CN117430749A - Itaconate/myrcene/furfuryl methacrylate copolymer, preparation method thereof and heat reversible rubber - Google Patents

Itaconate/myrcene/furfuryl methacrylate copolymer, preparation method thereof and heat reversible rubber Download PDF

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Publication number
CN117430749A
CN117430749A CN202210829308.1A CN202210829308A CN117430749A CN 117430749 A CN117430749 A CN 117430749A CN 202210829308 A CN202210829308 A CN 202210829308A CN 117430749 A CN117430749 A CN 117430749A
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China
Prior art keywords
itaconate
myrcene
furfuryl methacrylate
formula
methacrylate copolymer
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王润国
于杰
吉海军
赵帅男
王锐
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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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/30Introducing nitrogen atoms or nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/12Esters of phenols or saturated alcohols
    • C08F222/14Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates

Abstract

The invention discloses an itaconate/myrcene/furfuryl methacrylate copolymer, a preparation method thereof and heat reversible rubber. The itaconate/myrcene/furfuryl methacrylate copolymer contains structural units shown in the formula (I), the formula (II) and the formula (III):is prepared by high-temperature emulsion polymerization of components including itaconic acid ester, myrcene and furfuryl methacrylate. The heat reversible rubber of the invention has both the performance and thermoplastic processability of vulcanized rubber, is convenient for reprocessing and utilizing rubber leftover materials and waste products, and is preparedThe green rubber product provides an effective idea.

Description

Itaconate/myrcene/furfuryl methacrylate copolymer, preparation method thereof and heat reversible rubber
Technical Field
The invention relates to the technical field of chemical synthetic rubber, in particular to an itaconate/myrcene/furfuryl methacrylate copolymer, a preparation method thereof and a heat reversible rubber.
Background
Rubber is one of important basic industries and plays a role in national economy. Conventional rubbers can be classified into natural rubber and synthetic rubber. However, at present, natural rubber resources in China are limited, and the natural rubber resources are greatly dependent on import; most of the synthetic rubber is prepared from petrochemical resources, and the petrochemical resources face the problems of environmental pollution, non-renewable property and the like. Therefore, it is an important development direction in the rubber field to find a new rubber which can satisfy the excellent properties of the conventional rubber and solve the problems faced by the conventional rubber. The task group of Zhang Liqun university of Beijing and chemical industry proposed Bio-based engineering elastomers (Bio-based Engineering Elastomer), itaconate rubber was the next representative rubber in this concept.
It is known that green rubber is very low in strength and has certain physical and mechanical properties only after vulcanization by a crosslinking agent such as sulfur. However, the vulcanized rubber formed after chemical crosslinking is irreversible, so that the vulcanized rubber cannot be subjected to secondary processing and molding, a large amount of leftover materials and waste products are difficult to recycle through a thermoplastic processing method and are wasted, and a crosslinking technology capable of maintaining the structure and physical and mechanical properties of the vulcanized rubber and performing thermoplastic flow processing is sought, so that the rubber has both the vulcanized rubber performance and the repeatability, and the problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an itaconate/myrcene/furfuryl methacrylate copolymer, a preparation method thereof and a heat reversible rubber. The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is obtained by performing high-temperature emulsion polymerization on components comprising itaconic acid ester, myrcene and furfuryl methacrylate. The copolymer is subjected to Diels-Alder reaction with bismaleimide to obtain the novel thermal-reversible crosslinked full-bio-based synthetic rubber, which can be processed for multiple times and accords with the concept of green sustainable development. The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is dynamically crosslinked to prepare the itaconic acid ester/myrcene/furfuryl methacrylate copolymer type heat reversible rubber. The dynamic crosslinking is realized through Diles-Alder reaction, and the thermal reversible rubber is prepared through Diels-Alder reaction of furan groups in the itaconate rubber and bismaleimide. The raw materials used in the invention are all sourced from biological fermentation and do not depend on petrochemical resources. The thermal reversible crosslinking agent is used for replacing the traditional crosslinking agent to carry out chemical crosslinking on rubber, so that the thermoplastic processability of the crosslinked rubber is endowed while the crosslinked rubber has certain physical and mechanical properties, the recycling of waste rubber products is solved, and the resource utilization rate is improved.
