JPH06220157A - Liquid polymer composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of a specific hydride, a specified reactive diluent, a specific plasticizer and a specified polyisocyanate compound, having a low viscosity, excellent in operating efficiency and heat resistance and useful as an electrical insulating material, a coating, material, etc. CONSTITUTION:The objective composition is composed of (A) a hydrogenated hydroxyl group-containing liquid diene-based polymer in which >=60% conjugated diene-based monomer is bound through 1,4-bonds, (B) a reactive diluent composed of the hydrogenated hydroxyl group-containing liquid diene-based polymer in which >=60% 16-80C saturated dihydric alcohol and/or conjugated diene-based monomer is bound through 1,2-bonds, (C) a plasticizer such as a hydrogenated 1-decene oligomer in an amount of preferably 50-130 pts.wt. [based on 100 pts.wt. component (A)] and (D) a polyisocyanate compound such as tolylene diisocyanate. Furthermore, the content of hydroxyl groups in the component (B) is preferably 1-2.5 times expressed in terms of molar ratio based on that in the component (A). A cured product of this composition has <=50 JIS-A hardness.

Description

Detailed Description of the Invention

[0001]

The present invention has excellent heat resistance and workability,
The present invention relates to a liquid polymer composition that gives a cured product having a low hardness, and can be widely used as an electric insulating material, a protective material, a coating material, a paint, a waterproof material, and the like.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a liquid polymer composition for obtaining an elastic cured product or the like, a composition comprising a combination of various hydroxyl group-containing liquid diene polymers and a polyisocyanate compound has been investigated.
Among these liquid polymer compositions, as a liquid polymer composition which gives a cured product excellent in water resistance, heat resistance, weather resistance, electrical characteristics, etc., a hydride of a hydroxyl group-containing liquid isoprene-based polymer and polyisocyanate are used. A composition comprising a compound is known (JP-A-63-57626, JP-A-1).
-203421). However, since this composition has a high viscosity and is inferior in workability, it is important to select and use an appropriate viscosity reducing agent.

Therefore, the inventors of the present invention, as a liquid polymer composition for obtaining an elastic cured product excellent in water resistance, heat resistance, weather resistance, electrical properties, etc., are hydrogenated hydrates of isoprene-based polymers containing a hydroxyl group. A liquid polymer composition comprising a polyisocyanate compound and a hydride of a 1-decene oligomer has been proposed (Japanese Patent Application No. 3-355549). Thus, when the hydride of 1-decene oligomer is used as the plasticizer, the heat resistance is improved and the viscosity of the compound can be lowered as compared with the case of using other plasticizers. However, in order to obtain a cured product having a low hardness required for electric insulating materials and the like, it is necessary to add a considerable amount of a 1-decene oligomer hydride. Therefore, there is a problem in heat resistance of the obtained cured product. Specifically, the hardness change of the cured product after the heat resistance test is very large, or the cured product is melted, so that the heat resistance is not yet reliable.

Accordingly, the present inventors have made earnest studies to obtain a liquid polymer composition which has solved the above-mentioned conventional drawbacks, and as a result, by using a reactive diluent which is a specific polyol compound, these problems have been solved. The present invention has been completed based on this finding.

[0005]

That is, according to the present invention, 60% or more of the conjugated diene-based monomer has a 1,4-bond,
Hydrogenated hydroxyl group-containing liquid diene polymer (A), saturated dihydric alcohol having 16 to 80 carbon atoms and / or 60% or more of conjugated diene monomer is 1,2-bonded, hydroxyl group containing liquid diene system The present invention provides a liquid polymer composition comprising a reactive diluent (B) composed of a hydride of a polymer, a plasticizer (C) and a polyisocyanate compound (D), and a cured product thereof.

In the present invention, 60% or more of the conjugated diene monomer as the component (A) has 1,4-bonds,
A hydride of a hydroxyl group-containing liquid diene polymer is used. Here, as the component (A), 60% of the conjugated diene-based monomer is used.
The above is not a hydrogenation product of a liquid hydroxyl group-containing diene polymer having 1,4-bonds, but hydrogen of a liquid hydroxyl group-containing diene polymer having, for example, 1,2-bonds of 60% or more of a conjugated diene monomer. Even if a compound is used, the object of the present invention cannot be achieved.

The hydride of the hydroxyl group-containing liquid diene polymer used as the component (A) in the present invention generally has a number average molecular weight of 300 to 25,000, preferably 5
00 to 10000, and the hydroxyl group content is 0.
1 to 10 meq / g, preferably 0.3 to 7 meq / g. In terms of molecular structure, the total of cis-1,4 bonds and trans-1,4 bonds is 60% or more, preferably 70% or more. The hydroxyl group may be located at the end of the molecular chain or inside the molecular chain, but it is particularly desirable that it is located at the end of the molecular chain. In the present invention, it is also possible to use two or more kinds of hydroxyl group-containing liquid diene-based polymers, for example, a hydroxyl group-containing liquid isoprene-based polymer and a hydroxyl group-containing liquid isoprene-butadiene copolymer.

