CN115894786B - Modified conjugated diene-acrylonitrile rubber and preparation method and application thereof - Google Patents

Modified conjugated diene-acrylonitrile rubber and preparation method and application thereof Download PDF

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CN115894786B
CN115894786B CN202211280849.XA CN202211280849A CN115894786B CN 115894786 B CN115894786 B CN 115894786B CN 202211280849 A CN202211280849 A CN 202211280849A CN 115894786 B CN115894786 B CN 115894786B
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conjugated diene
acrylonitrile
rubber
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CN115894786A (en
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王庆刚
李仁辉
王亮
张娇娇
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Abstract

A modified conjugated diene-acrylonitrile rubber and a preparation method and application thereof. The invention belongs to the field of conjugated diene-acrylonitrile rubber and preparation thereof. The invention aims to solve the technical problem that the prior conjugated diene-acrylonitrile rubber has a single structure and poor comprehensive performance due to single performance. The modified conjugated diene-acrylonitrile rubber is prepared from conjugated diene, acrylonitrile and acrylic ester monomers, wherein the insertion rate of the acrylonitrile is 40-50%, the insertion rate of the acrylic ester monomers is 1-10%, and the molar content of trans-1, 4-structures in a poly conjugated diene chain segment is 80-99%. The preparation method comprises the following steps: under the conditions of no water, no oxygen and polar solvent, the polymer is polymerized by an azo free radical initiator. The modified conjugated diene-acrylonitrile rubber disclosed by the invention has excellent comprehensive performance and is applied to the fields of aerospace, automobiles, military, wires and cables, gaskets, fabric coatings or rubber gloves.

Description

Modified conjugated diene-acrylonitrile rubber and preparation method and application thereof
Technical Field
The invention belongs to the field of conjugated diene-acrylonitrile rubber and preparation thereof, and particularly relates to modified conjugated diene-acrylonitrile rubber and a preparation method and application thereof.
Background
Nitrile rubber (NBR) and valeronitrile rubber (MBR) are block copolymers prepared by free radical polymerization of Butadiene (BD) or isoprene and Acrylonitrile (AN) monomers, and the molecular structure of the block copolymers contains unsaturated double bonds and polar groups-CN, so that the block copolymers have excellent physical and mechanical properties, in particular heat aging resistance, oil resistance and the like.
The nitrile rubber has excellent oil resistance and mechanical property due to the existence of nitrile groups, is widely applied to the fields of aerospace, automobiles, military, wires and cables and the like, and can be used for producing various oil-resistant rubber products and the like due to the fact that the price of the nitrile rubber is far lower than that of fluororubber. Valeronitrile rubber (MBR) has wide application potential and lower cost in oil resistant rubber articles such as gaskets, fabric coatings, rubber gloves, and the like.
In the industrial field, due to the continuous development of industrial technology, the requirements on rubber are higher and higher, and the pure cyano and unsaturated carbon chain structure cannot meet all industrial requirements. The structure of butadiene and isoprene, which are the major components of the molecular structure, is closely related to rubber properties, but modification of such rubber molecular structure has been recently reported.
Disclosure of Invention
The invention aims to solve the technical problem that the prior conjugated diene-acrylonitrile rubber has a single structure and poor comprehensive performance due to single performance, and provides a modified conjugated diene-acrylonitrile rubber and a preparation method and application thereof.
The modified conjugated diene-acrylonitrile rubber is prepared from conjugated diene, acrylonitrile and acrylic ester monomers, wherein the insertion rate of the acrylonitrile is 40-50%, the insertion rate of the acrylic ester monomers is 1-10%, and the molar content of trans-1, 4-structures in a poly conjugated diene chain segment is 80-99%.
Further defined, the conjugated diene is butadiene or isoprene.
Still further defined, cis-1, 4-butadiene and 1, 2-butadiene are also included in the polybutadiene block, wherein the molar content of 1, 2-butadiene is 1-20%, while the sum of the molar contents of trans-1, 4-butadiene, cis-1, 4-butadiene and 1, 2-butadiene satisfies 100%.
