CN110982209B - Wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for wires and cables - Google Patents
Wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for wires and cables Download PDFInfo
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- CN110982209B CN110982209B CN201911413536.5A CN201911413536A CN110982209B CN 110982209 B CN110982209 B CN 110982209B CN 201911413536 A CN201911413536 A CN 201911413536A CN 110982209 B CN110982209 B CN 110982209B
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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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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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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Abstract
The invention discloses a wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for wires and cables, which is characterized by comprising the following raw materials in parts by weight: 40-60 parts of SEBS, 20-40 parts of white oil, 10-20 parts of POE thermoplastic elastomer, 5-10 parts of maleic anhydride grafted SEBS, 0.1-0.5 part of composite cross-linking agent, 10-20 parts of diethyl aluminum hypophosphite, 10-20 parts of zinc borate, 3-8 parts of zinc stearate and 1-3 parts of distearyl thiodipropionate. According to the invention, the SEBS and the POE are crosslinked, so that the tensile strength, the scratch resistance and the flame retardant property of the material are improved to a great extent. The invention is obtained by screening tests on the components and the proportion of the raw materials, the obtained technical scheme is a whole, and the components are mutually cooperated to play a role.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for wires and cables and a preparation method thereof.
Background
TPE (thermoplastic elastomer) is a thermoplastic elastomer material, has the characteristics of high strength, high resilience, injection molding processing, wide application range, environmental protection, no toxicity, safety and excellent colorability. TPE also has the advantages of soft touch, good weather resistance, fatigue resistance and temperature resistance, excellent processing performance, no need of vulcanization, recycling and cost reduction, and can be subjected to secondary injection molding, coated and bonded with matrix materials such as PP, PE, PC, PS, ABS and the like, and can be formed independently.
However, the conventional TPE material is not vulcanized, so that the wear resistance is poor, and the wear resistance requirement of a specific application field cannot be met. To solve this problem, many studies have been conducted in the prior art. For example, the domestic patent application with the application publication number of CN 107418126A discloses a wear-resistant high-flame-retardant halogen-free flame-retardant thermoplastic elastomer composition for wires and cables, which comprises the following raw materials in percentage by weight: 20-40% of SEBS; 20-40% of white oil; 10-30% of nylon; 5-10% of maleic anhydride grafted SEBS; 10-20% of diethyl aluminum hypophosphite; 10-20% of melamine cyanurate; 1 to 5 percent of other auxiliary agents. Aiming at the problem that a conventional halogen-free flame-retardant TPE cable material based on SEBS and polyolefin is poor in wear resistance, the invention provides a wear-resistant high-flame-retardant halogen-free flame-retardant thermoplastic elastomer composition. But the scratch resistance of the halogen-free flame-retardant thermoplastic elastomer composition has room for improvement. Therefore, the research of a thermoplastic elastomer material with a more reasonable formula and better scratch resistance is an urgent need.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a thermoplastic elastomer material with a more reasonable formula and better scratch resistance and a preparation method thereof. In order to realize the purpose, the invention adopts the following technical scheme:
the wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for the wires and cables comprises the following raw materials in parts by weight: 40-60 parts of SEBS, 20-40 parts of white oil, 10-20 parts of POE thermoplastic elastomer, 5-10 parts of maleic anhydride grafted SEBS, 0.1-0.5 part of composite cross-linking agent, 10-20 parts of diethyl aluminum hypophosphite, 10-20 parts of zinc borate, 3-8 parts of zinc stearate and 1-3 parts of distearyl thiodipropionate.
The flash point of the white oil is 155-166 ℃, and the kinematic viscosity at 40 ℃ is 6.54-15.2 m3/s；
The composite cross-linking agent is cyclohexanone peroxide and 2, 2-bis (allyloxymethyl) butane-1-alcohol according to the mass ratio of 3: 1;
the preparation method of the zinc borate comprises the following steps: adding 6L of water, 500g of zinc oxide and 100g of tetramethylethylenediamine into a 10L reaction kettle, fully and uniformly stirring, adding 1600g of boric acid for complete dissolution, heating to 110 ℃ for reaction for 4 hours, filtering after the reaction is finished, washing a filter cake for 3-5 times by using deionized water at 90 ℃, and finally drying at 110 ℃ for 8 hours to obtain the zinc oxide.
