WO2022057848A1 - 液体氢化丁腈橡胶及其制备方法和应用 - Google Patents

液体氢化丁腈橡胶及其制备方法和应用 Download PDF

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WO2022057848A1
WO2022057848A1 PCT/CN2021/118659 CN2021118659W WO2022057848A1 WO 2022057848 A1 WO2022057848 A1 WO 2022057848A1 CN 2021118659 W CN2021118659 W CN 2021118659W WO 2022057848 A1 WO2022057848 A1 WO 2022057848A1
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substituted
unsubstituted
group
carbonyl
nitrile rubber
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PCT/CN2021/118659
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English (en)
French (fr)
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詹正云
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赞南科技(上海)有限公司
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Priority to MX2023003157A priority Critical patent/MX2023003157A/es
Priority to EP21868670.7A priority patent/EP4215556A4/en
Priority to AU2021346019A priority patent/AU2021346019A1/en
Priority to CA3195494A priority patent/CA3195494A1/en
Priority to JP2023517754A priority patent/JP2023543415A/ja
Priority to US18/245,377 priority patent/US20230340237A1/en
Publication of WO2022057848A1 publication Critical patent/WO2022057848A1/zh

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
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    • C08K2201/00—Specific properties of additives
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
    • C08L2207/324—Liquid component is low molecular weight polymer

Definitions

  • the invention relates to a liquid hydrogenated nitrile rubber and a preparation method and application thereof.
  • Hydrogenated nitrile rubber plays a huge role in aerospace, petroleum, automobile and energy with its excellent properties.
  • Liquid hydrogenated nitrile rubber is one of the special grades of HNBR. It can be combined with rubber additives such as reinforcing fillers and vulcanization accelerators. After vulcanization, a vulcanized rubber with good elasticity, better fluidity and easier processing can be obtained.
  • it has important uses in special adhesives, sealants and special-shaped complex elastic products, especially it may be used as electromagnetic shielding coatings, oil-resistant coatings, battery corrosion-resistant coatings, sealing parts, damping and noise reduction coatings, etc.
  • the matrix material of special composite materials has attracted much attention.
  • LHNBR liquid hydrogenated nitrile butadiene rubber
  • LNBR liquid nitrile butadiene rubber
  • Patent CN104231118A discloses a hydrogenated hydroxyl-terminated liquid nitrile rubber and a preparation method thereof.
  • a catalytic hydrogenation system is composed of hydrazine hydrate-boric acid-hydrogen peroxide, and the liquid hydroxyl-terminated nitrile rubber is hydrogenated by liquid heterogeneous phase to obtain Hydrogenated hydroxy-terminated liquid nitrile rubber with no gel and more than 90% hydrogenation degree.
  • CN102481562A discloses a preparation method of liquid hydrogenated nitrile-butadiene rubber. During preparation, chlorobenzene solvent is used to dissolve nitrile-butadiene rubber, a certain amount of 1-hexene is added, stirred at 22° C. for 2 hours, and then a metathesis catalyst "1,3" is added.
  • the existing liquid hydrogenated nitrile rubber preparation technology still has some deficiencies, and there is still more room for better improvement in the diversity of product performance and applications.
  • the whole preparation process has experienced two process steps of metathesis degradation and hydrogenation, and the two steps have respectively adopted catalysts of two different metals and different purposes, and the molecular weight distribution of the final product is relatively narrow (PDI ⁇ 2.0 ), it may be difficult to take into account the fluidity during processing and the mechanical properties after curing (such as elasticity and strength, etc.), if the molecular weight is high, although the mechanical properties after curing are better, but the fluidity is relatively poor, not only the preparation process It is difficult to purify and dry, and it is not ideal for making adhesives, sealants, and casting complex elastic products.
  • the present invention provides a liquid hydrogenated nitrile-butadiene rubber and a preparation method and application thereof in order to solve the defect that the prior art is difficult to take into account the fluidity during processing of the liquid hydrogenated nitrile-butadiene rubber and the mechanical properties after curing.
  • the liquid hydrogenated nitrile rubber of the present invention has low molecular weight, wide molecular weight distribution, excellent fluidity during processing and excellent mechanical properties after curing; and the preparation method of the present invention is simple and feasible.
  • a liquid hydrogenated nitrile rubber wherein:
  • the acrylonitrile content is 15% to 50%
  • the hydrogenation saturation is 75% to 99.5%
  • the weight average molecular weight (Mw) is 3,000 ⁇ 60,000;
  • Molecular weight distribution index is 2.0 to 8.0;
  • the glass transition temperature (Tg) is lower than -28°C.
  • the acrylonitrile content of the liquid hydrogenated nitrile rubber is preferably 17% to 45%, such as 25%, 33% or 43%.
  • the hydrogenation saturation of the liquid hydrogenated nitrile rubber is preferably 80% to 99%, more preferably 90% to 99%, such as 91%, 92%, 95% or 96%.
  • the weight average molecular weight of the liquid hydrogenated nitrile rubber is preferably 5,000-50,000, more preferably 8,000-20,000 or 24,000-46,000.
  • the molecular weight distribution index (PDI) of the liquid hydrogenated nitrile rubber is preferably 2.0-6.0.
  • the glass transition temperature (Tg) of the liquid hydrogenated nitrile rubber is preferably lower than -35°C, more preferably lower than -40°C.
  • the extrapolated glass transition onset temperature (Tig) of the liquid hydrogenated nitrile rubber can be lower than -30°C, preferably lower than -35°C, more preferably lower than -45°C.
  • the extrapolated glass transition end temperature (Teg) of the liquid hydrogenated nitrile rubber can be lower than -25°C, preferably lower than 30°C, more preferably lower than -35°C.
  • the liquid hydrogenated nitrile rubber is preferably the liquid hydrogenated nitrile rubber shown in formula IIIa or IIIb,
  • liquid hydrogenated nitrile rubber preferably, in the liquid hydrogenated nitrile rubber:
  • the acrylonitrile content is 17% to 45%;
  • Hydrogenation saturation is 80% to 99%
  • the weight average molecular weight (Mw) is 5,000 ⁇ 50,000
  • Molecular weight distribution index is 2.0 to 6.0;
  • the glass transition temperature (Tg) is lower than -28°C.
  • liquid hydrogenated nitrile rubber preferably, in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 8,000 ⁇ 20,000
  • PDI Molecular weight distribution index
  • the glass transition temperature (Tg) is lower than -35°C.
  • liquid hydrogenated nitrile rubber preferably, in the liquid hydrogenated nitrile rubber:
  • the acrylonitrile content is 25% to 43%;
  • Hydrogenation saturation is 91% to 99%
  • the weight average molecular weight (Mw) is 24,000 ⁇ 46,000;
  • PDI Molecular weight distribution index
  • the glass transition temperature (Tg) is lower than -29°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 37,000 ⁇ 38,000;
  • the glass transition temperature (Tg) was -31.2°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 44,000 ⁇ 45,000;
  • the glass transition temperature (Tg) was -2.5°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 45,000 ⁇ 46,000;
  • the glass transition temperature (Tg) was -29.8°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 24,000 ⁇ 25,000;
  • PDI Molecular weight distribution index
  • the glass transition temperature (Tg) was -30.9°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 8,000 ⁇ 10,000;
  • PDI Molecular weight distribution index
  • the glass transition temperature (Tg) was -42.8°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 16,000 ⁇ 17,000;
  • the glass transition temperature (Tg) was -38.8°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the hydrogenation saturation is 91%
  • the weight average molecular weight (Mw) is 33,000 ⁇ 34,000;
  • PDI Molecular weight distribution index
  • the glass transition temperature (Tg) was -30.2°C.
  • liquid hydrogenated nitrile rubber in the liquid hydrogenated nitrile rubber:
  • the weight average molecular weight (Mw) is 33,000 ⁇ 34,000;
  • the glass transition temperature (Tg) was -32.9°C.
