JPS6076526A - Production of polyurethane - Google Patents

Abstract

PURPOSE:To produce a polyurethane having excellent physical properties, by reacting a polyisocyanate compound with a polymer polyol obtained by the polymerization of a monomer in a specific unsaturated polyol having a nitrogen-containing bond. CONSTITUTION:The objective polyurethane is produced by reacting (A) a polyisocyanate compound with (B) a polymer polyol obtained by the polymerization of a monomer containing polymerizable unsaturated group (e.g. acrylonitrile) in an unsaturated polyol having a nitrogen-containing group and composed of at least two compound of (i) an essentially saturated polyol having >=2 hydroxyl groups, (ii) an unsaturated polyhydroxyl compound having >=2 hydroxyl groups and a polymerizable unsaturated group and (iii) an unsaturated monohydroxyl compound having a hydroxyl group and a polymerizable unsaturated group, wherein the above compounds are bonded together through (iv) a polyisocyanate containing >=2 NCO groups. USE:Energy-absorption foam, foam for automobile sheet, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyurethane using a polymer polyol, and particularly to a method for producing polyurethane using a polymer polyol, and in particular, a method for producing polyurethane using a polyol having a specific polymerizable unsaturated group. The present invention relates to a method for producing polyurethane using a polymer polyol obtained by the above method.

Compounds and mixtures obtained by polymerizing monomers with polymerizable unsaturated groups in polyols such as polyether polyols and polyester polyols are called polymer polyols, and there are two main types of polymer polyols, such as polyurethane foam and polyurethane elastomer. One of these is a polymer polyol obtained by polymerizing monomers in a polyol that does not substantially contain polymerizable unsaturated groups, and the other is a polymer polyol obtained by polymerizing monomers in a polyol that has polymerizable unsaturated groups. The latter type of polymer polyol is considered to be superior in terms of dispersion stability, etc., but the ease of production and economic efficiency are still insufficient.The present invention uses the latter type. The present invention relates to a polymer polyol.

A monomer having a polymerizable unsaturated group in a polyol having a polymerizable unsaturated group (hereinafter referred to as an unsaturated polyol)
Regarding polymer polyols obtained by polymerizing monomers (hereinafter referred to as monomers), for example, Japanese Patent Publication No. 52-3439
It is described in Japanese Patent Publication No. 52-13834, etc.

In the inventions described in these publications, unsaturated polyols are produced by reacting saturated polyols with unsaturated polycarboxylic acids such as maleic anhydride and then adding alkylene oxide, or by adding alkylene oxide to saturated polyols such as 7lyl glycidyl ether It is manufactured by adding unsaturated epoxide. However, methods using unsaturated acids tend to leave unreacted carboxyl groups, and decomposition of ester groups in unsaturated polyols tends to occur during the production of polymer polyols, resulting in the production of carboxyl groups. There is a problem that it tends to become a polymer polyol with a high Use of a polymer polyol with a high acid value tends to interfere with the urethanization reaction during polyurethane production, making it impossible to obtain a good polyurethane.

Furthermore, one of the problems with conventional unsaturated polyols is that the polymerizable unsaturated groups are difficult to copolymerize with monomers. For example: In unsaturated polyether ester polyols obtained by reacting polyoxyalkyleneol with maleic anhydride and then reacting fullylene oxide such as propylene oxide, the polymerizable unsaturated groups are present between the polyether chains. exist. The polymerizable unsaturated groups embedded in the polymer chain are not easily copolymerized by themselves or with other heptamers. Therefore, it is considered that the polymerizable unsaturated group in the unsaturated polyol is more easily copolymerized with the monomer when it is present at or near the end of the polyol.

The present inventor previously solved the above two problems by using a nitrogen-containing bond-containing unsaturated polyol obtained by bonding an active hydrogen compound having a polymerizable unsaturated group to a polyol via a polyisocyanate compound. In this paper, we proposed a polymer polyol obtained by polymerizing monomers. However, in this case, if the unsaturated active hydrogen compound has two or more active hydrogens, the unsaturated group may not be located at the end of the polyol, so the activity of the unsaturated group may not be sufficient; When the polyol has a polyol, there is a problem that the number of hydroxyl groups in the polyol cannot be increased.

