CN110818973A - Thermal reversible crosslinking modified elastomer material and preparation method thereof - Google Patents
Thermal reversible crosslinking modified elastomer material and preparation method thereof Download PDFInfo
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- CN110818973A CN110818973A CN201911215339.2A CN201911215339A CN110818973A CN 110818973 A CN110818973 A CN 110818973A CN 201911215339 A CN201911215339 A CN 201911215339A CN 110818973 A CN110818973 A CN 110818973A
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- 239000000806 elastomer Substances 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 62
- 230000002441 reversible effect Effects 0.000 title claims abstract description 46
- 238000004132 cross linking Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 23
- 238000012650 click reaction Methods 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- -1 mercapto carboxyl compound Chemical class 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 14
- 229920002857 polybutadiene Polymers 0.000 claims description 14
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000459 Nitrile rubber Polymers 0.000 claims description 12
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- 239000003960 organic solvent Substances 0.000 claims description 12
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000013536 elastomeric material Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 239000012952 cationic photoinitiator Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 4
- 150000003254 radicals Chemical group 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 claims description 4
- CFPHMAVQAJGVPV-UHFFFAOYSA-N 2-sulfanylbutanoic acid Chemical compound CCC(S)C(O)=O CFPHMAVQAJGVPV-UHFFFAOYSA-N 0.000 claims description 3
- JSGPBRQYMLFVJQ-UHFFFAOYSA-N 2-sulfanylhexanoic acid Chemical compound CCCCC(S)C(O)=O JSGPBRQYMLFVJQ-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical class [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 claims description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012955 diaryliodonium Substances 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012949 free radical photoinitiator Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000007634 remodeling Methods 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 3
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/20—Incorporating sulfur atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a thermal reversible crosslinking modified elastomer material and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, grafting carboxyl onto a molecular chain of an elastomer with double bonds through sulfydryl-alkene click reaction, and then carrying out esterification reaction on the modified elastomer after carboxyl grafting and a polyepoxy compound to obtain the thermally reversible crosslinking modified elastomer material. The prepared thermal reversible crosslinking modified elastomer material has better mechanical property and solvent resistance under the condition of room temperature, has long service life, and can be remolded and molded under the heating condition, thereby realizing the recycling of the elastomer material. In addition, the invention can regulate and control the elongation at break and the breaking strength of the prepared thermal reversible crosslinking modified elastomer material by regulating the ratio of the mole number of epoxy groups in the polyepoxy compound to the mole number of carboxyl groups in the modified elastomer after carboxyl grafting.
Description
Technical Field
The invention relates to the field of chemical material preparation, in particular to a thermally reversible crosslinking modified elastomer material and a preparation method thereof.
Background
Rubber has a wide range of practical applications, but since it is difficult to reuse after modification, the generated waste causes environmental pollution, and a huge amount of rubber products are consumed every year, recycling and reuse thereof have become an important research subject. Meanwhile, the styrene thermoplastic elastomer SBC (TPE-S) is called "third generation synthetic rubber" because it has properties of both plastic and rubber due to physical crosslinking of the PB phase. On one hand, the SBC (TPE-S) material has the characteristics of excellent tensile strength, large surface friction coefficient, good low-temperature performance, excellent electrical performance, good processing performance, no need of crosslinking during use and the like, and is a thermoplastic elastomer with the largest consumption at present; on the other hand, SBC (TPE-S) materials such as SBS (polystyrene-butadiene-styrene) and SIS (polystyrene-isoprene-styrene) have disadvantages of low mechanical strength and easy aging.
Disclosure of Invention
The invention aims to provide a preparation method of a thermally reversible crosslinking modified elastomer material, the prepared thermally reversible crosslinking modified elastomer material has better mechanical property and solvent resistance under the condition of room temperature, the service life is long, the thermally reversible crosslinking modified elastomer material has thermoplasticity and can be processed and used again, and the performance of the prepared thermally reversible crosslinking modified elastomer material can be regulated and controlled by regulating the ratio of the mole number of epoxy groups in a polyepoxy compound to the mole number of carboxyl groups in a modified elastomer grafted by carboxyl groups in the preparation process.
The invention also aims to provide a thermally reversible crosslinking modified elastomer material which is prepared by the preparation method, has better mechanical property and solvent resistance under the room temperature condition, has long service life, is thermoplastic and can be processed and used again.
