JPS6181419A - Production of polyurethane - Google Patents

Abstract

PURPOSE:To obtain a polyurethane useful as an elastomer product, coating compound, etc. having improved hydrolyzing properties, mildew resistance, etc., by using a high polymer polyester polyol having a specific diol unit and carboxylic acid unit under a specific condition. CONSTITUTION:The aimed polyurethane is obtaind by a well-known ure thanization method by the use of (A) a high plymer polyester polyol containing (i) a unit based on a diol shown by the formula I, (ii) a carboxylic acid unit shown by the formula II (n is 1-10) and (iii) a carboxylic acid unit shown by the formula III (Ar is 6-10C arylene) in a molar ratio of ii/iii of 2/8-7/3, and (B) a polyisocyanate (e.g., 4,4'-diphenylmethane diisocyanate, etc.) The component A is obtained by subjecting a mixture of a diol (e.g., 3-methyl-1,5- pentanediol, etc.) capable of forming the unit i, an aliphatic carboxylic acid (e.g., adipic acid, etc.) capable of forming the unit ii, and an aromatic dicarboxylic acid (e.g., terephthalic acid, etc.) capable of forming the unit iii to polycondensation.

Description

[Detailed Description of the Invention] Industrial Application Field The present invention relates to polyester polyol and polyisocyanate? It relates to polyurethane (hereinafter sometimes referred to as polyester polyurethane) as a raw material.

BACKGROUND OF THE INVENTION Conventionally, polyurethane has been produced by reacting polyols and polyisocyanates, and, if desired, low-molecular compounds having active hydrogen atoms as raw materials. Recently, as polyols, acid components such as aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid, and relatively small number of carbon atoms such as ethylene glycol, propylene glycol, and 1,4-butanediol have been developed. Diol (hereinafter referred to as C2-4
diol), or diols having 5 to 6 carbon atoms such as polyalkylene glycol, neopentyl glycol, 1.5-bentanediol, and 1.6-hexane glycol (hereinafter referred to as C trodiol Polymer polyols such as polyester polyols obtained by condensation polymerization with diol components such as

However, conventional polyurethanes whose polymer polyols are polyester polyols obtained using C2-4 diols have poor hydrolysis resistance and mold resistance, and as a result, they have a relatively short period of time under high temperature and humidity conditions. In the meantime, the 'A side may become sticky or cracks may occur, resulting in limitations in usage.

On the other hand, as polyester polyols obtained from polycaprolactone polyol or 1,6-hexanediol, neopentyl glycol, and adipic acid, which have good hydrolysis resistance and specific yield, are known. However, although these polyurethanes have satisfactory hydrolysis resistance, they cannot be said to have excellent mold resistance either. Furthermore, the polyurethane has the following problems. That is,
When the polyurethane has a low hardness, there are problems such as high tackiness, hardening of the knot segment crystals over time, and other problems, even though there are many demands for its favorable texture in various fields. There are various problems in its production due to deterioration of physical properties, etc., and the reality is that a product of a satisfactory level has not yet been obtained. Therefore, when producing thermoplastic polyurethane pellets with low hardness, and furthermore when producing molded products such as films, tubes, and belts from the pellets, problems in particular tend to occur in terms of tackiness.

In view of the above facts, the present inventors developed a polyester-based polyurethane that has excellent hydrolysis resistance and mold resistance, is resistant to crystal whitening and hardening even with a flexible polyurethane composition, and is non-adhesive. Manufacturing method? According to the present invention, the above object is to provide a method for producing polyurethane from a high-molecular polyester polyol and a polyisocyanate, in which the polyester polyol is expressed as a diol-based unit by the formula %. Structural unit (I) 't-containing and as a dicarboxylic acid-based unit, the structural unit (II) represented by n (wherein represents an integer from 1 to 10) and the formula ( In the formula, Ar represents an arylene group having 6 to 10 carbon atoms).
The polyester polyol used in the present invention is achieved by a method for producing polyurethane characterized by using a polyester polyol containing the structural unit Cl11) in a molar ratio of 2/8 to 7/3.
i is a polyester diol, polyester triol, or polyester tetraol containing the structural units ([), (It), and (II), which can produce the structural unit (1), and a diol that can produce the structural unit (n). It is produced by condensation polymerization of a mixture of an aliphatic dicarboxylic acid capable of producing a lul, and an aromatic dicarboxylic acid capable of producing a structural unit (lu).