Still further defined, cis-1, 4-isoprene and 3, 4-isoprene are also included in the polyisoprene segment, wherein the molar content of 3, 4-isoprene is 1-20%, while the sum of the molar contents of trans-1, 4-isoprene, cis-1, 4-isoprene and 3, 4-isoprene satisfies 100%.
Further defined, the modified conjugated diene-acrylonitrile rubber has a number average molecular weight of 2 to 20 ten thousand g/mol and a molecular weight distribution (PDI) of 1.0 to 5.0.
Further defined, the acrylic monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-methyl methacrylate, and 2-ethyl methacrylate.
The preparation method of the modified conjugated diene-acrylonitrile rubber comprises the following steps:
under the anhydrous and anaerobic condition, the polymer is polymerized in polar solvent by azo radical initiator, the polymerization temperature is 50-120 ℃ and the polymerization time is 2-48h.
Further defined, the polar solvent is a ketone, alcohol or ester polar solvent.
Further defined, the ketone polar solvent includes acetone, cyclohexanone, isophorone, methyl isobutyl ketone, methyl ethyl ketone.
Further defined, the polar alcohol solvents include n-propanol, n-butanol, isopropanol, isobutanol, isooctanol, tert-butanol.
Still further defined, the polar solvents of esters include methyl acetate, ethyl acetate, n-propyl acetate, and dimethyl carbonate.
Further defined, the azo-based free radical initiator is any one of the following structures:
further defined, the molar ratio of the azo free radical initiator to conjugated diene, acrylonitrile and acrylic ester monomer is 1 (100-3000): (100-3000): (100-3000).
Further defined is a ratio of the sum of the volumes of conjugated diene, acrylonitrile and acrylate monomer to the volume of the polar solvent of 1 (1-5).
Further defined, the polymerization temperature is 70℃and the time is 24 hours.
The modified conjugated diene-acrylonitrile rubber is applied to the fields of aerospace, automobiles, military or wires and cables.
The modified conjugated diene-acrylonitrile rubber is applied to the fields of gaskets, fabric coatings or rubber gloves.
Compared with the prior art, the invention has the remarkable effects that:
the invention prepares the modified conjugated diene-acrylonitrile rubber with excellent comprehensive performance by taking conjugated diene, acrylonitrile and acrylic ester monomers as raw materials through efficient solution polymerization, and the obtained yield and the acrylonitrile doping ratio are higher than those of the existing conjugated diene-acrylonitrile rubber, and the specific advantages are as follows:
1) According to the invention, the acrylic ester monomer is introduced into the conjugated diene-acrylonitrile rubber system to prepare the modified conjugated diene-acrylonitrile rubber with a brand new structure, and a large number of ethylene or propenyl side groups on the main chain increase the distance between molecular chains, so that the acrylonitrile insertion rate is greatly improved, and the acrylonitrile content in the modified conjugated diene-acrylonitrile rubber is up to 50%.
2) The existence of the side group also facilitates the insertion of the acrylic ester monomer, so that the temperature resistance of the modified valeronitrile rubber is improved, but in order to ensure the comprehensive performance of the conjugated diene-acrylonitrile rubber, the invention controls the acrylic ester content within the range of 1-10 percent, and realizes the modification of the original molecular chain structure of the conjugated diene-acrylonitrile rubber, thereby realizing the dynamic balance between the oil resistance, the oxidation resistance and the temperature resistance of the modified conjugated diene-acrylonitrile rubber, further obtaining a conjugated diene-acrylonitrile rubber material with excellent comprehensive performance, and showing remarkable application prospect in the aspects of realizing the further modification of the nitrile rubber and the production of special nitrile rubber meeting industrial requirements.
3) The high-content trans-1, 4-structure enables the modified conjugated diene-acrylonitrile rubber to have more excellent tensile elasticity, thereby remarkably prolonging the service life.
