CN113637283A - High-strength high-resilience TPE (thermoplastic elastomer) thermoplastic elastomer and preparation method thereof - Google Patents
High-strength high-resilience TPE (thermoplastic elastomer) thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN113637283A CN113637283A CN202110977002.6A CN202110977002A CN113637283A CN 113637283 A CN113637283 A CN 113637283A CN 202110977002 A CN202110977002 A CN 202110977002A CN 113637283 A CN113637283 A CN 113637283A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000003086 colorant Substances 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 238000011049 filling Methods 0.000 claims abstract description 11
- -1 polyethylene Polymers 0.000 claims description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 229920001971 elastomer Polymers 0.000 claims description 17
- 239000000806 elastomer Substances 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 150000003440 styrenes Chemical class 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 238000012545 processing Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 3
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 2
- 238000005034 decoration Methods 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 26
- 229920001155 polypropylene Polymers 0.000 description 25
- 239000000155 melt Substances 0.000 description 13
- 239000005662 Paraffin oil Substances 0.000 description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HHKVOYUYPYZFHJ-SOFGYWHQSA-N (e)-3-(3,4-dihydroxyphenyl)-1-phenylprop-2-en-1-one Chemical compound C1=C(O)C(O)=CC=C1\C=C\C(=O)C1=CC=CC=C1 HHKVOYUYPYZFHJ-SOFGYWHQSA-N 0.000 description 1
- 101100325962 Arabidopsis thaliana BHLH80 gene Proteins 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a high-strength high-resilience TPE thermoplastic elastomer, which comprises the following main materials in parts by weight: hydrogenated styrene thermoplastic elastomer, filling oil, plasticizing reinforced resin, high-elastic composition, filler, antioxidant, lubricant and colorant. The TPE thermoplastic elastomer material prepared by processing hydrogenated styrene thermoplastic elastomer, filling oil, plasticizing reinforced resin, a high-elastic composition, a filler, an antioxidant, a lubricant and a coloring agent according to a certain proportion has the advantages of excellent rebound resilience, excellent mechanical property, good handfeel and softness, no toxicity, environmental protection, strong weather resistance, excellent wear resistance, excellent scratch resistance, good processing property, no need of vulcanization, simple processing technology and repeated recycling, can be widely applied to the manufacture of various living goods, industrial goods and outdoor goods, and is also suitable for the manufacture of various inner decorations and linings.
Description
Technical Field
The invention relates to the technical field of TPE (thermoplastic elastomer), in particular to a high-strength high-resilience TPE (thermoplastic elastomer) and a preparation method thereof.
Background
The thermoplastic elastomer TPE is a material with the characteristics of high elasticity, wide hardness range, excellent colorability and injection molding processing of rubber. The performance of the TPE is determined by the microstructure of the TPE, the TPE material does not contain unsaturated bonds, the property is relatively stable, the TPE material contains an ethylene-styrene rigid chain segment which is glassy at normal temperature, the material is endowed with a fixed shape, the service performance is ensured, and the TPE material also contains a butadiene flexible chain segment which is in a high-elastic state at normal temperature, so that the material is endowed with comfortable soft touch and elasticity; the TPE material does not introduce heavy metal in the production process, does not add toxic phthalate plasticizer, and accords with ROHS, REACH, EN71, PAHS and FDA environmental protection detection. The current world production of styrene TPE accounts for about half of all TPEs. However, the current TPE or TPE-based materials have the disadvantages of poor rebound resilience, poor surface scratch resistance, poor matching between mechanical properties and flexibility, etc., and these disadvantages greatly restrict the popularization and application of the TPE or TPE-based materials in some fields.
Disclosure of Invention
The invention aims to solve the problems of the background art, and provides a formula of a high-strength high-resilience TPE material and a preparation method thereof. The TPE thermoplastic elastomer material prepared by the invention has the advantages of excellent rebound resilience, excellent mechanical property, good handfeel flexibility, no toxicity, environmental protection, strong weather resistance, excellent wear resistance and scratch resistance, good processability, no need of vulcanization, simple processing technology and repeated recycling, can be widely applied to the manufacture of various living goods, industrial goods and outdoor goods, and is also applied to the manufacture of various inner ornaments and inner liners.