  • a preparation method of liquid hydrogenated nitrile rubber which comprises the following steps: under the protection of an inert gas, in an organic solvent, under the action of a catalyst, the nitrile rubber is sequentially subjected to a degradation reaction and a hydrogenation reduction reaction, or the nitrile The rubber is subjected to hydrogenation reduction reaction to obtain liquid hydrogenated nitrile rubber;
  • the catalyst comprises one or more of the Zhan Catalysts shown in general formula I:
  • L is an electron donating complex ligand; for example, L can be -PCy 3 or
  • L 1 and L 2 are independently halogen
  • n 0 or 1;
  • Y 1 is independently nitrogen, oxygen, sulfur, CH 2 , substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 6 -C 20 aryloxy, substituted or unsubstituted C 2 -C 20 heterocyclic aryl, carbonyl, carbonyl linked to substituted or unsubstituted C 1 -C 20 alkyl, linked to substituted or unsubstituted C 1 -C 20 alkoxy carbonyl group, imino group, substituted or unsubstituted C 1 -C 20 alkyl imino group or amino group represented by formula R c R d N-; wherein Rc and Rd are independently hydrogen , substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 2 -C 20 heterocyclyl, substituted or unsubstituted
  • X is nitrogen, oxygen, sulfur, CH, CH2 or carbonyl
  • Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C 1 -C 20 alkoxy, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 6 -C 20 aryl Oxy group, substituted or unsubstituted C 2 -C 20 heterocyclic aryl group, carbonyl group attached to substituted or unsubstituted C 1 -C 20 alkyl group, carbonyl group attached to substituted or unsubstituted C 1 -C 20 alkoxy group , imino, substituted or unsubstituted C 1 -C 20 alkylimino group or a group represented by formula R c R d N-; wherein, Rc and Rd are independently hydrogen, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 2 -C 20 heterocyclyl, substituted or unsubstituted C 1 -
  • R 1 is hydrogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkoxy, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 6 -C 20 aryloxy or substituted or unsubstituted C 2 -C 20 heterocyclyl;
  • R 2 is hydrogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkoxy, substituted or unsubstituted C 1 -C 20 alkylthio, substituted or unsubstituted C 1 -C 20 alkylsiloxy group, substituted or unsubstituted C 2 -C 20 heterocyclic group, substituted or unsubstituted C 6 -C 20 aryl group, C 6 -C 20 aryloxy group, aldehyde group , a carbonyl group connected to a substituted or unsubstituted C 1 -C 20 alkyl group, a carbonyl group connected to a substituted or unsubstituted C 6 -C 20 aryl group, a carbonyl group connected to a substituted or unsubstituted C 2 -C 20 heterocyclic group or A group represented by formula R c R d N-; wherein R
  • E is hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsilyl, C 1 -C 20 alkylsiloxy, C 2 -C 20 heterocyclyl, C 6 -C 20 aryl, C 6 -C 20 aryloxy, connecting C 1 -C 20 Carbonyl of alkyl, carbonyl connected to C 6 -C 20 aryl, carbonyl connected to C 2 -C 20 heterocyclic group, carbonyl connected to C 1 -C 20 alkoxy, connected to C 6 -C 20 aryloxy Carbonyl, carbonyl linked to C 6 -C 20 heterocyclyloxy, aminoacyl, carbonyl linked to C 1 -C 20 alkylamino, carbonyl linked to C 6 -C 20 arylamin
  • E 1 is hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsilyl, C 1 -C 20 alkylsiloxy, C 2 -C 20 heterocyclyl, substituted or unsubstituted amino, aminoacyl, carbonyl linked to C 1 -C 20 alkylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy group, sulfoxide group, sulfone group, aldehyde group, carbonyl group connected to C 1 -C 20 alkyl group, carbonyl group connected to substituted or unsubstituted C 6 -C 20 aryl group, substituted or unsubstituted A carbonyl group of a C 2 -C 20 heterocyclyl group, a carbonyl group connected to a C 1 -C 20 alkoxy group,
  • E 2 is hydrogen, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsilyl, C 1 -C 20 alkyl silicon Oxy group, aminoacyl, carbonyl linked to C 1 -C 20 alkylamino, carbonyl linked to C 6 -C 20 arylamino, carbonyl linked to C 2 -C 20 heterocyclylamino, C 6 -C 20 aryl , C 6 -C 20 aryloxy, C 2 -C 20 heterocyclic aryl, aldehyde group, carbonyl connected to C 1 -C 20 alkyl, carbonyl connected to C 6 -C 20 aryl, connected to C 2 -C Carbonyl of 20 heterocyclyl, carbonyl attached to C 1 -C 20 alkoxy, carbonyl attached to C 6 -C 20 aryloxy, carbonyl attached to C 2 -C
  • E 3 is hydrogen, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsiloxy, C 6 -C 20 aryl Oxy group, C 6 -C 20 aryl group, C 2 -C 20 heterocyclic aryl group, carbonyl group connected to C 1 -C 20 alkoxy group, carbonyl group connected to substituted or unsubstituted C 6 -C 20 aryloxy group, A carbonyl group attached to a substituted or unsubstituted C 6 -C 20 heterocyclyloxy group or a group represented by formula R c R d N-; wherein R c and Rd are independently hydrogen, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 2 -C 20 heterocyclyl, substituted or unsubstituted C 1 -C 20 alkyl, formy
  • E 4 , E 5 , E 6 and E 7 are independently hydrogen, halogen, nitro, nitrile, sulfoxide, sulfone, aldehyde, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted Substituted C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsilyl, C 1 -C 20 alksiloxy, substituted or unsubstituted C 2 -C 20 hetero Cyclic, substituted or unsubstituted amino, aminoacyl, carbonyl attached to substituted or unsubstituted C1 - C20 alkylamino, carbonyl attached to substituted or unsubstituted C6 - C20 arylamino, attached to substituted or unsubstituted C 2 -C 20 heterocyclylamino carbonyl, carbonyl linked to substituted or unsubstitute
  • the general formula I preferably includes one or more of the following compounds:
  • the general formula I is preferably formula 4aa, 4ab, 4f or 4v, more preferably formula 4aa or 4v.
  • the nitrile rubber refers to the rubber obtained by copolymerizing butadiene and acrylonitrile.
  • the acrylonitrile content of the nitrile rubber may be 15% to 50%, preferably 17% to 45%, such as 25%, 33% or 43%.
  • the weight average molecular weight of the nitrile rubber is 3,000-60,000.
  • the nitrile rubber can be liquid nitrile rubber, which is suitable for the case where the nitrile rubber is directly subjected to hydrogenation reduction reaction.
  • the Mooney viscosity of the nitrile rubber is 30-60.
  • the nitrile rubber can be solid nitrile rubber, which is suitable for the case where the nitrile rubber is subjected to a degradation reaction and a hydrogenation reduction reaction in sequence.
  • the molecular weight distribution index (PDI) of the nitrile rubber may be 2.0-8.0.
  • the structure of the nitrile rubber is shown in the following formula II, IIa or IIb:
  • the nitrile rubber of formula IIa represents a liquid nitrile rubber that is synthesized by an industrialized process and can be purchased on the market, which can be further hydrogenated to obtain a liquid hydrogenated nitrile rubber.
  • m 30-600, for example, it can be 30-500, or 30-400, or 30-300, or 30-200, or 30-100, or 50-80;
  • n 20-500, for example, 20-450, or 20-400, or can be 30-300, or 40-200, or 50-100, or 60-80;
  • the nitrile-butadiene rubber IIa and the nitrile-butadiene rubber IIb can be liquid nitrile-butadiene rubber, and the nitrile-butadiene rubber II can be solid nitrile-butadiene rubber.
  • the amount of the Jen's catalyst can be selected according to conventional methods in the art, preferably 0.005%-0.1%, more preferably 0.01%-0.05%, and the percentage is the Jen's catalyst The mass percentage of the nitrile rubber.
  • the temperature of the degradation reaction is preferably 60-100°C, more preferably 80°C.
  • the time of the degradation reaction can be selected according to conventional methods in the art, preferably 0.5-10 h, more preferably 1-6 h, more preferably 2-3 h.
  • the amount of hydrogen used in the hydrogenation reduction reaction can be the conventional amount for this type of reaction in the art, preferably the pressure of the reaction system reaches 2-15 MPa, more preferably 6-10 MPa, such as 8 MPa.
  • the temperature of the hydrogenation reduction reaction may be a conventional temperature of such a reaction, preferably 80-200°C, more preferably 100-180°C, still more preferably 130-160°C, for example 150°C °C.
  • the time of the hydrogenation reduction reaction can be selected according to conventional methods in the art, and can be 2-6 hours.
  • the organic solvent can be a common solvent for such reactions in the art, for example, one or more of chloroform, dichloroethane, acetone and chlorobenzene; preferably chlorobenzene, One or more of dichloroethane and chloroform; more preferably chlorobenzene or dichloroethane; most preferably chlorobenzene.
  • the amount of the organic solvent can be selected according to conventional methods in the art, and is preferably 100-300g nitrile rubber/1L organic solvent, such as 120g, 160g, 200g or 240g nitrile rubber/1L organic solvent.
  • the inert gas may be a commonly used inert gas for such reactions in the field, such as argon (Ar) or nitrogen.
  • post-treatment is preferably performed after the hydrogenation reduction reaction is completed.
  • the post-treatment can be carried out by conventional methods in the art, generally removing the organic solvent under negative pressure.
  • the temperature of the post-treatment may be 100-150°C, preferably 130-140°C.
  • the reaction process of the preparation method of the liquid hydrogenated nitrile rubber is shown in Route-1, under the protection of inert gas, in an organic solvent, pass hydrogen, and pass hydrogen
  • the nitrile rubber IIa is subjected to a hydrogenation reduction reaction to obtain a liquid hydrogenated nitrile rubber IIIa; wherein, the definitions of m, n, p and q are as described above.
  • the reaction flow of the preparation method of the liquid hydrogenated nitrile rubber is shown in Route-2, under the protection of an inert gas, in an organic solvent, adding the Jen's catalyst,
  • the nitrile-butadiene rubber II is subjected to a degradation reaction to obtain the nitrile-butadiene rubber IIb; then hydrogen is introduced to make the nitrile-butadiene rubber IIb undergo a hydrogenation reduction reaction to obtain a liquid hydrogenated nitrile-butadiene rubber IIIb; wherein, j, k, m', n', p 'and q' are defined as before.
  • a liquid hydrogenated nitrile rubber is prepared according to the preparation method of the liquid hydrogenated nitrile rubber.
  • a kind of degradation method of nitrile-butadiene rubber comprises the following steps: under the protection of inert gas, in organic solvent, under the action of Jen's catalyst shown in general formula I, make nitrile-butadiene rubber through degradation reaction;
  • the type and amount of the Jen's catalyst are as described above.
  • the nitrile rubber is as described above.
  • the type and amount of the organic solvent are as described above.
  • the inert gas is as described above.
  • the reaction flow of the method for degrading nitrile rubber is shown in Route-3, under the protection of inert gas, in an organic solvent, adding the Jens catalyst to make nitrile butadiene
  • the rubber II undergoes a degradation reaction to obtain a nitrile rubber IIb; wherein, the definitions of j, k, m' and n' are as described above.
  • a rubber compound comprising the liquid hydrogenated nitrile rubber, filler and vulcanizing agent.
  • the filler can be conventional in the art, preferably carbon black and/or white carbon black.
  • the carbon black is preferably carbon black N220, carbon black N-330, carbon black N550 or carbon black N774.
  • the silica is preferably precipitated silica, fumed silica or basic silica.
  • the precipitated silica refers to precipitated water & silica.
  • the fumed silica refers to fumed silica.
  • the basic white carbon black is preferably basic white carbon black AS-70.
  • the basic white carbon black AS-70 is a mixture of sodium aluminum silicate and silicon dioxide, wherein the mass fraction of silicon dioxide is 0.8%.
  • the vulcanizing agent may be conventional in the art, preferably 1,4-bis(tert-butylperoxyisopropyl)benzene (trade name F-40).
  • the rubber compound may also include other conventional rubber compounding agents in the art in addition to the vulcanizing agent, such as one of a co-vulcanizing agent, stearic acid, magnesium oxide, an accelerator and an anti-aging agent or variety.
