KR101903302B1 - Polyol composition for rigid polyurethane foam and process for producing rigid polyurethane foam - Google Patents

Abstract

The polyol composition for rigid polyurethane foam of the present invention is a polyol composition for rigid polyurethane foam which comprises at least a polyol compound, a foaming agent and a compatibilizing agent and is mixed with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam Wherein the blowing agent contains 1-chloro-3,3,3-trifluoropropene and the compatibilizing agent is? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N -Methylpyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide. According to the polyol composition for rigid polyurethane foam of the present invention, even when 1-chloro-3,3,3-trifluoropropene is used as the foaming agent, the stability of the stock solution such as separation inhibition is good and the physical properties of the rigid polyurethane foam It is possible to provide a polyol composition for rigid polyurethane foam capable of suppressing deterioration.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyol composition for rigid polyurethane foam and a method for producing rigid polyurethane foam. BACKGROUND OF THE INVENTION < RTI ID = 0.0 >

The present invention relates to a polyol composition for rigid polyurethane foam which contains, as an essential component, 1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as HFO-1233zd) as a foaming agent component and a rigid polyurethane foam And a method for producing the same.

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, followed by foaming and curing.

As the foaming agent, a freon compound such as CFC-11 has been used in the past. However, since the CFC-11 causes destruction of the ozone layer, it is prohibited to use it and is converted into HCFC-14lb. (HFC-245fa) or HFC-365mfc (Zero-HFC-245fa). However, the HFC-245fa and HFC-365mfc have a problem of a large GWP (global warming coefficient). As a result, development of foaming agents for HFO-1233zd, which has low ozone depletion potential and low global warming potential and is not flammable, has been under development (for example, Patent Documents 1 to 8).

[Patent Document 1] Japanese Patent Application Laid-Open No. 2011-500891 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-500892 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-500893 [Patent Document 4] JP-A-2013-64139 [Patent Document 5] Japanese Patent Application Laid-Open No. 2013-500386 [Patent Document 6] Japanese Patent Application Laid-open No. 2013-501844 [Patent Document 7] JP-A-2013-514452 [Patent Document 8] Japanese Patent Application Laid-Open No. 2013-504656

However, since HFO-1233zd has poor compatibility with polyol compounds, the polyol composition containing HFO-1233zd is liable to be separated when stored in a raw solution state, and has poor storage stability of the stock solution. Further, since HFO-1233zd has poor compatibility with the polyol compound, when the rigid polyurethane foam is produced, the mixing of the polyol compound as the raw material and the isocyanate component is poor, and as a result, the physical properties of the obtained rigid polyurethane foam are deteriorated . In addition, "poor storage stability of stock solution " does not mean that the reactivity after storage is deteriorated.

The object of the present invention is to provide a rigid polyurethane foam polyol composition which is excellent in preservation stability of a stock solution even when HFO-1233zd is used as a foaming agent and can suppress deterioration of physical properties of a rigid polyurethane foam, and And a method for producing the rigid polyurethane foam.

The polyol composition for rigid polyurethane foam of the present invention is a polyol composition for rigid polyurethane foam which comprises at least a polyol compound, a foaming agent and a compatibilizing agent and is mixed with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam Wherein the blowing agent contains HFO-1233zd and the compatibilizing agent is at least one selected from the group consisting of? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, Amide, and N, N-dimethylformamide.

A method for producing a rigid polyurethane foam according to the present invention is a method for producing a rigid polyurethane foam by mixing an isocyanate component with a polyol composition and foaming and curing the composition to form a rigid polyurethane foam. The polyol composition is at least a polyol compound, Wherein the blowing agent contains HFO-1233zd and the compatibilizing agent is selected from the group consisting of? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N - dimethylacetamide, and N, N-dimethylformamide.

According to the present invention, there is provided a rigid polyurethane foam polyol composition and a method for producing a rigid polyurethane foam, which are excellent in storage stability of a stock solution even when HFO-1233zd is used as a foaming agent and can suppress deterioration of physical properties of rigid polyurethane foam .

