CN115477726A - Modified butadiene-valeronitrile rubber with extremely high nitrile content as well as preparation method and application thereof - Google Patents
Modified butadiene-valeronitrile rubber with extremely high nitrile content as well as preparation method and application thereof Download PDFInfo
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- CN115477726A CN115477726A CN202211280830.5A CN202211280830A CN115477726A CN 115477726 A CN115477726 A CN 115477726A CN 202211280830 A CN202211280830 A CN 202211280830A CN 115477726 A CN115477726 A CN 115477726A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 239000005060 rubber Substances 0.000 title claims abstract description 51
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 36
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 30
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 15
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 238000003780 insertion Methods 0.000 claims abstract description 8
- 230000037431 insertion Effects 0.000 claims abstract description 8
- -1 azo free radical Chemical class 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 25
- 229920002857 polybutadiene Polymers 0.000 claims description 25
- 229920001195 polyisoprene Polymers 0.000 claims description 25
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical class C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000012512 characterization method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000806 elastomer Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 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 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 4
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 102100040409 Ameloblastin Human genes 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- 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
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A modified butadiene-valeronitrile rubber with extremely high nitrile content, a preparation method and application thereof. The invention belongs to the field of nitrile rubber modification. The invention aims to solve the technical problems of single structure and performance, and poor ageing resistance, stability and low-temperature resistance of the conventional nitrile rubber. The modified butadiene-valeronitrile rubber with extremely high nitrile content is prepared from butadiene, isoprene, acrylonitrile and acrylate monomers, wherein the insertion rate of the acrylonitrile is 40-60%, the insertion rate of the acrylate monomers is 1-10%, and the glass transition temperature is-30-0 ℃. The preparation method comprises the following steps: the polymer is prepared by initiating polymerization by azo free radical initiator in polar solvent under the anhydrous and anaerobic condition. The modified butadiene-acrylonitrile rubber with extremely high nitrile content and excellent comprehensive performance is prepared by high-efficiency solution quaternary polymerization, the macroscopic regulation and control of the glass transition temperature of the rubber are realized, and the acrylonitrile doping rate is improved.
Description
Technical Field
The invention belongs to the field of nitrile rubber modification, and particularly relates to modified butadiene-valeronitrile rubber with extremely high nitrile content, and a preparation method and application thereof.
Background
Nitrile rubbers are mainly copolymer products prepared by free-radical polymerization of Butadiene (BD) and Acrylonitrile (AN) monomers. Nitrile-butadiene rubber (NBR) 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, can be used for producing various oil-resistant rubber and other products due to the fact that the price of the nitrile-butadiene rubber (NBR) is far lower than that of fluororubber, and is an elastomer material mostly applied to sealing materials in the industrial field.
The major disadvantages of NBR are poor aging properties, resulting in oxidative and ozonolysis degradation, and lack of stability. Meanwhile, the nitrile rubber has higher regularity and higher glass transition temperature, so the low temperature resistance is poorer, and the application of the nitrile rubber is limited.
Disclosure of Invention
The invention aims to solve the technical problems of single structure and performance and poor ageing resistance, stability and low-temperature resistance of the conventional nitrile rubber, and provides a modified butadiene-valeronitrile rubber with extremely high nitrile content, and a preparation method and application thereof.
The modified butadiene-valeronitrile rubber with extremely high nitrile content is prepared from butadiene, isoprene, acrylonitrile and acrylate monomers, wherein the insertion rate of the acrylonitrile is 40-60%, the insertion rate of the acrylate monomers is 1-10%, and the glass transition temperature is-30-0 ℃.
Further defined, the trans1, 4-isoprene content in the polyisoprene block is 80 to 99 mole percent, and the trans1, 4-butadiene content in the polybutadiene block is 80 to 99 mole percent.
Further defined, the polyisoprene block also includes 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, cis-1, 4-isoprene and 3, 4-isoprene satisfies 100%.
