JPH0532753A - Novel polyester polyol and polyurethane resin composition using the same - Google Patents

Abstract

PURPOSE:To provide the title compound containing, as an acid component, 4-carboxy-1,8-octanedicarboxylic acid, not deteriorating workability with the viscosity rising, capable of giving polyurethane resins good in flexibility, mechanical strength and moist heat resistance. CONSTITUTION:Condensation reaction is made at 200 deg.C between (A) acid components made up of 4-carboxy-1,8-octanedicarboxylic acid and at least one kind of dibasic acid (e.g. adipic acid) and (B) a polyol component such as 1,6- hexanediol into a polyester polyol 2000 in molecular weight. This polyester polyol and 1,4-butanediol, etc., are then dissolved in a mixed solvent of cyclohexanone and toluene at the weight ratio 1:1, and, in the presence of a catalyst such as dibutyltin dilaurate, a polyisocyanate such as diphenylmethane diisocyanate is added to the resulting solution followed by reaction at 100 deg.C, thus giving the objective polyurethane resin excellent in mechanical strength and moist heat resistance with flexibility retained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyester polyol obtained by using a novel 4-carboxy-1,8-octanedicarboxylic acid suitable for producing a polyurethane resin having excellent durability and a polyurethane resin using the same. It relates to a composition.

[0002]

2. Description of the Related Art It is well known that a polyurethane which is useful for various purposes and uses has been produced and used by reacting a polyester polyol having a terminal hydroxyl group with a polyisocyanate and optionally a chain extender. There is.

Taking polyurethane elastomers as an example, thermoplastic polyurethanes can be used for injection molding, extrusion molding, calendering and the like by utilizing properties such as high elasticity, flexibility, abrasion resistance, cold resistance and strength. Examples thereof include molding, synthetic leather, elastic fibers, paints, adhesives, magnetic tape binders, and modification of polymers such as ABS resin, AS resin, polyvinyl chloride and its derivatives, and acetic acid fiber.

The prepolymer of the terminal isocyanate may be used for casting, for civil engineering and construction, or for foaming shoe soles and elastic foams. Examples of the polyester polyol having a terminal hydroxyl group include polycaprolactone diols represented by ε-caprolactone, polyester diols obtained from a low molecular weight diol and a dibasic acid such as adipate and ethylene obtained from 1,4-butanediol and adipic acid. Phthalates obtained from glycol and phthalic acid, polycarbonate diols, and copolyesters obtained by cocondensation, usually 500 to 6000 polyester diols are used.

However, all of the above polyester diols are substantially linear, and the resulting polyurethane resin has the drawbacks of poor heat resistance, hydrolysis resistance, and wet heat resistance.

As a method for improving the above-mentioned drawbacks, a method in which a triol such as glycerin or trimethylolpropane or a tricarboxylic acid such as trimellitic acid is used in combination and a partial cross-linking bond is introduced into the polyester molecule has been already used. There is. However, these polyesters have poor workability due to a large increase in viscosity, poor flexibility of the resulting polyurethane elastomer, poor compatibility of polyurethane with other polymers, and markedly reduced suitability for coating as magnetic tape binders. The current situation is that many restrictions are imposed on its use.

[0007]

In recent years, under increasingly demanding working and usage conditions, the object of the present invention is to maintain the elasticity, flexibility and cold resistance of the polyurethane resin. The object is to obtain a polyester polyol suitable for a polyurethane resin having greatly improved heat resistance and wet heat resistance.

[0008]

The inventors of the present invention have completed the present invention as a result of intensive studies to solve the above problems.

That is, the present invention relates to 4-carboxy-
The present invention provides a polyester polyol obtained by using 1,8-octanedicarboxylic acid and a polyurethane resin using the same.

(Structure) The polyester polyol used in the present invention is obtained by a reaction with a polyhydric alcohol using a mixture of 4-carboxy-1,8-octanedicarboxylic acid and preferably a dibasic acid as an acid component. Is.

The acid component of the present invention, 4-carboxy-
Examples of the dibasic acid mixed with 1,8-octanedicarboxylic acid include oxalic acid, malonic acid, dimethylmalonic acid,
Succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, 1,12 dodecanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 3-Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, o-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalic acid, 4,4′-
Examples thereof include sulfonyldibenzoic acid, 2,5-naphthalenedicarboxylic acid and the like, or lower alkyl esters thereof.

The mixing ratio of 4-carboxy-1,8-octanedicarboxylic acid and dibasic acid is preferably 0.
It is used in the range of 5 / 0.5 to 0.02 / 0.98.
4-carboxy-1,8 octane dicarboxylic acid is 0.0
When the molar ratio is 2 or less, the heat resistance and wet heat resistance of the resulting polyurethane resin are not improved, which is not preferable.
Further, if the molar ratio is 0.5 or more, the viscosity of the polyester polyol increases significantly, which is not preferable.

