JPH0364313A - Polyurethane form - Google Patents

Abstract

PURPOSE:To prepare a polyurethane foam excellent in the weathering properties by reacting a specific polyol compd. with a polyisocyanate. CONSTITUTION:A hydrogenated product of a liq., hydroxylated polyisoprene is used as a polyol compd. to react with a polyisocyanate (e.g. hexamethylene diisocyanate) to prepare a polyurethane foam.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyurethane foam, and more particularly to a polyurethane foam having excellent weather resistance.

[Prior art and problems to be solved by the invention] Polyurethane foam has good cushioning properties, excellent air permeability and sound absorption properties, and a wide range of specific gravity, so it is used in bedding, furniture, daily goods, electrical and electronic equipment, It is used in an extremely wide range of applications such as packaging materials and building materials.

It is known that this polyurethane foam can be produced by reacting a polyol compound and a polyisocyanate compound using a catalyst and foaming treatment using a blowing agent and other additives.

It is also known that for the foaming treatment, a chemical foaming method using water as a foaming agent and a physical foaming method using a halogenated hydrocarbon are employed.

By the way, although polyurethane foams obtained from conventionally used polyol compounds are excellent in the above-mentioned properties, they have the drawback of poor weather resistance, and an improvement has been desired.

The present invention aims to solve this conventional drawback and provide a polyurethane foam having excellent weather resistance.

[Means for Solving the Problems] In order to achieve the above object, the present inventor has conducted various studies on polyol compounds to be used as raw materials, and as a result,
It has been discovered that a polyurethane foam with improved weather resistance can be obtained by using a hydride of liquid polyisoprene containing hydroxyl groups, and the present invention has been completed based on this knowledge.

That is, according to the present invention, there is provided a polyurethane foam using a polyol compound and a polyisocyanate compound as raw materials, characterized in that a hydrogenated product of hydroxyl group-containing liquid polyisoprene is used as the polyol compound.

The present invention will be explained in detail below.

The hydride of hydroxyl group-containing liquid polyisoprene used in the present invention can be obtained by hydrogenating hydroxyl group-containing liquid polyisoprene.

The hydroxyl group-containing liquid polyisoprene used here is, for example, O, S to 100 parts by weight of isoprene ε isoprene.
A mixture with 200 parts by weight, preferably 1 to 50 parts by weight of hydrogen peroxide, is added to a solvent (e.g. aliphatic, cycloaliphatic or aromatic hydrocarbons, alcohols, ketones, esters, (e.g. ethers) or without (in this case isoprene itself is the solvent), 2
At a temperature of 0 to 300°C, preferably 30 to 200°C, normal pressure to 200 9/cl! G1 preferably normal pressure ~ 50kg
It can be produced by reacting for 0.1 to 10 hours under a pressure of /cys''G.

In addition to imprene homopolymer, the liquid polyisoprene includes copolymers such as isoprene-styrene copolymer, imprene-butadiene copolymer, isoprene-acrylonitrile copolymer, imprene-2-ethylhexyl acrylate copolymer, and imprene-octadecyl acrylate copolymer. It also includes.

The number average molecular weight of these hydroxyl group-containing liquid polyisoprene is 300 to 25,0QO1, preferably 500-1o,0
00, and the hydroxyl group content is 0.1 to tomeq/y,
Preferably it is 0.3-7 maq/g.

Next, by hydrogenating this hydroxyl group-containing liquid polyisoprene, a hydride of hydroxyl group-containing liquid polyisoprene can be obtained.

Hydrogenation of this hydroxyl group-containing liquid polyisoprene is carried out by dissolving the hydroxyl group-containing liquid polyisoprene in a solvent, and in the presence of a known hydrogenation catalyst such as nickel, palladium, ruthenium, or platinum, at a temperature of 20 to 300°C, preferably 30°C. ~200
℃8, hydrogen pressure 0, 5~200kg/crtr
"G, preferably 5-100 kg/cm2G and 0.
It can be carried out by reacting for 1 to 10 hours.

After the reaction is completed, the catalyst is filtered off and the solution is distilled under reduced pressure to remove the solvent and obtain a hydride of liquid polyisoprene containing hydroxyl groups.

The hydride of liquid polyisoprene containing hydroxyl groups has a number average molecular weight of 300 to 25,000. Preferably 500-10
,000, and the hydroxyl group content is o, x~xom
eq/y, preferably 0.3 to 7 meq/y.

