JPS61171745A - Foamed phenolic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having uniform and fine cell structure and high closed cell ratio, by compounding a specific phenol-modified surfactant and a novolac surfactant as essential components. CONSTITUTION:100pts.(wt.) of a resol-type phenolic resin precondensate is compounded with (A) 0.1-10pts., preferably 0.5-5pts. of (A1) an etherified product of a nonionic surfactant (e.g. polyoxyalkylene nonylphenyl ether) and a phenol having methylol group and (A2) an alkylene oxide adduct of a novolac phenolic resin, (B) an acidic curing agent (e.g. hydrochloric acid, monochloroacetic acid, etc.) and (C) an organic foaming agent having low boiling point (e.g. petroleum ether, naphtha, ethyl acetate, etc.), and the mixture is foamed to obtain the objective foam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to phenolic resin foam compositions, and in particular to
The present invention relates to a phenolic resin foam composition with a uniform and finer cell structure and a high closed cell ratio.

Phenolic resin foam has traditionally had excellent heat resistance, flame resistance, low smoke emission, cold resistance, and weather resistance, and in recent years, its flame resistance and low smoke emission have been highly praised and its use as a heat insulating material. is being attempted.

However, compared to existing insulation materials such as polystyrene foam and rigid urethane foam, phenolic resin foam has disadvantages such as brittle foam, slightly inferior insulation properties, and metal corrosion. When used as an insulating material, the thermal insulation properties have not yet been achieved.

The cell structure is largely responsible for the inferior insulation properties of phenolic resin foams compared to other insulation materials.

In other words, the cell structure of the phenol resin foam has few closed cells and is mainly formed of open cells, resulting in poor heat insulation properties, which we believe can be solved by increasing the closed cell ratio.

A method for producing a phenolic resin foam is to mix an acidic curing agent, an organic blowing agent, a foam stabilizer, etc. with a resol type resin initial condensate and foam the mixture at room temperature or under heating.

At this time, the component that greatly affects the structure of the foam is the surfactant used as a foam stabilizer. Oil fatty acid esters, nonionic surfactants such as polyoxyethylene dimethyl silicone, alone or in combination, dodecylbenzenesulfonate Na salt, dioctyl sulfosuccinate Na salt,
Anionic surfactants such as lauryl sulfate Na salt and polyoxyethylene nonylphenyl ether sulfate Na salt are used in combination with the above-mentioned nonionic surfactants, but the closed cell ratio is still insufficient to have satisfactory thermal insulation properties. I have not yet reached the point where I can obtain it.

The present inventors have conducted extensive research to solve these problems, and as a result they have arrived at the present invention. That is,
The present invention provides a phenolic resin foam composition containing a surfactant, an acidic curing agent, and a low-boiling point organic blowing agent. Surfactant (
A)] and an alkylene oxide adduct of a novolak phenol resin [novolak type surfactant (B)] are provided as essential components.

In the present invention, examples of the nonionic activator used in the etherification of a nonionic activator and a phenol having a methylol group include polyoxyalkylene nonylphenyl ether, polyoxyalkylene dodecylphenyl ether, polyoxyalkylene octylphenyl ether, etc. Polyoxyalkylene aralkyl phenyl ether such as polyoxyalkylene alkyl allyl ether, polyoxyalkylene distyrylated phenyl ether, polyoxyalkylene alkyl (or alkenyl) ether such as polyoxyalkylene lauryl ether, polyoxyalkylene oleyl ether, polyoxyalkylene Lauric acid ester, polio and ua7. Ya, 7o I, -4
7@:L7. Care, Yu. 1. Alkylene oxide derivatives such as oxyalkylene alkyl (or alkenyl) esters, polyoxyethylene, polyoxypropylene broth copolymers, polyoxyalkylene sorbitan oleate alkylamine alkylene oxide adducts, and alkylene oxide adducts of castor oil. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrenated oxide, etc., which are addition-polymerized by known synthesis methods to form individual adducts of each alkylene oxide, or block adducts of two or more types, Alternatively, two or more kinds of random adducts can be mentioned.

The number of moles of alkylene oxide added is 1 to 100°, preferably 10 to 60. Phenols having a methylol group are the reaction products of phenols and formalin or paraformaldehyde, and phenols have a phenolic OH group such as phenol, cresol, xylenol, bisphenol, etc., and active hydrogen that can be methylolated. Examples include phenolic compounds having the following.

The etherified product of the nonionic activator of the present invention and a phenol having a methylol group is prepared by using a lower alcohol as a solvent, adding a phenol, and heating the mixture at 80 to 100°C in the presence of an alkali catalyst.
This product is provided by methylolation of phenols and etherification of the nonionic surfactant by adding a nonionic surfactant in the presence of a solvent and removing the solvent under reduced pressure. Note that the manufacturing method is not limited to this, and any method may be used.

Next, in the present invention, the novolac phenol resin used for the alkylene oxide adduct of novolac phenol resin is one produced from phenols by a known synthesis method, and the phenols have 0 to 2 carbon atoms as substituents. Examples include those having 1 alkyl group, alkenyl group, or aralkyl group, and specific examples include phenol, cresol, ethylphenol,
These include allylphenol, benzylphenol, and distyrenated phenol.

