CN114752172B - Thermoplastic elastomer composition and preparation method and application thereof - Google Patents

Thermoplastic elastomer composition and preparation method and application thereof Download PDF

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CN114752172B
CN114752172B CN202210321467.0A CN202210321467A CN114752172B CN 114752172 B CN114752172 B CN 114752172B CN 202210321467 A CN202210321467 A CN 202210321467A CN 114752172 B CN114752172 B CN 114752172B
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thermoplastic elastomer
parts
pbat
elastomer composition
preparation
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CN114752172A (en
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陈炜鑫
陈平绪
叶南飚
郑明嘉
叶林铭
王刚
赵巍
邱贤亮
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Kingfa Science and Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions 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
    • C08L53/02Compositions 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
    • C08L53/025Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06Waxes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate

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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)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a thermoplastic elastomer composition, a preparation method and application thereof, and the thermoplastic elastomer composition comprises the following components in parts by weight: 5-30 parts of nonpolar thermoplastic elastomer, 5-40 parts of polar thermoplastic elastomer, 0.1-10 parts of tackifying resin, 5-40 parts of plasticizer, 0-20 parts of plastic, 0-50 parts of filler and 0-5 parts of auxiliary agent. The thermoplastic elastomer composition provided by the invention has good compatibility with PBAT, high fitting degree with the surface of PBAT, and is suitable for preparing PBAT rubber-coated products.

Description

Thermoplastic elastomer composition and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a thermoplastic elastomer composition, and a preparation method and application thereof.
Background
Thermoplastic elastomer (TPE) material is a novel polymer material between rubber and resin, can replace part of rubber, can modify plastic, and is increasingly applied in the fields of automobile industry, electronic appliances, wires and cables and the like.
The PBAT belongs to thermoplastic biodegradable plastics, is a copolymer of butanediol adipate and polybutylene terephthalate, has the characteristics of PBA and PBT, has good ductility and elongation at break, and has good heat resistance and impact resistance; in addition, the material also has excellent biodegradability, and is one of the best degradable materials which are very active in the research of biodegradable plastics and are applied to the market. Bio-based plastics cover a wide range of applications including packaging, food and beverage products, consumer electronics, automotive, agricultural/horticultural and toys, textiles and the like.
Thermoplastic elastomers are processed by encapsulation and injection molding, and commonly used products such as handles, grips, electronic materials and the like. The material gives the product comfortable touch, improves the holding property, improves the aesthetic degree of the product and the added value of the product, and can also improve the anti-falling performance of the plastic product. The molding process of the rubber coating injection bonding comprises 1) adopting a secondary injection molding process, namely fixing an injection molded hard material piece on a rubber coating mold, injecting and bonding a thermoplastic elastomer on the hard material piece at a proper temperature, and cooling to obtain the product. 2) And (3) double-color injection molding, namely, after the hard material is molded, rotating a mold, injecting and sticking the thermoplastic elastomer to the hard material workpiece, and cooling to obtain the product.
The rubber coating is formed by using the compatibility of soft rubber and hard rubber in softening and melting, the better the compatibility of the two materials is, the easier the adhesion is, and a layer of bonding layer is formed on the contact surface of the hard rubber and the soft rubber, so that the rubber coating adhesion of the soft rubber and the hard plastic is greatly improved. The injection molding temperature of the encapsulation injection molding varies depending on the hard gum material of the encapsulation. Because the temperature needs to be considered, the hard rubber and the soft rubber are softened, and the two materials can be promoted to achieve certain compatibility at the contact surface.
