CN117164760A - Functionalized fumarate/conjugated diene copolymer, preparation method thereof and bio-based elastomer - Google Patents

Functionalized fumarate/conjugated diene copolymer, preparation method thereof and bio-based elastomer Download PDF

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CN117164760A
CN117164760A CN202210573358.8A CN202210573358A CN117164760A CN 117164760 A CN117164760 A CN 117164760A CN 202210573358 A CN202210573358 A CN 202210573358A CN 117164760 A CN117164760 A CN 117164760A
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fumarate
conjugated diene
rubber
monomer
functionalized
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王润国
吉海军
杨慧
李利伟
孙超英
张立群
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
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    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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Abstract

The application discloses a functionalized fumarate/conjugated diene copolymer, a preparation method thereof and a bio-based elastomer. The functionalized fumarate/conjugated diene copolymer includes a fumarate structural unit, a conjugated diene monomer structural unit, and a third monomer structural unit. The functionalized fumarate/conjugated diene copolymer can be prepared into a bio-based elastomer to be applied to tread rubber, so that the process is greatly simplified, the VOC emission is reduced, and the bio-based green tire material has a very good application prospect.

Description

Functionalized fumarate/conjugated diene copolymer, preparation method thereof and bio-based elastomer
Technical Field
The application relates to the technical field of tires, in particular to a functionalized fumarate/conjugated diene copolymer based on bio-based da Zong chemical fumarate as a main raw material, a preparation method thereof and a bio-based elastomer.
Background
Continuing with the sustainable strategy, there are increasing restrictions on non-renewable resources, and many products are undergoing significant changes, and development and utilization of renewable resources are becoming the focus of current research, and it is believed that in the near future, renewable resource products will certainly become the main stream of future markets. For this reason, each large tire company attempts to produce green tires based on biomass resources of solar origin, and this prospective technical innovation undoubtedly has led to the long-term development of global tires.
At present, the preparation of bio-based synthetic rubber mainly has two directions: (1) The biomass raw material is fermented to obtain a bio-based monomer, the bio-based monomer is converted into a bio-based traditional monomer by means of catalysis and the like, and finally the bio-based traditional rubber is prepared by using a traditional chemical synthesis process. (2) The bio-based monomer is obtained through biomass raw material fermentation, reasonable molecular structure design is carried out, and the novel bio-based rubber is obtained through direct polymerization, so that the conversion process of the traditional intermediate bio-based monomer is omitted, the process is simplified, the efficiency is improved, and the two preparation directions are in parallel research and development states, and can be subjected to commercialized development. Among them, the development of biomass monomers, elastomer polymerization and application fields are the key points of current researches.
The present inventors have disclosed a bio-based engineering rubber prepared from bio-based chemicals itaconate and butadiene by emulsion polymerization and a method for preparing the same in "an itaconate/butadiene copolymer type bio-engineering rubber and a method for preparing the same" (CN 104945817 a). Subsequently, in a "fumarate/conjugated diene copolymer type biobased rubber, a method for producing the same and vulcanized rubber products thereof" (202110274367.2), a novel biobased polymer having a high molecular weight and a low glass transition temperature is produced by emulsion copolymerization of fumaric acid instead of itaconic acid as a main raw material and conjugated dienes, and the fumarate/conjugated diene copolymer type biobased rubber can be processed by a conventional rubber processing technique. The application of the coupling agent is also related to the application of the green tire, but the green tire is usually a white carbon black-coupling agent system at present, and a plurality of hydroxyl groups exist on the surface of the white carbon black, so that the white carbon black is easy to agglomerate, and the coupling agent is adopted to modify the white carbon black, so that the dispersibility of the filler is improved, and the rolling resistance is reduced. To further reduce the rolling resistance, the force between the rubber and the filler can be enhanced. The molecular chains can be connected to the filler through chemical bonds, so that the slip and friction loss can be reduced. Here we have improved the white carbon dispersion by introducing reactive monomers into the chain to form chemical bonds with the white carbon, simplifying the processing technique. Meanwhile, the distribution of the fumaric acid ester in the molecular chain can form physical bond with white carbon black to limit disordered movement of the chain, so that the functionalized fumaric acid ester elastomer can be an excellent matrix of the low-rolling-resistance green tire and is not reported at home and abroad.
