CN115073665B - Fumarate/conjugated diene copolymer type bio-based rubber, preparation method thereof and vulcanized rubber product thereof - Google Patents

Fumarate/conjugated diene copolymer type bio-based rubber, preparation method thereof and vulcanized rubber product thereof Download PDF

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CN115073665B
CN115073665B CN202110274367.2A CN202110274367A CN115073665B CN 115073665 B CN115073665 B CN 115073665B CN 202110274367 A CN202110274367 A CN 202110274367A CN 115073665 B CN115073665 B CN 115073665B
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fumarate
groups
rubber
conjugated diene
monomer
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CN115073665A (en
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王润国
吉海军
杨慧
李利伟
王嘉琦
张立群
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Beijing University of Chemical Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06Butadiene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/12Esters of phenols or saturated alcohols
    • C08F222/14Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/12Esters of phenols or saturated alcohols
    • C08F222/16Esters having free carboxylic acid groups, e.g. monoalkyl maleates or fumarates
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/08Isoprene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

Abstract

The present application relates to a fumarate/conjugated diene copolymer type biobased rubber, which is a copolymer comprising a fumarate monomer and a conjugated diene monomer, wherein the conjugated diene monomer may be selected from the group consisting of C n H 2n‑2 Wherein n is greater than or equal to 4, preferably 4 or 5; the general formula of the fumarate monomer is as follows:wherein R is 1 、R 2 Is a hydrogen atom or C 1~20 Preferably R 1 Is hydrogen, C 1‑10 Alkyl of (a); r is R 2 Is hydrogen, C 1‑10 Alkyl of (a); in the fumarate/conjugated diene copolymer, the mole percentage of the structural units derived from the fumarate in the copolymer is 1 to 99%, preferably 10 to 90%. The rubber of the application has excellent mechanical property and comprehensive performance in the aspect of tire application.

Description

Fumarate/conjugated diene copolymer type bio-based rubber, preparation method thereof and vulcanized rubber product thereof
Technical Field
The application relates to the field of chemical synthetic rubber, in particular to fumarate/conjugated diene copolymer type bio-based rubber, a preparation method thereof and vulcanized rubber products thereof.
Background
In recent years, due to concerns about ecological balance, sustainable economy and the like, the design and manufacture of sustainable polymers have seen great development potential, and the development and production of sustainable materials using biomass has become a steadily growing area of concern. The nature can provide a plurality of bases for the synthesis of sustainable polymers, and has more unique molecular structures in terms of green chemistry and alternative raw materials, so that novel bio-based green polymers for multiple application fields can be synthesized. Not only reduces the dependence on petrochemical resources, but also reduces the environmental pollution in the production and use processes of petrochemical products, and has important practical application value and wide development space.
Natural rubber is a typical biobased elastomer, taken directly from Brazilian rubber tree. However, natural rubber suffers from serious problems such as severe growth conditions of rubber trees and the threat of mycoses, and more people are allergic to proteins in natural rubber. The development of bio-based synthetic elastomers, in particular engineering applications, is therefore very important and urgent. In recent years, various types of bio-based synthetic elastomers have been developed, including bio-based isoprene rubber, bio-based ethylene propylene rubber and bio-based polyester elastomer, and the bio-based polyester rubber is prepared by converting biomass into conventional monomers and polymerizing the monomers by conventional means, and has high cost, and the molecular weight of the bio-based polyester rubber obtained by condensation polymerization is still relatively low.
At present, various polymerization methods have been used for preparing bio-based elastomers, and although the development of these polymerization means is significant in terms of sustainability, green environmental protection, low energy consumption have been lacking. In this case, aqueous low temperature emulsion polymerization techniques, which are of great importance for environmental protection and for promoting sustainable development of the rubber industry, will be more suitable, with the advantages of less solvent, lower energy consumption, more stable reactions, higher molecular weight products.
Fumaric acid is the C4 diacid, the simplest unsaturated dicarboxylic acid, found earliest in rhizoma corydalis and is also found in a variety of mushrooms and fresh beef. Can be used as acidity regulator, acidulant, antioxidant auxiliary agent, pickling promoter, perfume, and intermediate of synthetic resin and mordant.