Therefore, as a result of further investigation, the present inventor used a combination of an unsaturated active hydrogen compound having at least two active hydrogens and an unsaturated active hydrogen compound having one active hydrogen, and combined these with a polyisocyanate compound. It has been found that the nitrogen-containing bond-containing unsaturated polyol obtained can be used as an unsaturated polyol for producing a polymer polyol.

Furthermore, it has been found that hydroxyl groups are particularly preferred as active hydrogen compounds. The nitrogen-containing bond-containing unsaturated polyol obtained by bonding an unsaturated polyhydroxy compound to a substantially saturated polyol via a polyisocyanate compound may have an unsaturated group located at the end. Therefore, the nitrogen-containing bond-containing unsaturated polyol obtained by bonding these three components containing hydroxyl groups using a polyisocyanate compound not only has a large total number of unsaturated groups, but also has a large number of unsaturated groups located at the terminals. It has also been found that polyurethane foams obtained using the above polymer polyols are much harder than polyurethane foams using known polymer polyols. This stiff foam is a more desirable physical property for energy absorbing foam applications. That is, the energy-absorbing foam undergoes little deformation when stress is applied, and since it has nitrogen-containing bonds, the reaction rate in urethanization is improved.

It has also been found that the use of amine catalysts can also be reduced.

The present invention relates to a method for producing polyurethane using a polymer polyol obtained by polymerizing monomers in this nitrogen-containing bond-containing unsaturated polyol.
A method for producing polyurethane by reacting a polyol component containing a polymer polyol and a polyisocyanate component containing a polyisocyanate compound, wherein the polymer polyol is a substantially saturated polyol having at least two hydroxyl groups.

3. An unsaturated polyhydroxy compound having at least two hydroxyl groups and at least one polymerizable unsaturated group, and an unsaturated monohydroxy compound having one hydroxyl group and at least one polymerizable unsaturated group. A nitrogen-containing bond-containing compound in which at least two of the three component hydroxyl group-containing compounds are bonded via the polyisocyanate compound is used. A method for producing a polyurethane, characterized in that the polyol is a polymer polyol obtained by polymerizing a monomer having a polymerizable unsaturated group in a polyol containing a saturated polyol.

The polymer polyol in the present invention, which will be described later, is used as a raw material for polyurethane either alone or in combination with an active hydrogen compound such as another polyol that is normally used as a raw material for polyurethane. The active hydrogen compound to be combined with this polymer polyol is preferably a polyhydroxy compound containing at least two hydroxyl groups,
For example, polyether polyols and polyester polyols are used. In particular, polyether polyols are preferred, and polyether polyols include reference alcohols,
These are included in the range referred to below as substantially saturated polyols, such as polyether polyols and tetrahydrofuran polymers produced by adding fullkylene oxide to amines or other so-called initiators. In the present invention, the polyol component consisting of a polymer polyol alone or a mixture of polyols containing the same may further contain a catalyst, a foam stabilizer, a blowing agent, a filler, a crosslinking agent, a chain extender, a stabilizer, a coloring agent, and other additives. may be added. In the case of ordinary polyurethane foam production, catalysts, blowing agents, and foam stabilizers are often considered essential components.As catalysts, amine catalysts such as tertiary amines and organometallic compounds such as organotin compounds are suitable. Possible blowing agents include water, trichlorofluoromethane, and methyl chloride. As the foam stabilizer, an organosilicon compound-based surfactant is suitable.

Other raw materials for polyurethane are polyisocyanate compounds as described below. Polyurethane is obtained by reacting the above polyol component with this polyisocyanate component. As a method for producing polyurethane, conventional methods such as the Wanshicott method and the Prebotsmer method can be used. The most suitable polyurethane is polyurethane foam, and the use of polymer polyols results in highly elastic foams, which are excellent, for example, as energy-absorbing foams and foams for automobile seats.

The polymer polyol in the present invention will be explained in detail below.