60 of the above-mentioned conjugated diene-based monomers
A hydride of a hydroxyl group-containing liquid diene polymer in which 1% or more is 1,4-bond is a known hydroxyl group-containing liquid diene polymer in which 60% or more of a conjugated diene monomer is 1,4-bond. It can be obtained by hydrogenating using the method of. Here, the hydroxyl group-containing liquid diene polymer in which 60% or more of the conjugated diene monomer is 1,4-bonded can be obtained, for example, as follows.

Specifically, for example, one or more diene monomers having 4 to 22 carbon atoms (specifically, butadiene, isoprene, chloroprene, 1,3-pentadiene, cyclopentadiene, etc.) are replaced with hydrogen peroxide. , An azo compound having a hydroxyl group (for example, 2,2′-azobis [2-
Methyl-N- (2-hydroxyethyl) propionamide etc.] or a peroxide having a hydroxyl group (for example, cyclohexanone peroxide etc.) as a polymerization initiator,
By radical polymerization, a hydroxyl group-containing liquid diene polymer (for example, a hydroxyl group-containing liquid polyisoprene, a hydroxyl group-containing liquid isoprene-butadiene copolymer, etc.) can be obtained. When an isoprene-butadiene copolymer is produced as the hydroxyl group-containing liquid diene polymer, isoprene /
The copolymerization ratio can be changed within an arbitrary range of butadiene = 30/70 to 95/5 (wt / wt).

The amount of the polymerization initiator used in this case is 1.0 to 50 g, for example, when hydrogen peroxide is used, relative to 100 g of the diene monomer, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 5.0 to 100 g, and cyclohexanone peroxide, 5.0 to 100 g.
Is appropriate. The polymerization can be carried out without a solvent, but it is preferable to use a solvent because the reaction can be easily controlled. As the solvent, ethanol, isopropanol, n-butanol and the like are usually used. The reaction temperature is 80 to 150 ° C., and the reaction time is 0.5 to 15 hours.

At the time of polymerization, two or more kinds of diene monomers may be mixed and used. Further, with respect to the diene monomer, an addition polymerizable monomer having 2 to 22 carbon atoms (for example, butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid and its ester, methacrylic acid and its) at a ratio of 50 mol% or less. Ester, vinyl chloride, vinyl acetate, acrylamide, etc.) can also be added.

After the completion of the reaction, the solution is distilled under reduced pressure to remove the solvent, unreacted monomers and the like, and 60% or more of the conjugated diene-based monomer is 1,4-bonded and has a hydroxyl group-containing liquid diene polymer. Is obtained. Here, for example, when a diene monomer is anionically polymerized using a catalyst such as naphthalene dilithium to produce an isoprene living polymer or an isoprene-butadiene copolymer living polymer, and a monoepoxy compound or the like is further reacted, a conjugated diene is used. A hydroxyl group-containing liquid diene polymer in which 60% or more of the system monomers are 1,2-bonded will be obtained.

In the component (A) of the present invention, 60% or more of the conjugated diene monomer produced as described above is 1,4
It can be obtained by hydrogenating the bonded, hydroxyl group-containing liquid diene polymer by a known method using a homogeneous catalyst or a heterogeneous catalyst.

First, when a homogeneous catalyst is used, a saturated hydrocarbon such as hexane or cyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene is used as a solvent at room temperature to room temperature.
The hydrogenation reaction is carried out at a reaction temperature of 150 ° C. under a hydrogen pressure of atmospheric pressure to 50 kg / cm ² G. As the homogeneous catalyst, a Ziegler catalyst, which is a combination of a transition metal halide and an alkyl compound such as aluminum, alkaline earth metal or alkali metal, is used in an amount of about 0.01 to 0.1 mol% per polymer double bond. To do. The reaction is usually completed in 1 to 24 hours.

On the other hand, when a heterogeneous catalyst is used,
Hexane, cyclohexane, and other saturated hydrocarbons, benzene, toluene, xylene, and other aromatic hydrocarbons, diethyl ether, tetrahydrofuran (THF), dioxane, and other ethers, ethanol, isopropanol, 1-
Using alcohols such as butanol or the like or a mixed system thereof as a solvent, the hydrogenation reaction is carried out at a reaction temperature of room temperature to 200 ° C. under a hydrogen pressure of atmospheric pressure to 100 kg / cm ² G. As the heterogeneous catalyst, a catalyst such as nickel, cobalt, palladium, platinum, rhodium or ruthenium may be used alone or supported on a carrier such as silica, diatomaceous earth, alumina or activated carbon. The amount of the catalyst used is suitably 0.05 to 10% by weight based on the weight of the polymer. You may use these catalysts in mixture of 2 or more types.
The reaction is usually completed within 1 to 48 hours.

