CN115160724B - Super weather-proof recyclable thermoplastic elastomer material - Google Patents
Super weather-proof recyclable thermoplastic elastomer material Download PDFInfo
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- CN115160724B CN115160724B CN202210830198.0A CN202210830198A CN115160724B CN 115160724 B CN115160724 B CN 115160724B CN 202210830198 A CN202210830198 A CN 202210830198A CN 115160724 B CN115160724 B CN 115160724B
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 65
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- 229920001971 elastomer Polymers 0.000 claims abstract description 18
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- 239000011256 inorganic filler Substances 0.000 claims abstract description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 8
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229920001780 ECTFE Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229920006132 styrene block copolymer Polymers 0.000 claims description 4
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 3
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 3
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000013536 elastomeric material Substances 0.000 claims 2
- 239000004416 thermosoftening plastic Substances 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 21
- 230000006750 UV protection Effects 0.000 abstract description 14
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000007792 addition Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a super weather-proof recyclable thermoplastic elastomer material. The thermoplastic elastomer material comprises the following components in parts by mass: 100 parts of styrene elastomer, 20-100 parts of filling oil, 5-20 parts of plasticizing resin, 10-50 parts of fluororesin, 5-40 parts of compatilizer, 5-30 parts of inorganic filler and 1-15 parts of fluorine-containing coupling agent. The thermoplastic elastomer material has excellent ultraviolet resistance, still has high tensile strength retention rate and fracture tensile rate retention rate after high-dose irradiation, and ensures long-term use of the material in outdoor environment. Meanwhile, the thermoplastic elastomer material can be used as a reclaimed material to be added into a new formula after aging, and meanwhile, the reclaimed material added product is kept to keep the mechanical property equivalent to that of the original new product, so that the thermoplastic elastomer material has good recyclability.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a super weather-proof recyclable thermoplastic elastomer material.
Background
TPE (thermoplastic elastomer) has the characteristics of both rubber and thermoplastic plastics and has wide application in the fields of automobile parts, wires and cables, buildings, electric appliances and the like. For TPE materials to be used outdoors for long periods of time, it is desirable to have good uv resistance.
Researchers usually select different types of ultraviolet resistance additives to be added into the TPE formula to endow the material with ultraviolet resistance effects, such as: benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. In addition, inorganic ultraviolet absorbers such as nano zinc oxide, nano titanium dioxide and the like are also applied to the TPE material formula. In addition, people can realize the crosslinking reaction of the TPE material in the processing and production process by designing the TPE formula, and can also achieve the effect of ultraviolet resistance.
Although ultraviolet resistance can be achieved to a certain extent by adding benzophenone, benzotriazole and triazine ultraviolet absorbers, the compatibility of the ultraviolet absorbers with TPE is not ideal, and ultraviolet absorption auxiliary agents can be separated out on the surface of the material in the long-time placement or use process, so that the normal use of the material is affected; on the other hand, in the outdoor long-term use process, the degradation of the organic ultraviolet absorber can lead to the reduction of the ultraviolet resistance of the TPE material, and the service life of the TPE material is influenced.
The inorganic powder ultraviolet absorber such as nano titanium dioxide, nano zinc and the like has complex preparation process and higher preparation cost. And the inorganic powder ultraviolet absorber is difficult to realize uniform distribution in the polymer due to easy agglomeration of nano particles, so that the ultraviolet resistance of partial areas is reduced.
In the aspect of TPE crosslinking, peroxide, crosslinking auxiliary agent and the like are generally added to realize TPE crosslinking, but the crosslinking agent, the curing speed and the curing time can influence the ultraviolet resistance of the material, and the crosslinking agent, the curing speed and the curing time have a plurality of influence factors and complex process conditions.
