JPS6259665A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To improve strength and water resistance, by blending a cyclopentadiene monomer/vinyl-substd. arom. hydrocarbon copolymer or a cyclopentadiene monomer/unsaturated carboxylic acid copolymer with a polyurethane. CONSTITUTION:A compd. selected from among a cyclopentadiene monomer/ vinyl-substd. arom. hydrocarbon copolymer (A) (e.g., cyclopentadiene/styrene copolymer), a hydrogenated product (B) of component A, a cyclopentadiene monomer/ unsaturated carboxylic acid (anhydride) copolymer (C), and a hydrogenated product (D) of component C is prepd. 20-200pts.wt. said compd. is mixed with a mixture of 100pts.wt. polyol compd. (e.g., liquid hydroxyl group- terminated polybutadiene) and a polyisocyanate (e.g., diphenylmethane diisocyanate) for polyurethane to obtain the desired polyurethane compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyurethane composition, and more particularly to a polyurethane composition with improved mechanical properties and good water resistance.

[Prior art and problems to be solved by the invention] Polyurethane obtained by reacting a polyol compound and a polyisocyanate compound is widely used as a material for building materials, furniture, office equipment, electronic equipment, automobile parts, etc. . However, this polyurethane has low tensile strength, elongation,
It has poor mechanical properties such as tear strength. Therefore, various compounds have been blended in order to improve the physical properties of this polyurethane. One such compound is indene and vinyltoluene.

Petroleum resins containing C6 aromatic hydrocarbons such as methylstyrene as polymerization components are known. The polyurethane composition obtained by blending and curing this material has some mechanical properties that are superior to conventional polyurethane, but it is inferior in water resistance, especially hot water resistance, and can be used as a building material in hot and humid environments. This was inconvenient for use in automobile parts, etc.

[Means for solving problems]

The inventors of the present invention have conducted extensive research in order to resolve the above-mentioned problems and to develop a polyurethane composition that has sufficient mechanical properties of 17% and has good water resistance. As a result, it was discovered that a polyurethane composition obtained by blending a specific petroleum resin into a polyurethane mixture consisting of a polyol compound and a polyisocyanate compound and curing the mixture satisfies the above object, and based on this knowledge, the present invention was completed. Ta.

That is, the present invention is made by blending at least one compound selected from a cyclopentadiene monomer and a vinyl hydrogenate (D) into a polyurethane mixture consisting of a polyol compound and a polyisocyanate compound, and then curing the mixture. A polyurethane composition is provided.

Here, the polyol compound is not particularly limited, and the following hydroxyl group-containing liquid diene polymers and other types can be used.

The hydroxyl group-containing liquid diene polymer has a hydroxyl group within the molecule or at the end of the molecule and has a number average molecular weight of 300 to 25.
A liquid diene polymer having a Q 00, preferably 500 to 10,000 is used. Here, the content of hydroxyl groups is usually 0
．． 1-10 meq/g, preferably 0.3-7 me
q/g.

Examples of these liquid diene polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. There is. Specifically, butadiene homopolymer.

Inzolene homopolymer, butadiene-styrene copolymer, butadiene-isozolene copolymer.

Examples include butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, and the like. Among these, butadiene homopolymer is particularly preferred. These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in a liquid reaction medium in the presence of perlaxed hydrogen.

Other polyol compounds include primary polyols, secondary polyols,
Either a class polyol or a tertiary polyol may be used. Specifically, for example, 1,2-zolopylene glycol, dipropylene glycol, 1°2-butanediol, 1,
3-Butanediol.

2.3-butanediol, 1,2-bentanediol,
2,3-bentanediol, 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N,N-bis-2-hydroxyzolopylaniline,
Low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon, such as N,N'-bishydroxyisozolopyl-2-methylpiperazine, propylene oxide adduct of bisphenol A, and the like.

Further, as polyols, ethylene glycol, 1,3-zoropylene glycol, and 1,4-butanediol do not contain a hydroxyl group bonded to a secondary carbon.

1,5-bentanediol, 1,6-hexanediol, etc. can also be used. Diols are usually used as polyols, but triols.

Tetraol may be used, and its molecular weight is 50 to 50
Specific examples of p1 include polyoxypropylene triol and polyoxyethylene triol.

Moreover, a polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and has an incyanate group reactive with the hydroxyl group of the polyol compound. Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate.

Diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate.

Addition products of polyzolopylene glycol and tolylene diisocyanate are preferred, particularly MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, and the like.

There is no particular restriction on the blending ratio of the polyol compound and polyisocyanate compound. Usually, the molar ratio of the isocyanate group (NCO) of the polyisocyanate compound to the hydroxyl group (OH) of the polyol compound is NCO10H-0,
It is blended so that it becomes 25-25, preferably 0.5-15. If the solenoid ratio is outside the above range, it will be difficult to cure, which is not preferable.