In chinese patent CN104945817a bio-based engineering rubber prepared from bio-based chemicals itaconate and butadiene by emulsion polymerization and a method for preparing the same are disclosed. The method adopts redox reaction to generate free radical, can initiate polymerization reaction at normal temperature and normal pressure, and reduces energy consumption and operation difficulty in the polymerization process. The number average molecular weight of the polymer can reach 53000 ~ 1640000, and the weight average molecular weight can reach 110000 ~ 2892000. However, because the symmetry of the structure is low and more gel is easy to generate in the process of preparing the rubber, the bio-based monomer needs to be found, the structure symmetry is high, the polymerization process is stable, the traditional rubber processing technology can be utilized for processing, the conversion rate is high, the generated gel is little or even no, the mechanical property of the rubber and the comprehensive performance in the aspect of the application of the tire are finally improved, and an effective thought is provided for preparing the green tire.
Disclosure of Invention
The application aims to solve the technical problems of low molecular weight, poor comprehensive performance and the like of the bio-based rubber in the prior art, and provides the fumarate/conjugated diene copolymer bio-based rubber which has high molecular weight and excellent mechanical properties and comprehensive performance in the aspect of tire application.
The application also aims to solve the problems that the production cost of the bio-based rubber in the prior art is high, the traditional rubber processing technology is not easy to process, and the like, and provides a preparation method of the fumarate/conjugated diene copolymer type bio-based rubber.
In order to achieve one of the above objects, the present application is achieved by the following technical solutions:
the application provides a fumarate/conjugated diene copolymer type bio-based rubber, which is a copolymer containing a fumarate monomer and a conjugated diene monomer, wherein the conjugated diene monomer can be selected from C n H 2n-2 Wherein n is greater than or equal to 4, preferably 4 or 5; the general formula of the fumarate monomer is as follows:
wherein R is 1 、R 2 Is hydrogen sourceSon or C 1~20 Preferably R 1 Is hydrogen, C 1-10 Alkyl of (a); r is R 2 Is hydrogen, C 1-10 Alkyl of (a);
in the fumarate/conjugated diene copolymer, the mole percentage of the structural units derived from the fumarate in the copolymer is 1 to 99%, preferably 10 to 90%.
In a preferred embodiment of the foregoing aspect, the rubber comprises a fumarate/butadiene copolymer, wherein the fumarate/butadiene copolymer has the following structure:
wherein R is 1 、R 2 Is hydrogen atom or C1-10 alkyl, m=1-99%, x=1-50%, y=1-80%, z=1-40%, wherein R 1 、R 2 May be the same or different;
preferably, R 1 Is hydrogen, C 1-10 Alkyl of (a); r is R 2 Is hydrogen, C 1-10 M=10 to 90%, x=5 to 40%, y=5 to 80%, z=5 to 40%;
in the usual emulsion polymerization, the above x, y, z are affected by the copolymerization temperature, comonomer ratio and conversion, and are substantially in the above ranges.
It is further preferred that R1 and R2 are simultaneously alkyl groups of equal length (carbon number=1-5), because when the two ester groups of the fumarate are completely identical, the structural symmetry is higher, and there is some steric hindrance on both double bonds, so that the polymerization process is smoother and no gels are easily generated.
In the above technical scheme, the number average molecular weight (Mn) of the fumarate/conjugated diene copolymer is 10 to 100, preferably 20 to 50; the molecular weight distribution (Mw/Mn) is 1.5 to 5.0, preferably 2.5 to 4.5. When the molecular weight and the molecular weight distribution reach the values, the composite material can be ensured to have enough mechanical property and better processability, and is suitable for industrial application.
In order to achieve the second purpose, the application is realized by the following technical scheme:
the application provides a preparation method of a fumarate/conjugated diene copolymer type bio-based rubber, which comprises the step of performing emulsion polymerization on components comprising a fumarate monomer and a conjugated diene monomer; wherein the conjugated diene monomer is 1 to 99wt%, preferably 5 to 90wt%, based on the total mass of the fumarate monomer and the conjugated diene monomer.
In the above technical scheme, the fumarate monomer is at least one of dimethyl fumarate, monomethyl fumarate, diethyl fumarate, monoethyl fumarate, dipropyl fumarate, monopropyl fumarate, dibutyl fumarate, monobutyl fumarate, dipentyl fumarate, monopentyl fumarate, dihexyl fumarate, monohexyl fumarate, diheptyl fumarate, shan Gengzhi, dioctyl fumarate, monooctyl fumarate, dinonyl fumarate, monononyl fumarate, didecyl fumarate and monodecyl fumarate.
In the above technical scheme, the conjugated diene monomer includes butadiene, isoprene and conjugated dienes of the same kind.