In order to achieve the above object, the present invention provides a method for preparing a thermally reversible crosslinked modified elastomer material, comprising:
step 1, enabling an elastomer containing double bonds and a mercapto carboxyl compound to generate mercapto-alkene click reaction to obtain a modified elastomer after carboxyl grafting; wherein, the mercapto carboxyl compound is a compound which simultaneously contains carboxyl and mercapto in the molecular structure;
step 2, carrying out esterification reaction on the modified elastomer grafted by the carboxyl and a polyepoxy compound to obtain a thermally reversible crosslinked modified elastomer material; wherein the polyepoxy compound is a compound containing two or more epoxy groups in a molecule.
In some embodiments of the present invention, the elastomer containing double bonds is an isolated double bond-containing elastomer comprising at least one of a styrenic thermoplastic elastomer SBS, SIS, SIBS, butadiene, nitrile, natural, ethylene propylene diene monomer.
In some embodiments of the invention, the mercaptocarboxy compound comprises at least one of thioglycolic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptohexanoic acid.
In some embodiments of the present invention, in step 1, the ratio of the number of moles of mercapto groups in the mercapto carboxyl compound to the number of moles of double bonds in the double bond containing elastomer is 0.01:1 to 1: 1.
In some embodiments of the invention, step 1 comprises: dissolving an elastomer containing double bonds and a mercapto carboxyl compound in a first organic solvent, adding a photoinitiator, uniformly mixing, and carrying out mercapto-alkene click reaction under the condition of ultraviolet irradiation;
preferably, the mixing mode is stirring;
preferably, the first organic solvent includes at least one of tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, and xylene.
In some embodiments of the present invention, in step 1, the photoinitiator is a radical photoinitiator or a cationic photoinitiator;
preferably, the free radical photoinitiator comprises at least one of benzoin ethers and derivatives thereof, dialkoxyacetophenone and derivatives thereof, xanthone and derivatives thereof, thioether-containing benzophenones and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, benzophenone and derivatives thereof;
preferably, the cationic photoinitiator comprises at least one of diaryl iodide, triaryl sulfide, diaryl iodonium copper salt and ferrocenium salt;
preferably, the amount of the photoinitiator is 0.1 wt% to 30 wt% of the whole reaction system in the step 1.
In some embodiments of the invention, the polyepoxy compound comprises at least one of 4, 4-propylene oxide-biphenyl and 1, 6-hexanediol diglycidyl ether.
In some embodiments of the present invention, in the step 2, the ratio of the number of moles of epoxy groups in the polyepoxy compound to the number of moles of carboxyl groups in the modified elastomer after the carboxyl group grafting is 0.01:1 to 1: 1.
In some embodiments of the invention, step 2 comprises: dissolving the modified elastomer grafted by carboxyl and the polyepoxy compound in a second organic solvent, uniformly mixing, and performing crosslinking molding at the temperature of 60-120 ℃ to obtain a thermally reversible crosslinked modified elastomer material;
preferably, the mixing mode is stirring;
preferably, the second organic solvent includes at least one of tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, and xylene.
The invention also provides a thermal reversible crosslinking modified elastomer material prepared by the preparation method of the thermal reversible crosslinking modified elastomer material.
The invention has the beneficial effects that:
the invention provides a thermal reversible crosslinking modified elastomer material and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, grafting carboxyl onto a molecular chain of an elastomer with double bonds through sulfydryl-alkene click reaction, and then carrying out esterification reaction on the modified elastomer after carboxyl grafting and a polyepoxy compound to obtain the thermally reversible crosslinking modified elastomer material. Under the condition of room temperature, due to the existence of ester bond covalent crosslinking structure, the thermal reversible crosslinking modified elastomer material has better mechanical property and solvent resistance and long service life. In addition, under the heating condition, ester bonds in the thermally reversible crosslinked modified elastomer material can generate dynamic ester exchange reaction, so that the thermally reversible crosslinked modified elastomer material can be remolded under the heating condition, and the recycling of the elastomer material is realized. The invention can also regulate and control the performance of the prepared thermal reversible crosslinking modified elastomer material by regulating the ratio of the mole number of epoxy groups in the polyepoxy compound to the mole number of carboxyl groups in the modified elastomer after carboxyl grafting. The preparation method of the thermally reversible crosslinking modified elastomer material is simple, and has the advantages of easily obtained raw materials and lower cost.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is a stress-strain curve of a thermally reversible crosslink modified elastomer material in example 1;
FIG. 2 is a stress-strain curve of the thermally reversible crosslink modified elastomeric material of example 2;
FIG. 3 is a stress-strain plot of the thermoreversibly crosslinked modified elastomeric material of example 3 after being remolded.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The invention provides a preparation method of a thermal reversible crosslinking modified elastomer material, which comprises the following steps:
step 1, enabling an elastomer containing double bonds and a mercapto carboxyl compound to generate mercapto-alkene click reaction to obtain a modified elastomer after carboxyl grafting; wherein, the mercapto carboxyl compound is a compound which contains carboxyl and mercapto simultaneously in the molecular structure.
