JPS6327521A - Liquid polymer composition - Google Patents

Abstract

PURPOSE:A liquid polymer composition, containing a specific liquid polymer, polyol compound and polyamine compound, having improved heat aging and weather resistance as well as electrical characteristic, etc., and suitable for coating materials, adhesives, etc. CONSTITUTION:A liquid polymer composition obtained by blending 100pts.wt. liquid polymer having linked structural units expressed by formulas I and II in 0.01-0.99mol fraction and terminal groups expressed by formula III (R is alkyl, aryl or aralkyl having >=1 isocyanate groups) at both terminals of the polymer and 400-25,000 number-average molecular weight, preferably hydrogenated liquid polyisoprene having isocyanate groups at the terminals with preferably 5-1,000pts.wt. polyol compound, e.g. hydroxyl group-containing butadiene homopolymer, etc., and/or polyamine compound, e.g. hexamethylenediamine, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel liquid polymer compositions.

More specifically, the present invention can be applied to, for example, paints, adhesives,
The present invention relates to a liquid polymer composition suitable for waterproofing agents, electrical insulation materials, sealants, elastomers, etc., and capable of providing an elastic cured product with particularly excellent heat aging resistance.

[Conventional technology]

Conventionally, a composition of a liquid polybutadiene and a polyisocyanate compound having a hydroxyl group at the end of the molecular chain or inside the molecular chain has been known as a liquid polymer composition that provides an elastic cured product. It is used in adhesives, sealants, coating materials, electrical insulation materials, etc.

However, although the elastic cured product obtained from this composition has good electrical properties, it has the disadvantage of poor heat aging resistance and weather resistance. In order to improve such drawbacks, liquid polymer compositions using hydrogenated liquid polybutadiene having a hydroxyl group at the end of the molecular chain or inside the molecular chain are also known.

However, this hydride becomes solid when its precursor, hydroxyl group-containing polybutadiene, has a large number of 1,4-addition type skeletons, and when it has a large number of 1,2-addition type skeletons, However, it has the disadvantage that it cannot provide a cured product with excellent heat aging resistance.

[Problem that the invention seeks to solve]

The purpose of the present invention is to provide a liquid polymer composition that can provide an elastic body with particularly excellent heat aging resistance and can be suitably used in paints, adhesives, waterproofing agents, sealants, coating materials, electrical insulation materials, etc. It is something to do.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have discovered that the molecular chain has an alkyl group, an aryl group, or an aralkyl group having at least one isocyanate group at both ends of the molecular chain via a urethane bond. We discovered that a composition containing a novel liquid polymer with a specific structure and a polyol compound or a polyamine compound is suitable for that purpose.
Based on this knowledge, we have completed the present invention.

That is, the present invention provides (A) a polymer having a number average molecular weight of 4 having a terminal group represented by the following general formula m at both ends of a polymer consisting of a structural unit and a composition represented by the following general formula I,
The present invention provides a liquid polymer composition comprising a liquid polymer having a molecular weight of 0 to 25,000 and (B) a polyol compound and/or a polyamine compound.

71%3-4-Ctl t -CII-)-1-G-C1f
t -CHz-)-n R-HNCO-III (However, the molar fractions of units I and ■ are respectively 0.01-
0.99, in which R is an alkyl group, an aryl group, or an aralkyl group having at least one isocyanate group).The present invention will now be described in detail.

The liquid polymer used as component (A) in the composition of the present invention is a polymer having the above structure, and has an alkyl group having at least one incyanate group at both ends of the molecular chain via a urethane bond. group, aryl group or aralkyl group.

In this polymer, propylene equivalent units IL -G-CI, -CH→ and ethylene equivalent units ■+CHz-
They may be bonded alternately or randomly, or may be bonded to each other to form blocks.

Furthermore, the sum of the repeating number of propylene equivalent units and the repeating number of ethylene equivalent units is 2 to 500, preferably 1.
ranges from 0 to 400, and its mole fraction is 0.01N0
．． It is 09.

Among these liquid polymers, the liquid remaining isoprene hydride, which has an isocyanate group at the end of the molecular chain, has a form in which propylene equivalent units and ethylene equivalent units are bonded alternately.
For example, it can be represented by the general formula % (in which R and n have the same meanings as above), which is preferred because it can be easily produced using isoprene as a raw material.