One of the objects of the present invention is to provide an itaconate/myrcene/furfuryl methacrylate copolymer comprising structural units represented by the formula (I), the formula (II) and the formula (III):
wherein R is 1 And R is 2 Identical or different, each independently selected from H or C 1 ~C 10 Alkyl, preferably from C 4 ~C 10 Alkyl, and R 1 And R is 2 Not simultaneously H;
the molar content of the structural unit represented by the formula (I) is 50 to 80mol%, preferably 50 to 60mol%, the molar content of the structural unit represented by the formula (II) is 10 to 40mol%, preferably 30 to 40mol% (the molar content is the sum of the molar contents of the cis-myrcene structural unit and the trans-myrcene structural unit), and the molar content of the structural unit represented by the formula (III) is 1 to 15mol%, preferably 3 to 10mol%, based on 100mol% of the total molar amount of the structural units represented by the formula (I), the formula (II) and the formula (III).
The structural unit shown in the formula (I) is derived from an itaconate monomer, the structural unit shown in the formula (II) is derived from myrcene, and the structural unit shown in the formula (III) is derived from furfuryl methacrylate.
With the increase of the methylene number of the itaconate side chain, the movement capability of the side chain is increased, the flexibility of the molecular chain is increased, the Tg is reduced, and the prepared copolymer has relatively better physical properties, so R 1 And R is 2 Respectively and independently preferably from C 4 ~C 10 An alkyl group.
In a preferred embodiment of the present invention,
the number average molecular weight of the itaconate/myrcene/furfuryl methacrylate copolymer is 1-20 ten thousand, preferably 1-15 ten thousand; the molecular weight distribution coefficient is 1.5 to 4.5, preferably 1.7 to 2.5.
It is a second object of the present invention to provide a process for preparing the itaconate/myrcene/furfuryl methacrylate copolymer, which comprises the step of subjecting components comprising an itaconate monomer, myrcene and furfuryl methacrylate to high-temperature emulsion polymerization.
In a preferred embodiment of the present invention,
the structural formula of the itaconate monomer is as follows:
wherein R is 1 And R is 2 Identical or different, each independently selected from H or C 1 ~C 10 Alkyl, and R 1 And R is 2 Not simultaneously H;
the itaconate monomer is preferably at least one of monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monopropyl itaconate, dipropyl itaconate, monobutyl itaconate, dibutyl itaconate, monopentyl itaconate, dipentyl itaconate, monohexyl itaconate, dihexyl itaconate Shan Gengzhi, diheptyl itaconate, monooctyl itaconate, dioctyl itaconate, monononyl itaconate, dinonyl itaconate, monodecyl itaconate, didecyl itaconate, and more preferably dibutyl itaconate. The itaconate with short side chain in the itaconate monomer can be obtained by purchase, and the itaconate with long side chain can be obtained by conventional esterification reaction in the prior art.
In a preferred embodiment of the present invention,
the weight of the itaconic acid ester monomer is 50-80%, preferably 50-70%, more preferably 50-60% based on 100% of the total weight of the itaconic acid ester monomer and myrcene; and/or the number of the groups of groups,
the mass ratio of the myrcene to the furfuryl methacrylate is (1-40): 1, preferably (2-15): 1.
In a preferred embodiment of the present invention,
mixing and pre-emulsifying an itaconate monomer, myrcene, furfuryl methacrylate, a molecular weight regulator, deionized water, an emulsifier and an electrolyte, adding an initiator, and polymerizing at 65-75 ℃ for 6-10 h to obtain the itaconate/myrcene/furfuryl methacrylate copolymer.
In a preferred embodiment of the present invention,
the initiator is selected from at least one of azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, ammonium persulfate and potassium persulfate as usual in the art: and/or the number of the groups of groups,
the emulsifier is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, disproportionated potassium abietate, sodium fatty acid, potassium oleate, sodium oleate and alkylphenol polyoxyethylene ether which are common in the art: and/or the number of the groups of groups,
the dosage of the emulsifier is 1-10wt%, preferably 2-8wt% of the total weight of the itaconate monomer, myrcene and furfuryl methacrylate; and/or the number of the groups of groups,
the initiator is used in an amount of 0.03 to 5wt%, preferably 0.03 to 3wt%, based on the total weight of the itaconate monomer, myrcene and furfuryl methacrylate.
