CN108456416B - Thermoplastic elastomer composition for low-temperature rubber-coated nylon and preparation method thereof - Google Patents
Thermoplastic elastomer composition for low-temperature rubber-coated nylon and preparation method thereof Download PDFInfo
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- CN108456416B CN108456416B CN201710092080.1A CN201710092080A CN108456416B CN 108456416 B CN108456416 B CN 108456416B CN 201710092080 A CN201710092080 A CN 201710092080A CN 108456416 B CN108456416 B CN 108456416B
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- 229920001778 nylon Polymers 0.000 title claims abstract description 54
- 239000004677 Nylon Substances 0.000 title claims abstract description 51
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229920001971 elastomer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000005060 rubber Substances 0.000 title description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 33
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 33
- 239000000806 elastomer Substances 0.000 claims abstract description 26
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 14
- 239000002480 mineral oil Substances 0.000 claims abstract description 11
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920006132 styrene block copolymer Polymers 0.000 claims description 6
- 150000003440 styrenes Chemical class 0.000 claims description 6
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims 2
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims 1
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 abstract description 14
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- -1 compatilizer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010193 shuanglong Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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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- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a thermoplastic elastomer composition for low-temperature encapsulated nylon and a preparation method thereof, and the composition comprises the following raw materials in percentage by mass: 10% -25%, thermoplastic polyurethane elastomer: 30% -40%, mineral oil: 15% -30%, low-melting polyamide resin: 10% -20%, compatibilizer: 3 to 15 percent. The coating of the composition of the invention, nylon and nylon fiber-added products can be realized by an injection molding machine at a lower temperature under the condition of not using any adhesive; the product also has better bonding effect on nylon and fiber products which are used for many times; the elastomer composition has high tearing strength and fluidity and wide application prospect.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a thermoplastic elastomer material which can be firmly coated on the surface of a nylon material by secondary injection molding or double-color injection molding at a lower injection molding temperature through an injection molding machine without using any adhesive.
Background
The TPE material of thermoplastic elastomer integrates the soft touch feeling of the traditional vulcanized rubber, high elasticity and the thermoplasticity processability of common plastics with a novel material, can be formed independently and can be coated on the plastic materials such as PP, PE, ABS, PC, PA and the like in a secondary injection molding or double-color injection molding mode, so that the inner layer of the TPE material is a plastic product, and the outer layer of the TPE material is a TPE product, so that the TPE product has the rigidity and strength of plastics and the soft touch feeling, shock resistance, slip resistance, insulation and other properties of the TPE product, is environment-friendly, nontoxic, excellent in colorability and recyclable, and is widely applied to the fields such as stationery, toys for children, tool handles and the like.
The TPE product is easy to coat PP, PE, PS, PC, ABS and the like, but the coating of nylon materials, particularly glass fiber reinforced nylon, has a lot of problems, and although a plurality of manufacturers release the nylon coated products, the products really meeting the requirements of customers are few. The existing nylon encapsulated TPE mainly has the following defects: 1. the injection molding temperature of the TPE coated nylon is too high and reaches more than 260 ℃, and the TPE coated nylon is easy to damage nylon products, such as product deformation, sprue sintering and the like. 2. More varieties of nylon, particularly nylon and fiber are added, the recycling of nylon and fiber products can be involved in the injection molding process, the coating effect of part of TPE alloy on some new nylon materials is better, but the adhesion performance of the recycled nylon is poor, so that the application of the recycled nylon is greatly limited.
3. The tearing strength of the nylon coated product is relatively low, and the tearing strength of the nylon coated product in the current market is generally less than 30N/mm, so that the product is easy to tear and damage in the using process.
In the Chinese patent CN201310516549.1, PA6, PA66, TPU and SEBS are directly extruded and blended to improve the polarity of TPE, so that the adhesion between TPE and nylon is realized, but the melting points of PA6 and PA66 are higher, so that the extrusion temperature of the product reaches over 240 ℃, and the high extrusion temperature is very easy to cause the degradation of TPU products, and the unstable adhesion performance and the reduced physical property of the products are caused.
In the chinese patent CN201510700126.4 and chinese patent CN200580007176.9, the anhydride functional group in the maleic anhydride grafted polymer reacts with the terminal amino group in the polyamide to realize coating adhesion, which has the advantage of high adhesion strength of high temperature adhesion nylon, but the encapsulation temperature is above 220 ℃, so the adhesion strength of the TPE product to nylon is poor at low temperature, and deformation of nylon and sintering of the gate are easily caused during high temperature coating.
