JPH04161402A - Hydrogenated compound of liquid diene-based copolymer and liquid polymer composition containing the same compound - Google Patents

Abstract

PURPOSE:To obtain the subject polymer capable of providing a cured material having improved heat resistance and weather resistance and excellent in other properties, e.g. mechanical properties and water resistance by halogenating and hydrogenating an active hydrogen group-containing liquid diene-based polymer. CONSTITUTION:A hydrogenated compound of a halogenated active hydrogen- containing liquid diene-based polymer. The above-mentioned hydrogenated compound is obtained, e.g. by halogenating an active hydrogen group-containing diene-based polymer using a halogenation agent such as carbon tetrachloride in the presence of a radical polymerization initiator in a hydrocarbon solvent and subsequently hydrogenating the resultant halogenated polymer in the presence of a Zieglar catalyst in a hydrocarbon solvent. In addition, as the raw material active hydrogen group-containing liquid diene-based polymer, a hydroxyl group-containing polymer synthesized by radical polymerization of a diene-based monomer such as butadiene in the presence of a polymerization initiator such as hydrogen peroxide is preferable.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a liquid diene polymer hydride and a liquid polymer composition containing the same. The present invention relates to a hydrogenated product of a liquid diene monopolymer that can provide a cured product, and a liquid polymer composition containing the hydrogenated product.

[Conventional technology] Used in a wide range of applications, including electrical insulation materials, elastic bodies, coating materials, lining materials, paints, adhesives, inks, waterproofing materials, sealing materials, retaining materials, and vibration-proofing materials. Conventionally, compositions comprising a liquid diene polymer containing active hydrogen groups and a polyisocyanate compound have been known as liquid polymer compositions that can be used.

The cured product obtained from this liquid polymer composition has excellent electrical properties, rubber elasticity, and water resistance, but has the disadvantage of poor heat resistance and weather resistance.

In order to overcome this drawback, attempts have been made to use hydrides of liquid diene polymers containing active hydrogen groups. It is intended to reduce the double bonds of a liquid diene polymer containing active hydrogen groups by hydrogenating it, thereby improving its stability against heat and light.

However, although a cured product obtained from a liquid polymer combination acid consisting of a polymer hydride and a polyisocyanate compound has a certain degree of improvement in heat resistance and weather resistance, it is still at a sufficiently satisfactory level. This has not yet been achieved, and further improvement of the layer has been desired.

[Problems to be Solved by the Invention] The present invention provides a liquid diene-based polymer that can provide a cured product that has further improved heat resistance and weather resistance and maintains good properties such as mechanical properties and water resistance. It is an object of the present invention to provide a hydride of a polymer and a liquid polymer composition containing the same.

"Means for Solving the Problems" In order to achieve the above object, the present inventors focused on the liquid diene polymer to be used, and as a result of extensive studies, the present inventors have developed a liquid diene polymer containing halogenated active hydrogen groups. It was discovered that by using a hydride of a combination, heat resistance and weather resistance were further improved, and a cured product with good other properties could be obtained, and based on this knowledge, the present invention was completed. Ta.

That is, according to the present invention, there is provided a hydride of a halogenated active hydrogen group-containing liquid diene polymer, and a liquid polymer composition comprising a hydride of this polymer and a polyincyanate compound.

The present invention will be explained in detail below.

The hydride of the halogenated liquid diene polymer containing active hydrogen groups in the present invention can be obtained by halogenating and hydrogenating the liquid diene polymer containing active hydrogen groups.

It can also be obtained by hydrogenating a liquid diene polymer containing a precursor group of active hydrogen groups and halogenating a hydride of the liquid polymer containing active hydrogen groups.

The order of halogenation and hydrogenation is not particularly limited.

First, after halogenation, hydrogenation may be performed, or after hydrogenation, halogenation may be performed. The former method is usually adopted.

Examples of the liquid diene polymer include liquid homopolymers or copolymers of diene monomers such as butadiene, isoprene, chloroprene, and pentadiene.

