JP6566517B2 - Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam - Google Patents

Description

  The present invention relates to a polyol composition for rigid polyurethane foam and rigid polyurethane foam containing 1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as HFO-1233zd) as an essential component as a blowing agent component. It relates to a manufacturing method.

  Rigid polyurethane foam is a well-known material as a heat insulating material, a lightweight structural material, and the like. Such a rigid polyurethane foam is formed by mixing a polyol composition containing a polyol compound and a foaming agent as essential components and an isocyanate component, and then foaming and curing the mixture.

  In the past, CFC-11 and other chlorofluorocarbon compounds were used as the foaming agent, but the CFC-11 was prohibited from use because it caused the destruction of the ozone layer, and was switched to HCFC-141b. Are switched to HFC-245fa and HFC-365mfc, which have an ozone layer depletion coefficient of zero, but the HFC-245fa and HFC-365mfc have a problem that the GWP (global warming potential) is large. Therefore, development as a foaming agent of HFO-1233zd that has a low ozone layer depletion coefficient and a global warming coefficient and is not flammable is proceeding (for example, Patent Documents 1 to 8).

Special table 2011-500891 gazette Special table 2011-500892 gazette Special table 2011-50093 gazette JP 2013-64139 A Special table 2013-500386 gazette Special table 2013-501844 gazette Special table 2013-514442 gazette Special table 2013-504656 gazette

  However, since HFO-1233zd has poor compatibility with the polyol compound, the polyol composition containing HFO-1233zd is likely to be separated when stored in the state of the stock solution, and the stock solution storage stability is poor. Moreover, since HFO-1233zd has poor compatibility with the polyol compound, when the hard polyurethane foam is produced, the mixing of the raw material polyol compound and the isocyanate component is poor, and as a result, the physical properties of the resulting rigid polyurethane foam are lowered. Turned out to be. Note that “poor stock storage stability” does not mean that the reactivity deteriorates after storage.

  The present invention has been made in view of the above circumstances, and the object thereof is a rigid polyurethane foam that has good stock storage stability even when HFO-1233zd is used as a foaming agent, and that can suppress a decrease in physical properties of the rigid polyurethane foam. Polyol composition, and a method for producing a rigid polyurethane foam.

  The polyol composition for rigid polyurethane foam of the present invention contains at least a polyol compound, a foaming agent, and a compatibilizing agent, and is mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam. A foam polyol composition, wherein the blowing agent contains HFO-1233zd, and the compatibilizer is γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N -1 or more types chosen from the group which consists of dimethylacetamide and N, N- dimethylformamide are contained.

  The method for producing a rigid polyurethane foam of the present invention is a method for producing a rigid polyurethane foam in which an isocyanate component and a polyol composition are mixed, foamed and cured to obtain a rigid polyurethane foam, and the polyol composition contains at least a polyol compound. A foaming agent and a compatibilizing agent, wherein the foaming agent contains HFO-1233zd, and the compatibilizing agent is γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, 1 or more types chosen from the group which consists of N, N-dimethylacetamide and N, N-dimethylformamide are contained.

  According to the present invention, even when HFO-1233zd is used as the foaming agent, the stock solution storage stability is good, and further, the polyol composition for a rigid polyurethane foam capable of suppressing the deterioration of the properties of the rigid polyurethane foam, and the method for producing the rigid polyurethane foam Can be provided.

<Polyol composition for rigid polyurethane foam>
The polyol composition for rigid polyurethane foam of this embodiment contains at least a polyol compound, a foaming agent, and a compatibilizing agent, and is mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam. Polyurethane foam polyol composition, wherein the foaming agent contains HFO-1233zd, and the compatibilizer is γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, It contains at least one selected from the group consisting of N-dimethylacetamide and N, N-dimethylformamide.

[Polyol compound]
As the polyol compound, known polyol compounds for rigid polyurethane foam can be used without limitation. Examples of such polyol compounds include tertiary amino group-containing polyol compounds, aliphatic polyol compounds, and aromatic polyol compounds.

  The tertiary amino group-containing polyol compound is an alkylene oxide using a primary or secondary amine as an initiator, specifically, propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran or the like. It is a polyfunctional polyol compound obtained by ring-opening addition polymerization of one or more kinds.