  • a co-vulcanizing agent such as one of a co-vulcanizing agent, stearic acid, magnesium oxide, an accelerator and an anti-aging agent or variety.
  • the auxiliary vulcanizing agent is preferably N,N'-m-phenylene bismaleimide (trade name PDM).
  • the accelerator is preferably 2-mercaptobenzimidazole zinc salt (MBZ).
  • the antioxidant is preferably 4,4'-bis(dimethylbenzyl)diphenylamine (Antioxidant 445).
  • the sizing material in parts by mass, includes: 100 parts of liquid hydrogenated nitrile rubber, 50 parts of carbon black N-330, 10 parts of white carbon black AS-70, 1, 14 parts of 4-bis(tert-butylperoxyisopropyl)benzene (F-40), 0.5 part of N,N'-m-phenylene bismaleimide (PDM), 0.5 part of stearic acid, magnesium oxide 6 parts, 0.5 part by weight of 2-mercaptobenzimidazole zinc salt (MBZ) and 1.0 part by weight of 4,4'-bis(dimethylbenzyl)diphenylamine (anti-aging agent 445)
  • the rubber compound can be prepared by a conventional method in the art, which generally includes kneading each component.
  • the mixing can be carried out in an internal mixer using methods conventional in the art.
  • the kneading is preferably staged kneading.
  • a vulcanized rubber is prepared by vulcanizing the rubber material.
  • the vulcanization can be performed by a conventional method in the art.
  • the vulcanization preferably includes: using an electric heating plate vulcanizer to perform a first-stage vulcanization on the rubber compound under the condition of 180°C ⁇ 8 minutes; and then subjecting the product obtained by the first-stage vulcanization to a second-stage vulcanization under the condition of 150°C ⁇ 4 hours. After vulcanization, it is cooled to room temperature to obtain vulcanizate.
  • the Shore hardness of the vulcanizate may be above 60, preferably above 80.
  • the breaking strength of the vulcanizate may be 4-8 MPa.
  • the elongation at break of the vulcanizate may be above 160, preferably above 190.
  • the 100% tensile strength of the vulcanizate may be 3-4 MPa.
  • the industrial products preferably include sealants, adhesives, coatings, potting materials or elastic products.
  • the coating is preferably an electromagnetic shielding coating, an oil-resistant coating, a battery corrosion-resistant coating or a damping and noise reduction coating.
  • the binder is preferably a solid propellant binder or an ablative material binder.
  • the elastic articles are especially shaped complex elastic articles.
  • Acrylonitrile content refers to the mass percentage content of polyacrylonitrile fragments in nitrile rubber or hydrogenated nitrile rubber.
  • Hydrogenation degree (Hydrogenation Degree): the degree of hydrogenation of the olefinic double bond in the polymer, expressed by the iodine value method.
  • PDI Molecular weight distribution index
  • Mooney viscosity Mooney viscosity mentioned in the present invention is Mooney viscosity [ML(1+4)100°C], which is an index to measure the average molecular weight and plasticity of rubber.
  • Glass transition temperature (Tg) refers to the temperature at which the highly elastic state is transformed into the glassy state or the glass table is transformed into the highly elastic state. Glass transition is an inherent property of amorphous polymer materials and a macroscopic manifestation of the transformation of polymer motion forms. It directly affects the performance and process performance of materials.
  • the glass transition temperature (Tg) is located at the extrapolated glass transition onset temperature. (Tig) and the extrapolated glass transition end temperature (Teg).
  • the reagents and raw materials used in the present invention are all commercially available.
  • the liquid hydrogenated nitrile rubber has both excellent fluidity during processing and excellent physical properties after vulcanization, and has unique application value in the field of special rubber.
  • the method provided by the preparation technology in the present invention simplifies the preparation process method of the prior art, adopts the same metal catalyst system, can realize that degradation and hydrogenation reduction can be completed at one time in the same process, and effectively and easily prepare liquids for various purposes
  • Hydrogenated nitrile rubber broadens the application field of liquid hydrogenated nitrile rubber and has obvious technical advantages.
  • the Jen's catalyst used in the following examples is the compound 4aa or 4v in the general formula I, which is recorded in the company's authorized patent CN200910175790.6, and the specific structural formula is as follows:
  • Glass transition temperature (Tg) Using DSC8500 differential scanning calorimeter, according to the standard GB/T 29611-2013 "Determination of glass transition temperature of raw rubber by differential scanning calorimetry (DSC)" method test.
  • PDI Molecular weight and molecular weight distribution index
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) is 37950, molecular weight distribution index is 2.1, acrylonitrile content is 33%, hydrogenation degree is 92% (iodine value: 24), glass transition temperature (Tg) was -31.2°C (Tig: -31.7°C; Teg: -26.9°C).
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) of 44960, molecular weight distribution index of 2.2, acrylonitrile content of 33%, hydrogenation degree of 96% (iodine value: 14), glass transition temperature (Tg) was -32.5°C (Tig: -36.1°C; Teg: -28.8°C).
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) of 45140, molecular weight distribution index of 2.2, combined acrylonitrile content of 33%, hydrogenation degree of 99% (iodine value: 8), glass transition temperature (Tg) was -29.8°C (Tig: -33.5°C; Teg: -26.2°C).
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) of 243.5 million, molecular weight distribution index of 2.4, acrylonitrile content of 33%, hydrogenation degree of 99% (iodine value: 8), glass transition
  • Mw molecular weight
  • Tg glass transition
  • Tig -31.5°C
  • Teg -27.2°C
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) of 8210, molecular weight distribution index of 2.7, acrylonitrile content of 33%, hydrogenation degree of 99% (iodine value: 8), glass transition temperature (Tg) was -42.8°C (Tig: -49.8°C; Teg: -36.2°C).
  • liquid nitrile rubber [acrylonitrile mass content of 33%, molecular weight (Mw) of 15780, molecular weight distribution index of 3.2] and 500mL of anhydrous chlorobenzene were added to a 1L stainless steel reactor, and the mixture was heated to 60%.
  • Jen's catalyst (4aa) under nitrogen sealing conditions the dosage is 0.03% of the nitrile rubber, and then introduce hydrogen until the pressure reaches 8MPa, then heat up to 150 °C, and react for 4 hours to obtain a liquid hydrogenated nitrile rubber with a high degree of hydrogenation solution.
  • the obtained liquid hydrogenated nitrile rubber raw rubber has a product yield of more than 98%.
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) of 16250, molecular weight distribution index of 3.3, acrylonitrile content of 33%, hydrogenation degree of 99% (iodine value: 7), glass transition temperature (Tg) was -38.8°C (Tig: -44.5°C; Teg: -33.9°C).
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) is 33420, molecular weight distribution index is 4.3, acrylonitrile content is 43%, hydrogenation degree is 91% (iodine value: 25), glass transition temperature (Tg) was -30.2°C (Tig: -34.7°C; Teg: -26.9°C).
  • liquid nitrile rubber [acrylonitrile mass content of 25%, molecular weight (Mw) of 32770, molecular weight distribution index of 5.5] and 500mL of anhydrous chlorobenzene were added to a 1L stainless steel reactor, and the mixture was heated to 60%.
  • Jen's catalyst (4aa) under nitrogen sealing conditions the dosage is 0.03% of the nitrile rubber, and then introduce hydrogen until the pressure reaches 8MPa, then heat up to 150 °C, and react for 4 hours to obtain a liquid hydrogenated nitrile rubber with a high degree of hydrogenation solution.
  • the obtained liquid hydrogenated nitrile rubber raw rubber has a product yield of more than 98%.
  • the characteristic parameters of the obtained liquid hydrogenated nitrile rubber raw rubber are: molecular weight (Mw) of 33950, molecular weight distribution index of 5.6, acrylonitrile content of 25%, hydrogenation degree of 95% (iodine value: 13), glass transition temperature (Tg) was -32.9°C (Tig: -36.6°C; Teg: -29.4°C).
  • the sizing material includes: 100 parts of liquid hydrogenated nitrile rubber (raw rubber obtained in Example 3), 14 parts of F-40, 0.5 part of PDM, 0.5 part of stearic acid, 6 parts of magnesium oxide, 50 parts of carbon black N-330, 10 parts of white carbon black AS-70, 0.5 parts by weight of MBZ and 1.0 parts by weight of antioxidant 445.
  • Kneading first put each component of the rubber compound into the kneader machine, and force it to remove the rubber after kneading at 30 ⁇ 60°C for 8-10min; Thin pass or grind 3-5 times on a mill or three-roll mill, and park for 12 hours after unloading to obtain the required rubber compound.
  • Vulcanization Use an electric heating plate vulcanizer to vulcanize the above-mentioned rubber compound in one stage under the condition of 180°C ⁇ 8 minutes; and then carry out the second-stage vulcanization of the sample obtained by one-stage vulcanization under the condition of 150°C ⁇ 4 hours. Cool to room temperature to obtain vulcanizate.
  • Example 4 Using the liquid hydrogenated nitrile rubber raw rubber obtained in Example 4, other preparation steps and conditions are the same as those in Example 9, to obtain a vulcanizate, and the performance test results are shown in Table 2.