Disclosure of Invention
Aiming at the defects and defects in the prior art, the invention develops the thermoplastic elastomer material which can be firmly coated on the surface of the nylon material at a lower injection molding temperature without any adhesive through an injection molding machine, and meanwhile, the invention also has better adhesion effect on the repeatedly recycled nylon, and has high tearing strength, good fluidity and wide application range.
In order to achieve the above purpose, the technical solution of the invention is as follows:
a thermoplastic elastomer composition (also referred to as TPE/TPU alloy) for low temperature encapsulated nylon comprising the following components in mass percent based on the total mass of the composition:
hydrogenated styrenic thermoplastic elastomer: 10% -25%, preferably 15% -24%;
thermoplastic polyurethane elastomer: 30% -40%, preferably 31% -35%;
low-melting polyamide resin: 10% -20%, preferably 12% -18%;
a compatilizer: 3% -15%, preferably 5% -14%;
mineral oil: 15% -30%, preferably 16% -25%.
In the present invention, the hydrogenated styrene-based thermoplastic elastomer is preferably at least one of a hydrogenated styrene butadiene styrene block copolymer (SEBS), a hydrogenated styrene isoprene styrene block copolymer (SEPS) and a hydrogenated styrene butadiene/isoprene styrene block copolymer (SEEPS) having a number average molecular weight of 20000 to 300000, and is preferably an SEBS having a number average molecular weight of 70000 to 200000. The elastomer component can not only improve the flexibility and rebound resilience of the alloy, but also improve the surface hand feeling and the skid resistance of the alloy, and the products are in a wide variety of markets, such as G1650, G1651, G1652, G1657, A1535, A1536, 1750 and the like of the Cortenus corporation; 6150,6151, 6152, 6154, etc. of Taiwan rubber company; 9550, 9551, 9552, 9554, etc. of taiwan Li Changrong; 501, 502, 503 and the like of Yueyang petrochemical in Hunan; 4033, 4055, 8004, 8006, 1020, 2104, 4077, and the like, of jequiry, japan.
In the present invention, the thermoplastic polyurethane elastomer (TPU) is one or more of polyester thermoplastic polyurethane, polyether thermoplastic polyurethane, polycarbonate thermoplastic polyurethane and polycaprolactone thermoplastic polyurethane in any combination, preferably polyester and/or polyether thermoplastic polyurethane with a hard segment content of 15wt.% to 50wt.%, and a tensile strength of 12 to 50MPa, and more preferably polyester thermoplastic polyurethane with a hard segment content of 20wt.% to 40wt.%, and a tensile strength of 15 to 40 MPa. By controlling the hard segment content and the tensile strength of the TPU components, the alloy product has the characteristics of low hardness, high strength and high polarity, and the hand feeling comfort level of the product and the bonding performance of nylon are improved. The specific product market has: WHT-1180, WHT-1185, WHT-1560, WHT-1565, WHT-1570, WHT-1575, WHT-1580, WHT-8170, WHT-8180, WHT-8185 and the like of Wanhua chemical group GmbH. The meaning of hard segment: the TPU is synthesized by three raw materials, namely oligomer diol, a chain extender and isocyanate, wherein the oligomer diol provides a soft segment, a urethane group generated by the reaction of the chain extender and the diisocyanate provides a hard segment, and the content of the hard segment refers to the weight fraction of the hard segment in the TPU.
In the invention, the mineral oil is one or more of paraffin oil and naphthenic oil with aromatic hydrocarbon (CA) content less than 20% and a flash point of 180-260 ℃, preferably paraffin oil (white oil) with a flash point of 200-260 ℃, and the white oil with a high flash point can reduce heat loss of the white oil in the processing process of the alloy and improve the compatibility of the white oil and matrix resin. The method specifically comprises the following steps: 150N, 250N, 500N of Korea Shuanglong; 150N, 500N of Taiwan Taidai; KN4006 and KN4010 of Kelamayi, xinjiang.
