JPH03220206A - Liquid hydrogenated telechelic nitrile rubber and its production - Google Patents

Abstract

PURPOSE:To obtain a liquid hydrogenated telechelic nitrile rubber desirable for the synthesis of a useful block polymer by hydrogenating a liquid telechelic nitrile rubber under mild conditions in the presence of a specified rhodium complex catalyst so that only the olefinically unsaturated double bonds may be selectively hydrogenated and the functional groups may remain substantially unhydrogenated. CONSTITUTION:A liquid telechelic rubber comprising 6-450 repeating units of a conjugated diene and 3-225 repeating units of formula I (wherein R'1 is hydrogen or methyl) and has a substituent containing a functional group such as -OH, -SH, -N=C=O, a group of formula II or a group of formula III on each end is hydrogenated at 20-130 deg.C under a hydrogen pressure of 1-30 kg/cm<2> in the presence of a tris(triphenylphosphine)rhodium (I) halide as a catalyst in a polar solvent or an aromatic hydrocarbon solvent so that at least 90% of the olefinically unsaturated double bonds of the conjugated diene part may be hydrogenated and at least 80% of the cyano groups and the terminal functional groups may remain unhydrogenated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new telekeric liquid hydrogenated nitrile rubber and a method for producing the same.

More specifically, a new liquid hydrogenated nitrile rubber that has reactive functional groups at both ends and a liquid nitrile rubber that has reactive functional groups at both ends are used as raw materials, and a specific rhodium complex catalyst is used to produce a mild rubber. This invention relates to a method for producing novel telekeric liquid hydrogenated nitrile rubbers under conditions in which substantially no functional groups are hydrogenated and only olefinically unsaturated double bonds are selectively hydrogenated.

[Prior Art] Various methods have been proposed for producing hydrogenated nitrile rubber by hydrogenating nitrile rubber (butadiene-acrylonitrile copolymer), and the polymer has properties such as heat resistance, oil resistance, sour gasoline resistance, and weather resistance. It is known to have excellent properties.

For example, a known method is to selectively hydrogenate the carbon-carbon unsaturated bonds of nitrile rubber while retaining the cyano groups using a homogeneous catalyst, tris-(triphenylphosphine) rhodium halide (I). Method (Unexamined Japanese Patent Publication No. 6
0-60106), a method of selectively hydrogenating with a rhodium hydride complex (Japanese Patent Application Laid-Open No. 115303/1982),
A method of selective hydrogenation using a ruthenium complex (Vf Patent Application No. 62-42937, JP-A No. 62-181304,
JP-A-64-45403, JP-A-64-45404), etc. are known. In addition, a method using supported noble metals as a heterogeneous catalyst (Japanese Patent Publication No. 35641/1983, Japanese Patent Publication No. 63-35641,
3-35642, Japanese Patent Publication No. 62-82803), etc. are also known.

On the other hand, liquid rubber having functional groups at both ends (telekeric) has recently been used as a polymer for synthesizing multicomponent/multiphase polymers with clear structures (branched polymers, network polymers, block graft polymers, etc.). It is attracting attention as a building block.

Telekerik liquid nitrile rubber is already commercially available.
It has applications as a structural adhesive, resin modifier, and rocket fuel binder, but its range of use is limited.

On the other hand, liquid hydrogenated nitrile rubber has not been known until now, although it may be useful as a soft segment of a new block polymer or as a composition.

Therefore, the present inventors previously invented a method for producing liquid hydrogenated nitrile rubber having carboxyl groups at both ends by hydrogenating liquid nitrile rubber having carboxyl groups at both ends using a specific dihydrorodium compound under specific conditions. An application was filed (Japanese Patent Application No. 118143-1983).

The present invention is a further improvement on this and provides a telechelic liquid hydrogenated nitrile rubber having not only carboxyl groups at both terminals but also other functional groups and a method for producing the same.

[Problem to be solved by the invention]

As is well known, liquid nitrile rubber that has various functional groups at both ends is expected to have oil-resistant properties because it has cyano groups, and various compositions can be created by tli extension and crosslinking reactions using the functional groups at both ends. It can also be applied to soft segments of block polymers with special properties by condensation with other polymers.

However, these liquid nitrile rubbers have olefinic unsaturated double bonds, so they themselves have the disadvantage of poor heat resistance and weather resistance, so it is virtually impossible to meet the conditions in the composition or in blocking by condensation reaction. There was a problem that the method of synthesis was limited. The present invention overcomes the above-mentioned problems by selectively hydrogenating olefinic unsaturated bonds and obtains a telechelic liquid hydrogenated nitrile rubber that substantially retains cyano groups and terminal functional groups, and has completely new properties. The object of the present invention is to make it possible to use the block polymer in soft segments and compositions having the following properties.

[Means to solve the problem]

As a result of research to solve the above problems, the present inventors used tris(triphenylphosphine) rhodium(I) halide as a catalyst in a polar solvent or an aromatic hydrocarbon solvent, and found that By conducting a hydrogenation reaction under the conditions, only the olefinically unsaturated double bonds of the conjugated diene part of telekeric liquid nitrile rubber having a specific structure are selectively hydrogenated, and the cyano group and both terminal functional groups are hydrogenated. We found a way to minimize this and completed the present invention.