4) Compared with the traditional emulsion polymerization, the solvent free radical polymerization has higher yield, and the solution can be recovered by the method, so that the production cost is greatly reduced, and the method is more environment-friendly.
Drawings
FIG. 1 is a modified nitrile rubber prepared in example 4 1 HNMR spectrogram;
FIG. 2 is a modified nitrile rubber prepared in example 4 13 C NMR spectrum;
FIG. 3 is a DSC spectrum of the modified nitrile rubber prepared in example 4;
FIG. 4 shows the nitrile rubber prepared in the comparative example 1 HNMR spectrogram;
FIG. 5 is a modified valeronitrile rubber prepared in example 14 1 HNMR spectra.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Modified nitrile rubber
Example 1: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, a solution of azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) acrylonitrile (15.0 mL,230mmol,1000 equiv.) methyl methacrylate (4.9 mL,46mmol,200 equiv.) and cyclohexanone (39.9 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) were sequentially added under an argon atmosphere, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 39.5%, the acrylonitrile content was 47.6% and the methyl methacrylate content was 5.9%; characterization of number average molecular weight M by GPC n 8.1X10 times 4 g/mol, a molecular weight distribution PDI of 1.9; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 88.5% in the 1, 4-polybutadiene chain.
Example 2: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, a solution of azobisisovaleronitrile (AMBN, 487mg, 253. Mu. Mol,1.1 equiv.) was added sequentially, acrylonitrile (15.0 mL,230mmol,1000 equiv.) and a solution of methyl methacrylate (4.9 mL,46mmol,200 equiv.) and butadiene (20.0 mL,230mmol,1000 equiv.) in cyclohexanone (39.9 mL) under an argon atmosphere, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and dried in vacuo to constant weight to give a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 34.8%, the acrylonitrile content was 45.8% and the methyl methacrylate content was 6.0%; characterization by GPCAverage molecular weight M n Is 6.6X10 4 g/mol, a molecular weight distribution PDI of 1.7; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 89.2% in the 1, 4-polybutadiene chain.
Example 3: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask under argon atmosphere, azodiisoheptanenitrile (ABVN, 62.9mg, 235. Mu. Mol,1.1 equiv.) was added sequentially, a solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) of methyl methacrylate (4.9 mL,46mmol,200 equiv.) and cyclohexanone (39.9 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) was reacted at 70℃for 24 hours, quenched and washed three times with cold methanol, and dried in vacuo to constant weight to give a modified nitrile rubber elastomer, which was gel-free.
The calculated yield was 35.7%, the acrylonitrile content was 40.4% and the methyl methacrylate content was 4.5%; characterization of number average molecular weight M by GPC n 4.5X10 4 g/mol, a molecular weight distribution PDI of 2.0; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 88.8% in the 1, 4-polybutadiene chain.
Example 4: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) was added sequentially under argon atmosphere, a solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) of n-butyl acrylate (6.6 mL,46mmol,200 equiv.) and cyclohexanone (41.6 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) was reacted at 70℃for 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free.
The modified nitrile rubber elastomer obtained in this example 1 H NMR spectrum, 13 The C NMR spectrum and DSC spectrum are shown in FIGS. 1-3.
The calculated yield was 35.1%, the acrylonitrile content was 40.0% and the n-butyl acrylate content was 3.2The%; characterization of number average molecular weight M by GPC n 8.0X10 4 g/mol, a molecular weight distribution PDI of 2.7; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 92.6% in the 1, 4-polybutadiene chain.
Example 5: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) was added sequentially under argon atmosphere, a solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) of methyl acrylate (4.2 mL,46mmol,200 equiv.) and cyclohexanone (39.2 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) was reacted at 70℃for 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 43.5%, the acrylonitrile content was 42.0% and the methyl acrylate content was 4.2%; characterization of number average molecular weight M by GPC n 6.5X10 4 g/mol, a molecular weight distribution PDI of 2.2; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 91.0% in the 1, 4-polybutadiene chain.
