% aqueous sodium hydroxide solution (246 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 24 hours. By reacting, H— (CH ₂ ) ₅ —O— (CH ₂ ) ₆ —O— (CH ₂ ) ₅ —H was produced.

_{<H- (CH 2) 9 -O-} (CH 2) 2 -O- (CH 2) 9 -H manufacturing>
H (CH ₂ ) ₉ Cl (49 g) and HO (CH ₂ ) ₂ OH (6.2 g) in 50% aqueous sodium hydroxide solution (20 g) in the presence of TBAH (catalytic amount) at 80 ° C. By reacting for 12 hours, H— (CH ₂ ) ₉ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₉ —H was produced.

_{<H- (CH 2) 10 -O-} (CH 2) 2 -O- (CH 2) 10 -H manufacturing>
H (CH ₂ ) ₁₀ Cl (106 g) and HO (CH ₂ ) ₂ OH (12.4 g) in a 50% aqueous sodium hydroxide solution (40 g) in the presence of TBAH (catalytic amount) at 80 ° C. By reacting for 12 hours, H— (CH ₂ ) ₁₀ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₁₀ —H was produced.

_{<H- (CH 2) 12 -O-} (CH 2) 2 -O- (CH 2) 12 -H manufacturing>
H (CH ₂ ) ₁₂ Cl (123 g) and HO (CH ₂ ) ₂ OH (12.4 g) in 50% aqueous sodium hydroxide (40 g) in the presence of TBAH (catalytic amount) at 80 ° C. By reacting for 12 hours, H— (CH ₂ ) ₁₂ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₁₂ —H was produced.

_{<H- (CH 2) 5 -O} - [(CH 2) 2 -O] 2 - (CH 2) 5 -H of production>
H (CH ₂ ) ₅ Cl (58 g) and HO [(CH ₂ ) ₂ O] ₂ OH (19 g) were added in 50% aqueous sodium hydroxide (70 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 5 -O} - [(CH 2) 2 -O] 2 - was (CH ₂₎ to produce a ₅ -H.

_{<H- (CH 2) 6 -O} - [(CH 2) 2 -O] 2 - (CH 2) a ₆ -H production>
H (CH ₂ ) ₆ Cl (44 g) and HO [(CH ₂ ) ₂ O] ₂ OH (13 g) were added in 50% aqueous sodium hydroxide (48 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 6 -O} - [(CH 2) 2 -O] 2 - was (CH ₂₎ a ₆ -H prepared.

_{<H- (CH 2) 7 -O} - [(CH 2) 2 -O] 2 - (CH 2) 7 -H of production>
H (CH ₂ ) ₇ Cl (40 g) and HO [(CH ₂ ) ₂ O] ₂ OH (10.6 g) in 50% aqueous sodium hydroxide solution (20 g) in the presence of TBAH (catalytic amount) By reacting at 80 ° C. for 12 hours, H— (CH ₂ ) ₇ —O — [(CH ₂ ) ₂ —O] ₂ — (CH ₂ ) ₇ —H was produced.

_{<H- (CH 2) 8 -O} - [(CH 2) 2 -O] 2 - (CH 2) 8 -H of production>
H (CH ₂ ) ₈ Cl (89 g) and HO [(CH ₂ ) ₂ O] ₂ OH (21 g) in a 50% aqueous sodium hydroxide solution (80 g) in the presence of TBAH (catalytic amount), 75 H— (CH ₂ ) ₈ —O — [(CH ₂ ) ₂ —O] ₂ — (CH ₂ ) ₈ —H was produced by reacting at 24 ° C. for 24 hours.

_{<H- (CH 2) 9 -O} - [(CH 2) 2 -O] 2 - (CH 2) 9 -H manufacturing>
H (CH ₂ ) ₉ Cl (30 g) and HO [(CH ₂ ) ₂ O] ₂ OH (6.5 g) were mixed with TBAH (catalytic amount) in 50% aqueous sodium hydroxide solution (12.3 g). presence, 80 ° C., by reacting 12 _{hours, H- (CH 2) 9 -O} - was prepared _{(CH 2) 9 -H - [} (CH 2) 2 -O] 2.

_{<H- (CH 2) 10 -O} - [(CH 2) 2 -O] 2 - (CH 2) 8 -H of production>
H (CH ₂ ) ₁₀ Cl (61.5 g) and H (CH ₂ ) ₈ O [(CH ₂ ) ₂ O] ₂ H (38 g) in 50% aqueous sodium hydroxide (34.8 g) , TBAH (catalytic amount) presence, 75 ° C., by reaction for 24 _{hours, H- (CH 2) 10 -O} - [(CH 2) 2 -O] 2 - was (CH ₂₎ to produce a ₈ -H .

_{<H- (CH 2) 10 -O} - [(CH 2) 2 -O] 2 - (CH 2) 10 -H manufacturing>
H (CH ₂ ) ₁₀ Cl (106 g) and HO [(CH ₂ ) ₂ O] ₂ OH (21 g) were added in 50% aqueous sodium hydroxide (40 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 10 -O} - [(CH 2) 2 -O] 2 - was (CH ₂₎ to produce a ₁₀ -H.

_{<H- (CH 2) 12 -O} - [(CH 2) 2 -O] 2 - (CH 2) 12 -H manufacturing>
H (CH ₂ ) ₁₂ Cl (86 g) and HO [(CH ₂ ) ₂ O] ₂ OH (15 g) were added in 50% aqueous sodium hydroxide (28 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., H- (CH ₂₎ by reacting 12 hours _{12 -O - [(CH 2)} 2 -O] 2 - was (CH ₂₎ to produce a ₁₂ -H.

