JPH06306136A - Production of foamed synthetic resin - Google Patents

Abstract

PURPOSE:To produce a high-quality foamed synthetic resin without using a chlorofluorocarbon which is a substance of destruction of the ozone layer by reacting a specific active hydrogen compd. component with a polyisocyanate compd. in the presence of a specific blowing agent. CONSTITUTION:A hydrocarbon having a part or the whole of H atoms substituted with F atoms (e.g. CF2HCH3 or C6F6) is used as the blowing agent and a polyether polyol comprising an alkylene oxide adduct of a polysaccharide and/or a monosaccharide is used as at least a part of the active hydrogen compd. component in the process for producing a foamed synthetic resin by reacting an active hydrogen compd. component comprising active hydrogen compds. each having at least two isocyanate-reactive active hydrogen groups with a polyisocyanate compd. in the presence of a blowing agent comprising a low-boiling org. compd. Thus, it is produced a high-quality foamed synthetic resin without using a chlorofluorocarbon such as R11 being in danger of destroying the ozone layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a foamed synthetic resin such as polyurethane foam, and more particularly to a method for producing a foamed synthetic resin using a specific foaming agent.

[0002]

2. Description of the Related Art A foamed synthetic resin is produced by reacting an active hydrogen compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group with a polyisocyanate compound in the presence of a catalyst and a foaming agent. It is widely practiced.

Examples of active hydrogen compounds include polyhydroxy compounds and polyamine compounds. Examples of the foamed synthetic resin obtained include polyurethane foam, polyisocyanurate foam, and polyurea foam. Further, examples of the foamed synthetic resin having a relatively low foaming include microcellular polyurethane elastomer and microcellular polyurethane urea elastomer.

Various compounds are known as a foaming agent for producing the foamed synthetic resin, but trichlorofluoromethane (R-11) is mainly used. Also,
Water is usually used together with R-11. In addition, when foaming is performed by the floss method or the like, dichlorodifluoromethane having a lower boiling point (gaseous at room temperature and normal pressure) is used together with them.
(R-12) is also used.

[0005]

[Problems to be Solved by the Invention] Chlorofluorinated hydrocarbons such as R-11 and R-12, which have been widely used in the past and are extremely stable in the atmosphere, reach the ozone layer above the atmospheric layer without being decomposed. Then, it was thought that the decomposition products would be destroyed by the action of ultraviolet rays and the decomposition products would destroy the ozone layer.

Since some of the above-mentioned chlorinated fluorinated hydrocarbons used as a blowing agent leak into the atmosphere, there is a fear that their use may be a cause of ozone layer depletion. Has been done. 1,1-Dichloro-2,2,2-trifluoroethane (R-123) and 1 are considered to be less dangerous because they have hydrogen atoms in the molecule and decompose before reaching the ozone layer in the atmosphere. , 1-Dichloro-1-fluoroethane (R-1
41b), monochlorodifluoromethane (R-22) and the like have been proposed as foaming agents and are widely used, but these substances also have ozone depletion potentials and cannot be an essential solution. Therefore, in place of such chlorinated fluorinated hydrocarbons, it is desired to develop a foaming agent that is less likely to cause ozone layer depletion and a foamed synthetic resin manufacturing technique.

[0007]

The present invention has been made to solve the above-mentioned problems, and comprises an active hydrogen compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group and a polyisocyanate compound. In the method for producing a foamed synthetic resin by reacting in the presence of a low-boiling organic compound blowing agent, as the low-boiling organic compound blowing agent, a hydrocarbon in which some or all of hydrogen atoms are replaced by fluorine atoms is used, The present invention proposes a method for producing a foamed synthetic resin characterized by using a polyether polyol obtained by adding an alkylene oxide to a polysaccharide and / or a monosaccharide as at least a part of a hydrogen compound.