The purpose of the invention can be realized by the following technical scheme:
a high-strength high-resilience TPE thermoplastic elastomer comprises the following raw materials in parts by weight: 50-200 parts of hydrogenated styrene thermoplastic elastomer, 80-300 parts of filling oil, 10-200 parts of plasticizing reinforced resin, 0-180 parts of high-elastic composition, 0-150 parts of filler, 0.2-4 parts of antioxidant, 0.2-5 parts of lubricant and 0-30 parts of colorant;
wherein the lubricant is one or more of polyethylene wax, erucamide, oleamide, stearate, silicone oil and silicone.
As a further scheme of the invention: the high-elastic composition comprises: one or two blends of thermoplastic polyester elastomer and thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer is a polyether polyurethane elastomer; the thermoplastic polyester elastomer is a linear block copolymer containing polybutylene terephthalate polyester hard segments, aliphatic polyester or polyether soft segments.
As a further scheme of the invention: the filler comprises at least one of talcum powder, diatomite, calcium carbonate, clay, argil and white carbon black, the antioxidant comprises phosphite auxiliary antioxidant and hindered phenol main antioxidant, and the colorant is one or more of inorganic colorant, organic colorant and fluorescent whitening agent.
A preparation method of a TPE thermoplastic elastomer with high strength and high resilience comprises the following specific operation steps:
the method comprises the following steps: adding an oil-extended hydrogenated styrene-based thermoplastic elastomer and an extender oil into a high-speed heating mixer to obtain a styrene-based elastomer mixture;
step two: weighing and sequentially adding a filler, an antioxidant, a coloring agent, a plasticizing reinforced resin and a high-elastic composition on the basis of 100 parts of the prepared styrene-based elastomer mixture, and stirring and mixing to obtain a premix;
step three: and (3) putting the premix into an extruder, controlling the processing temperature of a plasticizing melting zone and a melt conveying zone, and melting, extruding and granulating the premix by the extruder to obtain the TPE thermoplastic elastomer material.
As a further scheme of the invention: in the first step, the high-speed heating mixer is stirred for a set time of 2-40 minutes.
As a further scheme of the invention: in the second step, the stirring time is 3-8 minutes.
As a further scheme of the invention: in the third step, the length-diameter ratio of the twin-screw extruder adopted for extrusion is 20: 1-80: 1, the length-diameter ratio of the single-screw extruder is 15: 1-75: 1.
as a further scheme of the invention: in the third step, the temperature of melt blending extrusion is 180-270 ℃, and the temperature of the first section is controlled below 140 ℃.
The invention has the beneficial effects that:
the TPE thermoplastic elastomer material prepared by the invention has the advantages of excellent rebound resilience, excellent mechanical property, good handfeel flexibility, no toxicity, environmental protection, strong weather resistance, excellent wear resistance and scratch resistance, good processability, no need of vulcanization, simple processing technology, repeated recycling and wide hardness range, provides a larger selection space for product designers, does not generate harmful gas during product processing, and has superiority.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Reference example 1
A high-strength high-resilience TPE thermoplastic elastomer is prepared from the following raw materials: 50-200 parts of hydrogenated styrene thermoplastic elastomer, 80-300 parts of filling oil, 10-200 parts of plasticizing reinforced resin, 0-180 parts of high-elasticity composition, 0-150 parts of filler, 0.2-4 parts of antioxidant, 0.2-5 parts of lubricant and 0-30 parts of colorant.
Wherein the styrene-based elastomer is one or more blends of styrene-butadiene-styrene block copolymer, styrene-ethylene/butylene-styrene block copolymer, styrene-ethylene/propylene-styrene block copolymer and styrene-ethylene/propylene-styrene block copolymer; the molecular weight Mn is more than or equal to 10000, the hydrogenation degree is more than or equal to 98 percent, and the PS block proportion is 25 to 40 percent;
the hydrogenated styrene-based thermoplastic elastomer is a triblock copolymer which is terminated by polystyrene, an ethylene-butylene copolymer obtained by hydrogenating polybutadiene is used as a middle section, and the glass transition temperature of the ethylene-butylene copolymer is-35 ℃.