In this polymer, the repeating number n of isoprene units is selected in the range of 2 to 500, preferably 10 to 400. The liquid polymer represented by the general formula (rV) can be obtained by reacting a polyisocyanate compound with a hydrogenated liquid polyisoprene having a hydroxyl group at the end of the molecular chain.
It can be easily manufactured.

Liquid polyisoprene having a hydroxyl group at the end of its molecular chain can be obtained by polymerizing isoprene in the presence of hydrogen peroxide. In this reaction, hydrogen peroxide is usually 0.5 to 20 parts by weight per 100 parts by weight of isoprene.
It is preferably used in an amount of 1 to 50 parts by weight. Also,
Although a reaction solvent is not necessarily required, the reaction is usually carried out in a solvent.

Examples of this solvent include aliphatic and alicyclic solvents such as n-hexane, n-hebutane, cyclohexane, cycloheptane, benzene, toluene, xylene and ethylbenzene
Aromatic hydrocarbons, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, 1so-propyl alcohol, n-butyl alcohol, 1so-butyl alcohol, 5ec-butyl alcohol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Examples include esters such as methyl acetate, ethyl acetate, butyl acetate, and cellosolve acetate, and ethers such as diisopropyl ether, dioxane, and tetrahydrofuran.

There is no particular restriction on the reaction temperature, but it is usually 20 to 3
00°C, preferably in the range of 30 to 200°C.

Further, the reaction may be carried out under normal pressure or under increased pressure, but when the reaction is carried out under increased pressure,
0 kg/cj-G or less, preferably 50 kg/ad-G
The following pressures are desirable:

Further, the reaction time depends on the reaction temperature and reaction pressure, but is generally selected within the range of -100 hours, preferably from 1 to 50 hours.

After carrying out the polymerization reaction in this manner, the reaction-completed liquid is washed with water, and then the solvent, monomer, and low-boiling seafood are distilled off under reduced pressure to obtain liquid polyisoprene having a hydroxyl group at the end of the molecular chain. .

The number average molecular weight of this material is desirably in the range of 300 to 25,000, preferably 500-toooo, and the hydroxyl group content is such that the OH number is 0.1 to 10.
meq/g, preferably 0.3~? m eq / H
It is desirable that it be within the range of .

Next, the liquid polyisoprene having a hydroxyl group at the end of its molecular chain is hydrogenated. In this hydrogenation reaction, although a solvent is not necessarily required, the reaction is usually carried out in a solvent. As the solvent, the solvents mentioned in the above polymerization reaction can be used. As the hydrogenation catalyst, catalysts commonly used in hydrogenation reactions, such as nickel-based, palladium-based, ruthenium-based, platinum-based catalysts, are used. These catalysts may be used alone or in combination of two or more, or may be supported on a carrier such as activated carbon.

There is no particular restriction on the temperature of the hydrogenation reaction, but it is usually 2
The temperature is selected within the range of 0 to 300°C, preferably 30 to 200°C. Further, the reaction may be carried out under normal pressure or under increased pressure, but when the reaction is carried out under increased pressure, the reaction rate is 200 kg/cj-G or less, preferably 100 kg/cj-G.
The reaction time is preferably the pressure below ad-G, the reaction temperature,
Although it depends on the reaction pressure, the type of catalyst, etc., it is generally selected in the range of 0.001 to 100 hours, preferably 1 to 50 hours.

After the hydrogenation reaction completed liquid is separated from the catalyst, the solvent is distilled off under reduced pressure to obtain a hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain. The number average molecular weight of this product is 300 to 25,000, preferably SOO to 1
It is desirable that the hydroxyl group content is in the range of 0.0000 and the OH value is 0.1 to 10. Preferably 0.
3~? It is desirable that m e be in the range of 47 g.

By reacting the thus obtained hydrogenated liquid polyisoprene having a hydroxyl group at the end of the molecular chain with a polyisocyanate compound, a liquid polymer represented by the general formula (IV) can be obtained.

This polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and has an isocyanate group reactive with the hydroxyl group of the hydride of the hydroxyl group-containing liquid polyisoprene. Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI): liquid modified diphenylmethane diisocyanate, polymethylene poly Phenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2゜4-diisocyanate, addition reaction product of polypropylene glycol and tolylene diisocyanate, etc., especially MDI, liquid Modified diphenylmethane diisocyanate, tolylene diisocyanate, and the like are preferred.

