CN115073665A - 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 PDFInfo
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Abstract
The invention relates to a fumarate/conjugated diene copolymer type bio-based rubber, which is a copolymer containing fumarate monomers and conjugated diene monomers, wherein the conjugated diene monomers can be selected from C n H 2n‑2 At least one of (a), wherein n.gtoreq.4, preferably 4 or 5; the fumarate monomer has the following general formula:
wherein R is 1 、R 2 To hydrogen atomsSeed or C 1～20 Preferably, R 1 Is hydrogen, C 1‑10 Alkyl groups of (a); r 2 Is hydrogen, C 1‑10 Alkyl groups of (a); in the fumarate/conjugated diene copolymer, the mol percentage content of the structural unit derived from the fumarate in the copolymer is 1-99%, preferably 10-90%. The rubber has excellent mechanical property and comprehensive performance in the aspect of tire application.
Description
Technical Field
The invention relates to the field of chemically synthesized rubber, in particular to fumarate/conjugated diene copolymer type bio-based rubber, a preparation method thereof and a vulcanized rubber product thereof.
Background
In recent years, due to concerns about ecological balance and sustainable economy, the design and manufacture of sustainable polymers has been facing a greater momentum, and the development and production of sustainable materials using biomass has become a steadily growing area of interest. The nature can provide a lot of foundations for the synthesis of sustainable polymers, and has more unique molecular structures in the aspects 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 pollution to the environment in the production and use processes of petrochemical products, and has important practical application value and wide development space.
Natural rubber is a typical bio-based elastomer, taken directly from hevea brasiliensis. However, natural rubber faces serious problems, such as severe growth conditions and fungal disease threats for rubber trees and increasing human allergies to proteins in natural rubber. The development of bio-based synthetic elastomers, particularly engineering applications, is therefore of great importance and urgency. 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 elastomers, and the preparation process of such bio-based polyester rubbers is to convert biomass into conventional monomers and then polymerize the monomers by conventional means, so that the cost is high, and the molecular weight of the bio-based polyester rubber obtained by condensation polymerization is still low.
Currently, various polymerization methods have been used to prepare bio-based elastomers, and although the development of these polymerization means is significant in terms of sustainability, they are still deficient in terms of green and environmental protection, low energy consumption. Under the circumstances, the aqueous low-temperature emulsion polymerization technology which has important significance for environmental protection and promotion of sustainable development of the rubber industry is more suitable, and the emulsion polymerization has the advantages of less solvent, lower energy consumption, more stable reaction and higher molecular weight product.
Fumaric acid is a C4 dibasic acid, the simplest unsaturated dicarboxylic acid, was first discovered from corydalis tuber, and is also present in a variety of mushrooms and fresh beef. Can be used as acidity regulator, acidifying agent, antioxidant auxiliary agent, pickling promoter, and perfume, and also can be used as intermediate of synthetic resin and mordant.
Chinese patent CN104945817A discloses a bio-based engineering rubber prepared by emulsion polymerization of bio-based chemicals of itaconate and butadiene and a preparation method thereof. The method adopts redox reaction to generate free radicals, 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 can reach 53000-1640000, and the weight average molecular weight can reach 110000-2892000. However, due to the fact that the structural symmetry of the rubber is low, more gel is easily generated in the rubber preparation process, a bio-based monomer needs to be found, the structural symmetry of the bio-based monomer is high, the polymerization process is stable, the bio-based monomer can be processed by utilizing the traditional rubber processing technology, the conversion rate is high, the generated gel is little or even not, the mechanical property of the rubber and the comprehensive performance of the rubber in the aspect of tire application are finally improved, and an effective thought is provided for the preparation of green tires.
Disclosure of Invention
One of the purposes of the invention is 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 provide a fumarate/conjugated diene copolymer type bio-based rubber which not only has high molecular weight, but also has excellent mechanical properties and comprehensive performance in the aspect of tire application.
The invention also aims to solve the problems that the production cost of the bio-based rubber is high, the bio-based rubber is not easy to process by using the traditional rubber processing technology and the like in the prior art, and provides the preparation method of the fumarate/conjugated diene copolymer type bio-based rubber, which has low production cost and simple and easy operation process.