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Abstract

本发明公开了一种液体氢化丁腈橡胶及其制备方法和应用。该液体氢化丁腈橡胶中：丙烯腈含量为15％～50％；加氢饱和度为75％～99.5％；重均分子量(Mw)为3,000～60,000；分子量分布指数(PDI)为2.0～8.0；玻璃化转变温度(Tg)低于-28℃。该液体氢化丁腈橡胶分子量较低、分子量分布较宽，同时具有加工时优异的流动性和固化后优异的力学性能，在特种橡胶领域具有独特的应用价值；并且其制备方法工艺简单可行。

Description

液体氢化丁腈橡胶及其制备方法和应用 技术领域
本发明涉及一种液体氢化丁腈橡胶及其制备方法和应用。
背景技术
氢化丁腈橡胶(HNBR)以其优异的性能在航空航天、石油、汽车以及能源等发挥着巨大的作用。液体氢化丁腈橡胶是HNBR的特殊品级产品之一，它可与补强填充剂、硫化促进剂等橡胶助剂配合，经过硫化可获得具有良好弹性、流动性更好、更易加工的硫化胶。另外，它在特种胶粘剂、密封剂以及异形复杂弹性制品方面具有及其重要的用途，尤其是它可能作为电磁屏蔽涂层、耐油涂层、电池耐腐蚀涂层密封配件、阻尼降噪涂层等特殊复合材料的基体材料而备受关注。
据文献资料报道，制备液体氢化丁腈橡胶(LHNBR)的技术路线有两条：其一是通过对液体丁腈橡胶(LNBR)进行溶液催化加氢来制备，其二是通过对固体丁腈橡胶进行溶解、复分解降解、溶液催化加氢等工序来制备。专利CN104231118A公开了一种氢化端羟基液体丁腈橡胶及其制备方法，以水合肼-硼酸-过氧化氢组成催化加氢体系，通过液体非均相反应对液体端羟基丁腈橡胶进行加氢，得到了无凝胶且加氢度超过90％的氢化端羟基液体丁腈橡胶。CN102481562A公开了一种液体氢化丁腈橡胶的制备方法，制备时，先采用氯苯溶剂将丁腈橡胶溶解，加入一定量的1-己烯，22℃下搅拌2hr随后加入复分解催化剂“1，3-双-(2，4，6-三甲基苯基)-2-咪唑亚甲基)(三环己基膦)-(苯基亚甲基)二氯化钌”(第二代格鲁布斯催化剂)，22℃下搅拌2hr，完成丁腈橡胶的复分解降解反应；然后加入氢化反应催化剂“三-(三苯基膦)-氯化铑”(威尔金森氏催化剂)，在138℃下搅拌加氢反应4hr；由此得到分子量(Mw)在10000～50000、分子量分布指数(PDI)小于2.0的液体氢化丁腈橡胶。因为使用威尔金森氏催化剂等一些氢化还原催化剂在进行丁腈橡胶的氢化反应时仅对NBR中的碳碳双键进行加氢反应，所以其氢化反应结果是不可能改变相应液体氢化丁腈橡胶的分子量分布指数(PDI)。
显然现有液体氢化丁腈橡胶的制备技术还是有些不足之处，产品性能和应用所需的多样性仍有更多更好提升的空间。诸如CN102481562A所公开的方法，整个制备过程经历了复分解降解和加氢两个工艺步骤，两个步骤分别采用了二种不同金属、不同用途的催化剂，最终所得产品的分子量分布比较窄(PDI＜2.0)，可能难于兼顾加工时的流动性和固化后的力学性能(如：弹性和强度等)，假如分子量较高时，虽然固化后的力学性能较好，但流动性就比较差，不但制备过程时净化、干燥比较困难，而且在用于制作胶粘剂、密封剂以及浇注成型异形复杂弹性制品时很不理想。
发明内容
本发明为了解决现有技术难于兼顾液体氢化丁腈橡胶加工时的流动性和固化后的力学性能的缺陷，从而提供了一种液体氢化丁腈橡胶及其制备方法和应用。本发明的液体氢化丁腈橡胶分子量较低、分子量分布较宽，同时具有加工时优异的流动性和固化后优异的力学性能；并且本发明的制备方法工艺简单可行。
为了实现上述目的，本发明采用如下技术方案：
技术方案之一：
一种液体氢化丁腈橡胶，其中：
丙烯腈含量为15％～50％；
加氢饱和度为75％～99.5％；
重均分子量(Mw)为3,000～60,000；
分子量分布指数(PDI)为2.0～8.0；
玻璃化转变温度(Tg)低于-28℃。
本发明中，所述液体氢化丁腈橡胶的丙烯腈含量较佳地为17％～45％，例如25％、33％或43％。
本发明中，所述液体氢化丁腈橡胶的加氢饱和度较佳地为80％～99％，更佳地为90％～99％，例如91％、92％、95％或96％。
本发明中，所述液体氢化丁腈橡胶的重均分子量较佳地为5,000～50,000，更佳地为8,000～20,000或24,000～46,000。
本发明中，所述液体氢化丁腈橡胶的分子量分布指数(PDI)较佳地为2.0～6.0。
本发明中，所述液体氢化丁腈橡胶的玻璃化转变温度(Tg)较佳地低于-35℃，更佳地低于-40℃。
本发明中，所述液体氢化丁腈橡胶的外推玻璃化转变起始温度(Tig)可低于-30℃，较佳地低于-35℃，更佳地低于-45℃。
本发明中，所述液体氢化丁腈橡胶的外推玻璃化转变结束温度(Teg)可低于-25℃，较佳地低于30℃，更佳地低于-35℃。
本发明中，所述液体氢化丁腈橡胶较佳地为式IIIa或IIIb所示的液体氢化丁腈橡胶，
Figure PCTCN2021118659-appb-000001
其中，p＝1～150；p’＝1～150；q＝30～590；q’＝30～590；n＝20～500；n’＝20～500。
本发明中，较佳地，所述液体氢化丁腈橡胶中：
丙烯腈含量为17％～45％；
加氢饱和度为80％～99％；
重均分子量(Mw)为5,000～50,000；
分子量分布指数(PDI)为2.0～6.0；
玻璃化转变温度(Tg)低于-28℃。
本发明中，较佳地，所述液体氢化丁腈橡胶中：
丙烯腈含量为33％；
加氢饱和度为99％；
重均分子量(Mw)为8,000～20,000；
分子量分布指数(PDI)为2.5～3.5；
玻璃化转变温度(Tg)低于-35℃。
本发明中，较佳地，所述液体氢化丁腈橡胶中：
丙烯腈含量为25％～43％；
加氢饱和度为91％～99％；
重均分子量(Mw)为24,000～46,000；
分子量分布指数(PDI)为2.1～5.6；
玻璃化转变温度(Tg)低于-29℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为33％；
加氢饱和度为92％；
重均分子量(Mw)为37,000～38,000；
分子量分布指数(PDI)为2.1；
玻璃化转变温度(Tg)为-31.2℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为33％；
加氢饱和度为96％；
重均分子量(Mw)为44,000～45,000；
分子量分布指数(PDI)为2.2；
玻璃化转变温度(Tg)为-2.5℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为33％；
加氢饱和度为99％；
重均分子量(Mw)为45,000～46,000；
分子量分布指数(PDI)为2.2；
玻璃化转变温度(Tg)为-29.8℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为33％；
加氢饱和度为99％；
重均分子量(Mw)为24,000～25,000；
分子量分布指数(PDI)为2.4；
玻璃化转变温度(Tg)为-30.9℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为33％；
加氢饱和度为99％；
重均分子量(Mw)为8,000～10,000；
分子量分布指数(PDI)为2.7；
玻璃化转变温度(Tg)为-42.8℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为33％；
加氢饱和度为99％；
重均分子量(Mw)为16,000～17,000；
分子量分布指数(PDI)为3.3；
玻璃化转变温度(Tg)为-38.8℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为43％；
加氢饱和度为91％；
重均分子量(Mw)为33,000～34,000；
分子量分布指数(PDI)为4.3；
玻璃化转变温度(Tg)为-30.2℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶中：
丙烯腈含量为25％；
加氢饱和度为95％；
重均分子量(Mw)为33,000～34,000；
分子量分布指数(PDI)为5.6；
玻璃化转变温度(Tg)为-32.9℃。
技术方案之二：
一种液体氢化丁腈橡胶的制备方法，其包括以下步骤：在惰性气体保护下，在有机溶剂中，在催化剂的作用下，使丁腈橡胶依次经降解反应和氢化还原反应，或使丁腈橡胶经氢化还原反应，得液体氢化丁腈橡胶；其中，所述催化剂包括通式I所示的詹氏催化剂(Zhan Catalysts)中的一种或多种：
Figure PCTCN2021118659-appb-000002
本发明中，所述通式I在CN200910175790.6、US12684410和WO2011079439A1中皆有记载，在通式I中各个取代基的定义参见CN200910175790.6、US12684410和WO2011079439A1。
在通式I中：L为一种给电子的络合物配体；例如L可以为-PCy 3或
Figure PCTCN2021118659-appb-000003
L 1和L 2独立地为卤素；
n＝0或1；
n＝1时，Y 1独立地为氮、氧、硫、CH 2、取代或未取代的C 1-C 20烷基、取代或未取代的C 6-C 20芳基、取代或未取代的C 6-C 20芳氧基、取代或未取代的C 2-C 20杂环芳基、羰基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 1-C 20烷氧基的羰基、亚氨基、取代或未取代的C 1-C 20烷基亚胺基或如式R cR dN-所示的氨基；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基或取代或未取代的C 2-C 20杂环基甲酰基；或者Rc、Rd和N原子连接成环；
X为氮、氧、硫、CH、CH 2或羰基；
Y为氮、氧、CH、亚甲基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20 芳基、取代或未取代的C 6-C 20芳氧基、取代或未取代的C 2-C 20杂环芳基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 1-C 20烷氧基的羰基、亚氨基、取代或未取代的C 1-C 20烷基亚胺基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基或取代或未取代的C 2-C 20杂环基甲酰基；或者Rc、Rd和N原子连接成环；X表示的基团连接的母体为Y，Y表示的基团连接的母体为X；
