JPS5845982B2 - Curable polymer composition - Google Patents

Description

[Detailed description of the invention] This invention relates to curable polymer compositions.

More specifically, the present invention relates to a curable polymer composition that has excellent workability and provides a cured product with excellent mechanical and electrical properties and deterioration resistance.

BACKGROUND ART Conventionally, as a method for producing polyurethane, there has been a method in which, for example, an organic compound having active hydrogen is reacted with an organic compound having incyanate, and various methods are known for this purpose.

For example, a hydrogenated butadiene liquid polymer is used as the organic compound having active hydrogen, and a polyurethane resin obtained by reacting this with an incyanate compound is known to have excellent deterioration resistance and weather resistance. This is described in Publication No. 28037 and the like.

However, when a mixture is obtained by blending various inorganic fillers with the above-mentioned polyurethane resin and used to manufacture cast products, large-sized products, special products, etc., the above-mentioned mixture has a high viscosity and has a long pot life. Because the length is extremely short, workability is very poor, and the manufactured cast products contain many voids, making them not only unsuitable as electrical insulating materials but also having extremely poor mechanical properties.

Therefore, the present inventors conducted intensive research to solve the above-mentioned drawbacks, and found that: - Mineral oil or mineral It has been found that a curable polymer composition with low viscosity and a long pot life can be obtained by mixing a mixture of oil and vegetable oil or a mixture containing at least one type of phenolic compound with an incyanate compound.

That is, the object of the present invention is to obtain a curable polymer composition that has a low viscosity and a long pot life even when an inorganic filler is added.

Hydrogenated butadiene liquid polymers used in the present invention include, for example, butadiene homopolymers having two or more hydroxyl groups in the molecule and 80% or more of trans and cyst 4 bonds as a fine structure of butadiene chains, or styrene. , a hydrogenated butadiene liquid polymer consisting of a copolymer with a vinyl monomer such as acrylonitrile, acrylic acid, or methacrylic acid.

In the case of a copolymer, the content of monomers other than butadiene is preferably 50% or less, preferably 30% or less.

As an example of the butadiene liquid polymer, for example, American ARC
Poly bd, R-45, R-4 manufactured by O Chemical Company
Examples include 5HT1C8-15 and CN-15.

In addition, when hydrogenating butadiene liquid polymer, catalysts used in ordinary catalytic reduction methods, such as platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, nickel-based catalysts, cobalt-based catalysts, or metal oxide or sulfide catalysts, are used. These catalysts can be used in combination or with carriers such as carbon, diatom, calcium carbonate, asbestos, and glass fiber.

Further, hydrogenation can be carried out without a solvent or in the presence of a solvent using hydrogen gas by either a normal pressure method or a high pressure method, and the reaction temperature can be arbitrarily selected within the range of room temperature to about 150°C.

When hydrogenation is carried out in the above-mentioned solvent, any solvent can be used as long as it dissolves both the butadiene liquid polymer and the produced hydrogenated product.

Hydrogenation can also be carried out in a suspended state. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, ethyl ether, tetrahydrofuran,
ether or cyclic ether compounds such as dioxane,
Alcohols, aliphatic carboxylic acids, esters, etc. can be used alone or in combination.

Next, the inorganic filler used in the curable polymer composition of the present invention will be described.

Examples of the inorganic filler include calcium carbonate, clay, calcined clay, silane-modified clay, Merck, silica, silica sand, pumice powder, slate powder, mica powder, asbestos, aluminum hydroxide, aluminum sulfate, barium sulfate, and sulfuric acid. Calcium, molybdenum dioxide, graphite, antimony oxide, zinc oxalate, and the like are preferably used.

It is preferable to use these inorganic fillers with an average particle size of 150μ or less, and one type can be used alone or two or more types of inorganic fillers can be used in combination.
Furthermore, inorganic fillers of the same type or different types having different particle sizes may be mixed and used.

These inorganic fillers can be blended in an amount of 0 to 200 parts per 100 parts of the hydrogenated product of the butadiene liquid polymer, but in consideration of workability and physical properties of the cured product, it is 0 to 15 parts.
0 parts is preferred.

Next, the mineral oil and phenol compound used in the curable polymer composition of the present invention will be described.

The composition according to the present invention is characterized in that at least one compound selected from the mineral oil, a mixture of mineral oil and vegetable oil, or a phenol compound is added to the mixture of the hydrogenated butadiene liquid polymer and the inorganic filler. The purpose is to add

As the above-mentioned mineral oil, high-boiling point petroleum fractions such as paraffinic process oil, nandene-based floss oil, aromatic process oil, polymerized high-boiling point strongly aromatic oil, etc. are preferably used, as well as coconut oil, pine oil, etc. It can also be used in combination with vegetable oils such as.