After completion of the reaction, the catalyst is filtered off, and the solution is distilled under reduced pressure to remove the solvent, and the desired liquid diene having a hydroxyl group containing 1,4-bond of 60% or more of the conjugated diene monomer. A hydride of the polymer is obtained. The hydride of the hydroxyl group-containing liquid diene polymer thus obtained has a number average molecular weight of 300 to 25,000, preferably 500 to 10,000, and a hydroxyl group content of 0.
It is preferably 1 to 10 meq / g.

The hydrogenation rate of the hydride of the hydroxyl group-containing liquid diene polymer is preferably 50% or more, and more preferably 70% or more. In the present invention, for example, a mixture of a hydride of a hydroxyl group-containing liquid isoprene-based polymer and a hydride of a hydroxyl group-containing liquid isoprene-butadiene copolymer can be used. Where the hydrogenation rate,
That is, the ratio of hydrogenation of the unsaturated double bond in the polymer after the hydrogenation reaction is represented by the following formula.

[0018]

[Equation 1]

In the present invention, it is preferable to use, as the hydride of the hydroxyl group-containing liquid diene polymer, one having an average number of hydroxyl groups per molecule of 1.7 or more, particularly 2.0 or more. It is preferable from the viewpoint of obtaining a cured product having various physical properties. The average number of hydroxyl groups per molecule is represented by the following formula.

[0020]

[Equation 2]

Next, in the present invention, a reactive diluent is used as the component (B). In the reactive diluent used in the present invention, 60% or more of the saturated dihydric alcohol having 16 to 80 carbon atoms and / or the conjugated diene monomer is 1,2-
It is a hydride of a bonded hydroxyl group-containing liquid diene polymer.

Examples of the saturated dihydric alcohol having 16 to 80 carbon atoms include dimer diol obtained by reducing dimer acid ester.
The dimer diol is a linear or branched long-chain glycol, and some of them may have a cyclo ring in the molecule.

Specific examples of such a dimer diol include dimer acid having 36 carbon atoms (manufactured by Henkel Hakusui Co., Ltd.,
A dimer diol obtained by reducing the dimethyl ester of trade name; parsadime 288) can be mentioned. Also,
Long-chain dibasic acid having 22 carbon atoms (Okamura Oil Co., Ltd., trade name; IPS-22, IPU-22, etc.), long-chain dibasic acid having 20 carbon atoms (Okamura Oil Co., Ltd., trade name; SL-2
0, UL-20, SB-20, UB-20, etc.), a long-chain dibasic acid having 28 carbon atoms (Okamura Oil Co., Ltd., trade name; S
Long chain glycols obtained by reducing dimethyl esters such as T-2P) can be mentioned. Furthermore, carbon number 36, 72
Hydrogenated products of long-chain dibasic acids (manufactured by Arakawa Chemical Industry Co., Ltd., trade name; dimer diol KX-501 and the like).

The dimer acid is usually linoleic acid,
A polymer fatty acid obtained by polymerizing an unsaturated aliphatic monocarboxylic acid such as oleic acid, which is generally a mixture of a dimer as a main component, an unreacted monomer, and another higher-order polymer However, if necessary, a dimer acid having a dimer highly concentrated by vacuum distillation or the like may be used.

As the hydride of the hydroxyl group-containing liquid diene polymer in which 60% or more of the conjugated diene monomer forming the other component (B) has 1,2-bonds, hydroxyl group-containing 1,2- An example is a hydride of polybutadiene. The hydride of the hydroxyl group-containing 1,2-polybutadiene can be obtained by hydrogenating the hydroxyl group-containing 1,2-polybutadiene. Specific examples of such a hydride of a hydroxyl group-containing 1,2-polybutadiene include Nisso PBG, trade name of Nippon Soda Co., Ltd.
I-1000, trade name manufactured by Mitsubishi Kasei Co., Ltd .; Polytail HA and the like. These hydroxylated 1,2-polybutadiene hydrides have a 1,2-vinyl group content of 60 mol% or more.

In the present invention, as the component (B), the saturated dihydric alcohol and the hydride of the hydroxyl group-containing liquid diene polymer in which 60% or more of the conjugated diene monomer is 1,2-bonded, are used alone. Either used or both compounds are used in combination. The amount of the reactive diluent (B) to be added is determined by the number of moles of the hydroxyl group in the hydride of the hydroxyl group-containing liquid diene polymer (a) and the number of moles of the hydroxyl group in the reactive diluent (b). The ratio is in the range of (b) / (a) = 1.0 to 2.5, that is, the molar ratio of the hydroxyl group in the component (B) to the hydroxyl group in the component (A) is 1 to 2 ．
It is preferable to use it so that it is 5 times. If the molar ratio is too large, the hardness of the obtained cured product becomes large, which is not preferable.