Next, in the copolymerization reaction product of component (A), a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon, examples of the cyclopentadiene monomer include cyclopentadiene, methylcyclopentadiene, and ethylcyclopentadiene. and dimers, trimers, and codimers thereof.

Further, examples of vinyl-substituted aromatic hydrocarbons include styrene, α-methylstyrene, vinyltoluene, isozolobenylbenzene, and the like.

A copolymerization reaction product of a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon can be obtained by a copolymerization reaction of the cyclopentadiene monomer and the vinyl-substituted aromatic hydrocarbon.

An example of a preferred method for producing component (A) will be described below.

The cyclopentadiene monomer and the vinyl-substituted aromatic hydrocarbon are mixed in an aromatic hydrocarbon solvent such as xylene, and heated at a temperature of 220 to 320°C, preferably 250 to 30°C.
Heat to 0°C for 1-8 hours, preferably 1.5-5 hours. When the solvent is removed after the reaction is completed, the component (A) can be obtained.

In addition, this N component is not limited to the above-mentioned method, and those obtained by other methods can also be used. The structure of component (A) obtained by such a production method is not yet established, and although it is presumed to be a copolymer of a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon, it is It may also contain homopolymers of gene monomers.

Component (A) preferable in this invention has a content of 80 to 3 monomer units derived from a cyclopentadiene monomer.
0% by weight, preferably 60 to 40% by weight, a softening point of 40 to 160°C, preferably 70 to 140°C,
The bromine number is 30 to 110 g/iog, preferably 40 to 70 g/100 g.

Further, from the viewpoint of raw material components, a preferred (/k) component is a copolymerization reaction product obtained by copolymerizing cyclopentadiene and styrene.

Next, the hydrogenated product of the copolymerization reaction product of the cyclopentadiene monomer and the vinyl-substituted aromatic hydrocarbon, which is the component (B), can be produced by hydrogenating the component (N).

A preferred method for producing component (B) is shown below.

Ni, Pd, Co, Pt, Rht in a solvent such as a hydrocarbon such as cyclohexane or without using a solvent.
The component (A) is brought into contact with hydrogen in the presence of a system catalyst while heating at a temperature of 130 to 300°C, preferably 150 to 260°C, for 1 to 7 hours, preferably 2 to 5 hours.

Since the structure of the component (A) is not established, the obtained component (B) contains cyclopentadiene in addition to the hydrogenated product of the copolymerization reaction of a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon. It may contain hydrogenated homopolymers of gene monomers.

In the present invention, preferred component (B) has a monomer unit content derived from cyclopendadiene of 80 to 30% by weight, preferably 60 to 40% by weight, and a softening point of 5.
The temperature is 0 to 165°C, preferably 75 to 150°C, the bromine number is more than 3 and less than 7, and the degree of hydrogenation of the aromatic ring is 0 to 60.

Further, from the viewpoint of raw material components, the preferred component (B) is a hydrogenated product of a copolymerization reaction product obtained by copolymerizing cyclopentadiene and styrene.

Next, the copolymerization reaction product of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride, which is component (C), is prepared by combining the cyclopentadiene monomer and the following unsaturated dicarboxylic acid or its anhydride. It can be produced by copolymerization.

Here, examples of the unsaturated dicarboxylic acid include maleic acid, citraconic acid, itaconic acid, etc., and examples of the unsaturated dicarboxylic acid anhydride include anhydrides of the various unsaturated dicarboxylic acids mentioned above.

The preferred method for producing component (C) is the same as the method for producing component (A) above, except that the unsaturated dicarboxylic acid or its anhydride is used in place of the vinyl-substituted aromatic hydrocarbon, so its details are the same. Omit detailed explanation.

Although this component (C) is presumed to be a copolymer of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride, similar to component cA), it is a homopolymer of the cyclopentadiene monomer. It may contain.

Component (C) preferred in this invention has a monomer unit content derived from a cyclopentadiene monomer of 90 to 3.
0% by weight, preferably 80-40% by weight, the content of one unit of monomer derived from unsaturated dicarboxylic acid or its anhydride is 10-7.0% by weight, preferably 20-60% by weight.
p1 softening point in weight% is 60-200°C, preferably 9
0~180℃, bromine value f10~200g/10
0[, preferably 50 to 130 g/100 g, and an acid value of 100 to 500 mg KO)i/g, preferably 200 to 450 mg KOH/g.

Further, from the viewpoint of raw material components, the preferred component (C) is a copolymerization reaction product obtained by copolymerizing cyclopentadiene and maleic anhydride.