Optionally, the elastomer containing double bonds is an isolated double bond-containing elastomer, and the isolated double bond-containing elastomer includes at least one of styrene thermoplastic elastomers SBS, SIS, SIBS, butadiene rubber, nitrile rubber, natural rubber, and Ethylene Propylene Diene Monomer (EPDM).
Specifically, in the step 1, the ratio of the number of moles of mercapto groups in the mercaptocarboxy compound to the number of moles of double bonds in the elastomer containing double bonds is 0.01:1 to 1:1, for example, 0.01:1, 0.05:1, 0.1:1, 0.3:1, 0.5:1, 0.8:1, 1: 1.
Optionally, the mercapto carboxyl compound includes at least one of thioglycolic acid, mercaptopropionic acid, mercaptobutyric acid, and mercaptohexanoic acid.
Specifically, the step 1 includes: dissolving an elastomer containing double bonds and a mercapto carboxyl compound in a first organic solvent, adding a photoinitiator, uniformly mixing, and carrying out mercapto-alkene click reaction under the condition of ultraviolet irradiation.
Optionally, the mixing mode is stirring.
Specifically, the first organic solvent includes at least one of tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, and xylene.
Specifically, in the step 1, the photoinitiator is a radical photoinitiator or a cationic photoinitiator.
Preferably, the radical photoinitiator comprises at least one of benzoin ethers and derivatives thereof, dialkoxyacetophenones and derivatives thereof, xanthones and derivatives thereof, thioether-containing benzophenones and derivatives thereof, thioxanthones and derivatives thereof, anthraquinones and derivatives thereof, and benzophenones and derivatives thereof.
Preferably, the cationic photoinitiator comprises at least one of a diaryl iodide, a triaryl sulfide, a diaryl iodonium copper salt and a ferrocenium salt.
Optionally, the photoinitiator is used in an amount of 0.1 wt% to 30 wt%, such as 0.1 wt%, 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt% of the whole reaction system in step 1.
Step 2, carrying out esterification reaction on the modified elastomer grafted by the carboxyl and a polyepoxy compound to obtain a thermally reversible crosslinked modified elastomer material; wherein the polyepoxy compound is a compound containing two or more epoxy groups in a molecule.
By designing a polyepoxy compound containing two or more than two epoxy groups to react with the modified elastomer grafted by the carboxyl, a covalent crosslinking structure can be formed in the finally obtained thermally reversible crosslinking modified elastomer material, so that the performance of the thermally reversible crosslinking modified elastomer material is improved.
Optionally, the polyepoxy compound includes at least one of 4, 4-propylene oxide-biphenyl and 1, 6-hexanediol diglycidyl ether.
Specifically, in the step 2, the ratio of the number of moles of epoxy groups in the polyepoxy compound to the number of moles of carboxyl groups in the modified elastomer after the grafting of the carboxyl groups is 0.01:1 to 1:1, for example, 0.01:1, 0.05:1, 0.1:1, 0.3:1, 0.5:1, 0.8:1, 1: 1.
Specifically, the step 2 includes: and dissolving the modified elastomer grafted by carboxyl and the polyepoxy compound in a second organic solvent, uniformly mixing, and performing crosslinking molding at the temperature of 60-120 ℃ to obtain the thermally reversible crosslinked modified elastomer material.
Optionally, the mixing mode is stirring.
Specifically, the second organic solvent includes at least one of tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, and xylene.