Examples of active hydrogen groups include hydroxyl groups, amine groups, and carboxyl groups that can react with isocyanate groups. Particularly suitable are liquid diene polymers containing hydroxyl groups.

The active hydrogen group-containing liquid diene polymer is known or can be easily produced by a known method.

For example, a liquid diene polymer containing a hydroxyl group can be prepared by replacing the diene monomer with hydrogen peroxide, an azo compound having a hydroxyl group [for example, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide, etc.] ] Alternatively, a hydroxyl group-containing liquid diene polymer can be obtained by radical polymerization using a hydroxyl group-containing peroxide (such as cyclohexanone peroxide) as a polymerization initiator. The amount of the polymerization initiator to be used is, for example, 1.0 to 509.2.2' of hydrogen peroxide per 1009 of the diene monomer.
-azobis[2-methyl-N=(2-hydroxyethyl)-propionamide] 5.0 to 100 g and cyclohexanone peroxide 5.0 to 100 g are suitable. Although polymerization can be carried out without a solvent, it is preferable to use a solvent for ease of controlling the reaction. Ethanol, isopropanol, n-butasol, etc. are commonly used as the solvent. Suitable reaction temperature is 80 to 150°C and reaction time is 0.5 to 15 hours.

Furthermore, a hydroxyl group-containing liquid diene polymer can also be obtained by anionically polymerizing a diene monomer using a catalyst such as naphthalene dilithium to produce a Liching polymer, and then reacting with a monoepoxy compound or the like. Although polymerization can be carried out without a solvent, it is preferable to use a solvent from the same viewpoint as in the case of radical polymerization. Saturated hydrocarbons such as hexane and cyclohexane are used as the solvent. Reaction temperature is 50-100℃
A suitable reaction time is 1 to 10 hours.

After the reaction is completed, the solution is distilled under reduced pressure to remove the solvent and obtain a hydroxyl group-containing liquid diene polymer. The number average molecular weight of this hydroxyl group-containing liquid diene polymer is usually 30
It is 0 to 25,000, preferably 500 to 10,000, and the hydroxyl group content is usually 0.1-11-1 O/9, preferably 0.3 to 7 meq/g. Further, structurally, it is preferable that the total of cis-1,4 structure and trans-1,4 structure accounts for 70% or more.

The hydroxyl group may be located at the end of the molecular chain or within the molecular chain, but it is preferably located at the end of the molecular chain.

A liquid diene polymer containing a carpokyl group can be produced by reacting a liquid diene polymer containing a hydroxyl group with a dicarboxylic acid compound such as maleic anhydride. It can also be produced by polymerizing diene monomers using a radical initiator having a carboxyl group, such as azobiscyanopentanoic acid, in the same manner as in producing a hydroxyl group-containing liquid polymer. Also,
The amine group-containing liquid diene polymer is produced by polymerizing a diene monomer using a radical polymerization initiator having a nitrile group such as azobisisobutyronitrile, and the other steps are the same as in the production of the hydroxyl group-containing liquid polymer. The nitrile group-containing liquid diene polymer can be produced by hydrogenating the same. Furthermore, the nitrile group-containing liquid diene polymer can also be produced by copolymerizing a diene monomer with a heptamine having a nitrile group, such as acrylonitrile. By hydrogenating the nitrile group-containing liquid diene polymer thus obtained, an amino group-containing liquid diene polymer can be obtained.

In any case, the following additives may be added at a rate of 50+++ oA% or less based on the diene monomer during polymerization.

That is, addition polymerizable monomers having 2 to 22 carbon atoms, butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid and its esters, methacrylic acid and its esters, vinyl chloride, vinyl acetate, acrylamide, and the like.

It is also possible to use a mixture of two or more active hydrogen group-containing liquid diene polymers.

In the present invention, such a liquid diene polymer containing an active hydrogen group or a liquid diene polymer containing a precursor group of an active hydrogen group is rogogenated and hydrogenated at the same time.

The case where a liquid diene polymer containing an active hydrogen group is used as a raw material will be described below, but the same applies to a liquid diene polymer containing a precursor group of an active hydrogen group.