In the above technical scheme, preferably, the water-soluble component and the oil-soluble component are mixed first; adding conjugated diene monomer and pre-emulsifying, finally adding initiator to polymerize to obtain fumarate/conjugated diene copolymer latex, demulsifying by flocculant and drying to obtain raw rubber of the fumarate/conjugated diene copolymer bio-based rubber;
wherein the water-soluble components comprise deionized water, an emulsifier, an electrolyte, an activator and sodium hydrosulfite;
wherein the oil soluble component comprises a fumarate monomer and a chain transfer agent.
In the technical scheme, based on 100 parts by weight of the total mass of the fumarate monomer and the conjugated diene monomer,
100-300 parts of deionized water, preferably 150-250 parts; and/or the number of the groups of groups,
the emulsifier is 0.1-15 parts, preferably 2-10 parts; and/or the number of the groups of groups,
the electrolyte is 0.1-3 parts, preferably 0.1-1.5 parts; and/or the number of the groups of groups,
the activator is 0.01 to 0.2 part, preferably 0.02 to 0.1 part; and/or the number of the groups of groups,
0.01 to 0.05 part of sodium hydrosulfite, preferably 0.01 to 0.03 part of sodium hydrosulfite; and/or the number of the groups of groups,
the chain transfer agent is 0.01 to 0.4 part, preferably 0.03 to 0.25 part; and/or the number of the groups of groups,
the initiator is 0.01-5 parts, preferably 0.02-2 parts; and/or the number of the groups of groups,
the chain transfer agent is used in an amount of 0.01 to 0.4 weight percent, preferably 0.03 to 0.25 weight percent, based on the total mass of the fumarate monomer; and/or the number of the groups of groups,
the flocculant is used in an amount of 20 to 60wt%, preferably 30 to 50wt% based on the total weight of the copolymer latex.
In the above technical solution, the emulsifier may be an emulsifier commonly used in the rubber field, preferably at least one of Sodium Dodecyl Benzene Sulfonate (SDBS), sodium Dodecyl Sulfate (SDS), potassium disproportionated abietate, sodium fatty acid and alkylphenol ethoxylate (OP-10); for example, one or two, etc. Further preferred is a mixture of disproportionated potassium rosin and sodium fatty acid.
In the above technical solution, the electrolyte may be an electrolyte commonly used in the rubber field, preferably at least one of potassium phosphate, potassium chloride and sodium bicarbonate; for example, one or two, etc. Further preferred is potassium chloride.
In the above technical scheme, the activating agent may be an activating agent commonly used in the rubber field, preferably at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, sodium ferric ethylenediamine tetraacetate and tetrasodium ethylenediamine tetraacetate; for example, one or two, etc. Sodium formaldehyde sulfoxylate, ferrous sulfate, or ethylene diamine tetraacetic acid tetrasodium salt are further preferred.
The sodium hydrosulfite is sodium hydrosulfite.
In the technical scheme, the chain transfer agent is at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, carbon tetrabromide and isooctyl 3-mercaptopropionate; for example, one or two, etc. The special chain transfer agent with large chain transfer constant is added to regulate the molecular weight of the rubber product, and the chain transfer agent becomes free radical through chain transfer reaction, can initiate reaction, plays the role of active center, can be finally combined in the polymer to be consumed, and can effectively interfere excessive growth and branched crosslinking of macromolecular chains by a small amount of addition, so that gel is reduced.
In the above technical scheme, the initiator can be an initiator commonly used in the rubber field, preferably at least one of p-menthane hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide and cumene hydroperoxide; further preferred is p-menthane hydroperoxide or diisopropylbenzene hydroperoxide.
In the above technical scheme, the flocculant adopted in the demulsification and drying process can be a flocculant commonly used in the rubber field, preferably at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyandiamide formaldehyde condensate, epoxy amine compound and dilute sulfuric acid; further preferred are ethanol or epoxy amine compounds.
In the technical scheme, the pre-emulsification time is 1-5 hours, preferably 1-2 hours; the reaction temperature is 0-30 ℃, preferably 5-20 ℃, and the polymerization time is 3-20 h, preferably 4-12h.
It is a further object of the present application to provide a vulcanized rubber article comprising said fumarate/conjugated diene-based biobased rubber; preferably, the rubber composition further comprises 10-80 parts by mass of nano-filler, preferably white carbon black or carbon black, based on 100 parts by mass of rubber.
The fourth object of the present application is to provide a process for producing the vulcanized rubber article, which comprises kneading and vulcanizing components including the fumarate/conjugated diene copolymer type bio-based rubber; the vulcanization is preferably carried out by compression molding at 120-180 ℃.
In the technical scheme, the raw rubber of the fumarate/conjugated diene copolymer is mixed with the auxiliary agent, and the mixture is subjected to mould pressing vulcanization at 120-180 ℃ to prepare the vulcanized rubber product.