_{<H- (CH 2) 6 -O} - [(CH 2) 2 -O] 3 - (CH 2) 6 -H of production>
H (CH ₂ ) ₆ Cl (55 g) and HO [(CH ₂ ) ₂ O] ₃ OH (30 g) were added in 50% aqueous sodium hydroxide (80 g) in the presence of TBAH (catalytic amount) in the presence of 60%. ° C., by reaction for 24 _{hours, H- (CH 2) 6 -O} - [(CH 2) 2 -O] 3 - was (CH ₂₎ a ₆ -H prepared.

_{<H- (CH 2) 7 -O} - [(CH 2) 2 -O] 3 - (CH 2) 7 -H of production>
H (CH ₂ ) ₇ Cl (35 g) and HO [(CH ₂ ) ₂ O] ₃ OH (13 g) were added in 50% aqueous sodium hydroxide (17 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 7 -O} - [(CH 2) 2 -O] 3 - was (CH ₂₎ a ₇ -H prepared.

_{<H- (CH 2) 8 -O} - [(CH 2) 2 -O] 3 - (CH 2) 8 -H of production>
H (CH ₂ ) ₈ Cl (89 g), HO [(CH ₂ ) ₂ O] ₃ OH (30 g) in 50% aqueous sodium hydroxide (40 g) in the presence of TBAH (catalytic amount), 80 ° C., by reacting 12 _{hours, H- (CH 2) 8 -O} - [(CH 2) 2 -O] 3 - was (CH ₂₎ to produce a ₈ -H.

_{<H- (CH 2) 9 -O} - [(CH 2) 2 -O] 3 - (CH 2) 9 -H manufacturing>
H (CH ₂ ) ₉ Cl (36.6 g) and HO [(CH ₂ ) ₂ O] ₃ OH (15 g) in 50% aqueous sodium hydroxide (15 g) in the presence of TBAH (catalytic amount) By reacting at 80 ° C. for 12 hours, H— (CH ₂ ) ₉ —O — [(CH ₂ ) ₂ —O] ₃ — (CH ₂ ) ₉ —H was produced.

_{<H- (CH 2) 10 -O} - [(CH 2) 2 -O] 3 - (CH 2) 10 -H manufacturing>
H (CH ₂ ) ₁₀ Cl (40 g) and HO [(CH ₂ ) ₂ O] ₃ OH (30 g) in 50% aqueous sodium hydroxide solution (12.3 g) in the presence of TBAH (catalytic amount) By reacting at 80 ° C. for 12 hours, H— (CH ₂ ) ₁₀ —O — [(CH ₂ ) ₂ —O] ₃ — (CH ₂ ) ₁₀ —H was produced.

_{<H- (CH 2) 12 -O} - [(CH 2) 2 -O] 3 - (CH 2) 12 -H manufacturing>
H (CH ₂ ) ₁₂ Cl (74 g) and HO [(CH ₂ ) ₂ O] ₃ OH (18 g) were added in 50% aqueous sodium hydroxide solution (24 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 12 -O} - [(CH 2) 2 -O] 3 - was (CH ₂₎ to produce a ₁₂ -H.

_{<H- (CH 2) 6 -O} - [(CH 2) 2 -O] 4 - (CH 2) 6 -H of production>
H (CH ₂ ) ₆ Cl (55 g) and HO [(CH ₂ ) ₂ O] ₄ OH (39 g) were added in 50% aqueous sodium hydroxide (40 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 6 -O} - [(CH 2) 2 -O] 4 - was (CH ₂₎ a ₆ -H prepared.

_{<H- (CH 2) 7 -O} - [(CH 2) 2 -O] 4 - (CH 2) 5 -H of production>
H (CH ₂ ) ₇ O [(CH ₂ ) ₂ O] ₄ H (10.4 g), H (CH ₂ ) ₅ Cl (3.9 g) in 50% aqueous sodium hydroxide solution (7.1 g) Then, in the presence of TBAH (catalytic amount), the reaction is performed at 70 ° C. for 24 hours to produce H— (CH ₂ ) ₇ —O — [(CH ₂ ) ₂ —O] ₄ — (CH ₂ ) ₅ —H did.

_{<H- (CH 2) 8 -O} - [(CH 2) 2 -O] 4 - (CH 2) 4 -H of production>
And _{H (CH 2) 8 O [} (CH 2) 2 -O] 2 H (18.2g), H (CH 2) 4 O (CH 2) 2 O (CH 2) and ₂ Cl (19.5 g) Is reacted in a 50% aqueous sodium hydroxide solution (16.7 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 72 hours to give H— (CH ₂ ) ₈ —O — [(CH ₂ ) _2. —O] ₄ — (CH ₂ ) ₄ —H was prepared.

_{<H- (CH 2) 7 -O} - [(CH 2) 2 -O] 4 - (CH 2) 7 -H of production>
H (CH ₂ ) ₇ Cl (40 g) and HO [(CH ₂ ) ₂ O] ₄ OH (19 g) were added in 50% aqueous sodium hydroxide (20 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 7 -O} - [(CH 2) 2 -O] 4 - was (CH ₂₎ a ₇ -H prepared.