Meanwhile, by adopting the process of adding the organic ultraviolet absorber, the inorganic powder ultraviolet absorber or the TPE crosslinking, the mechanical property of the prepared TPE is seriously reduced after aging, and the TPE is difficult to recycle, so that serious resource waste is caused.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the super weather-proof recyclable thermoplastic elastomer material, and the fluorine-containing resin, the fluorine-containing coupling agent and the like are added into the TPE formula through a simple and efficient blending technology, so that the requirement of long-term outdoor use of the material is met by applying the good ultraviolet resistance of the fluorine-containing resin. In addition, the material is recyclable.
The technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a thermoplastic elastomer material, which comprises the following components in parts by mass:
100 parts of styrene elastomer
20-100 parts of filling oil
5 to 20 parts of plasticizing resin
10 to 50 parts of fluororesin
5-40 parts of compatilizer
5-30 parts of inorganic filler
1-15 parts of fluorine-containing coupling agent.
According to the invention, the fluororesin is added into the styrene elastomer, so that the fluororesin not only has excellent ultraviolet resistance, but also can obviously improve the ultraviolet resistance of the thermoplastic elastomer material; the thermoplastic elastomer material has good compatibility with styrene elastomer under the action of a compatilizer, can be uniformly dispersed in the thermoplastic elastomer material, and can not cause the problem of surface precipitation in the long-time placement or use process; the fluororesin is not obviously degraded, so that the thermoplastic elastomer material can be used as a reclaimed material to be added into a new formula after aging, and meanwhile, the reclaimed material added product is kept to keep the equivalent mechanical property of the original new product, and the reclaimed material has good recoverability. Meanwhile, the fluorine-containing coupling agent can synergistically improve the weather resistance of the thermoplastic elastomer material.
In some examples of the invention, the thermoplastic elastomer material comprises the following components in parts by mass:
100 parts of styrene elastomer
50 to 100 parts of filling oil
10 to 15 parts of plasticizing resin
10 to 50 parts of fluororesin
10 to 30 portions of compatilizer
10 to 25 portions of inorganic filler
3-10 parts of fluorine-containing coupling agent.
In some examples of the present invention, the styrenic elastomer comprises at least one of a styrene-butadiene-styrene block copolymer, a styrene-ethylene/butylene-styrene block copolymer, a styrene-ethylene/propylene-styrene block copolymer, a styrene-ethylene/propylene-styrene block copolymer.
In some examples of the invention, the filler oil comprises at least one of paraffinic oil, naphthenic oil.
In some examples of the present invention, the plasticizing resin includes at least one of polypropylene, polymethyl methacrylate (PMMA), ethylene-methyl methacrylate copolymer.
In some examples of the invention, the fluororesin includes at least one of polyvinylidene fluoride (PVDF), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and novel fluoropolymers (EFEP).
In some examples of the invention, the fluorine-containing coupling agent includes at least one of heptadecafluorodecyl trimethoxysilane, perfluorodecyl triethoxysilane, dodecafluoroheptyl propyl methyl dimethoxy silane, perfluorooctyl triethoxysilane.
In some examples of the invention, the inorganic filler comprises at least one of calcium carbonate, silica, titanium dioxide.
In some embodiments of the invention, the inorganic filler has a particle size of 10 to 100nm.
In some examples of the invention, the compatibilizing agent comprises at least one of a maleic anhydride grafted styrene-butadiene block copolymer (SEBS-MAH), a polymethyl methacrylate-methyl butyrate-methyl methacrylate block copolymer (acrylic triblock copolymer), a polystyrene-butadiene-methyl methacrylate block copolymer.
A second aspect of the present invention provides a method for producing the thermoplastic elastomer material, comprising the steps of: and mixing the styrene elastomer after absorbing and filling oil with plasticizing resin, fluororesin, fluorine-containing coupling agent, inorganic filler and compatilizer, and carrying out melt extrusion to obtain the thermoplastic elastomer material.