In the above technical scheme, the auxiliary agent is a common auxiliary agent in the rubber field, preferably zinc oxide, stearic acid, an anti-aging agent 4020, an anti-aging agent RD, an accelerator CZ, an accelerator NS, sulfur and the like. The mass ratio of the raw rubber to the auxiliary agent is 100: (8-15), further preferably 100:12.7.
compared with the prior art, the application has the following beneficial effects: the fumarate monomer is derived from bulk bio-based chemical fumaric acid, and has wide application in industrial production. The fumarate/conjugated diene copolymer is prepared by using a low-temperature redox emulsion polymerization technology, is environment-friendly, has low energy consumption, and is simple in process and suitable for industrial production. The molecular weight of the prepared polymer is 15 ten thousand-50 ten thousand, and the molecular weight distribution is 2.5-4.0. The prepared raw rubber can be processed and molded by adopting a traditional rubber process, has excellent mechanical property and wide and adjustable glass transition temperature range, and can meet the engineering application of rubber. Compared with itaconic acid ester/butadiene copolymer type bio-based engineering rubber, the structure is more regular and symmetrical, the dispersion of white carbon black in a rubber matrix is facilitated, the wet skid resistance of the rubber can be improved, the rolling resistance of the rubber is reduced, and the comprehensive performance of the fumaric acid ester/conjugated diene copolymer type bio-based rubber can be compared with that of solution polymerized styrene butadiene rubber (SSBR) through reasonable structural design.
Drawings
FIG. 1 is a fumarate/butadiene copolymer latex prepared in example 2;
FIG. 2 is a raw state of the fumarate/butadiene copolymer prepared in example 2;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the fumarate/butadiene copolymer prepared in examples 3 and 4;
FIG. 4 shows the glass transition temperatures of the fumarate/butadiene copolymers prepared in examples 3 and 4.
Detailed Description
The present application is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present application and should not be construed as limiting the scope of the present application, and some insubstantial modifications and adjustments of the present application by those skilled in the art from the present disclosure are still within the scope of the present application.
DSC: the test conditions were as follows using a SATRE System DSC tester manufactured by METTLEDO company, switzerland: the temperature is firstly increased from room temperature to 100 ℃, the temperature rising rate is 20 ℃/min, the temperature is kept at 100 ℃ for 3min, then the temperature is reduced from 100 ℃ to-80 ℃ with the temperature reducing rate of 20 ℃/min, and then the temperature is increased to 100 ℃ with the temperature rising rate of 10 ℃/min. The heat change during the second temperature increase was recorded. The glass transition temperature is the intermediate point of the hot melt transition in the curve.
GPC: the test was performed using a Waters 515 HPLC pump and Waters 2410 R1 Detector gel chromatography system manufactured by Waters Inc. of America, using polystyrene as a standard and tetrahydrofuran as the mobile phase.
1 H-NMR: bruker AV400MHz high resolution liquid nuclear magnetic resonance spectrometer for nuclear magnetic resonance spectroscopy with deuterated chloroform (CDCl) 3 ) As solvent, test was performed with Tetramethylsilane (TMS) as internal standard.
The raw materials used in the examples are all commercial medicines.
Example 1
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of dimethyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere (3 times of deoxidization by nitrogen pumping), 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide p-menthane is added for initiating polymerization, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the dimethyl fumarate/butadiene copolymer raw rubber is obtained after drying to constant weight by a vacuum oven, and PDMFB-40 is recorded. The structural unit of the dimethyl fumarate monomer accounts for 35% of the copolymer through nuclear magnetic integration calculation. Conversion was 66%, mn=16.1×10 4 ,Mw/Mn=2.86。
100.0g of the raw rubber of the dimethyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dimethyl fumarate/butadiene copolymer vulcanized rubber.
Example 2
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of diethyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added to initiate polymerization of menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven, so as to obtain diethyl fumarate/butadiene copolymer rubber, and PDEFB-40 is recorded. The structural unit of the diethyl fumarate monomer accounts for 33% of the copolymer through nuclear magnetic integration calculation. Conversion was 71%, mn=24.3×10 4 ,Mw/Mn=3.49。
100.0g of the raw rubber of the diethyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the diethyl fumarate/butadiene copolymer vulcanized rubber.
