CN115894786A - 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 PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 93
- 239000005060 rubber Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 31
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 150000001993 dienes Chemical class 0.000 claims abstract description 11
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000003780 insertion Methods 0.000 claims abstract description 8
- 230000037431 insertion Effects 0.000 claims abstract description 8
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- -1 azo free radical Chemical class 0.000 claims abstract description 4
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- 229920002857 polybutadiene Polymers 0.000 claims description 26
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- 238000000034 method Methods 0.000 claims description 10
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- 239000000463 material Substances 0.000 claims description 4
- 125000002897 diene group Chemical group 0.000 claims description 2
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- 230000000977 initiatory effect Effects 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract description 3
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- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
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- 238000006243 chemical reaction Methods 0.000 description 35
- 238000012512 characterization method Methods 0.000 description 34
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 23
- 239000000806 elastomer Substances 0.000 description 22
- 238000009826 distribution Methods 0.000 description 20
- 239000012300 argon atmosphere Substances 0.000 description 19
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 18
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- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 7
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- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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Images
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- 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
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 conventional conjugated diene-acrylonitrile rubber has a single structure and single performance, so that the comprehensive performance is poorer. The modified conjugated diene-acrylonitrile rubber is prepared from conjugated diene, acrylonitrile and acrylate monomers, wherein the insertion rate of the acrylonitrile is 40-50%, the insertion rate of the acrylate monomers is 1-10%, and the molar content of a trans-1, 4-structure in a poly-conjugated diene chain segment is 80-99%. The preparation method comprises the following steps: the polymer is prepared by the polymerization initiated by azo free radical initiator under the conditions of no water, no oxygen and polar solvent. The modified conjugated diene-acrylonitrile rubber has excellent comprehensive performance and is applied to the fields of aerospace, automobiles, military affairs, wires and cables, gaskets, fabric coatings or rubber gloves.
Description
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, particularly heat and 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 and other products due to the price of the nitrile rubber is far lower than that of fluororubber. The valeronitrile rubber (MBR) has wide application potential and lower cost in oil-resistant rubber products such as gaskets, fabric coatings, rubber gloves and the like.
In the industrial field, due to the continuous development of industrial technology, the requirement on rubber is higher and higher, and the simple cyano and unsaturated carbon chain structure can not meet all industrial requirements. The structures of butadiene and isoprene, which are the main parts of the molecular structures, are closely related to rubber properties, but few reports are made about the modification of the molecular structures of such rubbers.
Disclosure of Invention
The invention aims to solve the technical problems of poor comprehensive performance caused by single structure and single performance of the conventional conjugated diene-acrylonitrile rubber, 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 acrylate monomers, wherein the insertion rate of the acrylonitrile is 40-50%, the insertion rate of the acrylate monomers is 1-10%, and the molar content of a trans-1, 4-structure in a poly-conjugated diene chain segment is 80-99%.
Further defined, the conjugated diene is butadiene or isoprene.
More specifically, the polybutadiene block also comprises cis-1, 4-butadiene and 1, 2-butadiene, wherein the molar content of the 1, 2-butadiene is 1-20%, and the sum of the molar contents of the trans-1, 4-butadiene, the cis-1, 4-butadiene and the 1, 2-butadiene is 100%.
More specifically, the polyisoprene chain segment also comprises cis-1, 4-isoprene and 3, 4-isoprene, wherein the molar content of the 3, 4-isoprene is 1-20%, and the sum of the molar contents of the trans-1, 4-isoprene, the cis-1, 4-isoprene and the 3, 4-isoprene meets 100%.
Further limited, 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 acrylate monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl 2-methacrylate, and ethyl 2-methacrylate.
The preparation method of the modified conjugated diene-acrylonitrile rubber comprises the following steps:
the material is prepared by initiating polymerization by azo free radical initiator in polar solvent under anhydrous and oxygen-free conditions, wherein the polymerization temperature is 50-120 ℃, and the polymerization time is 2-48h.
Further limited, the polar solvent is a ketone, alcohol or ester polar solvent.