Because the polarity of the TPE material is weaker at present, the compatibility between the TPE material and the molecules of the material with strong polarity is poor, and the TPE material has the problems of poor encapsulation effect and poor bonding effect when being used for encapsulating the molecules of the material with strong polarity. Although PBAT is used as a material with strong polarity, the thermoplastic elastomer still cannot achieve stronger adhesiveness to the PBAT encapsulation, because the nonpolar olefin chain segment in the PBAT molecular structure is longer, the flexibility is better, the molecular chain mobility is better, the Van der Waals force formed by the polar elastomer and the ester group in the PBAT is easily broken by the internal force of the molecular chain mobility, and the adhesiveness cannot be stably formed, so that the TPE coated PBAT still belongs to the technical difficulty.
Disclosure of Invention
In order to solve the above-mentioned shortcomings in the prior art, an object of the present invention is to provide a thermoplastic elastomer composition, a preparation method and an application thereof, which can improve the compatibility between the thermoplastic elastomer composition and PBAT and the adhesion between the thermoplastic elastomer composition and PBAT.
In order to achieve the purpose, the invention adopts the following technical scheme: a thermoplastic elastomer composition comprising the following components in parts by weight: 5-30 parts of nonpolar thermoplastic elastomer, 5-40 parts of polar thermoplastic elastomer, 0.1-10 parts of tackifying resin, 5-40 parts of plasticizer, 0-20 parts of plastic, 0-50 parts of filler and 0-5 parts of auxiliary agent;
The non-polar thermoplastic elastomer comprises at least one of the following copolymers: (a) Copolymers obtained by polyaddition of two or more of styrene, butadiene and isoprene; (b) A copolymer obtained by subjecting two or more of styrene, butadiene and isoprene to addition polymerization to a re-hydrogenation;
In certain embodiments of the present invention, the non-polar thermoplastic elastomer is selected from one of a styrene-butadiene copolymer, a styrene-isoprene copolymer, a butadiene-isoprene copolymer, a styrene-butadiene-isoprene copolymer, a hydrogenated styrene-butadiene copolymer, a hydrogenated styrene-isoprene copolymer, a hydrogenated butadiene-styrene copolymer, a styrene-hydrogenated isoprene copolymer, a butadiene-hydrogenated isoprene copolymer, a hydrogenated styrene-butadiene-isoprene copolymer, a styrene-hydrogenated butadiene-isoprene copolymer, a styrene-butadiene-hydrogenated isoprene copolymer, a hydrogenated styrene-hydrogenated butadiene-isoprene copolymer, a styrene-hydrogenated butadiene-hydrogenated isoprene copolymer, a hydrogenated styrene-hydrogenated butadiene-hydrogenated isoprene copolymer. The nonpolar thermoplastic elastomer is not limited to the above list. It is understood that the non-polar thermoplastic elastomers may be used in the present system to improve the adhesion of the thermoplastic elastomer composition to the PBAT material.
In certain embodiments of the present invention, the polar thermoplastic elastomer is one or a combination of polyurethane, nylon-based elastomer, ethylene vinyl acetate copolymer, ethylene- (meth) acrylate. The polar thermoplastic elastomer is not limited to the above list. It is understood that polar thermoplastic elastomers may be used in the present system to improve the adhesion of the thermoplastic elastomer composition to the PBAT material.
According to the invention, the ester group (-COOR 1) in the polar thermoplastic elastomer and the ester group (-COOR 2) in the PBAT are utilized to carry out ester exchange reaction to improve the compatibility of the thermoplastic elastomer composition and the PBAT, and the tackifying resin is added to improve the compatibility of the nonpolar thermoplastic elastomer and the polar thermoplastic elastomer, so that the excellent adhesive property with the PBAT material is finally obtained.
Preferably, the thermoplastic elastomer composition comprises the following components in parts by weight:
Preferably, the tackifying resin is one or more of rosin resin, epoxy resin and phenolic resin. By adding a tackifying resin containing hydroxyl or epoxy groups, the compatibility of the nonpolar thermoplastic elastomer with the polar thermoplastic elastomer can be improved, and more preferably the tackifying resin has a relative molecular weight of less than 1000. The tackifying resin with low molecular weight is beneficial to improving the molecular chain activity of the thermoplastic elastomer, can be more fully contacted and reacted with PBAT molecular chains, and improves the encapsulation firmness.