Figure PCTCN2021118659-appb-000004
之间为单键或双键；
R 1为氢、取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20芳基、取代或未取代的C 6-C 20芳氧基或取代或未取代的C 2-C 20杂环基；
R 2为氢、取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 1-C 20烷硫基、取代或未取代的C 1-C 20烷基硅氧基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 6-C 20芳基、C 6-C 20芳氧基、醛基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 6-C 20芳基的羰基、连接取代或未取代的C 2-C 20杂环基的羰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基或取代或未取代的C 2-C 20杂环基甲酰基；或者Rc、Rd和N原子连接成环；
E为氢、卤素、硝基、腈基、亚砜基、砜基、醛基、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷基硅氧基、C 2-C 20杂环基、C 6-C 20芳基、C 6-C 20芳氧基、连接C 1-C 20烷基的羰基、连接C 6-C 20芳基的羰基、连接C 2-C 20杂环基的羰基、连接C 1-C 20烷氧基的羰基、连接C 6-C 20芳氧基的羰基、连接C 6-C 20杂环基氧基的羰基、氨基酰基、连接C 1-C 20烷基氨基的羰基、连接C 6-C 20芳基氨基的羰基、连接C 2-C 20杂环基氨基的羰基、脲基、取代或未取代的C 1-C 20烷基脲基、取代或未取代的C 6-C 20芳基脲基、取代或未取代的C 2-C 20杂环基脲基、连接C 1-C 20烷基氨基的磺酰基、连接C 6-C 20芳基氨基的磺酰基、连接C 2-C 20杂环基氨基的磺酰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取 代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环基磺酰基；或者Rc、Rd和N原子连接成环；
E 1为氢、卤素、硝基、腈基、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷基硅氧基、C 2-C 20杂环基、取代或未取代的氨基、氨基酰基、连接C 1-C 20烷基氨基的羰基、C 6-C 20芳基、C 6-C 20芳氧基、亚砜基、砜基、醛基、连接C 1-C 20烷基的羰基、连接取代或未取代的C 6-C 20芳基的羰基、连接取代或未取代的C 2-C 20杂环基的羰基、连接C 1-C 20烷氧基的羰基、连接C 6-C 20芳基氧基的羰基、连接C 2-C 20杂环基氧基的羰基、脲基、取代或未取代的C 1-C 20烷基脲基、取代或未取代的C 6-C 20芳基脲基或取代或未取代的C 2-C 20杂环基脲基；
E 2为氢、卤素、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷基硅氧基、氨基酰基、连接C 1-C 20烷基氨基的羰基、连接C 6-C 20芳基氨基的羰基、连接C 2-C 20杂环基氨基的羰基、C 6-C 20芳基、C 6-C 20芳氧基、C 2-C 20杂环芳基、醛基、连接C 1-C 20烷基的羰基、连接C 6-C 20芳基的羰基、连接C 2-C 20杂环基的羰基、连接C 1-C 20烷氧基的羰基、连接C 6-C 20芳基氧基的羰基、连接C 2-C 20杂环基氧基的羰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环基磺酰基；或者Rc、Rd和N原子连接成环；
E 3为氢、卤素、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷基硅氧基、C 6-C 20芳氧基、C 6-C 20芳基、C 2-C 20杂环芳基、连接C 1-C 20烷氧基的羰基、连接取代或未取代的C 6-C 20芳氧基的羰基、连接取代或未取代的C 6-C 20杂环基氧基的羰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环基磺酰基；或者Rc、Rd和N原子连接成环；
E 4、E 5、E 6和E 7独立地为氢、卤素、硝基、腈基、亚砜基、砜基、醛基、取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷硅氧基、取代或未取代的C 2-C 20杂环基、取代或未取代的氨基、氨基酰基、连接取代或未取代的C 1-C 20烷基氨基的羰基、连接取代或未取代的C 6-C 20芳基氨基的羰基、连接取代或未取代的C 2-C 20杂环基氨基的羰基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 6-C 20芳基的羰基、连接取代或未取代的C 2-C 20杂环基的羰基、连接取代或未取代的C 1-C 20烷氧基的羰基、连接取代或未取代的C 6-C 20芳氧基的羰基、连接取代或未取代的C 6-C 20杂环基氧基的羰基、脲基、取代或未取代的C 1-C 20烷基脲基、取代或未取代的C 6-C 20芳基脲基、取代或未取代的C 2-C 20杂环基脲基、取代或未取代的C 6-C 20芳基、取代或未取代的C 6-C 20芳氧基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环基磺酰基；或者Rc、Rd和N原子连接成环。
本发明中，所述的通式I较佳地包括下述化合物中的一种或多种：
Figure PCTCN2021118659-appb-000005
Figure PCTCN2021118659-appb-000006
Figure PCTCN2021118659-appb-000007
所述的通式I较佳地为式4aa、4ab、4f或4v，更佳地为式4aa或4v。
本发明中，所述丁腈橡胶指由丁二烯和丙烯腈共聚得到的橡胶。
本发明中，所述丁腈橡胶的丙烯腈含量可为15％～50％，较佳地为17％～45％，例如 25％、33％或43％。
本发明中，较佳地，所述丁腈橡胶的重均分子量为3,000～60,000。此时，所述丁腈橡胶可为液体丁腈橡胶，适用于使丁腈橡胶直接经氢化还原反应的情况。
本发明中，较佳地，所述丁腈橡胶的门尼粘度为30～60。此时，所述丁腈橡胶可为固体丁腈橡胶，适用于使丁腈橡胶依次经降解反应和氢化还原反应的情况。
本发明中，所述丁腈橡胶的分子量分布指数(PDI)可为2.0～8.0。
本发明中，较佳地，所述丁腈橡胶的结构如下列式II、IIa或IIb所示：
Figure PCTCN2021118659-appb-000008
其中，
式II的丁腈橡胶表示固体丁腈橡胶，其中j＝100-6,000，例如可以为200-6000，或者为300-6000，或者为400-6000，或者为500-6000，或者600-6,000，或者800-6,000，或者1,200-6,000，或者2,000-6,000；k＝50-5000，例如可以为300-5000，或者为500-5000，或者为800-5000，或者为1000-5000，或者为2000-5000；
式IIa的丁腈橡胶表示通过工业化工艺合成并且可以在市场上购买得到的液体丁腈橡胶，其可以进一步进行氢化而制得液体氢化丁腈橡胶，在式IIa中m＝30-600，例如可以为30-500，或者为30-400，或者可以为30-300，或者为30-200，或者为30-100，或者50-80；n＝20-500，例如可以为20-450，或者为20-400，或者可以为30-300，或者为40-200，或者为50-100，或者60-80；
式IIb的丁腈橡胶表示通过对式II的固体丁腈橡胶进行降解而获得的液体丁腈橡胶， 其也可以进一步进行氢化而制得液体氢化丁腈橡胶，在式IIb中m’＝30-600，例如可以为30-500，或者为30-400，或者可以为30-300，或者为30-200，或者为30-100，或者50-80；n’＝20-500，例如可以为20-450，或者为20-400，或者可以为30-300，或者为40-200，或者为50-100，或者60-80。
根据本发明的一个实施方式，j＞m’；k＞n’。
本发明中，丁腈橡胶IIa和丁腈橡胶IIb可为液体丁腈橡胶，丁腈橡胶II可为固体丁腈橡胶。
本发明中，所述詹氏催化剂的用量可根据本领域常规的方法进行选择，较佳地为0.005％-0.1％，更佳地为0.01％～0.05％，所述百分比为所述詹氏催化剂占所述丁腈橡胶的质量百分比。
本发明中，所述降解反应的温度较佳地为60～100℃，更佳地为80℃。所述降解反应的时间可根据本领域常规的方法进行选择，较佳地为0.5～10h，更佳地为1～6h，更佳地为2～3h。
本发明中，所述氢化还原反应中氢气的用量可为本领域此类反应的常规用量，较佳地为使反应体系的压力达到2～15MPa，更佳地达到6～10Mpa，例如8MPa。
本发明中，所述氢化还原反应的温度可为此类反应的常规温度，较佳地为80～200℃，更佳地为100～180℃，进一步更佳地为130～160℃，例如150℃。所述氢化还原反应的时间可根据本领域常规的方法进行选择，可为2～6h。
本发明中，所述有机溶剂可为本领域此类反应的常用溶剂，例如可为三氯甲烷、二氯乙烷、丙酮和氯苯中的一种或多种；较佳地为氯苯、二氯乙烷和三氯甲烷中的一种或多种；更佳地为氯苯或二氯乙烷；最佳地为氯苯。所述有机溶剂的用量可根据本领域常规方法进行选择，较佳地为100～300g丁腈橡胶/1L有机溶剂，例如120g、160g、200g或240g丁腈橡胶/1L有机溶剂。
本发明中，所述惰性气体可为本领域此类反应的常用惰性气体，例如氩气(Ar)或氮气。
本发明中，所述氢化还原反应完成后较佳地进行后处理。所述后处理可采用本领域常规方法进行，一般负压除去有机溶剂即可。所述后处理的温度可为100～150℃，较佳 地为130～140℃。
在本发明一较佳的实施方案中，所述液体氢化丁腈橡胶的制备方法的反应流程如路线-1所示，在惰性气体保护下，在有机溶剂中，通入氢气，在通入氢气的同时或之后加入所述詹氏催化剂，使丁腈橡胶IIa进行氢化还原反应，得到液体氢化丁腈橡胶IIIa；其中，m、n、p和q的定义如前所述。