Examples of the polyhydric alcohol of the present invention include ethylene glycol, diethylene glycol, 1,
2-propanediol, 1,3-propanediol,
1,4-butanediol, 1,6-hexanediol,
1,8-octanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol,
2,2,4-trimethyl-1,6-hexanediol,
3-methyl 1,5-pentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol,
Examples include pentaerythritol, trimethylolpropane, glycerin, and 3-methyl-1,3,5-hydroxypentane, with diols being preferred.

The dibasic acid or polyhydric alcohol used in the polyester polyol of the present invention may be used alone or as a mixture of two or more kinds. The polyester polyol of the present invention can also be used as a copolyester with a caprolactone monomer such as ε-caprolactone and 1,6-hexane polycarbonate.

The hydroxyl value of the polyester polyol of the present invention is preferably 20 to 300. A range deviating from these ranges is not preferable because excellent performances required for the present invention, especially for elastomers, cannot be obtained.

At least two of the carboxyl groups of 4-carboxy-1,8-octanedicarboxylic acid are preferably esterified, but the remaining one carboxyl group is esterified as an ester group or as a carboxyl group depending on the purpose. It can be used as a base.

The polyester polyol using the above-mentioned various raw materials can be obtained by a usual dehydration condensation reaction in an alcohol component excess system. For example, in the presence of an esterification catalyst such as dibutyltin oxide, tetraisopropyl titanate, antimony trioxide, zinc acetate, etc., the above raw materials are heated at 130 to 280 ° C., preferably 150 to 220 ° C.
It can be obtained by esterification reaction at ° C. If necessary, in the presence of the above catalyst, under a vacuum of 0.5 to 1.0 mmHg.
The condensation reaction may be carried out at 0 to 250 ° C.

The polyester polyol thus obtained is used in various applications as a polyurethane resin obtained by reaction with an organic diisocyanate. The polyurethane resin in the present invention is composed of the above-mentioned polyester polyol, organic diisocyanate and optionally a chain extender, and a conventionally known polyester polyol and / or polyether polyol.

The organic diisocyanates used in the present invention include aliphatic, alicyclic and aromatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate,
1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylenediene Isocyanate,
2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
Examples thereof include 1,5-naphthylene diisocyanate and the like, or a mixture of two or more kinds.

Examples of the chain extender used in the present invention as required include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6. -Hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,6 hexanediol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane , 1,4-dihydroxyethylcyclohexane,
3-methyl-1,5-pentanediol or the like alone or 2
Mixtures of more than one species are mentioned.

Examples of conventionally known polyester polyols and / or polyether polyols used in the present invention include ethylene glycol, diethylene glycol, 1,3-propylene glycol, and the like.
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 2,2-dimethyl-1,3
-Propanediol, 2,2,4-trimethyl-1,6
Hexanediol, bishydroxyethoxybenzene,
1,4-Cyclohexanediol, 1,4-dimethylolcyclohexane, 1,4-dihydroxyethylcyclohexane, 3-methyl-1,5-pentanediol, etc., or a mixture of two or more thereof, and oxalic acid, malonic acid, Dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid,
1,12 dodecanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, o-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalic acid Polyester polyols obtained from dibasic acids such as 4,4′-sulfonyldibenzoic acid and 2,5-naphthalenedicarboxylic acid, polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, ε- Examples thereof include polycaprolactone polyols obtained by ring-opening addition polymerization of a lactone such as caprolactone in the presence of glycol, polycarbonate polyols, and copolyesters obtained by cocondensation.

The conventionally known polyester polyol and / or polyether polyol used as required in the present invention preferably have a hydroxyl value of 20 to 300. The equivalent ratio of polyol to polyisocyanate used in the polyurethane resin of the present invention is preferably 2/1 to 1/2
However, if it is out of these ranges, various performances required in the present invention cannot be obtained, which is not preferable.

The polyurethane resin of the present invention is produced by a usual method. That is, in the presence of a solvent-free system or an organic solvent, a polyol and optionally a chain extender and an organic diisocyanate are reacted, or a polyol is previously reacted with an organic diisocyanate to form a prepolymer having a terminal isocyanate group, and chain extension is performed on the prepolymer. The agent may be reacted. During the urethanization reaction, a catalyst that accelerates the urethanization reaction may be used.

The polyurethane resin of the present invention can be used in a form depending on the purpose of use. For example, a liquid, a block, a powder, an organic solvent solution, an aqueous solution and the like can be mentioned. The polyurethane resin using the polyester polyol obtained in the present invention can be applied to various uses due to its excellent performance.

For example, as a polyurethane resin having a partial network structure, various properties such as fluidity, tackiness, resistance to moist heat, compression set, and permanent elongation are improved.
A thermoplastic polyurethane suitable for extrusion molding and injection molding can be obtained and can be used, for example, for shoe soles, belts, film materials, sheet materials, automobile parts and the like.