Based on the preparation method of the thermally reversible crosslinked modified elastomer material, the invention also provides the thermally reversible crosslinked modified elastomer material prepared by the method.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Step 1, according to the proportion that the ratio of the mole number of sulfydryl in mercaptopropionic acid to the mole number of double bonds in cis-butadiene rubber (BR9000) is 10%, dissolving cis-butadiene rubber and mercaptopropionic acid in toluene, adding a proper amount of photoinitiator 907, wherein the mass percentage of the photoinitiator 907 in the whole reaction system is 10%, uniformly stirring, and then carrying out sulfydryl-alkene click reaction under the condition of ultraviolet irradiation to obtain carboxyl modified cis-butadiene rubber (namely the modified elastomer after carboxyl grafting).
And 2, dissolving the carboxyl modified butadiene rubber and 4, 4-epoxypropane-biphenyl (namely a polyepoxy compound) in toluene according to different proportions, uniformly stirring, and carrying out crosslinking molding under the heating condition of 110 ℃ to obtain the thermally reversible crosslinking modified elastomer material.
In the step 2, the different ratios refer to ratios of the number of moles of epoxy groups in the 4, 4-epoxypropane-biphenyl to the number of moles of carboxyl groups in the carboxyl-modified butadiene rubber of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% and 100%.
Table 1 shows the elongation at break and the strength at break of the thermoreversibly crosslinked modified elastomer material in the tensile test in example 1. FIG. 1 is a stress-strain graph of the thermoreversibly cross-linked modified elastomeric material of example 1.
TABLE 1
In table 1 and fig. 1, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% and 100% represent the ratio of the number of moles of the epoxy group in the 4, 4-epoxypropane-biphenyl in step 2 to the number of moles of the carboxyl group in the carboxyl-modified butadiene rubber, respectively.
As can be seen from table 1 and fig. 1, when the ratio of the mole number of the epoxy group in the 4, 4-epoxypropane-biphenyl to the mole number of the carboxyl group in the carboxyl group-modified butadiene rubber is changed between 10% and 100%, the elongation at break and the strength at break of the thermoreversibly cross-linked modified elastomer material are also changed, that is, the invention can adjust and control the performance of the thermoreversibly cross-linked modified elastomer material by adjusting the ratio of the mole number of the epoxy group in the polyepoxy compound to the mole number of the carboxyl group in the modified elastomer grafted with the carboxyl group, thereby being capable of meeting different product requirements.
Example 2
Step 1, according to the proportion that the ratio of the mole number of sulfydryl in mercaptopropionic acid to the mole number of double bonds in SBS (polystyrene-butadiene-styrene) is 10%, dissolving SBS and mercaptopropionic acid in toluene, adding a proper amount of photoinitiator 907, wherein the mass percentage of the photoinitiator 907 in the whole reaction system is 10%, uniformly stirring, and then carrying out sulfydryl-alkene click reaction under the condition of ultraviolet irradiation to obtain the SBS (namely the modified elastomer after carboxyl grafting) after carboxyl modification.
And 2, dissolving the SBS subjected to carboxyl modification and 1, 6-hexanediol diglycidyl ether (namely the polyepoxy compound) in toluene according to different proportions, uniformly stirring, and carrying out crosslinking molding under the heating condition of 110 ℃ to obtain the thermally reversible crosslinking modified elastomer material.
In the step 2, the different ratios refer to ratios of the number of moles of epoxy groups in the 1, 6-hexanediol diglycidyl ether to the number of moles of carboxyl groups in the SBS after carboxyl modification of 0, 20%, 40%, 60%, 80% and 100%, wherein 0 represents that the amount of the 1, 6-hexanediol diglycidyl ether used is 0.
Table 2 shows the elongation at break and the strength at break of the thermoreversibly crosslinked modified elastomer material in the tensile test in example 2; FIG. 2 is a stress-strain graph of the thermally reversible crosslink modified elastomeric material of example 2.
TABLE 2
In table 2 and fig. 2, 0, 20%, 40%, 60%, 80% and 100% represent the ratio of the number of moles of epoxy groups in the 1, 6-hexanediol diglycidyl ether in step 2 to the number of moles of carboxyl groups in the SBS after carboxyl modification, respectively.
As can be seen from table 2 and fig. 2, when the ratio of the number of moles of epoxy groups in 1, 6-hexanediol diglycidyl ether to the number of moles of carboxyl groups in SBS modified with carboxyl groups is changed between 0 and 100%, the elongation at break and the strength at break of the thermoreversible cross-linked modified elastomer material are also changed, that is, the invention can adjust the elongation at break and the strength at break of the thermoreversible cross-linked modified elastomer material by adjusting the ratio of the number of moles of epoxy groups in the polyepoxy compound to the number of moles of carboxyl groups in the modified elastomer grafted with carboxyl groups, thereby being capable of satisfying different product requirements.