It is possible to obtain a halogenated diene polymer containing active hydrogen groups by using a diene polymer containing active hydrogen groups as a raw material and halogenating it by well-known methods such as ion addition and radical addition. can.

When carrying out halogenation by ion addition, a saturated hydrocarbon such as hexane/chlorohexane, an aromatic hydrocarbon such as benzene, toluene, xylene, or chloroform is used as a solvent, and the reaction temperature is 1 to 4 at room temperature to 80°C.
Halogenation is carried out by blowing in halogen gas for about 8 hours.

When performing halogenation by radical addition, a halogenating agent consisting of halogenated methane such as carbon tetrachloride, chloroform, diethylene chloride, triethylene chloride, trichlorobromomethane, dichlorodibromomethane, etc., as well as benzoyl peroxide, methyl ethyl ketone peroxide, etc. In the presence of a radical initiator, the reaction temperature is 0 to 100°C for a time window of 1 to 48 hours. Moreover, the reaction can also be initiated by ultraviolet rays, radiation, etc., without using a radical initiator.

After the reaction is completed, volatile components are removed by blowing in an inert gas such as nitrogen, and the solution is distilled under reduced pressure to remove the solvent and obtain a liquid diene polymer containing halogenated active hydrogen groups. This halogenated active hydrogen group-containing liquid diene polymer has a number average molecular weight of 300 to 25,000.
, preferably SOO to 10,000, and the active hydrogen group content is desirably 0.1 to 10 meq/g. In addition, the halogenation rate is calculated from 5 to 5 unsaturated double bonds present per molecule of the active hydrogen group-containing liquid diene polymer.
80% is preferable.

Note that the halogenation rate is expressed by the following formula.

Halogenation rate (%) --x l OOA = amount of double bonds in liquid diene polymer containing active hydrogen groups (if active hydrogen groups are generated by hydrogenation, Double bond content) B-Double bond content of halogenated active hydrogen group-containing liquid diene polymer (or liquid diene polymer containing active hydrogen group precursor group) Active hydrogen group-containing liquid diene type When a polymer is excessively halogenated, the rubber elasticity of the cured product is lost,
If the degree of halogenation is extremely low, the effect of halogenation will not be obtained, and sufficient heat resistance and weather resistance will not be obtained.

Note that the halogen used in the present invention may be any of chlorine, bromine, and iodine, but chlorine and bromine are preferable from the viewpoint of reactivity.

The present invention generally comprises a halogenated active hydrogen group-containing liquid diene polymer or an active hydrogen group-containing precursor group produced as described above by a known method using a homogeneous catalyst or a heterogeneous catalyst. The desired polymer hydride is obtained by hydrogenating the liquid diene polymer.

For example, when using a homogeneous catalyst, a saturated hydrocarbon such as hexane or cyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene is used as a solvent, and the
At a reaction temperature of °C and under a hydrogen pressure of normal pressure to 50 kg/cm"G,
A hydrogenation reaction takes place. As a homogeneous catalyst, a Ziegler catalyst made of a combination of a transition metal halide and an alkylated product of aluminum, an alkaline earth metal, or an alkali metal, etc., is used, with a concentration of 0.01-
Use approximately 0.1+uffi%. The reaction is usually 1-24
Finish in time.

When using a heterogeneous catalyst, saturated hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diethyl ether, tetrahydrofuran, and dioxane, and alcohols such as ethanol and isopropanol. or a mixture thereof as a solvent, hydrogenation reaction is carried out at a reaction temperature of room temperature to 200°C and a hydrogen pressure of normal pressure to 100 kg/cm"G.Heterogeneous catalysts include nickel, cobalt, palladium, Catalysts such as platinum, rhodium, and ruthenium are used alone or supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon.The appropriate amount is 0.05 to 10 wt% based on the weight of the polymer. These catalysts may be used in combination.The reaction is usually completed in 1 to 48 hours.