The molecular weight regulator is at least one of dodecyl mercaptan, 3-mercaptobutyrate, mercaptoethanol, thioglycollic acid and isooctyl 3-mercaptopropionate, which are common in the field, and the dosage of the molecular weight regulator is adjusted according to the actual situation.
The electrolyte is selected from at least one of potassium chloride, phosphoric acid, potassium hydroxide, EDTA tetrasodium salt, etc., which is common in the art, or is adjusted according to the actual situation.
The preparation method of the itaconate/myrcene/furfuryl methacrylate copolymer preferably comprises the following steps:
mixing an itaconate monomer, myrcene, furfuryl methacrylate, a molecular weight regulator, deionized water, an emulsifier and an electrolyte, pre-emulsifying for 1h at 20-30 ℃, adding an initiator, and polymerizing at 65-75 ℃ for 6-10 h to obtain the itaconate/myrcene/furfuryl methacrylate copolymer, preferably polymerizing at 68-72 ℃ for 7-9 h to obtain the itaconate/myrcene/furfuryl methacrylate copolymer.
In the preparation method, the polymerization further comprises a demulsification and drying step after the polymerization is finished, wherein the demulsification and drying step can be selected from the common methods in the field.
Specifically, the preparation method may be: mixing itaconic acid ester monomer, myrcene, furfuryl methacrylate, a molecular weight regulator, deionized water, an emulsifier and an electrolyte, pre-emulsifying for 1h at 20-30 ℃, adding an initiator, and polymerizing for 6-10 h at 65-75 ℃ to obtain the itaconic acid ester/myrcene/furfuryl methacrylate copolymer latex, and demulsifying and drying to obtain crude rubber (namely itaconic acid ester/myrcene/furfuryl methacrylate copolymer).
Preferably, an activator and an oxygen scavenger may also be added to the process;
the activator is selected from at least one of ferrous sulfate, EDTA-FeNa, sodium silicate, etc. which are common in the field, and the dosage of the activator is conventional or is adjusted according to the actual condition.
The deoxidizer is selected from at least one of common deoxidizers in the field, preferably sodium hydrosulfite, sulfite, dimethyl ketoxime and the like, and the dosage of the deoxidizer is conventional or is adjusted according to the requirements of actual situations.
It is a further object of the present invention to provide a thermoreversible rubber comprising the itaconate/myrcene/furfuryl methacrylate copolymer of one of the objects of the present invention or the itaconate/myrcene/furfuryl methacrylate copolymer prepared by the method of the second object of the present invention; the thermoreversible rubber further comprises bismaleimide; the bismaleimide is preferably at least one of diphenylmethane bismaleimide, bismaleimide hexane, bismaleimide butane, bismaleimide ethane and bismaleimide triethylene glycol; and/or the molar amount of the bismaleimide is 10-100%, preferably 20-80%, more preferably 50-75% of the molar amount of the furan group in the itaconate/myrcene/furfuryl methacrylate copolymer. The molar amount of furan groups in the itaconate/myrcene/furfuryl methacrylate copolymer is obtained by nuclear magnetic integration.
The fourth object of the present invention is to provide a method for producing a thermoreversible rubber according to the third object of the present invention, comprising a step of kneading and hot-press-molding components including an itaconate/myrcene/furfuryl methacrylate copolymer and bismaleimide; the kneading temperature is preferably 100 to 130 ℃, more preferably 110 to 120 ℃; and/or the mixing time is 5-30 min, more preferably 10-20 min; and/or, the hot press molding temperature is preferably 140 to 190 ℃, more preferably 150 to 170 ℃.
Specifically, the preparation method comprises the steps of blending itaconic acid ester/myrcene/furfuryl methacrylate copolymer and a cross-linking agent bismaleimide through an internal mixer, controlling the temperature to be 100-130 ℃, preferably 110-120 ℃, then molding the mixture into sheets on a flat vulcanizing machine at 140-190 ℃, and after the molded sheets are processed through an open mill, molding the sheets on the flat vulcanizing machine at 140-190 ℃ again.
In the preparation process, the mixing, open milling and tabletting processes of the raw material components can adopt the rubber processing process which is common in the prior art. The equipment used is also the equipment for rubber processing in the prior art, such as mixers, kneaders, internal mixers, open mills, vulcanizing machines and the like.
