CN114539473B - Solution-clustered alternate nitrile rubber, preparation method thereof and obtained product - Google Patents

Solution-clustered alternate nitrile rubber, preparation method thereof and obtained product Download PDF

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CN114539473B
CN114539473B CN202111671163.9A CN202111671163A CN114539473B CN 114539473 B CN114539473 B CN 114539473B CN 202111671163 A CN202111671163 A CN 202111671163A CN 114539473 B CN114539473 B CN 114539473B
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nitrile
nitrile rubber
acrylonitrile
butadiene
free radical
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CN114539473A (en
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王庆刚
王亮
朱广乾
刘敏
周丽
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Abstract

The application provides a solution-clustering alternating nitrile rubber, a preparation method thereof and an obtained product, and belongs to the technical field of free radical polymerization. The application provides a solution-clustered alternating nitrile rubber, which has a structural sequence general formula shown in a formula (1): - (B-A-B-A-B-B-A) n Wherein B is a butadiene unit, A is an acrylonitrile unit, and n is any integer value within the range of 53-1065; the adjustable range of the number average molecular weight of the nitrile rubber is 2-40 ten thousand g/mol, the molecular weight distribution PDI is 1.5-4.0, the insertion rate of acrylonitrile in the nitrile rubber is 35-50%, and the AB alternation degree is at least 81%. The obtained solution clustering alternating nitrile rubber has a microstructure copolymer which shows similar alternating copolymerization sequences through nuclear magnetic analysis, and the cross-linking side reaction is well controlled in the copolymerization process, so that the method has good industrial application prospect.

Description

Solution-clustered alternate nitrile rubber, preparation method thereof and obtained product
Technical Field
The application belongs to the technical field of free radical polymerization, and particularly relates to a solution clustering alternating nitrile rubber, a preparation method thereof and an obtained product.
Background
The nitrile rubber is mainly a binary copolymer of butadiene and acrylonitrile, has good oil resistance and excellent physical and mechanical properties, and has wide application in the fields of automobiles, wires and cables, adhesives, oil-resistant rubber plates for printing and the like. Nitrile rubber has polarity due to acrylonitrile content, and the characteristics of the nitrile rubber change greatly due to the change of acrylonitrile content, and the acrylonitrile content influences the rotation difficulty and intermolecular acting force in a rubber molecular chain, so that the flexibility of the molecular chain and the physical and mechanical properties including heat resistance are influenced. The hydrogenated nitrile rubber is the best high-temperature sealing material in the market and is widely used in the fields of aerospace, oilfield exploitation and deep sea exploration. At present, hydrogenated nitrile rubber is monopolized by both the japanese rayleigh company and the allangerhans, and is one of the clear materials for the neck technology in the country.
The emulsion polymerization method is currently used in the industrial production of most nitrile rubber. However, the process steps are complicated, the economic cost is high, the post-treatment separation is troublesome, and the performance of the product is affected by the existence of emulsifier residues in the product. Patent application CN 102653579A reports a method for preparing nitrile rubber by simple process, which can adopt continuous emulsion polymerization or batch emulsion polymerization, and the introduction of unsaturated amine or phenol anti-aging agent monomer makes the obtained nitrile rubber have more excellent heat resistance and anti-oxidative aging property; but the resulting polymerization product is mainly a medium nitrile product with a low acrylonitrile content. Patent application CN 109320655A discloses a method for preparing powder nitrile rubber with extremely high nitrile content by emulsion polymerization. The nitrile rubber has high conversion rate and simplified post-treatment flow, but the obtained product is a crosslinked product with gel content of more than 75%.
In general, the prior patents optimize the aspects of emulsion polymerization process flow, polymerization activity, nitrile content controllability and the like, but have the defects: the polymerization components are numerous, and the reaction cost is high. Moreover, with the development of even more excellent properties of hydrogenated nitrile rubber in various fields, which are comparable to nitrile rubber, how to simply effect hydrogenation of nitrile rubber has become a serious consideration for industrialization of nitrile rubber.