After the reaction is completed, the catalyst is filtered off and the solution is distilled under reduced pressure to remove the solvent and obtain a hydride of a liquid diene polymer containing halogenated active hydrogen groups.

The hydrogenation rate (hydrogenation rate) of unsaturated double bonds in the polymer after the hydrogenation reaction is expressed by the following formula.

Hydrogenation rate (%) - - ~90
%.

The hydride of the halogenated active hydrogen group-containing liquid diene polymer thus obtained usually has a number average molecular weight of 300 to 25,000. Preferably 500-10000
It is desirable that the active hydrogen group content is o, l-zomeq/y.

In the present invention, hydrides of two or more halogenated active hydrogen group-containing liquid diene polymers may be used.

In addition, in order to obtain a cured product having good physical properties, the average number of active hydrogen groups per molecule of the hydride of the halogenated active hydrogen group-containing liquid diene polymer used is preferably 1.7 or more, More preferably, it is 2.0 or more.

The average number of active hydrogen groups per molecule can be expressed by the following formula.

Average number of active hydrogen groups per molecule = □×E D = Active hydrogen group content (meq/g) E-Number average molecular weight Active hydrogen groups may be located either at the end of the molecular chain or inside the molecular chain, but at the end of the molecular chain It is desirable to have one in

The present invention provides a hydrogenated product of a liquid diene polymer containing a halogenated active hydrogen group, and also provides a liquid polymer composition comprising a hydrogenated product of this polymer and a polyisocyanate compound.

The polyiso/anate compound used in the present invention is
It is a compound having two or more isocyanate groups in one molecule, and has an isocyanate group reactive with the active hydrogen group of the hydride of the halogenated active hydrogen group-containing liquid diene polymer.

Examples of such polyiso/anate compounds include the usual aromatic, aliphatic and cycloaliphatic ones,
For example, tolylene diisocyanate (TDI), hexamethylene diisocyanate, dodecane diisonanate, diphenylmethane diisocyanate (MDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate. (TMXDI), transcyclohexane-1,4-diisocyanate, phenylene diinocyanate, naphthalene-1,5-diisocyanate, o-
Toluidine diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6.11-undecane triisocyanate, 1,8-diisocyanate- 4-Isona-untomethyloctane, 1,3.6-hexamethylene triisocyanate, hiscycloheptane triisocyanate, isopropylbenzene-2,4-diisocyanate, trimethylhexamethylene diisocyanate, inphorone diisocyanate (IPDI) , hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclized trimer of the above polyisocyanate compound (incyanurate modified product), ethylene glycol, trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene ether glycol,
Addition reaction products of polyol compounds such as polyester polyols, acrylic polyol diene polyols, partially saponified ethylene-vinyl acetate copolymers, and castor oil-based polyols with the above-mentioned polyisocyanate compounds are used. Particularly preferred are hydrogenated diphenylmethane diisocyanate and carbodiimide-modified diphenylmethane diisocyanate.

Also, these polyisocyanate compounds can be used in combination of two or more, and the isocyanate groups of these polyiso/anate compounds can be blocked with a blocking agent such as phenol, xylenol, methyl ethyl ketone oxime, and ε-caprolactam. So-called blocked isocyanate compounds can also be used.

There is no particular restriction on the ratio of these components, but usually the isocyanate group (N G O ) is blended so that the molar ratio (NCO/H) is 0.5 to 25, preferably 0.5 to 15.

In addition, polyol compounds, polyamine compounds, etc. described below,
When compounding a compound having an active hydrogen group that reacts with an incyanate group, the incyanate group (N
GO) at the ratio (N CO/H) or molar ratio as shown above.

The liquid polymer composition of the present invention is composed of the hydride of the halogenated active hydrogen group-containing liquid diene polymer and the polyincyanate compound, but other additives may be added as desired. can.

Additives that may be added as desired include polyol compounds, polyamine compounds, inorganic fillers, organic fillers, catalysts (curing accelerators), viscosity modifiers, solvents, tackifying resins,
Examples include anti-aging agents, antioxidants, ultraviolet absorbers, flame retardants, antifoaming agents, and antifoaming agents.