≪ Polyol composition for rigid polyurethane foam &

The rigid polyurethane foam polyol composition of the present embodiment is a rigid polyurethane foam polyol containing at least a polyol compound, a foaming agent and a compatibilizing agent, and is mixed with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam Wherein the blowing agent contains HFO-1233zd and the compatibilizing agent is selected from the group consisting of? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, Acetamide, N, N-dimethylformamide, and the like.

[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 obtained by reacting an alkylene oxide, specifically, propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran Is a polyfunctional polyol compound obtained by ring-opening addition polymerization.

Examples of the primary or secondary amine initiator which is an initiator of the tertiary amino group-containing polyol compound include aliphatic primary and secondary monoamines such as ammonia, methylamine and ethylamine, ethylenediamine, hexamethylenediamine, N, Aliphatic primary and secondary polyamines such as N, N'-dimethylethylenediamine and the like; aromatic primary to secondary mono to polyamines such as aniline, diphenylamine, toluene diamine, diphenylmethanediamine and N-methyl aniline; Amines, monoethanolamine, diethanolamine, and other alkanolamines. 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. When the content of the tertiary amino group-containing polyol compound is higher than that of the polyol compound having a tertiary amino group, it is effective for increasing the reactivity and manifesting the physical properties. If the content is more than 60% by weight, It causes the cause.

The aliphatic polyol compound is a polyol initiator which is obtained by reacting an aliphatic or alicyclic polyfunctional active hydrogen compound with an alkylene oxide, specifically a cyclic ether such as propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran , Preferably PO or PO and EO, which is a polyfunctional oligomer obtained by ring-opening addition polymerization.

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

Examples of the aromatic polyol compound include a polyol compound obtained by adding the above-mentioned 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.

Examples of the polyol compound obtained by adding the above-described alkylene oxide to the polyfunctional active hydrogen compound include at least one of PO, EO and SO, preferably PO or PO and EO in the hydroquinone, bisphenol A and Mannich, Compounds are specifically exemplified.

Examples of ester polyol compounds of aromatic polycarboxylic acids and polyfunctional alcohols include ester polyol compounds obtained by reacting terephthalic acid, orthophthalic acid, isophthalic acid and the like with hydroxyl-terminated alcohols such as ethylene glycol and diethylene glycol.

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

The polyol compound may be at least one selected from the group consisting of ethylene glycol (EG), triethylene glycol, diethylene glycol (DEG), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Glycols such as dipropylene glycol (DPG), and triols such as glycerin and trimethylol propane.

〔blowing agent〕

The blowing agent contains HFO-1233zd, which has a low ozone depletion potential and low global warming potential and is not flammable.

It is preferable that the foaming agent further contains water. By adding water, the vapor pressure of the polyol composition can be lowered. The content of water is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total amount of the polyol compound.

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

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

[Commercialization agent]

The compatibilizing agent may be at least one selected from the group consisting of? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethylsulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide and N, And the like. Wherein the HFO-1233zd is at least one member selected from the group consisting of? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide and N, , The storage stability of the stock solution such as inhibition of separation of the polyol composition can be improved. Further, it is preferable that the HFO-1233zd is at least one compound selected from the group consisting of? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide and N, , It is possible to suppress the deterioration of the physical properties of the rigid polyurethane foam. The reason for this is unclear, but is considered as follows.

Since HFO-1233zd is poorly compatible with hydrophilic polyol compounds, HFO-1233zd is blooming when the isocyanate component is subjected to a foam hardening reaction with a polyol compound in a foaming stock solution composition obtained by mixing a hydrophobic isocyanate component and a hydrophilic polyol composition I think. As a result, HFO-1233zd in the foamed stock solution composition inhibits foaming and curing reaction of the isocyanate component and the polyol compound, and as a result, it is presumed that the foam property decreases. N, N-dimethylacetamide and N, N-dimethylformamide can be prepared by reacting HFO-1233zd with a polyol compound such as? -butyrolactone,? -caprolactone, methoxypropylacetate, dimethylsulfoxide, It is considered that the strength of the rigid polyurethane foam can be improved. Of these, γ-butyrolactone and / or ε-caprolactone are preferable from the viewpoints of improving the compatibility between HFO-1233zd and the polyol compound and from the viewpoint of improving the physical properties of the rigid polyurethane foam, and γ-butyrolactone Is more preferable.

