CN114605788A - Thermoplastic elastomer material bonded with double-component glue and preparation method and application thereof - Google Patents
Thermoplastic elastomer material bonded with double-component glue and preparation method and application thereof Download PDFInfo
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- CN114605788A CN114605788A CN202210176222.3A CN202210176222A CN114605788A CN 114605788 A CN114605788 A CN 114605788A CN 202210176222 A CN202210176222 A CN 202210176222A CN 114605788 A CN114605788 A CN 114605788A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
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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
- 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
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- 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
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Abstract
The invention relates to a thermoplastic elastomer material bonded with double-component glue and a preparation method and application thereof. The material comprises the following components in parts by weight: 9-32 parts of styrene elastomer; 8-32 parts of white oil; 20-50 parts of a polyester elastomer; 4-10 parts of ethylene-acrylate copolymer; 10-32 parts of filler. The material and the double-component glue have good bonding performance, and the material has proper hardness.
Description
Technical Field
The invention belongs to the technical field of elastomer materials, and particularly relates to a thermoplastic elastomer material bonded with double-component glue, and a preparation method and application thereof.
Background
Thermoplastic elastomer (TPE) for short, rubber, plastic, compatilizer and filler, and the like are blended by a double-screw extruder to produce the thermoplastic elastomer material. At present, thermoplastic elastomers are widely applied to a plurality of industries such as automobiles, household electrical appliances, buildings, wires and cables and the like.
In practical application, when acrylic acid or PUR double-component glue is adopted to bond a TPE workpiece and the surface of an aluminum plate or an iron plate, the surface polarity of TPE of a conventional SEBS/PP base material is weak, no reaction group exists, and the bonding force between the surface of TPE and the glue is poor.
Chinese patent CN106189041A discloses components of a solvent-bondable, kink-resistant and transparent infusion tube material including a thermoplastic styrene elastomer, random copolymer polypropylene, an adhesion promoter, an antioxidant, a lubricant and the like, the material has the characteristics of high resilience, high strength and the like, and simultaneously has the bonding strength and kink resistance equivalent to those of the traditional PVC infusion tube material, but the bonding force of the material and double-component glue is to be improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a thermoplastic elastomer material bonded with two-component glue and a preparation method and application thereof, so as to overcome the defect of poor bonding force between the thermoplastic elastomer material and the two-component glue in the prior art.
The invention provides a thermoplastic elastomer material which comprises the following components in parts by weight:
the polyester elastomer is a linear block copolymer of a polybutylene terephthalate hard segment and a polyether soft segment, and the weight ratio of the polybutylene terephthalate hard segment to the polyether soft segment is (30-50): (50-70).
Preferably, the material components comprise the following components in parts by weight:
preferably, the styrene elastomer comprises one or more of hydrogenated poly (styrene-b-isoprene), hydrogenated poly (styrene-b-butadiene-b-styrene), hydrogenated poly (styrene-b-isoprene-b-styrene), and hydrogenated poly (styrene-b-isoprene/butadiene-b-styrene).
Preferably, the white oil comprises one or more of naphthenic oil and paraffinic oil.
Preferably, the polyether soft segment is non-crystalline polyether, and more preferably, the non-crystalline polyether comprises one or more of polyethylene glycol ether, polypropylene glycol ether and polybutylene glycol ether.
Preferably, the mass fraction of the acrylate in the ethylene-acrylate copolymer is 6-12%.
Preferably, the filler is a filler with a surface coated with silane.
Preferably, the mass fraction of silane in the filler is 1-5%.
Preferably, the filler of the surface-coated silane comprises one or more of calcium carbonate, talcum powder and wollastonite of which the surface is coated with silane.
Preferably, the filler with the surface coated with the silane is obtained by mixing and stirring a silane coupling agent and the filler. The formula for calculating the mass fraction of the silane is as follows: weight of silane coupling agent/weight of filler 100%.
Preferably, the silane coupling agent comprises one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane).
Preferably, the stirring time is 5-10 min.
Preferably, the material further comprises 0-8 parts of additives.
Preferably, the additive comprises one or more of an antioxidant, a UV resistant agent and mineral powder.
Preferably, the antioxidant comprises one or more of pentaerythritol ester, phosphite ester and dialkyl ester of thiodipropionic acid.