That is, the present invention is based on the general formula (I> 1 -(-CH2-CI-f-CH2-CH2-+...(
6 to 450 repeating units represented by I> (wherein R represents hydrogen and/or a C1 to C4 alkyl group)
and general formula (II), and the number of olefinically unsaturated double bonds in the molecule is 0 to 20 per molecule, and both ends of each molecule have a substituent represented by the following general formula (A) formula. A telekeric liquid hydrogenated nitrile rubber (hereinafter referred to as the first invention) comprising:

(In the formula, R2 represents hydrogen or methyl group) consisting of 3 to 225 repeating units, furkyl,
R4R5 is hydrogen or C
1 to C8 alkyl, alkylene, phenyl, or aryl; Z is a C1 to C15 fullylene, phenylene, or alkyl-substituted phenylene; R is C1 to C15;
8 alkyl, fullkylene, phenyl, 7 aryl groups, each group alkylene, phenyl, aryl, R1 is hydrogen or C1 to C8 alkyl, fullkylene, phenyl,
Each represents a multiple of 7 reels.

n = Q to 8) and 6 to 450 conjugated diene repeating units and a repeating group represented by the formula (III) 1 -(-CH2-C+ (III> N (wherein R1' represents hydrogen or a methyl group) A telekeric liquid rubber consisting of 3 to 225 units and having a substituent containing a functional group represented by the following formula (B) at both ends of the molecule is placed in a polar solvent or an aromatic hydrocarbon solvent and treated with tris-( as a catalyst). Using rhodium (I) halide (triphenylphosphine), temperature 20-130℃, hydrogen pressure 1-30Kg/CI
A telekeric liquid hydrogen characterized by hydrogenating at least 90% or more of the olefinically unsaturated double bonds in the conjugated diene moiety in i, and making the retention rate of the cyano group and the functional groups at both ends 80% or more. The present invention provides a method for producing nitrile rubber (hereinafter referred to as the second invention).

(B) Formula %Formula % Rl is hydrogen or C1 (However, R2'-R34 to C8 represents an alkyl, alkylene, phenyl, or 7-aryl group.) The functional group of the telekeric liquid nitrile rubber used in the second invention is ( B) water II group, carboxyl group, as shown in the formula
#l Anhydride group, epoxy group, isocyanate group (substituted)
These are an amino group, a piperidyl group, and an ester group.

Note that among the substituents containing formula (B), the preferred substituent represented by formula (A) is selected in the first invention, and the two formulas are not completely different.

The telekeric liquid hydrogenated nitrile rubber of the first invention has two types of repeating units, namely the general formula (I) (wherein R1 represents hydrogen and/or a C4-C4 furkyl group).
and general formula (II) 2 (wherein R2 represents hydrogen or a methyl group), and has a functional group represented by formula (A) at both ends of the molecule. The number of the above repeating units in the telekerik liquid hydrogenated nitrile rubber is 6 to 450 repeating units of formula (I>, especially 10
The number of repeating units of formula CIH is preferably 3 to 225, particularly preferably 3 to 100. Roughly,
The number of olefinically unsaturated double bonds in the molecule is 0 to 20, particularly preferably 0 to 5. That is, if the number exceeds 20, depending on the molecular weight, heat resistance and weather resistance deteriorate, which is not preferable. Note that this copolymer is usually a random copolymer.

Both terminal functional groups in the above-mentioned telekeric liquid hydrogenated nitrile rubber are represented by the formula (^).

U / (However, A) R3 in the formula is hydrogen or 01 to C8 alkyl,
R4゜R5 is hydrogen or C-C alkyl, alky8lene, phenyl, aryl, or 2 is 01-C
15 fullkylene, phenylene, alkyl-substituted phenylene group, R is 01 to C8 alkyl, fullkylene,
Each of phenyl and aryl groups represents a polygroup of alkylene, phenyl, and aryl. R7 represents hydrogen or a polygroup of 01 to C8 alkyl, alkylene, phenyl, and aryl, respectively.

n=Q~8) It is sufficient that these functional groups are mainly attached to both ends of the molecule, and the remainder may or may not be attached in the middle.

Further, these may be obtained by hydrogenating the raw material telekeric liquid nitrile rubber, or may be obtained by converting it into other substituents in a post-reaction after hydrogenation.

The telekeric liquid hydrogenated nitrile rubber of the present invention is a block polymer (block polymer) which has excellent heat resistance, weather resistance, oil resistance, gasoline resistance, chemical resistance, etc., by using existing reactions such as dehydration reaction and condensation reaction with other suitable polymers or monomers. It can be used in soft segments of diblocks, triblocks, multiblocks, etc., or as a highly functional curing agent in compositions.

Although the liquid hydrogenated nitrile rubber for the first injection can be produced by various methods, it can be produced particularly efficiently by the second invention as shown below.

That is, the second invention has a conjugated diene repeating unit and (meta)
A liquid rubber consisting of acrylonitrile repeating units and having a substituent having a functional group represented by the formula (B) at both ends of the molecule is placed in a polar solvent or an aromatic hydrocarbon solvent, and tris-(triphenylphosphine) halogen is used as a catalyst. This is a method for producing the telekeric liquid hydrogenated nitrile rubber of the first invention, by carrying out a hydrogenation reaction using rhodium chloride (I) at a specific temperature and hydrogen pressure.

