CN116655855A - Thermoplastic elastomer with shape memory performance and preparation method thereof - Google Patents
Thermoplastic elastomer with shape memory performance and preparation method thereof Download PDFInfo
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- CN116655855A CN116655855A CN202310511018.7A CN202310511018A CN116655855A CN 116655855 A CN116655855 A CN 116655855A CN 202310511018 A CN202310511018 A CN 202310511018A CN 116655855 A CN116655855 A CN 116655855A
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- diene monomer
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 45
- 230000007334 memory performance Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 12
- -1 polypropylene Polymers 0.000 claims abstract description 40
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 29
- 239000004743 Polypropylene Substances 0.000 claims abstract description 28
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 239000011976 maleic acid Substances 0.000 claims abstract description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 7
- 239000000203 mixture Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 238000004073 vulcanization Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004033 plastic Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 239000012781 shape memory material Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 150000001734 carboxylic acid salts Chemical class 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229920000431 shape-memory polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002677 supramolecular polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
-
- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
Abstract
The invention provides a thermoplastic elastomer with shape memory performance and a preparation method thereof, belonging to the technical field of high polymer materials. The invention adopts the binary unsaturated carboxylic acid and the metal additive, two molecules of carboxylic acid in one molecule of maleic acid can react with the metal additive in situ to generate unsaturated carboxylate, and the unsaturated carboxylate polymer generated after grafting polymerization has stronger ionic interaction among molecules, so that the performance of the material can be improved, the unsaturated carboxylate is subjected to polymerization reaction and grafting reaction between ethylene propylene diene monomer and polypropylene molecular chains under the action of a vulcanizing agent, the vulcanizing agent is decomposed to generate free radicals to initiate the polymerization reaction of the unsaturated carboxylate, and meanwhile, the free radicals abstract hydrogen on the ethylene propylene diene monomer and polypropylene molecular chains to generate high molecular free radicals, so that the unsaturated carboxylate is grafted to the ethylene propylene diene monomer and polypropylene molecular chains, and the shape memory performance of the thermoplastic elastomer is improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a thermoplastic elastomer with shape memory performance and a preparation method thereof.
Background
The shape memory material is a material that is capable of responding to external stimuli, such as heat, light, electricity, magnetic fields, solvents, etc., and is capable of changing its shape upon application of one or more external stimuli, respectively referred to as a thermal, photo, electro, etc., shape memory material. In the whole deformation process, firstly, the material deforms and is fixed into a temporary shape under the action of external force, and then the material returns to a permanent shape from the temporary shape under the action of external stimulus. The shape memory material comprises a metal material, a ceramic material, a polymer material and the like, wherein the shape memory polymer material has the advantages of low density, low cost, excellent deformability, deformation restorability and the like. At present, shape memory polymer materials are applied to heat-shrinkable tubes used in the cable industry, heat-shrinkable films or labels used in the packaging industry, heat-shrinkable toys and the like. The shape memory polymer material is expected to be applied to the wider fields of biological medicine, aviation devices, soft robots and the like.
Various methods for preparing shape memory materials by using high molecular materials are available, including various types such as block copolymers, interpenetrating network polymers, crosslinked polymers, and supramolecular polymer networks. Most of the materials listed above have a fully crosslinked structure and their recycling properties are limited. The thermoplastic elastomer material prepared by the dynamic vulcanization method generally has a microscopic morphology of a sea-island structure and has the property of being capable of being repeatedly processed, but the unmodified dynamic vulcanization thermoplastic elastomer is poor in shape memory performance.
In the prior art, the unsaturated carboxylate is generated by in-situ reaction of methacrylic acid, acrylic acid, metal oxide and the like, and the product of the unsaturated carboxylate under the action of a vulcanizing agent can improve the shape memory performance of the thermoplastic elastomer, but the problem that the prepared thermoplastic elastomer is poor in shape memory performance still exists.
Disclosure of Invention
Accordingly, the present invention is directed to a thermoplastic elastomer having shape memory properties and a method for preparing the same. The thermoplastic elastomer provided by the invention has excellent shape memory performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a thermoplastic elastomer with shape memory property, which is prepared from the following raw materials in parts by mass:
ethylene propylene diene monomer rubber: 40-80 parts of polypropylene: 20-60 parts of vulcanizing agent: 0.2 to 2.5 parts of binary unsaturated carboxylic acid: 1.2-20 parts of metal additive: 0.4-8 parts of metal additive comprising metal oxide and/or metal hydroxide.