In order to achieve one of the purposes, the invention is realized by the following technical scheme:
the invention provides a fumarate/conjugated diene copolymer type bio-based rubber, which is a copolymer containing fumarate monomers and conjugated diene monomers, wherein the conjugated diene monomers can be selected from C n H 2n-2 At least one of (a), wherein n.gtoreq.4, preferably 4 or 5; the fumarate monomer has the following general formula:
wherein R is 1 、R 2 Is a hydrogen atom or C 1～20 Preferably, R 1 Is hydrogen, C 1-10 Alkyl groups of (a); r 2 Is hydrogen, C 1-10 Alkyl groups of (a);
in the fumarate/conjugated diene copolymer, the mol percentage content of the structural unit derived from the fumarate in the copolymer is 1-99%, preferably 10-90%.
In a preferred embodiment of the above aspect, the rubber comprises a fumarate/butadiene copolymer, wherein the fumarate/butadiene copolymer has the following structure:
wherein R is 1 、R 2 Is a hydrogen atom or an alkyl group of C1-10, wherein m is 1-99%, x is 1-50%, y is 1-80%, and z is 1-40%, wherein R is 1 、R 2 May be the same or different;
preferably, R 1 Is hydrogen, C 1-10 Alkyl groups of (a); r 2 Is hydrogen, C 1-10 10-90% of alkyl, 5-40% of x, 5-80% of y, and 5-40% of z;
in general emulsion polymerization, the above x, y, z are substantially in the above range, influenced by copolymerization temperature, comonomer ratio and conversion.
It is further preferable that R1 and R2 are alkyl groups of equal length (carbon number ═ 1-5) at the same time, because when two ester groups of the fumarate are identical, the structural symmetry is higher, and the double bonds both have a certain steric hindrance, so that the polymerization process is more stable and gel is not easily generated.
In the above technical solution, the number average molecular weight (Mn) of the fumarate/conjugated diene copolymer is 10 to 100 ten thousand, preferably 20 to 50 ten thousand; the molecular weight distribution (Mw/Mn) is from 1.5 to 5.0, preferably from 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 properties and better processing performance, and is suitable for industrial application.
In order to achieve the second purpose, the invention is realized by the following technical scheme:
the invention provides a preparation method of fumarate/conjugated diene copolymer type bio-based rubber, which comprises the steps of carrying out emulsion polymerization on components comprising fumarate monomers and conjugated diene monomers; wherein the conjugated diene monomer accounts for 1-99 wt%, preferably 5-90 wt% of the total mass of the fumarate monomer and the conjugated diene monomer.
In the above technical solution, 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, monoheptyl fumarate, dioctyl fumarate, monooctyl fumarate, dinonyl fumarate, monononyl fumarate, didecyl fumarate and monodecyl fumarate.
In the above technical scheme, the conjugated diene monomer comprises butadiene, isoprene and similar conjugated dienes.
In the above technical scheme, preferably, the water-soluble component and the oil-soluble component are mixed first; adding a conjugated diene monomer, pre-emulsifying, adding an initiator, polymerizing to obtain fumarate/conjugated diene copolymer latex, performing demulsification by using a flocculant, and drying to obtain raw rubber of the fumarate/conjugated diene copolymer type 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 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 presence of a gas in the gas,
0.1-15 parts of emulsifier, preferably 2-10 parts; and/or the presence of a gas in the atmosphere,
0.1-3 parts of electrolyte, preferably 0.1-1.5 parts; and/or the presence of a gas in the gas,
the activating agent is 0.01-0.2 part, preferably 0.02-0.1 part; and/or the presence of a gas in the gas,
the sodium hydrosulfite accounts for 0.01-0.05 part, preferably 0.01-0.03 part; and/or the presence of a gas in the gas,
the chain transfer agent is 0.01-0.4 part, preferably 0.03-0.25 part; and/or the presence of a gas in the gas,
the initiator is 0.01-5 parts, preferably 0.02-2 parts; and/or the presence of a gas in the gas,
the dosage of the chain transfer agent is 0.01-0.4 wt% of the total mass of the fumarate monomers, and preferably 0.03-0.25 wt%; and/or the presence of a gas in the atmosphere,
the amount of the flocculant is 20 to 60 wt%, preferably 30 to 50 wt%, 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, and is preferably at least one of Sodium Dodecyl Benzene Sulfonate (SDBS), Sodium Dodecyl Sulfate (SDS), disproportionated potassium rosinate, sodium fatty acid, and alkylphenol polyoxyethylene ether (OP-10); for example, one or two, etc. Further preferred is a mixture of potassium disproportionated rosin and sodium fatty acid.