Disclosure of Invention
In order to solve the above problems in the prior art, the present application provides a functionalized fumarate/conjugated diene copolymer type bio-based elastomer having high molecular weight and low rolling resistance characteristics. The application also provides a preparation method of the functionalized fumarate/conjugated diene copolymer type bio-based elastomer, which has the advantages of low production cost, simple process and environmental protection.
It is an object of the present application to provide a functionalized fumarate/conjugated diene copolymer comprising a fumarate structural unit, a conjugated diene monomer structural unit and a third monomer structural unit.
The content of the fumarate structural unit is 1 to 95% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight, based on the total mass of the structural units; the content of the conjugated diene monomer structural unit is 1 to 98wt%, preferably 5 to 89wt%, more preferably 10 to 80wt%; the content of the third monomer structural unit is 0.1 to 30% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight.
The fumarate structural unit is derived from a fumarate having a structure as shown in formula (I),
wherein R is 1 、R 2 Each independently is a hydrogen atom or C 1-20 And R is an alkyl group of 1 、R 2 Not both hydrogen, preferably R 1 Each independently is a hydrogen atom or C 1-10 Is a hydrocarbon group.
The fumaric acid ester is preferably at least one selected from 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.
The conjugated diene monomer structural unit is derived from conjugated diene, and the conjugated diene has a general formula of C n H 2n-2 Wherein n.gtoreq.4, n is preferably 4 or 5.
The conjugated diene monomer is preferably at least one selected from butadiene, isoprene, myrcene, ocimene, farnesene and dienes of the same kind.
The third monomer structural unit is derived from a third monomer, wherein the third monomer is selected from at least one of an epoxy group-containing olefin monomer, a carboxyl group-containing olefin monomer, and a hydroxyl group-containing olefin monomer.
Among them, the epoxy group-containing olefin monomers preferably include, but are not limited to, at least one of glycidyl methacrylate, glycidyl acrylate, diglycidyl tricarboxylic acid ester, triglycidyl tricarboxylic acid ester, propenyl glycidyl ether, glycidyl methacrylate, and the like; the carboxyl group-containing hydrocarbon monomer preferably includes, but is not limited to, at least one of acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, itaconic anhydride, and the like; the hydroxyl group-containing olefin monomer is preferably, but not limited to, at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like.
In a preferred embodiment of the foregoing technical scheme, the specific structure of the functionalized fumarate/conjugated diene copolymer is represented by the following formula (II):
wherein R is 1 、R 2 Each independently is a hydrogen atom or C 1-20 And R is an alkyl group of 1 、R 2 Are not hydrogen at the same time; m=1 to 95%, x+y+z=1 to 98%, n=0.1 to 30%, where R 1 、R 2 May be the same or different;
preferably, R 1 、R 2 Is hydrogen, C 1-10 Alkyl of (a); m=10 to 90%, x+y+z=5 to 89%, n=0.5 to 15%.
In the above technical scheme, the number average molecular weight of the functionalized fumarate/conjugated diene copolymer is 10 to 80 tens of thousands, preferably 15 to 60 tens of thousands; the molecular weight distribution is 1.5 to 5.0, preferably 2.0 to 3.5.
The application carries out functionalization modification on the fumarate/conjugated diene copolymer, namely the functionalized fumarate/conjugated diene copolymer type bio-based elastomer is obtained by copolymerizing a third monomer with the function of white carbon black with the fumarate and the conjugated diene.
It is a second object of the present application to provide a process for preparing the functionalized fumarate/conjugated diene copolymer comprising the steps of:
mixing fumaric acid ester, a third monomer, an emulsifier, an activator and water, adding conjugated diene in an inert atmosphere, pre-emulsifying, adding an initiator for polymerization reaction, and demulsifying and drying.
In the above technical scheme, the polymerization reaction temperature is 0 ℃ to 80 ℃, preferably 5 ℃ to 75 ℃.
In the technical scheme, the polymerization time is 3-48 h, preferably 4-24 h.
According to a preferred embodiment, the preparation steps may be: mixing a fumarate monomer, a third monomer, an emulsifying agent, an activating agent, deionized water and the like in proportion, replacing the system with nitrogen atmosphere, adding a diene monomer, pre-emulsifying, adding an initiator to finally obtain functionalized fumarate/conjugated diene copolymer latex, and demulsifying and drying by a flocculating agent to obtain raw rubber.
