JPH03172314A - Resin dope for production of water-expandable urethane foam - Google Patents

Abstract

PURPOSE:To obtain the subject dope giving a foam having uniform cell structure without causing the destruction of ozonosphere by mixing a polyfunctional polyol mixture, a hydrophilic solvent, an organic polysiloxane copolymer, a tertiary amine catalyst and water. CONSTITUTION:The objective dope is produced by mixing (A) a mixture of 2 to 4-functional polyols (e.g. ethylene glycol, trimethylol propane and pentaerythritol), (B) preferably 0.5-10wt.% of a hydrophilic solvent (e.g. methanol or cellosolve), (C) preferably 0.5-3wt.% of an organic polysiloxane copolymer, (D) preferably 0.1-3wt.% of a tertiary amine catalyst (e.g. N,N,N',N'- tetramethylhexamethylenediamine) and (E) preferably 0.5-10.0wt.% of water.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin stock solution used in the production of polyurethane foam, which is widely used for heat insulation, dew condensation prevention, and the like.

(Conventional technology) Polyurethane foam has excellent heat insulation properties, so L
It is widely used as a cold or heat insulating material in PG tankers, reefers, electric refrigerators, chemical plants, etc., or as a dew condensation prevention material on the walls of buildings.

When producing polyurethane foam, a foam with a high expansion ratio cannot be obtained by water foaming alone, so a haloalkane foaming agent has been used alone or in combination with water. However, in recent years, the depletion of the ozone layer by haloalkanes has come into focus.
It has been desired to develop a resin stock solution for producing polyurethane foam that has a high expansion ratio without using haloalkanes.

(Problems to be Solved by the Invention) In order to obtain a high expansion ratio through water foaming, hydrophilicity of the polyol mixture is essential. However, even if a homogeneous resin stock solution is obtained by dissolving water in a hydrophilic polyol, when producing polyurethane foam, when organic polyisocyanate is mixed, water is The problem was that the foam separated and a uniform highly foamed product could not be obtained.

(Means for Solving the Problems) The present inventors have conducted intensive research on a resin stock solution that can produce highly foamed polyurethane foam without separating water even when organic polyisocyanate is mixed with water-containing polyol. , arrived at the present invention. That is, the present invention is as follows.

A resin stock solution for producing water-foamed polyurethane foam having a high expansion ratio, which is obtained by mixing a di- to tetrafunctional polyol mixture, a hydrophilic solvent, an organic polysiloxane polymer, a tertiary amine catalyst, and water.

The 2-4 functional polyols used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene ether glycol, neopentyl glycol, 1.4
-butanediol, 1.3-butanediol, 1.6-
Hexanediol, bisphenol A, etc. or alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. are added to these! 1 or 2f! l
Bifunctional polyols represented by addition polymerization of one or more of these, trimethylolpropane, glycerin, etc., trifunctional polyols represented by addition polymerization of the above alkylene oxides, pentaerythritol, etc., or the above-mentioned polyols, etc. Tetrafunctional polyols represented by addition polymerization of alkylene oxide, other alkanolamines such as triethanolamine, jetanolamine, ethylenediamine, etc., or addition polymerization of the above alkylene oxide to these, etc. Or you can mix 2 or more Ken. In addition to the above polyols, polyol resins such as polyester polyols and acrylic polyols may also be used in combination.

Hydrophilic solvents are generally referred to as coupler solvents that promote dissolution of organic substances in water, and examples of alcohols include methanol, ethanol, isopropyl alcohol, propyl alcohol, l-butanol, 2-butanol, Examples include methyl cellosolve, cellosolve, butyl cellosolve, isobutyl cellosolve, methyl calpitol, ethyl calpitol, butyl calpitol, isobutyl calpitol, and the like. Examples of ethers include ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether. Furthermore, there are ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, as well as dimethylformamide, N-methyl-2-
Pyrrolidone is mentioned as an example. These hydrophilic solvents may be used alone or in combination of two or more. It is also possible to use a hydrophilic solvent and a non-aqueous solvent such as xylene, toluene, etc. in combination. The amount of the hydrophilic solvent used is 0.00 parts by weight in 100 parts by weight of the resin stock solution (the following parts indicate parts by weight).
5 to 10 parts. If the amount of hydrophilic solvent used is less than 0.5 parts or is not used, the uniformity of the cell size of the foam will be poor and the density of the foam will become large, which is undesirable, and in particular, the foam may not be formed. Also, when the amount of the hydrophilic solvent used exceeds 10 parts, only the same unfavorable foam as described above is obtained.