Still further defined, the ketone polar solvent includes acetone, cyclohexanone, isophorone, methyl isobutyl ketone, methyl ethyl ketone.
More particularly, the alcoholic polar solvent includes n-propanol, n-butanol, isopropanol, isobutanol, isooctanol, and t-butanol.
More specifically, the polar solvent of the ester type includes 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 limit, the mol ratio of the azo free radical initiator to the conjugated diene, the acrylonitrile and the acrylate monomer is 1 (100-3000) to (100-3000).
Further, the ratio of the sum of the volumes of the conjugated diene, the acrylonitrile and the acrylate monomer to the volume of the polar solvent is 1 (1-5).
Further defined, the polymerization temperature was 70 ℃ and the time was 24 hours.
The modified conjugated diene-acrylonitrile rubber is applied to the fields of aerospace, automobiles, military affairs or wires and cables.
The modified conjugated diene-acrylonitrile rubber is applied to the field of gaskets, fabric coatings or rubber gloves.
Compared with the prior art, the invention has the following remarkable effects:
the modified conjugated diene-acrylonitrile rubber with excellent comprehensive performance is prepared by taking conjugated diene, acrylonitrile and acrylate monomers as raw materials through efficient solution polymerization, the yield and the acrylonitrile doping rate of the modified conjugated diene-acrylonitrile rubber are higher than those of the conventional conjugated diene-acrylonitrile rubber, and the modified conjugated diene-acrylonitrile rubber has the following specific advantages:
1) The invention prepares a modified conjugated diene-acrylonitrile rubber with a brand new structure composition by introducing acrylate monomers into a conjugated diene-acrylonitrile rubber system, and a large amount of ethylene or propenyl side groups on a main chain increase the distance between molecular chains, so that the insertion rate of acrylonitrile is greatly improved, and the content of acrylonitrile in the modified conjugated diene-acrylonitrile rubber reaches 50 percent.
2) The existence of the side group also facilitates the insertion of the acrylate monomer, thereby improving the temperature resistance of the modified valeronitrile rubber, but in order to ensure the comprehensive performance of the conjugated diene-acrylonitrile rubber, the invention controls the content of the acrylate within the range of 1-10 percent, realizes the modification of the original molecular chain structure of the conjugated diene-acrylonitrile rubber, thereby achieving 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 prospects in the aspects of realizing the further modification of the nitrile rubber and meeting the production of special nitrile rubber with industrial requirements.
3) The high content of trans-1, 4-structure enables the modified conjugated diene-acrylonitrile rubber to have more excellent tensile elasticity, thereby obviously prolonging the service life.
4) The method has the advantages that the yield of the solvent free radical polymerization is higher than that of the traditional emulsion polymerization, and the solution can be recycled, so that the production cost is greatly reduced, and the method is more environment-friendly.
Drawings
FIG. 1 shows the preparation of a modified nitrile rubber as prepared in example 4 1 HNMR spectrogram;
FIG. 2 shows the preparation of modified nitrile rubber according to 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 preparation of a nitrile rubber according to the comparative example 1 HNMR spectrogram;
FIG. 5 is a view of a modified valeronitrile rubber prepared in example 14 1 HNMR spectrogram.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional and commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are used without limitation to the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates only the singular.
Modified nitrile rubber
Example 1: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), methyl methacrylate (4.9mL, 46mmol, 200equiv.) and butadiene (20.0mL, 230mmol, 1000equiv.) in cyclohexanone (39.9 mL) solution are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 39.5%, the acrylonitrile content was 47.6%, and the methyl methacrylate content was 5.9%; number average molecular weight M by GPC n Is 8.1X 10 4 g/mol, molecular weight distribution PDI of 1.9; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 88.5%.
Example 2: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisovaleronitrile (AMBN, 487mg, 253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), methyl methacrylate (4.9mL, 46mmol, 200equiv.) and butadiene (20.0mL, 230mmol, 1000equiv.) are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 34.8%, the acrylonitrile content was 45.8%, and the methyl methacrylate content was 6.0%; characterization of the number average molecular weight M by GPC n Is 6.6X 10 4 g/mol, molecular weight distribution PDI of 1.7; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 89.2%.