_{<H- (CH 2) 8 -O} - [(CH 2) 2 -O] 4 - (CH 2) 8 -H of production>
H (CH ₂ ) ₈ Cl (89 g) and HO [(CH ₂ ) ₂ O] ₄ OH (39 g) were added in 50% aqueous sodium hydroxide (40 g) in the presence of TBAH (catalytic amount) in the presence of 80%. H— (CH ₂ ) ₈ —O — [(CH ₂ ) ₂ —O] ₄ — (CH ₂ ) ₈ —H was produced by reacting at 12 ° C. for 12 hours.

_{<H- (CH 2) 9 -O} - [(CH 2) 2 -O] 4 - (CH 2) 9 -H manufacturing>
H (CH ₂ ) ₉ Cl (44 g) and HO [(CH ₂ ) ₂ O] ₄ OH (17 g) were added in 50% aqueous sodium hydroxide solution (18 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 hours, H- (CH _{2) 9} -O - was (CH ₂₎ to produce a _{9 -H - [(CH 2)} 2 -O] 4.

_{<H- (CH 2) 10 -O} - [(CH 2) 2 -O] 4 - (CH 2) 10 -H manufacturing>
H (CH ₂ ) ₁₀ Cl (88 g) and HO [(CH ₂ ) ₂ O] ₄ OH (32 g) were added in 50% aqueous sodium hydroxide solution (33 g) in the presence of TBAH (catalytic amount) in the presence of 80%. ° C., by reacting 12 _{hours, H- (CH 2) 10 -O} - [(CH 2) 2 -O] 4 - was (CH ₂₎ to produce a ₁₀ -H.

_{<H- (CH 2) 12 -O} - [(CH 2) 2 -O] 4 - (CH 2) 12 -H manufacturing>
H (CH ₂ ) ₁₂ Cl (74 g) and HO [(CH ₂ ) ₂ O] ₄ OH (23 g) in a 50% aqueous sodium hydroxide solution (24 g) at 80 ° C. in the presence of TBAH (catalytic amount). By reacting for 12 hours, H— (CH ₂ ) ₁₂ —O — [(CH ₂ ) ₂ —O] ₄ — (CH ₂ ) ₁₂ —H was produced.

_{<H- (CH 2) 6 -O} - [(CH 2) 2 -O] 5 - (CH 2) a ₆ -H production>
H (CH ₂ ) ₆ O (CH ₂ ) ₂ O (CH ₂ ) ₂ Cl (45 g) and HO (CH ₂ ) ₂ OH (4.5 g) in 50% aqueous sodium hydroxide solution (15 g) , TBAH (catalytic amount) presence, 80 ° C., by reacting 12 _{hours, H- (CH 2) 6 -O} - [(CH 2) 2 -O] 5 - the (CH ₂₎ to produce a ₆ -H .

_{<H- (CH 2) 8 -O} - [(CH 2) 2 -O] 5 - (CH 2) 8 -H of production>
H (CH ₂ ) ₈ O (CH ₂ ) ₂ O (CH ₂ ) ₂ Cl (71 g) and HO (CH ₂ ) ₂ OH (6.2 g) were added in 50% aqueous sodium hydroxide solution (40 g). H- (CH ₂ ) ₈ —O — [(CH ₂ ) ₂ —O] ₅ — (CH ₂ ) ₈ —H was produced by reacting at 80 ° C. for 12 hours in the presence of TBAH (catalytic amount). .

_{<H- (CH 2) 10 -O} - [(CH 2) 2 -O] 5 - (CH 2) 10 -H manufacturing>
H (CH ₂ ) ₁₀ O (CH ₂ ) ₂ O (CH ₂ ) ₂ Cl (45 g) and HO (CH ₂ ) ₂ OH (3.5 g) in 50% aqueous sodium hydroxide solution (11 g) , TBAH (catalytic amount) presence, 80 ° C., by reacting 12 _{hours, H- (CH 2) 10 -O} - [(CH 2) 2 -O] 5 - the (CH ₂₎ to produce a ₁₀ -H .

_{<H- (CH 2) 8 -O} - [(CH 2) 2 -O] 6 - (CH 2) 8 -H of production>
H (CH ₂ ) ₈ O (CH ₂ ) ₂ O (CH ₂ ) ₂ Cl (71 g) and HO [(CH ₂ ) ₂ O] ₂ H (10.6 g) were mixed with 50% aqueous sodium hydroxide ( 20 g) in the presence of TBAH (catalytic amount) at 75 ° C. for 12 hours, thereby causing H— (CH ₂ ) ₈ —O — [(CH ₂ ) ₂ —O] ₆ — (CH ₂ ) ₈ —. H was produced.

_{<H- (CH 2) 10 -O} - [(CH 2) 2 -O] 6 - (CH 2) 10 -H manufacturing>
H (CH ₂ ) ₁₀ O (CH ₂ ) ₂ O (CH ₂ ) ₂ Cl (30 g) and HO [(CH ₂ ) ₂ O] ₂ H (4 g) were mixed with 50% aqueous sodium hydroxide (7. 5 g), in the presence of TBAH (catalytic amount), the reaction is carried out at 80 ° C. for 12 hours, whereby H— (CH ₂ ) ₁₀ —O — [(CH ₂ ) ₂ —O] ₆ — (CH ₂ ) ₁₀ — H was produced.

_{<H- (CH 2) 10 -O} - [(CH 2) 2 -O] 7 - (CH 2) 10 -H manufacturing>
H (CH ₂ ) ₁₀ O (CH ₂ ) ₂ O (CH ₂ ) ₂ Cl (43 g) and HO [(CH ₂ ) ₂ O] ₃ H (8.2 g) were mixed with 50% aqueous sodium hydroxide solution (8.2 g). 11 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 12 hours, thereby causing H— (CH ₂ ) ₁₀ —O — [(CH ₂ ) ₂ —O] ₇ — (CH ₂ ) ₁₀ —. H was produced.