In addition, alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrenated oxide, etc., and these can be addition-polymerized by known synthesis methods to form individual adducts of each alkylene oxide, block adducts of two or more types, or two or more types of block adducts. It is a random addition of more than one species.

The number of moles of alkylene oxide added is 1 to 100°, preferably 5 to 50, and the number of nuclei of the novolak phenol resin is preferably 2 to 20.

The blending amount of the surfactants (A) and (B) of the present invention is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resol type phenolic resin initial condensate.

Furthermore, the surfactants (A) and (B) of the present invention can also be used in combination with at least one other conventionally used surfactant.

Next, examples of acidic curing agents that can be used in the present invention include hydrochloric acid,
Inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as monochloroacetic acid, P-toluenesulfonic acid, benzenesulfonic acid, β-naphthalenesulfonic acid, and phenolsulfonic acid, all of which can act as strong acids, are preferred. Use one type or a mixture of two or more types.

Examples of organic blowing agents include volatile petroleum compounds such as petroleum ether, naphtha, pentane, and hexane, low molecular weight fatty acid esters such as ethyl acetate, ketones such as methyl ethyl ketone and acetone, and lower aliphatic compounds such as methyl alcohol and ethyl alcohol. -hydric alcohols, as well as methylene chloride, carbon tetrachloride, trichloroethane, and dichloromethylene.

Examples include low boiling point halogenated hydrocarbons such as fluorotrichloromethane and trifluorotrichloroethane.

The resol-type phenolic resin initial condensate used in the present invention is produced by reacting phenols and aldehydes in an equimolar ratio or in an excess of aldehyde in the presence of an alkaline catalyst.

Phenols include phenol, cresol, ethylphenol, propylphenol, and bisphenol A.
, bisphenol F, and examples of aldehydes that react with phenols include formaldehyde, acetaldehyde, paraformaldehyde, and the like.

In addition, alkaline catalysts include magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium hydroxide,
Examples include potassium hydroxide, ammonium hydroxide, hexamethylenetetramine, and the like.

The surfactants (A) and (B) of the present invention have extremely good compatibility with the resol type phenolic resin initial condensate. Therefore, the bubbles during foaming are fine and uniform, so
The foaming pressure generated within the cells is relatively small, so that the cell membrane is not destroyed and a phenolic resin foam with a high closed cell ratio can be obtained.

Further, to the phenolic resin foam composition of the present invention, for example, organic or inorganic fibrous substances, plasticizers such as ethylene glycol and tung oil, and flame retardants such as trischloroethyl phosphate may be added.

The present invention will be explained in detail below with reference to Examples.

Example 1-13. Comparative Examples 1 to 5 Phenol 1.0 mol Formaldehyde (37% aqueous solution) 2.0 mol 30% caustic soda aqueous solution 3% by weight relative to phenol A reaction was carried out according to a conventional method at the above mixing ratio, and after the reaction was completed, caustic soda was added using lactic acid. and adjust the system to pH 6-7.

Next, dehydration was performed under reduced pressure until the water content became 15% by weight to obtain a resol type phenolic resin.

This is called resin A.

Next, the etherified product of the nonionic surfactant and phenol having a methylol group used in Example 1 [phenol-modified surfactant (A)] was prepared by mixing 1.8 g of caustic soda, 94 g of phenol, and 37% of phenol in 100 g of ethanol. 81 g of formalin was added and reacted at 80 to 100°C for 3 hours, and then nonylphenol ethylene oxide adduct (P=
10.0 mol) was added and the solvent was removed under reduced pressure at 100 to 120°C.

The number of nonylphenol ethylene oxide adducts (p=to, o mol) before synthesis is 13.5, and the number of tones of the product of the present invention produced by the above synthesis method is 6.5, which indicates that the desired reaction I confirmed that I was getting something.

The etherification products of nonionic surfactants and ferrules having a methylol group in Examples 2 to 13 [phenol-modified surfactants (A)] were also prepared using the nonionic surfactants and phenols listed in the table below. Manufactured in the same manner.

Phenol-modified surfactant (A) and novolak type surfactant (B) shown in Table 1 for 00 parts by weight of resin Al.
A composition prepared at the blending ratio shown in Table 1 was mixed with 4.0 parts by weight as a foam stabilizer and Freon 11320 as a foaming agent.
．． Add 0 parts by weight and mix with high speed stirring. After that, phenolsulfonic acid (purity 63%) was used as a curing catalyst.
After adding 0 parts by weight and stirring and mixing at a high speed of 3000 to 5000 r, p, m for 20 to 40 seconds, the mixture was immediately poured into a container and foamed and hardened at 50 to 80°C.

As shown in the table, the obtained foam had a uniform cell structure and a high closed cell ratio as a whole.

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Claims (1)

[Claims] In a phenolic resin foam composition containing a surfactant, an acidic curing agent, and a low-boiling point organic blowing agent, an etherified product of a nonionic surfactant and a phenol having a methylol group, and an alkylene oxide of a novolak phenolic resin are used. A phenolic resin foam composition characterized by containing an adduct as an essential component.