In the present invention, a polyurethane foam can be produced using a mixture of the hydrogenated liquid polyisoprene and a hydroxyl group-containing liquid diene polymer as a raw material.

The hydroxyl group-containing liquid diene polymer may be any liquid diene polymer having these functional groups in the molecule, preferably at the end, and various polymers can be used without particular limitation. In addition, these liquid diene polymers have a number average molecular weight of 300 to 25,000, preferably 5.
00 to 10,000 diene polymers and diene copolymers having 4 to 12 carbon atoms, as well as combinations of these diene monomers and σ-olefinic addition-polymerizable monomers having 2 to 22 carbon atoms! There is a union. These liquid diene polymers are modified by adding an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof;
It also includes things. Specific examples include butadiene homopolymer isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, and the like. Among these liquid diene polymers, polymers or copolymers having a viscosity of 500 poise (at 30° C.) or less and a microstructure containing 1,4-bonds of 50% or more are preferably used. The average number of functional groups per molecule of these liquid diene polymers is 1 or more, preferably 2 to 4 m.

The composition of this mixture is 20% of hydroxyl group-containing liquid polybutadiene.
~70% by weight, preferably 25-60% by weight can be used.

By using such a mixture, the viscosity of the composition is reduced, workability is improved, and the strength of the foam can be improved.

Next, the polyisocyanate compound used in the present invention is 1
It is an organic compound having two or more isocyanate groups in the molecule, and has an isocyanate group reactive with the hydroxyl group of the hydride of the hydroxyl group-containing liquid polyisoprene. Examples of polyisocyanate compounds include the customary aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate, polymethylene poly Phenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diincyanate, inpropylbenzene-2,4-diincyanate,
Hexamethylene diamine diincyanate, inphorone diincyanate, hydrogenated diphenylmethane diincyanate, tolylene diisocyanate, cyclization of hexamethylene diisocyanate, trimethylolpropane and tolylene diisocyanate, addition of hexamethylene diisocyanate, etc. Examples include reactants such as addition reaction products of polypropylene glycol and tolylene diisocyanate, and particularly preferred are MDI, liquid modified diphenylmethane diisocyanate, and tolylene diisocyanate.

There is no particular restriction on the blending ratio of these components, but usually the molar ratio (NCOloH) of the incyanate group (NGO) of the polyisocyanate compound to the hydroxyl group (OH) of the hydride of the hydroxyl group-containing liquid polyisoprene is It is blended so that it becomes 0.5-25, preferably 0.5-15.

The polyurethane foam of the present invention can be obtained by reacting a hydride of a hydroxyl group-containing liquid polyisoprene with a polyisocyanate compound, usually in the presence of a catalyst, and performing a foaming treatment.

The catalysts used here include monoamines such as triethylamine (TEA) and N,N-dimethylcyclohexylamine (DMEDA), and cyamines such as N
, N, N', N'-tetramethylethylenediamine (T
MEDA), N, N, N'', No-tetramethylpropane-1,3-diamine (TMPDA), N, N
, N'', No-Tetramethylhexane-1,6-diamine (TMHMDA), etc., as triamines, N, N
, N', N", N"-pentamethyldiethylenetriamine (PMDETA), N, N, N', N", N"-pentamethyldipropylenetriamine (PMDPTA), tetramethylguanidine (TMG), and other cyclic amines. as, triethylenediamine (TEDA), N,
N″-dimethylpiperazine (DMP), N-methyl-N
'-(2-dimethylamino)-ethylpiperazine (TM
NAEP), N-methylmorpholine (NMMO), N.
(N',N'-dimethylaminoethyl)-7ulfoline (
DMAEMO), 1,2-dimethylimidazole (DM
Alcohol amines include dimethylaminoethanol (DMEA), dimethylaminoethoxyethanol (DMAEE), N,N,N'-)limethylaminoethyl-ethanolamine (TMA E E A
), N-methyl-N'-(2-hydroxyethyl)-piperazine (MHEP), N-(2-hydroxyethyl)
- As ether amines such as morpholine (HEMO), bis(2-dimethylaminoethyl) ether ('B
DMEE), ethylene glycol bis(3-dimethyl)
-aminopropyl ether (TMEGDA), etc. can be used.

There are no particular restrictions on the foaming process, and conventionally known chemical foaming methods and physical foaming methods can be employed.