Since the fluorinated hydrocarbon of the present invention does not contain chlorine atoms, it reaches the atmosphere and does not destroy the ozone layer even if it is decomposed by ultraviolet rays. Especially CF ₂ HCH
₃ , CF ₃ CFH ₂ , CF ₃ CF ₂ H, CH ₂ F ₂ , CF ₃ CH ₃ , CF ₃ CF ₂ CF ₂ H, CF ₃ CFHCF
₃ , CHF ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CFH ₂ , CF ₃ CHFCHF ₂ , CF ₃ CH ₂ CF ₃ , CF 2H
CF ₂ CFH ₂ , CF ₃ CF ₂ CH ₃ , CF ₂ HCHFCF ₂ H, CF ₃ CHFCFH ₂ , CF ₃ CH ₂ CHF
₂ , CFH ₂ CF ₂ CFH ₂ , CF ₂ HCF ₂ CH ₃ , CF ₂ HCHFCFH ₂ , CF ₃ CHFCH ₃ , CF ₂
HCH ₂ CF ₂ H, CF ₃ CH ₂ CFH ₂ , CFH ₂ CF ₂ CH ₃ , CH ₂ FCHFCH ₂ F, CF ₂ HCHF
CH ₃ , CH ₂ FCH ₂ CF ₂ H, CF ₃ CH ₂ CH ₃ , CH ₃ CF ₂ CH ₃ , CH ₂ FCHFCH ₃ , CH ₂
FCH ₂ CH ₂ F, CHF ₂ CH ₂ CH ₃ , CH ₃ CHFCH ₃ , CH ₂ FCH ₂ CH ₃ , CF ₃ CF ₂ CF ₂
CH ₃ , CF ₃ CH ₂ CH ₂ CF ₃ , CF ₃ CHFCF ₂ CH ₃ , CF ₃ CHFCHFCF ₃ , CF ₃ CF ₂ C
F ₂ CH ₂ F, CF ₃ CHFCH ₂ CF ₃ , CH ₃ CF ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CHFCHF ₂ , CF
₃ CF ₂ CH ₂ CHF ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFCH ₃ , CF ₃ CH (CF ₃ ) CH
₃ , CH ₃ CF (CF ₃ ) CHF ₂ , CH ₃ CH (CF ₃ ) CH ₂ F, CH ₃ CH (CF ₃ ) CHF ₂ , CH ₂
FCF (CF ₃ ) CH ₂ F, CH ₃ CF (CHF ₂ ) CHF ₂ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₁₀ , C
Compounds such as ₅ F ₁₂ , C ₆ F ₁₄ , C ₇ F ₁₆ , C ₅ F ₁₀ , C ₆ F ₁₂ , and C ₆ F ₆ have boiling points close to those of conventional blowing agents R-11 and R-12. It can be used as a foaming agent in place of these.

However, the above-mentioned fluorinated hydrocarbon has a poor solubility in an active hydrogen compound and thus has a poor mixing property of a foamed synthetic resin, and thus the obtained foam has a problem that sufficient strength cannot be obtained. Therefore, by using a polyether polyol obtained by adding an alkylene oxide to a polysaccharide and / or a monosaccharide as an active hydrogen compound in which a foaming agent is preliminarily mixed, the number of functional groups is increased and sufficient strength is obtained, which is a good foam synthetic resin. Can be obtained. At this time, the amount of the foaming agent used in the present invention is 5 to 150% by weight based on all active hydrogen compounds, and the polyether polyol in which the alkylene oxide is added to the polysaccharide and / or monosaccharide in the present invention is based on all active hydrogen compounds. It is preferable to use at least 15% by weight or more.

The fluorine-containing compound-based foaming agent in the present invention can be used alone or in combination with other foaming agents. In particular, water is often used together with the fluorine-containing compound-based foaming agent. Examples of the blowing agent that can be used in combination with water other than water include, for example, a fluorinated halogenated hydrocarbon-based blowing agent containing chlorine and other low-boiling halogenated hydrocarbons, low-boiling hydrocarbons, and inert gases.