The blending ratio of the mineral oil or a mixture of mineral oil and vegetable oil is based on 100 parts of the hydrogenated product of the butadiene liquid polymer.
It is preferable to add 10 to 50 parts.

If the blending ratio is less than 10 parts, the effect of lowering the viscosity will be extremely small, and if it is more than 50 parts, the physical properties of the cured product will be significantly reduced.

In addition, the blending ratio when added in combination with the phenol compound described in detail later is also the hydrogenated butadiene liquid polymer i.
It is preferably 10 to 50 parts based on oo parts.

Next, examples of the above-mentioned phenolic compounds include monophenols such as phenol, cresol, 3-methyl-4
-isopropylphenol, 3methyl-6-butylphenol, 2,6-sibutylphenol, 2,6-dibutyl-4-methylphenol, 2,6-dibutyl-4-methoxyphenol, 2,4-dimethyl-6-butylphenol, 2- Methyl-4,6-cyamylphenol, butylated cresol mixture, cyclohexylated cresol, alkylated cresol, styrenated phenol, 4-
Butylphenol, alkylated phenol, triphthyl-P-phenylphenol, 2,6-sibutyl-(α
-dimethylamino) -P cresol substituted phenol derivatives, substituted phenol modified products, etc. can be used.

In addition, examples of polyphenols include 2,5-dibutylhydroquinone, 2,5-cyamylhydroquinone,
Hydroquinone monobenzyl ether, 2,4,5-
Trihydroxybutyrophenone, P-dimethoxybenzene, resorcin derivatives, pyrocatechol, etc., and bisphenols such as bisphenol A14.4
'-Dioxydiphenyl, ≦1,1-bis(4-hydroxyphenyl)-cyclohexane, 1,1'-methylenebis(2-methatol), 4,4'-bis(2,6-
dibutyl)phenol, 2,2'-methylenebis(4-
methyl-6-butylphenol), 2,2-methylenebis(4-ethyl-6-butylphenol), 4.
4'methylenebis(2-methyl-6-butylphenol→, 3-methyl-6-butylphenol derivative, 4.4
'-Methylenebis(2,6-sibutylphenol), 4
・4'-butylidene bis(3-methyl-6-butylphenol), 2,2'-methylenebis(4-methyl-6-
methylcyclohexylphenol), nonylene-2,4
-xylenol, 1,3,5-trimethyl-2,4,6
-Tris(3,5-dibutyl-4hydroxylbesidyl)benzene, 2,6-bis(2-hydroxy-3butyl-5-methylbenzyl)P-cresol, alkylated bisphenol, methylenated alkylphenol, polybutylated bisphenol A1 Polyphenol derivatives, hindered bisphenols, high molecular weight hindered phenols, etc. can be used.

Other thiobisphenols include 4,4′thiobis(
3-methyl-6-butylphenol), 4,4'-thiobis(2-methyl-6-butylphenol), 2,2'
-thiobis(4-methyl-6butylphenol), thiobis(cyamylphenol), ■・1′-thiobis(2
-naphthol), dialkylphenol-sulfide,
Phenol sulfides, etc. can also be used.

Note that two or more of these phenol compounds can also be used in combination.

The phenol compound is 0.5 to 50 parts by weight, preferably 1 part by weight, based on ioo parts by weight of the hydrogenated butadiene liquid polymer.
~10 parts by weight is added.

Next, the curing agent used in the curable polymer composition of the present invention will be described.

A wide variety of organic isocyanates or mixtures thereof can be used as hardeners.

As the isocyanate, for example, meta-phenylene,
Diisocyanate, 2.4-tolylene diisocyanate,
2,6-tolylene diisocyanate, naphthalene-1.
5-diisocyanate, cumene-2・4-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, xylylene diisocyanate, ■-methoxyphenyl-2・
4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl 4,47-biphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4',4''-triphenylmethane diisocyanate, polymethylene Polyphenylisocyanate, 2,4,6-triisocyanate, 4,4'-dimethyldiphenylmethane 2,2',5,5'-tetraisocyanate, etc. can be used.

The blending ratio of the isocyanate is such that a molar ratio of isocyanate groups to hydroxyl groups in the hydrogenated butadiene liquid polymer is from 0.95 to 12.

If the ratio of the isocyanate groups is less than 0.95, crosslinking of the cured product will not be sufficient, resulting in poor physical properties.