Here, the raw material liquid nitrile rubber having a substituent having a functional group represented by formula (B) at both ends is different from the liquid hydrogenated nitrile rubber of the first invention to be produced and the substituents at both ends of the molecule. They may be the same or different. That is, in the method of the second invention, since the functional groups of formula (B) are not substantially hydrogenated, these functional groups may be introduced in advance before hydrogenation, or the functional groups of formula (B) may be introduced in advance. After hydrogenating the liquid nitrile rubber having a specific functional group according to the second invention, reacting the retained functional group with a compound having another functional group represented by formula (B) as a post-reaction, There is no problem even if a different functional group is introduced.

The telekeric liquid nitrile rubber used as a raw material has the same structure (type, number and arrangement order of repeating units, etc.) as the liquid hydrogenated nitrile rubber of the first invention to be produced. Specifically, 6 to 450 conjugated diene repeating units,
In particular, 10 to 200 repeating units are preferred, and 3 to 225 (meth)acrylonitrile repeating units are particularly preferred, particularly 3 to 100 repeating units. These copolymers are usually random copolymers.

In addition, the formula (
The liquid nitrile rubber having a substituent having a functional group represented by B) may have the same or different substituents bonded to both terminal positions of the molecule (or to other positions).

-The number of functional groups in the molecule that are the same as both ends is 1.5~
2.5L, preferably 1.8 to 2.2 pieces.

Even if the number of functional groups is greater or less than this range, it is possible to retain the functional groups and selectively hydrogenate only olefinically unsaturated double bonds by the method of the second invention, but it is possible to selectively hydrogenate only olefinically unsaturated double bonds. This is disadvantageous because it is difficult to carry out the reaction uniformly when forming a block of liquid hydrogenated nitrile rubber by condensation or the like or when compounding it with other resins to obtain a composition. Particularly when forming blocks, those in this range have an increased molecular weight and exhibit thermoplasticity.

A known method is used to introduce functional groups to both ends of the raw material.

The most typical method uses an azobis-based radical initiator with functional groups at both ends, and polymerizes a conjugated diene and (meth)acrylonitrile in a solvent that has a low chain transfer constant and dissolves the initiator. be.

That is, by appropriately determining the polymerization conditions, disproportionation of propagating radicals and chain transfer can be minimized, and by prioritizing recombination of terminal radicals of conjugated diene or (meth)crylonitrile, initiator residues can be left at both ends. Insert a functional group.

Examples of such initiators include the following.

2.2°-azobis[2-methyl-N-(2-hydroxyethyl)-propioamide, 2.2′-azobis[2
-Methyl=N-(2-hydroxy10-pyl)-propioamide, 2,2'-azobis[2-(hydroxyethyl)propionitrile), 2,2'-azobis[2-(
hydroxyethyl)propionitrile), 2.2'-
Azobis[2-(hydroxypropyl)propionitrile), 2.2'-Azohis[2-(hydroxybutyl)propionitrile), 5.5'-Azobis[5-cyano-2-hexanol], 2.2 '-Azobis [4-
(Hydroxybutyl)isobutyrate), 2,2°-
Azobis(3-(hydroxybutyl)isobutyrate)
, 2.2'-azobis[2~(hydroxy70 pill)
isobutyrate], 2.2°-azobis[2-(hydroxyethyl)isobutyrate], hydrogen peroxide solution, etc. (thereby, hydroxyl groups can be introduced at both ends. If necessary, a chain transfer agent having a hydroxyl group) may coexist.

Also, 4,4°-7zodos(4-cyanopentanoic acid), 3
．． By using an azobis-based initiator such as 3'-azobis (3-cyanobutanoic acid), 5,5° azobis (5-cyanohexanoic acid), 4,4°-azobis (4-cyano-2-hexanoic acid), etc. Carboxylic acids can be introduced at both ends. In particular, it is preferable to use 4,4°-azobis(4-cyanopentanoic acid) in a tertiary alcohol as an initiator (Japanese Patent Publication No. 43-28474, JP-A-56-133305).

2.2°-azobis(N-(4-aminophenyl)2-
Methylpropioamidine cotetrahydrochloride, 2
．． 2'-azobis(2-methylpropioamidine) and hydrochloride, 2,2'-azobis(2-methylpropioamido) cybide, etc., with amino groups at both ends,
An amide group can be introduced.

Roughly dimethyl 2,2'-azobis(2-methyl 10bionate), diethyl 2,2'-azobis(2-methylpropionate), dimethyl 3,3'-azobis(3-
methylbutyrate), diethyl 3,3゛-azobis(3
-methyl 1 thilate) etc. to introduce ester groups at both ends.

It is also possible to convert these terminal functional groups into other functional groups by a rapid reaction. For example, hydroxyl groups may be introduced at both ends by reacting ethanolamine or propatoolamine with C0OH at both ends of a liquid nitrile rubber having carboxyl groups at both ends in the presence of an alkali hydroxide.

The purpose of introducing acid anhydride groups at both ends can be achieved by reacting a liquid nitrile rubber containing hydroxyl groups at both ends with anhydrous trimellitic acid chloride at a low temperature.

Furthermore, by reacting a liquid nitrile rubber having carboxyl groups at both ends with a diamine such as ethylenediamine or hexamethylene diamine in large excess, it is possible to introduce 7-mino groups at both ends. In order to introduce isocyanate groups at both ends, a liquid nitrile rubber having water IQ groups at both ends may be reacted with a diisocyanate such as hexamethylene diisocyanate or tolylene diisocyanate.

These methods may use any known means and are not limited to the above examples.