A polyol compound is a compound having two or more hydroxyl groups in one molecule, and includes low molecular weight polyols, polymerized polyols, and castor oil polyols.

As the low molecular weight polyol, any of -class polyol, secondary polyol, and tertiary polyol may be used. Specifically, for example, 1.2-brobylene glyconol
Dipropylene glycol, 112-butanediol, 1
, 3-butanediol to 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-hydroxypropylaniline, N,N-bishydroxyisopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A, etc. Low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon are mentioned.

Furthermore, as polyols, ethylene glycol diethylene glycol-1,3-propylene glycol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol, trimethylol, which does not contain a hydroxyl group bonded to a secondary carbon Propane, pentaerythritol, dipentaerythritol, etc. can also be used. The molecular weight of these polyols is preferably in the range of 50 to 500.

The present invention includes polyether polyols and modified products thereof used as polyurethane raw materials, polytetraethylene ether glycol, tetrahydro-7-alkylene oxide copolymerized polyolefin epoxy resin-modified polyoleate polyester polyols, polydiene polyols, partially kephized ethylene Polymerizable polyols such as vinyl acetate copolymers are used.

The number average molecular weight of these polyols is usually 500 to 10
It is 000.

Castor oil-based polyols such as Sarani, castor oil, hydrogenated castor oil, and castor oil transesterified products can be used.

Two or more of these polyol compounds may be used in combination.

The polyamine compound that can be used in the present invention has two
It is a compound with an amino group having more than 1 active hydrogen.

Specifically, aliphatic polyamines such as hexamethylene diamine and polyoxypropylene polyamine, 3.3'-
Aliphatic polyamines such as dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dicyclo-4,4
°-Diaminodiphenylmethane, 3.5-diethyltoluene-2,4-diamine, 3.5-diethyltoluene-
Examples include aromatic polyamines such as 2,6-diamine.

The blending ratio of these polyol compounds or polyamine compounds is usually 1 to 1000 parts by weight, preferably 1 to 1001 parts by weight of the hydride of the halogenated active hydrogen group-containing liquid diene polymer. is blended in an amount of 3 to 200 parts by weight.

Inorganic fillers include zinc, asbestos, alumina, aluminum, kaolin clay, glass spheres, glass flakes, glass fiber, and carbon (channel black, 7 Arnes black, acetylene black, thermal black).
, carbon fiber, nepheline, cryolite, graphite,
Silica, wollastonite, diatomaceous earth, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, aluminum hydroxide, magnesium hydroxide, slate powder,
Zeolite, quartz powder, calcium carbonate, magnesium carbonate, talc, potassium titanate, boron nitride, feldspar powder,
Copper, nickel, molybdenum disulfide, barium sulfate, whiting, waxite clay, mica, ceracola, etc. may be mentioned.

Organic fillers include rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood flour, cotton, hemp, wool,
Natural yarn fibers such as rope, synthetic fibers such as nylon, polyester, vinylon, acetate, acrylic, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyethylene phthalate, polybutylene phthalate,
Examples include synthetic resin powders or granules such as polymethyl methacrylate, polyvinyl chloride, epoxy resins, and phenol resins.

There are no particular restrictions on the amount of these inorganic fillers and organic fillers, but usually, based on 100 parts by weight of the hydride of the halogenated active hydrogen group-containing liquid diene polymer,
The amount is 0.5 to 500 parts by weight, preferably 5 to 200 parts by weight.

In order to accelerate the curing reaction, triethylenediamine, tetramethylguanidine, N,N,N',N'-tetramethylhexane-1,6-diamine, N,N,N'
, N'', N''-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, l,2-dimethylimidazole, N-methyl-N'-(2-dimethylamino)-ethylpiperazine, diazabicycloundecene Tertiary amines or their carboxylic acid salts such as stannath octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin diacetate, dioctyltin mercaptide, dioctyltin thiocarboxylate , phenylmercury propionate,
An organometallic compound such as lead octenoate can be added as a catalyst (hardening accelerator). These catalysts are used in a maximum tot amount of parts per 100 parts by weight of the hydride of the halogenated active hydrogen group-containing liquid diene polymer. If it is used in an amount exceeding 10 parts by weight, not only the curing accelerating effect reaches its limit, but also the risk of local abnormal reaction (gelation) increases, which is undesirable.