The filling oil is one or more of paraffin oil, naphthenic oil, straight-chain paraffin oil and aromatic oil, has a flash point of more than 200 deg.C, and has a kinematic viscosity of more than 10mm at 40 deg.C2S; in particular to paraffin oil, the CA is less than or equal to 5, the CN is less than or equal to 40, and the CP is more than or equal to 65.
The plasticizing reinforced resin is one or more blends of polypropylene, polyethylene, polyolefin elastomer, polystyrene, and styrene-butadiene copolymer; preferably, when the plasticizing reinforcing resin contains the copolymerized polypropylene, the content of the copolymerized polypropylene is 10 wt%, the melt index of the copolymerized polypropylene is 0.5g/10min, and the polymerization unit of the copolymerized polypropylene comprises at least one of ethylene, butene, hexene and octene; when the plasticizing reinforced resin contains homopolymerized polypropylene, the content of the homopolymerized polypropylene is 10 wt%, and the melt index of the homopolymerized polypropylene is 0.5g/10 min; when the plasticizing reinforced resin contains polyethylene, the content of the polyethylene is 10 wt%, the melt index of the polyethylene is 0.5g/10min, and the polyethylene comprises at least one of high-density polyethylene, low-density polyethylene and linear low-density polyethylene.
The high-elastic composition comprises: thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, and the like. The thermoplastic polyurethane elastomer is a polyether polyurethane elastomer; the thermoplastic polyester elastomer is a linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segment and aliphatic polyester or polyether soft segment. The thermoplastic polyester elastomer has the characteristics of high strength, high elasticity, oil resistance, acid and alkali resistance, high temperature resistance, excellent dynamic mechanical property and the like, and the use temperature range is-50 ℃.
The filler comprises at least one of talcum powder, diatomite, calcium carbonate, clay, argil and white carbon black; the lubricant is one or more of stearate such as polyethylene wax, erucamide, oleamide, calcium stearate, zinc stearate and the like, silicone oil and silicone;
the antioxidant comprises phosphite ester auxiliary antioxidant and hindered phenol main antioxidant, the hindered phenol main antioxidant is 1076 antioxidant or 1010 antioxidant, and the phosphite ester auxiliary antioxidant is 168 antioxidant or 619F antioxidant.
The colorant is at least one of an inorganic colorant, an organic colorant and a fluorescent brightener.
The invention also provides a preparation method of the TPE material with high strength and high resilience, which comprises the following specific operation steps:
the method comprises the following steps: firstly, weighing the thermoplastic styrene elastomer and the filling oil which can be filled with oil according to the parts by weight, adding the thermoplastic styrene elastomer and the filling oil into a high-speed heating mixer, and stirring for 40 minutes at a high speed to prepare a styrene elastomer mixture with uniform oil absorption;
step two: based on 100 parts of the prepared elastomer mixture, the filler, the antioxidant, the lubricant, the colorant, the plasticizing reinforced resin and the high-elasticity composition are weighed in parts by weight and sequentially added, stirred for 3 minutes and stirred and mixed to obtain a premix, and the rotating speed of a high-speed heating mixer is 10 Hz.
Step three: and (2) putting the fully mixed premix into an extruder, controlling the processing temperature of a plasticizing melting area and a melt conveying area, continuously and quantitatively adding the premix in the first section of the solid conveying area of the extruder by using a metering pump, and melting, extruding and granulating the premix by using the extruder to obtain the TPE thermoplastic elastomer material.
Reference example 2
The difference from the reference example 1 is that:
the glass transition temperature is 0 ℃;
when the plasticizing reinforced resin contains the copolymerized polypropylene, the content of the copolymerized polypropylene is 30 wt%, the melt index of the copolymerized polypropylene is 3.5g/10min, and the polymerization unit of the copolymerized polypropylene comprises at least one of ethylene, butene, hexene and octene; when the plasticizing reinforced resin contains the homopolymerized polypropylene, the content of the homopolymerized polypropylene is 30 wt%, and the melt index of the homopolymerized polypropylene is 3.5g/10 min; when the plasticizing reinforced resin contains polyethylene, the content of the polyethylene is 40 wt%, and the melt index of the polyethylene is 25g/10 min;
stirring for another 5 minutes, stirring and mixing to obtain a premix, and heating at a high speed with the rotating speed of the mixer at 15 Hz.