As the substantially saturated polyol which is one of the raw materials for producing the polymer polyol, various high molecular weight polyols used as raw materials for polyurethane can be used. Examples include Daiho Moe fp+-/7-1 ester polyol, and hydrocarbon polymers having a hydroxyl group at the end. Preferred are polyether polyols, such as polyether polyols prepared by adding alkylene oxide to active hydrogen-containing compounds such as polyhydroxy compounds, phosphoric acid, and amines, and polyether polyols made of cyclic ether polymers. Specifically, glycol, glycerin, trimethylolpropane, pentaerythritol, nrubitol, dextrose and other polyhydric alcohols, jetanolamine.

Triethanolamine and other flukanolamines, bisphenol A, phenol-formaldehyde condensates, and other polyhydric phenols.

Ethylene oxide in ethylene diamine, diaminodiphenylmethane and other amines.

Propylene oxide, butylene oxide, epichlorohydrin and other fullkylene oxides.

Furthermore, there are polyether polyols to which epoxides such as styrene oxide and glycidyl ether are added, and polyether polyols such as tetrahydrofuran polymers. Two or more of these can be used in combination, and in the case of diols, it is particularly preferable to use them in combination with triols. Preferred polyether polyols are polyether polyols having a molecular weight per OH group of 300 to 2,500,
Particularly preferred are polyether polyols having a molecular weight of 600 to 2,000 per OH group and a number of hydroxyl groups of 2 to 4.

This high molecular weight polyol is a polyol having substantially no polymerizable unsaturated groups. The above-mentioned polyether polyols and polyester polyols usually do not have polymerizable unsaturated groups in their constituent compounds (for example, polyhydroxy compounds or alkylene oxides), or even if they do have them, they are polymerized during polyol production. If so, it is considered that it does not contain a polymerizable unsaturated group. However, in some cases, unsaturated groups may be generated during polyol production due to side reactions. For example, a normal polyether polyol produced by adding an alkylene oxide that does not have a polymerizable unsaturated group to an active hydrogen-containing compound that does not have a polymerizable unsaturated group may contain a small amount of unsaturated groups. Known l, )ru. This is believed to result from a side reaction in the addition reaction of alkylene oxides, especially propylene oxide. The present invention can use conventional polyether polyols having appreciably less unsaturated groups.

As the unsaturated polyhydroxy compound, a compound having at least two hydroxyl groups and at least one polymerizable unsaturated group, such as an unsaturated polyhydric alcohol or an unsaturated polyhydric phenol, is particularly preferably used. is an unsaturated polyhydric alcohol. This unsaturated polyhydric alcohol contains two or more hydroxyl groups, such as unsaturated polyol, unsaturated polyester polyol, unsaturated polyether ester polyol, etc., in addition to unsaturated polyhydric alcohol in the normal sense. Compound -・-and--+E J-+Maya Misaki,--
+1. For example, 2-butene-1,4-
diol, 3-butene-1,2-diol, glycerol allyl ether, trimethylolpropane allyl ether, pentaerythritol vinyl ether.

2,5-dimethyl-3-hexene-2,5-diol,
1,5-hexadiene-3,4-dio Jtz,t,4
There are polyhydric alcohols having one or more unsaturated bonds, such as -butynediol. Unsaturated polyhydric alcohols in a broader sense include unsaturated polyhydric alcohols in a narrower sense and unsaturated polyhydric alcohols obtained by adding epoxides such as fullkylene oxide to other unsaturated active hydrogen compounds having at least two active hydrogens. ether polyol, at least 2
It can be obtained by adding 7lyl glycidyl ether, 1-vinylcyclohexane-3,4-epoxide, butadiene monoepoxide and other epoxides having unsaturated groups to an active hydrogen compound having active hydrogens, either alone or together with other epoxides. unsaturated polyether polyol,
An unsaturated polyester polyol or polyol obtained from a polybasic acid and a polyhydric alcohol containing at least one residue of an unsaturated polybasic acid or an unsaturated polyhydric alcohol in the narrow sense is reacted with an unsaturated polybasic acid, and then an epoxide is formed. There are unsaturated polyether ester polyols obtained by reacting. Of course, the present invention is not limited to these, and compounds having at least two hydroxyl groups and at least one polymerizable unsaturated group can be used.