Next, the hydrogenated product of the copolymerization reaction product of the cyclopentadiene monomer and the unsaturated dicarboxylic acid or its anhydride, which is the component (D), can be produced by hydrogenating the component (C). can.

A preferred method for producing component CD) is substantially the same as the method for producing component (B), except that component (C) is used instead of component (A), so detailed explanation thereof will be omitted.

The obtained component (D), like the above-mentioned component (A), contains a hydrogenated copolymer of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride, as well as a homolog of the cyclopentadiene monomer. May contain hydrogenated products of polymers.

Component (D) preferred in this invention has a content of 90 to 3 monomer units derived from a cyclopentadiene monomer.
0% by weight, preferably 80 to 40% by weight, and the content of one monomer unit derived from an unsaturated dicarboxylic acid or its anhydride is 10 to 70% by weight, preferably 20 to 60% by weight, softening. point is 60-200℃, preferably 10
0-190℃, bromine number 10-100g/100
g1 is preferably 15 to 50 g/100 g, and the acid value is 100 to 500 mgKOH/g, preferably 150
~400mgKOH/g.

In addition, from the viewpoint of raw material components, <D) component which is preferable is a hydrogenated product of a copolymerization reaction product obtained by copolymerizing cyclopentadiene and maleic anhydride.

The polyurethane composition of the present invention is obtained by blending at least one compound selected from the components (A) to (D) above into the polyurethane mixture consisting of the above-mentioned polyol compound and polyisocyanate compound, and then curing the mixture. However, the blending ratio of components (A) to (DJ) is such that the total amount of components (A) to (D) is 20 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the polyol compound. .

In addition to the above-mentioned components, other additives may be added to the polyurethane composition of the present invention, if necessary.

In particular, it is preferable to add a curing accelerator such as dibutyltin dilaurate or stannous octoate. The blending ratio of the curing accelerator is usually 0.01 to 1.00 parts by weight, preferably 0.0 parts by weight, per 100 parts by weight of the polyol compound.
It is 3 to 0.30 parts by weight.

The composition of the present invention is produced by blending, kneading, and curing the above-mentioned raw materials. Normally, each raw material except the polyincyanate compound and curing accelerator is first blended,
After kneading with a commonly used kneading machine such as a three-roll paint mill roll or a Dalton mixer, a polyisocyanate compound is added and mixed, and a curing accelerator is further added and mixed. Mixed lines.

The temperature during mixing is 10-150'C1, preferably 15-150'C1
The temperature is 100° C., and the mixing time can be set until sufficient mixing is achieved. The liquid composition thus obtained was
℃, preferably 80-1300C for 10-180 minutes, preferably 20-1o.

The polyurethane composition of the present invention is produced by curing for a few minutes.

〔Effect of the invention〕

The polyurethane composition of the present invention thus obtained has sufficient mechanical properties, and these properties are based on C'9 aromatic hydrocarbons such as indene, vinyltoluene, and methylstyrene as the main polymerization components. It is also improved compared to polyurethane compositions obtained by blending and curing petroleum resins.

Furthermore, the polyurethane composition of the present invention has excellent water resistance compared to the above-mentioned polyurethane compositions.

Therefore, the polyurethane composition of the present invention can be effectively used as a material for building materials, furniture, office equipment, electronic equipment, automobile parts, medical equipment parts, etc., and is particularly useful as a material for parts where water resistance is desired.

〔Example〕

Next, the present invention will be explained in detail using examples.

Production Example 1 Cyclopentadiene-styrene copolymerization reaction product ((A
) Preparation of component) In a polymerization reaction vessel equipped with a stirrer and purged with nitrogen, 100 g of xylene (solvent) and 100 g of cyclopentadiene, ! : Charge 100g of styrene and heat at 260°.
The copolymerization reaction was carried out for 2 hours while heating the mixture to C and stirring.

After the reaction was completed, xylene was removed to obtain 180 g of a cyclopentadiene-styrene copolymerization reaction product. The softening point of this cyclopentadiene-styrene copolymerization reaction product is 91°C, the content of styrene as a monomer unit is 50% by weight, the bromine number is 56g/100g, and the acid value is It was 1 mgKOH/g or less, and the Gardner hue was 8.

Production Example 2 Preparation of hydrogenated product of cyclopentadiene-styrene copolymerization reaction product (component (B)) In a reaction vessel equipped with a stirrer and purged with nitrogen, add the cyclopentadiene-styrene copolymerization product obtained in the production of component (A) above. 100 g of the reaction product, 1'00 g of cyclohexane (solvent), and 5 g of Pd catalyst (supporting 0.5% by weight of Pd metal) were charged, and hydrogen was injected under pressure.
The hydrogenation reaction was carried out at 0 Kg/crrt2G, heated to 2000C, and stirred for 4 hours.