A third aspect of the present invention provides the use of the thermoplastic elastomer material in the manufacture of outdoor equipment. The thermoplastic elastomer material has excellent ultraviolet resistance, can be used in outdoor environment for a long time, and can be applied to the fields of automobiles, buildings, electronic equipment and the like.
A fourth aspect of the present invention is to provide a thermoplastic elastomer recycled material comprising an a-component and a B-component, the mass ratio of the B-component being 1% to 30% relative to the total mass of the a-component and the B-component;
wherein the component A comprises the following raw materials in parts by mass:
100 parts of styrene elastomer
20-100 parts of filling oil
5 to 20 parts of plasticizing resin
10 to 50 parts of fluororesin
5-40 parts of compatilizer
5-30 parts of inorganic filler
1-15 parts of fluorine-containing coupling agent;
the component B is recovered after aging after mixing, melting and extruding the following raw materials in parts by mass:
100 parts of styrene elastomer
20-100 parts of filling oil
5 to 20 parts of plasticizing resin
10 to 50 parts of fluororesin
5-40 parts of compatilizer
5-30 parts of inorganic filler
1-15 parts of fluorine-containing coupling agent.
The material of the component A with the new formula and the recovered component B are mixed again and extruded in a melting way, so that the recycling of the material can be realized. And the reclaimed materials (component B) can be mixed with the new materials (component A) according to a larger proportion, thereby greatly saving resources.
In some examples of the invention, the mass ratio of the B component is 5% to 20%, preferably 10% to 20%, relative to the total mass of the a component and the B component.
In some examples of the invention, the aging is 100MJ/m 2 And the irradiation dose is preferably 100 to 1500MJ/m 2 More preferably 200 to 1000MJ/m 2 。
In some examples of the invention, the raw material composition of the a-and B-components is the same, or different, preferably the same. The materials for the A and B components are as defined above.
Compared with the prior art, the invention has the following beneficial effects:
the thermoplastic elastomer material has excellent ultraviolet resistance, still has high tensile strength retention rate and fracture tensile rate retention rate after high-dose irradiation, and ensures long-term use of the material in outdoor environment. Meanwhile, the thermoplastic elastomer material can be used as a reclaimed material to be added into a new formula after aging, and meanwhile, the reclaimed material added product is kept to keep the mechanical property equivalent to that of the original new product, so that the thermoplastic elastomer material has good recyclability.
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples. The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the processes used, unless otherwise specified, are all conventional in the art.
The present invention provides a super weatherable, recyclable thermoplastic elastomer material having the composition shown in table 1.
Firstly, placing a styrene elastomer and filling oil into a high-speed mixer to be stirred for 5 minutes, adding plasticizing resin, fluororesin, compatilizer, coupling agent and inorganic filler after the styrene elastomer fully absorbs the filling oil, and stirring at a high speed for 20 minutes; and (3) carrying out melt extrusion, cooling, granulating and drying on the mixed materials by a double-screw extruder to obtain the super weather-resistant recyclable thermoplastic elastomer material.
The obtained super weather-resistant recyclable thermoplastic elastomer material is subjected to aging test, and the test method comprises the following steps: at a temperature of 50+/-2 ℃ and a humidity of 20+/-10%, the wavelength range is 300-400 nm, and the irradiation density is 75W/m 2 The irradiation dose is 400MJ/m 2 Under the condition, the tensile strength and the elongation at break of the thermoplastic elastomer material before and after the irradiation were tested according to ASTM D-412, and the retention of the tensile strength and the retention of the elongation at break after the irradiation compared with those before the irradiation were calculated, and the results are shown in Table 1.
TABLE 1 raw material compositions (parts by mass) and weather resistance test results for thermoplastic elastomer materials of examples 1 to 5
As a comparison, comparative examples 1 to 8 are provided below, corresponding thermoplastic elastomer materials were obtained according to the same preparation method, and weather resistance tests were performed, and the compositions and weather resistance test results of the thermoplastic elastomer materials of comparative examples 1 to 8 are shown in tables 2, 3.