The foaming agent in the chemical foaming method is water, and the foaming agent in the physical foaming method is CF2Cl2. CHC! 2F.

CC15F,, CHxCQt, CCl1fF-CCff
A halogenated hydrocarbon such as ijF is used.

In chemical foaming treatment, a predetermined amount of hydroxyl group-containing liquid polyisoprene hydride, polyisocyanate compound,
The polyurethane foam is produced by heating and mixing the catalyst and water, as well as optional surfactants and other additives.

As the surfactant, for example, polydimethylsiloxane, polydimethylsiloxane-polyoxyalkylene block copolymer, sodium salt of sulfonated lysylinate, ethylene oxide of alkylphenol, etc. are used.

In the physical foaming process, polyurethane foam can be obtained using a blowing agent in almost the same way as the chemical foaming process, but the difference is that the above-mentioned halogenated hydrocarbon is used as the blowing agent, printing by heating and mixing, and the use of the blowing agent. The difference is that the heat treatment is performed at a temperature above the boiling point.

Also, as a physical foaming treatment! ! [Foaming can also be achieved by stirring alone.

The present invention uses a hydrogenated liquid polyisoprene containing hydroxyl groups as a polyol compound, and reacts and foams a polyisocyanate compound in the presence of a catalyst to obtain a polyurethane foam. A hydride of liquid polyisoprene may be used, or a portion thereof may be used in place of the hydroxyl group-containing liquid diene polymer.

(I) When manufacturing a polyurethane foam) A mixture of a conventionally used polyol compound and a hydrogenated hydroxyl group-containing liquid polyisoprene can be used as a raw material.

There is no particular me ratio for this mixture, but usually 20 parts by weight of a hydride of liquid polyisoprene containing hydroxyl groups is added to 100 parts by weight of the conventionally used polyol compound.
It is blended in an amount of 80 g parts, preferably 30 to 70 parts by weight.

Use of this mixture has the advantage that the viscosity of the foamable composition can be reduced and workability can be improved.

In producing polyurethane foam, the ratio of incyanate groups (NGO) to hydroxyl groups (OH) of the hydride of hydroxyl group-containing liquid polyisoprene (NGOloH
) is 0.5 or more and less than 1.5, the hydride of hydroxyl group-containing liquid polyisoprene or the polyol compound containing it and the blowing agent water or physical blowing agent are heated at 0 to 120°C.
Mix and stir preferably at 15 to 100°C for 1 to 60 minutes, preferably 2 to 45 minutes, and then N G Olo H
A polyisocyanate compound is added so that the amount of
0.5 seconds to 10 minutes at 100°C, preferably 1 second to 7 minutes
Mix and stir for a minute to obtain a foamable composition.

Note that when water is used as a blowing agent, a reaction occurs between the water and the polyisocyanate compound, so it is necessary to take this into account and increase the amount of the polyisocyanate compound added. Specifically, the N COlo H ratio is 3.
It is preferable to increase the amount to less than 0.

This foamable composition is poured into a predetermined mold, and in the case of chemical foaming, the foaming composition is heated to 0 to 120°C, preferably 15 to 100°C.
For 0 seconds to 60 minutes, preferably 1 to 45 minutes, in the case of physical foaming, heating is performed above the boiling point of the physical foaming agent to obtain a polyurethane foam.

Hydroxyl group (O
The ratio of incyanate groups (NGO) to H) (NC
OloH) is 3.0 or more and less than 25, the hydride or polyol compound containing the hydroxyl group-containing liquid polyisoprene and additives such as catalysts are heated to 0 to 120'O, preferably 15 to 100°C. Mix and stir for 1 to 10 minutes, preferably 2 to 80 minutes, and then
A polyisocyanate compound is added so that H is 3.0 or more and less than 25, and the temperature is 0-120°C, preferably 15-120°C.
10-240 minutes at 100°C, preferably 30-18
Mix and stir for 0 minutes to obtain a foamable prepolymer composition.

Water as a blowing agent is added to the foamable prepolymer composition at a temperature of 0 to 120°C, preferably 15 to Zo.