The preparation method of the wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for the wires and the cables comprises the following steps of:
(1) mixing SEBS with white oil to obtain oil-filled SEBS;
(2) mixing the oil-filled SEBS with the rest components, adding the mixture into a double-screw extruder together for melting, mixing, extruding and granulating, wherein the extruding and granulating are divided into four melting and mixing areas: the temperature of the first zone is 190-200 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 210-220 ℃, the temperature of the fourth zone is 190-200 ℃, the residence time of the whole extrusion process is lmin-2min, and the pressure is 21-29 MPa.
Compared with the prior art, the wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for the wires and cables has the advantages of more reasonable formula and more excellent scratch resistance. According to the invention, the SEBS and the POE are crosslinked, so that the tensile strength, the scratch resistance and the flame retardant property of the material are improved to a great extent. The invention is obtained by screening tests on the components and the proportion of the raw materials, the obtained technical scheme is a whole, and the components are mutually cooperated to play a role.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with examples and comparative examples, but it should be understood that these descriptions are intended to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
The SEBS adopted in the embodiment of the invention is American Keteng G1651, the aluminum diethylphosphinate is New Jiangsu Lisside Material Co., Ltd LFR-8001, the maleic anhydride grafted SEBS is American Keteng 1901, the POE thermoplastic elastomer is American Dow 8003, the white oil is No. 10 white oil of special oil products Co., Ltd, Saipahan, the flash point is 160 ℃, and the kinematic viscosity at 40 ℃ is 9.8 m3S; other raw materials are general-purpose and commercially available or self-made.
Example 1:
the wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for the wires and cables comprises the following raw materials in parts by weight: 50 parts of SEBS, 30 parts of white oil, 15 parts of POE thermoplastic elastomer, 8 parts of maleic anhydride grafted SEBS, 0.3 part of composite cross-linking agent, 15 parts of diethyl aluminum hypophosphite, 15 parts of zinc borate, 5 parts of zinc stearate and 2 parts of distearyl thiodipropionate.
The white oil is No. 10 white oil of Suzhou Seapahan special oil product Co., Ltd, has a flash point of 160 ℃, and has a kinematic viscosity of 9.8 m at 40 DEG C3/s
The composite cross-linking agent is cyclohexanone peroxide and 2, 2-bis (allyloxymethyl) butane-1-alcohol according to the mass ratio of 3: 1;
the preparation method of the zinc borate comprises the following steps: adding 6L of water, 500g of zinc oxide and 100g of tetramethylethylenediamine into a 10L reaction kettle, fully and uniformly stirring, adding 1600g of boric acid for complete dissolution, heating to 110 ℃ for reaction for 4 hours, filtering after the reaction is finished, washing a filter cake for 3 times by using deionized water at 90 ℃, and finally drying at 110 ℃ for 8 hours to obtain the zinc oxide.
The preparation method of the wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for the wires and the cables comprises the following steps:
(1) mixing SEBS with white oil to obtain oil-filled SEBS;
(2) mixing the oil-filled SEBS with the rest components, adding the mixture into a double-screw extruder together for melting, mixing, extruding and granulating, wherein the extruding and granulating are divided into four melting and mixing areas: the temperature of the first zone is 190 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the residence time of the whole extrusion process is 2min, and the pressure is 25 MPa.