The nitrile rubber prepared by emulsion polymerization needs to be separated, dried and then hydrogenated in solution, but compared with the nitrile rubber prepared by solution polymerization, the nitrile rubber prepared by solution polymerization can simplify the separation step and realize one-pot hydrogenation reaction under certain conditions. Patent application CN 103080161A discloses a method for preparing nitrile rubber from solution, which has simple polymerization components, convenient operation, subsequent hydrogenation in the same solvent, and simple process flow. But the polymerization conversion rate is not high, the obtained nitrile rubber is mainly of medium-high nitrile grade (31% -35%), and the nitrile content controllability is general. In addition, the arrangement of the butadiene and acrylonitrile copolymer sequences has a critical effect on the polymer properties, but little detail analysis of the microstructure of nitrile rubber has been made in the prior art.
Research shows that the heat resistance, oil resistance and physical and mechanical properties of the alternating copolymer nitrile rubber are improved along with the increase of the alternation degree. However, the materials are based on extremely high nitrile butadiene rubber products, and are difficult to industrially prepare. Therefore, how to find a method with simple operation and high polymerization efficiency, based on a definite microscopic sequence structure, to realize the preparation of high-to-extremely high-grade nitrile rubber, is an effective path for solving the current important demands of the hydrogenated nitrile rubber industrialization and the national nitrile rubber industry.
Disclosure of Invention
The application provides a solution-clustered alternate nitrile rubber, a preparation method thereof and an obtained product, wherein the method is based on a novel and simple free radical solution polymerization method, wherein a complete catalytic polymerization system can be formed by solution polymerization only by proper azo nitrile free radical initiator and solvent, and the initiator can be added for many times to realize high-yield polymerization, and the method is simple to operate and convenient to post-treat.
In order to achieve the aim, the application provides a solution-clustered alternating nitrile rubber, which has the following structural sequence general formula:
-(B-A-B-A-B-B-A) n -，
wherein B is a butadiene unit, A is an acrylonitrile unit, and n is any integer value within the range of 53-1065;
the adjustable range of the number average molecular weight of the nitrile rubber is 2-40 ten thousand g/mol, the molecular weight distribution PDI is 1.5-4.0, the insertion rate of acrylonitrile in the nitrile rubber is 35-50%, and the AB alternation degree is at least 81%.
The application also provides a preparation method of the solution-clustered alternating nitrile rubber, which is characterized by comprising the following steps:
under the condition of no water and oxygen, adding solvent, nitrile free radical initiator, butadiene monomer and acrylonitrile monomer into a reactor according to a preset feeding sequence, polymerizing for 4-48 h at 50-100 ℃, quenching, washing and vacuum drying to obtain the solution-clustered alternate nitrile rubber.
It will be appreciated that for the polymerization temperature and polymerization time described above, one skilled in the art can determine the half-life of the different initiators in combination, for example, preferably at 70℃for 12 hours. Further, in the scheme, the yield of the obtained soluble clustered alternating nitrile rubber can reach 81.4%. In the production of a plant, the yield is generally controlled to 30% to 40% in order to suppress branching and crosslinking of the copolymer, and the yield is high enough to meet the high standards of the production of the plant when the yield reaches 50%. The yield of the solution-cluster alternating nitrile rubber obtained by the method is about 50%, the highest yield can reach 81.4% under the condition that the ratio of the initiator to the comonomer is 1/100, the production needs can be satisfied, and the preparation method is simple to operate, convenient to post-treat, economical and efficient.
Preferably, the nitrile free radical initiator is fed in a batch process during the polymerization, wherein the number of batch feeds is 1< n <10, n being an integer.
Preferably, the feeding sequence is as follows:
sequentially adding a nitrile free radical initiator and a solvent into a reactor, adding an acrylonitrile monomer and a butadiene monomer to react for a specific time after the nitrile free radical initiator and the solvent are completely dissolved, and then sequentially adding a specific equivalent of nitrile free radical initiator and the solvent to completely dissolve for copolymerization reaction to obtain nitrile rubber; or alternatively
Sequentially adding an acrylonitrile monomer and a butadiene monomer solution into a reactor, after uniformly mixing and completely dissolving, adding a nitrile free radical initiator to react for a specific time, and sequentially adding a nitrile free radical initiator with a specific equivalent weight and a solvent to completely dissolve for copolymerization reaction to obtain nitrile rubber; or alternatively
Sequentially adding an acrylonitrile monomer and a nitrile free radical initiator into a reactor, after uniformly mixing, adding a butadiene monomer to react for a specific time, and sequentially adding a nitrile free radical initiator with a specific equivalent weight and a solvent to completely dissolve for copolymerization reaction to obtain nitrile rubber; or alternatively
And sequentially adding butadiene monomers, nitrile free radical initiators and solvents into the reactor, adding acrylonitrile monomers to react for a specific time after uniformly mixing, and sequentially adding the nitrile free radical initiators with specific equivalent weights and the solvents to completely dissolve for copolymerization reaction to obtain the nitrile rubber.