These telechelic liquid nitrile rubbers are mainly obtained by radical polymerization in solution, or derivatives thereof.

Note that the term "liquid" as used herein includes a liquid that is viscous at room temperature, becomes liquid at 1.00° C. or lower, and is flaky at room temperature.

Moreover, the weight average molecular weight of these telekeric liquid nitrile rubbers is 500 to 10,000. Especially 700-7.00
0 is preferred, and roughly 1,000 to 5,000 is preferred. If the molecular weight exceeds 10,000, the polymer will not be liquid and the concentration of end groups will decrease, so even if it is hydrogenated, the reactivity of subsequent reactions (for example, blocking) will be poor, which is not preferable. On the other hand, if the molecular weight is lower than 500, the viscosity becomes too low and handling is troublesome, and the physical properties of the polymer after hydrogenation cannot be expected, which is not preferable.

Conjugated dienes used in the production of such liquid nitrile rubber generally include 1,3-butadiene, isoprene, 1.
Examples include 3-pentadiene and 2,3-dimethylbutadiene. Two or more kinds of these may be copolymerized. In order for the hydrogenated liquid nitrile rubber to be industrially advantageously developed and to obtain good physical properties in the post-reaction, 1,3-butadiene,
Isoprene is preferred. Although the microstructure of the conjugated diene is not specifically defined, when butadiene is used in radical polymerization, the microstructure of the resulting polymer is approximately 20% 1,2-vinyl, approximately 20% cis, and approximately 60% trans. Therefore, when hydrogenated, the (meth)acrylonitrile content and molecular weight, etc. (therefore, it may not become liquid but flake-like. If it is necessary to maintain the liquid state, 1,3-butadiene and isoprene may be added depending on the conditions. It is desirable to increase the number of alkyl groups in the side chain by copolymerizing with.

Strictly speaking, the general formula <I> is a mixture of the following three types of structures.

1 -(-CH2-CI(-CH2-CH2+).

CH3 (However, R1 represents hydrogen and/or a C1 to C4 furkyl group.) On the other hand, examples of the nitrile group-containing vinyl monomer that can be copolymerized with a conjugated diene include acrylonitrile and meta-7-acrylonitrile. Also optionally alkyl (meta)
7 acrylate and a vinyl aromatic compound may be copolymerized.

Typical examples of these are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc., styrene, p-methylstyrene, α-methylstyrene, diphenylethylene, etc.

The number of these conjugated diene and nitrile group-containing vinyl monomer units may be within the ranges mentioned above, and the number may vary depending on the molecular weight, etc. Expressed in weight%, the conjugated diene units are in the range of 50 to 95% by weight, and the nitrile group-containing vinyl monomer units are in the range of 5 to 50% by weight. If the nitrile group-containing vinyl monomer unit is less than 5% by weight, oil resistance will be lost, which is not preferred. Moreover, if it exceeds 50% by weight, it becomes resinous, which is not preferable. 1 to 20% by weight of vinyl aromatic hydrocarbon or alkyl acrylate may be included instead of the conjugated diene or nitrile group-containing vinyl monomer. Preferably, the amount of conjugated diene units is 60 to 85% by weight, and the amount of nitrile group-containing monomer units is 15 to 40% by weight.

The hydrogenation method of the second invention includes dissolving the above-mentioned telechelic liquid nitrile rubber in a suitable polar solvent or aromatic hydrocarbon solvent, adding a catalyst, degassing, thoroughly purging with hydrogen, and raising the temperature to a predetermined temperature. , carried out by bubbling molecular hydrogen under stirring.

A method of selectively hydrogenating the olefinically unsaturated double bonds in the telekeric liquid nitrile rubber of the second invention and substantially not hydrogenating the cyano groups and functional groups (functional groups represented by formula (8)). The catalyst used is tris-(triphenylphosphine)rhodium (I>chloride (Wilki, n
5 on 1 body). This catalyst may be used alone or in combination with triphenylphosphine.

Any hydrogenation solvent can be used as long as it dissolves the polymer to be hydrogenated, but preferably a solvent that dissolves the catalyst under the reaction conditions is suitable.

Examples of organic solvents that can be used in the second invention include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, ketones, and esters of basic polar solvents. Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-hebutane, etc.; examples of alicyclic hydrocarbons include cyclopentane, methylcyclopentane, and cyclohexane; examples of aromatic hydrocarbons include Ethers include benzene, toluene, xylene, chlorobenzene, etc., and ethers include tetrahydrofuran (THF), tetrahydropyran (TH
Examples of ketones include acetone, methyl ethyl ketone, and methyl butyl ketone. These solvents may be used alone or in combination of two or more. Preferred are THF, benzene, toluene, acetone, and methyl ethyl ketone, which are industrially available at low cost and have the ability to dissolve both polymer catalysts.

However, the hydrogenation activity is not limited to solvents other than these.

The hydrogenation reaction of the second invention is carried out in an amount of 1 to 50% by weight, preferably 5 to 25% by weight based on the liquid nitrile rubber solvent.
It is carried out in a solution with a concentration of .

The hydrogenation reaction of the present invention generally involves maintaining the telekeric liquid rubber solution at a predetermined temperature, adding a catalyst under stirring, and then introducing hydrogen gas to pressurize it to a predetermined pressure.
Therefore, it will be implemented.

Further, the catalyst may be added to the telekeric liquid nitrile rubber solution as it is, or may be added after being dissolved in the above solvent.