Diels-Alder cycloaddition reaction of diene compound containing conjugated double bond and dienophile compound containing double bond has thermal reversibility, and the reaction can be used for thermal reversibility crosslinking of polymer, and the principle is as follows:
the itaconic acid ester/myrcene/furfuryl methacrylate copolymer has furan groups in the molecule, can be subjected to Diels-Alder reaction with the cross-linking agent bismaleimide to prepare the thermoreversible cross-linked rubber, and has simple and convenient processing process and avoids complicated processing technology, so the thermoreversible cross-linked rubber based on the itaconic acid ester/myrcene/furfuryl methacrylate copolymer is a very promising green material.
The itaconate/myrcene/furfuryl methacrylate copolymer has higher molecular weight and simple preparation process.
The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is prepared by high-temperature emulsion polymerization, and the introduced itaconic acid ester, myrcene and furfuryl methacrylate belong to biological base monomers, so that the concept of sustainable development at present is met; secondly, the existence of furan groups on furfuryl methacrylate can enable the furfuryl methacrylate and bismaleimide to generate Diels-Alder reaction to form novel thermal reversible crosslinked synthetic rubber, thereby conforming to the present environmental protection, saving resources and realizing sustainable development concept.
Sustainable materials of biomass are receiving increasing attention due to resource shortages and deterioration of environmental conditions caused by excessive development of fossil resources. According to the method, ternary emulsion copolymerization is carried out on myrcene, itaconic acid ester and furfuryl methacrylate, so that the full-biobased rubber with furan groups is obtained, and compared with butadiene rubber, an idea is provided for realizing carbon peak and carbon neutralization, and the sustainable development idea is met. And then, the furan group is introduced to form a thermally reversible dynamic covalent bond with maleimide, so that the rubber can be repeatedly recycled and hot-pressed for use in comparison with the traditional sulfur-vulcanized rubber, and the rubber meets the ideas of environmental protection, energy conservation and environmental protection.
The invention synthesizes the novel thermal reversible cross-linked all-bio-based itaconic acid ester synthetic rubber through reasonable structural design. The rubber has the performance and thermoplastic processability of vulcanized rubber, is convenient for reprocessing and utilizing rubber scraps and waste products, and provides an effective thought for preparing green rubber products.
Drawings
FIG. 1 is a schematic illustration of dibutyl itaconate/myrcene/furfuryl methacrylate copolymers prepared in examples 1-4 of the present invention 1 H-NMR spectra, wherein curves 1-4 correspond to examples 1-4, respectively;
FIG. 2 is a schematic illustration of dibutyl itaconate/myrcene/furfuryl methacrylate copolymer prepared in examples 1-4 of the present invention 1 An enlarged plot of the H-NMR spectrum at 6.2-8.0 chemical shift, where curves 1-4 correspond to examples 1-4, respectively.
Detailed Description
The present invention will be described in detail with reference to the following specific embodiments and the accompanying drawings, and it is necessary to point out that the following embodiments are merely for further explanation of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adaptations of the invention based on the present disclosure will remain within the scope of the invention.
The monomers and auxiliaries used in the examples below are all commercially available.
Example 1
The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is prepared based on high-temperature emulsion polymerization, and concretely comprises the following components: 8g of an emulsifier (sodium dodecyl sulfonate, the using amount of the emulsifier is 4% of the total monomer using amount), 25g of electrolyte (potassium chloride aqueous solution, the mass concentration is 2%), 375g of deionized water, 0.1g of dodecyl mercaptan, 114g of dibutyl itaconate (DBI), 80g of Myrcene (MY) and 6g of Furfuryl Methacrylate (FMA) are added into a 1L three-neck flask, the mixture is plugged by a glass plug after nitrogen is introduced, pre-emulsified for 1h at 30 ℃, 0.48g of potassium persulfate is added, the temperature is raised to 70 ℃ for reaction for 8h, the copolymer latex is obtained, the emulsion breaking is carried out by ethanol, and the mixture is dried to constant weight by a blast oven, so that the itaconic acid ester/myrcene/furfuryl methacrylate copolymer is recorded as PDBIMFA-3. Calculated conversion was 85%, mn=14700 and molecular weight distribution coefficient was 1.89. The content of each structural unit in the resulting copolymer is shown in Table 1.