As the unsaturated polyhydroxy compound having at least two hydroxyl groups in the present invention, unsaturated polyhydric alcohols in the broad sense described above (hereinafter referred to as unsaturated polyhydric alcohols unless otherwise specified) are preferable, particularly unsaturated polyhydric alcohols in the narrow sense. Polyhydric alcohols, particularly unsaturated polyhydric alcohols having 3 to 10 carbon atoms, are preferred. As unsaturated polyhydric alcohols other than unsaturated polyhydric alcohols in the narrow sense, those with relatively low molecular weight are preferable.
Its molecular weight is not particularly limited, but is 4,000
A value of 0 or less, particularly 3,000 or less is suitable. The number of hydroxyl groups in the unsaturated polyhydroxy compound is 2 to 8, especially 2.
-4 is preferred, and 2 is particularly suitable. Further, the number of polymerizable unsaturated groups in one molecule is not particularly limited, but 1 to 4 is appropriate, and 1 to 2 is particularly preferable.

The most preferred unsaturated polyhydroxy compounds are 3-butene-1,2-diol or 2-butene-1,4-diol.

The unsaturated monohydroxy compound is a compound having one hydroxyl group and at least one polymerizable unsaturated group. The polymerizable unsaturated group is preferably a polymerizable double bond, and the number is 1.
Preferably. This hydroxyl group is an alcoholic hydroxyl group or a phenolic hydroxyl group. Various compounds can be used as unsaturated monohydroxy compounds. For example, unsaturated monools, monoesters of unsaturated monocarboxylic acids and dihydric alcohols, monoesters of unsaturated dihydric alcohols and monocarboxylic acids, phenols with alkenyl side chain groups, unsaturated polyether monools, etc. There is.

As the unsaturated monool, ethylene alcohol having 3 to 6 carbon atoms is particularly preferred. Specific compounds include, for example, allyl alcohol, 2-buten-1-ol,
Examples include 3-buten-2-ol, 3-buten-1-ol, and pronogyl alcohol. Examples of monoesters of unsaturated monocarboxylic acids and dihydric alcohols include monoesters of acrylic acid, methacrylic acid, crotonic acid, itaconic acid and other unsaturated monocarboxylic acids and ethylene glycol, propylene glycol, butylene glycol and other dihydric alcohols. Examples of esters include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl acrylate. Examples of monoesters of unsaturated dihydric alcohols and monocarboxylic acids include butyne diol
-Misaki 2, 1. Th t/ 4t 4L 1 7
Examples of the phenol having a +L)y-11-side group include oxystyrene and hydroxy d-methylstyrene. Other unsaturated monohydroxy compounds other than those mentioned above include, for example, N-methylolacrylamides and monomethylaminoethyl methacrylate-1. Although the molecular weight is not particularly limited, it is preferably 1000 or less, particularly 500 or less. Among these, particularly preferred compounds are monoesters of acrylic acid or methacrylic acid with ethylene glycol, propylene glycol or butylene gelicol, allyl alcohol and hydroxy d-methylstyrene.

The polyisocyanate compound is a compound having at least two isocyanate groups ('-Neo),
There are aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and others. Preferably, it is an aromatic polyisocyanate. Specifically, for example, tolylene diisocyanate (TDI),
diphenylmethane diincyanate (MDI), polymethylene polyphenylisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate,
Examples include hexamethylene diisocyanate and inphorone diisocyanate. As these incyanate compounds, it is also possible to use modified polyisocyanate compounds that have been modified using compounds having active hydrogen such as polyhydric alcohols and amines, or using other methods.

