JPH01313542A - Production of expanded synthetic resin - Google Patents

Abstract

PURPOSE:To make it possible to produce a good expanded synthetic resin having little fear of destroying an ozone layer by reacting a specified active hydrogen compound with a polyisocyanate compound in the presence of a specified low- boiling halohydrocarbon blowing agent. CONSTITUTION:An expanded synthetic resin is produced by reacting an active hydrogen compound having at least two NCO group-reactive active hydrogen functional groups (e.g., a polyether polyol prepared by reacting glycerol with propylene oxide) with a polyisocyanate compound (e.g., polymethylenepolyphenyl isocyanate) in the presence of a low-boiling halohydrocarbon blowing agent. In the above production, 1,1-dichloro-2-fluoroethylene is used as said blowing agent. Although trichloromonofluoromethane (hereinafter referred to as R-11) has been chiefly used as a blowing agent, it has a fear of destroying an ozone layer. Because the above blowing agent of this invention has a b.p. of 37.3 deg.C and a double bond, it has little fear of destroying an ozone layer, and because it has a b.p. close to that of R-11, it can be used as a substitute for R-11.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing a foamed synthetic resin such as a polyurethane foam, and in particular a method for producing a foamed synthetic resin characterized by the use of a specific blowing agent. It is about the method.

[Prior Art] It is widely practiced to produce a foamed synthetic resin by reacting an active hydrogen compound having two or more active hydrogen-containing groups capable of reacting with an isocyanate group with a polyisocyanate compound in the presence of a catalyst and a blowing agent. ing. Examples of active hydrogen compounds include polyhydroxy compounds and polyamine compounds. Examples of the foamed synthetic resin that can be obtained include polyurethane foam, polyisocyanurate foam, and polyurea foam. In addition, examples of foamed synthetic resins with relatively low foaming include microcellular polyurethane elastomer and microcellular polyurethane urea elastomer.

Although various compounds are known as blowing agents for producing the above-mentioned foamed synthetic resin, trichlorofluoromethane (R-11) is mainly used. Also, usually R-
Water is further used in combination with 11. Furthermore, when foaming is carried out by the cross method etc., dichlorodifluoromethane (R
-12) is used in combination. Various proposals have been made that other relatively low-boiling chlorinated fluorinated hydrocarbons can be used as blowing agents;
With the exception of No. 11 and R-12, they have not yet come into widespread use. It has also been proposed to use other low boiling point halogenated hydrocarbon blowing agents, such as methylene chloride, in place of the chlorinated fluorinated hydrocarbon blowing agents.

[Problems to be solved by the invention] Chlorinated fluorinated hydrocarbons that are extremely stable in the atmosphere, such as R-11 and R-12, which have been widely used in the past, reach the ozone layer above the atmospheric layer without being decomposed. There, it was thought that it would be decomposed by the action of ultraviolet rays, etc., and that the decomposed products could destroy the ozone layer. Chlorinated fluorinated hydrocarbons as mentioned above were used as blowing agents.

Because some of it leaks into the atmosphere, it is feared that its use may be part of the cause of ozone layer depletion. Therefore, in place of R-11 and R-12, it is desired to develop a blowing agent that is less likely to cause ozone layer depletion.

[Means for Solving the Problems] The present invention provides the following inventions to solve the above-mentioned problems.

2 active hydrogen-containing functional groups that can react with isocyanate groups
In a method for producing a foamed synthetic resin by reacting an active hydrogen compound having the above and a polyisocyanate compound in the presence of a low boiling point halogenated hydrocarbon blowing agent, the low boiling point halogenated hydrocarbon blowing agent is 1.1- dichloro-2
- A method for producing a foamed synthetic resin characterized by using fluoroethylene.

1,1-dichloro-2-fluoroethylene, which is the blowing agent in the present invention, is a compound whose i point is 37.3°C, and because it is a fluorinated hydrocarbon containing hydrogen and having a double bond, it There is considered to be little risk of destruction. Furthermore, since its boiling point is close to that of R-11, it can be used as a blowing agent in place of R-11.