Further defined, the polybutadiene block also includes cis-1, 4-butadiene and 1, 2-butadiene, wherein the molar content of 1, 2-butadiene is 1-20%, and the sum of the molar contents of trans-1, 4-butadiene, cis-1, 4-butadiene and 1, 2-butadiene satisfies 100%.
Further defined, the modified nitrile butadiene rubber of very high nitrile content 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 butadiene-valeronitrile rubber with extremely high nitrile content 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 particularly, the polar solvent of the ester type includes methyl acetate, ethyl acetate, n-propyl acetate, and dimethyl carbonate.
Further, the azo-based radical initiator is any one of the following structures:
further limiting, the mol ratio of the azo free radical initiator to the butadiene, isoprene, acrylonitrile and acrylate monomers is 1 (100-3000) to (100-3000); (100-3000): (100-3000).
Further, the ratio of the sum of the volumes of the butadiene, the isoprene, the acrylonitrile and the acrylate monomers to the volume of the polar solvent is 1 (1-5).
Further defined, the polymerization temperature was 70 ℃ and the time was 24 hours.
Compared with the prior art, the invention has the following remarkable effects:
the modified butadiene-acrylonitrile rubber with extremely high nitrile content and excellent comprehensive performance is prepared by taking butadiene, isoprene, acrylonitrile and acrylate monomers as raw materials through high-efficiency solution quaternary polymerization, the macroscopic regulation and control of the glass transition temperature of the rubber are realized, the acrylonitrile doping rate is improved, and the specific advantages are as follows:
1) According to the invention, an acrylate monomer is introduced into a nitrile rubber system, and meanwhile, polybutadiene on the original nitrile rubber main chain is partially replaced by polyisoprene, so that the modified butadiene-acrylonitrile rubber with a brand-new structure composition is prepared, the distance between molecular chains is increased by a large number of ethylene and propenyl side groups on the main chain, the acrylonitrile insertion rate is greatly increased, the acrylonitrile content in the modified butadiene-acrylonitrile rubber reaches 60%, and then the butadiene-acrylonitrile rubber with ultrahigh acrylonitrile content is prepared.
2) The introduction of the propenyl side group facilitates the insertion of the acrylate monomer on one hand, thereby realizing the macroscopic regulation and control of the glass transition temperature; on the other hand, compared with the vinyl side group, the propenyl side group improves the limiting capacity on the movement of a molecular chain, so that the stability of the rubber is obviously improved.
3) According to the invention, the polybutadiene on the original nitrile rubber main chain is partially replaced by polyisoprene, the regularity of a molecular chain is damaged, and the glass transition temperature is reduced, so that the macroscopic regulation and control of the glass transition temperature of the rubber are realized, the low temperature resistance of the rubber is improved, and meanwhile, the crystallinity is reduced due to the regularity damage of the macromolecular chain, therefore, the flexibility is improved, and the rubber has more excellent elasticity. In addition, the addition of polyisoprene improves the defect of poor aging resistance, and provides possibility for diversification of the rubber.
4) The butadiene-valeronitrile rubber consists of two structural units of butadiene and isoprene, so that the butadiene-valeronitrile rubber has very excellent compatibility with isoprene rubber and butadiene rubber, and is a novel multifunctional rubber material with excellent performance.
5) 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 is a schematic representation of a very high nitrile modified butyl valeronitrile rubber prepared in example 1 1 H NMR spectrum;
FIG. 2 is a DSC of a very high nitrile modified valeronitrile rubber prepared in example 1;
FIG. 3 is a DSC of the butyronitrile rubber prepared in comparative example 1.
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 do not 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 the singular.
Example 1: the preparation method of the modified butadiene-valeronitrile rubber with extremely high nitrile content in the embodiment comprises the following steps:
azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol and 11 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), butadiene (10.0 mL,115mmol, 500equiv.), n-butyl acrylate (6.6 mL,46mmol, 200equiv.) and isoprene (11.5 mL,115mmol, 500equiv.) are sequentially added into a 120mL reaction bottle under argon atmosphere, 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 butadiene-valeronitrile rubber elastomer with extremely high nitrile content, and the system is free of gel. The obtained modified butadiene-valeronitrile rubber elastomer with extremely high nitrile content 1 The HNMR spectrogram and the DSC spectrogram are shown in figures 1 and 2.