_{<H- (CH 2) 5 -O-} (CH 2) 2 -O- (CH 2) 4 -H of production>
H (CH ₂ ) ₄ O (CH ₂ ) ₂ OH (177.3 g) was reacted with thionyl chloride (267.8 g) in dry pyridine (177.8 g) for 3 hours (0 ° C. → 80 ° C.) to give H ( CH ₂ ) ₄ O (CH ₂ ) ₂ Cl was synthesized. After H (CH ₂ ) ₄ O (CH ₂ ) ₂ Cl was purified by distillation, H (CH ₂ ) ₅ OH (5.0 g), H (CH ₂ ) ₄ O (CH ₂ ) ₂ Cl (10.9 g) and Is reacted in a 50% aqueous sodium hydroxide solution (2.6 g) in the presence of TBAH (catalytic amount) at 80 ° C. for 19 hours to give H— (CH ₂ ) ₅ —O— (CH ₂ ) ₂ —. O— (CH ₂ ) ₄ —H was prepared.

_{<H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) 2 -Cl manufacturing>
H (CH ₂ ) ₄ O (CH ₂ ) ₂ O (CH ₂ ) ₂ OH (162 g) was reacted with thionyl chloride (119 g) in dry pyridine (79 g) for 4 hours (0 ° C. → 100 ° C.) to form H- _{(CH 2) 4 -O- (CH} 2) 2 -O- (CH 2) was synthesized ₂ -Cl.

_{<H- (CH 2) 6 -O-} (CH 2) 2 -O- (CH 2) 2 -Cl manufacturing>
H (CH ₂ ) ₆ O (CH ₂ ) ₂ O (CH ₂ ) ₂ OH (250 g) was reacted with thionyl chloride (240 g) in dry pyridine (160 g) for 4 hours (0 ° C. → 80 ° C.) to produce H- and _{(CH 2) 6 -O- (CH} 2) 2 -O- (CH 2) was synthesized ₂ -Cl.

_{<H- (CH 2) 7 -O-} (CH 2) 2 -O- (CH 2) 2 -Cl manufacturing>
Reaction of H (CH ₂ ) ₇ O (CH ₂ ) ₂ O (CH ₂ ) ₂ OH (85 g) with thionyl chloride (74.4 g) in dry pyridine (49.4 g) for 4 hours (0 ° C. → 80 ° C.) by H- and _{(CH 2) 7 -O- (CH} 2) 2 -O- (CH 2) was synthesized ₂ -Cl.

_{<H- (CH 2) 8 -O-} (CH 2) 2 -O- (CH 2) 2 -Cl manufacturing>
H (CH ₂ ) ₈ O (CH ₂ ) ₂ O (CH ₂ ) ₂ OH (180 g) was reacted with thionyl chloride (150 g) in dry pyridine (100 g) for 5 hours (0 ° C. → 80 ° C.) to produce H- and _{(CH 2) 8 -O- (CH} 2) 2 -O- (CH 2) was synthesized ₂ -Cl.

<Production of H— (CH ₂ ) ₆ —O— (CH ₂ ) ₆ —OH>
H (CH ₂ ) ₆ Cl (87.6 g) and HO (CH ₂ ) ₆ OH (510 g) in 50% aqueous sodium hydroxide solution (50 g) in the presence of TBAH (catalytic amount) at 80 ° C. by reacting 24 hours, H- and _{(CH 2) 6 -O- (CH} 2) to produce a ₆ -OH.

_{<H- (CH 2) 8 -O-} (CH 2) 4 -OH manufacturing>
H (CH ₂ ) ₈ Cl (112.9 g) and HO (CH ₂ ) ₄ OH (500 g) in 50% aqueous sodium hydroxide (35 g) in the presence of TBAH (catalytic amount) at 80 ° C. By reacting for 24 hours, H— (CH ₂ ) ₈ —O— (CH ₂ ) ₄ —OH was produced.

_{<H- (CH 2) 8 -O-} (CH 2) a ₆ -OH production>
H (CH ₂ ) ₈ Cl (183.9 g) and HO (CH ₂ ) ₆ OH (500 g) in 50% aqueous sodium hydroxide solution (61 g) in the presence of TBAH (catalytic amount) at 80 ° C. by reacting 19 _{hours, H- (CH 2) 8 -O-} (CH 2) was produced ₆ -OH.

_{<H- (CH 2) 6 -O-} (CH 2) 5 -COOH manufacturing>
H (CH ₂ ) ₆ O (CH ₂ ) ₆ OH (22.7 g) is present in the presence of catalysts Na ₂ WO ₄ .2H ₂ O (0.8 g) and (C ₆ H ₁₃ ) ₄ NHSO ₄ (1.0 g). Then, it was oxidized with 30% hydrogen peroxide (35.9 g) at 90 ° C. for 4 hours to produce H— (CH ₂ ) ₆ —O— (CH ₂ ) ₅ —COOH.

_{<H- (CH 2) 8 -O-} (CH 2) 3 -COOH manufacturing>
H (CH ₂ ) ₈ O (CH ₂ ) ₄ OH (22.5 g) is present in the presence of catalysts Na ₂ WO ₄ .2H ₂ O (0.8 g) and (C ₆ H ₁₃ ) ₄ NHSO ₄ (1.0 g). Then, it was oxidized with 30% aqueous hydrogen peroxide (33.6 g) at 90 ° C. for 4 hours to produce H— (CH ₂ ) ₈ —O— (CH ₂ ) ₃ —COOH.

