JPH01313538A - 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, hexafluorocyclobutene is used as said blowing agent. Although trichlorofluoromethane (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 1.1 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. The foamed synthetic resins obtained include, for example, 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 froth method, etc., dichlorodifluoromethane (gaseous at room temperature and pressure), which has a lower boiling point (gaseous at room temperature and pressure)
? -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 -11 and R-12, they have not yet been widely used, and other low-boiling halogenated hydrocarbon blowing agents such as methylene chloride can be used instead of chlorinated fluorinated hydrocarbon blowing agents. It is also proposed to use

[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. The chlorinated fluorinated hydrocarbons used as blowing agents are thought to be decomposed by the action of ultraviolet rays, etc., and the decomposed products destroy the ozone layer.
It is feared that its use may be part of the cause of ozone layer depletion, as some of it leaks into the atmosphere, so it is recommended that it be used instead of such 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, hexafluorocyclobutene is used as the low boiling point halogenated hydrocarbon blowing agent. A method for producing a foamed synthetic resin, characterized by using.

Hexafluorocyclobutene, which is a blowing agent in the present invention, is a compound with a boiling point of 1.1°C, and since it is a fluorinated hydrocarbon having a double bond, it is thought that there is little risk of the ozone layer being destroyed. Furthermore, its boiling point is R-11
Since it is close to that, it can be used as an alternative blowing agent.

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 halogenated hydrocarbons, low-boiling 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 hexafluorocyclobutene.

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 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 the same as the main component and further containing 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, polyether polyols are preferably composed of one or more polyether polyols, or are preferably composed mainly of polyester polyols, polyhydric alcohols, polyamines, alkanolamines, and other active hydrogen compounds. Preferred are polyether polyols 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 polyhydric alcohol-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 novolac-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 A1, resorcinol, and the like. 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, alicyclic, or aliphatic polyisocyanates having two or more isocyanate groups, mixtures of two or more thereof, and modified polyisocyanates obtained by modifying them. Specifically, for example, polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate (commonly known as crude MDI), xylylene diisocyanate, inphorone diisocyanate, hexamethylene diisocyanate, prepolymer type modified products thereof, and nurate. There are modified forms, urea modified forms, 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 roughly divided into rigid polyurethane foam and semi-rigid polyurethane foam! The present invention is particularly applicable to the production of rigid polyurethane foam, urethane-modified polyin cyanurate foam, and other rigid foams, which are fields in which halogenated hydrocarbon blowing agents are used in large quantities. Useful. 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 rigid foams, the amount of halogenated hydrocarbon blowing agent used in the present invention is 5% based on the active hydrogen compound.
~150% by weight, especially 20-60% by weight are suitable.

In addition, at the same time, water is 0 to 0 to the active hydrogen compound.
It is preferable to use 10% by weight, especially 1 to 5% by weight.On the other hand, in the case of flexible polyurethane foams, semi-rigid polyurethane foams, and microcellular elastomers, the halogenated hydrocarbon blowing agent in the present invention is In the case of soft urethane foam and semi-rigid urethane foam, water is preferably used in an amount of 0 to 10% by weight, and in the case of microcellular elastomer, water is preferably used in an amount of 0 to 5% by weight.

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. trade name)
A mixed solution of 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 Hegisafluorocyclobutene, and polymethylene polyphenylisocyanate (MD Kasei (trade name: PAPI135) was mixed at a liquid temperature of 20°C,
200+amX It was placed in a 200mm x 200mm wooden box and foamed for evaluation. Further, as a comparative example, R-11 was similarly foamed and evaluated. The amount of foaming agent used was adjusted so that the core density of the foam was 30±2 kg/m3.

The results are shown in Table 1.

The criteria for judgment are as follows.

0: Equivalent to or better than R-11 Δ: Slightly inferior to R-11 .8 30.0
Compressive strength Δ oO Thermal conductivity o OO [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.

Procedural amendment

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 hexafluorocyclobutene as a low-boiling halogenated hydrocarbon foaming agent.