Preferably, in a fed-batch polymerization process, the reaction time for the first feed is from 2h to 48h, preferably 12h; the reaction time for the second addition is 2h to 48h, preferably 12h.
Preferably, the equivalent ratio of nitrile radical initiator required for the second to first charge is 1/1 during the fed-batch polymerization.
It will be appreciated that the number of batch feeds may also be 2, 3,4, 5, 6, 7, 8 or 9, the above list being given for the case of feeds with n=2, and so on for the case of feeds with n=3, 4, 5, 6, 7, 8 or 9, each feed still having a reaction time of from 2h to 48h, preferably 12h; as for the fed-batch polymerization, the amount of the nitrile radical initiator to be fed each time is sufficient to ensure that the equivalent ratio of the nitrile radical initiator required for the last and the previous feeds is kept at 1/1.
Preferably, the nitrile radical initiator is any compound of azo-containing CN capable of forming free radicals, and is at least one selected from azo diisobutyronitrile AIBN, azo diisoheptonitrile ABVN and azo diisovaleronitrile AMBN; the solvent is at least one aromatic hydrocarbon solvent selected from toluene, ethylbenzene, xylene, chlorobenzene, benzotrifluoride, 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene and the like.
Preferably, the equivalent ratio of the butadiene monomer to the acrylonitrile monomer is 8/2-4/6, the equivalent ratio of the nitrile radical initiator to the comonomer of butadiene and acrylonitrile is 1/100-1/1000, and the volume ratio of the solvent to the comonomer of butadiene and acrylonitrile is 1/1-1/2.
Preferably, the temperature of the vacuum drying is 30-50 ℃ and the time is 12-24 hours.
The application also provides hydrogenated nitrile rubber, which is prepared from the solution-clustered alternating nitrile rubber according to the technical scheme or the solution-clustered alternating nitrile rubber prepared by the preparation method according to the technical scheme.
Compared with the prior art, the application has the advantages and positive effects that:
1. the acrylonitrile content of the nitrile rubber provided by the application is in the range of 35-50%, and the nitrile rubber can be used for preparing nitrile rubber products with high nitrile content to extremely high nitrile content, and has extremely wide application range. The number average molecular weight is 2 ten thousand-40 ten thousand g/mol, and the molecular weight distribution is 1.5-4.0. Compared with the traditional preparation method, the nitrile rubber provided by the application has the advantages of higher yield, wider controllability of nitrile content, no gel, better oil resistance, higher wear resistance, better low temperature resistance and ozone resistance, and is mainly applied to various oil-resistant rubber products, cable rubber materials, flexible packages and the like.
2. The initiation system is different from emulsion polymerization commonly used in industrial systems, adopts a simple solution polymerization reaction system, can effectively prepare butadiene with different acrylonitrile contents by copolymerization of acrylonitrile by a single initiator and a solvent system, and can carry out corresponding hydrogenation reaction under the same solvent.
And 3, the initiation system adopts a batch feed solution polymerization method of the initiator, so that the stability of free radical active species in the system is ensured, and the polymerization yield of the nitrile rubber is greatly improved.
4. The initiation system can realize the preparation of nitrile rubber with different number average molecular weights by changing the types of nitrile initiators; the control of the acrylonitrile insertion rate can be realized through the regulation and control of the comonomer proportion.
5. The polybutadiene chain segment 1, 4-selectivity content of the nitrile rubber prepared by the application is above 90%, so that the nitrile rubber has better tensile elasticity and is durable.