  Examples of the primary or secondary amine initiator that is an initiator of the tertiary amino group-containing polyol compound include aliphatic primary and secondary monoamines such as ammonia, methylamine, and ethylamine, ethylenediamine, and hexamethylene. Aliphatic primary to secondary polyamines such as diamine, N, N′-dimethylethylenediamine, aromatic primary to secondary mono to aniline, diphenylamine, toluenediamine, diphenylmethanediamine, N-methylaniline, etc. Illustrative are alkanolamines such as polyamines, monoethanolamine and diethanolamine. The content of the tertiary amino group-containing polyol compound is preferably 10 to 60% by weight and more preferably 20 to 50% by weight in the polyol compound. Tertiary amino group-containing polyol compounds are effective in increasing reactivity and manifesting physical properties. When the amount is less than 10% by weight, no increase in reactivity is observed. When the amount exceeds 60% by weight, the reaction becomes too fast. Causes foam burns and cracks.

  Aliphatic polyol compounds are aliphatic or alicyclic polyfunctional active hydrogen compounds as polyol initiators, alkylene oxides, specifically propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran, etc. It is a polyfunctional oligomer obtained by ring-opening addition polymerization of one or more of the above cyclic ethers, preferably PO or PO and EO.

  As the polyol initiator of the aliphatic polyol compound, glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, Examples include triols such as glycerin, tetrafunctional alcohols such as pentaerythritol, polyfunctional alcohols such as sorbitol and sucrose, water, and the like.

  Examples of the aromatic polyol compound include a polyol compound obtained by the above-described method of adding an alkylene oxide to a polyfunctional active hydrogen compound having an aromatic ring in the molecule, and an ester polyol compound of an aromatic polycarboxylic acid and a polyfunctional alcohol. Is done.

  As a polyol compound obtained by adding the above-mentioned alkylene oxide to a polyfunctional active hydrogen compound, hydroquinone, bisphenol A, Mannich or the like is added to at least one of PO, EO, SO, preferably PO or PO and EO. Specific examples are compounds having ring-opening addition.

  Specific examples of ester polyol compounds of aromatic polycarboxylic acids and polyfunctional alcohols include ester polyol compounds obtained by reacting hydroxyl-terminated alcohols of terephthalic acid, orthophthalic acid, isophthalic acid, etc. with ethylene glycol, diethylene glycol, etc. .

  The polyol compound preferably has a hydroxyl value of 200 to 2000 mgKOH / g. Among these polyol compounds, when a tertiary amino group-containing polyol compound or an aliphatic polyol compound is used, an effect of reducing the viscosity of the polyol composition can be obtained.

  The polyol compound is ethylene glycol (EG), triethylene glycol, diethylene glycol (DEG), 1,4-butanediol, 1,6-hexanediol (1,6-HD), neopentyl glycol, diethylene glycol, dipropylene glycol. It may also contain glycols such as (DPG), triols such as glycerin and trimethylolpropane.

[Foaming agent]
The foaming agent contains HFO-1233zd which has a low ozone depletion coefficient and a global warming coefficient and is not flammable.

  The foaming agent preferably further contains water. By adding water, the vapor pressure of the polyol composition can be reduced. The water content is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total polyol compound.

  The foaming agent may further contain a known foaming agent for rigid polyurethane foam.

  The content of the foaming agent is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the total polyol compound.

[Compatibilizer]
The compatibilizer is at least one selected from the group consisting of γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide. contains. One or more selected from the group consisting of the HFO-1233zd and γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide. By using it together, the stock solution storage stability such as the suppression of the separation of the polyol composition can be improved. One or more selected from the group consisting of the above HFO-1233zd and γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide. By using together, it is possible to suppress a decrease in physical properties of the rigid polyurethane foam. The reason is not clear, but is considered as follows.

  Since HFO-1233zd has poor compatibility with the hydrophilic polyol compound, the isocyanate component undergoes foam curing reaction with the polyol compound in the foamed stock solution composition in which the hydrophobic isocyanate component and the hydrophilic polyol composition are mixed. In this case, HFO-1233zd is considered to bloom. As a result, it is estimated that HFO-1233zd in the foaming stock solution composition inhibits the foaming and curing reaction of the isocyanate component and the polyol compound, and as a result, the foam physical properties are lowered. γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide improve the compatibility of HFO-1233zd with polyol compounds. Therefore, it is considered that the strength of the rigid polyurethane foam can be improved. Among these, γ-butyrolactone and / or ε-caprolactone are preferable, and γ-butyrolactone is more preferable from the viewpoint of improving the compatibility between HFO-1233zd and the polyol compound and improving the physical properties of the rigid polyurethane foam.