Example 3
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of diisopropyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added for initiating polymerization of menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the obtained product is dried to constant weight by a vacuum oven, so as to obtain diisopropyl fumarate/butadiene copolymer raw rubber, and the PDPiFB-40 is recorded. The structural unit of the diisopropyl fumarate monomer accounts for 31% of the copolymer through nuclear magnetic integration calculation. Conversion was 82%,Mn=33.1×10 4 ,Mw/Mn=3.52。
100.0g of the diisopropyl fumarate/butadiene copolymer rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the diisopropyl fumarate/butadiene copolymer rubber sulfide.
Example 4
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of dibutyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added to initiate polymerization of menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven, so that the dibutyl fumarate/butadiene copolymer rubber is obtained and is recorded as PDBFB-40. The structural unit of the dibutyl fumarate monomer accounts for 29% of the copolymer through nuclear magnetic integration calculation. Conversion was 82%, mn=45.8×10 4 ,Mw/Mn=3.83。
100.0g of the raw rubber of the dibutyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dibutyl fumarate/butadiene copolymer vulcanized rubber.
Example 5
Adding 30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of dipentyl fumarate into a reaction kettle, sealing the kettle and replacing the kettle with nitrogen atmosphere, adding 360g of butadiene, and pre-emulsifying at 25 DEG C1h, adding 0.6g of hydrogen peroxide to initiate polymerization, reacting at 10 ℃ for 8h to obtain copolymer latex, decompressing to remove butadiene, demulsifying with 500g of ethanol, drying to constant weight by a vacuum oven to obtain raw rubber of the dipentyl fumarate/butadiene copolymer, and recording PDPEFB-40. The structural unit of the dipentyl fumarate monomer accounts for 28% of the copolymer through nuclear magnetic integration calculation. Conversion was 78%, mn=46.2×10 4 ,Mw/Mn=3.98。
100.0g of the raw rubber of the dipentyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the vulcanized rubber of the dipentyl fumarate/butadiene copolymer.
Example 6
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of dihexyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added for initiating polymerization of menthane, the reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven to obtain dihexyl fumarate/butadiene copolymer raw rubber, and PDHxFB-40 is recorded. The structural unit of the dihexyl fumarate monomer accounts for 23% of the copolymer through nuclear magnetic integration calculation. Conversion was 74%, mn=31.2×10 4 ,Mw/Mn=2.98。
100.0g of the raw rubber of the dihexyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dihexyl fumarate/butadiene copolymer vulcanized rubber.
Example 7
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of diheptyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added to initiate polymerization of the menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the raw rubber of the diheptyl fumarate/butadiene copolymer is obtained after drying to constant weight by a vacuum oven, and PDHpFB-40 is recorded. The structural unit of the diheptyl fumarate monomer accounts for 20% of the copolymer through nuclear magnetic integration calculation. Conversion was 64%, mn=23.5×10 4 ,Mw/Mn=2.74。
100.0g of the raw rubber of the diheptyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the diheptyl fumarate/butadiene copolymer vulcanized rubber.
Example 8
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of dioctyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by a nitrogen atmosphere, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added for initiating polymerization of the menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven, so as to obtain dioctyl fumarate/butadiene copolymer raw rubber, and PDOFB-40 is recorded. The structural unit of dioctyl fumarate monomer accounts for 21% of the copolymer through nuclear magnetic integration calculation. Conversion was 59%, mn=18.5×10 4 ,Mw/Mn=2.66。
100.0g of the dioctyl fumarate/butadiene copolymer rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dioctyl fumarate/butadiene copolymer rubber sulfide.
Example 9
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of dinonyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added for initiating polymerization of menthane, the reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven to obtain dinonyl fumarate/butadiene copolymer raw rubber, and PDNFB-40 is recorded. The structural unit of the dinonyl fumarate monomer accounts for 23% of the copolymer through nuclear magnetic integration calculation. Conversion was 56%, mn=16.7x10 4 ,Mw/Mn=2.61。
The raw rubber of the dinonyl fumarate/butadiene copolymer, which is 100.0g, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age resistor 4020,1.0g of age resistor RD,1.0g of accelerator CZ,1.2g of accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the vulcanized rubber of the dinonyl fumarate/butadiene copolymer.
Example 10
Adding 30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of didecyl fumarate into a reaction kettle, sealing the kettle and replacing the kettle with nitrogen atmosphere, adding 360g of butadiene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of the menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, decompressing to remove the butadiene, demulsifying with 500g of ethanol, and drying in a vacuum ovenDrying to constant weight to obtain didecyl fumarate/butadiene copolymer rubber, and recording PDDFB-40. The structural unit of the didecyl fumarate monomer accounts for 17% of the copolymer through nuclear magnetic integration calculation. Conversion was 52%, mn=15.5×10 4 ,Mw/Mn=2.37。
100.0g of the didecyl fumarate/butadiene copolymer rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the didecyl fumarate/butadiene copolymer vulcanized rubber.