TABLE 2 raw material compositions (parts by mass) and weather resistance test results of comparative examples 1 to 3 thermoplastic elastomer materials
TABLE 3 raw material compositions (parts by mass) and weather resistance test results of comparative examples 4 to 8 thermoplastic elastomer materials
Analysis of tables 1 to 3 can be seen:
(1) Examples 1 to 5 in a thermoplastic elastomer material, a fluororesin and a fluorine-containing coupling agent were added at the same time, and the resulting material absorbed 400MJ/m 2 The retention rate of tensile strength after irradiation dose is above 80%, the retention rate of elongation at break is above 74%, and the anti-aging performance is good.
(2) Comparative examples 1 to 3, compared with examples 1 to 5, eliminate the fluorine-containing coupling agent, and the resulting material showed a significant decrease in the retention of tensile strength and retention of elongation at break after absorbing the same irradiation dose, wherein the retention of tensile strength was reduced to 67.3% or less and the retention of elongation at break was reduced to 66.8% or less, indicating that the weather resistance of the thermoplastic elastomer material could be significantly improved by the addition of the fluorine-containing coupling agent.
(3) Comparative examples 4 to 8 the amount of the fluorine-containing coupling agent was adjusted based on the omission of the fluorine-containing coupling agent in comparative examples 1 to 5. It can be seen that the retention of tensile strength of the obtained material was further reduced to 45.2% and the elongation at break was reduced to 40.8% without the addition of the fluororesin, and the weather resistance was poor, indicating that the addition of the fluororesin was advantageous for improving the weather resistance of the thermoplastic elastomer material. Meanwhile, as the addition amount of the fluororesin increases, the retention rate of the tensile strength and the retention rate of the breaking tensile rate of the thermoplastic elastomer material after irradiation also gradually increase, which further indicates that the addition of the fluororesin contributes to the improvement of the weather resistance of the thermoplastic elastomer material, and the weather resistance is obviously improved along with the increase of the addition amount of the fluororesin.
In addition, example 1 was aged (irradiation dose 400MJ/m 2 ) The resulting material was crushed, granulated, and then added to the same new formulation as in example 1 in different mass ratios, and the tensile strength retention and elongation at break retention before and after the addition of the reclaimed material were calculated as shown in Table 4 below (tensile strength retention and elongation at break retention in Table 4 are both the performance ratios corresponding to the sample without the addition of the reclaimed material).
TABLE 4 influence of different recovery additions on the properties of thermoplastic elastomer materials
| Recycle duty/% | 10 | 20 | 30 | 40 |
| Tensile strength retention/% | 100.3 | 98.6 | 95.3 | 88.7 |
| Elongation at break retention/% | 99.7 | 98.2 | 96.1 | 82.5 |
The result shows that the aged material can be added into the new formula in a higher proportion, and obvious side effects on the mechanical properties of the thermoplastic elastomer material can not be caused when the reclaimed material accounts for 10% -20%, so that the mechanical properties equivalent to those of the new material are maintained, and the reclaimed material has good recyclability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A thermoplastic elastomer material characterized by: the thermoplastic elastomer material comprises the following components in parts by mass:
100 parts of styrene elastomer
20-100 parts of filling oil
5-20 parts of plasticizing resin
10-50 parts of fluororesin
5-40 parts of compatilizer
5-30 parts of inorganic filler
1-15 parts of fluorine-containing coupling agent;
the fluorine-containing coupling agent comprises at least one of heptadecafluorodecyl trimethoxy silane, perfluorodecyl triethoxy silane, dodecafluoroheptyl propyl methyl dimethoxy silane and perfluorooctyl triethoxy silane;
the fluororesin includes at least one of polyvinylidene fluoride and an ethylene-chlorotrifluoroethylene copolymer.