It is also preferred to handle the catalyst under a dry, inert atmosphere. An inert atmosphere means an atmosphere that does not react with any participants in the hydrogenation reaction, such as helium, neon, argon, and the like. Air, oxygen, and water are not preferred because they oxidize or deteriorate the catalyst.

On the other hand, the preferable addition amount of the catalyst in the second invention is 0.11111101 to 111111110+ as rhodium atoms to the telechelic liquid nitrile rubber TOOGC.
(0.05-5% by weight as catalyst), preferably 0.5
e+mo I~5-101. In addition, when triphenylphosphine is coexisting, the amount of these should be 0.1 to
5% by weight is preferred.

Within this range of addition amount, it is possible to selectively hydrogenate the olefinically unsaturated double bonds without substantially hydrogenating the cyano groups and functional groups in the liquid nitrile rubber. Although the hydrogenation reaction proceeds even if the amount of catalyst exceeds 11 mmol, depending on the conditions, some types of functional groups may undergo hydrogenation, resulting in insufficient selectivity. 0
．． Even if it is less than 1 mmol, there is selectivity, but the hydrogenation reaction is extremely slow and it takes a long time to perform quantitative hydrogenation, which is not preferable.

In the hydrogenation reaction of the second invention, it is preferable that hydrogen gas is blown into the polymer under stirring to sufficiently bring the polymer into contact with the hydrogen gas. The hydrogenation reaction is generally carried out at a temperature of 20 to 130°C, preferably 50 to 100°C.

If the temperature is low, the hydrogenation rate is slow and requires a long time, so it is not practical. On the other hand, if the temperature is too high, the catalyst may be deactivated or some terminal functional groups may undergo hydrogenation, which is undesirable.

The pressure of hydrogen used in the hydrogenation reaction can range from 1 to 30! j/-
or suitable. If the hydrogen pressure is low, the hydrogenation rate will slow down and virtually reach a plateau, making it difficult to increase the hydrogenation rate; if the pressure is too high, the solvent and some types of functional groups will be hydrogenated, etc. tends to cause side reactions and gelation. A more preferable hydrogenation pressure is 2 to 20 Ky/~, but the optimum hydrogen pressure is selected in correlation with the amount of catalyst added, etc., and in practice, as the amount of the preferred catalyst decreases, the hydrogen pressure increases toward the high pressure side. It is preferable to select and implement it.

The hydrogenation reaction time in the second invention is usually several minutes to 50 hours. The hydrogenation reaction time is appropriately selected within the above range by selecting other hydrogenation reaction conditions.

The hydrogenation reaction of the present invention may be carried out in any manner such as batchwise or continuous. The progress of the hydrogenation reaction can be monitored by tracking the amount of hydrogen absorbed.

By the method of the second invention, the cyano group and the above-mentioned functional groups are not substantially hydrogenated, and similarly the solvent is not hydrogenated, selectively leaving 90% or more of the olefinically unsaturated double bonds, preferably 95% or more. % or more of hydrogenated telekeric liquid hydrogenated nitrile rubber (first invention) can be obtained.

The telekerik liquid hydrogenated nitrile rubber solution subjected to the hydrogenation reaction according to the method of the second invention is preferably freed of catalyst residues and the polymer is isolated from the solution. For example, the polymer may be precipitated by adding a poor solvent for the polymer such as alcohol to the reaction solution after hydrogenation, or the polymer may be recovered using a thin film distiller, with the latter being more preferred. Even if catalyst residues (rhodium, etc.) remain in the polymer, they do not particularly affect the physical properties of the polymer, but deashing is preferable from an economic standpoint.In this case, to effectively remove the catalyst, acidic polar It is preferable to add a solvent or water to the polymer hydrogenation reaction solution together with the VA acid and III-free acid and stir at high speed.

In addition, the liquid hydrogenated nitrile rubber having carboxyl groups at both ends obtained according to the second invention may be converted to a water RI group by reacting with ethanolamine, propatoolamine, etc. by a known method, or the liquid hydrogenated nitrile rubber having carboxyl groups at both ends Hydrogenated nitrile rubber with hexamethylene diisocyanate (HM)
DI), tolylene diisocyanate (TD I) W
The telechelic liquid hydrogenated nitrile rubber of the first invention can also be obtained by a post-reaction in which diisocyanate is reacted to convert it into isocyanate groups.

〔Effect of the invention〕

The telechelic liquid hydrogenated nitrile rubber of the present invention, which has a carboxylic acid group at both ends, can be produced by polycondensing it with diamines and caprolactams. A novel polyamide elastomer having polyamide in the hard segment and hydrogenated nitrile rubber in the soft segment can be obtained by polycondensing with low molecular weight dicarboxylic acids and caprolactam. A polyamide elastomer can also be obtained by direct condensation with a polyamide oligomer.

In addition, by esterifying and polycondensing telechelic liquid nitrile rubber with hydroxyl groups at both terminals with terephthalic acid diesters and low molecular weight diols, a new polyester elastomer having polyester in the hard segment and hydrogenated nitrile rubber in the soft segment can be obtained. be able to.

These one lastomers have good heat resistance, oxidation resistance, oil resistance, weather resistance, etc., and can also be used as reactive compositions by adding additives such as ultraviolet absorbers, oils, and fillers. It can be said to be an extremely useful polymer industrially, as it can be used for the purpose of improving impact resistance or imparting flexibility by blending it with other elastomers or resins.