In the present invention, viscosity modifiers such as plasticizers such as dioctyl athalate, process oils such as paraffinic, naphthenic, and aromatic oils, olefin oligomers, alkylbenzenealkyldiphenylethanes, and silicone oils can also be blended.

There are no particular restrictions on the formulation of these viscosity modifiers, but
Usually, the amount is 500 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of the hydride of the halogenated active hydrogen group-containing liquid diene polymer.

Furthermore, to reduce viscosity, hydrocarbon solvents such as n-hexane, cyclohexane, toluene, and xylene, ketone solvents such as methyl ethyl ketone, and cyclohexanone,
Ester solvents such as butyl acetate, ether solvents such as tetrahydrofuran, and solvents such as N,N-diethylformamide and dimethyl sulfoxide may be blended.

There are no particular restrictions on the amount of these solvents, but it is usually 200 parts by weight or less, preferably 100 parts by weight or less, per 100 parts by weight of the hydride of the halogenated active hydrogen group-containing liquid diene polymer. .

Tackifier resins such as alkylphenol resins, terpene resins, terpenephenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic and alicyclic and aromatic petroleum resins to adjust adhesive strength and adhesive strength. It is also possible to mix.

Hindered phenol to improve heat resistance and weather resistance.
Antioxidants such as hindered amines and benzotriazoles, antioxidants, ultraviolet absorbers, flame retardants such as phosphorus compounds, halogen compounds, and antimony oxide, antifoaming agents such as silicone compounds, and antifoaming agents such as zeolite and quicklime. May be blended.

In the present invention, a liquid polymer composition is prepared by blending the above components in the above proportions. In preparing the composition,
Using a mixing device, a kneading device, etc., at a temperature of 0 to 120°C, preferably 15 to 100°C, for 0.5 seconds to 8 hours,
Preferably, the mixture is stirred for 1 second to 5 hours.

Usually, a method called the Funshot method or a method called the prepolymer method is used to prepare the composition.

In the one-shot method, first, at least the components other than the polyincyanate compound are blended and mixed at the temperature and time described above to obtain a mixture.

The polyisocyanate compound and additional components 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.

At this time, preferred incyanate group/active hydrogen group (NG
O/H) is 0.5 to 2.5 in molar ratio.

The prepolymer method uses hydrides, polyol compounds, and polyamine compounds of liquid diene polymers containing halogenated active hydrogen groups with a predetermined isocyanate group/active hydroxyl group molar ratio (NGO/H) in the range of 1.7 to 25. A prepolymer is obtained by reacting at least one of the above and a polyisocyanate compound in the presence or absence of some or all of other additives. The reaction temperature is the same as above, and the reaction time is usually 0.11 to 10 hours, preferably 0.5 hours.
~8 hours. The remaining components are mixed with this prepolymer at the above temperature and time to obtain a liquid polymer composition. Preferred isocyanate group/active hydrogen group (NG
O/H) is 0.5 to 2.5 in molar ratio.

The liquid polymer composition thus prepared can be used for various purposes, and can be cured to give various forms of cured products by curing treatment.

[Example] Hereinafter, the present invention will be explained in more detail by giving production examples, examples, and comparative examples.

Production Example 1 (1) Preparation of hydroxy acid-containing liquid polyisoprene In a stainless steel pressure-resistant reaction vessel, 200 g of isoprene was added at a concentration of 2.
40g of 0% hydrogen peroxide and 10% Improper Tools
0 g was charged, and the reaction was carried out at a temperature of 120° C. and a reaction time of 2 hours.