There is no particular restriction on the ratio of the polyisocyanate compound to the hydride, but usually the hydroxyl group (
The molar ratio of isocyanate groups (NGO) to OH) of the polyisocyanate compound is 1.5 to 20. It is desirable to use both in a ratio of preferably 1.8 to 15.

This reaction may be carried out in the absence of a solvent or in a solvent. As the solvent, those mentioned in the case of the polymerization reaction can be used. There is no particular restriction on the reaction temperature, but it is usually selected in the range of 0 to 200°C, preferably 15 to 150°C. In addition, the reaction may be carried out under normal pressure or under increased pressure, but
When the reaction is carried out under pressure, 100 kg/c[a-
A pressure of less than G, preferably less than 50 kg/cd-G is desirable.

The reaction time depends on the reaction temperature and the like, but is generally selected in the range of 0.1 to 100 hours, preferably 1 to 50 hours.

After carrying out the reaction in this manner, the remaining polyisocyanate compound in the reaction-completed liquid is distilled off under reduced pressure to obtain a liquid polymer represented by the general formula (rV). The number average molecular weight of this material is desirably in the range of 400 to 26,000, preferably 500 to 10,000, and the content of isocyanate groups is in the range of 0.1 to 20% by weight, preferably 0.5 to 15% by weight. It is desirable that the In the composition of the present invention, if desired, the residual polyisocyanate compound may be used as the component (A) without performing an operation of distilling off the residual polyisocyanate compound.

In addition, the liquid polymer (■) obtained from isoprene has
In the polymer, 1. A small amount of structural units resulting from dipolymerization or 3,4 polymerization may be included.

The liquid polymer having a main chain consisting of propylene-equivalent units and ethylene-equivalent units of the present invention is not only produced from isoprene but also, for example, by copolymerizing ethylene and propylene in the presence of an azo compound containing a hydroxyl group. It can also be obtained by reacting the obtained Seikyo Seishin 5 polyisocyanate compound.

In the composition of the present invention, a polyol compound and/or a polyamine compound is used as component (B). As the polyol compound, a hydroxyl group-containing liquid diene polymer can be used. This hydroxyl group-containing diene polymer has a hydroxyl group within the molecular chain or at the end of the molecular chain, and preferably has a number average molecular weight of 300 to 25,000;
More preferably, a liquid diene polymer having a molecular weight of 500 to 10,000 is used. There is no particular restriction on the content of hydroxyl groups in this polymer, but the OH value is usually 0.1 to 1 Q
meq/g, preferably 0.3-7 me
q in the range of 7g is used.

Examples of the liquid diene polymer include diene polymers and diene copolymers containing hydroxyl groups and having 4 to 12 carbon atoms, and furthermore, combinations of these diene monomers and α-olefinic addition-polymerizable monomers having 2 to 22 carbon atoms. Examples include copolymers of Specifically, butadiene homopolymers containing hydroxyl groups, isoprene homopolymers, butadiene-styrene cobo-rimers, butadiene-isoprene copolymers,
Examples include butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, and the like. These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in the presence of hydrogen peroxide in a liquid reaction medium.

Further, hydrogenated products of these hydroxyl group-containing diene polymers can also be used.

Furthermore, as other polyol compounds, any of -class polyols, secondary polyols, and tertiary polyols may be used. Specifically, for example, 1.2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1.3-butanediol, 2.3-butanediol, 1.2-bentanediol, 2,3-bentanediol. , 2゜5-hexanediol, 2.4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N,N-bis-2-hydroxypropylaniline, N,N'bishydroxyisopropyl -2-methylpiperazine, bisphenol A
low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon, such as propylene oxide adducts.

Furthermore, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1.5-bentanediol, 1.6-hexanediol, etc. that do not contain a hydroxyl group bonded to a secondary carbon can also be used as the polyol. However, it is also possible to use relatively high amounts of polyol compounds such as polypropylene glycol, polyoxytetramethylene glycol, polyethylene glycol, and polycaprolactone glycol. Diols are usually preferably used as the polyol compound, but triols and tetraols may also be used, and those having a molecular weight in the range of 50 to 50,000 are preferred.