Further, similar effects can be expected from these telekeric liquid hydrogenated nitrile rubbers as compositions.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

The hydrogenation rate and (meth)acrylonitrile content of the polymer were determined by 'H-NMR method (JEOL GX27() FT
-NMR, 270MH2). Furthermore, the hydroxyl value before and after hydrogenation was determined by the titration method specified in the Japanese Industrial Standards, and the carboxylic acid value was determined by the KO8 titration method (Polymer Analysis Handbook (Asakura Shoten) P581).

The amount of maleic anhydride added, the acid anhydride groups before and after hydrogenation, and the amine value were determined by potentiometric titration.

Titration of isocyanate groups was determined by reacting with dibutyl amine and then titrating excess dibutylamine with HCl2.

Qualitative confirmation of functional groups was performed by FT-IR (JEO
JIR-100FT-IR) manufactured by L.

1111-1-N was made into a 5% (w/v) deuterium chloroform solution (containing 0.1% TMS) and laminated 200 times at 50°C, and FT-IR was applied as a toluene solution on a KBr plate. , toluene was dried by heating and measured in dry air at room temperature (50 times in total).

The polymers used in the Examples are the following polymers or polymers obtained by the preparation method.

(1) Polymer A B, F, both-terminated carboxylic acid liquid nitrile rubber (butadiene-acrylonitrile copolymer) manufactured by Goodrich, MW = 3,500, AN content 18%
, acid value 5.67x 110-4e g, (Hycar
CTBN 1300x 8) (2) Polymer B B, F, manufactured by Goodrich, both terminal carboxylic acid liquid tolyl rubber (butadiene-acrylonitrile copolymer>, Mw = 3,500, AN content 28%,
Acid value 5.42x to-4eq/g, (Hycar C
TBN 1300x13) (3) Polymer C B, F, liquid nitrile rubber with piperidyl groups at both ends (butadiene-acrylonitrile copolymer), manufactured by GOOdriCh, MW = 3,500, AN content 11
．． 5%, amine value 5.32x 10'eq/g, (H
ycar＾TBN 1300x16) (4) Polymer D Made by Idemitsu Petrochemical ■ Liquid nitrile rubber with hydroxyl groups at both ends (butadiene-acrylonitrile copolymer), MW =
4,400, ANN content 15% hydroxyl value 5,20x
1o-'eq, /! iF, (CN-15) (5) Polymer E 50 g of polymer [) was placed in a flask with an internal volume of 500@g equipped with a stirrer, and 250 tj of toluene was added to avoid complete dissolution and maintained at O'C. Anhydrous trimellitic acid chloride (manufactured by Aldrich > 4.64 g (0.02
86 mmol> was dissolved in 1 to 507 toluene and added dropwise over 30 minutes with stirring, followed by further reaction for 2 hours. Then add the polymer solution to a large amount of methanol,
The polymer was precipitated. Mix the polymer with methanol (
It was washed and vacuum dried at 60°C for 24 hours. The acid value was measured by potentiometric titration and was 8.62X 10-'eM.
It was 9. The hydroxyl groups were almost quantitatively replaced by acid anhydride groups.

(6) Polymer F Add isopropanol 709, 30 g of acrylonitrile, 16.7 g of 60% hydrogen peroxide, and 70 g of butadiene to an autoclave with an internal volume of 11 and a stirrer, and add 120 g of
"C (heated and stirred to start polymerization. After 1 hour, the autoclave was rapidly cooled to stop polymerization.

Add 300at7 of toluene to this and dissolve it uniformly, resulting in 3005ml of water! After washing the solution three times with water to remove unreacted hydrogen peroxide, unreacted sulfur and solvent were distilled off under reduced pressure to obtain 60 g of polymer. The molecular weight, AN content, and hydroxyl value determined by GPC, 'H-\MR1 titration are as shown in Table 1.

(7) Polymer G (Polymerization of liquid nitrile rubber with hydroxyl groups at both ends) 70 g of isopropanol was placed in an autoclave with an internal volume of 1N and equipped with a stirrer.
30 g of acrylonitrile, 31.4 g of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-probioamide (Wako 111 Pharmaceutical Reagent VA086) and 70 g of butadiene were added in this order, and the mixture was reacted at 70°C for 72 hours. Ta.

After the reaction was completed, methanol was added and the upper layer was removed by decantation, 100 d of methanol was added to the precipitated liquid rubber, and the remaining initiator was removed by washing three times, followed by drying under reduced pressure to obtain 65 g of polymer. The analysis results are shown in Table 1.

(8) Polymer H (polymerization of liquid nitrile rubber with carboxyl groups at both ends) Polymerization of polymer G except that 4,4°-azobis(4-cyanopentane #l) (manufactured by Aldrich, special grade reagent) was used as a radical initiator. Polymer 569 was obtained using exactly the same method as above. The analysis results are shown in Table 1.

(9) Polymer I (polymerization of liquid nitrile rubber containing methyl ester groups at both ends) Except that 39 g of dimethyl 2.2"-azodos(2-methylpropionate) was used as the initiator and the reaction time was 24 hours. Polymer 4 was prepared in exactly the same manner as Polymer G.
I got 0g. The analysis results are shown in Table 1.

Maintained at 60'C under stirring.