In the technical scheme, the fumarate accounts for 1-95 wt%, preferably 5-90 wt%, more preferably 10-80 wt% of the total monomers; the conjugated diene accounts for 1 to 98wt%, preferably 5 to 89wt%, more preferably 10 to 80wt% of the total monomer; the third monomer accounts for 0.1 to 30wt%, preferably 0.5 to 15wt%, and more preferably 1 to 10wt% of the total monomer.
In the above technical scheme, based on 100 parts by weight of the total mass of the fumarate and the conjugated diene,
100-400 parts of water, preferably 150-300 parts;
the emulsifier is 0.5-15 parts, preferably 1-10 parts;
the activator is 0.01 to 0.3 part, preferably 0.02 to 0.2 part;
the initiator is 0.01-5 parts, preferably 0.02-2 parts.
In the above technical solution, the emulsifier may be an emulsifier commonly used in the emulsion polymerization field, preferably at least one of potassium oleate, potassium oleate disproportionated abietic acid, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium fatty acid, and ethoxylated alkyl phenol ammonium sulfate; and different types of emulsifying agents and compound emulsifying agents are selected according to the third monomer.
In the above technical scheme, the activating agent may be an activating agent commonly used in the field of emulsion polymerization, preferably at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, ferric sodium ethylenediamine tetraacetate, tetrasodium ethylenediamine tetraacetate, and sodium bisulphite; sodium formaldehyde sulfoxylate, ferrous sulfate, or ethylene diamine tetraacetic acid tetrasodium salt are further preferred.
In the above technical scheme, the initiator may be an initiator commonly used in the emulsion polymerization field, preferably one or more of p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide, dibenzoyl peroxide, ammonium persulfate and potassium persulfate.
In the above technical scheme, the flocculant adopted in the demulsification and 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, dicyandiamide formaldehyde condensate, epoxy amine compound and dilute sulfuric acid.
In the technical scheme, the pre-emulsification time is 1-5 h, preferably 1-2 h.
In the technical scheme, electrolyte can be added, and the electrolyte can be 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. The electrolyte is 0.1 to 3 parts, preferably 0.1 to 1.5 parts, based on 100 parts by mass of the total of the fumarate and the conjugated diene.
It is a further object of the present application to provide a biobased elastomer comprising said functionalized fumarate/conjugated diene copolymer.
Preferably, the bio-based elastomer comprises a rubber matrix and a mating filler.
Every 100 weight parts of rubber matrix is correspondingly matched with 30 to 120 parts of filler; wherein, the rubber matrix can be singly blended by using one or several functionalized fumarate/conjugated diene copolymers or can be blended by using 5 to 40 parts of conjugated diene rubber (the total weight of the functionalized fumarate/conjugated diene copolymer and the conjugated diene rubber is 100 parts), and the conjugated diene rubber is at least one of natural rubber, epoxy natural rubber, butadiene rubber, epoxy butadiene rubber and styrene butadiene rubber; the filler is white carbon black and/or carbon black.
The bio-based elastomer can contain various auxiliary agents commonly used in the field, such as zinc oxide, stearic acid, a coupling agent, an accelerator, an anti-aging agent, a vulcanizing agent and the like, and the dosage of the bio-based elastomer is conventional or is adjusted according to the requirements of actual situations.
According to a preferred embodiment of the application, the bio-based elastomer comprises the following components:
based on 100 parts by weight of the rubber matrix, the following components in parts by weight:
the white carbon black and/or carbon black comprises one or more of white carbon black VN3, white carbon black 1165, white carbon black A200, white carbon black 383, carbon black N110, carbon black N220, carbon black N234, carbon black N330 and carbon black N550.
The anti-aging agent can be selected from N-phenyl-2-naphthylamine (D-proof), N-isopropyl-N '-phenyl p-phenylenediamine (4010 NA-proof), N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine (4020-proof) and 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD-proof) but is not limited to the above types.
The accelerator can be selected from diphenylguanidine (D promoter), 2-mercaptobenzothiazole (M promoter), N-cyclohexyl 2-benzothiazole sulfenamide (CZ promoter) and N-tertiary butyl-2-benzothiazole sulfenamide (NS promoter) but is not limited to the above.