Example 6: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) was added sequentially under argon atmosphere, a solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) of ethyl acrylate (5.5 mL,46mmol,200 equiv.) and cyclohexanone (40.5 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) was reacted at 70℃for 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 34.6%, the acrylonitrile content was 49.3% and the ethyl acrylate content was 3.6%; characterization of number average molecular weight M by GPC n Is 7.1X10 × 10 4 g/mol, a molecular weight distribution PDI of 2.6; characterization by NMR: polybutadiene segment 1, 4-selectivity content of90.4%, the 1, 2-selectivity was 9.6%, and the trans-1, 4-selectivity in the 1, 4-polybutadiene chain was 88.8%.
Example 7: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) was added sequentially under argon atmosphere, a solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) of propyl acrylate (5.7 mL,46mmol,200 equiv.) and cyclohexanone (40.7 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) was reacted at 70℃for 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 37.9%, the acrylonitrile content was 44.7%, and the propyl acrylate content was 3,2%; characterization of number average molecular weight M by GPC n 5.4X10 4 g/mol, a molecular weight distribution PDI of 2.2; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 85.4% in the 1, 4-polybutadiene chain.
Example 8: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) was added sequentially under argon atmosphere, a solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) of isobutyl acrylate (6.6 mL,46mmol,200 equiv.) and cyclohexanone (41.6 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) was reacted at 70℃for 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 32.8%, the acrylonitrile content was 44.7% and the isobutyl acrylate content was 3.8%; characterization of number average molecular weight M by GPC n Is 7.4X10 4 g/mol, a molecular weight distribution PDI of 2.0; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 88.4% in the 1, 4-polybutadiene chain.
Example 9: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, an azodiisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) and isobornyl acrylate (9.6 mL,46mmol,200 equiv.) and cyclohexanone (44.6 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) were sequentially added under an argon atmosphere, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and dried in vacuo to constant weight to give a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield is 33.7%, the acrylonitrile content is 40.7%, and the isobornyl acrylate content is 4.8%; characterization of number average molecular weight M by GPC n 8.9X10 4 g/mol, a molecular weight distribution PDI of 2.0; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 89.4% in the 1, 4-polybutadiene chain.
Example 10: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, a solution of azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) was added sequentially, acrylonitrile (15.0 mL,230mmol,1000 equiv.) and a solution of methyl methacrylate (4.9 mL,46mmol,200 equiv.) and butadiene (20.0 mL,230mmol,1000 equiv.) in cyclohexanone (39.9 mL) under an argon atmosphere, the system was moved to 80℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 36.5%, the acrylonitrile content was 44.7% and the methyl methacrylate content was 4.8%; characterization of number average molecular weight M by GPC n 8.3X10 4 g/mol, a molecular weight distribution PDI of 2.5; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 89.2% in the 1, 4-polybutadiene chain.
Example 11: the preparation method of the modified nitrile rubber comprises the following steps:
in a 120mL reaction flask, a solution of azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) was added sequentially, acrylonitrile (15.0 mL,230mmol,1000 equiv.) and a solution of methyl methacrylate (4.9 mL,46mmol,200 equiv.) and butadiene (20.0 mL,230mmol,1000 equiv.) in cyclohexanone (39.9 mL) under an argon atmosphere, the system was moved to 90℃to react for 24 hours, quenched and washed three times with cold methanol, and dried in vacuo to constant weight to give a modified nitrile rubber elastomer, the system was gel-free.
The calculated yield was 35.5%, the acrylonitrile content was 45.7% and the methyl methacrylate content was 3.2%; characterization of number average molecular weight M by GPC n Is 7.2X10 4 g/mol, a molecular weight distribution PDI of 2.7; characterization by NMR: the polybutadiene block had a 1, 4-selectivity of 90.4%, a 1, 2-selectivity of 9.6% and a trans-1, 4-selectivity of 84.2% in the 1, 4-polybutadiene chain.