After the reaction was completed, the solvent, catalyst, etc. were removed to obtain 100 g of a hydrogenated cyclopentadiene-styrene copolymerization reaction product.

This hydrogenated product had a softening point of 109° C., a bromine number of 5.1 g/l 00 g, a degree of aromatic ring hydrogenation of 34 g, and a Gardner hue of 1 or less. Note that the acid value was 1 mgKOH/g or less.

Production Example 3 Preparation of Cyclopentadiene-Maleic Anhydride Copolymerization Product (C) Component In a polymerization reaction vessel equipped with a stirrer and purged with nitrogen, 40 g of xylene (solvent), 100 g of cyclopentadiene, and 35 g of maleic anhydride were placed. 260℃
The copolymerization reaction was carried out for 3 hours while heating and stirring.

After the reaction was completed, xylene was removed to obtain 127 g of a cyclopentadiene-maleic anhydride copolymerization reaction product.

The softening point of this cyclopentadiene-maleic anhydride copolymerization product was 142°C, the content of cyclopentadiene as a monomer unit was 75% by weight, and the bromine number was 64g/100g. , acid value is 233mgKOH
/g and Gardner hue was 18 or more.

Production Example 4 Preparation of hydrogenated product of cyclopentadiene-maleic anhydride copolymerization reaction product (component (D)) In a reaction vessel equipped with a stirrer and purged with nitrogen, tacyclobentadiene obtained in the production of component (C) Maleic anhydride copolymerization reaction product 100
g, 100 g of tetrahydrofuran (solvent), and Pd catalyst 5
(supporting 0.5% by weight of Pd metal), hydrogen was injected to give a pressure of 30 Kg/CIK''G, and the temperature was 200°C.
The hydrogenation reaction was carried out for 3.5 hours under stirring.

After the reaction is completed, the solvent, catalyst, etc. are removed to obtain hydrogenated product 10 of the cyclopentadiene-maleic anhydride copolymerization reaction product.
1g was obtained.

This hydrogenated product has a softening point of 158°C, a bromine value of 16 g/100 g, and an acid value of 230 mg KOI (7
It had a Gardner hue of 16.

Shown in the table.

Examples 1 to 8 and Comparative Examples 1 to 4 Predetermined amounts of each of the polyol compounds and blends (prepared to 28 mesh or less) shown in Table 1 were kneaded by passing them through a 2B three paint mill roll three times, and then kneading the predetermined amounts A polyisocyanate compound was added thereto, and the mixture was allowed to warm at room temperature for about 10 minutes, and a predetermined amount of a curing accelerator was added thereto, and the mixture was heated at room temperature for about 5 minutes. The obtained liquid composition was heated to 300×150 at 120°C for 30 minutes.
wI! It was pressure-cured to a size of (pressure=2t). Subsequently, post-curing was performed at 120° C. for 60 minutes.

Regarding the obtained polyurethane composition, JIS K2SO
Physical properties were measured according to 3. In addition, a hot water resistance test was conducted using the method described below.

After measuring the weight and hardness of a sample punched into a size of 20×20 mEI, it was immersed in hot water maintained at 70° C. for 72 hours. After immersion, the moisture on the surface of the sample was wiped and the weight and hardness of the sample were measured to calculate the weight change rate and hardness change before and after immersion in hot water.

Claims (6)

[Claims] (1) A polyurethane mixture consisting of a polyol compound and a polyisocyanate compound, a copolymerization reaction product (A) of a cyclopentadiene monomer and a vinyl-substituted aromatic hydrocarbon (A), hydrogen of the reaction product (A) Additive (B), a copolymerization reaction product (C) of a cyclopentadiene monomer and an unsaturated dicarboxylic acid or its anhydride, and a hydrogenated product (D) of the reaction product (C)
A polyurethane composition formed by blending and curing at least one compound selected from the following. (2) A patent for blending 20 to 200 parts by weight of at least one compound selected from component (A), component (B), component (C), and component (D) to 100 parts by weight of the polyol compound. A composition according to claim 1. (3) The composition according to claim 1, wherein the polyol compound is a hydroxyl group-terminated liquid polybutadiene or a polyoxypropylene triol. (4) The composition according to claim 1, wherein the polyisocyanate compound is diphenylmethane diisocyanate. (5) The composition according to claim 1, wherein component (A) is a cyclopentadiene-styrene copolymerization reaction product. (6) The composition according to claim 1, wherein component (C) is a cyclopentadiene-maleic anhydride copolymerization reaction product.