As the fluorinated halogenated hydrocarbon containing chlorine, R-123, R-141b, R-22, 1,2-dichloro-1,1,2-trifluoroethane (R123a), 1-chloro-1 , 1-Difluoroethane (R142b), 3,3-Dichloro-1,1,1,2,2-pentafluoropropane (R225ca), 1,3-Dichloro-1,1,2,2,3-pentafluoropropane (R225cb), 3-chloro-1,1,2,2-tetrafluoropropane (R244ca), 1-chloro-1,2,2,3-tetrafluoropropane (R244cb), 3-chloro-1,1, 2,2,3-Pentafluoropropane (R235ca), 1,1-dichloro-1,2,2-
CFCs such as trifluoropropane (R243cc) may be used alone or in combination and appropriately used in combination with the foaming agent in the present invention. Although these compounds have an ozone depletion potential by themselves, their use amount can be reduced by using them together with the blowing agent of the present invention.

Other low-boiling halogenated hydrocarbons include halogenated hydrocarbons containing no fluorine atom such as methylene chloride and fluorine-containing halogenated hydrocarbons other than the above. Low-boiling hydrocarbons include butane, pentane and hexane, and inert gases include air and nitrogen.

The polyether polyol obtained by adding an alkylene oxide to a polysaccharide and / or a monosaccharide according to the present invention may be used alone, and may also be used as an active hydrogen compound having an active hydrogen-containing functional group capable of reacting with another isocyanate group. Can be used together. The active hydrogen compound that can be used in combination is a compound having an active hydrogen-containing functional group such as a hydroxyl group or an amino group, or a mixture of two or more kinds of the compounds. In particular, a compound having two or more hydroxyl groups, a mixture thereof, or a mixture containing the compound as a main component and further containing polyamine or the like is preferable.

As the compound having two or more hydroxyl groups, a widely used polyol is preferable, but a compound having two or more phenolic hydroxyl groups (for example, a phenol resin initial condensation product) can also be used. Examples of polyols include polyether polyols, polyester polyols, polyhydric alcohols, and hydroxyl group-containing diethylene-based polymers. In particular, a polyester polyol, a polyhydric alcohol, a polyamine, which contains only one or more polyether polyols as a main component,
The combined use with alkanolamine and other active hydrogen compounds is preferable.

The polyether polyol is preferably a polyether polyol obtained by adding a cyclic ether to a polyhydric alcohol, an alkanolamine, or another initiator, particularly propylene oxide or ethylene oxide. Further, as the polyol, it is also possible to use a polyol composition mainly referred to as a polymer polyol or a graft polyol in which fine particles of a vinyl polymer are dispersed in a polyether polyol. The polysaccharide and / or monosaccharide in the present invention can also be used as a mixing initiator with the above-mentioned polyhydric alcohol, alkanolamine and other initiators.

Polyester polyols include polyhydric alcohol-polyhydric carboxylic acid condensation type polyols and cyclic ester ring-opening polymer type polyols. Polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol and dipropylene. Examples include glycol, glycerin, trimethylolpropane, pentaerythritol, diethanolamine and triethanolamine.

As the compound having two or more phenolic hydroxyl groups, a resol-type initial condensate obtained by condensation-bonding phenols with an excess of formaldehyde in the presence of an alkali catalyst, and when synthesizing this resol-type initial condensate There are benzylic type initial condensates reacted in a non-aqueous system, and novolak type initial condensates obtained by reacting excess phenols with formaldehydes in the presence of an acid catalyst. The molecular weight of these initial condensates is preferably about 200 to 10,000.

In the above description, the phenols mean those in which one or more carbon atoms of the skeleton forming the benzene ring are directly bonded to the hydroxyl group, and also include those having other substituted bonding group in the same structure. Typical examples include phenol, cresol, bisphenol A, resorcinol and the like. The formaldehydes are not particularly limited, but formalin, paraformaldehyde and the like are preferable.

The hydroxyl value of the polyol or the mixture of active hydrogen compounds is often selected from about 20 to 1000 according to the purpose.

As the polyisocyanate compound, aromatic, alicyclic or aliphatic polyisocyanates having an average of two or more isocyanate groups, a mixture of two or more kinds thereof, and a modified one thereof are obtained. There are modified polyisocyanates. Specifically, for example, polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (commonly known as crude MDI), xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, prepolymer modified products thereof, and nurate modified products thereof. , Modified urea, etc.