Example 11
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 120g of dibutyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 480g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added to initiate polymerization of menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven, so that the dibutyl fumarate/butadiene copolymer rubber is obtained and is recorded as PDBFB-20. The structural unit of the dibutyl fumarate monomer accounts for 12% of the copolymer through nuclear magnetic integration calculation. Conversion was 55%, mn=18.7x10 4 ,Mw/Mn=2.69。
100.0g of the raw rubber of the dibutyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dibutyl fumarate/butadiene copolymer vulcanized rubber.
Example 12
Adding 30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate and 0.5g of ethylenediamine tetraacetic acid into a reaction kettleThe preparation method comprises the steps of sealing a kettle, replacing the kettle with nitrogen, adding 240g of butadiene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of the menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, decompressing to remove butadiene, demulsifying with 500g of ethanol, drying to constant weight through a vacuum oven to obtain dibutyl fumarate/butadiene copolymer raw rubber, and recording PDBFB-60. The structural unit of the dibutyl fumarate monomer accounts for 52% of the copolymer through nuclear magnetic integration calculation. Conversion was 78%, mn=37.5×10 4 ,Mw/Mn=3.58。
100.0g of the raw rubber of the dibutyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dibutyl fumarate/butadiene copolymer vulcanized rubber.
Example 13
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 480g of dibutyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 120g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added to initiate polymerization of menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, the butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven, so that the dibutyl fumarate/butadiene copolymer rubber is obtained, and PDBFB-80 is recorded. The structural unit of the dibutyl fumarate monomer accounts for 76% of the copolymer through nuclear magnetic integration calculation. Conversion was 70%, mn=23.0×10 4 ,Mw/Mn=2.74。
100.0g of the raw rubber of the dibutyl fumarate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dibutyl fumarate/butadiene copolymer vulcanized rubber.
Example 14
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 240g of dibutyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogen atmosphere, 360g of isoprene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added for initiating polymerization of menthane, the copolymer latex is obtained after reaction for 8h at 10 ℃, isoprene is removed, demulsification is carried out by 500g of ethanol, and the mixture is dried to constant weight by a vacuum oven, so as to obtain dibutyl fumarate/isoprene copolymer rubber, and PDBFI-40 is recorded. The structural unit of the dibutyl fumarate monomer accounts for 56% of the copolymer through nuclear magnetic integration calculation. Conversion was 72%, mn=25.4×10 4 ,Mw/Mn=2.75。
100.0g of the raw rubber of the dibutyl fumarate/isoprene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of an anti-aging agent 4020,1.0g of an anti-aging agent RD,1.0g of an accelerator CZ,1.2g of an accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dibutyl fumarate/isoprene copolymer vulcanized rubber.
Comparative example 1
Dibutylitaconate/butadiene copolymer crude rubber (this comparative example preparation was selected from example 11 in CN 104945817A)
Adding 30g of disproportionated potassium abietate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.5g of ethylene diamine tetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tertiary dodecyl mercaptan and 360g of dibutyl itaconate into a reaction kettle, sealing the kettle and replacing the kettle with nitrogen atmosphere, adding 240g of butadiene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of the menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, decompressing to remove the butadiene, demulsifying with 500g of ethanol, drying to constant weight through a vacuum oven,the dibutyl itaconate/butadiene copolymer rubber was obtained and was noted as PDBIB-60. Calculated conversion was 72%, mn=30.2×10 4 ,Mw/Mn=3.89。
100.0g of dibutyl itaconate/butadiene copolymer rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age resistor 4020,1.0g of age resistor RD,1.0g of accelerator CZ,1.2g of accelerator NS,1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the dibutyl itaconate/butadiene copolymer/white carbon black vulcanized rubber.
Comparative example 2
100.0g of NR (tobacco flake rubber), 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age resistor 4020,1.0g of age resistor RD,1.0g of accelerator CZ,1.2g of accelerator NS,1.5g of sulfur, 65.0g of white carbon 1165 and 6.5g of Si69 are uniformly mixed on a two-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression molding vulcanization at 150 ℃ to prepare the NR/white carbon vulcanized rubber.
TABLE 1 Performance test results for comparative examples samples
The above properties were tested according to the following criteria: tensile test: tensile strength, tensile stress (300%), elongation at break (GB/T528-2009) tested according to ASTM D412 standard (dumbbell specimen); hardness experiment: according to ASTM D395.