Example 3: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisoheptonitrile (ABVN, 62.9mg,235 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), methyl methacrylate (4.9mL, 46mmol, 200equiv.) and butadiene (20.0mL, 230mmol, 1000equiv.) in cyclohexanone (39.9 mL) solution are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24 hours, quenched by cold methanol and washed for three times, and dried in vacuum until the weight is constant to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 35.7%, the acrylonitrile content was 40.4%, and the methyl methacrylate content was 4.5%; characterization of the number average molecular weight M by GPC n Is 4.5 multiplied by 10 4 g/mol, molecular weight distribution PDI of 2.0; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%,1, 2-selectivityThe content was 9.6%, and the trans-1, 4-selective content in the 1, 4-polybutadiene chain was 88.8%.
Example 4: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), n-butyl acrylate (6.6 mL,46mmol, 200equiv.) and butadiene (20.0 mL,230mmol, 1000equiv.) in cyclohexanone (41.6 mL) solution are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24h, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
Modified nitrile rubber elastomer obtained in this example 1 H NMR spectrum, 13 The C NMR spectrum and the DSC spectrum are shown in FIGS. 1-3.
The calculated yield is 35.1%, the acrylonitrile content is 40.0%, and the n-butyl acrylate content is 3.2%; characterization of the number average molecular weight M by GPC n Is 8.0X 10 4 g/mol, molecular weight distribution PDI of 2.7; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 92.6%.
Example 5: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), methyl acrylate (4.2 mL,46mmol, 200equiv.) and butadiene (20.0 mL,230mmol, 1000equiv.) in turn are added into a 120mL reaction bottle under argon atmosphere, the system is moved to 70 ℃ for reaction for 24h, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 43.5%, the acrylonitrile content was 42.0%, and the methyl acrylate content was 4.2%; characterization of the number average molecular weight M by GPC n Is 6.5X 10 4 g/mol, molecular weight distribution PDI of 2.2; characterization by NMR: 1, 2-Selective content of the polybutadiene segment of 90.4%The selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 91.0%.
Example 6: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), ethyl acrylate (5.5 mL,46mmol, 200equiv.), and butadiene (20.0 mL,230mmol, 1000equiv.) in turn are added into a 120mL reaction flask under argon atmosphere, the system is moved to 70 ℃ for reaction for 24h, quenched and washed with cold methanol three times, and dried under vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 34.6%, the acrylonitrile content was 49.3%, and the ethyl acrylate content was 3.6%; characterization of the number average molecular weight M by GPC n Is 7.1 × 10 4 g/mol, molecular weight distribution PDI is 2.6; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 88.8%.
Example 7: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), propyl acrylate (5.7mL, 46mmol, 200equiv.), and butadiene (20.0mL, 230mmol, 1000equiv.) in cyclohexanone (40.7 mL) solution are sequentially added into a 120mL reaction bottle under argon atmosphere, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 37.9%, the acrylonitrile content was 44.7%, and the propyl acrylate content was 3,2%; characterization of the number average molecular weight M by GPC n Is 5.4X 10 4 g/mol, molecular weight distribution PDI of 2.2; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 85.4%.
Example 8: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), isobutyl acrylate (6.6 mL,46mmol, 200equiv.) and butadiene (20.0 mL,230mmol, 1000equiv.) are added in turn into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24h, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 32.8%, the acrylonitrile content was 44.7%, and the isobutyl acrylate content was 3.8%; number average molecular weight M by GPC n Is 7.4X 10 4 g/mol, molecular weight distribution PDI of 2.0; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 88.4%.
Example 9: the preparation method of the modified nitrile rubber of the embodiment comprises the following steps:
under argon atmosphere, azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), isobornyl acrylate (9.6 mL,46mmol, 200equiv.) and butadiene (20.0 mL,230mmol, 1000equiv.) in turn are added into a 120mL reaction flask, the system is moved to 70 ℃ for reaction for 24h, quenched by cold methanol and washed three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 33.7%, the acrylonitrile content was 40.7%, and the isobornyl acrylate content was 4.8%; characterization of the number average molecular weight M by GPC n Is 8.9 multiplied by 10 4 g/mol, molecular weight distribution PDI is 2.0; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 89.4%.