Example 2
The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is prepared based on high-temperature emulsion polymerization, and concretely comprises the following components: 8g of an emulsifier (sodium dodecyl sulfonate, the using amount of the emulsifier is 4% of the total monomer using amount), 25g of electrolyte (potassium chloride aqueous solution, the mass concentration is 2%), 375g of deionized water, 0.1g of dodecyl mercaptan, 110g of dibutyl itaconate (DBI), 80g of Myrcene (MY) and 10g of Furfuryl Methacrylate (FMA) are added into a 1L three-neck flask, the mixture is plugged by a glass plug after nitrogen is introduced, pre-emulsified for 1h at 30 ℃, 0.48g of potassium persulfate is added, the temperature is raised to 70 ℃ for 8h after reaction, the emulsion is broken by ethanol, and the mixture is dried to constant weight by a blast oven, so that the itaconic acid ester/myrcene/furfuryl methacrylate copolymer is obtained, and the PDBIMFA-5 is recorded. Calculated, the conversion was 91%, mn=83000, and the molecular weight distribution coefficient was 2.33. The content of each structural unit in the resulting copolymer is shown in Table 1.
Example 3
The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is prepared based on high-temperature emulsion polymerization, and concretely comprises the following components: 8g of an emulsifier (sodium dodecyl sulfonate, the using amount of the emulsifier is 4% of the total monomer using amount), 25g of electrolyte (potassium chloride aqueous solution, the mass concentration is 2%), 375g of deionized water, 0.1g of dodecyl mercaptan, 106g of dibutyl itaconate (DBI), 80g of Myrcene (MY) and 14g of Furfuryl Methacrylate (FMA) are added into a 1L three-neck flask, the mixture is plugged by a glass plug after nitrogen is introduced, pre-emulsified for 1h at 30 ℃, 0.48g of potassium persulfate is added, the temperature is raised to 70 ℃ for reaction for 8h, the copolymer latex is obtained, the emulsion breaking is carried out by ethanol, and the mixture is dried to constant weight by a blast oven, so that the itaconic acid ester/myrcene/furfuryl methacrylate copolymer is recorded as PDBIMFA-7. Calculated, the conversion was 88%, mn=61000, and the molecular weight distribution coefficient was 2.05. The content of each structural unit in the resulting copolymer is shown in Table 1.
Example 4
The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is prepared based on high-temperature emulsion polymerization, and concretely comprises the following components: 8g of an emulsifier (sodium dodecyl sulfonate, the using amount of the emulsifier is 4% of the total monomer using amount), 25g of electrolyte (potassium chloride aqueous solution, the mass concentration is 2%), 375g of deionized water, 0.1g of dodecyl mercaptan, 102g of dibutyl itaconate (DBI), 80g of Myrcene (MY) and 18g of Furfuryl Methacrylate (FMA) are added into a 1L three-neck flask, the mixture is plugged by a glass plug after nitrogen is introduced, pre-emulsified for 1h at 30 ℃, 0.48g of potassium persulfate is added, the temperature is raised to 70 ℃ for reaction for 8h, the copolymer latex is obtained, the emulsion breaking is carried out by ethanol, and the mixture is dried to constant weight by a blast oven, so that the itaconic acid ester/myrcene/furfuryl methacrylate copolymer is recorded as PDBIMFA-9. Calculated, the conversion was 87%, mn=90600, and the molecular weight distribution coefficient was 2.11. The content of each structural unit in the resulting copolymer is shown in Table 1.
Example 5
The itaconic acid ester/myrcene/furfuryl methacrylate copolymer is prepared based on high-temperature emulsion polymerization, and concretely comprises the following components: 8g of an emulsifier (sodium dodecyl sulfonate, the using amount of the emulsifier is 4% of the total monomer using amount), 25g of electrolyte (potassium chloride aqueous solution, the mass concentration is 2%), 375g of deionized water, 0.1g of dodecyl mercaptan, 122g of dibutyl itaconate (DBI), 60g of Myrcene (MY) and 18g of Furfuryl Methacrylate (FMA) are added into a 1L three-neck flask, the mixture is plugged by a glass plug after nitrogen is introduced, pre-emulsified for 1h at 30 ℃, 0.48g of potassium persulfate is added, the temperature is raised to 70 ℃ for 8h after reaction, the emulsion is broken by ethanol, and the mixture is dried to constant weight by a blast oven, so that the itaconic acid ester/myrcene/furfuryl methacrylate copolymer is obtained, namely PDBIMFA-9 (2). Calculated, the conversion was 83%, mn= 100500, and the molecular weight distribution coefficient was 2.25. The content of each structural unit in the resulting copolymer is shown in Table 1.