The weight ratio of HFO-1233zd in the polyol composition to the weight of HFO-1233zd in the polyol composition and the weight ratio of HFO-1233zd in the polyol composition to the weight of HFO-1233zd in the polyol composition, (Weight of HFO-1233zd) :( (? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N -Dimethylacetamide and N, N-dimethylformamide)) is preferably from 99.5: 0.5 to 70:30 from the viewpoint of the stock stability of the stock solution and the deterioration of the physical properties of the hard polyurethane foam , And more preferably from 99: 1 to 80:20.

[Other components]

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 triethylenediamine, N-methylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, Based catalysts such as tributyltin dilaurate, tributyltin dilaurate, 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 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. The tertiary amine catalyst also promotes the formation of isocyanurate bonds. A catalyst for promoting the production of isocyanurate bond and a catalyst for promoting the formation of urethane bond may be used in combination. Metal catalysts, quaternary ammonium salt catalysts, acid block catalysts, imidazole catalysts can also be used.

As the foam stabilizer, a known stabilizer for hard polyurethane foam can be used without limitation. As the foam stabilizer, a graft copolymer or block copolymer of polydimethylsiloxane and polydimethylsiloxane and polyalkylene oxide is usually used. As the polyalkylene oxide, a random copolymer or block copolymer of polyethylene oxide, polypropylene oxide, ethylene oxide and propylene oxide having an average molecular weight of 5000 to 8000 is used. The polydimethylsiloxane and the graft copolymer or the block copolymer of the polydimethylsiloxane and the polyalkylene oxide or the graft copolymer or the block copolymer of the polydimethylsiloxane and the polydimethylsiloxane and the polyalkylene oxide, A foam stabilizer may be used.

Examples of the flame retardant include metal compounds such as halogen-containing compounds, organic phosphoric acid esters, antimony trioxide, aluminum hydroxide and the like. When the flame retardant is added in excess, for example, the organic phosphoric acid ester may deteriorate the physical properties of the obtained rigid polyurethane foam, and if excessive addition of metal compound powder such as antimony trioxide is effected, And the like, and the amount thereof to be added is limited to such a range that does not cause such a problem.

Specific examples of the plasticizer include tris (2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical Co., Ltd.), tris ( (TMCPP, manufactured by Daihachi Chemical Co., Ltd.), tributoxyethyl phosphate (TBEP, manufactured by Rhodia), tributylphosphate, triethylphosphate, cresylphenylphosphate, dimethylmethylphosphate and the like , And at least one of these can be used. The addition amount of the plasticizer is preferably 5 to 50 parts by weight based on 100 parts by weight of the polyol compound. If it exceeds this range, the plasticizing effect can not be sufficiently obtained, and the physical properties of the foam may be deteriorated.

The polyol composition of the present embodiment can be produced by continuously producing rigid polyurethane foam such as a slab stock form and a sandwich panel, a rigid polyurethane foam sandwich panel injection-injected, a urethane foam Lt; / RTI >

≪ Production method of rigid polyurethane foam >

The method for producing a rigid polyurethane foam of the present embodiment is a method for producing a rigid polyurethane foam by mixing an isocyanate component and the polyol composition and foaming and curing the mixture to form a rigid polyurethane foam.