Example 10: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), methyl methacrylate (4.9mL, 46mmol, 200equiv.) and butadiene (20.0mL, 230mmol, 1000equiv.) in cyclohexanone (39.9 mL) solution are sequentially added into a 120mL reaction bottle, the system is moved to 80 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 36.5%, the acrylonitrile content was 44.7%, and the methyl methacrylate content was 4.8%; characterization of the number average molecular weight M by GPC n Is 8.3X 10 4 g/mol, molecular weight distribution PDI of 2.5; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 89.2%.
Example 11: the preparation method of the modified nitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), methyl methacrylate (4.9mL, 46mmol, 200equiv.) and butadiene (20.0mL, 230mmol, 1000equiv.) in cyclohexanone (39.9 mL) solution are sequentially added into a 120mL reaction bottle, the system is moved to 90 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified nitrile rubber elastomer, and the system has no gel.
The calculated yield was 35.5%, the acrylonitrile content was 45.7%, and the methyl methacrylate content was 3.2%; characterization of the number average molecular weight M by GPC n Is 7.2X 10 4 g/mol, molecular weight distribution PDI of 2.7; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 90.4%, the 1, 2-selectivity content was 9.6%, and the trans-1, 4-selectivity content in the 1, 4-polybutadiene chain was 84.2%.
Comparative example: the preparation method of the nitrile rubber of the embodiment is carried out according to the following steps:
in a 120mL reaction flask, under an argon atmosphere, rings of azobisisobutyronitrile (AIBN, 41.6mg, 253. Mu. Mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.) and butadiene (20.0 mL,230mmol, 1000equiv.) were added in this orderAnd (3) moving the system to 70 ℃ to react for 24h by using hexanone (39.9 mL) solution, quenching by using cold methanol and washing for three times, and drying in vacuum to constant weight to obtain the modified nitrile-butadiene rubber elastomer, wherein the system has no gel. The obtained modified nitrile rubber elastomer 1 The HNMR spectrum is shown in FIG. 4.
The calculated yield was 37.5%, the acrylonitrile content was 24.0%, and the number average molecular weight M was determined by GPC n Is 7.0X 10 4 g/mol, the molecular weight distribution PDI is 1.8; characterization by NMR: the 1, 4-selectivity content of the polybutadiene block was 80.6%, the 1, 2-selectivity content was 19.4%, and the trans-1, 4-selectivity content of the polybutadiene block was 72.5%.
Modified nitrile rubber
Example 12: the preparation method of the modified valeronitrile rubber of the embodiment comprises the following steps:
azodiisobutyronitrile (AIBN, 41.6mg,230 mu mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), isoprene (23.1 mL,230mmol, 1000equiv.), n-butyl acrylate (6.6 mL,46mmol, 200equiv.) and cyclohexanone (41.6 mL) are sequentially added into a 120mL reaction bottle under argon atmosphere, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified valeronitrile rubber elastomer, and the system has no gel.
The calculated yield is 42.2%, the acrylonitrile content is 51.0%, the n-butyl acrylate content is 2.9%, and the nitrile rubber belongs to a modified valeronitrile rubber with extremely high nitrile content; characterization of the number average molecular weight M by GPC n Is 7.3X 10 4 g/mol, the molecular weight distribution PDI is 1.8; characterization by NMR: the 1, 4-selectivity content of the polyisoprene segment was 84.7%, the 3, 4-selectivity content was 15.3%, and the trans-1, 4-selectivity content of the polyisoprene segment was 83.0%.
Example 13: the preparation method of the modified valeronitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisovaleronitrile (AMBN, 48.7mg,230 mu mol,1.1 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), isoprene (23.1mL, 230mmol, 1000equiv.), n-butyl acrylate (6.6mL, 46mmol, 200equiv.) and cyclohexanone (41.6 mL) are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed by cold methanol for three times, and dried in vacuum to constant weight to obtain the modified valeronitrile rubber elastomer, and the system has no gel.