During the reaction, the pressure reached a maximum of 8 kg/cra"G. After the reaction was completed, the reaction mixture was put into a separating funnel, 6009 water was added, and after standing for 311 cm, the oil layer was separated. From this oil layer, 2 mm of the solvent and low boiling point component
11 g was distilled off at 100° C. for 2 hours to obtain hydroxyl group-containing liquid polyisoprene (yield: 66% by weight). The number average molecular weight of this product is 2240, and the hydroxyl group content is 0.9
6 m eq / 9, viscosity is 64 voids / 30 °C,
The bromine number was 220g/100g. The average number of hydroxyl groups per molecule at this time was 2.15. Also, 'H-
The results of structural analysis by NMR show that the trans-1,4 structure 5
7%, cis-1,4 structure 33%, 1.2 structure 6%, 3.
4 structure was 4%.

(2) Preparation of halogenated hydroxyl group-containing liquid polyisoprene 100 g of the hydroxyl group-containing liquid polyisoprene obtained in Production Example 1 (1) and 1000 g of chloroform as a solvent were charged into a reaction vessel, and heated at 45°C for 6 hours using chlorine gas. 50cc/
The halogenation was carried out by blowing at a speed of min. After the reaction was completed, nitrogen gas was sufficiently blown in to remove chlorine gas, and then 2
The solvent was distilled off under the conditions of mrrHg, 110°C, and 2 hours. As a result, halogenated hydroxyl group-containing liquid polyisoprene was obtained. The number average molecular weight of this product is 34
1O1 hydroxyl group content is 0.61meQ/s+, viscosity is 1
50 poise/30°C, and the bromine number is 1149/10
0 g, and the halogenation rate was 48%.

100 g of the halogenated hydroxyl group-containing liquid polyisoprene obtained in (2) of Production Example 1, 5 g of a ruthenium carbon catalyst with a ruthenium content of 5% by weight, and 100 g of cyclohexane as a solvent were charged into a reaction vessel, and the reaction volume was 50 kg/cm.
Hydrogenation reaction was carried out at 150° C. for 6 hours under hydrogen pressure of G. After the reaction was completed, the catalyst was separated and removed from the reaction solution through a 0.45μ membrane filter, and then 2 tnm
The solvent was distilled off under conditions of Hg, 110° C., and 2 hours. As a result, a hydride of halogenated hydroxyl group-containing liquid polyimprene was obtained. The number average molecular weight of this product is 34
50, hydroxyl group content is 0.63me q/9, viscosity is 9
The temperature was 70 poise/30°C, the bromine number was 1 g/1009, the halogenation rate was about 49%, and the hydrogenation rate was about 51%. The average number of hydroxyl groups per molecule at this time was 2.17.

Production Example 2 (1) Preparation of hydride of hydroxyl group-containing liquid polyisoprene 100 g of hydroxyl group-containing liquid polyisoprene obtained in Production Example 1 (1), 5 g of a ruthenium carbon catalyst with a ruthenium content of 5% by weight, and 100 g of cyclohexane as a solvent.
g was charged into a reaction vessel, and a hydrogenation reaction was carried out at 150°C for 45 minutes under a hydrogen pressure of 50 ky/cm2G. After the reaction was completed, the catalyst was separated and removed from the reaction solution through a 0.45μ membrane filter, and then filtered at 2 mmHy, 11
The solvent was distilled off at 0°C for 2 hours. As a result, a hydride of liquid polyisoprene containing hydroxyl groups was obtained. The number average molecular weight of this product is 2250, and the hydroxyl group content is o, c
+7 meq/g, viscosity was 731 voids/30°C, bromine number 989/1009, and hydrogenation rate was about 55%. The average number of hydroxyl groups per molecule at this time was 2.18.