The vulcanizing agent comprises sulfur, peroxide and other substances, but is not limited to the above substances.
The coupling agent is preferably a silane coupling agent.
The side chain of the functionalized fumarate/conjugated diene copolymer type bio-based elastomer contains a large number of polar ester groups, so that physical bonding can be formed between the functionalized fumarate/conjugated diene copolymer type bio-based elastomer and white carbon black, and the sliding and disordered movement of molecular chains are reduced; meanwhile, functional third monomers such as epoxy groups introduced into the chain can form chemical bonding with the white carbon black, so that the interface effect of the white carbon black and the filler can be enhanced, the filler dispersion is further improved, and the rolling resistance of the tread rubber can be greatly reduced under the combined action of physical and chemical bonding in the molecular chain. Even without silane coupling agent, even uniform dispersion of the filler can be achieved at a proper amount, thereby reducing VOC emissions.
The preparation method of the bio-based elastomer comprises the steps of mixing and vulcanizing components comprising the rubber matrix and the matched filler.
The specific preparation steps of the bio-based elastomer are preferably as follows:
(1) and (3) mixing: adding the functionalized fumarate/conjugated diene copolymer into an internal mixer, and banburying for 1-2 min; adding white carbon black and/or carbon black, zinc oxide, stearic acid, an anti-aging agent and an optional coupling agent, controlling the temperature within the range of 120-150 ℃, banburying for 3-5 min, and discharging rubber to obtain a section of mixed rubber material;
(2) two-stage mixing: putting the first section of rubber compound prepared in the step (1) into an internal mixer or an open mill, adding an accelerator and a vulcanizing agent, controlling the temperature below 100 ℃, mixing for 3-5 min, and then discharging rubber sheets;
(3) and (3) vulcanization process: and (3) standing the rubber compound for 16-24 h, and then vulcanizing and forming at 150-180 ℃ to obtain a vulcanized rubber product.
The fourth object of the application is to provide the application of the bio-based elastomer in tread rubber, and the bio-based elastomer green tire tread rubber with low rolling resistance can be provided.
Compared with the prior art, the main chain of the fumaric acid based on bulk bio-based chemicals is constructed into the elastomer with a carbon-carbon structure through emulsion copolymerization, and the elastomer contains functional monomers, so that the diversity of adjustable monomers and the different effects of the functional monomers are highlighted, and further, the structure and the performance are modified more comprehensively. In the aspect of the composite material, the white carbon black can be uniformly dispersed in the rubber matrix due to the existence of the third monomer and the side chain ester group, so that the composite material has good dynamic performance and heat generation. More importantly, the presence of the third monomer can reduce or even eliminate the use of a coupling agent, greatly simplify the process, reduce VOC emission and be a biological-based green tire material with very good application prospect.
Drawings
FIG. 1 is an infrared spectrum of raw rubber of diethyl fumarate/butadiene/glycidyl methacrylate copolymer of example 1.
FIG. 2 is a nuclear magnetic spectrum of raw rubber of diethyl fumarate/butadiene/glycidyl methacrylate copolymer of example 1.
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.
The raw materials used in the examples are all commercially available.
Example 1
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 240g of diethyl fumarate, 18g of glycidyl methacrylate and replacing the mixture with nitrogen, 360g of butadiene are added into a 3L reaction kettle, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added to initiate polymerization of the menthane, reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, 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 diethyl fumarate/butadiene/glycidyl methacrylate copolymer rubber. The number average molecular weight Mn was 20.5 ten thousand and the molecular weight distribution was 2.75.
Adding 100.0g of raw rubber of the diethyl fumarate/butadiene/glycidyl methacrylate copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a first section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 2
Raw rubber of diethyl fumarate/butadiene/glycidyl methacrylate copolymer was prepared in the same manner as in example 1.
Adding 100.0g of raw rubber of the diethyl fumarate/butadiene/glycidyl methacrylate copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 6g of si69, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 3
25g of sodium dodecyl benzene sulfonate, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 240g of diethyl fumarate, 18g of methacrylic acid and replacing the mixture with nitrogen atmosphere are added into a 3L reaction kettle, 360g of butadiene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of p-menthane hydroperoxide is added for initiating polymerization, the reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, butadiene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and the copolymer latex is obtained after the mixture is dried to constant weight by a vacuum oven. The number average molecular weight Mn was 18.4 ten thousand and the molecular weight distribution was 3.47.