The calculated yield is 37.6 percent, the acrylonitrile content is 49.1 percent, the n-butyl acrylate content is 3.6 percent, and the nitrile rubber belongs to modified valeronitrile rubber with extremely high nitrile content; characterization of the number average molecular weight M by GPC n Is 6.8 multiplied by 10 4 g/mol, molecular weight distribution PDI of 2.1; characterization by NMR: the 1, 4-selectivity content of the polyisoprene segment was 84.7%, the 3, 4-selectivity content was 15.3%, and the trans-1, 4-selectivity content of the polyisoprene segment was 83.0%.
Example 14: the preparation method of the modified valeronitrile rubber of the embodiment comprises the following steps:
under argon atmosphere, azodiisovaleronitrile (AMBN, 48.7mg,230 mu mol,1.1 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), isoprene (23.1mL, 230mmol, 1000equiv.), n-butyl acrylate (6.6mL, 46mmol, 200equiv.) and toluene (41.6 mL) are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified valeronitrile rubber elastomer, and the system has no gel. The resulting nitrile rubber elastomer 1 The HNMR spectrum is 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 nitrile rubber belongs to a modified valeronitrile rubber with extremely high nitrile content; characterization of the number average molecular weight M by GPC n Is 7.0X 10 4 g/mol, molecular weight distribution PDI is 1.9; characterization by NMR: the 1, 4-selectivity content of the polyisoprene segment was 82.6%, the 3, 4-selectivity content was 17.4%, and the trans-1, 4-selectivity content of the polyisoprene segment was 99.0%.
Example 15: the preparation method of the modified valeronitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisovaleronitrile (AMBN, 48.7mg,230 mu mol,1.1 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), isoprene (23.1mL, 230mmol, 1000equiv.), isobutyl acrylate (6.6mL, 46mmol, 200equiv.) and toluene (41.6 mL) are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed by cold methanol for three times, and dried in vacuum to constant weight to obtain the modified valeronitrile rubber elastomer, and the system has no gel.
The calculated yield is 40.5%, the acrylonitrile content is 46.5%, the isobutyl acrylate content is 2.1%, and the modified valeronitrile rubber belongs to the ultra-high nitrile content modified valeronitrile rubber; characterization of the number average molecular weight M by GPC n Is 6.3X 10 4 g/mol, molecular weight distribution PDI of 1.9; characterization by NMR: the 1, 4-selectivity content of the polyisoprene segment was 82.5%, the 3, 4-selectivity content was 17.5%, and the trans-1, 4-selectivity content of the polyisoprene segment was 99.0%.
Example 16: the preparation method of the modified valeronitrile rubber of the embodiment comprises the following steps:
in a 120mL reaction flask, azodiisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), isoprene (23.1 mL,230mmol, 1000equiv.), methyl acrylate (6.6 mL,46mmol, 200equiv.) and toluene (41.6 mL) were added in this order under an argon atmosphere, the system was moved to 70 ℃ to react for 24h, quenched and washed with cold methanol three times, and dried under vacuum to constant weight to obtain a modified valeronitrile rubber elastomer, and the system was free of gel.
The calculated yield is 46.5%, the acrylonitrile content is 43.5%, the methyl acrylate content is 2.1%, and the nitrile rubber belongs to the modified valeronitrile rubber with extremely high nitrile content; number average molecular weight M by GPC n Is 5.5X 10 4 g/mol, molecular weight distribution PDI of 2.4; characterization by NMR: the 1, 4-selectivity content of the polyisoprene segment was 82.8%, the 3, 4-selectivity content was 17.1%, and the trans-1, 4-selectivity content of the polyisoprene segment was 99.0%.
Example 17: the preparation method of the modified valeronitrile rubber of the embodiment is carried out according to the following steps:
under argon atmosphere, azodiisovaleronitrile (AMBN, 48.7mg,230 mu mol,1.1 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), isoprene (23.1mL, 230mmol, 1000equiv.), ethyl acrylate (6.6mL, 46mmol, 200equiv.) and toluene (41.6 mL) are sequentially added into a 120mL reaction bottle, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed with cold methanol for three times, and dried in vacuum to constant weight to obtain the modified valeronitrile rubber elastomer, and the system has no gel.