Reference example 3
The difference from the reference example 1 is that:
the glass transition temperature is 20 ℃;
when the plasticizing reinforced resin contains the copolymerized polypropylene, the content of the copolymerized polypropylene is 60 wt%, the melt index of the copolymerized polypropylene is 5.0g/10min, and the polymerization unit of the copolymerized polypropylene comprises at least one of ethylene, butene, hexene and octene; when the plasticizing reinforced resin contains homopolymerized polypropylene, the content of the homopolymerized polypropylene is 50 wt%, and the melt index of the homopolymerized polypropylene is 5.0g/10 min; when the plasticizing reinforced resin contains polyethylene, the content of the polyethylene is 60 wt%, and the melt index of the polyethylene is 50g/10 min;
stirring for another 8 minutes, stirring and mixing to obtain a premix, and heating at a high speed and at a rotating speed of 25 Hz.
Example 1
A high-strength high-resilience TPE material comprises the following raw materials in parts by weight: 100 parts of hydrogenated styrene thermoplastic elastomer, 150 parts of filling oil, 33 parts of plasticizing reinforced resin, 50 parts of high-elastic composition, 58 parts of filler, 1 part of antioxidant, 0.8 part of lubricant and 7 parts of colorant.
Wherein, the hydrogenated styrene thermoplastic elastomer adopts SEBS7554, the high-elastic composition adopts thermoplastic polyester elastomer, the filling oil adopts paraffin oil, the filler is 800-mesh light calcium carbonate, the antioxidant is obtained by mixing 1010 antioxidant and 168 antioxidant according to the mass ratio of 1:1, and the lubricant adopts silicone master batch. The melt index of the copolymerization polypropylene adopted by the plasticizing reinforced resin is 5.0g/10min, and the melt index of the homopolymerization polypropylene is 10g/10 min.
The preparation method of the TPE material with high strength and high resilience comprises the following steps: the SEBS is firstly heated slowly in a stirrer and mixed for 3min at the rotating speed of 22Hz, then paraffin oil is slowly added and mixed for 30min at the rotating speed of 22Hz, then calcium carbonate, an antioxidant, a colorant, a lubricant, a polyester elastomer and polypropylene are added, the temperature is controlled to be not higher than 75 ℃, the mixture is mixed for 20min, and after discharging, the SEBS is granulated by a co-rotating parallel double-screw extruder to obtain the SEBS. Wherein the feeding speed of the co-rotating parallel double screw extruder is 15rpm/min, the screw speed is 400rpm/min, the length-diameter ratio of the screw is 52:1, the processing temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 210 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 220 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the tenth zone is 220 ℃, the temperature of the eleventh zone is 210 ℃, the temperature of the twelfth zone is 210 ℃ and the temperature of the thirteenth zone is 205 ℃. The extraction is carried out in the front area of the machine head by using a vacuum pump, and the vacuum pressure is lower than 0.01 MPa.
Example 2
A high-strength high-resilience TPE material comprises the following raw materials in parts by weight: 90 parts of hydrogenated styrene thermoplastic elastomer, 130 parts of filling oil, 30 parts of plasticizing reinforced resin, 0 part of high-elastic composition, 35 parts of filler, 1 part of antioxidant, 0.8 part of lubricant and 7 parts of colorant.
Wherein, the hydrogenated styrene thermoplastic elastomer adopts SEBSSYH-503T, and other formula raw materials and the preparation method are the same as the example 1.
Examples 3 to 6
In examples 3-6, the preparation method was the same as that of example 1, and the high-strength and high-resilience TPE material was obtained according to the corresponding raw material ratios in Table 1.
