JPH02120338A - Production of foamed synthetic resin - Google Patents

Abstract

PURPOSE:To get rid of the possibility of destroying the ozone layer by using a specified foaming agent when a polyurethane foam is produced by a reaction in the presence of a low-b.p. halogenated hydrocarbon foaming agent. CONSTITUTION:When a foamed polyurethane is produced by reacting an active hydrogen compd. having two or more active hydrogen functional groups capable of reacting with an NCO group, such as polyether polyol, with a polyisocyanate compd. in the presence of a low-b.p. halogenated foaming agent, at least one compd. selected from the following compd. A to E is used as a foaming agent. It is suitable that the amt. of use is 5-150wt.%, especially 20-60wt.% based on the active hydrogen compd. A: ClF2C-CF2-CF2-CHF2 (b.p.: 50.2 deg.C), B: CH3- CHF-CH2-CH3 (b.p.: 25.5 deg.C), C: FH2C-CH2-CH2-CH3 (b.p.: 32.5 deg.C), D: F3C-CCl=CH- CH-CF3 (b.p.: 32.2 deg.C), and E: 1,2-dichloro-3,3,4,4-tetrafluorocyclobutene-1 (b.p.: 67.1 deg.C).

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] An active hydrogen compound having two or more active hydrogen-containing groups that can react with an incyanate group and a polyisocyanate!・It is widely practiced to produce foamed synthetic resins by reacting compounds in the presence of catalysts and blowing agents. Active hydrogen compounds include, for example, polyhydroxy compounds and polyamine compounds. Examples of the resin include polyurethane foam, polyisocyanurate foam,
Examples include 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 (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 such as those mentioned above used as blowing agents,
Because some of it leaks into the atmosphere, there are concerns that its use could 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 incyanate 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 halogenated hydrocarbon blowing agent, the low-boiling halogenated hydrocarbon blowing agent is l-chloro- 1, 1,
2,2゜3.3,4.4-octafluorobutane, 2-
Fluorobutane, 1-fluorobutane, 2-fluoro-1,1
, 1,4,4,4-hexafluoro-2-butene and 1
．． A method for producing a foamed synthetic resin, characterized in that at least one selected from 2-dichlorotetrafluorocyclobutene-1 is used.

1-chloro-1,1゜2, which is a blowing agent in the present invention;
2.3.3.4.4-octafluorobutane, 2-fluorobutane, ■-fluorobutane, 2-fluoro-1,1,1
, 4°・1.4-hexafluoro-2-butene and 1.
2-Dichlorotetrafluorocyclobutene-1 has boiling points of 50.2°C, 32.5°C, and 325.5°C, respectively.
Since the compound is a chlorinated fluorinated hydrocarbon containing hydrogen atoms and has a temperature of 2.2° C. and 67.1° C., it is thought that there is little risk of the ozone layer being destroyed. 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 used in combination with the above-mentioned halogenated hydrocarbon blowing agent in the case of a large amount of water.
2. Other low-boiling halogenated hydrocarbons, low-boiling hydrocarbons, inert gases, etc. Although R-11 and R-12 themselves may cause ozone layer depletion,
1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 2-fluorobutane, l-fluorobutane, 2-fluoro-1,1,l, 4.4.4-hexafluoro The amount used can be reduced by using it in combination with at least one selected from -2-butene and 1,2-dichlorotetrafluorocyclobutene-1.

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 amino 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, 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 in which fine particles of vinyl polymer are dispersed in a mainly polyether polyol called a polymer polyol or kraft 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. The hydroxyl value of the polyol or its foothold is often selected from about 20 to 1,000 depending on the purpose.

Examples of polyisocyanate compounds include aromatic, alicyclic, or aliphatic polyisocyanates having two or more incyanate groups, mixtures of two or more thereof, and modified polyisocyanates obtained by modifying them. Specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate (common name: crude-MDI)
Examples include polyisocyanates such as xylylene diisocyanate, inphorone diisocyanate, and hexamethylene diisocyanate, as well as prepolymer-type modified products, nurate-modified products, and urea-modified products thereof.

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 incyanate groups to react with each other, such as a carboxylic acid metal salt, is used depending on the purpose. Furthermore, many foam stabilizers are used to form good bubbles. Examples of foam stabilizers include silicone foam stabilizers and fluorine-containing compound foam stabilizers. Examples of additives that can be used include fillers, stabilizers, colorants, and flame retardants.

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 foams obtained by using polyols or polyol mixtures having 200 to 1000 hydroxyl groups and aromatic polyisocyanate compounds. When producing these hard foams, the amount of halogenated hydrocarbon blowing agent used in the present invention is 5 to 150% based on the active hydrogen compound.
Weight percentages are suitable, especially 20 to 60 weight percent. In addition, 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 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 0 to 1 water.
In the case of a microcellular elastomer, it is preferable to use water 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: Polyether polyol with a hydroxyl value of 420 made by reacting glycerin with propylene oxide Polyol B: Polyether polyol with a hydroxyl value of 450 made by reacting sucrose with propylene oxide and ethylene oxide Polyol C: Propylene oxide with toluene diamine The foaming evaluation of 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 ■ trade 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 a mixed solution of the blowing agent of the present invention, and polymethylene polyphenylisocyanate ( MD Kasei (trade name: PAP1135) was mixed at a liquid temperature of 20°C, and 200 m
The mixture was placed in a wooden box measuring 200 mm x 200 mm and foamed for evaluation.

Further, as a comparative example, R-11 was similarly foamed and evaluated.

The amount of foaming agent used is determined when the core density of the foam is 30±2K.
g/m".

The results are shown in the table below.

The criteria for judgment are as follows.

○: Equivalent to or better than R-11 △: Slightly inferior to R-11 X: Inferior to R-11 Table 1? Encyclopedia [1-chloro-1,1,2,2,3,3,
4,4-octafluorobutane" Table 2 Blowing agent "2-fluorobutane" Table 3 Blowing agent "1-fluorobutane" [Effects of the invention] The present invention provides the following advantages: - 1,1,1,4,4,4-hexafluoro-2-1-tene, etc. (in order to produce good foamed synthetic resin) It is possible.

table Foaming agent

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. In the method for producing a resin, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 2-fluorobutane, 1-fluorobutane, 2 - A foamed synthetic resin characterized by using at least one member selected from fluoro-1,1,1,4,4,4-hexafluoro-2-butene and 1,2-dichlorotetrafluorocyclobutene-1. manufacturing method.