Figure PCTCN2021118659-appb-000009
路线-1
在本发明另一较佳的实施方案中，所述液体氢化丁腈橡胶的制备方法的反应流程如路线-2所示，在惰性气体保护下，在有机溶剂中，加入所述詹氏催化剂，使丁腈橡胶II进行降解反应得丁腈橡胶IIb；再通入氢气，使丁腈橡胶IIb进行氢化还原反应，得到液体氢化丁腈橡胶IIIb；其中，j、k、m’、n’、p’和q’的定义如前所述。
Figure PCTCN2021118659-appb-000010
路线-2
技术方案之三：
一种液体氢化丁腈橡胶，其根据所述液体氢化丁腈橡胶的制备方法制得。
技术方案之四：
一种丁腈橡胶的降解方法，其包括以下步骤：在惰性气体保护下，在有机溶剂中，在通式I所示的詹氏催化剂的作用下，使丁腈橡胶经降解反应；
Figure PCTCN2021118659-appb-000011
其中，所述詹氏催化剂的种类和用量均如前所述。
其中，所述丁腈橡胶如前所述。
其中，所述降解反应的温度和时间均如前所述。
其中，所述有机溶剂的种类和用量均如前所述。
其中，所述惰性气体均如前所述。
在本发明一较佳的实施方案中，所述丁腈橡胶的降解方法的反应流程如路线-3所示，在惰性气体保护下，在有机溶剂中，加入所述詹氏催化剂，使丁腈橡胶II进行降解反应得丁腈橡胶IIb；其中，j、k、m’和n’的定义如前所述。
Figure PCTCN2021118659-appb-000012
路线-3
技术方案之五：
一种胶料，其包含所述液体氢化丁腈橡胶、填料和硫化剂。
本发明中，所述填料可为本领域常规，较佳地为炭黑和/或白炭黑。所述炭黑较佳地为炭黑N220、炭黑N-330、炭黑N550或炭黑N774。所述白炭黑较佳地为沉淀白炭黑、气相白炭黑或碱性白炭黑。所述沉淀白炭黑是指沉淀水&二氧化硅。所述气相白炭黑是指气相二氧化硅。所述碱性白炭黑较佳地为碱性白炭黑AS-70。所述碱性白炭黑AS-70为硅酸铝钠类和二氧化硅的混合物，其中二氧化硅的质量分数为0.8％。
本发明中，所述硫化剂可为本领域常规，较佳地为1，4-双(叔丁基过氧异丙基)苯(商品名F-40)。
本发明中，所述胶料还可包括除所述硫化剂之外的本领域常规的其他橡胶配合剂，例如助硫化剂、硬脂酸、氧化镁、促进剂和防老剂中的一种或多种。
其中，所述助硫化剂较佳地为N，N′-间苯撑双马来酰亚胺(商品名PDM)。
所述促进剂较佳地为2-巯基苯并咪唑锌盐(MBZ)。
所述防老剂较佳地为4，4’-双(二甲基苄基)二苯胺(防老剂445)。
在本发明一较佳的实施方案中，按质量份数计，所述胶料包括：液体氢化丁腈橡胶100份，炭黑N-330 50份，白炭黑AS-70 10份，1，4-双(叔丁基过氧异丙基)苯(F-40)14份，N，N′-间苯撑双马来酰亚胺(PDM)0.5份，硬脂酸0.5份，氧化镁6份，2-巯基苯并咪唑锌盐(MBZ)0.5重量份和4，4’-双(二甲基苄基)二苯胺(防老剂445)1.0重量份
本发明中，所述胶料可采用本领域常规的方法制备得到，一般包括将各组分混炼即可。所述混炼可采用本领域常规的方法在密炼机中进行。所述混炼较佳地为分段混炼。
技术方案之六：
一种硫化胶，其由所述胶料经硫化制得。
本发明中，所述硫化可采用本领域常规的方法进行。所述硫化较佳地包括：采用电热平板硫化机，在180℃×8分钟条件下对所述胶料进行一段硫化；再将一段硫化制得的产物在150℃×4小时条件下进行二段硫化后，冷却至常温，即得硫化胶。
本发明中，所述硫化胶的邵氏硬度可为60以上，较佳地为80以上。所述硫化胶的断裂强度可为4～8MPa。所述硫化胶的断裂伸长率可为160以上，较佳地为190以上。所述硫化胶的100％定伸强度可为3～4MPa。
技术方案之七：
一种所述液体氢化丁腈橡胶、所述胶料或所述硫化胶在工业制品中的应用。
其中，所述工业制品较佳地包括密封剂、粘结剂、涂层、灌封材料或弹性制品。所述涂层较佳地为电磁屏蔽涂层、耐油涂层、电池耐腐蚀涂层或阻尼降噪涂层。所述粘结剂较佳地为固体推进剂粘结剂或烧蚀材料粘结剂。所述弹性制品尤其是异形复杂弹性制品。
术语定义
丙烯腈含量(ACN％)：是指丁腈橡胶或氢化丁腈橡胶中聚丙烯腈片段的质量百分比含量。
加氢饱和度(Hydrogenation Degree)：聚合物中的烯烃双键的加氢程度，表示方法碘值法。
分子量分布指数(PDI)：聚合物中重均分子量和数均分子量之比称为多分散性指数，即分子量分布指数(PDI)。
门尼粘度：本发明所述门尼粘度均为门尼粘度[ML(1+4)100℃]，是衡量橡胶平均分子量及可塑性的一个指标。
玻璃化转变温度(Tg)：是指由高弹态转变为玻璃态或玻璃台装变为高弹态的温度。玻璃化转变是非晶态高分子材料固有的性质，是高分子运动形式转变的宏观体现，它直接影响材料的使用性能和工艺性能，玻璃化转变温度(Tg)位于外推玻璃化转变起始温度(Tig)与外推玻璃化转变结束温度(Teg)之间。
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：
1、本发明采用“詹氏催化剂”，通过独特的催化降解反应和/或氢化还原反应技术，制备得到了一种低分子量(Mw 3,000～60,000)、分子量分布较宽(PDI＝2.0～8.0)的液体氢化丁腈橡胶，其同时具有加工时优异的流动性和硫化后优异的物理性能，在特种橡胶领域具有独特的应用价值。
2、本发明中的制备技术所提供的方法简化了现有技术的制备工艺方法，采用同一金属催化剂体系，可实现降解和氢化还原在同一工序中一次完成，有效简便地制备各种用途的液体氢化丁腈橡胶，拓宽了液体氢化丁腈橡胶的应用领域，具有明显的技术优势。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
以下实施例中使用的詹氏催化剂为通式I中的化合物4aa或4v，在本公司已授权专利CN200910175790.6中有记载，具体结构式如下：
Figure PCTCN2021118659-appb-000013
以下实施例中所涉及的原料丁腈橡胶和产品液体氢化丁腈橡胶生胶以及胶料有关的特性参数均按照如下方法测试表达：
(1)丙烯腈含量：按照标准SH/T 1157.2-2015《生橡胶丙烯腈-丁二烯橡胶(NBR)中结合丙烯腈含量的测定第2部分：凯氏定氮法》所规定的方法测试，核磁氢谱测试评价作为辅助验证方法。
(2)加氢饱和度：按照标准SH/T 1763《腈类橡胶氢化丁腈橡胶(HNBR)中残留不饱和度的测定碘值法》所规定的方法测试。
(3)玻璃化转变温度(Tg)：采用DSC8500型差示扫描量热仪、按照标准GB/T 29611-2013《生橡胶玻璃化转变温度的测定差示扫描量热法(DSC)》所规定的方法测试。
(4)分子量及分子量分布指数(PDI)：采用ECS000113型常温凝胶渗透色谱仪(Z-1601)、按照标准GB/T21863-2008《凝胶凝胶渗透色谱法(GPC)用四氢呋喃做淋洗液》所规定的方法测试；
实施例1
在氮气置换条件下，往1L不锈钢反应釜中加入100g的丁腈橡胶[丙烯腈质量含量33％，门尼黏度ML(1+4)100℃为35]和500mL的无水氯苯，于60℃氮封条件下完全溶解后加入“詹氏催化剂”(4v)，用量为丁腈橡胶的0.03％，使丁腈橡胶在80℃下进行降解反应，反应1.5小时得到液体丁腈橡胶降解物；然后通入氢气至压力达到8MPa后升温至150℃，反应4小时，得到液体氢化丁腈橡胶溶液。将氢化反应产物的溶液在130℃下负压除去氯苯溶剂后，得到液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶的特性参数为：分子量(Mw)为37950，分子量分布指数为2.1，丙烯腈含量为33％，加氢度为92％(碘值：24)，玻璃化转变温度(Tg)为-31.2℃(Tig：-31.7℃；Teg：-26.9℃)。
实施例2
在氮气置换条件下，往1L不锈钢反应釜中加入100g的丁腈橡胶[丙烯腈质量含量33％，门尼黏度ML(1+4)100℃为35]和500mL的无水氯苯，于60℃氮封条件下完全溶解后加入“詹氏催化剂”(4v)，用量为丁腈橡胶的0.04％，使丁腈橡胶在80℃下进行降解反应，反应1小时得到液体丁腈橡胶；然后通入氢气至压力达到8MPa后升温至150℃，反应5小时，得到液体氢化丁腈橡胶溶液。将氢化反应产物的溶液在130℃下负压除去氯苯溶剂后，得到的液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶的特性参数为：分子量(Mw)为44960，分子量分布指数为2.2，丙烯腈含量为33％，加氢度为96％(碘值：14)，玻璃化转变温度(Tg)为-32.5℃(Tig：-36.1℃；Teg：-28.8℃)。
实施例3
在氮气置换条件下，往1L不锈钢反应釜中加入100g的丁腈橡胶[丙烯腈质量含量33％，门尼黏度ML(1+4)100℃为35]和500mL的无水氯苯，于60℃氮封条件下完全溶解后加入詹氏催化剂(4v)，用量为丁腈橡胶的0.05％，使丁腈橡胶在80℃下进行降解反应，反应1小时得到液体丁腈橡胶；然后通入氢气至压力达到8MPa后升温至150℃，反应6小时，得到高氢化度的液体氢化丁腈橡胶溶液。将氢化反应产物的溶液在130℃下负压除去氯苯溶剂后，得到的液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶特性参数为：分子量(Mw)为45140，分子量分布指数为2.2，结合丙烯腈含量为33％，加氢度为99％(碘值：8)，玻璃化转变温度(Tg)为-29.8℃(Tig：-33.5℃；Teg：-26.2℃)。
实施例4
在氮气置换条件下，往1L不锈钢反应釜中加入100g的丁腈橡胶[丙烯腈质量含量33％，门尼黏度ML(1+4)100℃为35]和500mL的无水氯苯，于60℃氮封条件下完全溶解后加入詹氏催化剂(4v)，用量为丁腈橡胶的0.06％，使丁腈橡胶在80℃下进行降解反应，反应2小时得到液体丁腈橡胶；然后通入氢气至压力达到8MPa后升温至150℃，反应6小时，得到高氢化度的液体氢化丁腈橡胶溶液。将氢化反应产物的溶液在130℃下负压除去氯苯溶剂后，得到的液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶的特性参数为：分子量(Mw)为24350万，分子量分布 指数为2.4，丙烯腈含量为33％，加氢度为99％(碘值：8)，玻璃化转变温度(Tg)为-30.9℃(Tig：-31.5℃；Teg：-27.2℃)。
实施例5