The polyisocyanate compound can react with the above-mentioned compound containing a hydroxyl group, resulting in a nitrogen-containing bond such as a urethane bond or an allophanate bond. Usually, this nitrogen-containing bond is a urethane bond. The polyisocyanate compound can react with any of the water groups of the above three hydroxyl group-containing compounds. This reaction occurs in the presence or absence of a catalyst at room temperature to elevated temperature, but the reaction conditions are not particularly limited. It is disadvantageous that the number of incyanato groups in the zero reaction system that reacts with hydroxyl groups to form nitrogen-containing bonds is greater than the number of hydroxyl groups, and that the incyanato groups remain in the final reaction product. That is, in order for the final reaction product to be a nitrogen-containing bound gold-containing M1s polyol, the number of hydroxyl groups in the system must be in excess of the number of incyanate groups. One isocyanate group in the polyisocyanate compound reacts with a hydroxyl group in one of the above three hydroxyl group-containing compounds, and at least one other inocyanate group reacts with a hydroxyl group in the same or different hydroxyl group-containing compound. reacts. Therefore, above 3
At least two molecules of the component hydroxyl group-containing compound (that is, the same number a as the number of isocyanate groups that the polyisocyanate compound has) are bonded by the polyisocyanate compound.

One of the methods for producing a nitrogen-containing bond-containing unsaturated polyol is a method of reacting a mixture of the above three hydroxyl group-containing compounds with a polyisocyanate compound. In this method, it is thought that compounds having various nitrogen-containing bonds are produced depending on the proportion of each of the three hydroxyl group-containing compounds and the proportion of the polyisocyanate compound, and at least one unsaturated group among the produced compounds is considered to be produced. A compound having at least two hydroxyl groups is the nitrogen-containing bond-containing unsaturated polyol in the present invention.

Among various nitrogen-containing bond-containing unsaturated polyols.

Those having 1 to 4 unsaturated bonds are preferred, and those having 1 to 2 unsaturated bonds are particularly preferred. Among the impurities produced, polyols that do not have unsaturated groups (i.e., reaction products of substantially saturated polyols and polyisocyanate compounds) cause the viscosity of the reaction system to be particularly high even if the amount produced is large. However, there is no particular problem unless it is a compound in which an unsaturated polyhydroxy compound and an unsaturated monohydroxy compound are bonded via a polyisocyanate compound or an unsaturated monohydroxy compound)+ze111S/7 -)--k IP
Since Δyushi's summer death pressure is a compound that contains one or no hydroxyl group, it is not desirable for it to be present in large amounts, and unreacted unsaturated polyhydroxy compounds and unsaturated monohydroxy compounds It is also undesirable for a large amount of the polyisocyanate compound to remain, but it does not cause any problems if an unreacted substantially saturated polyol remains. It is preferable to use the compound in an amount approximately equal to or more than the total number of moles of the unsaturated monohydroxy compound and the unsaturated monohydroxy compound.

A preferred nitrogen-containing unsaturated polyol is produced by bonding an unsaturated polyhydroxy compound or an unsaturated monohydroxy compound to one molecule of a substantially saturated polyol via at least one molecule of a polyisocyanate compound.

However, there is no problem with an excess of substantially saturated polyol remaining unreacted, even if the unsaturated polyhydroxy compound and unsaturated monohydroxy compound used are all substantially saturated polyol. Nitrogen-containing bonds formed when one molecule of an unbalanced monohydroxy compound is bonded to one molecule of substantially saturated polyol, even if bonded, unreacted substantially saturated polyol may be present. The number of hydroxyl groups in the gold-containing unsaturated polyol is reduced by one compared to the original polyol. Therefore, when the saturated polyol is a diol, it becomes an unsaturated monool, and when it is a triol, it becomes an unsaturated diol. Therefore, it is preferred that the amount of unsaturated monohydroxy compound used relative to the substantially saturated polyol is limited;
The amount thereof is preferably such that the average number of hydroxyl groups in the produced nitrogen-containing gold-containing unsaturated polyol is 1.7 or more, particularly 2 or more. In addition, as the substantially saturated polyol, it is preferable to use a mixture of a diol and a polyol with a valence of 3 or more than a diol alone, or a polyol with a valence of 3 or more or a mixture thereof, and use of a polyisocyanate compound. The upper limit of the amount is limited by the viscosity of the resulting product containing the nitrogen-bound, gold-containing unsaturated polyol. Generally, as the amount of polyisocyanate compound used increases, the viscosity of the product increases. A highly viscous product causes various inconveniences, such as poor mixing, in the subsequent monomer polymerization step or in the step of producing polyurethane using the finished polymer polyol. Therefore, its viscosity is usually below 20,0OOCP/25℃, especially 1o,
It is preferable that the amount of the polyisocyanate compound used is adjusted so that the oooc p is 725°C or less.