In the present invention, a plasticizer is used as the component (C). As the plasticizer used here, those generally used can be used, but from the viewpoint of heat resistance, hydrogen of an α-olefin having 8 to 14 carbon atoms, particularly hydrogen of 1-decene oligomer. It is preferable to use a compound.

Here, the hydride of 1-decene oligomer means 1-decene, an organic peroxide, a coordinated anion catalyst,
It is a product obtained by hydrogenating the residual double bond of an oligomer polymerized by using a Friedel-Crafts type catalyst or the like, and is often sold under the name of poly-α-olefin (PAO). There are no particular restrictions on the catalyst used in this polymerization, but Friedel-type catalysts such as boron trifluoride and AlCl ₃ can be used.
Crafts-type catalysts are relatively used. The hydrogenation can be easily carried out using a catalyst such as Raney nickel or stabilized nickel.

The 1-decene oligomer hydride preferably has a kinematic viscosity at 40 ° C. of 45 to 100 cst. Here, if the kinematic viscosity is less than 45 cst, good heat resistance at high temperature cannot be obtained, while if the kinematic viscosity exceeds 100 cst, it becomes difficult to obtain a low-viscosity liquid polymer composition. , The workability will be inferior.

When a hydride of 1-decene oligomer is used as the component (C), the amount of addition is 30 to 100 parts by weight of the hydride of the liquid hydroxyl group diene polymer which is the component (A). 200 parts by weight, preferably 50 to 130 parts by weight.

The 1-decene oligomer hydride used in the present invention preferably has a total content of tetramers, pentamers and hexamers of 75% by weight or more. If the total content of the tetramer, pentamer and hexamer is less than 75% by weight, good heat resistance may not be obtained even if the kinematic viscosity falls within the above range. The contents of the tetramer, pentamer and hexamer can be determined by gas chromatography or the like.

The commercially available 1-decene oligomer is Idemitsu PAO 5002,5004,500.
6,5008,5010 (made by Idemitsu Petrochemical Co., Ltd.), I
H-30, IH-47, IH-63 (manufactured by Ethyl), P
AO 40, PAO 100 (manufactured by Uniroyal Corporation) and the like can be mentioned.

Other plasticizers include paraffin-based process oils (for example, trade name; PW-90 (manufactured by Idemitsu Kosan Co., Ltd.)) and ethylene-α-olefinic cooligomers (for example, trade name; Lucant HC). -20 (manufactured by Mitsui Petrochemical Co., Ltd.)] or a silicone type can be used.

Next, in the present invention, a polyisocyanate compound is used as the component (D). Here, the polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule,
It has a hydride of the hydroxyl group-containing liquid diene polymer as the component (A) and an isocyanate group reactive with the hydroxyl group in the reactive diluent as the component (B). Examples of the polyisocyanate compound include ordinary aromatic, aliphatic and alicyclic compounds.

Specifically, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, naphthalene-1,5.
Aromatic polyisocyanates such as -diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, and isopropylbenzene-2,4-diisocyanate can be mentioned.

Further, xylylene diisocyanate (XD
I), tetramethylxylylene diisocyanate (TM)
XDI) aliphatic-aromatic polyisocyanate (isocyanate group does not have an isocyanate group directly bonded to an aromatic ring through an aliphatic hydrocarbon, that is, an isocyanate group directly bonded to an aromatic ring in the molecule The polyisocyanate which does not have can be mentioned.

Further, hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11
-Undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3
Examples thereof include aliphatic polyisocyanates such as 6-hexamethylene triisocyanate and trimethylhexamethylene diisocyanate.

Further, transcyclohexane-1,4-
Diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MD
I), alicyclic polyisocyanates such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated tetramethyl xylylene diisocyanate can be mentioned.

In addition, cyclized trimers (isocyanurate modified products), burette modified products, ethylene glycol, 1,4-butanediol, propylene glycol, dipropylene glycol, of the above polyisocyanate compounds,
Trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene ether glycol, polyester polyol, acrylic polyol,
An addition reaction product of a polyol compound such as a polyalkadiene polyol, a hydrogenated product of a polyalkadiene polyol, a partially saponified ethylene-vinyl acetate copolymer, a castor oil-based polyol and the above polyisocyanate compound is used.

These polyisocyanate compounds may be used as a mixture of two or more thereof, and the isocyanate groups of these polyisocyanate compounds may be used as phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam. , Ethyleneimine, α
-A so-called blocked isocyanate compound blocked with a blocking agent such as pyrrolidone, diethyl malonate, sodium bisulfite and boric acid can also be used.