在氮气置换条件下，往1L不锈钢反应釜中加入100g的丁腈橡胶[丙烯腈质量含量33％，门尼黏度ML(1+4)100℃为35]和500mL的无水氯苯，于60℃氮封条件下完全溶解后加入詹氏催化剂(4v)，用量为丁腈橡胶的0.06％，使丁腈橡胶在80℃下进行降解反应，反应2.5小时得到液体丁腈橡胶；然后通入氢气至压力达到8MPa后升温至150℃，反应6小时后得到高氢化度的液体氢化丁腈橡胶溶液。将氢化反应产物的溶液在130℃下负压除去氯苯溶剂后，得到的液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶的特性参数为：分子量(Mw)为8210，分子量分布指数为2.7，丙烯腈含量为33％，加氢度为99％(碘值：8)，玻璃化转变温度(Tg)为-42.8℃(Tig：-49.8℃；Teg：-36.2℃)。
实施例6
在氮气置换条件下，往1L不锈钢反应釜中加入100g的液体丁腈橡胶[丙烯腈质量含量33％，分子量(Mw)为15780，分子量分布指数为3.2]和500mL的无水氯苯，于60℃氮封条件下加入詹氏催化剂(4aa)，用量为丁腈橡胶的0.03％，然后通入氢气至压力达到8MPa后升温至150℃，反应4小时后得到高氢化度的液体氢化丁腈橡胶溶液。将氢化反应产物的溶液在130℃下负压除去氯苯溶剂后，得到的液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶的特性参数为：分子量(Mw)为16250，分子量分布指数为3.3，丙烯腈含量为33％，加氢度为99％(碘值：7)，玻璃化转变温度(Tg)为-38.8℃(Tig：-44.5℃；Teg：-33.9℃)。
实施例7
在氮气置换条件下，往1L不锈钢反应釜中加入100g的液体丁腈橡胶[丙烯腈质量含量43％，分子量(Mw)为32660，分子量分布指数为4.3]和500mL的无水氯苯，于60℃氮封条件下加入詹氏催化剂(4aa)，用量为丁腈橡胶的0.02％，然后通入氢气至压力达到8MPa后升温至150℃，反应3小时后得到高氢化度的液体氢化丁腈橡胶溶液。将氢化反 应产物的溶液在130℃下负压除去氯苯溶剂后，得到的液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶的特性参数为：分子量(Mw)为33420，分子量分布指数为4.3，丙烯腈含量为43％，加氢度为91％(碘值：25)，玻璃化转变温度(Tg)为-30.2℃(Tig：-34.7℃；Teg：-26.9℃)。
实施例8
在氮气置换条件下，往1L不锈钢反应釜中加入100g的液体丁腈橡胶[丙烯腈质量含量25％，分子量(Mw)为32770，分子量分布指数为5.5]和500mL的无水氯苯，于60℃氮封条件下加入詹氏催化剂(4aa)，用量为丁腈橡胶的0.03％，然后通入氢气至压力达到8MPa后升温至150℃，反应4小时后得到高氢化度的液体氢化丁腈橡胶溶液。将氢化反应产物的溶液在130℃下负压除去氯苯溶剂后，得到的液体氢化丁腈橡胶生胶，产品收率＞98％。
所得液体氢化丁腈橡胶生胶的特性参数为：分子量(Mw)为33950，分子量分布指数为5.6，丙烯腈含量为25％，加氢度为95％(碘值：13)，玻璃化转变温度(Tg)为-32.9℃(Tig：-36.6℃；Teg：-29.4℃)。
实施例9
1、硫化胶的制备
按质量份数计，所述胶料包括：液体氢化丁腈橡胶(由实施例3所得生胶)100份，F-40 14份，PDM 0.5份，硬脂酸0.5份，氧化镁6份，炭黑N-330 50份，白炭黑AS-70 10份，MBZ 0.5重量份和防老剂445 1.0重量份。
按照以下工序步骤制备胶料和硫化胶：
(1)混炼：先将所述胶料的各组分投入捏合机机中，在30～60℃下混炼8-10min后强制排胶；然后，将一段混炼得到的胶料在开炼机或三辊磨上进行薄通或研磨3-5遍，卸料后停放12小时，即得所需胶料。
(2)硫化：采用电热平板硫化机，在180℃×8分钟条件下对上述胶料进行一段硫化；再将一段硫化制得的试样在150℃×4小时条件下进行二段硫化后，冷却至常温，即得硫化胶。
2、硫化胶性能测试
按照按GB/T 531.1-2008用GSD-719K型橡胶硬度仪测试邵尔A型硬度(邵氏硬度)；分别按照GB/T 528-2009、GB/T 529-2008和GB/T 532-2008测试标准，在AI-7000-LU型电子拉力试验机上测试拉伸性能和断裂性能。性能测试结果如表1所示。
表1硫化胶性能
邵氏硬度 82
断裂强度，MPa 7.6
断裂伸长率，％ 199
100％定伸强度，MPa 3.1
实施例10
采用由实施例4所得的液体氢化丁腈橡胶生胶，其他制备步骤和条件均与实施例9相同，制得硫化胶，其性能测试结果如表2所示。
表2硫化胶性能
邵氏硬度 67
断裂强度，MPa 4.8
断裂伸长率，％ 163
100％定伸强度，MPa 3.5

Claims (10)

  1. 一种液体氢化丁腈橡胶，其中：
    丙烯腈含量为15％～50％；
    加氢饱和度为75％～99.5％；
    重均分子量为3,000～60,000；
    分子量分布指数为2.0～8.0；
    玻璃化转变温度低于-28℃。
  2. 根据权利要求1所述的液体氢化丁腈橡胶，其特征在于，
    所述液体氢化丁腈橡胶的丙烯腈含量为17％～45％，例如25％、33％或43％；
    和/或，所述液体氢化丁腈橡胶的加氢饱和度为80％～99％，较佳地为90％～99％，例如91％、92％、95％或96％；
    和/或，所述液体氢化丁腈橡胶的重均分子量为5,000～50,000，较佳地为8,000～20,000或24,000～46,000；
    和/或，所述液体氢化丁腈橡胶的分子量分布指数为2.0～6.0；
    和/或，所述液体氢化丁腈橡胶的玻璃化转变温度低于-35℃，较佳地低于-40℃；
    和/或，所述液体氢化丁腈橡胶的外推玻璃化转变起始温度低于-30℃，较佳地低于-35℃，更佳地低于-45℃；
    和/或，所述液体氢化丁腈橡胶的外推玻璃化转变结束温度低于-25℃，较佳地低于30℃，更佳地低于-35℃；
    较佳地，所述液体氢化丁腈橡胶为式IIIa或IIIb所示的液体氢化丁腈橡胶，
    Figure PCTCN2021118659-appb-100001
    其中，p＝1～150；p’＝1～150；q＝30～590；q’＝30～590；n＝20～500；n’＝20～500；
    较佳地，所述液体氢化丁腈橡胶中：丙烯腈含量为17％～45％；加氢饱和度为80％～99％；重均分子量为5,000～50,000；分子量分布指数为2.0～6.0；玻璃化转变温度低于-28℃；
    较佳地，所述液体氢化丁腈橡胶中：丙烯腈含量为33％；加氢饱和度为99％；重均分子量为8,000～20,000；分子量分布指数为2.5～3.5；玻璃化转变温度低于-35℃；
    较佳地，所述液体氢化丁腈橡胶中：丙烯腈含量为25％～43％；加氢饱和度为91％～99％；重均分子量为24,000～46,000；分子量分布指数为2.1～5.6；玻璃化转变温度低于-29℃。
  3. 一种液体氢化丁腈橡胶的制备方法，其包括以下步骤：在惰性气体保护下，在有机溶剂中，在催化剂的作用下，使丁腈橡胶依次经降解反应和氢化还原反应，或使丁腈橡胶经氢化还原反应，得液体氢化丁腈橡胶；其中，所述催化剂包括通式I所示的詹氏催化剂中的一种或多种：
    Figure PCTCN2021118659-appb-100002
    在通式I中：L为一种给电子的络合物配体；
    L 1和L 2独立地为卤素；
    n＝0或1；
    n＝1时，Y 1独立地为氮、氧、硫、CH 2、取代或未取代的C 1-C 20烷基、取代或未取代的C 6-C 20芳基、取代或未取代的C 6-C 20芳氧基、取代或未取代的C 2-C 20杂环芳基、羰基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 1-C 20烷氧基的羰基、亚氨基、取代或未取代的C 1-C 20烷基亚胺基或如式R cR dN-所示的氨基；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基或取代或未取代的C 2-C 20杂环基甲酰基；或者Rc、Rd和N原子连接成环；
    X为氮、氧、硫、CH、CH 2或羰基；
    Y为氮、氧、CH、亚甲基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20芳基、取代或未取代的C 6-C 20芳氧基、取代或未取代的C 2-C 20杂环芳基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 1-C 20烷氧基的羰基、亚氨基、取代或未取代的C 1-C 20烷基亚胺基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基或取代或未取代的C 2-C 20杂环基甲酰基；或者Rc、Rd和N原子连接成环；X表示的基团连接的母体为Y，Y表示的基团连接的母体为X；
    Figure PCTCN2021118659-appb-100003
    之间为单键或双键；
    R 1为氢、取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20芳基、取代或未取代的C 6-C 20芳氧基或取代或未取代的C 2-C 20杂环基；
    R 2为氢、取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 1-C 20烷硫基、取代或未取代的C 1-C 20烷基硅氧基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 6-C 20芳基、C 6-C 20芳氧基、醛基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 6-C 20芳基的羰基、连接取代或未取代的C 2-C 20杂环基的羰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基或取代或未取代的C 2-C 20杂环基甲酰基；或者Rc、Rd和N原子连接成环；