When reacting the active hydrogen compound and the polyisocyanate compound, it is usually necessary to use a catalyst. As the catalyst, a metal compound catalyst such as an organic tin compound that promotes the reaction between the active hydrogen-containing group and an isocyanate group, a tertiary amine catalyst such as triethylenediamine, or the like can be used. Further, a polymerizing catalyst for reacting isocyanate groups such as carboxylic acid metal salt may be used depending on the purpose.

Further, a foam stabilizer for forming good bubbles is often used. Examples of the foam stabilizer include a silicone type foam stabilizer and a fluorine-containing compound type foam stabilizer. In addition, examples of the compounding agent that can be optionally used include a filler, a stabilizer, a colorant, and a flame retardant.

Using these raw materials, polyurethane foam, urethane-modified polyisocyanate foam, microcellular polyurethane elastomer, microcellular polyurethane urea elastomer, microcellular polyurea elastomer, and other foaming synthetic resins can be obtained. Polyurethane foams are roughly classified into rigid polyurethane foams, semi-rigid polyurethane foams, and flexible polyurethane foams.

The present invention is particularly useful in the production of rigid polyurethane foams, urethane-modified polyisocyanurate foams and other rigid foams, which is a field in which the amount of halogenated hydrocarbon-based blowing agent used is large. Among them, it is particularly useful for producing a rigid polyurethane foam obtained by using a polyol or a mixture of polyols having a hydroxyl value of about 200 to 1000 and an aromatic polyisocyanate compound.

When these rigid foams are produced, the amount of the specific foaming agent used in the present invention is appropriately 5 to 150% by weight, particularly 20 to 60% by weight, based on the active hydrogen compound. At the same time, it is preferable to use water in an amount of 0 to 10% by weight, particularly 1 to 5% by weight, based on the active hydrogen compound.

On the other hand, in the case of flexible polyurethane foam, semi-rigid polyurethane foam and microcellular elastomer, the amount of the specific foaming agent used in the present invention is
It is preferably about 5 to 150% by weight with respect to the active hydrogen compound. In the case of a flexible polyurethane foam or a semi-rigid polyurethane foam, it is preferable to use water in an amount of about 0 to 10% by weight, and in the case of a microcellular elastomer, it is preferable to use water in an amount of about 0 to 5% by weight.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

The following polyols were used in the polyol ratios shown below to evaluate the foaming of the specific foaming agents of this invention. Polyol a: Polyether polyol having a hydroxyl value of 420 obtained by reacting glycerin with propylene oxide Polyol b: Polyether polyol having a hydroxyl value of 450 obtained by reacting toluenediamine with propylene oxide and ethylene oxide Polyol c: Reacting propylene oxide with sucrose Polyether polyol with a hydroxyl value of 440

A; a: b: c = 50: 50: 0 B; a: b: c = 20: 80: 0 C; a: b: c = 40: 40: 20 D; a: b: c = 16:64:20 E; a: b: c = 10: 40: 50

The evaluation of foaming was performed as follows. That is,
In order to obtain a gel time of 45 seconds, 2 parts by weight of a silicone-based foam stabilizer, 2 parts by weight of water, and N, N-dimethylcyclohexylamine as a catalyst are added to 100 parts by weight of a polyol prepared by mixing the above A to E. Required amount, mixed solution consisting of the foaming agent shown in the upper left column of the table, and polymethylene polyphenyl isocyanate at a liquid temperature of 20 ℃, 200mm × 200mm × 200
It was put into a mm wooden box, foamed, and the compression strength (//) was evaluated. The amount of the foaming agent used was adjusted so that the core density of the foam was 30 ± 2 kg / m ³ . The core density and compressive strength (//) are also shown in the table.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

[0039]

[Table 9]

[0040]

[Table 10]

[0041]

[Table 11]

[0042]

[Table 12]

[0043]

[Table 13]

[0044]

[Table 14]

[0045]

[Table 15]

[0046]

[Table 16]

[0047]

[Table 17]

[0048]

[Table 18]

[0049]

[Table 19]

[0050]

[Table 20]

[0051]

[Table 21]

[0052]

[Table 22]

[0053]

[Table 23]

[0054]

[Table 24]

[0055]

[Table 25]

[0056]

[Table 26]