The mixing ratio of these polyisocyanate compounds is not particularly limited, but it is usually reacted with the hydroxyl group (OH) of the hydride of the hydroxyl group-containing liquid diene polymer as the component (A) and the isocyanate group. The ratio (NCO / OH) of the isocyanate group (NCO) of the polyisocyanate compound to the total number of hydroxyl groups in the reactive diluent having a hydroxyl group ((B) component) is finally 0.3 to 5, Preferably 0.5 to 2.5 finally
Blend so that

The term "finally" is used here because various methods are used in the actual production of the cured body. The methods are roughly classified into three methods, which are a one-shot method and prepolymer methods (1) and (2). In the one-shot method, first of all the components to be blended, components other than the polyisocyanate compound are blended and mixed to obtain a mixture. A polyisocyanate compound and a compounding agent component not used in the previous mixing are added to this mixture and mixed to obtain a liquid polymer composition. The preferable NCO / OH at this time is 0.5 to 2.5.

Further, in the prepolymer method (1), a compound having a hydroxyl group (a hydride of a hydroxyl group-containing liquid diene polymer and reactive dilution with a predetermined equivalent ratio NCO / OH in the range of 1.7 to 25) are used. At least one of the agents) is reacted with the polyisocyanate compound in the presence or absence of some or all of the other additives to obtain a prepolymer. The preferable NCO / OH at this time is 0.5 to
It is 2.5. In this case, since the molar ratio NCO / OH of the functional groups involved in the reaction when the prepolymer was obtained is substantially 1.0, the final NCO / OH is preferably 0.5 to 2.5. Within range.

Next, in the prepolymer method (2), all the components are blended in a predetermined equivalent ratio NCO / OH in the range of 1.7 to 5 and reacted to obtain a prepolymer. This prepolymer is reacted with moisture (water) in the air. Again, the final NCO / OH is preferably in the range 0.5-2.5. As described above, various methods are used in the actual production of the cured product, but the final NCO / OH
Is preferably in the range of 0.5 to 2.5.

In the present invention, as described above, the hydride (A) of the hydroxyl group-containing liquid diene polymer, the reactive diluent (B), the plasticizer (C) and the polyisocyanate compound are used as basic components. In order to further improve the mechanical properties of the liquid polymer composition, other components can be added depending on the purpose within the range not impairing the gist of the present invention.

In the present invention, various catalysts can be added to accelerate the reaction. Specifically, for example, triethylenediamine, tetramethylguanidine, N,
N, N'N'-tetramethylhexane-1,6-diamine, N, N, N'N "N" -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, N -Methyl-N '
-(2-Dimethylamino) ethylpiperazine, tertiary amines such as diazabicycloundecene and carboxylic acid salts of the tertiary amines, as well as stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marcaptide, Organometallic compounds such as dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, phenylmercuric propionate, lead octenoate can be added. The addition amount of these catalysts is at most 10 parts by weight with respect to 100 parts by weight of the hydride of the hydroxyl group-containing liquid diene polymer as the component (A). When the amount of the catalyst added exceeds 10 parts by weight, not only the curing acceleration effect reaches its ceiling but also the risk of local abnormal reaction (gelation) increases, which is not preferable.

In the present invention, in addition to the components directly involved in the reaction as described above, an inorganic / organic filler can be added if necessary. As the inorganic filler that can be used in the present invention, zinc, aluminum, copper,
Nickel, glass sphere, glass flake, glass fiber, carbon black (channel black, furnace black, acetylene black, thermal black), carbon fiber, graphite, asbestos, kaolin clay, wax clay, talc, kasumite, cryolite, kei Wollastonite, diatomaceous earth, slate powder, whiting, feldspar powder, mica, gypsum, quartz powder, finely divided silicic acid, attapulgite, sericite, volcanic ash, vermiculite, silica, alumina, zinc oxide, magnesium oxide, zirconium oxide,
Titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate, boron nitride, boron nitrite, molybdenum disulfide, etc. may be mentioned. it can.

The organic filler which can be used in the present invention includes natural fibers such as rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, cotton, hemp, wool and silk. , Nylon, polyester, vinylon, acetate, acrylic and other synthetic fibers, polyethylene, polypropylene, polystyrene, ABS resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, vinyl chloride resin, epoxy resin, phenolic resin and other synthetic resins Examples thereof include powder and granules. The blending amount of these inorganic fillers and organic fillers is not particularly limited, but is usually 0.5 to 100 parts by weight with respect to 100 parts by weight of the hydride of the hydroxyl group-containing liquid diene polymer as the component (A).
It is 500 parts by weight, preferably 5 to 200 parts by weight.