FIGS. 1 and 2 show dibutyl itaconate/myrcene/furfuryl methacrylate copolymers prepared in examples 1-4 of the present invention 1 H-NMR spectra were measured by AV-400 Nuclear magnetic resonance spectrometer from Bruker, where 6.34ppm, 6.38ppm and 7.40ppmThe small peak was derived from proton displacement of furan group, the peak at 5.06ppm was derived from myrcene, and the peak at 4.05ppm was derived from dibutyl itaconate, and this nuclear magnetic pattern demonstrates that examples 1-4 successfully synthesized itaconate/myrcene/furfuryl methacrylate copolymer.
Example 6
The preparation method of the thermoreversibly crosslinked full-bio-based itaconate rubber based on high-temperature emulsion polymerization specifically comprises the following steps:
40g of crude rubber (PDBIMFA-3) and 0.71g of diphenylmethane bismaleimide (calculated according to 25% of the molar amount of furan groups in 40g of PDBIMFA-3). The molar amount of furan groups in PDBIMFA-3 is obtained by nuclear magnetic integration.
And (3) placing the raw rubber in an internal mixer for plasticating for 3min, heating the internal mixer to 110 ℃, adding diphenylmethane bismaleimide for reacting for 10min, and taking out. And hot-press molding at 160 ℃ on a plate vulcanizing machine. After the mechanical properties are tested, the materials are sheared, processed by an open mill and taken out, and are subjected to hot press molding again at 160 ℃ on a flat vulcanizing machine, so that a smooth sheet can be formed, and the mechanical properties of each sample are tested to calculate the recovery rate. The recovery test results are shown in Table 2.
Example 7
The preparation method of the thermoreversibly crosslinked full-bio-based itaconate rubber based on high-temperature emulsion polymerization specifically comprises the following steps:
40g of crude rubber (PDBIMFA-3), 1.42g of diphenylmethane bismaleimide (converted to 50% of the molar amount of furan groups in 40g of PDBIMFA-3).
And (3) placing the raw rubber in an internal mixer for plasticating for 3min, heating the internal mixer to 110 ℃, adding diphenylmethane bismaleimide for reacting for 10min, and taking out. And hot-press molding at 160 ℃ on a plate vulcanizing machine. After the mechanical properties are tested, the materials are sheared, processed by an open mill and taken out, and are subjected to hot press molding again at 160 ℃ on a flat vulcanizing machine, so that a smooth sheet can be formed, and the mechanical properties of each sample are tested to calculate the recovery rate. The recovery test results are shown in Table 2.
Example 8
The preparation method of the thermoreversibly crosslinked full-bio-based itaconate rubber based on high-temperature emulsion polymerization specifically comprises the following steps:
40g of crude rubber (PDBIMFA-3) and 2.14g of diphenylmethane bismaleimide (calculated according to 75% of the molar amount of furan groups in 40g of PDBIMFA-3).
And (3) placing the raw rubber in an internal mixer for plasticating for 3min, heating the internal mixer to 110 ℃, adding diphenylmethane bismaleimide for reacting for 10min, and taking out. And hot-press molding at 160 ℃ on a plate vulcanizing machine. After the mechanical properties are tested, the materials are sheared, processed by an open mill and taken out, and are subjected to hot press molding again at 160 ℃ on a flat vulcanizing machine, so that a smooth sheet can be formed, and the mechanical properties of each sample are tested to calculate the recovery rate. The recovery test results are shown in Table 2.
Example 9
The preparation method of the thermoreversibly crosslinked full-bio-based itaconate rubber based on high-temperature emulsion polymerization specifically comprises the following steps:
40g of crude rubber (PDBIMFA-5) and 1.00g of diphenylmethane bismaleimide (calculated according to 25% of the molar amount of furan groups in 40g of PDBIMFA-5). The molar amount of furan groups in PDBIMFA-5 is obtained by nuclear magnetic integration.