[0057]

[Table 27]

[0058]

[Table 28]

[0059]

[Table 29]

[0060]

[Table 30]

[0061]

[Table 31]

[0062]

[Table 32]

[0063]

[Table 33]

[0064]

[Table 34]

[0065]

[Table 35]

[0066]

[Table 36]

[0067]

[Table 37]

[0068]

[Table 38]

[0069]

[Table 39]

[0070]

INDUSTRIAL APPLICABILITY The present invention has a possibility of depleting the ozone layer.
It has an effect that a good foaming synthetic resin can be produced without substantially using chlorinated fluorinated hydrocarbon such as R-11.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C08L 75:04 (72) Inventor Ichiro Kamemura 3 474 Tsukakoshi 2 Kosaku-ku Kawasaki-shi Kanagawa 2 Asahi Glass Co., Ltd. Company Tamagawa branch room

Claims (2)

[Claims] 1. A foamed synthetic resin is produced by reacting an active hydrogen compound having two or more active hydrogen-containing functional groups capable of reacting with an isocyanate group with a polyisocyanate compound in the presence of a low-boiling organic compound blowing agent. In the method, a hydrocarbon having a part or all of hydrogen atoms replaced by fluorine atoms is used as the low-boiling organic compound blowing agent, and an alkylene oxide is added to the polysaccharide and / or monosaccharide as at least a part of the active hydrogen compound. A method for producing a foamed synthetic resin, which comprises using an added polyether polyol. 2. A low-boiling organic compound blowing agent, CF ₂ HCH ₃ ,
CF ₃ CFH ₂ , CF ₃ CF ₂ H, CH ₂ F ₂ , CF ₃ CH ₃ , CF ₃ CF ₂ CF ₂ H, CF ₃ CFHCF ₃ ,
CHF ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CFH ₂ , CF ₃ CHFCHF ₂ , CF ₃ CH ₂ CF ₃ , CF ₂ HCF
₂ CFH ₂ , CF ₃ CF ₂ CH ₃ , CF ₂ HCHFCF ₂ H, CF ₃ CHFCFH ₂ , CF ₃ CH ₂ CHF ₂ ,
CFH ₂ CF ₂ CFH ₂ , CF ₂ HCF ₂ CH ₃ , CF ₂ HCHFCFH ₂ , CF ₃ CHFCH ₃ , CF ₂ HC
H ₂ CF ₂ H, CF ₃ CH ₂ CFH ₂ , CFH ₂ CF ₂ CH ₃ , CH ₂ FCHFCH ₂ F, CF ₂ HCHFCH
₃ , CH ₂ FCH ₂ CF ₂ H, CF ₃ CH ₂ CH ₃ , CH ₃ CF ₂ CH ₃ , CH ₂ FCHFCH ₃ , CH ₂ FC
H ₂ CH ₂ F, CHF ₂ CH ₂ CH ₃ , CH ₃ CHFCH ₃ , CH ₂ FCH ₂ CH ₃ , CF ₃ CF ₂ CF ₂ CH
₃ , CF ₃ CH ₂ CH ₂ CF ₃ , CF ₃ CHFCF ₂ CH ₃ , CF ₃ CHFCHFCF ₃ , CF ₃ CF ₂ CF ₂
CH ₂ F, CF ₃ CHFCH ₂ CF ₃ , CH ₃ CF ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CHFCHF ₂ , CF ₃ C
F ₂ CH ₂ CHF ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFCH ₃ , CF ₃ CH (CF ₃ ) CH ₃ ,
CH ₃ CF (CF ₃ ) CHF ₂ , CH ₃ CH (CF ₃ ) CH ₂ F, CH ₃ CH (CF ₃ ) CHF ₂ , CH ₂ FC
F (CF ₃ ) CH ₂ F, CH ₃ CF (CHF ₂ ) CHF ₂ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₁₀ , C ₅ F
Production of the foamed synthetic resin according to claim 1, wherein any one of ₁₂ , C ₆ F ₁₄ , C ₇ F ₁₆ , C ₅ F ₁₀ , C ₆ F ₁₂ , and C ₆ F ₆ is used alone or in combination. Method.