On the other hand, as the polyamine compound, any of diamine, triamine, and tetramine may be used, and any of -class polyamine, secondary polyamine, and tertiary polyamine may also be used. Specific examples of this polyamine compound include aliphatic amines such as hexamethylene diamine,
3. Alicyclic amines such as 3'-dimethyl-4,4'-diaminodicyclohexylmethane, aromas such as 4,4'-diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodiphenylmethane, etc. and triamines such as 2,4°6-tri(dimethylaminomethyl)phenol. In the composition of the present invention, the polyol compound and/or polyamine compound as the component (B) is preferably 1 to 1,500 parts by weight, more preferably 5 to 1,000 parts by weight, relative to 100 parts by weight of the liquid polymer as the component (A). It is blended in the proportion of If this blending ratio deviates from the above range, the composition will be difficult to cure.

The composition of the present invention may contain various additives as desired. Examples of additives that may be added as desired include mica, graphite, vermiculite, calcium carbonate,
Fillers such as slate powder may be mentioned.

Furthermore, plasticizers such as dioctyl phthalate are added as viscosity modifiers, extender oils such as aromatic, naphthenic, and paraffinic oils are added, and alkylphenol resins, terpene resins, and terpenephenol resins are used to adjust adhesive strength and adhesive strength. Tackifying resins such as resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic and aromatic petroleum resins can also be added. Further, curing accelerators such as dibutyltin dilaurate, stannous octoate, and polyethylene diamine can also be added. Furthermore, an anti-aging agent may be added to improve weather resistance, and a silicon compound or the like may be added as an antifoaming agent.

The composition of the present invention can be prepared by mixing the liquid polymer of component (A), the polyol compound and/or polyamine compound of component (B), and various optional additives, and thoroughly stirring the mixture.

The liquid polymer composition of the present invention prepared in this manner provides an elastic cured body having excellent heat aging resistance, weather resistance, electrical properties, etc. by curing treatment.

There are no particular restrictions on the conditions for the curing process, but the curing process is usually carried out by heating at a temperature of 0 to 120°C, preferably 15 to 70°C, for 0.5 to 75 hours, preferably 1 to 72 hours. be done.

The liquid polymer composition of the present invention can be used in a wide range of applications, such as paints, adhesives, sealants, coating materials, and various electrical insulating materials and elastomers, because it provides a cured elastic body with excellent properties when cured. Used for various purposes.

〔Example〕

Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples in any way.

Production Example 1 Isoprene 200 was added to 11 stainless steel pressure-resistant reaction vessels.
g, 16 g of a 50% by weight aqueous hydrogen peroxide solution, and 100 g of n-butyl alcohol were added, and a polymerization reaction was carried out at 120°C and a maximum pressure of 3 kg/cJ -Q- for 2 hours.

After the reaction was completed, the reaction solution was taken out, shaken with 600 g of water in a separatory funnel, and left to stand for 3 hours to separate the oil layer. This oil layer was heated to 100℃ under a reduced pressure of 2m*Hg.
The solvent, unreacted monomers and low-boiling components were distilled off, and liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained in a yield of 68 overlapping parts. The number average molecular weight of this product is 2150, and the OH value is 0.96 m eq /
g, and the viscosity was 56 poise/30°C.

Next, 100 g of the thus obtained liquid polyisoprene having a hydroxyl group at the end of the molecular chain, 10 g of cyclohexane
0g and 10g of 5wt% Ru-C catalyst were placed in a pressure-resistant reaction vessel made of 11 stainless steel, and hydrogen was added at 50kg/cIll.
4 at 140°C while maintaining the pressure of -G.
．． The hydrogenation reaction was carried out for 5 hours.

After the hydrogenation reaction was completed, the reaction solution was taken out and the catalyst therein was separated using a 0.45μ membrane filter, and the filtrate was treated for 2 hours at a vacuum of 2mm, 11g, and a temperature of 110°C. When the solvent was distilled off, hydride 1 of liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained.
01g was obtained. The number average molecular weight of this product is 2210
, OH value is 0.94 m eq / g, iodine value is 1
Hereinafter, the viscosity was 383 poise/30°C.