  Weight of HFO-1233zd in the polyol composition and each weight of γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide (Total weight of HFO-1233zd): (γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide 99.5: 0.5 to 70:30 is preferable, and 99: 1 to 80:20 is more preferable, from the viewpoint of stock solution storage stability and suppression of deterioration of physical properties of the rigid polyurethane foam. preferable.

[Other ingredients]
The polyol composition may contain a known catalyst for rigid polyurethane foam, a foam stabilizer, a flame retardant, a plasticizer, a colorant, an antioxidant, and the like.

  Examples of the catalyst include tertiary amines such as triethylenediamine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine and DBU. Metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate and tin octylate can be exemplified as the urethanization reaction catalyst. It is also preferable to use a catalyst that forms an isocyanurate bond that contributes to an improvement in flame retardancy in the structure of the polyurethane molecule. Examples of the catalyst for forming an isocyanurate bond include potassium acetate and potassium octylate. Some of the tertiary amine catalysts promote the formation of isocyanurate bonds. A catalyst that promotes the formation of isocyanurate bonds and a catalyst that promotes the formation of urethane bonds may be used in combination. Metal catalysts, quaternary ammonium salt catalysts, acid block catalysts, and imidazole catalysts can also be used.

  As the foam stabilizer, a known foam stabilizer for rigid polyurethane foam can be used without limitation. As the foam stabilizer, polydimethylsiloxane and a graft copolymer or block copolymer of polydimethylsiloxane and polyalkylene oxide are usually used. As the polyalkylene oxide, polyethylene oxide having a mean molecular weight of 5000 to 8000, polypropylene oxide, random copolymer or block copolymer of ethylene oxide and propylene oxide is used. Instead of the polydimethylsiloxane and the graft copolymer or block copolymer of polydimethylsiloxane and polyalkylene oxide, or together with the polydimethylsiloxane and the graft copolymer or block copolymer of polydimethylsiloxane and polyalkylene oxide A non-silicone foam stabilizer may be used.

  Examples of the flame retardant include metal compounds such as halogen-containing compounds, organophosphates, antimony trioxide, and aluminum hydroxide. These flame retardants, for example, may deteriorate the physical properties of the rigid polyurethane foam obtained when an excessive amount of organophosphate is added, and if excessively added metal compound powder such as antimony trioxide affects the foaming behavior of the foam. May occur, and the amount of addition is limited to a range that does not cause such a problem.

  Examples of the plasticizer include halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like. Specifically, tris (2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical Co., Ltd.) ), Tris (β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical Co., Ltd.), tributoxyethyl phosphate (TBEP, manufactured by Rhodia), tributyl phosphate, triethyl phosphate, cresyl phenyl phosphate, dimethylmethylphosphonate, etc. One or more of these can be used. The addition amount of the plasticizer is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polyol compound. If it exceeds this range, the plasticizing effect cannot be sufficiently obtained, and problems such as deterioration of the physical properties of the foam may occur.

  The polyol composition of this embodiment can be used for the production of continuously produced rigid polyurethane foams such as slabstock foams and sandwich panels, rigid polyurethane foam sandwich panels injected and injected, in-situ foamed rigid urethane foams, and the like.

<Method for producing rigid polyurethane foam>
The manufacturing method of the rigid polyurethane foam of this embodiment is a manufacturing method of the rigid polyurethane foam which mixes an isocyanate component and the said polyol composition, is foamed and hardened to make a rigid polyurethane foam.

  As the isocyanate component, liquid MDI is used because it is easy to handle, the reaction speed is excellent, the physical properties of the resulting rigid polyurethane foam are excellent, and the cost is low. As liquid MDI, crude (crude) MDI (c-MDI) (44V-10, 44V-20L, etc. (manufactured by Sumitomo Bayer Urethane Co., Ltd.)), uretonimine-containing MDI (Millionate MTL; manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. are used. The Among these polyisocyanate compounds, the use of crude (crude) MDI is particularly preferred in that the formed rigid polyurethane foam has excellent physical properties such as mechanical strength and is inexpensive.

  In addition to liquid MDI, other isocyanate components may be used in combination. Di- or polyisocyanate compounds and isocyanate components well known in the technical field of rigid polyurethane can be used without limitation. Prepolymers can also be used without limitation.

  In the method for producing the rigid polyurethane foam, the isocyanate group / active hydrogen group equivalent ratio (NCO index) in the mixing of the polyol composition and the isocyanate component is 50 to 500, more preferably 110 to 400.