Comparative example: the preparation method of the nitrile rubber comprises the following steps:
in a 120mL reaction flask, azodiisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.) and a solution of acrylonitrile (15.0 mL,230mmol,1000 equiv.) and cyclohexanone (39.9 mL) of butadiene (20.0 mL,230mmol,1000 equiv.) were sequentially added under an argon atmosphere, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified nitrile rubber elastomer, the system was gel-free. The obtained modified nitrile rubber elastomer 1 The HNMR spectra are shown in FIG. 4.
The calculated yield was 37.5% and the acrylonitrile content was 24.0%, the number average molecular weight M being characterized by GPC n Is 7.0X10 4 g/mol, a molecular weight distribution PDI of 1.8; characterization by NMR: the 1, 4-selectivity of the polybutadiene block was 80.6%, the 1, 2-selectivity was 19.4%, and the trans-1, 4-selectivity of the polybutadiene block was 72.5%.
Modified valeronitrile rubber
Example 12: the preparation method of the modified valeronitrile rubber comprises the following steps:
in a 120mL reaction flask, azobisisobutyronitrile (AIBN, 41.6mg, 230. Mu. Mol,1.1 equiv.) was added sequentially under argon atmosphere, acrylonitrile (15.0 mL,230mmol,1000 equiv.), isoprene (23.1 mL,230mmol,1000 equiv.), n-butyl acrylate (6.6 mL,46mmol,200 equiv.) and cyclohexanone (41.6 mL) in solution, the system was moved to 70℃to react for 24 hours, quenched and washed three times with cold methanol, and vacuum-dried to constant weight to obtain a modified valeronitrile rubber elastomer, the system was gel-free.
The calculated yield is 42.2%, the acrylonitrile content is 51.0%, the n-butyl acrylate content is 2.9%, and the modified valeronitrile rubber with extremely high nitrile content is prepared; characterization of number average molecular weight M by GPC n Is 7.3X10 4 g/mol, a molecular weight distribution PDI of 1.8; characterization by NMR: the 1, 4-selectivity of the polyisoprene chain segment was 84.7%, the 3, 4-selectivity was 15.3%, and the trans-1, 4-selectivity of the polyisoprene chain segment was 83.0%.
Example 13: the preparation method of the modified valeronitrile rubber comprises the following steps:
in a 120mL reaction flask under argon atmosphere, azobisisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.) acrylonitrile (15.0 mL,230mmol,1000 equiv.), isoprene (23.1 mL,230mmol,1000 equiv.), n-butyl acrylate (6.6 mL,46mmol,200 equiv.) and cyclohexanone (41.6 mL) were sequentially added, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified valeronitrile rubber elastomer, the system was gel-free.
The calculated yield is 37.6%, the acrylonitrile content is 49.1%, the n-butyl acrylate content is 3.6%, and the modified valeronitrile rubber with extremely high nitrile content is prepared; characterization of number average molecular weight M by GPC n 6.8X10 4 g/mol, a molecular weight distribution PDI of 2.1; characterization by NMR: the 1, 4-selectivity of the polyisoprene chain segment was 84.7%, the 3, 4-selectivity was 15.3%, and the trans-1, 4-selectivity of the polyisoprene chain segment was 83.0%.
Example 14: the preparation method of the modified valeronitrile rubber comprises the following steps:
in a 120mL reaction flask, azobisisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.) and acrylonitrile (15.0)mL,230mmol,1000 equiv.), isoprene (23.1 mL,230mmol,1000 equiv.), n-butyl acrylate (6.6 mL,46mmol,200 equiv.) and toluene (41.6 mL), the system was moved to 70℃for reaction 24h, quenched with cold methanol and washed three times, and dried under vacuum to constant weight to give a modified valeronitrile rubber elastomer, the system was gel-free. Obtained valeronitrile rubber elastomer 1 The HNMR spectra are shown in FIG. 5.