And (3) placing the raw rubber in an internal mixer for plasticating for 3min, heating the internal mixer to 110 ℃, adding diphenylmethane bismaleimide for reacting for 10min, and taking out. And hot-press molding at 160 ℃ on a plate vulcanizing machine. After the mechanical properties are tested, the materials are sheared, processed by an open mill and taken out, and are subjected to hot press molding again at 160 ℃ on a flat vulcanizing machine, so that a smooth sheet can be formed, and the mechanical properties of each sample are tested to calculate the recovery rate. The recovery test results are shown in Table 2.
Example 10
The preparation method of the thermoreversibly crosslinked full-bio-based itaconate rubber based on high-temperature emulsion polymerization specifically comprises the following steps:
40g of crude rubber (PDBIMFA-5) and 2.00g of diphenylmethane bismaleimide (calculated according to 50% of the molar amount of furan groups in 40g of PDBIMFA-5).
And (3) placing the raw rubber in an internal mixer for plasticating for 3min, heating the internal mixer to 110 ℃, adding diphenylmethane bismaleimide for reacting for 10min, and taking out. And hot-press molding at 160 ℃ on a plate vulcanizing machine. After the mechanical properties are tested, the materials are sheared, processed by an open mill and taken out, and are subjected to hot press molding again at 160 ℃ on a flat vulcanizing machine, so that a smooth sheet can be formed, and the mechanical properties of each sample are tested to calculate the recovery rate. The recovery test results are shown in Table 2.
Example 11
The preparation method of the thermoreversibly crosslinked full-bio-based itaconate rubber based on high-temperature emulsion polymerization specifically comprises the following steps:
40g of crude rubber (PDBIMFA-5) and 3.00g of diphenylmethane bismaleimide (calculated according to 75% of the molar amount of furan groups in 40g of PDBIMFA-5).
And (3) placing the raw rubber in an internal mixer for plasticating for 3min, heating the internal mixer to 110 ℃, adding diphenylmethane bismaleimide for reacting for 10min, and taking out. And hot-press molding at 160 ℃ on a plate vulcanizing machine. After the mechanical properties are tested, the materials are sheared, processed by an open mill and taken out, and are subjected to hot press molding again at 160 ℃ on a flat vulcanizing machine, so that a smooth sheet can be formed, and the mechanical properties of each sample are tested to calculate the recovery rate. The recovery test results are shown in Table 2.
TABLE 1 copolymer compositions of examples 1-5
TABLE 2 Performance test results for samples of examples 6-11
Note that:
the tensile test reference standard is GB/T528-2009.
The tensile strength of the secondary hot press molding refers to the tensile strength obtained by carrying out hot press molding again after the first hot press molding and stretch breaking of the sample and carrying out a tensile experiment.
The heat reversible efficiency means the ratio of the tensile strength of the rubber after the secondary molding to the tensile strength of the rubber after the primary molding.
As can be seen from the data in the table, the secondary molding still has higher mechanical strength and higher heat reversible efficiency, and the tensile strength of the secondary hot press molding of some examples is higher than that of the primary molding because the crosslinking reaction is more sufficient and a part of DA bonds are not opened. The thermal reversible elastomer prepared by the method has excellent mechanical property and high thermal reversible efficiency, and the prepared elastomer can be repeatedly used for a plurality of times, and most importantly, the elastomer is completely derived from biomass and accords with the sustainable development concept.

Claims (10)

1. An itaconate/myrcene/furfuryl methacrylate copolymer comprising structural units represented by formula (I), formula (II) and formula (III):
wherein R is 1 And R is 2 Identical or different, each independently selected from H or C 1 ~C 10 Alkyl, and R 1 And R is 2 Not simultaneously H;
the molar content of the structural unit represented by the formula (I) is 50 to 80mol%, the molar content of the structural unit represented by the formula (II) is 10 to 40mol%, and the molar content of the structural unit represented by the formula (III) is 1 to 15mol%, based on 100mol% of the total molar amount of the structural units represented by the formula (I), the formula (II) and the formula (III).
2. The itaconate/myrcene/furfuryl methacrylate copolymer of claim 1 wherein:
the R is 1 And R is 2 Identical or different, each independently selected from C 4 ~C 10 Alkyl, and R 1 And R is 2 Not simultaneously H; and/or the number of the groups of groups,
the molar content of the structural unit represented by the formula (I) is 50 to 60mol%, the molar content of the structural unit represented by the formula (II) is 30 to 40mol%, and the molar content of the structural unit represented by the formula (III) is 3 to 10mol%, based on 100% of the total molar amount of the structural units represented by the formula (I), the formula (II) and the formula (III)).