Typical diols that can produce the structural unit CI) are 3-
Methyl-1,5-bentanediol, formula % formula % (
). A part of the diol represented by the above formula (■) may be replaced with another diol within a range that does not impair the intended purpose of the present invention.

Substitutable diols include ethylene glycol, propylene glycol, lI4-butanediol, 1.6-
Diols having 2 to 12 carbon atoms such as hexanediol, diethylene glycol, and neopentyl glycol can be mentioned, but it goes without saying that those with a large number of carbon atoms are preferable when considering the hydrolysis process.

In addition, in addition to the above diol, trimethylolpropane,
There is no problem in using polyhydric alcohols such as glycerin and pentaerythritol in combination, and heat resistance,
Expected to improve oil resistance.

In any case, it is desirable that the structural unit (1) is in the range of 50 molti or more, preferably 70 molti or more of the diol component.

On the other hand, the structural unit based on the dicarboxylic acid component is represented by the following formula. In the formula (It), n represents an integer of 1 to 1o, and examples of the aliphatic dicarboxylic acid that can produce the formula (II) include co-phosphoric acid, glutaric acid, and aliphatic dicarboxylic acid. These dicarboxylic acids may be used not only as 1a, but also in combination of two or more. Further, in the formula (01), Ar is a phenylene group or a naphthylene group having an optional substituent having 6 to 10 carbon atoms, and
Specific examples of aromatic dicarboxylic acids that can produce II+') include terephthalic acid, isophthalic acid, orthophthalic acid,
Examples include 1,5-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2゜6-naphthalene dicarboxylic acid, etc., and mixtures thereof in arbitrary proportions, and alkyl esters thereof can also be used as the aromatic dicarboxylic acids. .

In the polyester polyol, structural unit (1)
/ (structural unit (II') and structural unit (III)
The molar ratio of (total of) is good as long as it is such that the molecular terminal of the produced polyester polyol becomes a hydroxyl group. In addition, the molar ratio of structural unit (■)/structural unit (III) is 2/
It is important that it be within the range of 8 to 7/3.

If the molar ratio is 7/3 or more, the intended purpose of the present invention, which is to provide non-stick properties and improve hydrolysis resistance, will not be achieved, and if it is 2/8 or less, the resulting polyurethane will have a low temperature. This is not preferable because it causes problems such as poor properties and a decrease in elongation.

In the present invention, there is no particular restriction on the method for producing polyester polyol, and any known middle stage of polyester condensation polymerization can be applied. 1. Structural units (1), (■) and (1) i are prepared by preparing the above-mentioned compounds that can be produced in a desired ratio, and then esterifying or It can be produced by carrying out transesterification and further condensation polymerization of the reaction product thus obtained at a high temperature of 200 to 300°C.In addition, as described above, the copolymerized polyester of all three components is simultaneously charged on this platform. Although it is possible to obtain a polyol, the following method may also be adopted.

That is, the polyester polyol contained in the structural units (1) and (n)' and the structural units (1) and (m)'c
Gold-containing polyester polyol sound Structural unit (■) / Structural unit (1) when synthesized separately to produce polyurethane
It is also possible to use a mixture of the two so that the molar ratio of the two satisfies 2/8 to 7/3.

The polyester polyol used in the present invention is typically 5
Molecular weights of 00 to 5000, preferably 800 to 3000 may be used. It goes without saying that it is preferable that the acid value and water content are as low as possible.

The polyinocyanate used in the present invention includes known aliphatic, alicyclic, and aromatic organic polyinocyanates containing two or more incyanate groups in the molecule, but especially 4.4 '-Diphenylmethane diisocyanate, p-phinyl diisocyanate, toluylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate-1-,4,4
In addition to diisonoanates such as '-dicyclohex/rumethane diiso/i, -t, there are triino/anates in which 3 cells of tridi/cyinone anate are added to 1 mole of trimethylolpropane or glycerin.

In addition, in the present invention, if desired, F) an excessive chain extender may be used. For example, ethylene glycol, 1.4
-) Ethane diol, xylene glycol, bishydroki/ethquin benzeno, neobennal glycol,
Contains 3.3'-cyclo4,4'-diaminodiphenylmethane, inphorondiami;/14.4'-diaminodiphenylmethane, hydrazine, dihydrazide, trimethylolpropane, glycerin, and the like.

Regarding the operating method to obtain polyurethane.