Drawings
FIG. 1 is a schematic illustration of a representative nitrile rubber prepared by free radical solution polymerization of the ABVN-toluene system provided in the examples of the present application 1 H NMR spectrum;
FIG. 2 is a 13C NMR spectrum of a representative nitrile rubber prepared by free radical solution polymerization of the ABVN-toluene system provided by the examples of the present application;
FIG. 3 is a GPC chart of a representative nitrile rubber prepared by free radical solution polymerization of the ABVN-toluene system provided in the examples of the present application.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Effect of different nitrile initiators on nitrile rubber copolymerization
Example 1 (azobisisoheptonitrile, initiator to comonomer ratio 1/1000)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel. The nitrile rubber elastomer obtained 1 H NMR spectrum, 13 The C NMR spectrum and GPC spectrum are shown in FIGS. 1 to 3.
The calculated yield is 53.3 percent, the acrylonitrile content is 46 percent, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 86%; characterization of number average molecular weight M by GPC n 111203g/mol and a molecular weight distribution PDI of 1.9; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 92% and a 1, 2-selectivity of 8%.
Example 2 (azobisisovaleronitrile)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisovaleronitrile (AMBN, 4.4mg, 23. Mu. Mol,1 equiv.) and acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) in this order under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, AMBN (4.4 mg,23 μmol,1 equiv.) was added, and the reaction was continued at 70 ℃ for 12 hours. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
Calculation ofThe yield is 51.0%, the acrylonitrile content is 45%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 85%; characterization of number average molecular weight M by GPC n 103690g/mol and a molecular weight distribution PDI of 2.0; wherein by NMR: the polybutadiene block has a 1, 4-selectivity of 92% and a 1, 2-selectivity of 8%.
Example 3 (azobisisobutyronitrile)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisobutyronitrile (AIBN, 3.7mg, 23. Mu. Mol,1 equiv.) with acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) in this order under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, AIBN (AIBN, 3.7mg, 23. Mu. Mol,1 equiv.) was added thereto, and the reaction was continued at 70℃for 12 hours. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 54.7%, the acrylonitrile content is 44%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 83%; characterization of number average molecular weight M by GPC n 93814g/mol and a molecular weight distribution PDI of 1.7; wherein by NMR: the polybutadiene block has a 1, 4-selectivity of 93% and a 1, 2-selectivity of 7%.
EXAMPLE 4 (1, 1' -azobis (cyclohexane carbonitrile))
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of 1, 1' -azobis (cyclohexanecarbonitrile) (MDEG, 5.6mg, 23. Mu. Mol,1 equiv.), acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) in this order under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, MDEG (5.6 mg, 23. Mu. Mol,1 equiv.) was added, and the reaction was continued at 70℃for 12 hours. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 30.9%, the acrylonitrile content is 40%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with high nitrile content; the degree of alternation is 81%; characterization of number average molecular weight M by GPC n 315753g/mol and a molecular weight distribution PDI of 1.8; characterization by NMR: polybutadiene block 1, 4-selectivity content of 90%The 1, 2-selectivity content was 10%.
As described above, any compound in which-CN-containing azo groups can form radicals can be used to obtain nitrile rubber by this method, but the benzene ring-containing initiator (example 4) is not superior to any of azodialkylnitriles in terms of nitrile rubber yield (examples 1 to 3). By varying the nitrile initiator type, a controlled transition of the acrylonitrile content from 40% (high nitrile content) to 46% (very high nitrile content) can be achieved, and this variation is independent of the amount of catalyst and the amount of solvent.
Influence of different nitrile initiator dosages on nitrile rubber copolymerization
Example 5 (initiator to comonomer ratio 1/500)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisoheptonitrile (ABVN, 11.4mg, 46. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,500 equiv.) and butadiene (2.0 mL,23mmol,500 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (11.4 mg,46 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 57.0%, the acrylonitrile content is 46%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 87%; characterization of number average molecular weight M by GPC n 66750g/mol and a molecular weight distribution PDI of 1.9; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 95% and a 3, 4-selectivity of 5%.
Example 6 (initiator to comonomer ratio 1/250)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisoheptonitrile (ABVN, 22.9mg, 92. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,250 equiv.) and butadiene (2.0 mL,23mmol,250 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (22.9 mg, 92. Mu. Mol,1 equiv.) and continued at 70℃for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 66.8%, the acrylonitrile content is 47%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 90%; characterization of number average molecular weight M by GPC n 51637g/mol and a molecular weight distribution PDI of 2.0; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 96% and a 1, 2-selectivity of 4%.