Preferably, the di-unsaturated carboxylic acid is maleic acid.
Preferably, the metal element in the metal additive includes magnesium or zinc.
Preferably, the sulfiding agent comprises dicumyl peroxide.
Preferably, the thermoplastic elastomer with shape memory property is prepared from the following raw materials in parts by mass:
ethylene propylene diene monomer rubber: 50-70 parts of polypropylene: 30-50 parts of vulcanizing agent: 0.5 to 1.8 parts of a dibasic unsaturated carboxylic acid: 1.855 to 11.13 parts of metal additive: 0.645 to 3.87 portions.
Preferably, the thermoplastic elastomer with shape memory property is prepared from the following raw materials in parts by mass:
ethylene propylene diene monomer rubber: 40-60 parts of polypropylene: 40-60 parts of vulcanizing agent: 0.6 to 0.7 part of binary unsaturated carboxylic acid: 2.597-8.904 parts of metal additive: 0.774-3.096 parts.
The invention also provides a preparation method of the thermoplastic elastomer with shape memory property, which comprises the following steps:
mixing ethylene propylene diene monomer, binary unsaturated carboxylic acid and a metal additive for in-situ reaction to obtain an ethylene propylene diene monomer-unsaturated carboxylate mixture;
and mixing the ethylene propylene diene monomer-unsaturated carboxylate mixture, polypropylene and a vulcanizing agent for dynamic vulcanization to obtain the thermoplastic elastomer with shape memory.
Preferably, the temperature of the in-situ reaction is 130-140 ℃ and the time is 10-30 min.
Preferably, the temperature of the dynamic vulcanization is 160-175 ℃ and the time is 3-10 min.
Preferably, the dynamic vulcanization is carried out in an internal mixer with a rotation speed of 60 to 70rpm.
The invention provides a thermoplastic elastomer with shape memory property, which is prepared from the following raw materials in parts by mass: ethylene propylene diene monomer rubber: 40-80 parts of polypropylene: 20-60 parts of vulcanizing agent: 0.2 to 2.5 parts of binary unsaturated carboxylic acid: 1.2-20 parts of metal additive: 0.4-8 parts of metal additive comprising metal oxide and/or metal hydroxide.
According to the invention, the binary unsaturated carboxylic acid and the metal additive are adopted, two molecules of carboxylic acid in one molecule of maleic acid can react with the metal additive in situ to generate unsaturated carboxylic acid salt, and the unsaturated carboxylic acid salt polymer generated after grafting polymerization has stronger ionic interaction among molecules, so that the performance of the material can be further improved, the unsaturated carboxylic acid salt is subjected to polymerization reaction and grafting reaction between ethylene propylene diene monomer and polypropylene molecular chains under the action of a vulcanizing agent, the vulcanizing agent is decomposed to generate free radicals to initiate the polymerization reaction of the unsaturated carboxylic acid salt, and meanwhile, the free radicals abstract hydrogen on the ethylene propylene diene monomer and polypropylene molecular chains to generate high molecular free radicals, so that the unsaturated carboxylic acid salt is grafted to the ethylene propylene diene monomer and polypropylene molecular chains, the interfacial bonding force and the stress transfer efficiency of rubber and plastic two phases are improved, and the shape memory performance of the thermoplastic elastomer is improved; and maleic acid can react with metal additives to generate unsaturated carboxylate, and redundant maleic acid can be dehydrated to generate maleic anhydride, and under the action of vulcanizing agent, maleic anhydride can be grafted on the molecular chains of ethylene propylene diene monomer and polypropylene, so that the interfacial binding force between rubber and plastic is further improved, and the shape memory performance of the material is further improved.
The raw materials of the invention are safe and environment-friendly, so that the problems of serious burn and poor operation safety caused by using corrosive substances such as methacrylic acid, acrylic acid and the like are avoided, the environment is not harmed by using acrylic acid, and adverse effects on aquatic organisms are avoided.
Furthermore, the binary unsaturated carboxylic acid-maleic acid used in the invention has the advantages of low risk and toxicity, environmental protection, high operation safety and solid particles at normal temperature, thereby being more beneficial to uniform mixing with ethylene propylene diene monomer, simplifying the processing technology and improving the production efficiency.