_{<H- (CH 2) 8 -O-} (CH 2) 5 -COOH manufacturing>
H (CH ₂ ) ₈ O (CH ₂ ) ₆ OH (27.1 g) is present in the presence of catalysts Na ₂ WO ₄ .2H ₂ O (0.8 g) and (C ₆ H ₁₃ ) ₄ NHSO ₄ (1.0 g). Then, it was oxidized with 30% hydrogen peroxide (35.1 g) at 90 ° C. for 4 hours to produce H— (CH ₂ ) ₈ —O— (CH ₂ ) ₅ —COOH.

<Production of H— (CH ₂ ) ₆ —O— (CH ₂ ) ₆ —O—CO—CH ₂ —CO—O— (CH ₂ ) ₆ —O— (CH ₂ ) ₆ —H>
After adding several drops of concentrated sulfuric acid to H (CH ₂ ) ₆ O (CH ₂ ) ₆ OH (11.1 g) and malonic acid HOOCCH ₂ COOH (2.7 g), the mixture was heated under reflux using an aspirator at 80 ° C. for 2 hours. Then, H— (CH ₂ ) ₆ —O— (CH ₂ ) ₆ —O—CO—CH ₂ —CO—O— (CH ₂ ) ₆ —O— (CH ₂ ) ₆ —H was produced.

_{<H- (CH 2) 6 -O-} (CH 2) 6 -O-CO- (CH 2) 4 -CO-O- (CH 2) 6 -O- (CH 2) a 6 -H production>
After adding few drops of concentrated sulfuric acid to H (CH ₂ ) ₆ O (CH ₂ ) ₆ OH (10.3 g) and adipic acid HOOC (CH ₂ ) ₄ COOH (3.7 g), using an aspirator at 80 ° C. for 2 hours. heating under reduced pressure to reflux _{Te, H- (CH 2) 6 -O-} (CH 2) 6 -O-CO- (CH 2) 4 -CO-O- (CH 2) 6 -O- (CH 2) 6 - H was produced.

_{<H- (CH 2) 6 -O-} (CH 2) 6 -O-CO- (CH 2) 6 -CO-O- (CH 2) 6 -O- (CH 2) a 6 -H production>
After adding several drops of concentrated sulfuric acid to H (CH ₂ ) ₆ O (CH ₂ ) ₆ OH (8.8 g) and suberic acid HOOC (CH ₂ ) ₆ COOH (19.5 g), aspirator at 100 ° C. for 4.5 hours Under reduced pressure using H— (CH ₂ ) ₆ —O— (CH ₂ ) ₆ —O—CO— (CH ₂ ) ₆ —CO—O— (CH ₂ ) ₆ —O— (CH ₂ ) _6- H was produced.

_{<H- (CH 2) 6 -O-} (CH 2) 6 -O-CO- (CH 2) 8 -CO-O- (CH 2) 6 -O- (CH 2) a 6 -H production>
After adding a few drops of concentrated sulfuric acid to H (CH ₂ ) ₆ O (CH ₂ ) ₆ OH (12.1 g) and sebacic acid HOOC (CH ₂ ) ₈ COOH (5.3 g), using an aspirator at 80 ° C. for 4 hours. heating under reduced pressure to reflux _{Te, H- (CH 2) 6 -O-} (CH 2) 6 -O-CO- (CH 2) 8 -CO-O- (CH 2) 6 -O- (CH 2) 6 - H was produced.

[Example 2: Production of nonionic surfactant]
A nonionic surfactant in which the linear alkyl chain portion of the linear alkylpolyoxyethylene ether was an oxaalkyl chain (C ₅ H ₁₁ —O—C ₆ H ₁₂ —) was produced.

_{<C 5 H 11 -O-C} 6 H 12 - preparation of _{(OCH 2 CH 2) n OH} >
By reacting C ₅ H ₁₁ OH (130 g) and BrC ₆ H ₁₂ Br (280 g) in a 50% aqueous sodium hydroxide solution (240 g) in the presence of TBAH (11 g) at 80 ° C. for 12 hours. to afford the _{C 5 H 11 OC 6 H 12} Br. C ₅ H ₁₁ OC ₆ H ₁₂ Br was identified by infrared spectrum and gas chromatography.

Subsequently, the obtained C ₅ H ₁₁ OC ₆ H ₁₂ Br (58 g) was mixed with HO (C ₂ H ₄ O) ₃ H (180 g) and Na (3.7 g) at 90 ° C. for 24 hours. It was produced _{C 5 H 11 OC 6 H 12} O (C 2 H 4 O) 3 H by reaction. The obtained C ₅ H ₁₁ OC ₆ H ₁₂ O (C ₂ H ₄ O) ₃ H was identified by infrared spectrum and gas chromatography.

Next, the obtained C ₅ H ₁₁ OC ₆ H ₁₂ O (C ₂ H ₄ O) ₃ H (64 g) was added to 80 ° C. for 12 hours in the presence of SOCl ₂ (31 g) and pyridine (20 g). It was reacted _to give the _{C 5 H 11 OC 6 H 12} O (C 2 H 4 O) 2 C 2 H 4 Cl. The obtained C ₅ H ₁₁ OC ₆ H ₁₂ O (C ₂ H ₄ O) ₂ C ₂ H ₄ Cl was identified by infrared spectrum and gas chromatography.