The organic polysiloxane copolymer referred to in the present invention is used as a regulating agent during foaming, and examples thereof include L-501, L-520, and L-532 manufactured by Nippon Unicar Co., Ltd.
,L-540,L,-544,L-3550,L-5
302, L-5305, L-5320, L-534
0, L-5350, L-54101L-5420, L
-5421, L-5710SL-5720, etc., and 5H-190,5) (-192,5) manufactured by Toshi Silicone Co., Ltd.
)1-193.5H-194,5H-195,5)l-
200, 5RX253, etc., F-114, F-121SF-122, F-220, F manufactured by Shin-Etsu Silicone Co., Ltd.
-230, F-258, F-260B, F-305,
F-306, F-317, F-341, F-601, F
-606, X-20-200,
There are TFA-4202 and the like.

The appropriate amount to be used is 0.5 to 3 parts per 100 parts of the resin stock solution.

Catalysts useful for the present invention include, for example, N;

N', N'-tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, dimethylbalmitylamine, trimethylaminoethylpiperazine, triethylamine, triethylenediamine, N, N, N
', N'-tetramethylpropanediamine, N,
N.

N', N-tetramethylhexanediamine, N, N,
N'.

N'-1,3-butanediamine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl)
Ether, N, N', N'-tris(dimethylaminoethyl)hexahydrotriazine, N, N',
Amines such as N"-(diethylaminopropyl)hexahydrotriazine, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(diethylaminomethyl)phenol, and tetramethylguanidine. Use thereof. The appropriate amount is 0.1 to 3 parts per 100 parts of the resin stock solution.

The water used in the present invention generates carbon dioxide gas by reaction with isocyanate and acts as a blowing agent.

The amount of water used varies depending on the amount of organic polyisocyanate used, but it is usually 0.5 to 1 part per 100 parts of the resin stock solution.
It is 0.0 part. If the amount of water used is outside the above range, the physical properties of the polyurethane foam produced, such as density and cell uniformity, will deteriorate.

The organic polyisocyanate used here is, for example, 2,
4- and 2.6-) lylene diisocyanate and mixtures thereof, as well as crude tolylene diisocyanate containing polynuclear bodies thereof, 4.4゛-diphenylmethane diisocyanate, 4,2゛-diphenylmethane diisocyanate, crude Polymethylene polyphenyl polyisocyanate (MDI-
CR), 1,5-naphthalene diisocyanate, 3,3
°-dimethyl-4,4'-biphenylene diisocyanate and the like. These isocyanates may be used alone or in combination of two or more. The appropriate amount to use is an equivalent ratio of isocyanato groups to active hydrogen in the resin stock solution of 0.8 to 1.1.

(Example) Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the examples, % does not indicate weight %.

Example 1 Adipic acid 660g, 1,4-butanediol 220g
g.

220 g of diethylene glycol, 65 g of limethylolpropane were placed in a 4-ton flask equipped with a stirrer, thermometer, and inert gas inlet tube, and the inert gas was passed through it.
The dehydration reaction was carried out at a reaction temperature of 80 to 240°C, and the acid value was 1.
．． When the temperature reached 0, the reaction was terminated and a polyester polyol was synthesized.

The resulting polyester polyol has a hydroxyl value of 80
KOHmg/g. The above polyester polyol 30g 1 polypropylene glycol EP505S15
g (manufactured by Mitsui Toatsu Chemical, hydroxyl value 54KOHm)
g/g, solid content 100%), propylene oxide addition polymer of pentaerythritol PH450, 30g (Mitsui Toatsu Chemical ■, hydroxyl value 450KOHmg/g)
.