Drawings
FIG. 1 is a scanning electron micrograph of the thermoplastic elastomer prepared in example 2 after xylene etching.
Detailed Description
The invention provides a thermoplastic elastomer with shape memory property, which is prepared from the following raw materials in parts by mass:
ethylene propylene diene monomer rubber: 40-80 parts of polypropylene: 20-60 parts of vulcanizing agent: 0.2 to 2.5 parts of binary unsaturated carboxylic acid: 1.2-20 parts of metal additive: 0.4-8 parts of metal additive comprising metal oxide and/or metal hydroxide.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
The ethylene propylene diene monomer rubber in the preparation raw materials of the thermoplastic elastomer provided by the invention is preferably 50-70 parts by mass, more preferably 40-60 parts by mass. The ethylene propylene diene monomer rubber adopted in the invention can provide the elastic restoring force required by the shape memory material and can also improve the elastic performance of the material.
Based on the mass parts of the ethylene propylene diene monomer, the mass parts of polypropylene in the preparation raw materials of the thermoplastic elastomer provided by the invention are preferably 30-50 parts, more preferably 40-60 parts. The invention adopts polypropylene to provide shape retention force required by shape fixation of the shape memory material, improves the rigidity of the material, and has compatibility with ethylene propylene diene monomer rubber superior to other resins.
Based on the mass parts of the ethylene propylene diene monomer rubber, the mass parts of the vulcanizing agent in the preparation raw materials of the thermoplastic elastomer provided by the invention are preferably 0.5-1.8 parts, and more preferably 0.6-0.7 parts. The vulcanizing agent adopted by the invention can crosslink the ethylene propylene diene monomer, and provide enough elastic restoring force for restoring the shape of the material, and in addition, the vulcanizing agent can initiate the polymerization reaction, grafting reaction and grafting reaction of maleic anhydride of unsaturated carboxylate. If the addition amount of the vulcanizing agent is excessive, the chain breakage of the polypropylene can be caused under high temperature and high shear, so that the mechanical strength of the material is reduced; too small an amount may result in too low a crosslinking degree of the rubber phase, and a decrease in mechanical properties and shape recovery.
In the present invention, the vulcanizing agent preferably includes dicumyl peroxide (DCP).
Based on the mass parts of the ethylene propylene diene monomer, the mass parts of the binary unsaturated carboxylic acid in the preparation raw materials of the thermoplastic elastomer provided by the invention are preferably 1.855-11.13 parts, more preferably 2.597-8.904 parts, and most preferably 4.452-6.678 parts. The binary unsaturated carboxylic acid adopted by the invention can react with the metal additive to generate unsaturated carboxylate and generate dehydration reaction.
In the present invention, the dibasic unsaturated carboxylic acid is preferably maleic acid.
Based on the mass parts of the ethylene propylene diene monomer rubber, the mass parts of the metal additive in the preparation raw materials of the thermoplastic elastomer provided by the invention are preferably 0.645-3.87 parts, more preferably 0.774-3.096 parts, and most preferably 1.02-2.322 parts. The metal additive adopted by the invention can react with the binary unsaturated carboxylic acid to generate unsaturated carboxylate, so that polymerization reaction and grafting reaction are carried out under the action of the vulcanizing agent.
In the present invention, the metal element in the metal oxide and the metal hydroxide preferably includes magnesium or zinc.
In the invention, the thermoplastic elastomer with shape memory property is preferably prepared from the following raw materials in parts by weight:
ethylene propylene diene monomer rubber: 50-70 parts of polypropylene: 30-50 parts of vulcanizing agent: 0.5 to 1.8 parts of a dibasic unsaturated carboxylic acid: 1.855 to 11.13 parts of metal additive: 0.645 to 3.87 parts, more preferably from the following raw materials by mass:
ethylene propylene diene monomer rubber: 40-60 parts of polypropylene: 40-60 parts of vulcanizing agent: 0.6 to 0.7 part of binary unsaturated carboxylic acid: 2.597-8.904 parts of metal additive: 0.774-3.096 parts.