Preferably, the plasticizer is one or more of paraffin oil, naphthenic oil, lipid plasticizer and petroleum resin.
Preferably, the plastic is one or more of polyethylene, polypropylene and polystyrene.
Preferably, the filler is one or more of calcium carbonate, talcum powder, wollastonite, mica, kaolin and silicon dioxide.
Preferably, the auxiliary agent is one or more of an antioxidant, a light stabilizer, a lubricant and an anti-hydrolysis agent.
The invention also provides a preparation method of the thermoplastic elastomer composition, which comprises the following steps:
Putting the nonpolar thermoplastic elastomer into a mixer, adding the plasticizer while stirring, and uniformly mixing to obtain a first mixture;
mixing the first mixture with other various materials to obtain a second mixture;
putting the second mixture into a double-screw extruder, extruding, granulating and drying to obtain a finished product;
The extrusion temperature of the double-screw extruder is 160-210 ℃, the heating length-diameter ratio of the obtained double-screw extruder is 36-60/1, and the residence time of materials in the screw is 30-80 s.
The invention also provides application of the thermoplastic elastomer composition in preparation of PBAT encapsulated products.
Preferably, the method comprises the following steps: the thermoplastic elastomer composition is adhered to the PBAT surface by an injection molding or embossing process.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the ester group (-COOR 1) in the polar thermoplastic elastomer and the ester group (-COOR 2) in the PBAT are utilized to carry out ester exchange reaction to improve the compatibility of the thermoplastic elastomer composition and the PBAT, and the tackifying resin is added to improve the compatibility of the nonpolar thermoplastic elastomer and the polar thermoplastic elastomer, so that the excellent adhesive property with the PBAT material is finally obtained.
Detailed Description
The technical solution of the present invention will be further described with reference to the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The starting materials used in the examples and comparative examples were all commercially available and the same was used in the parallel experiments.
The sources of the raw materials are as follows, but are not limited to:
nonpolar thermoplastic elastomer: styrene-butadiene copolymer, SEBS 1651, koteng.
Polar thermoplastic elastomer: polyurethane, TPU (TPU WHT-1885, wanhua);
Maleic anhydride grafted SEBS: SEBS FG1901, koteng;
Tackifying resin:
Rosin resin: foralyn 90A 90, isman, with a relative molecular weight of 300, was measured by gel chromatography.
Epoxy resin: CYD-011, baling petrochemical, has a relative molecular weight of 800, and is tested by gel chromatography.
Epoxy resin: CYD-017, baling petrochemical, relative molecular weight 1500, test method is gel chromatography.
And (3) a plasticizer: 90# white oil, PW-90, japan glows.
And (3) plastic: polypropylene: PP HP500N, middle sea shell
And (3) filling: heavy calcium carbonate, commercially available.
An antioxidant: irganox 1010, irgafos 168, commercially available.
Light stabilizers: cyasorb UV-3808pps, commercially available.
Preparation method
The thermoplastic elastomer compositions of examples 1 to 8 and comparative examples 1 to 6 were prepared as follows:
Putting the nonpolar thermoplastic elastomer into a mixer, adding the plasticizer while stirring, and uniformly mixing to obtain a first mixture;
mixing the first mixture with other various materials to obtain a second mixture;
putting the second mixture into a double-screw extruder, extruding, granulating and drying to obtain a finished product;
The extrusion temperature of the double-screw extruder is 160-210 ℃, the heating length-diameter ratio of the obtained double-screw extruder is 36-60/1, and the residence time of materials in the screw is 30-80 s.