    E为氢、卤素、硝基、腈基、亚砜基、砜基、醛基、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷基硅氧基、C 2-C 20杂环基、C 6-C 20芳基、C 6-C 20芳氧基、连接C 1-C 20烷基的羰基、连接C 6-C 20芳基的羰基、连接C 2-C 20杂环基的羰基、连接C 1-C 20烷氧基的羰基、连接C 6-C 20芳氧基的羰基、连接C 6-C 20杂环基氧基的羰基、氨基酰基、连接C 1-C 20烷基氨基的羰基、连接C 6-C 20芳基氨基的羰基、连接C 2-C 20杂环基氨基的羰基、脲基、取代或未取代的C 1-C 20烷基脲基、取代或未取代的C 6-C 20芳基脲基、取代或未取代的C 2-C 20杂环基脲基、连接C 1-C 20烷基氨基的磺酰基、连接C 6-C 20芳基氨基的磺酰基、连接C 2-C 20杂环基氨基的磺酰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基 甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环基磺酰基；或者Rc、Rd和N原子连接成环；
    E 1为氢、卤素、硝基、腈基、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷基硅氧基、C 2-C 20杂环基、取代或未取代的氨基、氨基酰基、连接C 1-C 20烷基氨基的羰基、C 6-C 20芳基、C 6-C 20芳氧基、亚砜基、砜基、醛基、连接C 1-C 20烷基的羰基、连接取代或未取代的C 6-C 20芳基的羰基、连接取代或未取代的C 2-C 20杂环基的羰基、连接C 1-C 20烷氧基的羰基、连接C 6-C 20芳基氧基的羰基、连接C 2-C 20杂环基氧基的羰基、脲基、取代或未取代的C 1-C 20烷基脲基、取代或未取代的C 6-C 20芳基脲基或取代或未取代的C 2-C 20杂环基脲基；
    E 2为氢、卤素、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷基硅氧基、氨基酰基、连接C 1-C 20烷基氨基的羰基、连接C 6-C 20芳基氨基的羰基、连接C 2-C 20杂环基氨基的羰基、C 6-C 20芳基、C 6-C 20芳氧基、C 2-C 20杂环芳基、醛基、连接C 1-C 20烷基的羰基、连接C 6-C 20芳基的羰基、连接C 2-C 20杂环基的羰基、连接C 1-C 20烷氧基的羰基、连接C 6-C 20芳基氧基的羰基、连接C 2-C 20杂环基氧基的羰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环基磺酰基；或者Rc、Rd和N原子连接成环；
    E 3为氢、卤素、C 1-C 20烷基、C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷基硅氧基、C 6-C 20芳氧基、C 6-C 20芳基、C 2-C 20杂环芳基、连接C 1-C 20烷氧基的羰基、连接取代或未取代的C 6-C 20芳氧基的羰基、连接取代或未取代的C 6-C 20杂环基氧基的羰基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环 基磺酰基；或者Rc、Rd和N原子连接成环；
    E 4、E 5、E 6和E 7独立地为氢、卤素、硝基、腈基、亚砜基、砜基、醛基、取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、C 1-C 20烷硫基、C 1-C 20烷硅基、C 1-C 20烷硅氧基、取代或未取代的C 2-C 20杂环基、取代或未取代的氨基、氨基酰基、连接取代或未取代的C 1-C 20烷基氨基的羰基、连接取代或未取代的C 6-C 20芳基氨基的羰基、连接取代或未取代的C 2-C 20杂环基氨基的羰基、连接取代或未取代的C 1-C 20烷基的羰基、连接取代或未取代的C 6-C 20芳基的羰基、连接取代或未取代的C 2-C 20杂环基的羰基、连接取代或未取代的C 1-C 20烷氧基的羰基、连接取代或未取代的C 6-C 20芳氧基的羰基、连接取代或未取代的C 6-C 20杂环基氧基的羰基、脲基、取代或未取代的C 1-C 20烷基脲基、取代或未取代的C 6-C 20芳基脲基、取代或未取代的C 2-C 20杂环基脲基、取代或未取代的C 6-C 20芳基、取代或未取代的C 6-C 20芳氧基或如式R cR dN-所示的基团；其中，Rc和Rd独立地为氢、取代或未取代的C 6-C 20芳基、取代或未取代的C 2-C 20杂环基、取代或未取代的C 1-C 20烷基、甲酰基、取代或未取代的C 1-C 20烷基甲酰基、取代或未取代的C 6-C 20芳基甲酰基、取代或未取代的C 2-C 20杂环基甲酰基、取代或未取代的C 1-C 20烷基磺酰基、取代或未取代的C 6-C 20芳基磺酰基或取代或未取代的C 2-C 20杂环基磺酰基；或者Rc、Rd和N原子连接成环。
  4. 根据权利要求3所述的液体氢化丁腈橡胶的制备方法，其特征在于，所述的通式I包括下述化合物中的一种或多种：
    Figure PCTCN2021118659-appb-100004
    Figure PCTCN2021118659-appb-100005
    Figure PCTCN2021118659-appb-100006
    所述的通式I较佳地为式4aa、4ab、4f或4v，更佳地为式4aa或4v；
    和/或，所述丁腈橡胶的丙烯腈含量为15％～50％，较佳地为17％～45％，例如25％、33％或43％；
    和/或，所述丁腈橡胶的重均分子量为3,000～60,000；
    和/或，较佳地，所述丁腈橡胶的门尼粘度为30～60；
    和/或，所述丁腈橡胶的分子量分布指数为2.0～8.0；
    较佳地，所述丁腈橡胶的结构如下列式II、IIa或IIb所示：
    Figure PCTCN2021118659-appb-100007
    其中，
    j＝100-6,000；k＝50-5000；
    m＝30-600；n＝20-500；
    m’＝30-600；n’＝20-500；
    和/或，所述詹氏催化剂的用量为0.005％-0.1％，较佳地为0.01％～0.05％，百分比为所述詹氏催化剂占所述丁腈橡胶的质量百分比；
    和/或，所述降解反应的温度为60～100℃，较佳地为80℃；所述降解反应的时间为0.5～10h，较佳地为1～6h，更佳地为2～3h；
    和/或，所述氢化还原反应中氢气的用量为使反应体系的压力达到2～15MPa，较佳地达到6～10Mpa，例如8MPa；
    和/或，所述氢化还原反应的温度为80～200℃，较佳地为100～180℃，更佳地为130～160℃，例如150℃；所述氢化还原反应的时间为2～6h；
    和/或，所述有机溶剂为三氯甲烷、二氯乙烷、丙酮和氯苯中的一种或多种；较佳地为氯苯、二氯乙烷和三氯甲烷中的一种或多种；更佳地为氯苯或二氯乙烷；最佳地为氯 苯；所述有机溶剂的用量较佳地为100～300g丁腈橡胶/1L有机溶剂，例如120g、160g、200g或240g丁腈橡胶/1L有机溶剂；
    和/或，所述惰性气体为氩气或氮气；
    和/或，所述氢化还原反应完成后进行后处理；所述后处理包括负压除去有机溶剂；所述后处理的温度较佳地为100～150℃，更佳地为130～140℃。
  5. 根据权利要求3或4所述的液体氢化丁腈橡胶的制备方法，其特征在于，所述液体氢化丁腈橡胶的制备方法的反应流程如路线-1所示，在惰性气体保护下，在有机溶剂中，通入氢气，在通入氢气的同时或之后加入所述詹氏催化剂，使丁腈橡胶IIa进行氢化还原反应，得到液体氢化丁腈橡胶IIIa；其中，m、n、p和q的定义如权利要求2或4所述；
    Figure PCTCN2021118659-appb-100008
    路线-1
    和/或，所述液体氢化丁腈橡胶的制备方法的反应流程如路线-2所示，在惰性气体保护下，在有机溶剂中，加入所述詹氏催化剂，使丁腈橡胶II进行降解反应得丁腈橡胶IIb；再通入氢气，使丁腈橡胶IIb进行氢化还原反应，得到液体氢化丁腈橡胶IIIb；其中，j、k、m’、n’、p’和q’的定义如权利要求2或4所述；
    Figure PCTCN2021118659-appb-100009
    路线-2。
  6. 一种液体氢化丁腈橡胶，其根据权利要求3～5中任一项所述的液体氢化丁腈橡胶的制备方法制得。
  7. 一种丁腈橡胶的降解方法，其包括以下步骤：在惰性气体保护下，在有机溶剂中，在通式I所示的詹氏催化剂的作用下，使丁腈橡胶经降解反应，得丁腈橡胶降解物；
    Figure PCTCN2021118659-appb-100010
    较佳地，所述詹氏催化剂及其用量如权利要求4所述；
    较佳地，所述丁腈橡胶如权利要求4所述；
    较佳地，所述降解反应的温度和时间如权利要求4所述；
    较佳地，所述有机溶剂及其用量如权利要求4所述；
    较佳地，所述惰性气体如权利要求4所述；
    较佳地，所述丁腈橡胶的降解方法的反应流程如路线-3所示，
    Figure PCTCN2021118659-appb-100011
    路线-3。
  8. 一种胶料，其包含权利要求1、2和5中任一项所述液体氢化丁腈橡胶、填料和硫化剂；
    所述填料较佳地为炭黑和/或白炭黑；所述炭黑较佳地为炭黑N220、炭黑N-330、炭黑N550或炭黑N774；所述白炭黑较佳地为沉淀白炭黑、气相白炭黑或碱性白炭黑；所述碱性白炭黑较佳地为碱性白炭黑AS-70；
    所述硫化剂较佳地为1，4-双(叔丁基过氧异丙基)苯；
    所述胶料较佳地还包括除所述硫化剂之外其他橡胶配合剂，例如助硫化剂、硬脂酸、氧化镁、促进剂和防老剂中的一种或多种；其中，所述助硫化剂较佳地为N，N′-间苯撑双马来酰亚胺；所述促进剂较佳地为2-巯基苯并咪唑锌盐；所述防老剂较佳地为4，4’-双(二甲基苄基)二苯胺；
    较佳地，按质量份数计，所述胶料包括：液体氢化丁腈橡胶100份，炭黑N-330 50份，白炭黑AS-70 10份，1，4-双(叔丁基过氧异丙基)苯14份，N，N′-间苯撑双马来酰亚胺0.5份，硬脂酸0.5份，氧化镁6份，2-巯基苯并咪唑锌盐0.5重量份和4，4’-双(二甲基苄基)二苯胺1.0重量份。
  9. 一种硫化胶，其由权利要求8所述的胶料经硫化制得。
  10. 一种权利要求1、2和5中任一项所述的液体氢化丁腈橡胶、权利要求8所述胶料或权利要求9所述硫化胶在工业制品中的应用。
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