In the above technical solution, the electrolyte may be an electrolyte commonly used in the rubber field, and is 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, and is preferably at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, ethylenediaminetetraacetic acid ferric sodium salt and ethylenediaminetetraacetic acid tetrasodium salt; for example, one or two, etc. Further preferred is sodium formaldehyde sulfoxylate, ferrous sulfate or ethylenediaminetetraacetic acid tetrasodium salt.
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 a large chain transfer constant is added to adjust the molecular weight of the rubber product, the chain transfer agent is changed into a free radical through a chain transfer reaction, the free radical can initiate the reaction to play a role of an active center and can be finally combined in a polymer to be consumed, and the excessive growth and the branching crosslinking of a macromolecular chain can be effectively interfered by adding a small amount of the chain transfer agent, so that the gel is reduced.
In the above technical solution, the initiator may be an initiator commonly used in the rubber field, and is 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 technical scheme, the flocculant adopted in the demulsification drying process can be a flocculant commonly used in the rubber field, and is preferably at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyanodiamide formaldehyde condensate, epoxy amine compounds and dilute sulfuric acid; further preferably ethanol or an epoxy amine compound.
In the technical scheme, the pre-emulsification time is 1-5 h, preferably 1-2 h; the reaction temperature is 0-30 ℃, the preferable temperature is 5-20 ℃, and the polymerization reaction time is 3-20 h, and the preferable time is 4-12 h.
The invention also aims to provide a vulcanized rubber product which comprises the fumarate/conjugated diene bio-based rubber; preferably, the rubber composition further comprises 10-80 parts by mass of nano filler based on 100 parts by mass of rubber, and the nano filler is preferably white carbon black or carbon black.
The fourth purpose of the invention is to provide a preparation method of the vulcanized rubber product, which comprises the steps of mixing and vulcanizing the components containing the fumarate/conjugated diene copolymer type bio-based rubber; the vulcanization is preferably a mold press vulcanization at 120-180 ℃.
In the technical scheme, the crude rubber of the fumarate/conjugated diene copolymer is blended with the auxiliary agent, and the mixture is subjected to mould pressing and vulcanization at the temperature of 120-180 ℃ to prepare the vulcanized rubber product.
In the technical scheme, the auxiliary agent is a commonly used auxiliary agent in the rubber field, and is 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), more preferably 100: 12.7.
compared with the prior art, the invention 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, so that the method is environment-friendly, low in energy consumption, simple in process and suitable for industrial production. The molecular weight of the prepared polymer is between 15 and 50 million, and the molecular weight distribution is between 2.5 and 4.0. The prepared crude rubber can be processed and molded by adopting the 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 itaconate/butadiene copolymer type bio-based engineering rubber, the structure of the bio-based engineering rubber is more regular and symmetrical, the dispersion of white carbon black in a rubber matrix is more facilitated, the wet skid resistance of the rubber can be improved, and the rolling resistance of the rubber can be reduced.
Drawings
FIG. 1 is a fumarate/butadiene copolymer latex prepared in example 2;
FIG. 2 is a raw state of a fumarate/butadiene copolymer prepared in example 2;
FIG. 3 is a nuclear magnetic hydrogen spectrum of a 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
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
DSC: the SATRE System DSC tester manufactured by METTLER TOLEDO of Switzerland is adopted, and the test conditions are as follows: the temperature is firstly increased from room temperature to 100 ℃, the heating rate is 20 ℃/min, the temperature is preserved for 3min at 100 ℃, then is reduced from 100 ℃ to-80 ℃, the cooling rate is 20 ℃/min, and then the temperature is increased to 100 ℃, and the heating rate is 10 ℃/min. The heat change during the second temperature rise was recorded. The glass transition temperature is the mid-point of the hot-melt transition in the curve.