Adding 100.0g of raw rubber of the diethyl fumarate/butadiene/methacrylic acid copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 4
Raw rubber of diethyl fumarate/butadiene/methacrylic acid copolymer was prepared in the same manner as in example 3.
Adding 100.0g of raw rubber of the diethyl fumarate/butadiene/methacrylic acid copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 6g of si69, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 5
25g of sodium dodecyl benzene sulfonate, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of sodium formaldehyde sulfoxylate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 240g of diethyl fumarate, 18g of glycidyl methacrylate and replacing nitrogen atmosphere are added into a 3L reaction kettle, 360g of isoprene is added, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of p-menthane hydroperoxide is added for initiating polymerization, reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, isoprene is removed under reduced pressure, demulsification is carried out by 500g of ethanol, and diethyl fumarate/isoprene/glycidyl methacrylate copolymer raw rubber is obtained through drying to constant weight by a vacuum oven. The number average molecular weight Mn was 15.6 ten thousand and the molecular weight distribution was 2.23.
Adding 100.0g of raw rubber of the diethyl fumarate/isoprene/glycidyl methacrylate copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a first section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 6
Raw rubber of diethyl fumarate/isoprene/glycidyl methacrylate copolymer was prepared in the same manner as in example 5.
Adding 100.0g of raw rubber of the diethyl fumarate/isoprene/glycidyl methacrylate copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 6g of si69, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 7
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 60g of diethyl fumarate, 18g of glycidyl methacrylate and replacing the mixture with nitrogen, adding 540g 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, and drying to constant weight through a vacuum oven to obtain diethyl fumarate/butadiene/glycidyl methacrylate copolymer rubber. The number average molecular weight Mn was 30.8 ten thousand and the molecular weight distribution was 3.40.
Adding 100.0g of raw rubber of the diethyl fumarate/butadiene/glycidyl methacrylate copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a first section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 8
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 540g of diethyl fumarate, 18g of glycidyl methacrylate and replacing the mixture with nitrogen, 60g of butadiene are added into a 3L reaction kettle, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added for initiating polymerization of the menthane, reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, 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 diethyl fumarate/butadiene/glycidyl methacrylate copolymer rubber. The number average molecular weight Mn was 16.8 ten thousand and the molecular weight distribution was 3.55.
Adding 100.0g of raw rubber of the diethyl fumarate/butadiene/glycidyl methacrylate copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a first section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 9
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 240g of dipropyl fumarate, 18g of glycidyl methacrylate and replacing the mixture with nitrogen, 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 butadiene, demulsifying with 500g of ethanol, and drying to constant weight through a vacuum oven to obtain the dipropyl fumarate/butadiene/glycidyl methacrylate copolymer rubber. The number average molecular weight Mn was 23.4 ten thousand and the molecular weight distribution was 2.88.
Adding 100.0g of the raw rubber of the dipropyl fumarate/butadiene/glycidyl methacrylate copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a first-stage rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 10
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 240g of dibutyl fumarate, 18g of glycidyl methacrylate and replacing the mixture with nitrogen, 360g of butadiene are added into a 3L reaction kettle, pre-emulsification is carried out for 1h at 25 ℃, 0.6g of hydrogen peroxide is added to initiate polymerization of the menthane, reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, 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 dibutyl fumarate/butadiene/glycidyl methacrylate copolymer rubber. The number average molecular weight Mn was 28.4 ten thousand and the molecular weight distribution was 2.82.
Adding 100.0g of the dibutyl fumarate/butadiene/glycidyl methacrylate copolymer raw rubber into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a first section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 11
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 240g of dipentyl fumarate, 18g of glycidyl methacrylate and replacing the mixture with nitrogen, 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 butadiene, demulsifying with 500g of ethanol, and drying to constant weight through a vacuum oven to obtain the dipentyl fumarate/butadiene/glycidyl methacrylate copolymer rubber. The number average molecular weight Mn was 26.1 ten thousand and the molecular weight distribution was 3.85.