Performance testing
The test is carried out according to the measurement standard VDI 2019, a PBAT rectangular plate with the thickness of 150 mm and 40mm and with the thickness of 2.0mm is manufactured by injection molding or mould pressing of a PBAT material, then the PBAT rectangular plate is placed into an encapsulation mould, and the thermoplastic elastomers of the examples 1-8 and the comparative examples 1-4 are adhered to the surface of the PBAT rectangular plate by injection molding or mould pressing of the PBAT rectangular plate. The thermoplastic elastomer soft gels of examples 1 to 8 and comparative examples 1 to 4 were peeled from the encapsulation test plate using a universal tester using a special jig, and the force during peeling was measured and recorded.
Test results
The thermoplastic elastomer composition formulations (parts by weight) and the performance test results of examples 1 to 8 are shown in Table 1:
TABLE 1
The thermoplastic elastomer composition formulations (parts by weight) and the performance test results of comparative examples 1 to 6 are shown in Table 2:
TABLE 2
Analysis of results
As is clear from comparative examples 1 and 2, comparative example 1 does not add tackifying resin, comparative example 2 adds only 0.05% tackifying resin, comparative example 1 has an encapsulation peel strength of 1.1N/mm, comparative example 2 has an encapsulation peel strength of 1.3N/mm, and has low encapsulation peel strength and poor adhesion. The encapsulation peel strength of the embodiment 1 of the invention is 5.3N/mm, the encapsulation effect is obviously better than that of the comparative example, and the thermoplastic elastomer composition has high adhesive strength with a PBAT rectangular plate and excellent encapsulation effect in the peeling process.
Comparative example 3 and comparative example 3, comparative example 3 did not incorporate a polar thermoplastic elastomer, resulting in an encapsulation peel strength of only 1.3N/m. Comparative example 3 and comparative example 4, comparative example 4 did not add a nonpolar thermoplastic elastomer, resulting in an encapsulation peel strength of only 1.0N/m, and it was found that the addition of both the polar thermoplastic elastomer and the nonpolar thermoplastic elastomer was necessary to obtain a good encapsulation effect.
Comparing examples 1-7 with example 8, the tackifying resin in example 8 has a molecular weight greater than 1000, resulting in an encapsulation peel strength of only 2.5N/m, and it is seen that a relative molecular weight of less than 1000 is beneficial for improving encapsulation robustness.
As can be seen from comparative examples 1 and comparative examples 5 to 6, the compositions of comparative examples 5 and 6 failed to achieve good encapsulation when coating PBAT.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and the present invention may also have other embodiments according to the above structures and functions, which are not listed one by one; although the invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention.

Claims (7)

1. Use of a thermoplastic elastomer composition for the preparation of a PBAT encapsulated article, characterized in that the thermoplastic elastomer composition comprises the following components in parts by weight:
5-30 parts of nonpolar thermoplastic elastomer;
5-40 parts of polar thermoplastic elastomer;
0.1-10 parts of tackifying resin;
5-40 parts of plasticizer;
0-20 parts of plastic;
0-50 parts of filler;
0-5 parts of auxiliary agent;
the non-polar thermoplastic elastomer comprises at least one of the following copolymers: (a) Copolymers obtained by addition polymerization of two or three of styrene, butadiene and isoprene; (b) A copolymer obtained by the addition polymerization of two or three of styrene, butadiene and isoprene, and a copolymer obtained by the hydrogenation of the two or three of styrene, butadiene and isoprene;
The polar thermoplastic elastomer is polyurethane;
The tackifying resin is rosin resin;
The tackifying resin has a relative molecular weight of less than 1000;
the thermoplastic elastomer composition is a thermoplastic elastomer composition for use in preparing PBAT encapsulated articles.
2. Use of the thermoplastic elastomer composition according to claim 1 for the preparation of PBAT encapsulated articles, comprising the following components in parts by weight:
15-29 parts of nonpolar thermoplastic elastomer;
10-39 parts of polar thermoplastic elastomer;
0.3-5 parts of tackifying resin;
5-40 parts of plasticizer;
0-20 parts of plastic;
0-50 parts of filler;
0-5 parts of auxiliary agent.