The calculated yield was 43.8%, acrylonitrileThe content of the butyl acrylate is 43.9 percent, the content of the n-butyl acrylate is 3.5 percent, and the butyl acrylate belongs to the butadiene valeronitrile rubber modified by extremely high nitrile content; characterization of the number average molecular weight M by GPC n Is 6.6X 10 4 g/mol, the molecular weight distribution PDI is 2.6, and the glass transition temperature is-14.8 ℃; characterization by NMR: the polybutadiene content is 16.9 percent, the 1, 4-butadiene selectivity content in the polybutadiene chain segment is 45.6 percent, and the 1, 2-butadiene selectivity content is 54.5 percent; the polyisoprene content was 35.6%, the selective content of 1, 4-isoprene in the polyisoprene segment was 76.1%, the selective content of 3, 4-isoprene was 23.9%, the selective content of trans1, 4-butadiene in the polybutadiene 1,4 segment was 85.4%, and the selective content of trans1, 4-isoprene in the polyisoprene 1,4 segment was 84.4%.
Example 2: the preparation method of the modified butadiene-valeronitrile rubber with extremely high nitrile content in the embodiment comprises the following steps:
azodiisovaleronitrile (AMBN, 48.7mg,253 mu mol and 11 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), butadiene (10.0mL, 115mmol and 500equiv.), n-butyl acrylate (6.6mL, 46mmol and 200equiv.) and isoprene (11.5mL, 115mmol and 500equiv.) and cyclohexanone (43.1 mL) are sequentially added into a 120mL reaction bottle under the argon atmosphere, the system is moved to 70 ℃ to react for 24 hours, cooled methanol is used for quenching and washing for three times, and the modified butadiene-valeronitrile rubber elastomer with extremely high nitrile content is obtained by vacuum drying until the weight is constant, and the system is free of gel.
The calculated yield is 40.8 percent, the acrylonitrile content is 52.3 percent, the n-butyl acrylate content is 3.7 percent, and the butadiene-valeronitrile rubber belongs to modified butadiene-valeronitrile rubber with high nitrile content; characterization of the number average molecular weight M by GPC n Is 7.2X 10 4 g/mol, the molecular weight distribution PDI is 2.1, and the glass transition temperature is-12.7 ℃; characterization by NMR: the polybutadiene content is 17.1%, the 1, 4-butadiene selectivity content in the polybutadiene block is 52.0%, and the 1, 2-butadiene selectivity content is 48.0%; the polyisoprene content was 36.9%, the selective content of 1, 4-isoprene in the polyisoprene block was 74.0%, the selective content of 3, 4-isoprene was 26.0%, the selective content of trans1, 4-butadiene in the polybutadiene 1,4 block was 87.4%, and the selective content of polyisoprene 1,4 chainThe selective content of trans1, 4-isoprene in the section is 85.8%.
Example 3: the preparation method of the modified butadiene-valeronitrile rubber with extremely high nitrile content in the embodiment comprises the following steps:
azodiisovaleronitrile (AMBN, 48.7mg,253 mu mol,11 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), butadiene (10.0mL, 115mmol, 500equiv.), n-butyl acrylate (6.6mL, 46mmol, 200equiv.) and isoprene (11.5mL, 115mmol, 500equiv.) and toluene (43.1 mL) are sequentially added into a 120mL reaction bottle under the argon atmosphere, the system is moved to 70 ℃ for reaction for 24 hours, quenched by cold methanol and washed for three times, and dried in vacuum to constant weight to obtain the modified butadiene-valeronitrile rubber elastomer with extremely high nitrile content, and the system is free of gel.