The invention also provides a preparation method of the thermoplastic elastomer with shape memory property, which comprises the following steps:
mixing ethylene propylene diene monomer, binary unsaturated carboxylic acid and a metal additive for in-situ reaction to obtain an ethylene propylene diene monomer-unsaturated carboxylate mixture;
and mixing the ethylene propylene diene monomer-unsaturated carboxylate mixture, polypropylene and a vulcanizing agent for dynamic vulcanization to obtain the thermoplastic elastomer with shape memory.
According to the invention, ethylene propylene diene monomer, binary unsaturated carboxylic acid and metal additives are mixed for in-situ reaction, so as to obtain an ethylene propylene diene monomer-unsaturated carboxylate mixture.
In the present invention, the mixing is preferably performed in an open mill.
In the invention, the temperature of the in-situ reaction is preferably 130-140 ℃ and the time is preferably 10-30 min, and in the process of the in-situ reaction, the di-unsaturated carboxylic acid and the metal additive react to obtain unsaturated carboxylate.
After the ethylene propylene diene monomer-unsaturated carboxylate mixture is obtained, the ethylene propylene diene monomer-unsaturated carboxylate mixture, polypropylene and a vulcanizing agent are mixed for dynamic vulcanization, so that the thermoplastic elastomer with shape memory performance is obtained.
The polypropylene is preferably added into an internal mixer, after being melted, the ethylene propylene diene monomer-unsaturated carboxylate mixture is added, and then the vulcanizing agent is added for dynamic vulcanization, so that the thermoplastic elastomer is obtained.
In the present invention, the temperature of the dynamic vulcanization is preferably 160 to 175 ℃, more preferably 165 ℃, and the time is 3 to 10min, more preferably 5min.
In the present invention, the rotational speed of the internal mixer is preferably 60 to 70rpm.
In order to further illustrate the present invention, the thermoplastic elastomer having shape memory properties and the method of preparing the same provided by the present invention are described in detail below with reference to examples, which should not be construed as limiting the scope of the present invention.
The formulation of the examples and comparative examples is shown in Table 1.
The preparation methods of examples 1 to 10 are as follows:
(1) Weighing raw materials according to the dosage of Table 1, setting the temperature of an open mill to be 50 ℃, uniformly mixing ethylene propylene diene monomer, magnesium oxide and maleic acid on the open mill by a left cutting knife, a right cutting knife and a triangle packing way, and then mixing at 135 ℃ until the magnesium oxide and the maleic acid completely react to prepare a uniform ethylene propylene diene monomer-unsaturated carboxylate mixture for later use;
(2) The rotation speed of the internal mixer is set to 60rpm, the temperature is set to 165 ℃, the metered polypropylene is added for 3min and then is completely melted, the ethylene propylene diene monomer-unsaturated carboxylate mixture is added, the vulcanizing agent is added after uniform mixing, dynamic vulcanization is carried out for 5min at 165 ℃, and the thermoplastic elastomer material is obtained after discharging.
Comparative example 1
(1) Weighing raw materials according to the dosage of Table 1, setting the temperature of an open mill to be 50 ℃, uniformly mixing ethylene propylene diene monomer and magnesium oxide on the open mill by a left cutter, a right cutter and a triangular bag, then adding methacrylic acid in a slow dropwise manner, uniformly mixing, and then mixing until the magnesium oxide and the methacrylic acid completely react to prepare a uniform ethylene propylene diene monomer and unsaturated carboxylate mixture for standby;
(2) The rotation speed of the internal mixer is set to 60rpm, the temperature is set to 165 ℃, the metered polypropylene is added for 3min and then is completely melted, the ethylene propylene diene monomer and unsaturated carboxylate mixture is added, the mixture is uniformly mixed, the vulcanizing agent is added for dynamic vulcanization for 5min, and the thermoplastic elastomer material is obtained after discharging.
Comparative example 2
(1) Weighing raw materials according to the dosage of Table 1, setting the temperature of an open mill to be 50 ℃, uniformly mixing ethylene propylene diene monomer and magnesium oxide on the open mill by a left cutter, a right cutter and a triangular bag, then adding acrylic acid in a slow dropwise manner, uniformly mixing, and then mixing until the magnesium oxide and the acrylic acid completely react to prepare a uniform ethylene propylene diene monomer and unsaturated carboxylate mixture for later use;
(2) The rotation speed of the internal mixer is set to 60rpm, the temperature is set to 165 ℃, the metered polypropylene is added for 3min and then is completely melted, the ethylene propylene diene monomer and unsaturated carboxylate mixture is added, the mixture is uniformly mixed, the vulcanizing agent is added for dynamic vulcanization for 5min, and the thermoplastic elastomer material is obtained after discharging.