As the isocyanate component, a liquid MDI is used from the viewpoints of ease of handling, reaction rate, physical properties of the obtained rigid polyurethane foam, low cost, and the like. Examples of the liquid MDI include Crude (MDI) (c-MDI) (44V-10, 44V-20L, etc. manufactured by Sumitomo Bayer Urethane Co., Ltd.), MDI containing uretonimine (Millionate MTL; ) Is used. Of these polyisocyanate compounds, the use of crude (crude) MDI is particularly preferable because of the excellent physical properties such as mechanical strength of the formed rigid polyurethane foam and the low cost.

In addition to the liquid MDI, other isocyanate components may be used in combination. In the technical field of rigid polyurethane, well-known di-polyisocyanate compounds and isocyanate components are usable without limitation. The 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.

By such a constitution, the foam hardening reaction is promoted, whereby a urethane bond, a urea bond and an isocyanurate bond are formed in a large amount in the resin constituting the rigid polyurethane foam, and the rigidity of the rigid poly Urethane foam can be produced.

The method of producing the rigid polyurethane foam according to the present embodiment can be applied to a rigid polyurethane foam continuously produced, such as a slab stock form and a sandwich panel, a rigid polyurethane foam sandwich panel injected into injection mold, a field foam rigid urethane foam shape and the like.

[Example]

Best Mode for Carrying Out the Invention Hereinafter, embodiments and the like showing the construction and effect of the present invention will be described.

<Evaluation method>

[Storage stability of stock solution of polyol composition]

The catalytic amount of the polyol composition was adjusted so that the gel time was 30 ± 10 seconds and left at 23 ° C. for one week. The state of separation and bubble formation was visually observed to determine the following criteria. Further, the evaluation does not indicate deterioration of reactivity.

detach

: No occurrence of layer separation in the polyol composition

X: Layer separation occurred in the polyol composition

Bubble generation

?: No occurrence of bubbles in the polyol composition

X: occurrence of air bubbles in the polyol composition

[Foam density]

The foam density was obtained according to JIS K 7222.

[Compressive strength of preform]

Based on JIS A9511 (foamed plastic insulating material), the compressive strength was measured in accordance with JIS K7220 (hard foamed plastic-method for obtaining compression characteristics).

[Thermal Conductivity]

Based on JIS A9511 (foamed plastic insulating material), the thermal conductivity was measured according to JIS A1412-2 (Method for measuring thermal resistance and thermal conductivity of a thermal insulator - Part 2: Heat flow method) (HFM method).

&Lt; Examples 1 to 8 and Comparative Examples 1 to 6 >

[Adjustment of polyol composition]

Table 1 shows the constituent materials of the polyol composition.

ingredient Contents Supplier Remarks Polyol A Mannich type polyether polyol Daichigogyo Seiyaku Co., Ltd. Hydroxyacid 350 mg KOH / g Polyol B Ethylenediamine-based polyether polyol Asahi Garas Co., Hydrogenation 450 mg KOH / g Polyol C TDA-based polyether polyol Asahi Garas Co., Hydroxyacid 400 mg KOH / g Polyol D Phthalic acid-based polyester polyol Hitachi Kasei Co., Ltd. Hydrogenation 250 mg KOH / g Polyol E Water-based polyether polyol Asahi Garas Co., Hydrogenation 450 mg KOH / g Flame retardant TMCPP (trismonochloropropylphosphate) Daishi-chikagakogo Corporation Foaming agent SH-193 (silicone surfactant) Toor Dow Corning Co., Ltd. Catalyst A Potassium octylate Toei Kako Co., Ltd. Catalyst B 1-methylimidazole Commercialization A ? -butyrolactone Mitsubishi Chemical Co., Commercialization agent B ? -caprolactone Commercialization C Methoxypropyl acetate HFC-245fa 1,1,1,3,3-pentafluoropropane Centralgaras Co., Ltd. Global Warming Potential: 1030 1-chloro-3,3,3, trifluoropropene Hanewell Japan Co., Ltd. Global warming coefficient: less than 1 Isocyanate component 44V-20L (crude diphenylmethane diisocyanate) Sumika Bayer Urethane Co., Ltd. NCO% = 31.0%

The polyol compositions of Examples 1 to 8 and Comparative Examples 1 to 6 were prepared by mixing and stirring the components shown in Table 1 in the formulations shown in Table 2 below.