In the method of reacting the mixture of the three hydroxyl group-containing compounds and the polyisocyanate compound described above, it is preferable that the amount of each component used is limited as described above, but the more preferable amount is as follows. That's right. First, the total number of moles of the unsaturated polyhydroxy compound and the unsaturated monohydroxy compound is 0.05 to 2.0 moles, particularly 0.1 to 2.0 moles, per mole of substantially saturated polyol.
It is 1.0 mol. The combination ratio of unsaturated polyhydroxy compound and unsaturated monohydroxy compound is 1/1 in molar ratio.
3 to 10/1, particularly preferably 1/2 to 8/1, the polyincyanate compound is 1 to 2 per mole of the total amount of the unsaturated polyhydroxy compound and the unsaturated monohydroxy compound.
It is preferred to use mol, especially 1 to 1.5 mol.

In a method other than the above, at least one component of the three hydroxyl group-containing compounds is reacted in advance with a polyisocyanate compound to form an incyanate compound having a nitrogen-containing bond and at least one isocyanate group, and this There is a method of reacting with the contained compounds. This method is similar to the prepolymer method for producing polyurethane from a polyol and a polyisocyanate compound. The hydroxyl compound with which the polyisocyanate compound is reacted in advance is preferably an unsaturated polyhydroxy compound, an unsaturated monohydroxy compound, or both. A nitrogen-containing gold-containing unsaturated compound having an incyanate group is obtained from an unsaturated monohydroxy compound and a diisocyanate compound, and these are reacted with a substantially saturated polyol. By doing so, a nitrogen-containing bound gold-containing unsaturated polyol is obtained. When these previously incyanated compounds are used alone,
Especially preferably, both the unsaturated polyhydroxy compound and the unsaturated monohydroxy compound are previously reacted with the polyisocyanate compound and then the substantially saturated This method involves reacting with a polyol. The amount of each component used in this method is preferably approximately the same as the conditions when using the mixture of the three hydroxyl group-containing compounds.

Of the above two methods, a particularly preferred method is the former method using a mixture of three hydroxyl group-containing compounds. Although the latter method yields a relatively controlled product with few impurities, it is complicated with a large number of steps and takes a long time to react. On the other hand, depending on the conditions such as the ratio of raw materials used, the former method not only provides a product that is almost the same as the latter method, but also is extremely easy to manufacture.6 In the present invention, the above two The present invention is not limited to these methods, as long as similar products can be obtained by other methods.

The nitrogen-containing bond-containing unsaturated polyol obtained by the above method may be a single compound, but in many cases it is a mixture of various compounds. This may include unreacted unsaturated polyhydroxy compounds, unsaturated monohydroxy compounds, substantially saturated polyols, etc., and may also include nitrogen-containing bond-containing polyols containing no unsaturated groups. This mixture can be applied as is to the next polymerization operation, or it can be applied after further removal of removable impurities. Further, the nitrogen-containing bond-containing unsaturated polyol or a mixture containing the same can be used diluted with a polyol, and as this polyol, a substantially saturated polyol, particularly a polyether polyol, is usually used, but
In some cases, it may be an unsaturated polyol. A feature of this nitrogen-containing bond-containing unsaturated polyol is that the unsaturated groups contained therein are easily copolymerized with monomers. This is because the unsaturated group is located at or near the end of the molecular chain of the polyol. In addition, unsaturated polyhydroxy compounds and unsaturated monohydroxy compounds are unsaturated groups in unsaturated polyether ester polyols using unsaturated dibasic acids and unsaturated polyether polyols using allyl glycidyl ether, which are described in the above reference. An unsaturated group that is more easily polymerized can be used. Moreover, the nitrogen-containing bonded gold-containing unsustainable polyol of the present invention is characterized in that it can be produced more easily than these known unsaturated polyols.