3. The itaconate/myrcene/furfuryl methacrylate copolymer of claim 1 wherein:
the number average molecular weight of the itaconate/myrcene/furfuryl methacrylate copolymer is 1-20 ten thousand, preferably 1-15 ten thousand; the molecular weight distribution coefficient is 1.5 to 4.5, preferably 1.7 to 2.5.
4. A process for the preparation of the itaconate/myrcene/furfuryl methacrylate copolymer as claimed in any one of claims 1 to 3, comprising the step of subjecting components comprising itaconate monomer, myrcene and furfuryl methacrylate to high temperature emulsion polymerization.
5. The method of manufacturing according to claim 4, wherein:
the structural formula of the itaconate monomer is as follows:
wherein R is 1 And R is 2 Identical or different, each independently selected from H or C 1 ~C 10 Alkyl, and R 1 And R is 2 Not simultaneously H;
the itaconate monomer is preferably at least one of monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monopropyl itaconate, dipropyl itaconate, monobutyl itaconate, dibutyl itaconate, monopentyl itaconate, dipentyl itaconate, monohexyl itaconate, dihexyl itaconate Shan Gengzhi, diheptyl itaconate, monooctyl itaconate, dioctyl itaconate, monononyl itaconate, dinonyl itaconate, monodecyl itaconate, didecyl itaconate.
6. The method of manufacturing according to claim 4, wherein:
the weight of the itaconic acid ester monomer is 50-80%, preferably 50-70%, based on 100% of the total weight of the itaconic acid ester monomer and myrcene; and/or the number of the groups of groups,
the mass ratio of the myrcene to the furfuryl methacrylate is (1-40): 1, preferably (2-15): 1.
7. The method of manufacturing according to claim 4, characterized in that the method comprises:
mixing and pre-emulsifying an itaconate monomer, myrcene, furfuryl methacrylate, a molecular weight regulator, deionized water, an emulsifier and an electrolyte, adding an initiator, and polymerizing at 65-75 ℃ for 6-10 h to obtain the itaconate/myrcene/furfuryl methacrylate copolymer.
8. The method of manufacturing according to claim 7, wherein:
the initiator is at least one of azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, ammonium persulfate and potassium persulfate: and/or the number of the groups of groups,
the emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, disproportionated potassium abietate, sodium fatty acid, potassium oleate, sodium oleate and alkylphenol polyoxyethylene ether: and/or the number of the groups of groups,
the dosage of the emulsifier is 1-10wt%, preferably 2-8wt% of the total weight of the itaconate monomer, myrcene and furfuryl methacrylate; and/or the number of the groups of groups,
the initiator is used in an amount of 0.03 to 5wt%, preferably 0.03 to 3wt%, based on the total weight of the itaconate monomer, myrcene and furfuryl methacrylate.
9. A thermoreversible rubber comprising the itaconate/myrcene/furfuryl methacrylate copolymer of any one of claims 1-3 or the itaconate/myrcene/furfuryl methacrylate copolymer prepared by the method of any one of claims 4-8; the thermoreversible rubber further comprises bismaleimide; the bismaleimide is preferably at least one of diphenylmethane bismaleimide, bismaleimide hexane, bismaleimide butane, bismaleimide ethane and bismaleimide triethylene glycol; and/or the molar amount of the bismaleimide is 10-100% of the molar amount of the furan group in the itaconate/myrcene/furfuryl methacrylate copolymer.
10. A method for producing the thermoreversible rubber according to claim 9, comprising a step of kneading and hot-press molding components including itaconate/myrcene/furfuryl methacrylate copolymer and bismaleimide; the kneading temperature is preferably 100 to 130 ℃, more preferably 110 to 120 ℃; and/or the mixing time is 5-30 min, more preferably 10-20 min; and/or, the hot press molding temperature is preferably 140 to 190 ℃, more preferably 150 to 170 ℃.
CN202210829308.1A 2022-07-15 2022-07-15 Itaconate/myrcene/furfuryl methacrylate copolymer, preparation method thereof and heat reversible rubber Pending CN117430749A (en)

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