In the invention, the low-melting point polyamide resin is polyamide resin with the melting point of 50-220 ℃ and the average carbon number between amido bonds in a molecular chain of 5-20, wherein the melting point test method is a DSC method, and the polyamide resin comprises copolyamide, hydroxymethylated polyamide, low-molecular weight polyamide resin (the melting point is polyamide resin with the temperature of 60-200 ℃) and polyamide elastomer, preferably copolyamide and/or polyamide elastomer with the melting point of 50-180 ℃ and the average carbon number between amido bonds in the molecular chain of 6-12. Because the polyamide resin has the characteristics of low melting point and high polarity, the processing temperature of the alloy can be reduced, and the compatibility between the alloy and a nylon product can be improved. Specific commercial products are: temperature ofHT-8100, HT-8113, of state Walter; anhui Yuhong HY-208 and HY-288; PEBAX elastomers 2533, 3533, 4033 from arkema, france, etc. The average carbon number between amide bonds in the molecular chain means the average carbon number between two amides (carbon atoms in the amide bond) in the polyamide resin, and for example, the average carbon number of the polyamide in the following formula is 6
In the invention, the compatilizer is: one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted styrene block copolymer, maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted ethylene propylene diene monomer rubber and amino terminated styrene block copolymer, and maleic anhydride grafted styrene block copolymer and/or maleic anhydride grafted ethylene-octene copolymer are preferred. The commercial varieties are numerous, and specifically include: kraton FG1901, FG1924 (maleic anhydride grafted hydrogenated styrene butadiene styrene block copolymer); nanjing plastomer ST-6 (maleic anhydride grafted polyethylene), POE-1 (maleic anhydride grafted ethylene-octene copolymer); dupont C250 (maleic anhydride grafted ethylene vinyl acetate copolymer); shanghai Cambridge NG1202 (maleic anhydride grafted polyethylene), NG8002 (maleic anhydride grafted ethylene propylene diene monomer), NG8003 (maleic anhydride grafted ethylene propylene diene monomer) and the like.
In the invention, the elastomer composition also comprises a filler and an auxiliary agent, and the elastomer composition can be filled with inert fillers such as calcium carbonate, barium sulfate, kaolin and the like to reduce the cost of the material; the addition amount of the filler is 0.1-30%, based on the total mass of the composition, a plurality of manufacturers for domestic production of calcium carbonate, such as a new Fujian southeast material, guangdong Zhongqi chess and the like, can add an antioxidant, an ultraviolet light absorber, a light stabilizer, a lubricant and other auxiliaries to improve the aging resistance of the product, the specific manufacturers of the antioxidant, the ultraviolet light absorber and the light stabilizer, such as BASF Ciba Fine chemical industry, li Anlong, taiwan double bond and the like, the manufacturers of the lubricant, such as British grass additive, high-density eastern chemical industry and the like, the addition amount is 0.1-3%, based on the total mass of other components in the composition except the filler.
In the invention, the preparation process of the thermoplastic elastomer composition for low-temperature encapsulated nylon is as follows: the hydrogenated styrene thermoplastic elastomer and the mineral oil are uniformly mixed according to a specified proportion, the thermoplastic polyurethane elastomer, the low-melting-point polyamide resin, the compatilizer, the filler and the auxiliary agent are added after the surface of the hydrogenated styrene thermoplastic elastomer is completely dry, and then the mixture is fully and uniformly mixed. And uniformly adding the mixed materials into a double-screw extruder through a feeder, wherein the temperature of the double-screw extruder is set to be 180-220 ℃, the feeding speed is set to be 20-50 revolutions per minute, and the rotating speed of a screw is set to be 200-400 revolutions per minute. Shearing at high speed by a double-screw extruder, mixing and plasticizing, bracing by an extruder head, cooling, plasticizing, granulating, drying and packaging.
The invention is a thermoplastic elastomer prepared by using hydrogenated styrene thermoplastic elastomer and TPU as matrix resin, because the composition is bonded with nylon Long Jiti in a physical bonding mode, and simultaneously, the composition has high fluidity, high polarity and compatibility with nylon resin, the product can coat and bond nylon and nylon fiber products at lower temperature, and has strong bonding force, high strength and good fluidity; meanwhile, the bonding performance of the product and nylon is not influenced by the recycling times of nylon, and the product can be coated and bonded with various recycled nylon and nylon fiber products. Therefore, the handle can be widely applied to industrial tool handles with higher requirements, and has remarkable economic and social benefits.
Detailed Description
The present invention will be further illustrated with reference to specific examples, but the scope of the present invention is not limited to these examples.