GPC: the tests were carried out using a Waters 515 HPLC pump and Waters 2410R 1 Detector gel chromatography system, manufactured by Waters corporation, USA, with polystyrene as a standard and tetrahydrofuran as a mobile phase.
1 H-NMR: NMR spectroscopy was performed with Bruker AV400MHz high resolution liquid NMR spectrometer using deuterated chloroform (CDCl) 3 ) As solvent, Tetramethylsilane (TMS) was used as internal standard for testing.
The raw materials used in the examples are all commercially available drugs.
Example 1
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of dimethyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle with nitrogen atmosphere (nitrogen is pumped for 3 times to remove oxygen), adding 360g of butadiene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying to constant weight by a vacuum oven to obtain raw dimethyl fumarate/butadiene copolymer rubber, and recording MFPDB-40. The structural units of the dimethyl fumarate monomer account for 35% of the copolymer by nuclear magnetic integration. Conversion of 66%, Mn 16.1X 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 age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of promoter CZ, 1.2g of promoter NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the vulcanized rubber of the dimethyl fumarate/butadiene copolymer.
Example 2
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of diethyl fumarate into a reaction kettle, sealing the kettle, 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 menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying by a vacuum oven to constant weight to obtain raw rubber of diethyl fumarate/butadiene copolymer, and recording the raw rubber of EFPDB-40. The structural units of the diethyl fumarate monomer accounted for 33% of the copolymer as calculated by nuclear magnetic integration. Conversion 71%, Mn 24.3X 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 age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of promoter CZ, 1.2g of promoter NS, 1.5g of sulfur, 65.0g of white carbon 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the vulcanized rubber of the diethyl fumarate/butadiene copolymer.
Example 3
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of diisopropyl fumarate into a reaction kettle, sealing the kettle, 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 menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying by a vacuum oven to constant weight to obtain diisopropyl fumarate/butadiene copolymer crude rubber, and recording the weight of PDFB-40. The structural unit of diisopropyl fumarate monomer accounts for 31 percent of the copolymer by nuclear magnetic integration calculation. Conversion was 82%, Mn 33.1X 10 4 ，Mw/Mn＝3.52。
100.0g of the diisopropyl fumarate/butadiene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of antioxidant 4020, 1.0g of antioxidant RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the diisopropyl fumarate/butadiene copolymer vulcanized rubber.
Example 4
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of dibutyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle with nitrogen atmosphere, adding 360g of butadiene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to menthane for initiating polymerization, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, and adding 500g of ethanolDemulsifying, drying by a vacuum oven to constant weight to obtain the dibutyl fumarate/butadiene copolymer crude rubber, and recording the weight as PDBFB-40. The structural unit of the dibutyl fumarate monomer accounts for 29 percent of the copolymer through nuclear magnetic integration calculation. Conversion was 82%, Mn 45.8X 10 4 ，Mw/Mn＝3.83。
100.0g of the dibutyl fumarate/butadiene copolymer raw rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression 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 formaldehyde sodium bisulfate, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of dipentyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle in a nitrogen atmosphere, adding 360g of butadiene, pre-emulsifying for 1 hour at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting for 8 hours at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying to constant weight by a vacuum oven to obtain dipentyl fumarate/butadiene copolymer crude rubber, and PDPeFB-40. The structural units of the diamyl fumarate monomer accounted for 28% of the copolymer as calculated by nuclear magnetic integration. Conversion of 78%, Mn 46.2X 10 4 ，Mw/Mn＝3.98。
100.0g of the diamyl fumarate/butadiene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of anti-aging agent 4020, 1.0g of anti-aging agent RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the diamyl fumarate/butadiene copolymer vulcanized rubber.
Example 6
30g of disproportionated potassium rosinate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate and 0.3g of formaldehyde-sulfuric acid are added into a reaction kettleSodium hydrogen, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of dihexyl fumarate, sealing the kettle, replacing the kettle with a nitrogen atmosphere, adding 360g of butadiene, pre-emulsifying at 25 ℃ for 1h, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting at 10 ℃ for 8h to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying in a vacuum oven to constant weight to obtain the dihexyl fumarate/butadiene copolymer crude rubber, and recording the PDHxFB-40. The structural units of the dihexyl fumarate monomer accounted for 23% of the copolymer as calculated by nuclear magnetic integration. Conversion 74%, Mn 31.2X 10 4 ，Mw/Mn＝2.98。
100.0g of the dihexyl fumarate/butadiene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of anti-aging agent 4020, 1.0g of anti-aging agent RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the dihexyl fumarate/butadiene copolymer vulcanized rubber.