  With such a structure, the foam curing reaction is promoted, and a urethane, urea bond, and isocyanurate bond are formed in the resin constituting the rigid polyurethane foam, and the physical properties, particularly compressive strength and physical properties of thermal conductivity are further improved. Polyurethane foam can be produced.

  The manufacturing method of the rigid polyurethane foam of this embodiment can be used for manufacturing a rigid polyurethane foam continuously produced such as a slabstock foam and a sandwich panel, a rigid polyurethane foam sandwich panel to be injected and injected, an in-situ foamed rigid urethane foam and the like. is there.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below.

<Evaluation method>
[Stock solution storage stability of polyol composition]
The amount of the catalyst in the polyol composition was adjusted so that the gel time was 30 ± 10 seconds, and after standing at 23 ° C. for 1 week, the state of separation and generation of bubbles was visually observed and judged according to the following criteria. In addition, the said evaluation does not represent the deterioration of reactivity.
・ Separation ○: No occurrence of layer separation in the polyol composition ×: Generation of layer separation in the polyol composition • Generation of bubbles ○: No generation of bubbles in the polyol composition ×: No bubbles in the polyol composition Occurrence

[Form density]
The foam density was determined according to JIS K 7222.

[Compressive strength of free form]
Based on JIS A9511 (foamed plastic heat insulating material), the compressive strength was measured according to JIS K7220 (hard foamed plastic-how to obtain compression characteristics).

〔Thermal conductivity〕
Based on JIS A9511 (foamed plastic insulation), in accordance with JIS A1412-2 (Measurement method of thermal resistance and thermal conductivity of thermal insulation materials-Part 2: Heat flow meter method) (HFM method), thermal conductivity Was measured.

<Examples 1-8, Comparative Examples 1-6>
[Preparation of polyol composition]
Table 1 shows the constituent materials of the polyol composition.

  The constituent materials shown in Table 1 were mixed and stirred with the formulation shown in Table 2 below to prepare polyol compositions of Examples 1 to 8 and Comparative Examples 1 to 6.

[Manufacture of rigid polyurethane foam]
Isocyanate component (crude diphenylmethane diisocyanate “Sumijoule 44V-20L” manufactured by Sumika Bayer Urethane Co., Ltd.) whose temperature was adjusted to 20 ° C. after adjusting the polyol compositions of Examples 1 to 8 and Comparative Examples 1 to 6 to 20 ° C. NCO%: 31%) and an NCO / OH equivalent ratio of 175 or 350 were mixed and stirred with a laboratory stirrer and foamed and cured to obtain a rigid polyurethane foam. Table 2 shows the evaluation results of the rigid polyurethane foam.

  From the results of Table 2, it can be seen that the polyol compositions according to Examples 1 to 8 are excellent in stock solution storage stability such as separation suppression even when HFO-1233zd is contained as a foaming agent. Moreover, the result of Table 2 shows that the rigid polyurethane foam manufactured using the polyol composition which concerns on Examples 1-8 as a raw material can suppress the fall of a physical property, even if it uses HFO-1233zd as a foaming agent.

Claims (4)

A polyol composition for a rigid polyurethane foam comprising at least a polyol compound, a foaming agent, a catalyst, and a compatibilizing agent, mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam,
The blowing agent contains 1-chloro-3,3,3-trifluoropropene;
The compatibilizer, .gamma.-butyrolactone, .epsilon.-caprolactone and containing one or more members selected from methoxypropyl acetate tape DOO or Ranaru group, for rigid polyurethane foams polyol composition. The 1-chloro-3,3,3 and weight trifluoropropene, .gamma.-butyrolactone, the sum of the weight of ε- caprolactone and methoxy propyl acetate tape preparative ratio ((1-chloro-3,3,3 trifluoropropene) :( .gamma.-butyrolactone, .epsilon.-caprolactone and the sum of the weight of methoxypropyl acetate tape g)) is 99.5: 0.5 to 70: 30, rigid polyurethane according to claim 1 Polyol composition for foam.   The polyol composition for rigid polyurethane foam according to claim 1 or 2, wherein the compatibilizer contains γ-butyrolactone. A method for producing a rigid polyurethane foam comprising mixing an isocyanate component and a polyol composition and foaming and curing to form a rigid polyurethane foam,
The manufacturing method of the rigid polyurethane foam whose said polyol composition is the polyol composition of any one of Claims 1-3.