Next, 50 g of the above hydride and 1 tolylene diisocyanate (TD+) were placed in a 300 ml separable flask.
Add 5.8g and heat at 25°C for 2 hours and at 70°C for 4 hours.
The reaction was carried out under normal pressure. The reaction solution was 2 mm and 1 g under reduced pressure.
Treatment was carried out at 110° C. for 4 hours to distill off residual tolylene diisocyanate, yielding 58.2 g of a hydrogenated liquid polyisoprene having an isocyanate group at the end of the molecular chain. The number average molecular weight of this product is 2610, and the NGO content is 3.
45% by weight (theoretical value 3.39% by weight), viscosity is 1850
Poise/30°C.

Production Example 2 In Production Example 1, after reacting the hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain with TDI,
The reaction product was used as is without any work-up.

The NGO content in the reaction product was 8.93% by weight, and the viscosity was 573 poise/30°C.

Production Example 3 100 g of 1,4-addition type liquid polybutadiene having a hydroxyl group at the end of the molecular chain, 100 g of cyclohexane, and 10 g of 5 wt% Ru-C catalyst were placed in a pressure-resistant reaction vessel No. 11.
A hydrogenation reaction was carried out at 140° C. for 4.5 hours while introducing hydrogen to maintain a pressure of 50 kg/cJ −G.

After the hydrogenation reaction was completed, the reaction solution was taken out, 500ml of toluene was added thereto, and the catalyst was separated using a 0.45μ membrane filter.
When treatment was carried out for 2 hours at a temperature of 110° C. and the solvent was distilled off, 96 g of a wax-like solid was obtained. The number average molecular weight of this product is 2920, and the OH value is 0.
It was 80 m eq/g.

In addition, 1, 4 which has a hydroxyl group at the end of the molecular chain used as a raw material
- Addition type liquid polybutadiene is manufactured by Idemitsu Arco ■, R-
45HT, number average molecular weight 2800.08 valence 0.82
m eq , / g, viscosity 50 poise/30°C, 1.
4-content is 80 mol%, 1.2-content is 20 mol%.

Production Example 4 A 1,2-addition liquid polybutadiene having hydroxyl groups inside the molecular chain (not all at the ends) was hydrogenated and post-treated in the same manner as in Production Example 1 to produce a highly viscous liquid hydride. Obtained. The number average molecular weight of this product is 2080. The OH value was 0.84 m eq / g, and the viscosity could not be measured at 30°C with a B-type viscometer.

Note that l has a hydroxyl group inside the molecular chain of the raw material.

2-addition type liquid polybutadiene is manufactured by Nippon Soda ■, Nf
SSOPB G-2000, number average molecular weight 2000
．． 08 value 0.85 m eq / g, viscosity 193
0 poise/30°C, 1,2-content 90 mol%, 1.4
- content of 10 mol%.

Examples 1 to 5, Comparative Example 1.2 The ingredients shown in the attached table were placed in a container with the indicated amount and stirred at 25°C for 2 minutes to prepare a composition.
The material was press hardened at 70° C. for 1 hour, and then cured at 70° C. for 15 hours to obtain a cured product. The physical properties of this cured product are shown in the table below.

(The following is a blank space) [Effects of the Invention] The liquid polymer composition of the present invention has a specific structure having an alkyl group, an aryl group, or an aralkyl group having at least one isocyanate group at both ends of the molecular chain via a urethane bond. It contains a liquid polymer and a polyol compound or a polyamine compound, and by curing treatment,
It can provide an elastic cured product with excellent heat aging resistance, weather resistance, electrical properties, etc., and can be used for example in paints, adhesives, waterproofing agents, etc.
Suitable for use in sealants, coating materials, various electrical insulation materials, elastomers, etc.

Claims (1)

[Claims] 1. (A) The following general formula III is added to both ends of a polymer consisting of structural units and compositions represented by the following general formulas I and II.
A number average molecular weight of 400 to 250 with a terminal group represented by
00 liquid polymer, (B) polyol compound and/
or a liquid polymer composition containing a polyamine compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ II ▲There are mathematical formulas, chemical formulas, tables, etc.▼ III (However, the mole fractions of units I and II are each 0.01
~0.99, and R in the formula is an alkyl group, aryl group, or aralkyl group having at least one isocyanate group) 2. The liquid polymer is a liquid polyisoprene having an isocyanate group at the end of the molecular chain. The liquid polymer composition according to claim 1, which is a hydride of.