A known urethanization reaction technique is used. for example,
A high-molecular polyester polyol and a low-molecular compound having active hydrogen are mixed and preheated to about 40 to 100'C, and then an opening is made in which the ratio of the number of active hydrogen atoms of these compounds to the No. It is obtained by adding a polyisocyanate adduct manufactured by Co., Ltd., stirring vigorously for a short period of time, and then standing at about 50 to 150°C.

It can also be carried out via a urethane prepolymer. Polyisocyanate compounds are usually used in very small excess in these reactions because they are usually affected by moisture, etc. 1 Dimethylformamide.

Diethylformamide, dimethyl sulfoxide.

Dimethylacetamide, tetrahydro7rane, isophylbanol, benzene, toluene, ethyl cellosolve,
It can also be carried out in one or more solvents such as trichlene. in this case.

It is convenient to use the nut in a range of 10 to 40 molecular weight in order to obtain a high molecular weight product.

The degree of polymerization of the obtained polyurethane is 10 in terms of number average molecular weight.
,000-1.50.000.

Next, some examples of uses of the polyurethane obtained by the present invention will be described.

(υ Substantially U-shaped 2J flood injection horiurethane beresoto 1', add CfL, I2 collapse and 44 out IJ and 21, extrusion molding, Kale/Dagger 0 work J lm (more elastomer accessories are left behind).

(2+ High-molecular polyester polyol, base polyester polyester, and extender are mixed together.

Alternatively, a high molecular weight polyester polyol and an organic polyino/anate are reacted in advance to prepare a prepolymer having a terminal incyate group or a terminal water group, and then a chain 1A is added to this prepolymer. Polyiso7anate is mixed and used to make cast elastomer products or for use in paints, adhesives, etc.

(8) In the methods (1) and (2) above, the polyurethane solution obtained by synthesizing polyurethane with Fi + M L from the polyurethane raw material, 4) The resulting polyurethane is used as a coating agent and impregnating agent for synthetic leather, artificial leather, textiles, etc., and as a texture control agent.

(The terminal isonoa non-togre polymer is dissolved in a solvent and a chain extender is added thereto to prepare a stable spinning dispersion. Elastic fibers are produced from this N solution by a wet or dry method.

(5) Various additives such as a foaming agent are blended into a high-molecular polyester polyol, an organic polyintho-inthoate or a prepolymer having a terminal incyanate group is added thereto, and the mixture is stirred at high speed and foamed to produce a foam product.

More specifically, the present invention's polyurethane sheets, sorts, films, rolls, Kia and Norirad tires, belts, hoses, and tubes.

Anti-vibration material, backing material 1 shoe sole (microcellular etc.),
It is useful for artificial leather, tJt fiber treatment agents, cushion materials, paints, adhesives, tooling agents, waterproofing agents, elastic fibers for flooring materials, etc.

Function: In the present invention, a polyurethane having excellent properties of each fl can be obtained as described below, but the reason for this cannot be explained by a single reason and is not necessarily clear.

However, if we organize and simplify the explanation, it can be estimated as follows.

In other words, since the polyurethane produced by the production method of the present invention contains a relatively long-chain diol-based structural unit ([) and an aromatic dicarboxylic acid-based structural unit (1) as structural units, it has good hydrolysis resistance. Excellent in sex. In addition, since it contains <D'tm unit CI) shown in the diol that has a side chain, it is possible to suppress the crystallinity in the structural unit (lit) K based on terephthalic acid, etc. The soft segment does not crystallize even during the synthesis of hardened polyurethane. In addition, it is non-adhesive because it contains an aromatic ring. Although the reason for the improvement in mold resistance is completely unknown, structural units (I), (II) and (I
ll) is thought to be deeply involved.

Testimonials j Next, the present invention will be explained in more detail using reference examples, examples, and comparisons tηj.

In Naomi@Examples and Comparative Examples, the hydrolysis resistance of polyurethane Note: A polyurethane film with a thickness of 60 μm was
An accelerated hydrolysis test was carried out in hot water at a temperature of 0.degree. C. for 2 weeks, and the retention rate of the logarithmic viscosity measured by re-bathing the film of No. 7 in DMF (dimethylformamide) was evaluated.

Regarding the evaluation of mold resistance, a molded polyurethane film with a thickness of 200 μm was attached to a glucose peptone agar culture medium, and a mixed spore suspension of five types of molds was inoculated at 30°C. Cultured at 90-95% humidity and observed the deterioration state of the surface ○Nao, Ko (7) K experiment ICuJ
IS Z 2911-1960 Mold resistance ig test description Aspergillus nickel ATCC9642, Penicillium luteum ATCC9644゜Rhizopus nigricans S, N, 32. to! J Coderma'r-I ATC
:C9645, Chaetomium globosum ATCC620
Five types of molds were used.