Moreover, an excess of one or two or more incyanate groups results in a decrease in the deterioration resistance of the cured product.

In carrying out the present invention, it is of course possible to use additives such as colorants and tackifiers as necessary.

The curable polymer composition of the present invention comprising the above-mentioned components has extremely superior workability compared to conventional compositions.

That is, since this composition has a low viscosity and a long pot life, it can be easily subjected to pouring and degassing operations such as casting, impregnation, or potting for the electrical industry, and therefore can provide an excellent cured product without voids. can.

Furthermore, this composition has good processability and moldability, and can be molded by various molding methods, and can also be used as an adhesive or a coating agent, and can be applied to an extremely wide range of other uses.

Further, the cured composition of the present invention has rubber-like elasticity and is particularly excellent in mechanical and electrical properties and deterioration resistance.

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below.

Example 1 Hydrogenation rate 98%, average number of hydroxyl groups 2.2, average molecular weight 290
As fillers, (1) calcium carbonate, (2) talc, (3
) hydrated alumina, and (4) calcined ray, four types of formulations were obtained, each containing 100 parts of each, and then Guiablack-H (manufactured by Mitsubishi Kasei, carbon black) was added to these.
2 parts and 5 parts of commercially available phenol as a phenol compound were added to each of them, and these were mixed by roll kneading each separately twice, heated to 100 ° C., and mixed with liquid MD I (manufactured by Upjohn Co., Ltd.). 12.1 parts of I5onate 143L (imported and sold by Mitsubishi Kasei) was added, vigorously stirred for 1 minute, and the change in viscosity at 100°C was measured.

These results are shown in Table 1. Among the four types of compositions obtained above, the composition using calcium carbonate as a filler was then degassed and mixed at 1'00°C for 3 minutes, and this was mixed into a 20 x 20 x 0.2 Cr/l sheet. It was poured into a mold to be molded and cured by heating at 120° C. for 16 hours.

Table 5 shows the main physical properties of this cured product.

Examples 2 to 5 The phenol compounds used in Example 1 above were converted into bisphenol A (Example 2), Tsukurak-200 (manufactured by Ohmukai Shinko Kagaku, alkylphenol) (Example 3), Tsukurak-
NS6 (same as before, alkyl bisphenol) (Example 4)
Four types of curable polymer compositions were obtained in the same manner as in Example 1, except that Tsukurak-8P (same as above, polyphenol) (Example 5) was used, and the viscosity change at 100°C was measured.

The results are shown in Table 1. Further, a cured product using calcium carbonate as a filler was formed into a sheet in the same manner as in Example 1, and the physical properties of this cured product were measured.

The results are shown in Table 5.

Examples 6 to 11 The above implementation was carried out by using mineral oil in place of the phenol used in Example 1 above, using only one type of calcium carbonate as a filler, and changing the amount of mineral oil blended as shown in Table 2. A total of six types of curable polymer compositions were obtained by the same method as in Example 1, and the viscosity change at 100°C was measured for each.

The mineral oils used were two types, as shown in Table 2: a naphthenic process oil ('['M-55, manufactured by Idemitsu Kosan) and a paraffinic process oil (MM-45, manufactured by Idemitsu Kosan).

In addition, cured products molded into sheets were obtained in the same manner as in Example 1 above, and the physical properties of each were measured, and the results are shown in Table 5.

Examples 12 to 14 The curable polymer composition obtained using calcium carbonate as a filler in Example 3 above was further supplemented with mineral oil (naphthenic process oil, Idemitsu Kosan's ■TM-55) 30
A curable polymer composition was prepared (Example 13) with the addition of

In addition, the blended amount of a phenol compound (Tsukurac-200, manufactured by Ohmukai Shinko Chemical Co., Ltd., alkylphenol) was smaller than that of Example 3 (Example 122 parts by weight) and Inukiki (Example 1410 parts by weight). The viscosity changes of these compositions were measured in the same manner as in Example 1, and the results are shown in Table 3.

In addition, Table 5 shows the physical properties measured for cured products obtained by molding these compositions into sheet shapes.

Example 15 The curing agent used in Example 13 (liquid MDI).

Upjohn) with another curing agent, namely TDI-65 (
Sumitomo Bayer Urethane is ■Desmodur T6
A curable polymer composition was obtained in the same manner as in Example 13 except that 5) was replaced with 7.27 parts, and the amount was changed to 7.27 parts.
As a result of measuring the viscosity change of this composition at 80°C,
The initial viscosity is 2.2 x 103 cp, which is 10
The time to reach 'cp was 40 minutes.