In the present invention, as other additives, tackifying resin, antiaging agent (antioxidant, ultraviolet absorber), flame retardant, defoaming agent, antifoaming agent, etc. are reacted as necessary. It can be added before, during or after the reaction.

That is, a tackifying resin can be used for adjusting the adhesive force and the adhesive force. Specific examples include alkylphenol resins, terpene resins, terpene phenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumarone resins, aliphatic and alicyclic and aromatic petroleum resins.

In order to improve heat resistance and weather resistance, hindered phenol type, hindered amine type and benzotriazole type anti-aging agents (antioxidants, ultraviolet absorbers) can be added.

Further, a flame retardant such as a phosphorus compound, a halogen compound or antimony oxide may be blended, a defoaming agent such as a silicone compound may be blended, or a foaming inhibitor such as zeolite or quick lime may be blended.

The liquid polymer composition of the present invention can be obtained by mixing the above-mentioned components, and this composition can be cured into a cured product generally by the following method. . First, as described above, the liquid polymer composition is prepared by mixing the predetermined components in a predetermined ratio. In preparing the composition, using a mixing device, a kneading device,
At a temperature of 0 to 120 ° C, preferably 15 to 100 ° C,
Stir and mix for 0.5 seconds to 8 hours, preferably 1 second to 5 hours. Usually, the method called the one-shot method as described above or the method called the prepolymer method is used for preparing the composition.

In the one-shot method, first, of the above-mentioned components, components other than at least the polyisocyanate compound are blended and mixed at the temperature and time described above to obtain a mixture. A polyisocyanate compound and an additive component not used in the previous mixing are added to this mixture and mixed at the above temperature and time to obtain a liquid polymer composition. Preferred N at this time
CO / OH is 0.5 to 2.5.

In the prepolymer method (1) of the prepolymer methods, the predetermined equivalent ratio NCO / OH is in the range of 1.7 to 25, and the hydride of the hydroxyl group-containing liquid diene polymer and the reactive diluent are used. At least one of them is reacted with the polyisocyanate compound in the presence or absence of some or all of the other additives to obtain a prepolymer. The reaction temperature is the same as above, and the reaction time is usually 0.1 to 10 hours, preferably 0.5 to 8 hours.
The remaining components are mixed with the prepolymer at the above temperature and time to obtain a liquid polymer composition. The preferable NCO / OH at this time is 0.5 to 2.5.

The prepolymer method (2) has a predetermined equivalent ratio N
CO / OH is added in the range of 1.7 to 5, and all the ingredients are added,
The prepolymer is obtained by reaction. The reaction temperature is the same as above, and the reaction time is usually 0.1 to 10 hours, preferably 0.5 to 8 hours. This prepolymer is reacted with moisture (water) in the air. The liquid diene polymer composition prepared in this manner can be given a cured product in various forms by being subjected to curing treatment by a conventional method, and can be used for various purposes. The hardness of the cured product thus obtained is approximately JIS A 50 or less, and the workability is excellent.

[0057]

EXAMPLES Next, the present invention will be described in detail with reference to Examples. Production Example 1 (1) Preparation of hydroxyl-terminated liquid polyisoprene In a pressure-resistant reaction vessel made of stainless steel having a volume of 1 liter, 200 g of isoprene, 40 g of hydrogen peroxide solution having a concentration of 20% and 100 g of isopropanol were charged, and the temperature was 120 ° C. and the reaction time was 2 hours. The reaction was carried out under the conditions of. The pressure reached a maximum of 8 kg / cm ² G during the reaction. After the reaction was completed, the reaction mixture was placed in a separating funnel, 600 g of water was added, and the mixture was shaken and allowed to stand for 3 hours, then, the oil layer was separated. From this oil layer, the solvent, the monomer and the low boiling point component are 2 mmHg, 100
It was distilled off under the conditions of 2 ° C. for 2 hours to obtain liquid polyisoprene having a hydroxyl group at the terminal of the molecular chain (yield: 66% by weight). This product had a number average molecular weight of 2,240, a hydroxyl group content of 0.96 meq / g, a viscosity of 64 poise / 30 ° C. and a bromine number of 220 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.15. In addition, ¹ H-NMR
The result of the structural analysis according to is that trans-1,4 bond is 57
%, Cis-1,4 bond 33%, 1,2 bond 6%,
3,4 bonds were 4%.