As a heptamer having a polymerizable unsaturated group, a heptamer having one polymerizable double bond is usually used, but is not limited to this. Specific monomers include acrylonitrile, styrene, Preferred are acrylamide, acrylic acid ester, methacrylate ester, vinyl acetate, etc., but are not limited to these. For example, styrene alone such as d-methylstyrene, dimethylstyrene, and halogenated styrene; olefins such as butadiene and isoprene; Acrylic derivatives such as tolyl methacrylate, butyl acrylate, and benzyl methacrylate, unsaturated fatty acid esters such as vinyl chloride, halogenated vinyl maleate diester, itaconic diester, and other esters can be used. These monomers can be used not only alone, but also in combination with other monomers to form a copolymer. The most preferred seven compounds are acrylonitrile alone, styrene alone,
It is a combination of acrylonitrile and styrene, or other monomers based on acrylonitrile or styrene.

A polymerization initiator is usually required to graft-polymerize the above-mentioned heptamer onto a nitrogen-containing bond-containing unsaturated polyol. However, in some cases, graft polymerization can be carried out using heat or radiation without using a polymerization initiator. 0 As the polymerization initiator, 1 Usually, a type of polymerization initiator that initiates polymerization by generating free radicals is used. It will be done. Specifically, for example, azobisisobutyronitrile, benzoyl peroxide, diisopropyloxydicarbonate,
Examples include acetyl oxide, di-t-butyl peroxide, dicumyl peroxide, silauroyl peroxide, and persulfates. Particularly preferred is azobisisobutyronitrile.

The polymerization reaction is carried out at a temperature higher than the decomposition temperature of the polymerization initiator, usually 80 to 1
It is carried out at 60°C. The amount of nanatsumer to be used is about 60% by weight or less, particularly 10 to 5% by weight, based on the total amount of the monomer and the total polyol including the nitrogen-containing unsaturated polyol used.
0% by weight is preferred. The polymer polyol produced after the polymerization reaction can be used as it is as a raw material for polyurethane, but it may also be subjected to post-treatment such as removing impurities such as decomposed products of the polymerization initiator. A feature of the polymer polyol in the present invention is that it has good dispersion stability. Conventional polymer polyols using saturated polyols did not have sufficient dispersion stability, and it was necessary to use acrylonitrile, which has good dispersion stability, as one of the monomer components. That is, a good polymer polyol could not be obtained unless most or all of the monomers were 7-crylonitrile.

Furthermore, the use of acrylonitrile was almost an essential requirement in conventional methods for producing polymer polyols using unsaturated polyols.In the polymer polyol of the present invention, it is possible to use monomers containing acrylonitrile. Of course, a polymer polyol with good dispersion stability can be obtained without using acrylonitrile at all. For example, styrene alone can be used to obtain polymer polyols with good stability.

The polymer polyol in this invention is usually an opaque dispersion. Polymer polyols using styrene alone are white dispersions, while those using acrylonitrile are colored dispersions. Although it is possible to obtain a relatively transparent polymer polyol depending on the reaction conditions, it is not necessary to use a particularly transparent polymer polyol as a polyurethane raw material, and a dispersion is sufficient.

The present invention will be specifically explained below using reference examples and examples, but the present invention is not limited only to these reference examples and examples.

Reference Examples 1 to 4 Comparative Examples 1 to 4 [Production of nitrogen-containing bond-containing unsaturated polyol] The method for producing the nitrogen-containing bond-containing unsaturated polyol used in the present invention and its production results will be described.

Polyol, unsaturated polyhydric alcohol, and diisocyanate as shown in Table 1 were charged into an autoclave No. 51 and held at 80° C. for 5 hours. In both cases, transparent and slightly viscous liquids were obtained. After confirming that there are no unreacted isocyanate groups using infrared absorption spectrum.

It was used as a raw material for the production of polymer polyols.

Reference Examples 5 to 10 Comparative Examples 5 to 9 A method for producing a polymer polyol composition according to the present invention and its production results will be described.