100 g of hydride of the hydroxyl group-containing liquid polyimprene obtained in (1) of Production Example 2, and 100 g of chloroform as a solvent.
9 was placed in a reaction vessel, and halogenation was carried out at 45° C. for 6 hours by blowing chlorine gas at a rate of 50 cc/min. After the reaction was completed, nitrogen gas was sufficiently blown in to remove chlorine gas, and then the solvent was distilled off under conditions of 21 raHg, 110° C., and 2 hours. As a result, a hydride of halogenated hydroxyl group-containing liquid polyimprene was obtained. The number average molecular weight of this product is 3180. Hydroxyl group content is 0.69m
eq/g, viscosity is 150 poise/30°C, rogenization rate is approximately 40%, and bromine number is 9.89/1009.
.

Production Example 3 Binding of hydride of hydroxyl group-containing liquid polyisoprene 1 - 100 g of hydroxyl group-containing liquid polyisoprene obtained in (1) of Production Example 1, 5 g of a ruthenium carbon catalyst with a ruthenium content of 5% by weight, and 100 g of cyclohexane as a solvent.
9 was charged into a reaction vessel, and a hydrogenation reaction was carried out at 150°C for 6 hours under a hydrogen pressure of 50 ky/cm"G. After the reaction was completed, the catalyst was separated and removed from the reaction solution through a 0.45μ membrane filter. After, 2IIIIII■9.1
The solvent was distilled off at 10°C for 2 hours. As a result, a hydride of liquid polyisoprene containing hydroxyl groups was obtained. The number average molecular weight of this product is 2250, and the hydroxyl group content is 0.
95me Q/9, viscosity was 731 poise/30°C, and bromine number was 89/1009. The average number of hydroxyl groups per molecule at this time was 2.18.

The halogen content was determined using a mixed indicator of diphenylcarbazone and bromophenol blue.
(NOx) *Mercury titration method for quantifying halogen with standard solution [Ken Ogino; Analytical Chemistry, 5.428 (1956)]
was used.

The amount of halogenated unsaturated double bonds in the sample was calculated from the obtained halogen content.

Examples 3 to 5, Comparative Examples 1 to 3 <Production example of cured product> Among the liquid polymer compositions shown in Table 1, the components excluding the polyisocyanate compound were blended, mixed and stirred at 60 ° C. for 2 hours, A polyisocyanate compound was added to this in the proportion shown in Table 1, and the mixture was mixed and stirred at 60° C. for 2 minutes to obtain a liquid polymer composition.

This composition was poured onto a 300x150x2s+m mold, pressed at 100°C for 2 hours, and then post-cured at 60°C for 15 hours to obtain a cured product.

Table 1 shows the evaluation results using this cured product.

As evaluation items for the cured product, heat resistance and weather resistance were evaluated by the following tests.

(1) Heat resistance test The obtained cured product was heated in a gear type oven at 130°C for 3 days. The physical properties after heating are JISK-
Measured in accordance with 6301.

(2) Weather resistance test The obtained cured product was continuously tested under the following conditions using a xenon sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.). The physical properties after the test were measured in accordance with JISK-6301.

Black panel temperature: 60℃ Humidity: 60% Cycle: 120 minutes of irradiation, 18 minutes of rain test time: 2
000 hours (hereinafter referred to as blank space) [Effects of the Invention] According to the present invention, a liquid diene system that can provide a cured product that has excellent heat resistance and weather resistance, and also has good other properties such as mechanical properties and water resistance. Polymer hydrides and liquid polymer compositions containing the same are provided.

For this reason, electrical insulation materials, elastic materials, coating materials, lining materials, paints, adhesives, inks, waterproof materials,
It is useful as a material that can be used in an extremely wide range of applications, such as encapsulants, retaining lumber, and vibration-proofing materials, and it will greatly contribute to the fields of electrical and electronic machinery parts manufacturing, civil engineering and construction, architecture, and building materials. be.

Patent applicant: Idemitsu Petrochemical Co., Ltd. ≧g

Claims (1)

[Scope of Claims] 1. A hydride of a halogenated active hydrogen group-containing liquid diene polymer. 2 Halogenation rate is 5-80%, hydrogenation rate is 5-95%
A hydride of the polymer according to claim 1. 3. A liquid polymer composition comprising a hydride of the polymer according to claim 1 and a polyisocyanate compound.