FIG. 1 is a scanning electron micrograph of the thermoplastic elastomer prepared in example 2 after xylene etching.
Table 1 formulation (parts by weight) of examples and comparative examples
The tensile test in the comparative examples and examples of the present invention was conducted with reference to GB/T528-2009, and the shape memory properties were the shape retention and shape recovery of the test materials after the tensile test specimen was deformed to 100%, and the results are shown in Table 2. The data of shape retention and shape recovery are affected by the rubber-to-plastic ratio and the amount of DCP, and comparative examples 1 and 2 have improved shape retention and shape recovery compared to example 2, which has the same rubber-to-plastic ratio and amount of DCP. When the DCP dosage or the rubber-plastic ratio is the same, the comparison example and the example are comparable, and the comparison between the example and the comparison example can prove that the thermoplastic elastomer material prepared by the invention has good physical and mechanical properties and shape memory properties; the rubber-plastic ratio of the comparative example 1, the comparative example 2 and the example 2 is 60/40, and the physical and mechanical properties and the shape memory properties of the example 2 are better than those of the comparative example 1 and the comparative example 2 under the condition of the same rubber-plastic ratio; as can be seen from the scanning electron microscope photograph of the embodiment 2, the microstructure of the thermoplastic elastomer material prepared by the invention is a sea-island structure, and the interface contact area of rubber and plastic phase is increased, thus reflecting that the rubber and plastic phase has better compatibility, and further leading the material to have better performance.
Table 2 comparative and example performance test results
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The thermoplastic elastomer with the shape memory performance is characterized by being prepared from the following raw materials in parts by mass:
ethylene propylene diene monomer rubber: 40-80 parts of polypropylene: 20-60 parts of vulcanizing agent: 0.2 to 2.5 parts of binary unsaturated carboxylic acid: 1.2-20 parts of metal additive: 0.4-8 parts of metal additive comprising metal oxide and/or metal hydroxide.
2. The thermoplastic elastomer with shape memory properties according to claim 1, wherein the di-unsaturated carboxylic acid is maleic acid.
3. Thermoplastic elastomer with shape memory properties according to claim 1, characterized in that the metallic element in the metallic additive comprises magnesium or zinc.
4. The thermoplastic elastomer with shape memory properties according to claim 1, wherein the vulcanizing agent comprises dicumyl peroxide.
5. Thermoplastic elastomer with shape memory properties according to any one of claims 1 to 4, characterized in that it is prepared from the following raw materials in parts by weight:
ethylene propylene diene monomer rubber: 50-70 parts of polypropylene: 30-50 parts of vulcanizing agent: 0.5 to 1.8 parts of a dibasic unsaturated carboxylic acid: 1.855 to 11.13 parts of metal additive: 0.645 to 3.87 portions.
6. Thermoplastic elastomer with shape memory properties according to any one of claims 1 to 4, characterized in that it is prepared from the following raw materials in parts by weight:
ethylene propylene diene monomer rubber: 40-60 parts of polypropylene: 40-60 parts of vulcanizing agent: 0.6 to 0.7 part of binary unsaturated carboxylic acid: 2.597-8.904 parts of metal additive: 0.774-3.096 parts.
7. The method for producing a thermoplastic elastomer having shape memory properties according to any one of claims 1 to 6, comprising the steps of:
mixing ethylene propylene diene monomer, binary unsaturated carboxylic acid and a metal additive for in-situ reaction to obtain an ethylene propylene diene monomer-unsaturated carboxylate mixture;
and mixing the ethylene propylene diene monomer-unsaturated carboxylate mixture, polypropylene and a vulcanizing agent for dynamic vulcanization to obtain the thermoplastic elastomer with shape memory.
8. The method according to claim 7, wherein the in-situ reaction is carried out at a temperature of 130 to 140 ℃ for a time of 10 to 30 minutes.
9. The method according to claim 7, wherein the dynamic vulcanization is carried out at a temperature of 160 to 175 ℃ for a time of 3 to 10 minutes.
10. The process according to claim 7 or 9, characterized in that the dynamic vulcanization is carried out in an internal mixer with a rotation speed of 60 to 70rpm.
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