The calculated yield is 44.5%, the acrylonitrile content is 44.7%, the n-butyl acrylate content is 3.0%, and the butadiene-valeronitrile rubber belongs to modified butadiene-valeronitrile rubber with extremely high nitrile content; characterization of the number average molecular weight M by GPC n Is 7.5X 10 4 g/mol, molecular weight distribution PDI of 1.8 and glass transition temperature of-13.0 ℃; characterization by NMR: the polybutadiene content was 21.4%, the 1, 4-butadiene selectivity content in the polybutadiene block was 44.4%, and the 1, 2-butadiene selectivity content was 55.6%; the polyisoprene content was 30.9%, the selective content of 1, 4-isoprene in the polyisoprene segment was 66.7%, the selective content of 3, 4-isoprene was 33.3%, the selective content of trans1, 4-butadiene in the polybutadiene 1,4 segment was 99.0%, and the selective content of trans1, 4-isoprene in the polyisoprene 1,4 segment was 86.8%.
Example 4: the preparation method of the modified butadiene-valeronitrile rubber with extremely high nitrile content in the embodiment comprises the following steps:
azodiisobutyronitrile (AIBN, 41.6mg,253 mu mol and 11 equiv.), acrylonitrile (15.0 mL,230mmol, 1000equiv.), butadiene (10.0 mL,115mmol, 500equiv.), n-butyl acrylate (6.6 mL,46mmol, 200equiv.) and isoprene (11.5 mL,115mmol, 500equiv.) are added in sequence in a 120mL reaction bottle under argon atmosphere, the system is moved to 70 ℃ for reaction for 24h, quenched with cold methanol and washed three times, and dried in vacuum to constant weight to obtain the modified butadiene-valeronitrile rubber elastomer with extremely high nitrile content, and the system is free of gel.
The calculated yield is 42.1%, the acrylonitrile content is 53.3%, the n-butyl acrylate content is 2.1%, and the butadiene-valeronitrile rubber belongs to modified butadiene-valeronitrile rubber with extremely high nitrile content; number average molecular weight M by GPC n Is 4.5 multiplied by 10 4 g/mol, the molecular weight distribution PDI is 2.0, and the glass transition temperature is-12.8 ℃; characterization by NMR: the polybutadiene content was 18.9%, the 1, 4-butadiene selectivity content in the polybutadiene block was 46.0%, the 1, 2-butadiene selectivity content was 54.0%, the polyisoprene content was 35.6%, the 1, 4-isoprene selectivity content in the polyisoprene block was 78.9%, the 3, 4-isoprene selectivity content was 21.1%, the trans1, 4-butadiene selectivity content in the polybutadiene 1,4 block was 99.0%, and the trans1, 4-isoprene selectivity content in the polyisoprene 1,4 block was 83.2%.
Comparative example 1: the preparation method of the nitrile butadiene rubber of the embodiment is carried out according to the following steps:
azodiisovaleronitrile (AMBN, 44.2mg,230 mu mol and 1 equiv.), acrylonitrile (15.0 mL 230mmol and 1000equiv.), butadiene (10.0 mL,115mmol and 500equiv.), isoprene (11.5 mL,115mmol and 500equiv.) and cyclohexanone (36.5 mL) are sequentially added into a 120mL reaction bottle under an 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 a valeronitrile rubber elastomer, the system is free of gel, and the DSC spectrum of the valeronitrile rubber elastomer is shown in figure 3.
The calculated yield is 33.7 percent, and the acrylonitrile content is 26.6 percent; characterization of the number average molecular weight M by GPC n Is 6.3X 10 4 g/mol, the molecular weight distribution PDI is 2.0, and the glass transition temperature is-8.1 ℃; characterization by NMR: the polybutadiene content was 30.7%, the 1, 4-butadiene selectivity content in the polybutadiene block was 54.0%, and the 1, 2-butadiene selectivity content was 46.0%; the polyisoprene content was 42.7%, the 1, 4-isoprene selectivity content in the polyisoprene segment was 67.1%, the 3, 4-isoprene selectivity content was 32.9%, and the trans1, 4-butylene in the polybutadiene 1,4 segmentThe content of selectivity of the alkene is 85.9 percent, and the content of selectivity of trans1, 4-isoprene in the 1,4 segment of polyisoprene is 85.0 percent.