Example 3
A film-formed sample of the thermally reversible crosslinked modified elastomer material prepared in example 2, in which the molar ratio of the epoxy group to the carboxyl group (i.e., the ratio of the number of moles of the epoxy group in the 1, 6-hexanediol diglycidyl ether to the number of moles of the carboxyl group in the SBS modified with the carboxyl group) was 60%, was cut into pieces, and a film was re-formed at 150 ℃ and 10MPa, and the process was repeated twice, and the films obtained by the two remolding processes were subjected to tensile tests, respectively.
Table 3 shows elongation at break and strength at break data in tensile test for the thermo-reversible cross-linked modified elastomer material remolded in example 3; FIG. 3 is a stress-strain plot of the thermoreversibly crosslinked modified elastomeric material of example 3 after being remolded.
TABLE 3
| Elongation at Break (%) | Breaking Strength (MPa) | |
| As received | 306.34 | 20.54 |
| First remodeling | 300.03 | 16.47 |
| Second remodeling | 290.78 | 15.23 |
As can be seen from table 3 and fig. 3, the elongation at break and the strength at break of the thermoreversible crosslinked modified elastomer material prepared in example 2 of the present invention are not greatly changed after the first remodeling and the second remodeling, which indicates that the mechanical properties of the thermoreversible crosslinked modified elastomer material prepared in the present invention are not greatly changed after the thermal remodeling.
Example 4
Step 1, according to the ratio of the mole number of sulfydryl in mercaptopropionic acid to the mole number of double bonds in cis-butadiene rubber (BR9000) of 0.5:1, dissolving cis-butadiene rubber and mercaptopropionic acid in toluene, adding a proper amount of photoinitiator 907, wherein the mass percentage of the photoinitiator 907 in the whole reaction system is 30%, uniformly stirring, and then carrying out sulfydryl-alkene click reaction under the condition of ultraviolet irradiation to obtain carboxyl modified cis-butadiene rubber (namely the modified elastomer after carboxyl grafting).
And 2, dissolving the carboxyl-modified butadiene rubber and 4, 4-epoxypropane-biphenyl (namely a polyepoxy compound) in toluene according to the ratio of the mole number of epoxy groups in the 4, 4-epoxypropane-biphenyl to the mole number of carboxyl groups in the carboxyl-modified butadiene rubber being 1:1, uniformly stirring, and carrying out crosslinking molding under the heating condition of 110 ℃ to obtain the thermally reversible crosslinking modified elastomer material.
Example 5
Step 1, according to the ratio of the mole number of sulfydryl in thioglycolic acid to the mole number of double bonds in nitrile rubber of 0.01:1, dissolving nitrile rubber and thioglycolic acid in toluene, adding a proper amount of photoinitiator 907, wherein the mass percentage of the photoinitiator 907 in the whole reaction system is 5%, stirring uniformly, and then carrying out sulfydryl-alkene click reaction under the condition of ultraviolet irradiation to obtain the nitrile rubber (namely the modified elastomer after carboxyl grafting) after carboxyl modification.
And 2, dissolving the nitrile rubber modified by the carboxyl and 1, 6-hexanediol diglycidyl ether (namely a polyepoxy compound) in toluene according to the ratio of the mole number of the epoxy group in the 4, 4-epoxypropane-biphenyl to the mole number of the carboxyl group in the nitrile rubber modified by the carboxyl group of 0.5:1, uniformly stirring, and carrying out crosslinking molding under the heating condition of 110 ℃ to obtain the thermally reversible crosslinking modified elastomer material.
Example 6
Step 1, according to the ratio of the mole number of sulfydryl in thioglycolic acid to the mole number of double bonds in nitrile rubber of 1:1, dissolving nitrile rubber and thioglycolic acid in toluene, adding a proper amount of photoinitiator 907, wherein the mass percentage of the photoinitiator 907 in the whole reaction system is 0.01%, uniformly stirring, and then carrying out sulfydryl-alkene click reaction under the condition of ultraviolet irradiation to obtain the nitrile rubber (namely the modified elastomer after carboxyl grafting) after carboxyl modification.