Comparative example 1:
a thermoplastic elastomer composition as distinguished from example 1 in that the white oil is No. 3 white oil from Special oils, Inc. Saipahan, Suzhou, having a flash point of 108 ℃ and a kinematic viscosity at 40 ℃ of 2.8 m3/s。
Comparative example 2:
a thermoplastic elastomer composition different from example 1 in that the white oil was No. 5 white oil from Special oils, Sopperware, Suzhou, having a flash point of 128 ℃ and a kinematic viscosity at 40 ℃ of 4.2 m3/s。
Comparative example 3:
a thermoplastic elastomer composition as distinguished from example 1 in that the white oil is No. 26 white oil from Special oils, Inc. Sappanhuang, Suzhou, having a flash point of 218 ℃ and a kinematic viscosity at 40 ℃ of 26.5 m3/s。
Comparative example 4:
a thermoplastic elastomer composition as distinguished from example 1 in that the white oil is No. 36 white oil from Special oils, Inc. Saipahan, Suzhou, having a flash point of 238 ℃ and a kinematic viscosity at 40 ℃ of 35.7 m3/s。
Comparative example 5:
a thermoplastic elastomer composition, which is different from example 1 in that the composite crosslinking agent is dicumyl peroxide, poly (triallyl isocyanurate) in a mass ratio of 1: 1;
comparative example 6:
a thermoplastic elastomer composition, which is different from example 1 in that the composite crosslinking agent is cyclohexanone peroxide and poly (triallyl isocyanurate) in a mass ratio of 3: 1;
comparative example 7:
a thermoplastic elastomer composition, which is different from example 1 in that the composite crosslinking agent is dicumyl peroxide, 2-bis (allyloxymethyl) butan-1-ol in a mass ratio of 3: 1;
comparative example 8:
a thermoplastic elastomer composition, which is different from the thermoplastic elastomer composition in example 1 in that the composite crosslinking agent is cyclohexanone peroxide and ethylene glycol diethyl diallyl ether in a mass ratio of 3: 1;
comparative example 9:
a thermoplastic elastomer composition, which is different from example 1 in that the complex crosslinking agent is cyclohexanone peroxide, 2-bis (allyloxymethyl) butan-1-ol, and the mass ratio of the two is 1: 1;
comparative example 10:
a thermoplastic elastomer composition, which is different from example 1 in that the composite crosslinking agent is cyclohexanone peroxide and 2, 2-bis (allyloxymethyl) butan-1-ol in a mass ratio of 5: 1;
comparative example 11:
a thermoplastic elastomer composition, which is different from example 1 in that zinc borate is prepared by a different method using triethylamine as a crystallization-directing agent instead of tetramethylethylenediamine.
Comparative example 12:
a thermoplastic elastomer composition, which is different from example 1 in that the zinc borate is prepared by a different method using sodium tert-butoxide as a crystal directing agent instead of tetramethylethylenediamine.
Comparative example 13:
a thermoplastic elastomer composition, different from example 1 in that the zinc borate was prepared by a different method using pyridine as a crystal directing agent instead of tetramethylethylenediamine.
Comparative example 14:
a thermoplastic elastomer composition, which is different from example 1 in that the zinc borate is prepared by a different method using DBU as a crystallization directing agent instead of tetramethylethylenediamine.
Comparative example 15:
a thermoplastic elastomer composition was prepared according to example 1 of the specification of the Chinese patent application having application publication No. CN 107418126A.
Comparative testing of the Properties of the thermoplastic elastomer compositions of inventive example 1 and comparative examples 1 to 15:
the prepared thermoplastic elastomer composition was injection molded into standard test specimens as specified in various test standards, tensile strength testing according to ISO 527-1-2012 "determination of tensile properties of plastics part 1: the testing temperature is 23 ℃ and the testing speed is 100mm/min according to the method specified in general rules; the scratch resistance test is carried out according to the method specified by the popular PV 3952 standard, the instrument is a 430P type scratch tester of Erichsen company, Germany, the diameter of a pressure head is 1 mm, the load is 10N, and the scratch rate is 500 mm/min; the test sample size was 100 × 50 × 3 mm; measuring the difference (Delta L) of the L values of the sample before and after scraping by a color difference meter to measure the scraping resistance, wherein the smaller Delta L is, the better the scraping resistance of the material is; the flame retardant rating test is carried out according to the method specified in GB/T2408-2008: test method B-vertical burn test.
The test results are shown in table 1.
TABLE 1
From the test results in table 1, it can be concluded that the thermoplastic elastomer composition of example 1 of the present invention has very excellent tensile strength, scratch resistance and flame retardancy; meanwhile, through the influence of the component differences of the comparative examples 1 to 15 and the example 1 on the final performance, the technical scheme of the invention is a whole and the components have synergistic action.