Example 7 (initiator to comonomer ratio 1/100)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisoheptonitrile (ABVN, 57.1mg, 230. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,100 equiv.) and butadiene (2.0 mL,23mmol,100 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (57.1 mg,230 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 81.4 percent, the acrylonitrile content is 49 percent, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 95%; characterization of number average molecular weight M by GPC n 22412g/mol, a molecular weight distribution PDI of 2.2; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 94% and a 1, 2-selectivity of 6%.
Example 8 (initiator to comonomer ratio 1/2500)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisoheptonitrile (ABVN, 2.3mg, 9.2. Mu. Mol,1 equiv.), acrylonitrile (1.5 mL,23mmol,2500 equiv.), and butadiene (2.0 mL,23mmol,2500 equiv) in this order under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (2.3 mg,9.2 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 35.3 percent, the acrylonitrile content is 41 percent, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with high nitrile content; the degree of alternation is 82%; characterization of number average molecular weight M by GPC n 146578g/mol and a molecular weight distribution PDI of 2.0;characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 96% and a 1, 2-selectivity of 4%.
In summary, in connection with examples 1, 5-8, it is shown that the ratio of initiator to comonomer is in the range of from 1/100 to 1/1000 is more suitable, whereas an excessively large ratio range (e.g.1/2500) affects the nitrile rubber yield, but has no significant effect on its properties.
Effect of different solvent types on nitrile rubber copolymerization
Example 9 (ethylbenzene solvent)
An ethylbenzene (3.5 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) and acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) were sequentially added to a 50mL reaction flask under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 49.6%, the acrylonitrile content is 43%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 84%; characterization of number average molecular weight M by GPC n 99001g/mol, a molecular weight distribution PDI of 2.0; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 96% and a 1, 2-selectivity of 4%.
Example 10 (xylene solvent)
A50 mL reaction flask was charged with a solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in xylene (3.5 mL) of acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) in this order under argon. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 50.1 percent, the acrylonitrile content is 44 percent, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 84%; characterization of number average molecular weight M by GPC n 135667 g-mol, molecular weight distribution PDI of 1.6; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 91% and a 3, 4-selectivity of 9%.
Comparative example 1 (hexane solvent)
A50 mL reaction flask was charged with a hexane (3.5 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours, and a gel-like solid was precipitated from the solution. The polymer was quenched with cold methanol and washed three times and dried under vacuum to constant weight to give a crosslinked nitrile rubber solid with a gel content of > 80%.
The calculated yield was 97.0%, and the obtained polymer was not able to be dissolved in most of organic solvents such as methylene chloride, chloroform, tetrahydrofuran, chlorobenzene, toluene, etc., and thus was not able to characterize the acrylonitrile content and molecular weight.
Comparative example 2 (cyclohexane solvent)
A50 mL reaction flask was charged with a solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in cyclohexane (3.5 mL) of acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) in this order under argon atmosphere. The reaction was carried out at 70℃for 12 hours, and a gel-like solid was precipitated from the solution. The polymer was quenched with cold methanol and washed three times and dried under vacuum to constant weight to give a crosslinked nitrile rubber solid with a gel content of > 80%.
The calculated yield was 99.0%, and the obtained polymer was a severely crosslinked product, which could not be dissolved in most organic solvents such as methylene chloride, chloroform, tetrahydrofuran, chlorobenzene, toluene, etc., and thus could not characterize the acrylonitrile content and molecular weight.
Experiments have shown that aryl benzene ring solvents are suitable for the copolymerization of nitrile rubber (examples 9-10), especially toluene solvents (example 1), whereas alkane solvents are unsuitable for the copolymerization (comparative examples 1-2).
Influence of different solvent dosage on copolymerization of preparing nitrile rubber by feeding solution in batches
Example 11 (toluene to comonomer volume ratio 1/2)
A50 mL reaction flask was charged with a toluene (1.9 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer with gel content less than 1%.
The calculated yield is 66.7%, the acrylonitrile content is 44%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 85%; characterization of number average molecular weight M by GPC n 102378g/mol and a molecular weight distribution PDI of 3.0; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 96% and a 1, 2-selectivity of 4%.
Example 12 (toluene to comonomer volume ratio of 2/1)
A50 mL reaction flask was charged with a toluene (7.0 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 48.2 percent, the acrylonitrile content is 42 percent, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 82%; characterization of number average molecular weight M by GPC n 83487g/mol and a molecular weight distribution PDI of 3.2; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 96% and a 1, 2-selectivity of 4%.