A predetermined amount of a nitrogen-containing bond-containing unsaturated polyol or a normal polyoxyalkylene polyol produced in Table 1 as shown in Table 2 was charged into a 5-liter autoclave, and the pressure reduction and nitrogen substitution operations were carried out as specified. After repeating the treatment at different temperatures, as shown in Table 2, the mixture of the remaining nitrogen-containing bond-containing unsaturated polyol or usually polyoxyalkylene polyol, a monomer having a polymerizable unsaturated group, and a polymerization initiator was added to the specified mixture. It was introduced into the autoclave while stirring at high speed.

Unreacted polymerizable unsaturated supermers were removed under reduced pressure to obtain the desired polymer polyol.

For comparison, when only a normal polyoxyalkylene polyol was used (Comparative Example 5), when styrene was used as a monomer, it separated and a uniform dispersion could not be obtained. In addition, those using an unsaturated group-containing polyol produced by reacting with ordinary polyesters (Comparative Example-6), those using only unsaturated polyhydroxy compounds as in Comparative Examples 7 and 8, and those using only unsaturated polyhydroxy compounds as in Comparative Example-9. If only a small amount of an unsaturated monohydroxy compound was used, and styrene was used as a 7-mer, only particles with a coarse particle size could be produced.

Examples 1 to 2 Comparative Example 1O A flexible urethane foam was manufactured using the polymer polyols manufactured in Reference Examples 9 and 10 in Table 2. For comparison, a case of foaming using polyoxypropylene triol (polyol B) having a molecular weight of 3000 will also be described.

100 g of polyol or polymer polyol, 1.2 g of silicone L 520, 1) abco 33
Lv (triethylenediamine 1, dipropylene glycol 3) 0.3g, T-9 (stannous octylate) 0
．． 3g, water 4. Table 3 shows the results of foaming by stirring and mixing Og, TDI-80 (ruene diisocyanate) to an index of 105.

It can be seen that, compared to Comparative Example 1O, the foam properties of Reference Examples 9 and 10 are superior, especially in terms of ILD.

Examples 3 to 5 Comparative Examples 11.12 High modulus foams were mold-foamed using the polymer polyols produced in Reference Examples 5, 6, and 7 and Comparative Example 6 shown in Table 2.

For comparison, a case of foaming using polyoxypropylene ethylene triol (polyol A) having a molecular weight of 5000 will also be described.

Polymer polyol (polyol A in the case of Comparative Example-11) 1flOg, polyol 240g Silicon L53
05 4.4g, Dabco 33LV 2.4g,
TDI-80/PAPI 135 (Chemical Upjohn, crude phenylene diisocyaner))-8072 in 12 g of water
0 mixed isocyanate was mixed to have an index of 105, put into an aluminum mold made of 400+am I took it out. The physical properties of the foam are shown in Table 4.

Compared to Comparative Example 11, the foam properties of the polymer polyols of Reference Examples 5, 6, and 7 were particularly poor in ILD.
It can be seen that the results are excellent. In addition, in Comparative Example 6, the reaction was slower than in Examples, and the mold could not be removed in 10 minutes at room temperature, so it was allowed to stand for 15 minutes. Form I
It was found that LD, compression set and χ were inferior.

Claims (1)

[Claims] 1. A method for producing polyurethane by reacting a polyol component containing a polymer polyol and a polyincyanate component containing a polyisocyanate compound,
The polymer polyol is a substantially saturated polyol having at least two hydroxyl groups, an unsaturated polyhydroxy compound having at least two hydroxyl groups and at least one polymerizable unsaturated group, and one hydroxyl group. and 3 of the unsaturated monohydroxy compound having at least one polymerizable unsaturated group.
Using a hydroxyl group-containing compound as a component and a polyincyanate compound having at least two incyanato groups, 8 to 3
A polyurethane characterized in that at least two of the component hydroxyl group-containing compounds are polymer polyols obtained by polymerizing a hexamer having a polymerizable unsaturated group in a polyol containing the polyisocyanate compound. manufacturing method. 2. The manufacturing method according to claim 1, wherein the polyurethane is polyurethane foam.