Example 7
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of diheptyl fumarate into a reaction kettle, sealing the kettle, 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 menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying by a vacuum oven to constant weight to obtain diheptyl fumarate/butadiene copolymer crude rubber, and recording PDHB-40. The constitutional unit of the diheptyl fumarate monomer accounts for 20% of the copolymer by nuclear magnetic integration calculation. Conversion 64%, Mn 23.5X 10 4 ，Mw/Mn＝2.74。
100.0g of the diheptyl fumarate/butadiene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of anti-aging agent 4020, 1.0g of anti-aging agent RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the diheptyl fumarate/butadiene copolymer vulcanized rubber.
Example 8
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of dioctyl fumarate into a reaction kettle, sealing the kettle, 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 menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying to constant weight by a vacuum oven to obtain dioctyl fumarate/butadiene copolymer crude rubber, and recording the weight of OFPDB-40. The structural unit of the dioctyl fumarate monomer accounts for 21 percent of the copolymer through nuclear magnetic integration calculation. Conversion 59%, Mn 18.5X 10 4 ，Mw/Mn＝2.66。
100.0g of the dioctyl fumarate/butadiene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the dioctyl fumarate/butadiene copolymer vulcanized rubber.
Example 9
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of dinonyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle in a nitrogen atmosphere, adding 360g of butadiene, pre-emulsifying for 1 hour at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting for 8 hours at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying to constant weight by a vacuum oven to obtain dinonyl fumarate/butadiene copolymer crude rubber, and recording PDNFB-40. Calculated by nuclear magnetic integral, the dinonyl fumarate monomerThe structural units of (a) account for 23% of the copolymer. Conversion 56%, Mn 16.7X 10 4 ，Mw/Mn＝2.61。
100.0g of the dinonyl fumarate/butadiene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of antioxidant 4020, 1.0g of antioxidant RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the dinonyl fumarate/butadiene copolymer vulcanized rubber.
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 formaldehyde sodium bisulfate, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of didecyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle in a nitrogen atmosphere, adding 360g of butadiene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying to constant weight by a vacuum oven to obtain didecyl fumarate/butadiene copolymer crude rubber, namely PDDFB-40. The structural unit of the didecyl fumarate monomer accounts for 17 percent of the copolymer through nuclear magnetic integration calculation. Conversion 52%, Mn 15.5X 10 4 ，Mw/Mn＝2.37。
100.0g of the didecyl fumarate/butadiene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of anti-aging agent 4020, 1.0g of anti-aging agent RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression 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 formaldehyde sodium bisulfate, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 120g of dibutyl fumarate are added into a reaction kettle, the kettle is sealed and replaced by nitrogenAdding 480g of butadiene in the atmosphere, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to p-menthane to initiate polymerization, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying by using 500g of ethanol, drying by using a vacuum oven to constant weight to obtain the dibutyl fumarate/butadiene copolymer crude rubber, and recording PDBFB-20. The structural unit of the dibutyl fumarate monomer accounts for 12 percent of the copolymer through nuclear magnetic integration calculation. Conversion 55%, Mn 18.7X 10 4 ，Mw/Mn＝2.69。
100.0g of the dibutyl fumarate/butadiene copolymer raw rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the dibutyl fumarate/butadiene copolymer vulcanized rubber.
Example 12
Adding 30g of disproportionated potassium rosinate, 10g of sodium fatty acid, 800g of deionized water, 0.1g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 360g of dibutyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle with nitrogen atmosphere, adding 240g of butadiene, pre-emulsifying for 1 hour at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting for 8 hours at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying by a vacuum oven to constant weight to obtain dibutyl fumarate/butadiene copolymer crude rubber, and recording PDBFB-60. The structural units of the dibutyl fumarate monomer account for 52% of the copolymer calculated by nuclear magnetic integration. Conversion was 78%, Mn 37.5X 10 4 ，Mw/Mn＝3.58。
100.0g of the dibutyl fumarate/butadiene copolymer raw rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the dibutyl fumarate/butadiene copolymer vulcanized rubber.