The obtained C ₅ H ₁₁ OC ₆ H ₁₂ O (C ₂ H ₄ O) ₂ C ₂ H ₄ Cl (30 g), HO (C ₂ H ₄ O) ₃ H (71 g), and Na (1. In the presence of 4 g), the reaction was carried out at 90 ° C. for 24 hours to obtain the objective surfactant C ₅ H ₁₁ OC ₆ H ₁₂ (OC ₂ H ₄ ) ₆ OH of the present invention. The obtained C ₅ H ₁₁ OC ₆ H ₁₂ (OC ₂ H ₄ ) ₆ OH was identified by infrared spectrum and gas chromatography.

The purity of the obtained final product (C ₅ OC ₆ (OCH ₂ CH ₂ ) ₆ OH; abbreviated as C ₅ OC ₆ E ₆ ) was 99.84% or more.

<Comparison between a nonionic surfactant having a linear alkyl chain part of an oxaalkyl chain and a nonionic surfactant having a linear alkyl chain>
The aqueous solution properties (phase diagram and bubble-breaking property) of C ₅ OC ₆ E ₆ were compared with nonionic surfactants (C ₁₂ (OCH ₂ CH ₂ ) ₆ OH; C ₁₂ E; (Abbreviated as ₆ ).

FIG. 2 shows a two-component phase diagram of a nonionic surfactant and water. The left side of FIG. 2 (the figure with “C ₁₂ E ₆ / water system” attached) is a binary system phase diagram of C ₁₂ E ₆ and water, and the right side of FIG. 2 (“C ₅ OC ₆ E ₆ / aqueous system” is The attached figure is a binary system phase diagram of C ₅ OC ₆ E ₆ and water.

In the case of C ₁₂ E ₆ , the melting point is about 26 ° C., and it may solidify in winter. When this is diluted with water at room temperature, it gels in the region of about 40 to 85% by weight (wt%) and mechanical stirring becomes impossible. In order to avoid this, it is necessary to dilute while heating to about 60 ° C. to avoid the gelation region, resulting in an extra energy loss.

In contrast, in C ₅ OC ₆ E ₆ , as shown in the right side of FIG. 2 (“C ₅ OC ₆ E ₆ / water system” is attached, the solid phase region has a lower melting point (pure nonionic surface activity). The melting point of the agent has shifted to a low temperature region due to -2.4 ° C. It can also be seen that the gel phase region is surprisingly reduced as compared with the case of having a linear alkyl chain as a hydrophobic group. It can be seen that the two-phase separation region of water and the surfactant phase indicated by 2φ in Fig. 2 is also moved to a high temperature region, and the liquid phase region is remarkably expanded by these effects. Since it has a melting point of −2.4 ° C., there is no concern about solidification when diluted with water, and since it is in the liquid phase region at any concentration near room temperature, it does not gel. It can be diluted to a concentration and no heating is required.

Further, even in C ₅ OC ₆ E ₆ , the critical micelle concentration is about 5 × 10 ⁻⁵ mol / L, which is the same as C ₁₂ E _6, and is not affected by oxaalkylation.

Further, the foam destroying the _C 5 _{OC 6 E} 6 3 _shows the results of a comparison with the foam destroying of _C 12 _{E 6.} In FIG. 3, the left sample (described as “C ₅ OC ₆ E ₆ ” at the bottom) is a 0.1% aqueous solution of C ₅ OC ₆ E ₆ , and the right sample (“C ₁₂ E ₆ ” at the bottom). wherein) is 0.1% aqueous solution of _C 12 _{E 6.} It can be seen that C ₅ OC ₆ E ₆ is less foaming than the existing C ₁₂ E ₆ immediately after shaking, and after 20 seconds, the foam completely disappears and exhibits strong foam breaking properties.

[Example 3: Production of plasticizer]
The alkyl chain portion of the phthalic acid dialkanol ester is replaced with an oxaalkyl chain (C ₆ H ₁₃ —O—C ₆ H ₁₂ — or C ₄ H ₉ —O—C ₂ H ₄ —O—C ₄ H ₈ —). A plasticizer with a different structure was produced.

<Plasticizer model compound _{H- (CH 2) 13 -O-} CO- (o-Ph) -CO-O- (CH 2) 13 -H manufacturing>
After adding a few drops of concentrated sulfuric acid to a reaction solution containing 1-tridecanol H (CH ₂ ) ₁₃ OH (5.0 g) and phthalic anhydride (11.1 g), the pressure was reduced using an aspirator at 100 ° C. for 4 hours and a half. It was heated to _reflux, H- and _{(CH 2) 13 -O-CO-} (o-Ph) -CO-O- (CH 2) a 13 -H prepared. The resulting H— (CH ₂ ) ₁₃ —O—CO— (o—Ph) —CO—O— (CH ₂ ) ₁₃ —H (abbreviated as “Pht (COOn13) ₂ ” as appropriate) is column chromatography. And purified by the Kugelrohr method and identified and tested for purity by infrared spectrum.

_{<H- (CH 2) 6 -O-} (CH 2) 6 -O-CO- (o-Ph) -CO-O- (CH 2) 6 -O- (CH 2) a 6 -H production>
After adding a few drops of concentrated sulfuric acid to the reaction solution containing H (CH ₂ ) ₆ O (CH ₂ ) ₆ OH (6.0 g) and phthalic anhydride (18.0 g), using an aspirator at 80 ° C. for 4 hours. heating under reduced pressure to reflux _{Te, H- (CH 2) 6 -O-} (CH 2) 6 -O-CO- (o-Ph) -CO-O- (CH 2) 6 -O- (CH 2) 6 - H was produced. The resulting _{H- (CH 2) 6 -O- (} CH 2) 6 -O-CO- (o-Ph) -CO-O- (CH 2) 6 -O- (CH 2) 6 -H ( " Pht (COO 6 O 6) ₂ ”, abbreviated as appropriate), was purified by column chromatography and Kugelrohr method, and identified and tested for purity by infrared spectrum.