Preferably, the UV resistant agent comprises one or more of hindered benzoate, benzotriazole and benzophenone.
Preferably, the mineral powder comprises one or more of calcium carbonate, talcum powder and wollastonite.
The invention also provides a preparation method of the thermoplastic elastomer material, which comprises the following steps:
premixing styrene elastomer and white oil, then mixing the obtained premix with other components, adding the mixed components into a double-screw extruder, and cooling and granulating after melt extrusion to obtain the thermoplastic elastomer material.
Preferably, the premixing temperature is normal temperature, and the premixing time is 3-6 h.
Preferably, the extrusion temperature is 165-215 ℃, and the residence time of the extrusion process is 55-105 s.
The invention also provides application of the thermoplastic elastomer material in automobiles or household appliances.
The test standard of the mass fraction of the acrylate in the ethylene-acrylate copolymer related to the invention is ASTM D4094-2007.
The two-component glue is two-component polyurethane glue and consists of a main agent and a curing agent, wherein the main agent is an active hydrogen-containing component (such as polyol containing hydroxyl), and the curing agent is a polyurethane prepolymer component containing-NCO groups.
The soft segment in the polyester elastomer can provide adhesive force, but the strong crystallinity of the hard segment is negative to the adhesive property, and after the polyester elastomer and the ethylene-acrylate copolymer are compounded, the ethylene-acrylate copolymer has poor compatibility with the hard segment of the polyester elastomer in a system, so that the crystallization property of the ethylene-acrylate copolymer is directly influenced, and the adhesive property is improved. The filler is an inert component, but after the surface is activated, the silane groups on the surface have higher activity and can react with the groups in the glue, so that the bonding performance can be further improved.
Advantageous effects
The invention adopts the compounding of the polyester elastomer and the ethylene-acrylate copolymer, and can obviously improve the bonding performance of the thermoplastic elastomer material and the two-component glue. And the filler with the surface coated with the silane can further improve the bonding performance of the thermoplastic elastomer material and the two-component glue. And the invention ensures that the thermoplastic elastomer material has proper hardness (20D-50D).
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
And (3) reagent sources:
styrene elastomer: hydrogenated poly (styrene-b-butadiene-b-styrene), SEBS G1651, kraton;
white oil: mineral white oil, PW-90, Japan Bright;
polyester elastomer 1: linear block copolymer of hard segment of polybutylene terephthalate and soft segment of polytetramethylene glycol ether, the weight ratio of the hard segment to the soft segment is 30:70, Hytrel 4053, DuPont;
polyester elastomer 2: linear block copolymer of hard segment of polybutylene terephthalate and soft segment of polytetramethylene glycol ether, the weight ratio of the hard segment to the soft segment is 50:50, Hytrel 7246, DuPont;
polyester elastomer 3: linear block copolymers of polybutylene terephthalate hard blocks and polyethylene glycol ether soft blocks at a weight ratio of hard blocks to soft blocks of 30:70, KOPEL KP3339UM, korea KOLON;
polyester elastomer 4: linear block copolymers of hard segments of polybutylene terephthalate and soft segments of polytetramethylene glycol ether, the weight ratio of the hard segments to the soft segments being 25:75, Hytrel 3078, DuPont;
polyester elastomer 5: a linear block copolymer of hard polybutylene terephthalate segments and soft polybutylene glycol segments, wherein the weight ratio of the hard segments to the soft segments is 56:44,
8238, DuPont;
ethylene-acrylic acid ester copolymer 1: escor 5000, Exxon Mobil and acrylate mass fraction of 6.4%;
ethylene-acrylic ester copolymer 2: escor 5110, Exxon Mobil, and the mass fraction of acrylic ester is 11.5%;
ethylene-acrylic acid ester copolymer 3: lucalan A2910M, Basel, acrylate mass fraction of 4.8%;
ethylene-acrylic ester copolymer 4: escor 5200, Exxon Mobil, and the mass fraction of acrylate is 13.1%;
filler 1: calcium carbonate (silane mass fraction is 1%) coated with silane is prepared by uniformly stirring 1kg of vinyltriethoxysilane (A-151, United states Co.) and 100kg of calcium carbonate (ACMLT02, Meilita) with a powder stirrer at 200 rpm for 5 min;
and (3) filling materials 2: the calcium carbonate (silane mass fraction is 5%) coated with silane is obtained by uniformly stirring 5kg of vinyltriethoxysilane (A-151, United states Co.) and 100kg of calcium carbonate (ACMLT02, Melita) with a powder stirrer at a speed of 200 rpm for 10 min;
filler 3: calcium carbonate (7% by mass of silane) with silane coated on the surface is obtained by uniformly stirring 7kg of vinyltriethoxysilane (A-151, United states Co.) and 100kg of calcium carbonate (ACMLT02, Meilita) with a powder stirrer at 200 rpm for 10 min;
filler 4: calcium carbonate (without silane coating), ACMLT02, merlitate;
additive:
antioxidant: hindered phenolic antioxidants, commercially available;
the additives (antioxidants) used in the examples and comparative examples were the same commercial products.