Example 13
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 480g of dibutyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle with nitrogen atmosphere, adding 120g of butadiene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying by a vacuum oven to constant weight to obtain dibutyl fumarate/butadiene copolymer crude rubber, and recording the dibutyl fumarate/butadiene copolymer crude rubber as PDB-80. The structural unit of the dibutyl fumarate monomer accounts for 76 percent of the copolymer through nuclear magnetic integration calculation. Conversion of 70%, Mn 23.0X 10 4 ，Mw/Mn＝2.74。
100.0g of the dibutyl fumarate/butadiene copolymer raw rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the dibutyl fumarate/butadiene copolymer vulcanized rubber.
Example 14
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, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 240g of dibutyl fumarate into a reaction kettle, sealing the kettle, replacing the kettle with nitrogen atmosphere, adding 360g of isoprene, pre-emulsifying for 1h at 25 ℃, adding 0.6g of hydrogen peroxide to initiate polymerization of menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing isoprene, demulsifying with 500g of ethanol, drying by a vacuum oven to constant weight to obtain dibutyl fumarate/isoprene copolymer crude rubber, and recording the weight of dibutyl fumarate/isoprene copolymer crude rubber as PDI-40. The structural unit of the dibutyl fumarate monomer accounts for 56 percent of the copolymer through nuclear magnetic integration calculation. Conversion 72%, Mn 25.4X 10 4 ，Mw/Mn＝2.75。
100.0g of the dibutyl fumarate/isoprene copolymer crude rubber, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon 1165 and 6.5gSi69 are uniformly mixed on a double-roll open mill to obtain a rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the dibutyl fumarate/isoprene copolymer vulcanized rubber.
Comparative example 1
Dibutyl itaconate/butadiene copolymer gum (this comparative example preparation method was selected from example 11 of 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 formaldehyde sodium bisulfate, 0.5g of ethylenediaminetetraacetic acid tetrasodium salt, 4g of potassium chloride, 0.1g of sodium hydrosulfite, 0.6g of tert-dodecyl mercaptan and 360g of dibutyl itaconate into a reaction kettle, sealing the kettle, 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 menthane, reacting for 8h at 10 ℃ to obtain copolymer latex, removing butadiene under reduced pressure, demulsifying with 500g of ethanol, drying by a vacuum oven to constant weight to obtain dibutyl itaconate/butadiene copolymer crude rubber, and recording the dibutyl itaconate/butadiene copolymer crude rubber as PDB-60. The conversion was calculated to be 72%, Mn ═ 30.2 × 10 4 ，Mw/Mn＝3.89。
100.0g of raw rubber of dibutyl itaconate/butadiene copolymer, 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are mixed uniformly on a double-roll mill to obtain rubber compound, and the rubber compound is subjected to compression vulcanization at 150 ℃ to prepare the vulcanized rubber of dibutyl itaconate/butadiene copolymer/white carbon black.
Comparative example 2
100.0g of NR (smoked sheet rubber), 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of age inhibitor 4020, 1.0g of age inhibitor RD, 1.0g of promoter CZ, 1.2g of promoter NS, 1.5g of sulfur, 65.0g of white carbon black 1165 and 6.5gSi69 are mixed uniformly on a double-roll open mill to obtain mixed rubber, and the mixed rubber is subjected to compression vulcanization at 150 ℃ to prepare the NR/white carbon black vulcanized rubber.
TABLE 1 Performance test results of the comparative examples of each example
The above properties were tested according to the following criteria: and (3) tensile test: testing according to ASTM D412 standard (dumbbell type test specimen), tensile strength, stress at definite elongation (300%), elongation at break (GB/T528-; hardness test: tested 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 from-80 to 100 ℃.