3. Use of a thermoplastic elastomer composition according to claim 1 or 2 for the preparation of PBAT encapsulated articles, wherein the plasticizer is one or more of paraffinic oil, naphthenic oil, ester plasticizer, petroleum resin; the plastic is one or more of polyethylene, polypropylene and polystyrene.
4. Use of a thermoplastic elastomer composition according to claim 1 or 2 for the preparation of PBAT encapsulated articles, wherein the filler is one or more of calcium carbonate, talc, wollastonite, mica, kaolin, silica.
5. Use of a thermoplastic elastomer composition according to claim 1 or 2 for the preparation of a PBAT encapsulated article, wherein the auxiliary agent is one or more of an antioxidant, a light stabilizer, a lubricant, an anti-hydrolysis agent.
6. Use of the thermoplastic elastomer composition according to claim 1 for the preparation of PBAT encapsulated articles, wherein the thermoplastic elastomer composition is adhered to the PBAT surface by injection molding or compression molding process.
7. Use of the thermoplastic elastomer composition according to claim 1 for the preparation of PBAT encapsulated articles, wherein the preparation process of the thermoplastic elastomer composition comprises the steps of:
Putting the nonpolar thermoplastic elastomer into a mixer, adding the plasticizer while stirring, and uniformly mixing to obtain a first mixture;
mixing the first mixture with other various materials to obtain a second mixture;
putting the second mixture into a double-screw extruder, extruding, granulating and drying to obtain a finished product;
The extrusion temperature of the double-screw extruder is 160-210 ℃, the length-diameter ratio of the double-screw extruder is 36-60/1, and the residence time of materials in the screw is 30-80 s.
CN202210321467.0A 2022-03-30 2022-03-30 Thermoplastic elastomer composition and preparation method and application thereof Active CN114752172B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02160886A (en) * 1989-11-24 1990-06-20 Maruzen Petrochem Co Ltd Hot-melt adhesive composition
CN103554819A (en) * 2013-10-28 2014-02-05 深圳市科聚新材料有限公司 Thermoplastic elastomer (TPE) alloy for nylon adhesive encapsulation and preparation method thereof
CN105694334A (en) * 2016-03-08 2016-06-22 安徽韧达高分子材料有限公司 TPE (thermal plastic elastomer) material for coating nylon and preparation method of TPE material
CN106366543A (en) * 2016-08-26 2017-02-01 宁波市青湖弹性体科技有限公司 High-performance thermoplastic elastomer for bonding nylon and preparation method of high-performance thermoplastic elastomer
CN107075316A (en) * 2015-08-28 2017-08-18 住友电气工业株式会社 Cladding pressure-sensitive adhesive sheet
CN112795172A (en) * 2020-12-29 2021-05-14 金发科技股份有限公司 PVC-coated thermoplastic elastomer composition and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02160886A (en) * 1989-11-24 1990-06-20 Maruzen Petrochem Co Ltd Hot-melt adhesive composition
CN103554819A (en) * 2013-10-28 2014-02-05 深圳市科聚新材料有限公司 Thermoplastic elastomer (TPE) alloy for nylon adhesive encapsulation and preparation method thereof
CN107075316A (en) * 2015-08-28 2017-08-18 住友电气工业株式会社 Cladding pressure-sensitive adhesive sheet
CN105694334A (en) * 2016-03-08 2016-06-22 安徽韧达高分子材料有限公司 TPE (thermal plastic elastomer) material for coating nylon and preparation method of TPE material
CN106366543A (en) * 2016-08-26 2017-02-01 宁波市青湖弹性体科技有限公司 High-performance thermoplastic elastomer for bonding nylon and preparation method of high-performance thermoplastic elastomer
CN112795172A (en) * 2020-12-29 2021-05-14 金发科技股份有限公司 PVC-coated thermoplastic elastomer composition and preparation method and application thereof

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