Fully mixing hydrogenated styrene thermoplastic elastomer and mineral oil until the surface of the elastomer is dry, then fully mixing the elastomer with thermoplastic polyurethane elastomer, low-melting-point polyamide, compatilizer, filler and auxiliary agent, and then carrying out high-speed shearing, mixing and granulation in an SHJ-42 twin-screw extruder of Nanjing Jieya extrusion equipment Limited company, wherein the temperature settings of each zone of the screw are respectively as follows: temperature in the first zone: the temperature of 180 ℃, the temperature of the second zone is 185 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 200 ℃, the temperature of the eighth zone is 195 ℃, the temperature of the ninth zone is 185 ℃ and the temperature of the neck mold is 180 ℃. The feed rate was set at 40 rpm, the screw speed was set at 400 rpm, and the elastomer particles were then overmolded with nylon and nylon fiber-reinforced material on a Haitian SA900 injection molding machine.
Hardness was measured according to ASTM D4420,
tensile strength and elongation at break were tested according to ASTM D412,
melt index was measured according to ASTM D1238 under 200 deg.C/5 kg.
The coating strength of the elastomer and the nylon matrix is tested according to GB/T2790-1995, wherein the bonding base material A is B30S of BASF, and the material is PA6; the adhesive base material B is B3EG6 of BASF, and the material is PA6+30% glass fiber material; b-1 is a recycled nylon material obtained by performing injection molding and crushing on B3EG6 for one time; and B-2 is a recycled nylon material obtained by performing secondary injection molding and crushing on B3EG 6.
The specific formulation is listed below in the table,
SEBS is 6151 and 6150,6151 of Taiwan rubber industry, the number average molecular weight is 20 ten thousand, and the number average molecular weight of 6150 is 8 ten thousand; SEPS is 1750 for american kraton polymer with a number average molecular weight of 8 ten thousand; SEEPS is 4077 from Coly, japan, and has a number average molecular weight of 10 ten thousand.
The hard segment content of the TPU is 20wt.% and the tensile strength is 25MPa for polyester TPU1560, 1570, 1575 and polyether TPU8170,1560 of Wanhua chemical group GmbH; 1570 hard segment content 25wt.%, tensile strength 28MPa;1575 hard segment content 28wt.% and tensile strength 30MPa.8170 has a hard segment content of 30wt.% and a tensile strength of 30MPa.
The mineral oil is 150N and 500N paraffin oil of Korean Bilong, wherein 150N flash point is 200 deg.C, and aromatic hydrocarbon content is less than 5%; the flash point of 500N is 230 ℃, and the aromatic hydrocarbon content is less than 5 percent
The naphthenic oil is 4010 refined by Xinjiang krameri, the flash point of the 4010 is 190 ℃, and the aromatic hydrocarbon content is less than 5%.
The low-melting-point polyamide resin is HT-8100 of Wenzhou Walter and a nylon elastomer 4033 and HT-8100 of Fangnational ARKRMA, the melting point of the low-melting-point polyamide resin is 80 ℃, and the average carbon atom number among amido bonds in a molecular chain is 10;4033 has a melting point of 170 ℃ and an average number of carbon atoms between amide bonds in the molecular chain of 12.
The compatibilizer was 1901 (SEBS grafted maleic anhydride) from Keteng, POE-1 (POE grafted maleic anhydride) from Nanjing plastetant, C250 (EVA grafted maleic anhydride) from Dupont chemical, NG8002 (EDPM grafted maleic anhydride) from Cambridge, shanghai.
The filler is 1250-mesh calcium carbonate of a new material in southeast of Fujian province, the antioxidant is B900 of Ciba fine chemical engineering, and the lubricant is zinc stearate of high-density commercial eastern chemical engineering.
Table 1:
table 2:
compared with the prior physical and chemical coating system, the product has better adhesive performance to nylon and nylon fiber base materials at 180 ℃, the adhesive temperature is reduced by about 20-40 ℃ compared with the prior nylon coating system, and the peel strength is gradually increased along with the increase of the temperature. Meanwhile, the product has better adhesive property for the nylon and fiber products which are recycled for many times, the recycling times basically do not influence the adhesive strength of the product and the nylon and fiber, and the tearing strength and the fluidity of the product are also obviously higher than those of the conventional nylon coating system.
The above-described embodiments are illustrative, but not restrictive, of the spirit of the invention, and any modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (16)
1. The thermoplastic elastomer composition for low-temperature encapsulated nylon is characterized by comprising the following components in percentage by mass:
hydrogenated styrenic thermoplastic elastomer: 10% -25%;
thermoplastic polyurethane elastomer: 30% -40%;
low-melting polyamide resin: 10% -20%;
a compatilizer: 3% -15%;
mineral oil: 15% -30%;
the low-melting-point polyamide resin is copolyamide and/or polyamide elastomer with the melting point of 50-180 ℃ and the average carbon atoms between amide bonds in molecular chains of 6-12.