As can be seen from the data in table 1: the mechanical property and dynamic mechanical property of the fumarate/conjugated diene copolymer composite material prepared by the invention can be regulated and controlled by the length of the fumarate side group and the monomer feed ratio. In this application, systematic studies were performed comparing their performance with that of NR. The diethyl fumarate/butadiene copolymer composite prepared in example 2 has the best mechanical properties and is superior to commercially available general purpose rubbers. The dynamic viscoelasticity changes regularly with the change of the length of the side group of the fumarate, and the preferred fumarate monomers are diethyl fumarate (example 2), diisopropyl fumarate (example 3), dibutyl fumarate (example 4) and diamyl fumarate (example 5), and the mechanical properties of the fumarate monomers are combined to find that all the fumarate monomers can meet the requirements of engineering application. Among different monomer ratios of the dibutyl fumarate/butadiene copolymer, the dynamic performance of the embodiment 12 is the best, the value of tan delta at 0 ℃ is higher than NR and ESBR1502, and the value of tan delta at 60 ℃ is better than ESBR1502 and SSBR2550 and is equivalent to SSBR 4602; compared with itaconate rubber (comparative example 1) with the same side group length and monomer ratio, the obtained product has more excellent mechanical strength and dynamic mechanical property, and the fumarate rubber has more application potential of green tread rubber. The vulcanized rubber product provided by the embodiment of the invention has mechanical properties meeting the requirements of engineering application and excellent dynamic viscoelasticity.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A fumarate/conjugated diene copolymer type bio-based rubber, said rubber being a copolymer comprising fumarate monomers and conjugated diene monomers, wherein said conjugated diene monomers may be selected from C n H 2n-2 At least one of (a), wherein n is not less than 4, preferably 4 or 5; the fumarate monomer has the following general formula:
wherein R is 1 、R 2 Is a hydrogen atom or C 1～20 Preferably, R 1 Is hydrogen, C 1-10 Alkyl groups of (a); r 2 Is hydrogen, C 1-10 Alkyl groups of (a);
in the fumarate/conjugated diene copolymer, the mol percentage content of the structural unit derived from the fumarate monomer in the copolymer is 1-99%, preferably 10-90%.
2. The rubber according to claim 1, wherein: the number average molecular weight of the fumarate/conjugated diene copolymer is 10 to 100 ten thousand, preferably 20 to 50 ten thousand; the molecular weight distribution is 1.5 to 5.0, preferably 2.5 to 4.5.
3. The process for producing a fumarate/conjugated diene type bio-based rubber according to claim 1 or 2, comprising the step of emulsion-polymerizing components comprising a fumarate monomer and a conjugated diene monomer; wherein the conjugated diene monomer accounts for 1-99 wt%, preferably 5-90 wt% of the total mass of the fumarate monomer and the conjugated diene monomer.
4. The method of claim 3, 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, monoeeptyl fumarate, dioctyl fumarate, monooctyl fumarate, dinonyl fumarate, monononyl fumarate, didecyl fumarate and monodecyl fumarate; and/or the presence of a gas in the gas,
the conjugated diene monomer comprises butadiene, isoprene and similar conjugated dienes.
5. A method according to claim 3, characterized by the steps of:
firstly, mixing a water-soluble component and an oil-soluble component; adding a conjugated diene monomer, pre-emulsifying, adding an initiator, polymerizing to obtain fumarate/conjugated diene copolymer latex, performing demulsification by using a flocculant, and drying to obtain raw rubber of the fumarate/conjugated diene copolymer type 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.
6. The method of claim 5, wherein:
based on 100 parts 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 presence of a gas in the gas,
0.1-15 parts of emulsifier, preferably 2-10 parts; and/or the presence of a gas in the gas,
0.1-3 parts of electrolyte, preferably 0.1-1.5 parts; and/or the presence of a gas in the atmosphere,
the activating agent is 0.01-0.2 part, preferably 0.02-0.1 part; and/or the presence of a gas in the atmosphere,
the sodium hydrosulfite accounts for 0.01-0.05 part, preferably 0.01-0.03 part; and/or the presence of a gas in the gas,
the chain transfer agent is 0.01-0.4 part, preferably 0.03-0.25 part; and/or the presence of a gas in the gas,
the initiator is 0.01-5 parts, preferably 0.02-2 parts; and/or the presence of a gas in the gas,
the dosage of the chain transfer agent is 0.01-0.4 wt% of the total mass of the fumarate monomers, and preferably 0.03-0.25 wt%; and/or the presence of a gas in the gas,
the amount of the flocculant is 20 to 60 wt%, preferably 30 to 50 wt%, of the total weight of the copolymer latex.