2. The thermoplastic elastomer material according to claim 1, characterized in that: the thermoplastic elastomer material comprises the following components in parts by mass:
100 parts of styrene elastomer
50-100 parts of filling oil
10-15 parts of plasticizing resin
10-50 parts of fluororesin
10-30 parts of compatilizer
10-25 parts of inorganic filler
3-10 parts of fluorine-containing coupling agent.
3. Thermoplastic elastomeric material according to claim 1 or 2, characterized in that: the styrene elastomer comprises at least one of a styrene-butadiene-styrene block copolymer, a styrene-ethylene/butylene-styrene block copolymer, a styrene-ethylene/propylene-styrene block copolymer, and a styrene-ethylene/propylene-styrene block copolymer.
4. Thermoplastic elastomeric material according to claim 1 or 2, characterized in that: the inorganic filler comprises at least one of calcium carbonate, silicon dioxide and titanium dioxide.
5. The method for producing a thermoplastic elastomer material according to any one of claims 1 to 4, characterized in that: the method comprises the following steps: and mixing the styrene elastomer after absorbing and filling oil with plasticizing resin, fluororesin, fluorine-containing coupling agent, inorganic filler and compatilizer, and carrying out melt extrusion to obtain the thermoplastic elastomer material.
6. Use of the thermoplastic elastomer material according to any one of claims 1 to 4 for the manufacture of outdoor equipment.
7. A thermoplastic elastomer recycled material characterized by: the composite material comprises a component A and a component B, wherein the mass ratio of the component B relative to the total mass of the component A and the component B is 1% -30%;
wherein the component A comprises the following raw materials in parts by mass:
100 parts of styrene elastomer
20-100 parts of filling oil
5-20 parts of plasticizing resin
10-50 parts of fluororesin
5-40 parts of compatilizer
5-30 parts of inorganic filler
1-15 parts of fluorine-containing coupling agent;
the component B is recovered after aging after mixing, melting and extruding the following raw materials in parts by mass:
100 parts of styrene elastomer
20-100 parts of filling oil
5-20 parts of plasticizing resin
10-50 parts of fluororesin
5-40 parts of compatilizer
5-30 parts of inorganic filler
1-15 parts of fluorine-containing coupling agent;
the fluorine-containing coupling agent comprises at least one of heptadecafluorodecyl trimethoxy silane, perfluorodecyl triethoxy silane, dodecafluoroheptyl propyl methyl dimethoxy silane and perfluorooctyl triethoxy silane;
the fluororesin includes at least one of polyvinylidene fluoride and an ethylene-chlorotrifluoroethylene copolymer.
8. The thermoplastic elastomer recycled material of claim 7, wherein: the mass ratio of the component B is 5% -20% relative to the total mass of the component A and the component B.
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|---|---|---|---|---|
| JP2008133437A (en) * | 2006-10-30 | 2008-06-12 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer and thermoplastic elastomer composition |
| JP2011057884A (en) * | 2009-09-11 | 2011-03-24 | Asahi Kasei E-Materials Corp | Thermally conductive resin composition and thermally conductive sheet using the same |
| CN104231518A (en) * | 2014-09-12 | 2014-12-24 | 南通普力马弹性体技术有限公司 | Thermoplastic styrene elastomer material and preparation method of thermoplastic styrene elastomer material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008133437A (en) * | 2006-10-30 | 2008-06-12 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer and thermoplastic elastomer composition |
| JP2011057884A (en) * | 2009-09-11 | 2011-03-24 | Asahi Kasei E-Materials Corp | Thermally conductive resin composition and thermally conductive sheet using the same |
| CN104231518A (en) * | 2014-09-12 | 2014-12-24 | 南通普力马弹性体技术有限公司 | Thermoplastic styrene elastomer material and preparation method of thermoplastic styrene elastomer material |
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| 魏忠诚编.《光纤材料制备技术》.北京邮电大学出版社,2016,第302页. * |
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