Then tris-(triphenylphosphine) rhodium (
I> Chloride (manufactured by Aldrich) 0.19g (0,
63% by weight) was suspended in 20 d of toluene and then added into the autoclave. Immediately 5, OK'l/
After increasing the pressure to ciG and reacting at the same temperature for 4 hours,
The temperature was returned to room temperature, and nitrogen substitution was performed.

Polymer A-1 was separated by removing the solvent in a membrane distiller. Each was vacuum dried at 60°C for 24 hours, and 1H-NM
Table 2 shows the results obtained by IR measurement.

(Left below) Examples 1 to 9 Polymers A-I were placed in a metal autoclave equipped with a stirrer, and 30 g of each polymer was mixed with 270 g of Na-dehydrated toluene.
Example 10 Polymer 507 of Example 2 and 12.6 g of dibutylamine were dissolved in g and the system was replaced with hydrogen.
(0.14 mol) was placed in a 11 autoclave and reacted under vacuum at 200°C for 2 hours. After the reaction was completed, unreacted dibutylamine was removed by vacuum degassing at the same temperature for 1 hour.The IR spectrum showed that the carboxylic acid was almost quantitatively converted to an amide, and a telechelic hydrogenation liquid with -NH2 at both terminals was found. Nitrile rubber was produced.

The polymer was taken out as it was, dried under vacuum at 60°C for 24 hours, and subjected to 1H-NMR1 terminal quantitative determination (potentiometric titration>, IR
Table 2 shows the results obtained from the measurements.

Example 11 50 g of the polymer obtained in Example 4 and 250 g of toluene
(J was placed in an autoclave, completely dissolved by stirring in the presence of N2, and the temperature was raised to 100°C. Hexamethylene diisocyanate (HMDI>9.69 (0,0
A solution of 21 mol) dissolved in 50 d toluene was added dropwise at the same temperature over 30 minutes. Stirring was continued for an additional 1 hour and 30 minutes, and toluene was distilled off under reduced pressure at 10 to 80'Cc.

The absorption of hydroxyl group from the IR spectrum (3350CIR-'
) almost disappears, and instead absorption of isocyanate groups (2
250, -1) was observed.

The polymer was taken out as it was, vacuum dried at 60° C. for 24 hours, and subjected to 'HNMR1 terminal quantitative determination (titration). Table 3 shows the results.

(The following is a blank space) Example 12 The reaction was carried out in the same manner as in Example 2 except that the reaction temperature was 40°C. Table 4 shows the results of analyzing the obtained polymer.

Example 13 Hydrogenation was carried out in the same manner as in Example 2 except that the hydrogen pressure was changed to 25 NJ/iG. Table 4 shows the results of analyzing the obtained polymer.

Example 14 The same procedure as in Example 2 was carried out except that the amount of catalyst was changed to 1.14 g (3.78% by weight).Table 4 shows the results of analysis of the obtained polymer.

(Left below) Table 4 Solvent: Toluene Reaction time: 4 hours Catalyst;
Tris (triphenylphosphine> rhodium (I) chloride poly? -; B, F, Goodrich t-1
ycar CTBN 1300

Next, 10 g of reduced nickel was added with 40% nickel (on a carrier), and a hydrogenation reaction was carried out for 10 hours while maintaining the hydrogen in the system at 5 ONg/ciG.

After the reaction was completed, the temperature was returned to room temperature and normal pressure, and the catalyst was filtered and separated by removing the solvent using a thin film distiller.

It was vacuum dried at 60° C. for 24 hours, and the results obtained from 'H-NMR1 terminal group determination (titration) are shown in Table 5.

Comparative Example 2 Rh/Si 0230SF (palladium supported amount: 5%, SiO2 average pore diameter: 200A) was added as a catalyst, hydrogen in the system was set to 50υ/aAG, and the reaction temperature was set to 90°C.
The same procedure as Comparative Example 1 was carried out except that.

The results are shown in Table 5.

(Left below) Table 5 Solvent: Tetrahydrofuran, reaction time = 10 hours, poly? -: B, F, Goodrich Hycar
CTBN 1300 x13 Application Example 1 125g of polymer obtained by the method of Example 2 above and ε-
Caprolactam (Wako Tsumugi Reagent Special Grade) 1503 and Hexamethylene Diamine (Wako Tsumugi Reagent Special Grade >3.20g
11 into a metal autoclave, then phosphorus $1
．． 0d, add 0.5g of Irganox 1010,
The mixture was heated to 220° C. under air stirring and allowed to react for 2 hours.

Then, the temperature was raised to 250°C, and the reaction was continued for an additional 2 hours. At the same temperature, unreacted ε-caprolactam was distilled off under reduced pressure, and the resulting polymer was extracted into water, vacuum-dried at 100° C. for 24 hours, and then compression molded at 220° C., and its physical properties were measured. The results are shown in Table 6.

Application example 2 131 g of the polymer obtained in Example 4 above and 1.4-
Butanediol (Wako Tsumugi reagent special grade) 112g and dimethyl terephthalate (Wako Tsumugi reagent special grade) 133
g into an 11 metal autoclave, then tetra(n
-butoxy) titanium (Tokyo Kasei Reagent Special Grade) o, sg, I
rganox 1010 1. Og case, normal pressure, 230
The transesterification reaction was carried out at ℃ for 3 hours with stirring. Polycondensation reaction was carried out under reduced pressure at 250°C for 3 hours, the polymer was extracted into water, vacuum dried at 100°C for 24 hours, and then
Compression molding was performed at 10°C, and physical properties were measured. The results are shown in Table 6.