Comparative example 2: the preparation method of the nitrile butadiene rubber of the embodiment is carried out according to the following steps:
azodiisobutyronitrile (AIBN, 37.8mg, 230. Mu. Mol,1 equiv.), acrylonitrile (15.0mL, 230mmol, 1000equiv.), butadiene (10.0mL, 115mmol, 500equiv.) and isoprene (11.5mL, 115mmol, 500equiv.) in toluene (36.5 mL) are sequentially added into a 120mL reaction bottle under an argon atmosphere, the system is moved to 70 ℃ for reaction for 24 hours, quenched and washed with cold methanol three times, and dried in vacuum to constant weight to obtain the valeronitrile rubber elastomer, and the system has no gel.
The calculated yield was 17.3% and the acrylonitrile content was 23.5%; characterization of the number average molecular weight M by GPC n Is 6.3X 10 4 g/mol, the molecular weight distribution PDI is 2.0, and the glass transition temperature is-9.1 ℃; characterization by NMR: the polybutadiene content is 35.0 percent, the selective content of 1, 4-butadiene in the polybutadiene chain segment is 66.6 percent, and the selective content of 1, 2-butadiene is 33.4 percent; the polyisoprene content was 41.5%, the selective content of 1, 4-isoprene in the polyisoprene segment was 71.8%, the selective content of 3, 4-isoprene was 28.2%, the selective content of trans1, 4-butadiene in the polybutadiene 1,4 segment was 99.9%, and the selective content of trans1, 4-isoprene in the polyisoprene 1,4 segment was 78.7%.
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 shall be subject to the protection scope of the claims.
Claims (10)
1. The modified butadiene-valeronitrile rubber with extremely high nitrile content is characterized by being prepared from butadiene, isoprene, acrylonitrile and acrylate monomers, wherein the insertion rate of the acrylonitrile is 40-60%, the insertion rate of the acrylate monomers is 1-10%, and the glass transition temperature is-30-0 ℃.
2. A modified butadiene-valeronitrile rubber with very high nitrile content, according to claim 1, wherein the molar content of trans1, 4-isoprene in the polyisoprene block is 80-99%, and the molar content of trans1, 4-butadiene in the polybutadiene block is 80-99%.
3. The modified butadiene-valeronitrile rubber with extremely high nitrile content as claimed in claim 2, wherein the polyisoprene block further comprises cis-1, 4-isoprene and 3, 4-isoprene, wherein the molar content of 3, 4-isoprene is 1-20%, and the polybutadiene block further comprises cis-1, 4-butadiene and 1, 2-butadiene, wherein the molar content of 1, 2-butadiene is 1-20%.
4. The modified butadiene-valeronitrile rubber with very high nitrile content as claimed in claim 1, wherein the number average molecular weight of the modified butadiene-valeronitrile rubber with very high nitrile content is 2-20 g/mol, and the PDI is 1.0-5.0.
5. A modified nitrile rubber with very high nitrile content as in claim 1, wherein the acrylate monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate.
6. A process for the preparation of very high nitrile modified nitrile rubber as in any of claims 1 to 5, wherein the process is carried out by 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.
7. The method of claim 6 wherein the molar ratio of azo-based free radical initiator to butadiene, isoprene, acrylonitrile, acrylate monomer is 1 (100-3000): 100-3000 (100-3000).
8. The method according to claim 6, wherein the ratio of the sum of the volumes of the butadiene, isoprene, acrylonitrile and acrylate monomers to the volume of the polar solvent is 1 (1-5).
9. The process according to claim 6, wherein the polymerization temperature is 70 ℃ and the time is 24 hours.
10. Use of a very high nitrile modified nitrile butadiene rubber according to any of claims 1 to 5.
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| WO2020135956A1 (en) * | 2018-12-27 | 2020-07-02 | Arlanxeo Deutschland Gmbh | Pulverulent mixture of precrosslinked nitrile rubbers |
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