100.0g of the raw rubber of the dipentyl fumarate/butadiene/glycidyl methacrylate copolymer is added into an internal mixer to be mixed for 1-2 min, 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like are added, the temperature is controlled at 120 ℃, and after mixing for 5min, rubber is produced, and a section of mixed rubber is obtained. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Example 12
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride, 240g of dihexyl fumarate, 18g of glycidyl methacrylate and replacing the mixture with nitrogen, 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 butadiene, demulsifying with 500g of ethanol, and drying to constant weight through a vacuum oven to obtain the dihexyl fumarate/butadiene/glycidyl methacrylate copolymer rubber. The number average molecular weight Mn was 22.3 ten thousand and the molecular weight distribution was 3.63.
100.0g of the raw rubber of the dihexyl fumarate/butadiene/glycidyl methacrylate copolymer is added into an internal mixer to be mixed for 1-2 min, 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like are added, the temperature is controlled at 120 ℃, and after mixing for 5min, rubber is produced, and a section of mixed rubber is obtained. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Comparative example 1
30g of disproportionated potassium abietate, 10g of sodium fatty acid, 900g of deionized water, 0.12g of ferrous sulfate, 0.3g of formaldehyde sodium bisulfate, 0.54g of ethylene diamine tetraacetic acid tetrasodium salt, 6g of potassium chloride and 240g of diethyl fumarate are added into a 3L reaction kettle and replaced by nitrogen atmosphere, 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 reaction is carried out for 8h at 10 ℃ to obtain copolymer latex, the butadiene is removed under reduced pressure, 500g of ethanol is used for demulsification, and the copolymer latex is dried to constant weight through a vacuum oven to obtain diethyl fumarate/butadiene copolymer rubber. The number average molecular weight Mn was 24.3 ten thousand and the molecular weight distribution was 3.49.
Adding 100.0g of raw rubber of the diethyl fumarate/butadiene copolymer into an internal mixer for banburying for 1-2 min, adding 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like, and banburying for 5min at 120 ℃ to obtain a section of rubber compound. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Comparative example 2
100.0g of ESBR1502 raw rubber is added into an internal mixer for banburying for 1-2 min, 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like are added, the temperature is controlled at 120 ℃, and the rubber is produced after banburying for 5min, so that a section of rubber compound is obtained. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
Comparative example 3
100.0g of SSB 2466 raw rubber is added into an internal mixer for banburying for 1-2 min, 60g of white carbon black, 5g of zinc oxide, 2g of stearic acid, 2g of 4020 and the like are added, the temperature is controlled at 120 ℃, and the rubber is produced after banburying for 5min, so that a section of rubber compound is obtained. Putting the first section of rubber compound into an internal mixer, adding 1.5g of CZ-promoting, 1.4g of D-promoting and 1.5g of sulfur, controlling the temperature below 90 ℃, mixing for 5min, and discharging tablets. After standing for 20 hours, the vulcanized rubber is obtained by vulcanization molding at 150 ℃.
The test was performed according to the following criteria: tensile strength (GB/T528-2009), elongation at break (GB/T528-2009);
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 ℃.
The abrasion of the Aclozenges GB/T1689-2014 determination of abrasion resistance of vulcanized rubber.
Table 1 results of performance testing of comparative examples samples
From the data in table 1, it can be seen that: the functionalized fumarate/conjugated diene copolymer type bio-based elastomer prepared by the application has excellent mechanical properties and dynamic mechanical properties, can be basically in the same level with the commercial solution polymerized styrene-butadiene rubber 2466 even if a coupling agent is not introduced, and can further improve the performance after the coupling agent is introduced. The functionalized fumarate/conjugated diene copolymer type bio-based elastomer meets engineering application requirements and has the potential for being used for a green tire tread. Meanwhile, the length of the side chain and the introduced amount of the third monomer can be regulated to further regulate dynamic performance, which is not listed one by one.

Claims (10)

1. A functionalized fumarate/conjugated diene copolymer comprising a fumarate structural unit, a conjugated diene monomer structural unit, and a third monomer structural unit.
2. The functionalized fumarate/conjugated diene copolymer according to claim 1, characterized in that:
the content of the fumarate structural units is 1 to 95wt%, preferably 5 to 90wt%, based on the total mass of the structural units; the content of the conjugated diene monomer structural unit is 1 to 98wt%, preferably 5 to 89wt%; the content of the third monomer structural unit is 0.1 to 30wt%, preferably 0.5 to 15wt%;
the number average molecular weight of the copolymer is 10 to 80 ten thousand, preferably 15 to 60 ten thousand; the molecular weight distribution is 1.5 to 5.0, preferably 2.0 to 3.5.