Further, the physical properties of a cured product obtained by molding this composition into a sheet shape are as shown in Table 5.

Example 16 Hydrogenated butadiene homopolymer 1 used in Example 13
00 parts was replaced with 100 parts of another polymer, that is, a hydrogenated styrene-butadiene copolymer having a hydrogenation rate of 87%, an average number of hydroxyl groups of 2.2, and a number average molecular weight of 3500, and further, the blending ratio of the liquid MDI was changed to 10 parts. , others are the same as in Example 13 above.
A curable polymer composition was obtained in the same manner as above, and the viscosity change of this composition at 100°C was measured. As a result, the initial viscosity was 2. OX], 03 cp, and the time required to reach 105 cp was 25 minutes.

Table 5 shows the physical properties of a cured sheet of this composition.

Examples 17-19 Hydrogenated butadiene homopolymer-1 with hydrogenation rate ioo%, average number of hydroxyl groups 2.28, number average molecular weight about 3000
5 parts of phenol was added as a phenol compound to 00 parts, and the mixture was heated and mixed at 80°C for 10 minutes.

Next, 7.2 parts of TDI-65 (mentioned above) was added as a curing agent and vigorously stirred for 1 minute to obtain a curable polymer composition (
Example] 7).

Also, in the same way, T was added as mineral oil at the same time as the phenol.
Combined use of 30 parts of M-55 (mentioned above) (Example 18)
and said TM55 as mineral oil in place of said phenol.
(Example 19) using 30 parts of the above-mentioned product was obtained, and the viscosity change at 80°C was measured for each.

The results are shown in Table 4. Comparative Example 1 A curable composition without the addition of phenol was obtained in Example 1, and the viscosity change of this composition at 100°C was measured. The viscosity was 105 cp.

Among these compositions, sheets were molded using calcium carbonate as a filler, but the viscosity rose rapidly, making casting impossible.

Comparative Example 2 In order to clarify the hydrogenation effect of butadiene liquid polymer, 100 parts of non-hydrogenated butadiene homopolymer (manufactured by ARCO Chemical Co., Ltd., polybd, R-45M) and 2 parts of Diablack-H (described above) were used. A cured product was obtained in the same manner as in Example 1 by adding 100 parts of calcium carbonate and 11.9 parts of liquid MDI (mentioned above).

Table 5 shows the physical properties of this cured product.

In Table 5, the mechanical properties were measured according to JISK-6301, and the electrical properties were measured according to JISK-6911.

As mentioned above, the curable polymer composition obtained by the present invention has a low viscosity, a long pot life, and excellent workability, and the cured product thereof has an excellent composition as is clear from Table 5. It has mechanical and electrical properties and resistance to deterioration.

By the way, in the above description, the present invention was described for the case of molding a sheet, but it goes without saying that it can be used for other purposes.

As explained above, this invention includes a system consisting of a hydrogenated product of butadiene polymer, an inorganic filler, and a curing agent, and one or more of a phenol compound, mineral oil, or a mixture of mineral oil and vegetable oil. By adding a combination of these, the resulting curable polymer composition has the effect of lowering the viscosity and lengthening the pot life.

Claims (1)

[Claims] 1. 0 parts by weight of a hydrogenated liquid butadiene polymer having at least two hydroxyl groups in the molecule, 0 parts by weight of an inorganic filler.
~220 parts by weight, 0.5 to 50 parts by weight of at least one type of mineral oil or a mixture of mineral oil and vegetable oil, or a phenol compound, and 1 hydroxyl group of the hydrogenated product.
A curable polymer composition comprising an incyanate compound that provides 0.95 to 1.2 moles of incyanate groups. 2 Hydrogenation rate of 98% as a hydrogenated product of liquid butadiene polymer
The curable polymer composition according to claim 1, which uses a hydrogenated butadiene homopolymer having an average number of hydroxyl groups of 2.2 and a number average molecular weight of about 2,900. 3 Hydrogenation rate of 87% as a hydrogenated product of liquid butadiene polymer
The curable polymer composition according to claim 1, which uses a hydrogenated styrene-butadiene copolymer having an average number of hydroxyl groups of 2.2 and a number average molecular weight of about 3,500. 4. The curable polymer composition according to any one of claims 1 to 3, which uses calcium carbonate as an inorganic filler. 5. The curable polymer composition according to any one of claims 1 to 4, which uses a naphthenic process oil as the mineral oil. 6. The curable polymer composition according to any one of claims 1 to 4, which uses paraffinic process oil as the mineral oil. 7. The curable polymer composition according to any one of claims 1 to 6, which uses phenol as the phenol compound.