Further, by leaving a part of the carboxyl group of 4-carboxy-1,8-octanedicarboxylic acid in the polyurethane chain, the pigment dispersibility is remarkably improved, so that various printing inks, magnetic rubbers, and bindings for magnetic recording media can be obtained. It can be used for applications such as agents and conductive resins. A carboxyl group-containing resin obtained by ionizing a carboxyl group-containing urethane with an amine is useful as a water-soluble resin.

[0027]

EXAMPLES The present invention will be described below with reference to examples.
These do not limit the invention in any way. All "parts" in the text mean "parts by weight".

[Example 1] 1,129 parts of 1,6-hexanediol were added to a 5 liter stainless steel reaction vessel equipped with a condenser, a thermometer and a stirrer.
-152 parts of carboxy-1,8 octane dicarboxylic acid,
1066 parts of adipic acid was subjected to a condensation reaction at 200 ° C. to obtain a polyester polyol (P-1) having a molecular weight of 2000.

334 parts of P-1 and 6 parts of 1,4-butanediol are dissolved in 400 parts of a mixed solvent having a weight ratio of cyclohexanone and toluene of 1: 1 and heated to 50 ° C. to be mixed uniformly. It was stirred. Further, 0.1 part of dibutyltin dilaurate was added to homogenize it, and then 60 parts of diphenylmethane diisocyanate was added and reacted at 100 ° C. When the weight average molecular weight of the polyurethane reached 100,000, an equimolar amount to the unreacted isocyanate group was obtained. A mixed solvent of methanol and cyclohexanone to toluene in a weight ratio of 1: 1 120
0 parts was added to obtain a polyurethane resin solution having a polyurethane resin concentration of 20%.

Example 2 In place of the polyester polyol of Example 1, 1,111 parts of 1,6-hexanediol,
4-Carboxy-1,8-octanedicarboxylic acid 298
Parts and 931 parts of adipic acid were subjected to a condensation reaction to obtain a polyurethane resin solution in the same manner as in Example 1 except that a polyester polyol (P-2) having a molecular weight of 2000 was used.

Comparative Example 1 1,146 parts of 1,6-hexanediol instead of the polyester polyol of Example 1,
A polyurethane resin solution was obtained in the same manner as in Example 1 except that the polyester polyol (P-3) having a molecular weight of 2000 obtained by subjecting 1205 parts of adipic acid to a condensation reaction was used.

Comparative Example 2 1119 parts of 1,6-hexanediol instead of the polyester polyol of Example 1,
Polyester polyol (P-4) obtained by condensation reaction of 168 parts of trimellitic acid and 1055 parts of adipic acid
A polyurethane resin solution was obtained in the same manner as in Example 1 except that was used.

The melt viscosity of the obtained polyester polyol and the viscosity of the polyurethane resin solution are shown in Table 1.

[0034]

[Table 1]

A cured resin solution was prepared as follows in order to evaluate the mechanical strength and resistance to moist heat of the obtained polyurethane resin. <Compounding> Polyurethane resin solution 40 parts Burnock D-750 0.8 part

A film was formed so that the thickness of the obtained cured resin solution after drying was 100 μm. The tensile strength test of the prepared film is carried out to measure the tensile strength and the elongation at break, and the prepared film is subjected to 70 ° C. and 95%.
After being left in the RH atmosphere for 2 weeks, a tensile strength test was performed to determine the retention rate with respect to the tensile strength before being left. The results are
Shown in 2.

[0037]

[Table 2]

The tensile test methods for the films in Table 2 are described below. Note 1) Tensile test A tensile strength and a breaking elongation were measured when a strip-shaped film having a width of 5 mm was pulled by a tensilon at a pulling speed of 300 mm / min.

[0039]

As is apparent from the above description, the polyester polyol containing 4-carboxy-1,8-octanedicarboxylic acid of the present invention does not deteriorate workability due to increase in viscosity and does not impair flexibility. It is possible to provide a polyurethane resin having excellent mechanical strength and excellent resistance to moist heat.

Claims (4)

[Claims] 1. A polyester polyol containing 4-carboxy-1,8-octanedicarboxylic acid as an acid component. 2. The polyester polyol according to claim 1, wherein the polyester polyol contains 4-carboxy-1,8-octanedicarboxylic acid and one or more kinds of dibasic acids. 3. A polyester polyol containing 4-carboxy-1,8-octanedicarboxylic acid and one or more dibasic acids, wherein the molar ratio of 4-carboxy-1,8-octanedicarboxylic acid to the dibasic acid is 0. 5 / 0.5 to 0.02 / 0.
The polyester polyol according to claim 1, which is 98. 4. A polyurethane resin composition comprising the polyester polyol of claim 1.