The relation between the loss factor (tan delta) and the temperature is tested by a dynamic viscoelastometer, the mode is stretching, and the test conditions are as follows: 10Hz, 0.3% strain, 3 ℃/min temperature rise from-80 to 100 ℃.
From the data in table 1, it can be seen that: the mechanical property and dynamic mechanical property of the fumarate/conjugated diene copolymer composite material prepared by the application can be regulated and controlled by the length of the fumarate side group and the monomer feeding ratio. In the present application, systematic studies were performed comparing the performance with that of NR. The diethyl fumarate/butadiene copolymer composite material prepared in example 2 had the best mechanical properties and was superior to commercially available general purpose rubber. The dynamic viscoelasticity changes regularly along with the change of the length of the lateral group of the fumarate, preferably the fumarate monomers are diethyl fumarate (example 2), diisopropyl fumarate (example 3), dibutyl fumarate (example 4) and dipentyl fumarate (example 5), and the mechanical properties of the dynamic viscoelasticity are combined to find that the dynamic viscoelasticity can meet the requirements of engineering application. In different monomer ratios of dibutyl fumarate/butadiene copolymer, the dynamic performance of example 12 is optimal, the tan delta value at 0 ℃ is higher than NR, ESBR1502, and the tan delta value at 60 ℃ is better than ESBR1502, SSBR2550 and is equivalent to SSBR 4602; comparing the obtained product with itaconic acid ester rubber (comparative example 1) with the same side group length and monomer ratio, the obtained product is found to be more excellent in mechanical strength and dynamic mechanical property, and the fumaric acid ester rubber has more application potential of green tread rubber. The mechanical properties of the vulcanized rubber product can meet engineering application, and the dynamic viscoelasticity is excellent.
The above-described embodiment is only a preferred embodiment of the present application, and is not intended to limit the present application in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.

Claims (18)

1. A fumarate/conjugated diene copolymer type biobased rubber which is a copolymer comprising a fumarate monomer and a conjugated diene monomer, wherein the conjugated diene monomer is selected from the group consisting of C n H 2n-2 Wherein n is greater than or equal to 4; the general formula of the fumarate monomer is as follows:
wherein R is 1 、R 2 Is a hydrogen atom or C 1~20 Alkyl of (a);
in the fumarate/conjugated diene copolymer, the mol percentage of structural units derived from a fumarate monomer in the copolymer is 10-90%; the number average molecular weight of the fumarate/conjugated diene copolymer is 20-50 ten thousand;
the preparation method of the fumarate/conjugated diene copolymer type bio-based rubber comprises the following steps:
firstly, mixing a water-soluble component and an oil-soluble component; adding conjugated diene monomer and pre-emulsifying, finally adding initiator to polymerize to obtain fumarate/conjugated diene copolymer latex, demulsifying by flocculant and drying to obtain raw rubber of the fumarate/conjugated diene copolymer bio-based rubber;
wherein the water-soluble components comprise deionized water, an emulsifier, an electrolyte, an activator and sodium hydrosulfite;
wherein the oil soluble component comprises a fumarate monomer and a chain transfer agent.
2. The rubber according to claim 1, wherein: n is 4 or 5.
3. The rubber according to claim 1, wherein: r is R 1 Is hydrogen or C 1-10 Alkyl of (a); r is R 2 Is hydrogen or C 1-10 Is a hydrocarbon group.
4. The rubber according to claim 1, wherein: the molecular weight distribution of the fumarate/conjugated diene copolymer is 1.5-5.0.
5. The rubber according to claim 4, wherein: the molecular weight distribution of the fumarate/conjugated diene copolymer is 2.5-4.5.
6. The method for producing a fumarate/conjugated diene biobased rubber according to any one of claims 1 to 5, comprising the steps of:
firstly, mixing a water-soluble component and an oil-soluble component; adding conjugated diene monomer and pre-emulsifying, finally adding initiator to polymerize to obtain fumarate/conjugated diene copolymer latex, demulsifying by flocculant and drying to obtain raw rubber of the fumarate/conjugated diene copolymer bio-based rubber;
wherein the water-soluble components comprise deionized water, an emulsifier, an electrolyte, an activator and sodium hydrosulfite;
wherein the oil soluble component comprises a fumarate monomer and a chain transfer agent;
wherein the conjugated diene monomer accounts for 5-90wt% based on the total mass of the fumarate monomer and the conjugated diene monomer.