A foamable composition is obtained by mixing and stirring at a temperature of 1 to 60 minutes, preferably 1 second to 7 minutes. Then, pour this foamable composition into a predetermined mold, and in the case of chemical foaming, o-1zo'
c, preferably at 15 to 100°C for 30 seconds to 60 minutes,
Preferably, for 1 to 45 minutes, in the case of physical foaming, heating is performed to a temperature higher than the boiling point of the physical foaming agent to obtain a polyurethane foam.

[Example] The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Reference Example I) Production of liquid polyisoprene having hydroxyl group at the end of the molecular chain.
0g, 16g of 50% by weight hydrogen peroxide solution and 100g of n-butyl alcohol, and heated at a temperature of 120°0.
The polymerization reaction was carried out while stirring for hours.

The reaction pressure rose to a maximum of 8&9/cm''G.

After the reaction was completed, the reaction product was cooled to room temperature and taken out from the reaction vessel. The reaction product was added to and mixed with 600 g of water in a separatory funnel, thoroughly shaken, and then allowed to stand at room temperature for 3 hours. The separated oil layer was heated at a temperature of 100°C under a vacuum of 2 rxrsHg for 2
Volatile components (solvent, isoprene, low-boiling components, etc.) were removed by preevaporation for a period of time, and liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained as a residue at a yield of 68% by weight.

The number average molecular weight of this liquid polyisoprene is 2150, and the hydroxyl group content is 0.96 meq/
g, and the viscosity is 62 po (se/l at 30°C).

The bromine number of this material was 240.

100 g of liquid polyisoprene having a hydroxyl group at the end of the molecular chain produced in i), 100 g of cyclohexane,
Ruthenium catalyst 5 with mass % concentration 109 was placed in an autoclave at a temperature of 140°C and a hydrogen pressure of 50 k.
g/ctx2G and stirred for 4.5 hours.

After the reaction is complete, remove the contents from the autoclave and
．． The catalyst was filtered through a 45 μm membrane filter, and the solvent was distilled off from the solution at 110° C. under a reduced pressure of 2 + Hg to obtain the desired hydride.

The bromine number of this hydride was i or less, the number average molecular weight was 221O, and the hydroxyl group content was 0.94 meq/g.

The components other than the polyisocyanate compound shown in Tables 1.3.5.68 and 1.3.5 of Comparative Example were blended, and so
The mixture was stirred and mixed for 5 minutes at 25° C., and then the polyisocyanate compound was added and mixed for 1 minute at 25° C. to prepare a foamable composition.

Subsequently, this foamable composition was
The polyurethane foam was poured into a mold and subjected to foam curing treatment at 50"0 for 1 minute to produce a polyurethane foam.

The tensile strength of this polyurethane foam was measured in accordance with JISK-6402. As an evaluation of weather resistance, polyurethane foam manufactured under the same conditions was subjected to a black panel temperature of 60°C, humidity of 60%, 18 minutes/120 minutes of rain, 200
A xenon irradiation test was conducted under 0-hour irradiation conditions, and the tensile strength was also measured.

These results are shown in Tables 1 and 2.

Example 2.4 and Comparative Example 2.4 The components shown in the table except for the polyisocyanate compound were blended and stirred and mixed at 80° 0 for 60 minutes, then the polyisocyanate compound was added and the mixture was heated at 25°C for 180 minutes. The mixture was stirred and mixed to prepare a foamable m-acid.

Subsequently, a polyurethane foam was produced from this foamed structure in the same manner as in Example 1, and its tensile strength was measured.

These results are shown in Tables 1 and 2.

(The following is a blank space) [Effects of the Invention] According to the present invention, a polyurethane foam with excellent weather resistance is provided, and a wide range of uses of polyurethane foams having various properties superior to those of the conventional ones are improved. Furthermore, its applications are expected to expand, and its contribution to the polyurethane industry is significant.

Claims (1)

[Scope of Claims] 1. A polyurethane foam made from a polyol compound and a polyisocyanate compound, characterized in that a hydrogenated product of liquid polyisoprene containing hydroxyl groups is used as the polyol compound. 2. In a polyurethane foam made from a polyol compound and a polyisocyanate compound, 80 to 30% by weight of a hydride of a hydroxyl group-containing liquid polyisoprene and a hydroxyl group-containing liquid diene polymer 2 are used as the polyol compound.
A polyurethane foam characterized by using a mixture of 0 to 70% by weight. 3. The polyurethane foam according to claim 2, wherein the hydroxyl group-containing liquid diene polymer is a hydroxyl group-containing liquid polybutadiene.