3. The functionalized fumarate/conjugated diene copolymer according to claim 1, characterized in that:
the fumarate structural unit is derived from a fumarate having a structure as shown in formula (I),
wherein R is 1 、R 2 Each independently is a hydrogen atom or C 1-20 And R is an alkyl group of 1 、R 2 Not both hydrogen, preferably R 1 Each independently is a hydrogen atom or C 1-10 Alkyl of (a);
the conjugated diene monomer structural unit is derived from conjugated diene, and the conjugated diene has a general formula of C n H 2n-2 Wherein n is greater than or equal to 4, and n is preferably 4 or 5;
the third monomer structural unit is derived from a third monomer, wherein the third monomer is selected from at least one of an epoxy group-containing olefin monomer, a carboxyl group-containing olefin monomer, and a hydroxyl group-containing olefin monomer.
4. The functionalized fumarate/conjugated diene copolymer of claim 3, wherein:
the fumaric acid ester is at least one selected from 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;
the conjugated diene is at least one selected from butadiene, isoprene, myrcene, ocimene, farnesene and dienes of the same kind;
the epoxy group-containing olefin monomer is at least one selected from glycidyl methacrylate, glycidyl acrylate, diglycidyl tricarboxylic acid ester, triglycidyltricarboxylic acid ester, propenyl glycidyl ether and glycidyl methacrylate; the carboxyl-containing olefin monomer is at least one selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate and itaconic anhydride; the hydroxyl-containing olefin monomer is at least one selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
5. The process for preparing a functionalized fumarate/conjugated diene copolymer according to any one of claims 1 to 4, comprising the following steps:
mixing fumaric acid ester, a third monomer, an emulsifier, an activator and water, adding conjugated diene in an inert atmosphere, pre-emulsifying, adding an initiator for polymerization reaction, and demulsifying and drying.
6. The method of manufacturing according to claim 5, wherein:
the polymerization temperature is 0-80 ℃, preferably 5-75 ℃; the polymerization time is 3 to 48 hours, preferably 4 to 24 hours;
the mass of the fumarate accounts for 1-95 wt% of the total monomers, and is preferably 5-90 wt%; the mass of the conjugated diene accounts for 1-98 wt% of the total monomers, preferably 5-89 wt%; the third monomer accounts for 0.1-30wt%, preferably 0.5-15wt% of the total monomer.
7. The method of manufacturing according to claim 5, wherein:
the emulsifier is at least one selected from potassium oleate, potassium oleate disproportionated abietate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium fatty acid and ethoxylated alkyl phenol ammonium sulfate; 0.5 to 15 parts of the emulsifier based on 100 parts of the total mass of the fumarate and the conjugated diene;
the activator is at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, ferric sodium ethylenediamine tetraacetate, tetrasodium ethylenediamine tetraacetate and sodium bisulphite; 0.01 to 0.3 part of the activator based on 100 parts by weight of the total mass of the fumarate and the conjugated diene;
the initiator is at least one selected from the group consisting of p-menthane hydroperoxide, dicumyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide, dibenzoyl peroxide, ammonium persulfate and potassium persulfate; the initiator is 0.01 to 5 parts based on 100 parts by weight of the total mass of the fumarate and the conjugated diene.
8. A biobased elastomer comprising the functionalized fumarate/conjugated diene copolymer of any one of claims 1-4.
9. The biobased elastomer of claim 8, comprising a rubber matrix and a mating filler, wherein:
every 100 weight parts of rubber matrix is correspondingly matched with 30 to 120 parts of filler; wherein, the rubber matrix can be singly used with one functionalized fumarate/conjugated diene copolymer or a mixture of several kinds, or 5 to 40 parts of conjugated diene rubber is used together, and the conjugated diene rubber is at least one selected from natural rubber, epoxy natural rubber, butadiene rubber, epoxy butadiene rubber and styrene butadiene rubber; the filler is white carbon black and/or carbon black.
10. Use of the biobased elastomer of claim 8 or 9 in tread band.
CN202210573358.8A 2022-05-25 2022-05-25 Functionalized fumarate/conjugated diene copolymer, preparation method thereof and bio-based elastomer Pending CN117164760A (en)

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