7. The method of claim 5, wherein:
the emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, disproportionated potassium rosinate, sodium fatty acid and alkylphenol ethoxylates; and/or the presence of a gas in the gas,
the electrolyte is at least one of potassium phosphate, potassium chloride and sodium bicarbonate; and/or the presence of a gas in the gas,
the activating agent is at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, ethylene diamine tetraacetic acid ferric sodium salt and ethylene diamine tetraacetic acid tetrasodium salt; and/or the presence of a gas in the gas,
the sodium hydrosulfite is sodium hydrosulfite; and/or the presence of a gas in the gas,
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 presence of a gas in the gas,
the initiator is at least one of p-menthane hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide and cumene hydroperoxide; and/or the presence of a gas in the gas,
the flocculating agent is at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyanodiamide formaldehyde condensate, epoxy amine compounds and dilute sulfuric acid; preferably at least one of ethanol or epoxy amine compounds.
8. The method of claim 5, wherein:
the pre-emulsification time is 1-5 h, preferably 1-2 h; and/or the presence of a gas in the gas,
the reaction temperature is 0-30 ℃, and preferably 5-20 ℃; and/or the presence of a gas in the gas,
the polymerization reaction time is 3-20 h, preferably 4-12 h.
9. A vulcanized rubber product comprising the fumarate/conjugated diene copolymer type bio-based rubber according to any one of claims 1 to 2; preferably, the rubber composition further comprises 10-80 parts by mass of nano filler based on 100 parts by mass of rubber, and the nano filler is preferably white carbon black or carbon black.
10. A process for producing a vulcanizate according to claim 9, comprising compounding and vulcanizing components comprising the fumarate/conjugated diene copolymer type bio-based rubber; the vulcanization is preferably a mold press vulcanization at 120-180 ℃.
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| CN116217809A (en) * | 2023-03-24 | 2023-06-06 | 山东京博中聚新材料有限公司 | Preparation method of bio-based rubber and vulcanized rubber |
| CN116925699A (en) * | 2023-07-13 | 2023-10-24 | 鞍山科顺建筑材料有限公司 | Low-temperature modified asphalt waterproof coiled material sizing composition, low-temperature modified asphalt waterproof coiled material sizing, and preparation method and application thereof |
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- 2022-01-24 WO PCT/CN2022/073364 patent/WO2022193837A1/en active Application Filing
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| GB1084862A (en) * | 1964-01-04 | 1967-09-27 | Basf Ag | Production of copolymers of butadiene |
| US6956093B1 (en) * | 2004-10-29 | 2005-10-18 | The Goodyear Tire & Rubber Company | Preparation of syndiotactic polybutadiene, rubber composition and tire with rubber component |
| CN105294939A (en) * | 2015-10-27 | 2016-02-03 | 北京化工大学 | Low-temperature-level hydrogenated acrylonitrile butadiene rubber crude rubber and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116217809A (en) * | 2023-03-24 | 2023-06-06 | 山东京博中聚新材料有限公司 | Preparation method of bio-based rubber and vulcanized rubber |
| CN116217809B (en) * | 2023-03-24 | 2024-03-29 | 山东京博中聚新材料有限公司 | Preparation method of bio-based rubber and vulcanized rubber |
| CN116925699A (en) * | 2023-07-13 | 2023-10-24 | 鞍山科顺建筑材料有限公司 | Low-temperature modified asphalt waterproof coiled material sizing composition, low-temperature modified asphalt waterproof coiled material sizing, and preparation method and application thereof |
| CN116925699B (en) * | 2023-07-13 | 2024-02-20 | 鞍山科顺建筑材料有限公司 | Low-temperature modified asphalt waterproof coiled material sizing composition, low-temperature modified asphalt waterproof coiled material sizing, and preparation method and application thereof |
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| WO2022193837A1 (en) | 2022-09-22 |
| CN115073665B (en) | 2023-08-29 |
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