And 2, dissolving the nitrile rubber modified by the carboxyl and 1, 6-hexanediol diglycidyl ether (namely a polyepoxy compound) in toluene according to the ratio of the mole number of the epoxy group in the 4, 4-epoxypropane-biphenyl to the mole number of the carboxyl group in the nitrile rubber modified by the carboxyl group of 0.01:1, uniformly stirring, and carrying out crosslinking molding under the heating condition of 110 ℃ to obtain the thermally reversible crosslinking modified elastomer material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for preparing a thermally reversible crosslinked modified elastomer material, comprising:
step 1, enabling an elastomer containing double bonds and a mercapto carboxyl compound to generate mercapto-alkene click reaction to obtain a modified elastomer after carboxyl grafting; wherein, the mercapto carboxyl compound is a compound which simultaneously contains carboxyl and mercapto in the molecular structure;
step 2, carrying out esterification reaction on the modified elastomer grafted by the carboxyl and a polyepoxy compound to obtain a thermally reversible crosslinked modified elastomer material; wherein the polyepoxy compound is a compound containing two or more epoxy groups in a molecule.
2. The method for preparing the thermally reversible crosslinked modified elastomer material according to claim 1, wherein the elastomer containing double bonds is an isolated double bond-containing elastomer, and the isolated double bond-containing elastomer comprises at least one of styrene-based thermoplastic elastomers SBS, SIS, SIBS, butadiene rubber, nitrile rubber, natural rubber, and ethylene propylene diene rubber.
3. The method for producing a thermoreversibly cross-linked modified elastomer material as claimed in claim 1, wherein said mercapto carboxyl compound comprises at least one of thioglycolic acid, mercaptopropionic acid, mercaptobutyric acid, and mercaptohexanoic acid.
4. The method for producing a thermoreversibly cross-linked modified elastomer material as claimed in claim 1, wherein in said step 1, the ratio of the number of moles of mercapto groups in said mercapto carboxyl compound to the number of moles of double bonds in said double bond-containing elastomer is from 0.01:1 to 1: 1.
5. The method for producing a thermoreversibly cross-linked modified elastomeric material as claimed in claim 1, wherein said step 1 comprises: dissolving an elastomer containing double bonds and a mercapto carboxyl compound in a first organic solvent, adding a photoinitiator, uniformly mixing, and carrying out mercapto-alkene click reaction under the condition of ultraviolet irradiation;
preferably, the mixing mode is stirring;
preferably, the first organic solvent includes at least one of tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, and xylene.
6. The method for producing a thermoreversibly cross-linked, modified elastomeric material according to claim 5, wherein in said step 1, said photoinitiator is a radical photoinitiator or a cationic photoinitiator;
preferably, the free radical photoinitiator comprises at least one of benzoin ethers and derivatives thereof, dialkoxyacetophenone and derivatives thereof, xanthone and derivatives thereof, thioether-containing benzophenones and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, benzophenone and derivatives thereof;
preferably, the cationic photoinitiator comprises at least one of diaryl iodide, triaryl sulfide, diaryl iodonium copper salt and ferrocenium salt;
preferably, the amount of the photoinitiator is 0.1 wt% to 30 wt% of the whole reaction system in the step 1.
7. The method for producing a thermoreversibly cross-linked modified elastomeric material as claimed in claim 1, wherein said polyepoxy compound comprises at least one of 4, 4-epoxypropane-biphenyl and 1, 6-hexanediol diglycidyl ether.
8. The method for producing a thermoreversibly cross-linked modified elastomer material as claimed in claim 1, wherein in said step 2, the ratio of the number of moles of epoxy groups in said polyepoxy compound to the number of moles of carboxyl groups in said modified elastomer after said carboxyl group grafting is from 0.01:1 to 1: 1.
9. The method for producing a thermoreversibly cross-linked modified elastomeric material as claimed in claim 1, wherein said step 2 comprises: dissolving the modified elastomer grafted by carboxyl and the polyepoxy compound in a second organic solvent, uniformly mixing, and performing crosslinking molding at the temperature of 60-120 ℃ to obtain a thermally reversible crosslinked modified elastomer material;
preferably, the mixing mode is stirring;
preferably, the second organic solvent includes at least one of tetrahydrofuran, alcohols, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, and xylene.
10. A thermally reversible crosslinked modified elastomer material, characterized by being obtained by the method for producing a thermally reversible crosslinked modified elastomer material according to any one of claims 1 to 9.
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