_{<H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) 4 -O-CO- (o-Ph) -CO-O- (CH 2) 4 -O- (CH 2 ) Production of _2- O— (CH ₂ ) ₄ —H>
After adding few drops of concentrated sulfuric acid to H (CH ₂ ) ₄ O (CH ₂ ) ₂ O (CH ₂ ) ₄ OH (5.7 g) and phthalic anhydride (18.0 g), using an aspirator at 80 ° C. for 4 hours. heating under reduced pressure to reflux _{Te, H- (CH 2) 4 -O-} (CH 2) 2 -O- (CH 2) 4 -O-CO- (o-Ph) -CO-O- (CH 2) 4 - O— (CH ₂ ) ₂ —O— (CH ₂ ) ₄ —H was prepared. The resulting _{H- (CH 2) 4 -O- (} CH 2) 2 -O- (CH 2) 4 -O-CO- (o-Ph) -CO-O- (CH 2) 4 -O- ( CH ₂ ) ₂ —O— (CH ₂ ) ₄ —H (abbreviated as “Pht (COO ₄ O ₂ O ₄ ) ₂ ” as appropriate) is purified by column chromatography and Kugelrohr method, and identification and purity test are performed by infrared spectrum. It was.

<Comparison between a plasticizer in which the linear alkyl chain portion is an oxaalkyl chain and a plasticizer having a linear alkyl chain>
The alkyl chain portion of the phthalic acid dialkanol ester is replaced with an oxaalkyl chain (C ₆ H ₁₃ —O—C ₆ H ₁₂ — or C ₄ H ₉ —O—C ₂ H ₄ —O—C ₄ H ₈ —). Thermoplastic properties (crystallinity and melting point and glass transition point) of a plasticizer model compound having a different structure are compared with those of a commercially available plasticizer having a branched alkyl chain having a similar chain length (iso-C ₁₃ H ₂₇ OCO (o-Ph) COOiso- C ₁₃ H ₂₇ ; appropriately abbreviated as “Pht (COOiso13) ₂ ”) and a plasticizer model compound Pht (COOn13) ₂ having a linear alkyl chain.

FIG. 5 shows infrared spectra of Pht (COOn13) ₂ , Pht (COO 6 O 6) ₂ , and Pht (COO 4 O ₂ O 4) ₂ . In FIG. 5, (A) shows the infrared spectrum pattern of _{Pht (COO4O2O4) 2, (B} ) shows the infrared spectrum pattern of _{Pht (COO6O6) 2,, (} C) is Pht _{(COOn13) 2} red The outer spectrum pattern is shown.

  According to FIG. 5, the infrared spectrum pattern of each compound was very similar, and it was shown that the primary structure and the three-dimensional structure of the molecular skeleton were equivalent.

The stretching vibration band of carbonyl C = O double bond (shown as (1) in FIG. 5) is used as the strength standard, and the ether C—O single bond stretching vibration band (shown as (2) in FIG. 5) and methylene CH ₂ scissors are used. The plasticizer produced this time was identified from the relative strength of the vibration band (indicated by (3) in FIG. 5). _That, Pht _{(COOn13) 2,} the relative intensities of Pht (COO6O6) 2, Pht ( COO4O2O4) 2 in order ether C-O single bond band is increased, the relative intensities of methylene CH ₂ bands by substitution of contrast ether oxygen atom Is decreasing. In addition, since no OH stretching vibration band derived from the raw material was observed in the 3000 to 3600 cm ⁻¹ region, it was shown that these samples had high purity.

The plasticizer model compound Pht (COOn13) ₂ having a linear alkyl chain has high crystallinity and a melting point of 26.1 ° C., which cannot be said to have thermophysical properties suitable as a plasticizer. On the other hand, the commercially available plasticizer Pht (COOiso13) ₂ having a branched alkyl chain has a melting point of −21.1 ° C., which is 47.2 ° C. lower than that of the model compound. Part of this decrease in melting point is due to the packing hindering effect of the branched chain. Furthermore, since the commercial product is a mixture of various compounds having various branched structures in the branched alkyl chain of the side chain, the polydisperse effect resulting from this is considered to be the cause of the melting point drop. Crystallization is significantly hindered by the above factors, and in fact, the crystallization rate is very slow even below the melting point, and only shows a glass transition point at -78.4 ° C. It is a feature of a commercially available plasticizer having a branched alkyl chain that it has such a crystallization inhibition effect and a low glass transition temperature.

In contrast, Pht (COO 6 O 6) ₂ having one ether oxygen atom produced this time has a melting point of −14.6 ° C. even in a monodisperse high-purity substance (40.7 ° C. lower than model compound Pht (COOn 13) ₂ ), A glass transition temperature of −88.6 ° C., clearly showing a melting point reduction effect and a crystallization inhibition effect comparable to commercially available products (shown in Table 2 are melting point and melting point reduction). By mixing Pht (COO6O6) ₂ with several kinds of compounds having various branched structures in the branched alkyl chain of the side chain, it is possible to further enhance the crystallization inhibitory effect due to the polydisperse effect. Pht (COO6O6) ₂ can be said to be effective as a plasticizer.