The calculated yield is 48.7%, the acrylonitrile content is 43.9%, the ethyl acrylate content is 2.1%, and the nitrile rubber belongs to modified valeronitrile rubber with extremely high nitrile content; characterization of the number average molecular weight M by GPC n Is 5.9X 10 4 g/mol, molecular weight distribution PDI is 2.4; characterization by NMR: the 1, 4-selectivity content of the polyisoprene segment was 85.4%, the 3, 4-selectivity content was 14.6%, and the trans-1, 4-selectivity content of the polyisoprene segment was 99.0%.
Example 18: the preparation method of the modified valeronitrile rubber of the embodiment comprises the following steps:
in a 120mL reaction flask, azodiisovaleronitrile (AMBN, 48.7mg, 230. Mu. Mol,1.1 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), isoprene (23.1mL, 230mmol, 1000equiv.), methyl 2-methacrylate (6.7mL, 46mmol, 200equiv.) and toluene (41.6 mL) were added in this order under argon atmosphere, the system was moved to 70 ℃ to react for 24h, quenched with cold methanol and washed three times, vacuum dried to constant weight to obtain a modified valeronitrile rubber elastomer, and the system was free of gel.
The calculated yield is 45.7%, the content of acrylonitrile is 43.0%, the content of 2-methyl methacrylate is 1.2%, and the nitrile rubber belongs to modified valeronitrile rubber with extremely high nitrile content; characterization of the number average molecular weight M by GPC n Is 4.1 × 10 4 g/mol, molecular weight distribution PDI of 2.6; characterization by NMR: the 1, 4-selectivity content of the polyisoprene segment was 80.4%, the 3, 4-selectivity content was 19.6%, and the trans-1, 4-selectivity content of the polyisoprene segment was 99.0%.
The above description is only a preferred embodiment of the present invention, and these embodiments are based on different implementations of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A modified conjugated diene-acrylonitrile rubber is characterized by being prepared from conjugated diene, acrylonitrile and acrylate monomers, wherein the insertion rate of the acrylonitrile is 40-50%, the insertion rate of the acrylate monomers is 1-10%, and the molar content of a trans-1, 4-structure in a poly-conjugated diene chain segment is 80-99%.
2. The modified conjugated diene-acrylonitrile rubber according to claim 1, wherein the conjugated diene is butadiene or isoprene.
3. The modified conjugated diene-acrylonitrile rubber according to claim 2, wherein the polybutadiene block further comprises cis-1, 4-butadiene and 1, 2-butadiene, and the molar content of 1, 2-butadiene is 1-20%.
4. The modified conjugated diene-acrylonitrile rubber according to claim 2, wherein the polyisoprene block further comprises cis-1, 4-isoprene and 3, 4-isoprene, and the molar content of 3, 4-isoprene is 1-20%.
5. The 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.
6. The modified conjugated diene-acrylonitrile rubber of claim 1, wherein the acrylate monomers comprise methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate.
7. The process for producing a modified conjugated diene-acrylonitrile rubber as claimed in any one of claims 1 to 6, which comprises the steps of:
the material is prepared by initiating polymerization by azo free radical initiator in polar solvent under anhydrous and oxygen-free conditions, wherein the polymerization temperature is 50-120 ℃, and the polymerization time is 2-48h.
8. The method as claimed in claim 7, wherein the molar ratio of the azo-based radical initiator to the conjugated diene, the acrylonitrile, and the acrylate-based monomer is 1 (100-3000): 100-3000, and the ratio of the sum of the volumes of the conjugated diene, the acrylonitrile, and the acrylate-based monomer to the volume of the polar solvent is 1 (1-5).
9. The process according to claim 7, wherein the polymerization temperature is 70 ℃ and the time is 24 hours.
10. Use of the modified conjugated diene-acrylonitrile rubber according to any one of claims 1 to 6.
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| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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