A process for the preparation of a thermoplastic elastomeric material comprising the steps of:
according to the mixture ratio in table 1 or table 2, styrene elastomer and white oil are premixed for 3-6h at normal temperature, then the obtained premix is mixed with other components, the mixed components are added into a double-screw extruder, and the thermoplastic elastomer material is obtained after cooling granulation after melt extrusion. Wherein the extrusion temperature is 165-215 ℃, and the residence time of the extrusion process is 55-105 s.
And (3) performance testing:
the thermoplastic elastomer material is dried in a forced air oven at 70-80 ℃ for 2-4 hours, and then the dried particles are made into standard sample bars on an injection molding machine for the following tests.
(1) Shore D hardness: the method is carried out according to the ISO 7619-2010 standard, and a Shore D hardness tester is adopted, the weight is 5kg, and the reading time is 15 s.
(2) The bonding strength test method comprises the following steps: the elastomer material is made into a 150 x 40mm rectangular plate with the thickness of 2.0mm by an injection molding process, and the rectangular plate and the iron plate are bonded together by two-component glue (the main agent is PEG, the curing agent is aromatic diisocyanate MDI, and the weight ratio of the main agent to the curing agent is 2: 1) (the bonding temperature is normal temperature, and the time is 5 min). And testing the bonding force by using a universal testing machine. The force during the peeling process was measured and recorded. The larger the value, the larger the peel strength, and when the peel force reaches 6.0N, it indicates that the application requirements can be met.
TABLE 1 example proportions (parts by weight)
TABLE 2 comparative example proportions (parts by weight)
As can be seen from tables 1 and 2, comparative example 1 did not add the polyester elastomer, comparative example 4 did not add the ethylene-acrylate copolymer, the peel force of both comparative example 1 and comparative example 4 was lower than that of example 1, and the hardness of comparative example 1 was not appropriate. Comparative example 2 added polyester elastomer hard and soft segments at a weight ratio of less than 30:70, comparative example 3 added polyester elastomer hard and soft segments at a weight ratio of greater than 50:50, comparative examples 2-3 both had lower peel forces than example 1, and comparative examples 2 and 3 had inadequate hardness. The mass fraction of the acrylate in the ethylene-acrylate copolymer added in the comparative example 5 is less than 6%, the mass fraction of the acrylate in the ethylene-acrylate copolymer added in the comparative example 6 is more than 12%, and the peeling force of the comparative examples 5 and 6 is lower than that of the example 1. Therefore, the compounding of the polyester elastomer and the ethylene-acrylate copolymer is adopted, the weight ratio of the hard segment to the soft segment in the polyester elastomer is within a certain range, and the mass fraction of the acrylate in the ethylene-acrylate copolymer is within a certain range, so that the bonding property of the thermoplastic elastomer material and the two-component glue can be obviously improved, and the thermoplastic elastomer material is ensured to have proper hardness (20-50D).
In example 12, the surface of the filler is not coated with silane, and the stripping force is lower than that in example 1, so that the coating of the surface of the filler with silane can further improve the bonding property of the thermoplastic elastomer material and the two-component glue and ensure that the thermoplastic elastomer material has proper hardness (20-50D).
Claims (10)
1. A thermoplastic elastomer material is characterized by comprising the following material components in parts by weight:
the polyester elastomer is a linear block copolymer of a polybutylene terephthalate hard segment and a polyether soft segment, and the weight ratio of the polybutylene terephthalate hard segment to the polyether soft segment is (30-50): (50-70).