Table 1 examples 3-6 raw material proportioning table (unit: parts by weight):
| raw materials | Example 3 | Example 4 | Example 5 |
| SEBS | 100 | 100 | 100 |
| PP | 23 | 29 | 32 |
| Paraffin oil | 100 | 120 | 100 |
| Light calcium carbonate | 55 | 55 | 55 |
| Polyester elastomer | 75 | 75 | 48 |
| Antioxidant agent | 1 | 1 | 1 |
| Lubricant agent | 0.8 | 0.8 | 0.8 |
| Coloring agent | 7 | 7 | 7 |
Example 4 differs from the starting materials of examples 3 and 5 in that: in example 4, SEBSYH-502 was used as the hydrogenated styrene-based thermoplastic elastomer.
Test example 1
Table 2 comparison of physical properties of the examples:
tensile strength: the measurement standard is DIN53504 and the tensile test rate is 200 mm/min;
tear strength: the measurement standard is ISO34-1 method A;
the elastic body material prepared in the embodiment 3 has better rebound resilience and tearing strength than other embodiments, has moderate hardness and good touch and softness, and the examples 1-4 show that the rating of the raw material SEBS has larger influence on the tearing strength of the TPE material; as can be seen from the combination of examples 1-3, the weight fraction of thermoplastic polyester elastomer in the elastomeric composition has a greater effect on the hand and resilience of the TPE material.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. The high-strength high-resilience TPE thermoplastic elastomer is characterized by comprising the following raw materials in parts by weight: 50-200 parts of hydrogenated styrene thermoplastic elastomer, 80-300 parts of filling oil, 10-200 parts of plasticizing reinforced resin, 0-180 parts of high-elastic composition, 0-150 parts of filler, 0.2-4 parts of antioxidant, 0.2-5 parts of lubricant and 0-30 parts of colorant;
wherein the lubricant is one or more of polyethylene wax, erucamide, oleamide, stearate, silicone oil and silicone.
2. A high strength and high resilience TPE thermoplastic elastomer as claimed in claim 1, wherein said elastomeric composition comprises: one or two blends of thermoplastic polyester elastomer and thermoplastic polyurethane elastomer.
3. The TPE thermoplastic elastomer with high strength and high resilience as claimed in claim 1, wherein the filler comprises at least one of talcum powder, diatomite, calcium carbonate, clay, pottery clay and white carbon black, the antioxidant comprises phosphite-based secondary antioxidant and hindered phenol-based primary antioxidant, and the colorant is one or more of inorganic colorant, organic colorant and fluorescent brightener.
4. A preparation method of a TPE thermoplastic elastomer with high strength and high resilience is characterized by comprising the following specific operation steps:
the method comprises the following steps: adding an oil-extended hydrogenated styrene-based thermoplastic elastomer and an extender oil into a high-speed heating mixer to obtain a styrene-based elastomer mixture;
step two: based on the prepared styrene-based elastomer mixture, sequentially adding a filler, an antioxidant, a coloring agent, a plasticizing reinforced resin and a high-elastic composition, and stirring and mixing to obtain a premix;
step three: and (3) putting the premix into an extruder, and melting, extruding and granulating the premix by the extruder to obtain the TPE thermoplastic elastomer.
5. The method of claim 4 for preparing a high strength and high resilience TPE thermoplastic elastomer is characterized in that: in the first step, the high-speed heating mixer is stirred for a set time of 2-40 minutes.
6. The method of claim 4 for preparing a high strength and high resilience TPE thermoplastic elastomer is characterized in that: in the second step, the stirring time is 3-8 minutes.
7. The method of claim 4 for preparing a high strength and high resilience TPE thermoplastic elastomer is characterized in that: in the third step, the length-diameter ratio of the twin-screw extruder adopted for extrusion is 20: 1-80: 1, the length-diameter ratio of the single-screw extruder is 15: 1-75: 1.
8. the method of claim 4 for preparing a high strength and high resilience TPE thermoplastic elastomer is characterized in that: in the third step, the temperature of melt blending extrusion is 180-270 ℃, and the temperature of the first section is controlled below 140 ℃.
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