Further, in Pht (COO 4 O ₂ O 4) ₂ having two ether oxygen atoms, the melting point was not observed even in the pure substance, and only the glass transition point was observed at −85.2 ° C. This result indicates that Pht (COO4O2O4) ₂ is superior to a commercial product in terms of thermophysical properties required as a plasticizer such as a crystallization inhibition effect and a measured glass transition point.

  As described above, the compound according to the present invention can be used to produce a modified compound in which a linear alkyl chain portion of the compound having a linear alkyl chain is an oxaalkyl chain. When the compound having a chain or a composition containing the compound is mixed, the melting point of the compound having a linear alkyl chain or a composition containing the same is decreased or lost, the glass transition point is decreased, the crystal / liquid crystal transition temperature is decreased. It is possible to perform significant modification of physical properties such as reduction, suppression of foaming property, and reduction of pour point.

  Therefore, a wide range of materials such as plasticizers, surfactants, liquid crystal molecules, elastomers, and synthetic resins can be modified to have excellent physical properties, and the influence on the shape of the molecular aggregate itself. Since it is possible to control the material properties over a wide range by adjusting the length of the oxaalkyl chain and the position of the oxygen atom and oxyalkylene group in the oxaalkyl chain, compared with other physical property modification methods In this case, it is advantageous in designing and controlling the three-dimensional structure.

  For this reason, application to a very wide range of materials, in particular, plasticizers, surfactants, liquid crystal molecules, elastomers, synthetic resins, adhesives, lubricating oils and the like can be expected. It can also be used as a foam suppressor and is very useful. Therefore, the present invention can be used in various chemical industries such as industrial material manufacturing industries, and is very useful.

It is a figure which shows typically the mode of competition with the van der Waals attraction of the methylene chain part between oxaalkyl chains, and the electrostatic repulsion between oxygen atoms. In Example illustrates the results of a two-component phase diagram of the C ₅ OC ₆ E ₆ and water, compared to two-component phase diagram of the C ₁₂ E ₆ and water. In _embodiments, a diagram showing the results of the foam destroying the C 5 _{OC 6 E 6,} was compared with foam destroying of _C 12 _{E 6.} It is a schematic diagram of the structure of the novel dicarboxylic acid dialkyl ester (an example) concerning this invention. It is a figure which shows the infrared spectrum pattern of Pht (COOn13) ₂ , Pht (COO6O6) ₂ , Pht (COO4O2O4) ₂ .

Claims (5)

The general formula of the following (1 ')
^{_{R 1 - (CH 2) i}} -O- (CH 2) l -R 2 (1')
(In the general formula (1 ′), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a halogen atom, an acryloyloxy group, a carboxyl group, an amino group, a cyano group, or a vinyl group. , I and l are each independently an integer of 2 to 20, and satisfy the relationship of i + l ≧ 6.)
The surfactant modifier as a raw material, to the surfactant modifier having a structure represented by in,
- _{(OCH 2} CH _{2) (wherein,} n is 3 or more and 40 or less.) N OH by introducing a hydrophilic group to have a structure represented by,
The following general formula (3)
R ³ -Hydrophilic group (3)
(In the formula, R ³ is a linear alkyl chain, the hydrophilic group is — (OCH ₂ CH ₂ ) _n OH, and n is 3 or more and 40 or less.)
The linear alkyl chain of the surfactant having a linear alkyl chain represented by the following general formula (2 ′)
_{- (CH 2) i -O- (} CH 2) l - (2')
(In general formula (2 ′), i and l are each independently an integer of 2 or more and 20 or less and satisfy the relationship of i + l ≧ 6.)
A method for producing a defoaming agent comprising a surfactant, comprising obtaining a defoaming agent comprising a surfactant having an oxaalkyl chain comprising a structure represented by the formula: The following formula H (CH ₂ ) ₄ O (CH ₂ ) ₂ O (CH ₂ ) ₄ OH
A linear alkyl chain of a phthalic acid dialkanol ester having a linear alkyl chain by reacting the plasticizer modifier with phthalic anhydride using a plasticizer modifier having a structure represented by Is represented by the following formula — (CH ₂ ) ₄ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₄ —
It is an oxaalkyl chain containing a structure represented by the following formula
_{H- (CH 2) 4 -O- (} CH 2) 2 -O- (CH 2) 4 -O-CO- (o-Ph) -CO-O- (CH 2) 4 -O- (CH 2) ₂ -O- _{(CH 2)} 4 -H
In; and obtaining a plasticizer represented method plasticizers. A defoaming agent comprising a surfactant,
The surfactant has the following general formula (3)
R ³ -Hydrophilic group (3)
In the surfactant having the structure represented by
In the general formula (3), the hydrophilic group is — (OCH ₂ CH ₂ ) _n OH, n is 3 or more and 40 or less,
R ³ is the following general formula (4 ′)
_{H- (CH 2) i -O- (} CH 2) l - (4')
(In the general formula (4 ′), i and l are each independently an integer of 2 or more and 20 or less and satisfy the relationship of i + l ≧ 6.)
A foam inhibitor , which is a compound having a structure represented by: A dicarboxylic acid diester compound represented by the following formula.
_{H- (CH 2) 4 -O- (} CH 2) 2 -O- (CH 2) 4 -O-CO- (o-Ph) -CO-O- (CH 2) 4 -O- (CH 2) ₂ -O- _{(CH 2)} 4 -H A plasticizer comprising the dicarboxylic acid diester compound according to claim 4.