(2) Preparation of Hydrogenated Hydroxyl-Terminated Liquid Polyisoprene 100 g of liquid polyisoprene having a hydroxyl group at the terminal of the molecular chain obtained as described in (1) above, 5 g of a ruthenium carbon catalyst having a ruthenium content of 5% by weight, and 100 g of cyclohexane was charged as a solvent, and a hydrogenation reaction was carried out at 150 ° C. for 6 hours under a hydrogen pressure of 50 kg / cm ² G. After completion of the reaction, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter, and then 2 mmHg, 110 ° C.
The solvent was distilled off under the condition of 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group at the molecular chain end was obtained. This compound has a number average molecular weight of 2310, a hydroxyl group content of 0.94 meq / g and a viscosity of 625 poise / 30.
C., bromine number was 2 g / 100 g. 1 at this time
The average number of hydroxyl groups per molecule is 2.17.

Production Example 2 (1) Preparation of hydroxyl-terminated liquid polyisoprene In a pressure-resistant reaction vessel made of stainless steel having a capacity of 1 liter, 200 g of isoprene, 100 g of hydrogen peroxide solution having a concentration of 30% and 300 g of isopropanol were charged, and the reaction was carried out at a temperature of 115 ° C. The reaction was carried out under the condition of 2.5 hours. The pressure reached a maximum of 7 kg / cm ² G during the reaction. After the reaction was completed, the reaction mixture was placed in a separating funnel, 600 g of water was added, and the mixture was shaken and allowed to stand for 3 hours, then, the oil layer was separated. From this oil layer, 2mmHg of solvent, monomer, low boiling point component,
It was distilled off under the condition of 100 ° C. for 2 hours to obtain liquid polyisoprene having a hydroxyl group at the terminal of the molecular chain (yield 71% by weight). This product had a number average molecular weight of 1,380, a hydroxyl group content of 1.55 meq / g and a viscosity of 46 poise / 30 ° C. At this time, the average number of hydroxyl groups per molecule is 2.
It was 14. Further, the results of structural analysis by ¹ H-NMR show that trans-1,4-bonds are 56% and cis-1,4-bonds are 56%.
Bonds were 33%, 1,2 bonds were 6%, and 3,4 bonds were 5%.

(2) Preparation of Hydrogenated Hydroxyl-Terminated Liquid Polyisoprene 100 g of liquid polyisoprene having a hydroxyl group at the molecular chain terminal obtained as in the above (1), 5 g of a ruthenium carbon catalyst having a ruthenium content of 5% by weight, and 100 g of cyclohexane was charged as a solvent, and a hydrogenation reaction was carried out at 150 ° C. for 6 hours under a hydrogen pressure of 50 kg / cm ² G. After completion of the reaction, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter, and then 2 mmHg, 110 ° C.
The solvent was distilled off under the condition of 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group at the molecular chain end was obtained. The number average molecular weight of this product was 1420, the hydroxyl group content was 1.54 meq / g, and the viscosity was 298 poise / 30.
C., bromine number was 1 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.19.

Production Example 3 (1) Preparation of Hydroxy Group-Containing Liquid Isoprene-Butadiene Copolymer 90 g of isoprene, 110 g of butadiene, 40 g of hydrogen peroxide solution having a concentration of 20% and 100 g of isopropanol are placed in a pressure resistant reaction vessel made of stainless steel having a volume of 1 liter. Preparation,
The reaction was carried out under the conditions of a temperature of 120 ° C. and a reaction time of 2 hours. The pressure reached a maximum of 8 kg / cm ² G during the reaction.
After the reaction was completed, put the reaction mixture in a separating funnel, and
After adding 00 g of water and shaking and leaving still for 3 hours, the oil layer was fractionated. From this oil layer, the solvent, the monomer and the low boiling point component were distilled off under the conditions of 2 mmHg, 100 ° C. and 2 hours to give a hydroxyl group-containing liquid isoprene-butadiene copolymer (yield 62
Wt%) was obtained. This compound had a number average molecular weight of 2,240, a hydroxyl group content of 0.91 meq / g, a viscosity of 44 poise / 30 ° C. and a bromine number of 215 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.04. The results of structural analysis by ¹ H-NMR showed that the isoprene content was 45% and the butadiene content was 55%. 84% of 1,4-bonds and 14 of 1,2-bonds
%, 3,4-bond was 2%.

(2) Preparation of Hydrogenated Hydroxyl-Terminated Liquid Isoprene-Butadiene Copolymer Hydroxyl-terminated liquid isoprene-obtained as in (1) above
Butadiene copolymer 100 g, ruthenium content 5% by weight
5 g of the ruthenium carbon catalyst and 100 g of cyclohexane as a solvent were charged, and a hydrogenation reaction was carried out at 150 ° C. for 6 hours under a hydrogen pressure of 50 kg / cm ² G. After completion of the reaction, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter, and then 2 mmHg, 110 ° C.
The solvent was distilled off under the condition of 2 hours. As a result, a hydride of a liquid isoprene-butadiene copolymer having a hydroxyl group at the terminal of the molecular chain was obtained. The number average molecular weight of this product is 23
50, the hydroxyl group content is 0.94 meq / g, and the viscosity is 4
It was 31 poise / 30 ° C. and the bromine number was 1 g / 100 g. The average number of hydroxyl groups per molecule at this time is 2.21.
Is.