Example 13 (toluene to comonomer volume ratio 5/1)
A50 mL reaction flask was charged with a toluene (17.5 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 36.1 percent, the acrylonitrile content is 40 percent, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with high nitrile content; the degree of alternation is 81%; characterization of number average molecular weight M by GPC n 90124g/mol and a molecular weight distribution PDI of 3.4; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 94% and a 1, 2-selectivity of 6%.
Comparative example 3 (solvent free)
To a 50mL reaction flask under argon atmosphere, azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) and acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) were added sequentially. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h.
The gel-like solid is precipitated from the solution, the polymer is washed twice with cold methanol and dried in vacuo to constant weight to give a gel-like solid. The calculated yield was 94.0%. The obtained polymer is a severely crosslinked product, and cannot be dissolved in most organic solvents such as dichloromethane, chloroform, tetrahydrofuran, chlorobenzene, toluene and the like, so that the acrylonitrile content and the molecular weight cannot be characterized.
Experiments have shown that too much solvent reduces the yield (examples 12, 13) but has no significant effect on its properties, while too little solvent results in cross-linking side reactions (comparative example 3). Therefore, a ratio of 1/1 to 1/2 (examples 1 and 11) of the solvent to the comonomer is preferable, and particularly a ratio of 1/1 of the solvent to the comonomer is preferable.
Effect of butadiene to acrylonitrile equivalent ratio on nitrile rubber copolymerization
Example 14 ([ BD ]/[ AN ] = 8/2)
A50 mL reaction flask was charged with a toluene (3.9 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (0.6 mL,9mmol,390 equiv.) and butadiene (3.3 mL,37mmol,1610 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 30.0%, the acrylonitrile content is 29%, and the acrylonitrile-butadiene rubber belongs to nitrile butadiene rubber with medium nitrile content; the degree of alternation is 86%; characterization of number average molecular weight M by GPC n 42713g/mol and a molecular weight distribution PDI of 1.9; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 93% and a 1, 2-selectivity of 7%.
Example 15 ([ BD ]/[ AN ] = 7/3)
A50 mL reaction flask was charged with a toluene (3.7 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.), acrylonitrile (0.9 mL,14mmol,610 equiv.) and butadiene (2.8 mL,32mmol,1390 equiv.) in this order under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 33.0%, the acrylonitrile content is 33%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with medium and high nitrile content; the degree of alternation is 87%; characterization of number average molecular weight M by GPC n 62739g/mol and a molecular weight distribution PDI of 1.8; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 94% and a 1, 2-selectivity of 6%.
Example 16 ([ BD ]/[ AN ] = 6/4)
A50 mL reaction flask was charged with a toluene (3.7 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.2 mL,18mmol,800 equiv.) and butadiene (2.5 mL,28mmol,1200 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
Calculate the yield39.0 percent and 36 percent of acrylonitrile, belonging to nitrile rubber with high nitrile content; the degree of alternation is 87%; characterization of number average molecular weight M by GPC n 89231g/mol and a molecular weight distribution PDI of 1.9; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 95% and a 1, 2-selectivity of 5%.
Example 17 ([ BD ]/[ AN ] = 4/6)
A50 mL reaction flask was charged with a toluene (3.4 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.8 mL,28mmol,1220 equiv.) and butadiene (1.6 mL,18mmol,780 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 55.0%, the acrylonitrile content is 43%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 85%; characterization of number average molecular weight M by GPC n 103857g/mol and a molecular weight distribution PDI of 2.2; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 96% and a 1, 2-selectivity of 4%.
Comparative example 4 ([ BD ]/[ AN ] =3/7)
A50 mL reaction flask was charged with a toluene (3.3 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (2.1 mL,32mmol,1390 equiv.) and butadiene (1.2 mL,14mmol,610 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h.
The gel-like solid is precipitated from the solution, the polymer is washed twice with cold methanol and dried in vacuo to constant weight to give a gel-like solid. The calculated yield was 93.0%. The obtained polymer is a severely crosslinked product, and cannot be dissolved in most organic solvents such as dichloromethane, chloroform, tetrahydrofuran, chlorobenzene, toluene and the like, so that the acrylonitrile content and the molecular weight cannot be characterized.