The calculated yield is 41.5%, the acrylonitrile content is 49.5%, the n-butyl acrylate content is 2.9%, and the modified valeronitrile rubber with extremely high nitrile content is prepared; characterization of number average molecular weight M by GPC n Is 7.0X10 4 g/mol, a molecular weight distribution PDI of 1.9; characterization by NMR: the 1, 4-selectivity content of the polyisoprene chain segment is 82.6%, the 3, 4-selectivity content is 17.4%, and the trans-1, 4-selectivity content of the polyisoprene chain segment is 99.0%.
Example 15: the preparation method of the modified valeronitrile rubber comprises the following steps:
in a 120mL reaction flask under argon atmosphere, azobisisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.) acrylonitrile (15.0 mL,230mmol,1000 equiv.), isoprene (23.1 mL,230mmol,1000 equiv.), isobutyl acrylate (6.6 mL,46mmol,200 equiv.) and toluene (41.6 mL) were sequentially added, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified valeronitrile rubber elastomer, the system was gel-free.
The calculated yield is 40.5%, the acrylonitrile content is 46.5%, the isobutyl acrylate content is 2.1%, and the modified valeronitrile rubber with extremely high nitrile content is prepared; characterization of number average molecular weight M by GPC n 6.3X10 4 g/mol, a molecular weight distribution PDI of 1.9; characterization by NMR: the 1, 4-selectivity content of the polyisoprene chain segment is 82.5%, the 3, 4-selectivity content is 17.5%, and the trans-1, 4-selectivity content of the polyisoprene chain segment is 99.0%.
Example 16: the preparation method of the modified valeronitrile rubber comprises the following steps:
in a 120mL reaction flask, under an argon atmosphere, azobisisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.) was added sequentially, acrylonitrile (15.0 mL,230mmol,1000 equiv.), isoprene (23.1 mL,230mmol,1000 equiv.), methyl acrylate (6.6 mL,46mmol,200 equiv.) and toluene (41.6 mL) in solution, and the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum-dried to constant weight to obtain a modified valeronitrile rubber elastomer, which was gel-free.
The calculated yield is 46.5%, the acrylonitrile content is 43.5%, the methyl acrylate content is 2.1%, and the modified valeronitrile rubber with extremely high nitrile content is prepared; characterization of number average molecular weight M by GPC n Is 5.5X10 4 g/mol, a molecular weight distribution PDI of 2.4; characterization by NMR: the 1, 4-selectivity content of the polyisoprene chain segment is 82.8%, the 3, 4-selectivity content is 17.1%, and the trans-1, 4-selectivity content of the polyisoprene chain segment is 99.0%.
Example 17: the preparation method of the modified valeronitrile rubber comprises the following steps:
in a 120mL reaction flask, an azodiisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.) solution, acrylonitrile (15.0 mL,230mmol,1000 equiv.), isoprene (23.1 mL,230mmol,1000 equiv.), ethyl acrylate (6.6 mL,46mmol,200 equiv.) and toluene (41.6 mL) were sequentially added under an argon atmosphere, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified valeronitrile rubber elastomer, the system was gel-free.
The calculated yield is 48.7%, the acrylonitrile content is 43.9%, the ethyl acrylate content is 2.1%, and the modified valeronitrile rubber with extremely high nitrile content is prepared; characterization of number average molecular weight M by GPC n Is 5.9X10 4 g/mol, a molecular weight distribution PDI of 2.4; characterization by NMR: the 1, 4-selectivity content of the polyisoprene chain segment is 85.4%, the 3, 4-selectivity content is 14.6%, and the trans-1, 4-selectivity content of the polyisoprene chain segment is 99.0%.