Examples 1 to 7 and Comparative Examples 1 to 5 Of the compositions shown in Table 1, the raw materials except the polyisocyanate compound were blended and mixed and stirred at 60 ° C. for 2 hours to give a blend of the liquid polymer. Obtained. A polyisocyanate compound was added thereto at a ratio shown in Table 1, and mixed and stirred at 60 ° C. for 2 minutes to obtain a liquid polymer composition. 300 x 150 x 2
It was poured onto a mold having a size of mm, pressed at 60 ° C. for 2 hours, and then cured at 60 ° C. for 15 hours to obtain a cured product. The evaluation results using this cured product are shown in Table 1.

The heat resistance and workability of the cured product were evaluated by the following methods. (1) Heat resistance test The cured product obtained as described above was heated in a gear type oven at 150 ° C for 1 week. Physical properties after heating JIK K
It measured based on 6301. The weight change rate from the initial weight is shown in Table 1 as the weight loss due to heating.

(2) Workability The obtained liquid polymer composition was put in a 500 ml glass bottle, kept at 25 ° C. for 1 minute in a constant temperature water bath, and then the viscosity was measured with a B8M type viscometer (No. 4 rotor). . The obtained viscosity results were evaluated according to the following criteria. ◯: Viscosity is less than 50 poise Δ: Viscosity is 50 poise or more and less than 100 poise X: Viscosity is 100 poise or more Generally, when the viscosity of the compound is 100 poise or more, defoaming operation, casting, impregnation, coating and other operations are performed. Becomes difficult.

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[Table 1]

[Footnote of Table 1] 1); Dimer diol KX-501 (manufactured by Arakawa Chemical Industry Co., Ltd.), a weight ratio of a saturated dihydric alcohol having 36 carbon atoms to a saturated dihydric alcohol having 72 carbon atoms 133: 8 mixture, hydroxyl group content = 3.62 meq / g 2); hydride of hydroxyl group-containing liquid 1,2-polybutadiene (manufactured by Mitsubishi Kasei Co., Ltd.), hydroxyl group content = 0.93 m
eq / g, Mn = 2180, 1,2 bonds 91% 3); Hydration of hydroxyl group-containing liquid 1,2-polybutadiene (manufactured by Nippon Soda Co., Ltd.), hydroxyl group content = 1.29 meq /
g, Mn = 1400, 1,2 bond 93% 4); 1-decene oligomer (Idemitsu Petrochemical Co., Ltd.)
Manufactured), kinematic viscosity = 70.3 cst (37.8 ° C.), 4, 5,
Content of hexamer = 98.1 wt% 5); Dibutyltin dilaurate (manufactured by Kyodo Chemical Co., Ltd.) 6); Hindered phenolic antioxidant (manufactured by Ciba-Geigy Co., Ltd.) 7); Hydrogenated MDI (Sumitomo Bayer Urethane Industry Co., Ltd.
, Isocyanate content = 31.8% 8); liquid modified MDI containing diphenylmethane diisocyanate as a main component (manufactured by Nippon Polyurethane Industry Co., Ltd.),
Isocyanate content = 28.8% 9); Number of moles of hydroxyl group in reactive diluent / number of moles of hydroxyl group in hydride (A) of liquid diene polymer containing hydroxyl group

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According to the present invention, a liquid polymer composition having a low viscosity and excellent workability can be obtained. Moreover, the cured product obtained by curing the composition has good heat resistance at high temperatures and low hardness (JIS A 50 or less). Therefore, the present invention can be effectively used as an electric insulating material, a coating material, a paint, a waterproof material, a protective material and the like.

Claims (4)

[Claims] 1. A hydride (A) of a hydroxyl group-containing liquid diene polymer in which 60% or more of a conjugated diene monomer is 1,4-bonded, a saturated dihydric alcohol having 16 to 80 carbon atoms and / or Reactive diluent (B) and plasticizer (C) consisting of a hydride of a hydroxyl group-containing liquid diene polymer in which 60% or more of the conjugated diene monomer is 1,2-bonded.
And a liquid polymer composition comprising the polyisocyanate compound (D). 2. The component (A) is a hydride of a hydroxyl group-containing liquid isoprene polymer and / or a hydride of a hydroxyl group-containing liquid butadiene-isoprene copolymer.
The liquid polymer composition described. 3. With respect to the hydroxyl group in the component (A),
The liquid polymer composition according to claim 1 or 2, wherein the hydroxyl group in the component (B) has a molar ratio of 1 to 2.5. 4. A cured product of the liquid polymer composition according to claim 1, which has a hardness of JIS A 50 or less.