Claims (1)
1. The wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for the wires and cables is characterized by comprising the following raw materials in parts by weight: 50 parts of SEBS, 30 parts of white oil, 15 parts of POE thermoplastic elastomer, 8 parts of maleic anhydride grafted SEBS, 0.3 part of composite cross-linking agent, 15 parts of diethyl aluminum hypophosphite, 15 parts of zinc borate, 5 parts of zinc stearate and 2 parts of distearyl thiodipropionate;
the white oil is No. 10 white oil of Suzhou Seapahan special oil products Co., Ltd;
the composite cross-linking agent is cyclohexanone peroxide and 2, 2-bis (allyloxymethyl) butane-1-alcohol according to the mass ratio of 3: 1;
the preparation method of the zinc borate comprises the following steps: adding 6L of water, 500g of zinc oxide and 100g of tetramethylethylenediamine into a 10L reaction kettle, fully and uniformly stirring, adding 1600g of boric acid for complete dissolution, heating to 110 ℃ for reaction for 4 hours, filtering after the reaction is finished, washing a filter cake for 3 times by using deionized water at 90 ℃, and finally drying at 110 ℃ for 8 hours to obtain the zinc oxide-based catalyst;
the preparation method of the wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for the wires and the cables comprises the following steps:
(1) mixing SEBS with white oil to obtain oil-filled SEBS;
(2) mixing the oil-filled SEBS with the rest components, adding the mixture into a double-screw extruder together for melting, mixing, extruding and granulating, wherein the extruding and granulating are divided into four melting and mixing areas: the temperature of the first zone is 190 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the residence time of the whole extrusion process is 2min, and the pressure is 25 MPa.
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| CN201911413536.5A CN110982209B (en) | 2019-12-31 | 2019-12-31 | Wear-resistant halogen-free flame-retardant thermoplastic elastomer composition for wires and cables |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014162901A (en) * | 2013-02-27 | 2014-09-08 | Mitsubishi Chemicals Corp | Flame-retardant polyolefin resin composition |
| CN105504346A (en) * | 2015-12-16 | 2016-04-20 | 安徽壹石通材料科技股份有限公司 | Preparation method of novel zinc borate flame-retardant material |
| CN105860412A (en) * | 2016-04-27 | 2016-08-17 | 安徽中鼎橡塑制品有限公司 | Halogen-free flame-retardant thermoplastic elastomer material for electric wires and cables and preparation method of material |
| CN107418126A (en) * | 2017-05-16 | 2017-12-01 | 江苏鼎启忠华新材料科技有限公司 | Electric wire wear-resisting high-flame-retardanthalogen-free halogen-free flame-retardant thermoplastic elastomer composition and preparation method thereof |
| CN108456429A (en) * | 2018-01-15 | 2018-08-28 | 东莞市安拓普塑胶聚合物科技有限公司 | A kind of thermoplastic elastomer (TPE) and its preparation method and application that Applicable temperature range is wide |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014162901A (en) * | 2013-02-27 | 2014-09-08 | Mitsubishi Chemicals Corp | Flame-retardant polyolefin resin composition |
| CN105504346A (en) * | 2015-12-16 | 2016-04-20 | 安徽壹石通材料科技股份有限公司 | Preparation method of novel zinc borate flame-retardant material |
| CN105860412A (en) * | 2016-04-27 | 2016-08-17 | 安徽中鼎橡塑制品有限公司 | Halogen-free flame-retardant thermoplastic elastomer material for electric wires and cables and preparation method of material |
| CN107418126A (en) * | 2017-05-16 | 2017-12-01 | 江苏鼎启忠华新材料科技有限公司 | Electric wire wear-resisting high-flame-retardanthalogen-free halogen-free flame-retardant thermoplastic elastomer composition and preparation method thereof |
| CN108456429A (en) * | 2018-01-15 | 2018-08-28 | 东莞市安拓普塑胶聚合物科技有限公司 | A kind of thermoplastic elastomer (TPE) and its preparation method and application that Applicable temperature range is wide |
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