In summary, AN increase in the acrylonitrile equivalent ratio in the comonomer increases the yield (examples 1, 14-17), but results in the occurrence of crosslinking side reactions when [ BD ]/[ AN ] is not greater than 3/7. Also, by varying the monomer ratio of butadiene to acrylonitrile (examples 1, 14-17), a controlled transition of acrylonitrile content from 29% (medium nitrile content) to 46% (very high nitrile content) was achieved, this variation being independent of catalyst and solvent amounts.
Examples of the implementation of the copolymerization of nitrile rubber with different times of addition
Example 18 (number of charges n=3)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisoheptonitrile (ABVN, 5.7mg, 23. Mu. Mol,1 equiv.) in the order acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, with the addition of ABVN (5.7 mg,23 μmol,1 equiv.) and continued at 70 ℃ for 12h. The reaction was then transferred to a liquid nitrogen bath, with additional ABVN (5.7 mg,23 μmol,1 equiv.) and the reaction was continued at 70 ℃ for 12h. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 60.0%, the acrylonitrile content is 46%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 86%; characterization of number average molecular weight M by GPC n 114236g/mol and a molecular weight distribution PDI of 1.9; characterization by NMR: the polybutadiene block has a 1, 4-selectivity of 92% and a 1, 2-selectivity of 8%.
Example 19 (number of charges n=4)
A50 mL reaction flask was charged with a toluene (3.5 mL) solution of azobisisovaleronitrile (AMBN, 4.4mg, 23. Mu. Mol,1 equiv.) and acrylonitrile (1.5 mL,23mmol,1000 equiv.) and butadiene (2.0 mL,23mmol,1000 equiv.) in this order under an argon atmosphere. The reaction was carried out at 70℃for 12 hours. The reaction was transferred to a liquid nitrogen bath, AMBN (4.4 mg,23 μmol,1 equiv.) was added, and the reaction was continued at 70 ℃ for 12 hours. The reaction was then transferred to a liquid nitrogen bath, AMBN (4.4 mg,23 μmol,1 equiv.) was added, and the reaction was continued at 70 ℃ for 12 hours. The reaction was continued to be transferred to a liquid nitrogen bath, AMBN (4.4 mg,23 μmol,1 equiv.) was added, and the reaction was continued at 70 ℃ for 12 hours. Quenching with cold methanol, washing for three times, and vacuum drying to constant weight to obtain nitrile rubber elastomer, wherein the system has no gel.
The calculated yield is 69.0%, the acrylonitrile content is 45%, and the acrylonitrile-butadiene rubber belongs to nitrile rubber with extremely high nitrile content; the degree of alternation is 85%; characterization of number average molecular weight M by GPC n 109836g/mol and a molecular weight distribution PDI of 2.0; wherein by NMR: 92% and a 1, 2-selectivity content of 8%.
Performance testing
Taking the solution-clustered alternating nitrile rubber described in example 16 as an example, hydrogenated nitrile rubber was prepared and tested for performance to obtain the following parameters:
combined acrylonitrile content% Mooney viscosity ML (1+4) 100C Iodine number g (100 g) -1
36 85 4
The parameter is consistent with the Japanese rayleigh company product Zetpol2000, which shows that the product hydrogenated by the solution-clustered alternate nitrile rubber can be compared with the international monopoly product of hydrogenated nitrile rubber, the problem of neck blocking of the country on the technical material is solved to a certain extent, and the preparation method of the solution-clustered alternate nitrile rubber provided by the application has the advantages of simple operation, convenient post-treatment, high product yield and higher market application prospect.

Claims (10)

1. The solution-clustered alternating nitrile rubber is characterized by having the following structural sequence general formula:
-(B-A-B-A-B-B-A) n -，
wherein B is a butadiene unit, A is an acrylonitrile unit, and n is any integer value within the range of 53-1065;
the adjustable range of the number average molecular weight of the nitrile rubber is 2-40 ten thousand g/mol, the molecular weight distribution PDI is 1.5-4.0, the insertion rate of acrylonitrile in the nitrile rubber is 35-50%, and the AB alternation degree is at least 81%.