100% solids). Alkylene oxide addition polymer of ethylenediamine AE302.15g (manufactured by Mitsui Toatsu Chemical Co., Ltd., hydroxyl value 750KOHmg/g, solid content 10
0%) were mixed and stirred to obtain polyol (A). To this, organic polysiloxane copolymer L-5421 (manufactured by Nippon Unicar Co., Ltd.), pentamethyldiethylenetriamine as a catalyst, N-methyl-2-pyrrolidone, and water were mixed and stirred, and MD
I-CR-200 (manufactured by Mitsui Toatsu Chemical, NGO content 3
0%, solid content 100%) to produce polyurethane foam. The blending ratio is shown in Table-1.

Example 2 Organopolysiloxane copolymer L-5421, pentamethyldiethylenetriamine, N-methyl-2-pyrrolidone, water, and xylene as catalysts were mixed and stirred in the polyol (A) obtained in Example, and MDI- CR-200 was added to produce a foam. The blending ratio is shown in Table-1.

Example 3 Polypropylene glycol EP551C 45g (manufactured by Mitsui Toatsu Chemical Co., Ltd., hydroxyl value 56KOHmg/g
, solid content 106%), 35 g of propylene oxide addition polymer of pentaerythritol PH450, 5 g of triethanolamine, and 5 g of diethylene glycol were mixed and stirred to obtain polyol (B).

In addition, organic polysiloxane copolymer L-5421, catalyst pentamethyldiethylenetriamine, tetramethylhexamethylenediamine, N-methyl-2-pyrrolidone,
Mix and stir water and isobutyl cellosolve, and MDI-CR
-200 was added to produce a foam.

The blending ratio is shown in Table-1.

Example 4 252 g of phthalic anhydride, 12 1,4-butanediol
9g1 Adipic acid 368g, 1.6-hexanediol 190g, neopentyl glycol 170g, )
17 g of limethylolpropane was placed in the same apparatus as in Example 1,
A polyester polyol was synthesized by the method.

The resulting polyester polyol has a hydroxyl value of 64
KOHmg/g. 17g of the above polyester polyol, polypropylene glycol EP551CIO
g, 450.60 g of pentaerythritol propylene oxide addition polymer PE were mixed and stirred to form polyol (C).
I got it.

Organic polysiloxane copolymer L-5421, catalyst pentamethyldiethylenetriamine, isobutyl cellosolve, and water were mixed and stirred, and MDI-CR-200 was added thereto to produce a foam. The blending ratio is shown in Table-1.

Comparative Examples 1-3 Polyols (A), (B), (C) obtained in Examples 1-4
Water and a catalyst were mixed and stirred, and MDI-CR-200 was added to produce polyurethane foam. The blending ratio is shown in Table-1.

Comparative Example 4 Organic polysiloxane copolymer L-5421, water, and a catalyst were mixed and stirred in the polyol (A) obtained in Example 1, and MDI-CR-200 was added thereto to produce a polyurethane foam. The blending ratio is shown in Table-1.

The density and cell appearance (size, uniformity) of the produced polyurethane foam were evaluated by the following methods. The results are shown in Table-2.

- Density (according to the method of CJrSA 9514) Cut the foam into a size of approximately 20 mm x 20 mm x 20 mm, measure the length, width, height, and weight to calculate the density.

This is done three times for each point, and the number average is taken as the density.

・Cell appearance Measure the largest cell diameter and the smallest cell diameter.

Then, the difference between the maximum diameter and the minimum diameter is taken, and this is taken as uniformity.

(Effects of the invention) The present invention enables the creation of a uniform cell structure with a high expansion ratio by using a hydrophilic solvent and only water foaming without using haloalkane foaming agents, which cause ozone layer depletion. A polyurethane foam was obtained.

Claims (3)

[Claims] (1) A resin stock solution for producing water-foamed polyurethane foam having a high expansion ratio, which is obtained by mixing a di- to tetrafunctional polyol mixture, a hydrophilic solvent, an organic polysiloxane copolymer, a tertiary amine catalyst, and water. (2) 0.5 to 0.5 parts by weight of hydrophilic solvent in 100 parts by weight of resin stock solution
The resin stock solution for producing water-foamed polyurethane foam according to claim (1), characterized in that 10.0 parts by weight is used. (3) 0.5 to 10.0 parts of water in 100 parts by weight of resin stock solution
The resin stock solution for producing water-foamed polyurethane foam according to claim 1, characterized in that part by weight is used.