Example 18: the preparation method of the modified valeronitrile rubber comprises the following steps:
in a 120mL reaction flask under argon atmosphere, azodiisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.) acrylonitrile (15.0 mL,230mmol,1000 equiv.), isoprene (23.1 mL,230mmol,1000 equiv.), methyl 2-methacrylate (6.7 mL,46mmol,200 equiv.) and toluene (41.6 mL) were sequentially added, the system was moved to 70℃for reaction 24 hours, quenched and washed three times with cold methanol, and vacuum dried to constant weight to obtain a modified valeronitrile rubber elastomer, the system was gel-free.
The calculated yield is 45.7%, the acrylonitrile content is 43.0%, the 2-methyl methacrylate content is 1.2%, and the modified valeronitrile rubber with extremely high nitrile content is prepared; characterization of number average molecular weight M by GPC n 4.1X10 times 4 g/mol, a molecular weight distribution PDI of 2.6; characterization by NMR: the 1, 4-selectivity content of the polyisoprene chain segment is 80.4%, the 3, 4-selectivity content is 19.6%, and the trans-1, 4-selectivity content of the polyisoprene chain segment is 99.0%.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (3)

1. The preparation method of the modified conjugated diene-acrylonitrile rubber is characterized in that the modified conjugated diene-acrylonitrile rubber is prepared from conjugated dienes, acrylonitrile and acrylic ester monomers, wherein the insertion rate of the acrylonitrile is 40-50%, the insertion rate of the acrylic ester monomers is 1-10%, the mol content of trans-1, 4-structures in a poly conjugated diene chain segment is 80-99%, and the acrylic ester monomers comprise methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate; the conjugated diene is butadiene or isoprene, the polybutadiene chain segment also comprises cis-1, 4-butadiene and 1, 2-butadiene, wherein the molar content of the 1, 2-butadiene is 1-20%, the polyisoprene chain segment also comprises cis-1, 4-isoprene and 3, 4-isoprene, and the molar content of the 3, 4-isoprene is 1-20%;
the preparation method comprises the following steps:
under the anhydrous and anaerobic condition, the polymer is polymerized in polar solvent by azo radical initiator, the polymerization temperature is 70 ℃ and the polymerization time is 24h.
2. The process for producing a modified conjugated diene-acrylonitrile rubber according to claim 1, wherein the modified conjugated diene-acrylonitrile rubber has a number average molecular weight of 2 to 20 ten thousand g/mol and a PDI of 1.0 to 5.0.
3. The method according to claim 1, wherein the molar ratio of azo-based free radical initiator to conjugated diene, acrylonitrile, and acrylic acid ester monomer is 1 (100-3000): (100-3000): (100-3000), and the ratio of the sum of volumes of conjugated diene, acrylonitrile, and acrylic acid ester monomer to the volume of polar solvent is 1 (1-5).
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Publication number Priority date Publication date Assignee Title
US4656219A (en) * 1982-03-27 1987-04-07 Nippon Zeon Co., Ltd. Rubber member having oil resistance and resistance to deterioration
US5089576A (en) * 1989-04-07 1992-02-18 Nippon Zeon Co., Ltd. Process for producing conjugated diene copolymer
CN112778457A (en) * 2020-12-31 2021-05-11 中国科学院青岛生物能源与过程研究所 Controllable preparation method of conjugated diene and polar olefin monomer copolymer
CN115109193A (en) * 2022-07-13 2022-09-27 中国科学院青岛生物能源与过程研究所 Nitrile rubber solution system capable of being directly hydrogenated and controllable preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656219A (en) * 1982-03-27 1987-04-07 Nippon Zeon Co., Ltd. Rubber member having oil resistance and resistance to deterioration
US5089576A (en) * 1989-04-07 1992-02-18 Nippon Zeon Co., Ltd. Process for producing conjugated diene copolymer
CN112778457A (en) * 2020-12-31 2021-05-11 中国科学院青岛生物能源与过程研究所 Controllable preparation method of conjugated diene and polar olefin monomer copolymer
CN115109193A (en) * 2022-07-13 2022-09-27 中国科学院青岛生物能源与过程研究所 Nitrile rubber solution system capable of being directly hydrogenated and controllable preparation method and application thereof

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