2. The method for preparing the solution-clustered alternating nitrile rubber according to claim 1, wherein,
under the condition of no water and oxygen, adding solvent, nitrile free radical initiator, butadiene monomer and acrylonitrile monomer into a reactor according to a preset feeding sequence, polymerizing for 4-48 h at 50-100 ℃, quenching, washing and vacuum drying to obtain the solution-clustered alternate nitrile rubber.
3. The process according to claim 2, wherein the nitrile free radical initiator is fed in a batch process during the polymerization, wherein the number of batch feeds is 1< n <10, n being an integer.
4. A method of preparation according to claim 2 or 3, wherein the sequence of addition is:
sequentially adding a nitrile free radical initiator and a solvent into a reactor, and adding an acrylonitrile monomer and a butadiene monomer to react for a specific time after the nitrile free radical initiator and the solvent are completely dissolved; then adding a nitrile free radical initiator with specific equivalent weight and a solvent in sequence to completely dissolve the nitrile free radical initiator and the solvent for copolymerization reaction to obtain nitrile rubber; or alternatively
Sequentially adding an acrylonitrile monomer and a butadiene monomer solution into a reactor, after uniformly mixing and completely dissolving, adding a nitrile free radical initiator to react for a specific time, and sequentially adding a nitrile free radical initiator with a specific equivalent weight and a solvent to completely dissolve for copolymerization reaction to obtain nitrile rubber; or alternatively
Sequentially adding an acrylonitrile monomer and a nitrile free radical initiator into a reactor, after uniformly mixing, adding a butadiene monomer to react for a specific time, and sequentially adding a nitrile free radical initiator with a specific equivalent weight and a solvent to completely dissolve for copolymerization reaction to obtain nitrile rubber; or alternatively
And sequentially adding butadiene monomers, nitrile free radical initiators and solvents into the reactor, adding acrylonitrile monomers to react for a specific time after uniformly mixing, and sequentially adding the nitrile free radical initiators with specific equivalent weights and the solvents to completely dissolve for copolymerization reaction to obtain the nitrile rubber.
5. The process of claim 4, wherein the reaction time of the first charge is from 2 hours to 48 hours during the fed-batch polymerization; the reaction time of the second feeding is 2-48 h.
6. A process according to claim 3, wherein the equivalent ratio of nitrile radical initiator required for the second to first charge is 1/1 during the fed-batch polymerization.
7. The preparation method according to claim 2, wherein the nitrile radical initiator is azo-CN radical-forming compound, and is at least one selected from azobisisobutyronitrile AIBN, azobisisoheptonitrile ABVN, and azobisisovaleronitrile AMBN; the solvent is at least one selected from toluene, ethylbenzene, xylene, chlorobenzene, benzotrifluoride, 1,3, 5-trimethylbenzene and 1,2, 4-trimethylbenzene.
8. The process according to claim 2, wherein the equivalent ratio of butadiene monomer to acrylonitrile monomer is 8/2 to 4/6, the equivalent ratio of nitrile radical initiator to comonomer of butadiene and acrylonitrile is 1/100 to 1/2500, and the volume ratio of solvent to comonomer of butadiene and acrylonitrile is 1/1 to 5/1.
9. The method according to claim 2, wherein the vacuum drying is performed at a temperature of 30-50 ℃ for a time of 12-24 hours.
10. The hydrogenated nitrile rubber is characterized in that the hydrogenated nitrile rubber is prepared by adopting the solvent-cluster alternating nitrile rubber prepared by the preparation method of claim 1 or any one of claims 2-9.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5033519B1 (en) * 1970-07-28 1975-10-31
US3917554A (en) * 1968-10-04 1975-11-04 Bridgestone Tire Co Ltd Butadiene-acrylonitrile alternating copolymer solution-type adhesive
JPS549234B1 (en) * 1969-12-03 1979-04-23
CN104185645A (en) * 2011-08-02 2014-12-03 朗盛德国有限责任公司 Process for producing nitrile rubbers in organic solvents

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917554A (en) * 1968-10-04 1975-11-04 Bridgestone Tire Co Ltd Butadiene-acrylonitrile alternating copolymer solution-type adhesive
JPS549234B1 (en) * 1969-12-03 1979-04-23
JPS5033519B1 (en) * 1970-07-28 1975-10-31
CN104185645A (en) * 2011-08-02 2014-12-03 朗盛德国有限责任公司 Process for producing nitrile rubbers in organic solvents

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