Comparative Application Example 1 The reaction was carried out in the same manner as Application Example 1 except that Polymer B was used. The obtained polymer was gelled, and ① lastomer was not obtained. The results are shown in Table 6.

Comparative Application Example 2 The reaction was carried out in the same manner as Application Example 2 except that Polymer D was used. The obtained polymer was gelled, and ① lastomer was not obtained. The results are shown in Table 6.

Comparative Application Example 3 The same method as Application Example 1 was used except that the cheleteric liquid polymer was hydrogenated poly-1-tadiene (8 Pa, Cl-1000) having carboxyl groups at both ends.

The results are shown in Table 6.

Comparative Application Example 4 The same method as Application Example 2 was carried out except that polytetrahydrofuran [poly(tetramethyleneoxy)glycol, Mitsubishi Kasei PTMG, molecular weight 2000] having hydroxyl groups at both terminals was used as the Keleterik liquid polymer. The results are shown in Table 6.

IR spectrum of the liquid hydrogenated nitrile rubber with carboxyl groups at both ends obtained in Example 1 and the raw material A polymer, 'l
-1-1-N spectrum, oxidation (titration) and elemental analysis were measured. The attribution results are shown below.

1. Attribution of IR spectrum (Kautschuk+G
(JIIl [Ii to unststoffe 42. J
ahrgang, Nr, 3/89°P194-19
7> 2236ci-1-CN 1714cm1 vicinity -〇〇〇H 1 723ait -fCH2→1 n≧4 Hydrogenated butadiene structure device: JIR-100FT-II2 manufactured by JEOL,
Assignment of 'l-t NMR velocity (50°C.

5CAN in CDCN3 (200 times) and hydrogenation rate measurement 0.8-1.0 ppm -CH3 methyl proton (
3I) 1.0-2.5pl) II methylene proton and others 2.5-2.7ppII -C methine proton (
1H)CN 4.1-5.2t)F)III Bd-1,2C
H2 methylene proton (2H) 5.2-5.5ppm ad -1,4Cl-1=
Methine proton (2H) 5.5-5.8ppm Bd -1,2CH=methine proton (1h) Apparatus i: Gx-270FT-NMR No. 1 manufactured by JEOL
The IR spectrum shown in the figure shows -CN (22
3ZcI&-1> and -COOH(1714cII&
-1) was completely retained, butadiene in the middle disappeared, and it was found that hydrogenation occurred. 'H-NM in Figure 2
In the R spectrum, 4.7 to 5.8 ppm of olefinic protons almost completely disappeared, and the hydrogenation rate determined from each signal intensity was 99%.

31 valent The acid values determined by titration are shown in the table below.

[Brief explanation of drawings]

Figure 1 (a) is the IR spectrum of polymer A (CTBN1300x8), and Figure 1 (b) is the IR spectrum of polymer A (CTBN1300x8).
Figure 2 (a) is the 'H-NMR spectrum of polymer A (CTBN1300X8), and Figure 2 (b) is the 'H-NMR spectrum of polymer A (CTBN1300X8).
It is a H-NMR spectrum.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, R^1 is hydrogen and/or C_1 to C_4
6-4 repeating units (representing an alkyl group)
50 units and general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼………………(II) (However, R^2 in the formula represents hydrogen or methyl group) Repeating units 3 to 225 and the number of olefinically unsaturated double bonds in the molecule is 0.
A telekeric liquid hydrogenated nitrile rubber having ~20 substituents at both ends of the molecule represented by the following general formula (A). (A) Formula -OH, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^3 in formula (A) is hydrogen or C_1 to C_8
each alkyl, phenyl, aryl group, R^4, R
^5 is hydrogen or an alkyl, alkylene, phenyl, or aryl group of C_1 to C_8, and Z is C_1 to C_8.
Each group of alkylene, phenylene, and alkyl-substituted phenylene in _1_5, R^6 is alkyl of C_1 to C_8,
Each group of alkylene, phenyl, and aryl, R^6' is a cyano group or C_1 to C_8 alkylalkylene,
For each phenyl and aryl group, R^7 is hydrogen or C_
Each represents an alkyl, alkylene, phenyl, or aryl group of 1 to C_8. n=0-8) 2. 6-450 conjugated diene repeating units and formula (III)
▲There are mathematical formulas, chemical formulas, tables, etc.▼………………(III
) (However, R_1' in the formula represents hydrogen or a methyl group.)
A telekeric liquid rubber consisting of 3 to 225 repeating units represented by the following formula and having a substituent containing a functional group represented by the following formula (B) at both ends of the molecule is placed in a polar solvent or an aromatic hydrocarbon solvent and treated with a catalyst. As Tris-(
triphenylphosphine) rhodium (I) halide
temperature 20~130℃, hydrogen pressure 1~30kg/
A telechelic, characterized in that at least 90% or more of the olefinically unsaturated double bonds in the conjugated diene moiety are hydrogenated in cm^2, and the retention rate of the cyano group and the functional groups at both ends is 80% or more. A method for producing liquid hydrogenated nitrile rubber. (8) Formula -OH, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -N=C=O, -
SH, -NR_2'R_3', ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_2', R_3', R_4' are hydrogen or C_
Represents each group of 1 to C_8 of alkyl, alkylene, phenyl, and aryl. )