The halogenated hydrocarbon blowing agents in the present invention can be used alone or in combination with other blowing agents. In particular, water is often used in combination with the halogenated hydrocarbon blowing agent. Other blowing agents that can be used in combination with other than ice fields include, for example, the current blowing agents R-11 and R-
12゜Other low boiling point halogenated hydrocarbons, low boiling point hydrocarbons, inert gases, etc. Although R-11 and R-12 may cause ozone layer destruction by themselves, their usage can be reduced by using them in combination with 1,1-dichloro-2-fluoroethylene. Other low-boiling halogenated hydrocarbons include halogenated hydrocarbons that do not contain fluorine atoms, such as methylene chloride, and fluorine-containing halogenated hydrocarbons other than those mentioned above. Low-boiling hydrocarbons include butane and hexane, and inert gases include air and nitrogen.

2 active hydrogen-containing functional groups that can react with isocyanate groups
The active hydrogen compound having the above is a compound having two or more active hydrogen-containing functional groups such as a hydroxyl group or an amine 7 group, or a mixture of two or more such compounds. Particularly preferred are compounds having two or more hydroxyl groups, mixtures thereof, or mixtures containing these as the main component and further containing a polyamine or the like. As the compound having two or more hydroxyl groups, widely used polyols are preferred, but compounds having two or more phenolic hydroxyl groups (for example, phenol resin initial condensate) can also be used. Polyols include polyether polyols, polyester polyols,
Examples include polyhydric alcohols and diethylene polymers containing hydroxyl groups. In particular, it is preferable to use only one or more types of polyether polyols, or to use them as a main component in combination with polyester polyols, polyhydric alcohols, polyamines, alkanolamines, and other active hydrogen compounds. The polyether polyol is preferably a polyether polyol obtained by adding a cyclic ether, particularly an alkylene oxide such as propylene oxide or ethylene oxide, to a polyhydric alcohol, saccharide, alkanolamine, or other initiator. Further, as the polyol, it is also possible to use a polyol composition called a polymer polyol or a graft polyol, in which fine particles of a vinyl polymer are dispersed in a mainly polyether polyol. Polyester polyols include polyalgol-polycarboxylic acid condensation polyols and cyclic ester ring-opening polymer polyols, and polyhydric alcohols include ethylene glycol, propylene glycol,
These include diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, jetanolamine, and triethanolamine. Compounds having two or more phenolic hydroxyl groups include resol-type initial condensates in which phenols are condensed and bonded with excess formaldehyde in the presence of an alkali catalyst; There are benzylic-type precondensates made by reacting excess phenols with formaldehyde in the presence of an acid catalyst, and novolak-type precondensates. The molecular weight of these initial condensates is preferably 200 to 10,000. Here, phenols mean those in which one or more carbon atoms of the skeleton forming a benzene ring are directly bonded to a hydroxyl group, and there are no other compounds in the same structure. Also included are those having a substituted bonding group. Typical examples include phenol, cresol, bisphenol A, and resorcinol. Further, formaldehydes are not particularly limited, but formalin and paraformaldehyde are preferred. The hydroxyl value of the polyol or the mixture of active hydrogen compound hydrogen is often selected from about 20 to 1000 depending on the purpose.

Examples of polyisocyanate compounds include aromatic and alicyclic compounds having two or more isocyanate groups.

Alternatively, there are aliphatic polyisocyanates, mixtures of two or more thereof, and modified polyisocyanates obtained by modifying them. Specifically, for example, polyisocyanates such as tolylene diisocyanate-1, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate (commonly known as crude MDI), xylylene diisocyanate, inholone diisocyanate, and hexamethylene diisocyanate, and their precursors. There are polymer type modified products, nurate modified products, urea modified products, etc.