2. The thermoplastic elastomer composition according to claim 1, comprising the following components in mass percent:
hydrogenated styrenic thermoplastic elastomer: 15% -24%;
thermoplastic polyurethane elastomer: 31% -35%;
low-melting polyamide resin: 12% -18%;
a compatilizer: 5% -14%;
mineral oil: 16 to 25 percent.
3. The thermoplastic elastomer composition of claim 1, wherein the hydrogenated styrenic thermoplastic elastomer is selected from one or more of SEBS, SEPS, SEEPS having a number average molecular weight of 20000 to 300000.
4. The thermoplastic elastomer composition according to claim 3, wherein said hydrogenated styrenic thermoplastic elastomer is selected from the group consisting of SEBS having a number average molecular weight of 70000 to 200000.
5. The thermoplastic elastomer composition of claim 1, wherein the thermoplastic polyurethane elastomer is one or more of a polyester thermoplastic polyurethane, a polyether thermoplastic polyurethane, and a polycarbonate thermoplastic polyurethane.
6. The thermoplastic elastomer composition of claim 5 wherein said polyester thermoplastic polyurethane is a polycaprolactone thermoplastic polyurethane.
7. The thermoplastic elastomer composition of claim 5, wherein the thermoplastic polyurethane elastomer is a polyester and/or polyether thermoplastic polyurethane having a hard segment content of 15wt.% to 50wt.% and a tensile strength of 12 to 50 MPa.
8. The thermoplastic elastomer composition of claim 7 wherein the thermoplastic polyurethane elastomer is a polyester thermoplastic polyurethane having a hard segment content of 20wt.% to 40wt.% and a tensile strength of 15 to 40 MPa.
9. The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein: the mineral oil is one or more of paraffin oil and naphthenic oil with aromatic hydrocarbon content less than 20% and flash point of 180-260 ℃.
10. The thermoplastic elastomer composition according to claim 9, wherein the mineral oil is a paraffin oil having a flash point of 200 to 260 ℃.
11. The thermoplastic elastomer composition of any one of claims 1-8, wherein the compatibilizer is: one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted styrene block copolymer, maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted ethylene propylene diene monomer rubber and amino terminated styrene block copolymer.
12. The thermoplastic elastomer composition of claim 11, wherein the compatibilizer is: maleic anhydride grafted styrene block copolymers and/or maleic anhydride grafted ethylene-octene copolymers.
13. The thermoplastic elastomer composition according to any one of claims 1 to 8, further comprising a filler selected from one or more of calcium carbonate, barium sulfate and kaolin in an amount of 0.1 to 30% based on the total mass of the composition and an auxiliary selected from one or more of an antioxidant, an ultraviolet light absorber, a light stabilizer and a lubricant in an amount of 0.1 to 3% based on the total mass of the other components in the composition.
14. A process for the preparation of a thermoplastic elastomer composition as claimed in any one of claims 1 to 13, comprising the steps of:
fully mixing hydrogenated styrene thermoplastic elastomer and mineral oil until the surface of the elastomer is dry, then fully mixing the elastomer with thermoplastic polyurethane elastomer, low-melting-point polyamide resin, compatilizer, filler and auxiliary agent, and extruding and granulating the mixed material through a double-screw extrusion system.
15. The method of claim 14, wherein the mixed material is fed into a twin-screw extruder through a feeder, the temperature of the twin-screw extruder is set to be 180 ℃ to 220 ℃, the feeding speed is set to be 20 to 50 rpm, and the screw rotation speed is set to be 200 to 400 rpm.
16. Use of the thermoplastic elastomer composition according to any one of claims 1 to 13 or the thermoplastic elastomer composition obtained by the production method according to any one of claims 14 to 15 for coating nylon or nylon-fiber-reinforced articles.
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| US11697733B2 (en) | 2019-01-09 | 2023-07-11 | Avient Corporation | Thermoplastic polyurethane compounds exhibiting stain resistance and enhanced UV stability |
| CN113272385A (en) | 2019-01-09 | 2021-08-17 | 艾维恩股份有限公司 | Thermoplastic polyurethane compounds exhibiting improved stain resistance |
| US20220081561A1 (en) * | 2019-01-09 | 2022-03-17 | Avient Corporation | Thermoplastic polyurethane compounds exhibiting enhanced stain resistance |
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