7. The method according to claim 6, wherein:
the fumarate monomer is at least one of dimethyl fumarate, monomethyl fumarate, diethyl fumarate, monoethyl fumarate, dipropyl fumarate, monopropyl fumarate, dibutyl fumarate, monobutyl fumarate, dipentyl fumarate, monopentyl fumarate, dihexyl fumarate, monohexyl fumarate, diheptyl fumarate, shan Gengzhi, dioctyl fumarate, monooctyl fumarate, dinonyl fumarate, monononyl fumarate, didecyl fumarate and monodecyl fumarate; and/or the number of the groups of groups,
the conjugated diene monomer comprises butadiene and isoprene.
8. The method according to claim 6, wherein:
based on 100 parts by mass of the total of the fumarate monomer and the conjugated diene monomer,
100-300 parts of deionized water; and/or the number of the groups of groups,
0.1-15 parts of emulsifying agent; and/or the number of the groups of groups,
0.1-3 parts of electrolyte; and/or the number of the groups of groups,
0.01-0.2 part of activating agent; and/or the number of the groups of groups,
0.01-0.05 part of sodium hydrosulfite; and/or the number of the groups of groups,
0.01-0.4 part of chain transfer agent; and/or the number of the groups of groups,
0.01-5 parts of initiator; and/or the number of the groups of groups,
the consumption of the chain transfer agent is 0.01-0.4wt% of the total mass of the fumarate monomer; and/or the number of the groups of groups,
the dosage of the flocculant is 20-60wt% of the total weight of the copolymer latex.
9. The method according to claim 8, wherein:
based on 100 parts by mass of the total of the fumarate monomer and the conjugated diene monomer,
150-250 parts of deionized water; and/or the number of the groups of groups,
2-10 parts of an emulsifying agent; and/or the number of the groups of groups,
0.1-1.5 parts of electrolyte; and/or the number of the groups of groups,
0.02-0.1 part of activating agent; and/or the number of the groups of groups,
0.01-0.03 part of sodium hydrosulfite; and/or the number of the groups of groups,
0.03-0.25 part of chain transfer agent; and/or the number of the groups of groups,
0.02-2 parts of initiator; and/or the number of the groups of groups,
the chain transfer agent is used in an amount of 0.03-0.25wt% of the total mass of the fumarate monomer; and/or the number of the groups of groups,
the flocculant is used in an amount of 30-50wt% based on the total weight of the copolymer latex.
10. The method according to claim 6, wherein:
the emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, disproportionated potassium abietate, sodium fatty acid and alkylphenol ethoxylates; and/or the number of the groups of groups,
the electrolyte is at least one of potassium phosphate, potassium chloride and sodium bicarbonate; and/or the number of the groups of groups,
the activator is at least one of formaldehyde sodium bisulfate, ferrous sulfate, ferric sodium ethylenediamine tetraacetate and tetrasodium ethylenediamine tetraacetate; and/or the number of the groups of groups,
the sodium hydrosulfite is sodium hydrosulfite; and/or the number of the groups of groups,
the chain transfer agent is at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, carbon tetrabromide and isooctyl 3-mercaptopropionate; and/or the number of the groups of groups,
the initiator is at least one of p-menthane hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide and cumene hydroperoxide; and/or the number of the groups of groups,
the flocculant is at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyandiamide formaldehyde condensate, epoxy amine compound and dilute sulfuric acid.
11. The method according to claim 10, wherein:
the flocculant is at least one of ethanol or epoxy amine compounds.
12. The method according to claim 6, wherein:
the pre-emulsification time is 1-5 h; and/or the number of the groups of groups,
the polymerization temperature is 0-30 ℃; and/or the number of the groups of groups,
the polymerization reaction time is 3-20 h.
13. The method according to claim 12, wherein:
the pre-emulsification time is 1-2 h; and/or the number of the groups of groups,
the polymerization temperature is 5-20 ℃; and/or the number of the groups of groups,
the polymerization reaction time is 4-12h.
14. A vulcanized rubber article comprising the fumarate/conjugated diene copolymer type biobased rubber as defined in any one of claims 1 to 5.
15. The vulcanized rubber article according to claim 14, wherein: and 10-80 parts by mass of nano filler based on 100 parts by mass of rubber.
16. The vulcanized rubber article according to claim 15, wherein: the nano filler is white carbon black or carbon black.
17. A process for the preparation of a vulcanized rubber article as defined in claim 14, comprising mixing and then vulcanizing the components comprising said fumarate/conjugated diene copolymer type biobased rubber.
18. The method of manufacturing according to claim 17, wherein: the vulcanization is carried out by compression molding at 120-180 ℃.
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