[Preparation of Rigid Polyurethane Foam]

The temperature of the polyol composition of Examples 1 to 8 and Comparative Examples 1 to 6 was adjusted to 20, and an isocyanate component (Sumiru 44V-20L, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO%: 31%) and an NCO / OH equivalent ratio of 175 or 350 were mixed and stirred with a laboratory stirrer, followed by foaming and curing to obtain a hard polyurethane foam. The evaluation results of the hard polyurethane foam are shown in Table 2.

No
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Polyol A 50 50 50 50 Polyol B 20 30 30 20 20 20 30 Polyol C 30 20 20 30 30 30 20 Polyol D 100 100 100 100 100 100 100 Polyol E 50 50 50 Flame retardant 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Foaming agent 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Catalyst A 4 4 4 4 4 4 4 4 4 4 4 4 4 Catalyst B One One One One One One One 5 One One One One One One water One One One One One One One One HFC-245fa 40 40 1-chloro-3,3,3, trifluoropropene 40 25 25 40 25 25 25 25 40 25 40 25 Commercialization A 5 5 7.5 5 5 5 5 Commercialization agent B 5 Commercialization C 5 R liquid sum [g] 167 153 155.5 167 153 153 153 153 162 167 162 148 162 148 NCOINDEX 175 175 175 350 350 350 350 350 175 175 175 175 350 350 (1-chloro-3,3,3, trifluoropropene / compatibilizing agent) ratio 89/11 83.3 / 17.7 76.9 / 23.1 83.3 / 17.7 83.3 / 17.7 83.3 / 17.7 83.3 / 17.7 83.3 / 17.7 Free density [kg / m 3] 31.2 33.2 33.5 32.9 35.1 34.8 34.2 35.0 30.8 30.8 30.9 34 32.3 35.4 Storage stability
detach ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ △ × × bubble ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○ ○ ○ Compressive strength (KPa) 199 166 170 227 280 290 289 287 265 160 184 162 220 276 Thermal conductivity (W / mK) 0.02256 0.02333 0.02320 0.02131 0.02270 0.02200 0.02210 0.02272 0.02297 0.02300 0.02273 0.02362 0.02150 0.02290 Comprehensive judgment ○ ○ ○ ○ ○ ○ ○ ○ × × × × × ×

From the results shown in 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 inhibition even when HFO-1233zd is contained as a foaming agent. From the results shown in Table 2, it can be seen that the rigid polyurethane foam prepared using the polyol composition of Examples 1 to 8 as a raw material can suppress deterioration of physical properties even when HFO-1233zd is used as the 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, and mixing with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam,
Wherein the foaming agent contains 1-chloro-3,3,3-trifluoropropene,
Wherein the compatibilizing agent is selected from the group consisting of? -Butyrolactone,? -Caprolactone, methoxypropyl acetate, dimethylsulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide and N, Containing at least one selected,
Wherein the weight ratio of the 1-chloro-3,3,3-trifluoropropene to the weight of the 1-chloro-3,3,3-trifluoropropene is selected from the group consisting of γ-butyrolactone, ε-caprolactone, methoxypropyl acetate, dimethyl sulfoxide, - (1-chloro-3,3,3-trifluoropropene) :(? -Butyrolactone,? -Caprolactone,? -Caprolactone, The sum of the respective weights of methoxypropyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide) is 99.5: 0.5 to 70:30, Polyol composition for polyurethane foam. delete The method according to claim 1,
The polyol composition for rigid polyurethane foam, wherein the compatibilizing agent contains? -Butyrolactone. A method for producing a rigid polyurethane foam by mixing an isocyanate component with a polyol composition and foaming and curing the mixture to form a rigid polyurethane foam,
Wherein the polyol composition is the polyol composition according to any one of claims 1 to 3. A method for producing a rigid polyurethane foam,