The tackiness was evaluated by extruding polyurethane into water at 200° C. using an extruder, pelletizing it, and evaluating the tackiness of the pellets at that time. In the case of stickiness, the pellets stuck in a block shape and the pellets stuck to a large extent were evaluated as X, those that stuck a little were Δ, and those that had no stickiness and the pellets did not stick were evaluated as ○. The thermoplastic polyurethane pellets marked with ○ do not have tackiness even when extruded into a film using a T-die, but those marked with × or Δ are difficult to form into films.

Regarding crystal whitening, a polyurethane film with a thickness of 60 μm was exposed to IA during ffff1ffl, and the whitening state of the film was observed, and those that whitened were marked with an X, and those that remained transparent were marked with an ○.

Low-temperature flexibility was evaluated by coating and drying polyurethane melting on the artificial leather substrate and measuring the bending resistance at -20"C (the thickness of the polyurethane film on the substrate was 20μ). The bending resistance was measured using a bending tester with a stroke width (3 cm at the longest, L cm at the shortest) and a bending frequency of 8,600 times/hour.10
If there is no change after more than the force, use Q, and if there is some damage, use Δ.
, If the substrate is damaged enough to be visible, it is marked with an X.

The hardness is determined according to the method of JLS-Kei301.

The raw materials used in the Silkworm Examples, Examples, and Comparative Examples are indicated by abbreviations, and the relationship between the No. 1 number and the compound is as follows (Table 1).

Table 1 Reference Example 1 (Manufacture of polyester polyol) 3-methyl-1,5-bentanediol 317.27,
Terephthalic acid 174? and adipine [146P (3MP
D/TA/AD molar ratio: 2.6/1/1'') was esterified under normal pressure while nitrogen gas was passed through and condensed water was distilled off at a temperature of about 195°C. When the value was below about 1, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction.

In this way, a polyester polyol (hereinafter referred to as polyester A)'ft having a hydrochloric value of 56 and an acid value of 0.2 was obtained.

This polyester AH1 is liquid at room temperature and has a molecular weight of approximately 20.
It was 00.

Reference Examples 2 to 11 Polyester B-K was obtained in the same manner as in Glue Example 1 using the diol component and dicarboxylic acid component shown in Table 2 in the molar ratio of the diol component and dicarboxylic acid component in Reference Example 1. Table 2 shows the molecular weight and acid value of the obtained polyester.

Margin table below 2 Example 1 Polyester A produced in Reference Example 1 was heated at 110°C in vacuum.
The molar ratio of polyester A/4,4'-diphenylmethane diisocyanate/1,4-butanediol ( After mixing in the ratio of 1/2/1 (X/Y/Z in Table 3), the mixture was fed into a two-wheel screw extruder and
Melt polymerize at 220°C, then cut this melt polymerized polyurethane in water to form a polyurethane/vellet wog.
I built A.

Regarding the obtained polyurethane, the performance of each strain was measured. The results are shown in Table 4.

Examples 2 to 9 and Comparative Examples 1 to 6 Polyester polyol, polyisocyanate, and chain extender shown in Table 3 Molar ratio (X/Y/Z) shown in Table 3 above
Polyurethane was used in the same manner as in Example 1. Obtained. 2. When bishydroethoxype/zene was used as a chain extender, it was melted by heating.

Table 4 shows one notable batch of the obtained polyurethane.

J", -1"I' White table 3 Clothes 4 Effects of the invention The present invention! ! ! Boliureta/ obtained by the manufacturing method is
It has excellent hydrolysis resistance and mold resistance, and exhibits flexibility even at low temperatures, yet does not cause crystal whitening or hardening, and is non-adhesive. In terms of mechanical properties, it is comparable to conventional polyurethane.

Claims (1)

[Claims] (1) In a method for producing polyurethane from a high-molecular polyester polyol and a polyisocyanate, the polyester polyol contains a structural unit (I) represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ as a diol-based unit, Units based on dicarboxylic acids include the structural unit (II) represented by the formula ▲ mathematical formulas, chemical formulas, tables, etc. (in the formula, n represents an integer from 1 to 10) and the formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Ar represents an arylene group having 6 to 10 carbon atoms)
A method for producing polyurethane, comprising using a polyester polyol containing the structural unit (III) represented by the formula in a molar ratio of structural unit (II)/structural unit (III) of 2/8 to 7/3. .