2. Thermoplastic elastomeric material according to claim 1, characterized in that said material components comprise, in parts by weight:
3. thermoplastic elastomeric material according to claim 1, characterized in that said styrene elastomer comprises one or more of hydrogenated poly (styrene-b-isoprene), hydrogenated poly (styrene-b-butadiene-b-styrene), hydrogenated poly (styrene-b-isoprene/butadiene-b-styrene).
4. The thermoplastic elastomer material according to claim 1, wherein the white oil comprises one or more of naphthenic oil and paraffinic oil; the soft polyether segment is non-crystalline polyether, and the non-crystalline polyether comprises one or more of polyethylene glycol ether, polypropylene glycol ether and polybutylene glycol ether.
5. Thermoplastic elastomeric material according to claim 1, characterized in that said ethylene-acrylate copolymer has a mass fraction of acrylates ranging from 6% to 12%; the filler is a filler with the surface coated with silane.
6. Thermoplastic elastomeric material according to claim 5, characterized in that said filler has a silane mass fraction of between 1 and 5%; the filler with the surface coated with the silane comprises one or more of calcium carbonate, talcum powder and wollastonite with the surface coated with the silane.
7. The thermoplastic elastomer material as claimed in claim 5, wherein the filler with the surface coated with silane is obtained by mixing and stirring a silane coupling agent with the filler, wherein the silane coupling agent comprises one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (β -methoxyethoxy) silane).
8. Thermoplastic elastomeric material according to claim 1, characterized in that it further comprises 0-8 parts of additives; the additive comprises one or more of an antioxidant, a UV resistant agent and mineral powder.
9. A process for the preparation of a thermoplastic elastomeric material according to any one of claims 1 to 8, comprising the steps of:
premixing styrene elastomer and white oil, then mixing the obtained premix with other components, adding the mixed components into a double-screw extruder, and cooling and granulating after melt extrusion to obtain the thermoplastic elastomer material.
10. Use of a thermoplastic elastomeric material according to any one of claims 1 to 8 in automobiles or household appliances.
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| CN202210176222.3A CN114605788A (en) | 2022-02-25 | 2022-02-25 | Thermoplastic elastomer material bonded with double-component glue and preparation method and application thereof |
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| CN202210176222.3A CN114605788A (en) | 2022-02-25 | 2022-02-25 | Thermoplastic elastomer material bonded with double-component glue and preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000063644A (en) * | 1998-08-21 | 2000-02-29 | Mitsubishi Chemicals Corp | Thermoplastic elastomer composition |
| US20010041772A1 (en) * | 2000-01-28 | 2001-11-15 | Tetsuo Masubuchi | Thermoplastic elastomer composition |
| JP2012025848A (en) * | 2010-07-23 | 2012-02-09 | Sumitomo Chemical Co Ltd | Liquid composition and method for production of copper-clad laminate |
| 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 |
| CN107118494A (en) * | 2017-06-04 | 2017-09-01 | 泉州盈创新材料技术开发有限公司 | A kind of high bonding wear-resistant thermoplastic elastomer and preparation method thereof |
| CN107312242A (en) * | 2017-07-24 | 2017-11-03 | 合肥会通新材料有限公司 | A kind of PP composite material being easily bonded and preparation method thereof |
-
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- 2022-02-25 CN CN202210176222.3A patent/CN114605788A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000063644A (en) * | 1998-08-21 | 2000-02-29 | Mitsubishi Chemicals Corp | Thermoplastic elastomer composition |
| US20010041772A1 (en) * | 2000-01-28 | 2001-11-15 | Tetsuo Masubuchi | Thermoplastic elastomer composition |
| JP2012025848A (en) * | 2010-07-23 | 2012-02-09 | Sumitomo Chemical Co Ltd | Liquid composition and method for production of copper-clad laminate |
| 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 |
| CN107118494A (en) * | 2017-06-04 | 2017-09-01 | 泉州盈创新材料技术开发有限公司 | A kind of high bonding wear-resistant thermoplastic elastomer and preparation method thereof |
| CN107312242A (en) * | 2017-07-24 | 2017-11-03 | 合肥会通新材料有限公司 | A kind of PP composite material being easily bonded and preparation method thereof |
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