When reacting active hydrogen compounds and polyisocyanate compounds, the use of catalysts is usually required. As a catalyst,
Metal compound catalysts such as organotin compounds and tertiary amine catalysts such as triethylenediamine are used to promote the reaction between active hydrogen-containing groups and isocyanate groups. Further, a polymerization catalyst that causes isocyanate groups to react with each other, such as a carboxylic acid metal salt, is used depending on the purpose. Furthermore, foam stabilizers are often used to form good foam. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. Other optional additives include fillers, stabilizers, colorants, flame retardants, and the like.

Using these raw materials, polyurethane foam, urethane-modified polyisocyanate foam, microcellular polyurethane elastomer, microcellular polyurethane urea elastomer, microcellular polyurea elastomer, and other foamed synthetic resins can be obtained.

Polyurethane foam can be broadly divided into rigid polyurethane foam, semi-rigid polyurethane foam, and flexible polyurethane foam. The present invention is particularly useful in the production of rigid polyurethane foams, urethane-modified polyisocyanurate foams, and other rigid foams, which are fields in which halogenated hydrocarbon blowing agents are used in large quantities. Among these, it is particularly useful in the production of rigid polyurethane foam obtained by using a polyol or polyol mixture having a hydroxyl value of 200 to 1000 and an aromatic polyisocyanate compound. When producing these hard foams, the amount of halogenated hydrocarbon blowing agent used in the present invention is 5 to 1% per active hydrogen compound.
50% by weight, especially 20-60% by weight, is suitable. In addition, at the same time, water is 0 to 10% relative to the active hydrogen compound.
Preference is given to using % by weight, especially 1 to 5% by weight. On the other hand, in the case of flexible polyurethane foam, semi-rigid polyurethane foam, and microcellular elastomer, the halogenated hydrocarbon blowing agent in the present invention is preferably used in an amount of 5 to 150% by weight based on the active hydrogen compound. For soft urethane foam and semi-hard urethane foam, add water to o
-101% by weight, and in the case of a microcellular elastomer, preferably 0 to 5% by weight of water.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

[Example] Foaming evaluation of the halogenated hydrocarbon blowing agent in the present invention was conducted for the following polyols.

Polyolumi: A polyether polyol with a hydroxyl value of 420 made by reacting glycerin with propylene oxide Polyol B: A polyether polyol with a hydroxyl value of 450 made by reacting sucrose with propylene oxide and ethylene oxide Polyol C: A polyether polyol with a hydroxyl value of 450 made by reacting propylene oxide with sucrose Polyol C: Propylene oxide mixed with toluene diamine The foaming evaluation of the reacted polyether polyol having a hydroxyl value of 440 was carried out as follows. For 100 parts by weight of polyol, silicone foam stabilizer (Shin-Etsu Chemical Co., Ltd. product name)
2 parts of F-338), 1 part of water, the necessary amount of N,N-dimethylcyclohexylamine as a catalyst to give a gel time of 45 seconds, an appropriate amount of 1,1-dichloro-2-fluoroethylene, and polymethylene. Polyphenylisocyanate) (MD Kasei ■ Product name PAP1135) at a liquid temperature of 2.
The mixture was mixed at 0° C., placed in a 200 mm x 200 mm x 200 mm wooden box, and foamed for evaluation. Further, as a comparative example, R-11 was similarly foamed and evaluated. The amount of foaming agent used is based on the foam core density of 30±2 kg/m3.
It was adjusted so that

The results are shown in Table 1.

The criteria for judgment are as follows.

Q: Equivalent to or better than R-11 Δ: Slightly inferior to R-11 30.3
Compressive strength OΔ O Thermal conductivity Δ 00 [Effects of the invention] The present invention produces a good foamed synthetic resin without substantially using chlorinated fluorinated hydrocarbons such as R-11, which may cause ozone layer depletion. It is something that can be manufactured.

Claims (1)

[Claims] 1. Foaming synthesis 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 halogenated hydrocarbon blowing agent. A method for producing a foamed synthetic resin, the method comprising using 1,1-dichloro-2-fluoroethylene as a low-boiling halogenated hydrocarbon foaming agent.