CN106633356B - A kind of ethylene and tetra fluoloethylene copolymer resin heat-shrinkage material and preparation method thereof - Google Patents
A kind of ethylene and tetra fluoloethylene copolymer resin heat-shrinkage material and preparation method thereof Download PDFInfo
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- CN106633356B CN106633356B CN201611237585.4A CN201611237585A CN106633356B CN 106633356 B CN106633356 B CN 106633356B CN 201611237585 A CN201611237585 A CN 201611237585A CN 106633356 B CN106633356 B CN 106633356B
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- ethylene
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
-
- 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
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/06—Making preforms having internal stresses, e.g. plastic memory
- B29C61/08—Making preforms having internal stresses, e.g. plastic memory by stretching tubes
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of ethylene and TFE copolymer (ETFE) heat-shrinkage material, are grouped as: 95~98 parts of ETFE resin by the group of following following parts by weight meter；2~5 parts of ternary fluororubber；0.1~0.5 part of acid absorbent；0~10 part of color master batch；The ETFE resin is a kind of fluoroplastics made of the ratio alternating polymerization of ethylene and tetrafluoroethene according to molar ratio 1:1.Ternary fluororubber is by three kinds of polymerized monomers: vinylidene fluoride and perfluoro methyl vinyl ether and tetrafluoroethene, the fluorubber being polymerized according to certain mol proportion example.ETFE heat-shrinkage material of the invention has the characteristics that good, colorless and transparent, the resistant to high temperatures cracking of temperature tolerance, electrical insulation capability are excellent and fire retardant, can satisfy the performance indicator requirement of MIL STD SAE-AMS-DTL 23053/14.
Description
Technical field
The present invention relates to a kind of ethylene of electric insulation protection purposes and tetra fluoloethylene copolymer resin (ETFE) to be heat-shrinked material
Material and preparation method thereof.
Background technique
Tetra fluoloethylene copolymer resin (ETFE) is one of melt processible fluoropolymer composition kind, excellent with mechanical performance,
The feature that high temperature resistant, dielectric strength are high, resistivity is high, dissipation factor is low, dielectric constant is low.Using ETFE as the thermal contraction material of main material
Material, not only has the above advantages, and also has the function of being heat-shrinked.Have for space flight and aviation, communication, electronic apparatus and locomotive industry
The application field of the particular/special requirements such as high temperature resistant, transparent flame-retarding, high mechanical damage, high frequency tolerant, high insulation, has wide application
Prospect.The present invention applies for the content of protection, can satisfy the demand of above-mentioned application.
Summary of the invention
The technical problem to be solved in the present invention is that: high temperature resistant, thoroughly can not be met comprehensively by solving existing conventional heat-shrinkable tube
The deficiency of the particular/special requirements such as bright fire-retardant, high mechanical damage, high frequency tolerant, high insulation, provides ethylene and tetra fluoloethylene copolymer resin
(ETFE) heat-shrinkage material and preparation method thereof, can solve presently, there are the problem of and contradiction.
In order to solve the above-mentioned technical problem, the present invention proposes a kind of following technical scheme: ETFE heat-shrinkage material, under
The group of column in parts by weight is grouped as:
The ETFE resin is a kind of fluorine made of the ratio alternating polymerization of ethylene and tetrafluoroethene according to molar ratio 1:1
Plastics；
The ternary fluororubber is by three kinds of polymerized monomers: vinylidene fluoride and perfluoro methyl vinyl ether and tetrafluoro second
Alkene, fluorubber made of binary polymerization；
The acid absorbent is the mixture of one of following substance or two or more of them substance: lightweight oxidation
Magnesium, calcium hydroxide, calcium oxide, zinc oxide and lead oxide, the maximum particle diameter of above-mentioned substance require to be no more than 10 microns.
The above technical solution is further limited in that: the fusing point of the ETFE resin is 250~280 DEG C, melt flow
Dynamic rate is 1~8g/10min, and density is 1.68~1.72g/cm3。
The above technical solution is further limited in that: the Mooney viscosity of the ternary fluororubber is 25~65ML1+
10 121 DEG C of@, nominal fluorine contents 63%~68%, specific gravity are 1.86~1.90.
In order to solve the above-mentioned technical problem, the present invention proposes a kind of following technical scheme: preparation side of ETFE heat-shrinkable tube
Method comprising following steps:
Step 1: weigh according to parts by weight 95~98 parts of ETFE resin, 2~5 parts of ternary fluororubber, acid absorbent 0.1~
0.5 part, 0~10 part of color master batch are uniformly mixed with high-speed mixer, are put into the twin-screw that heating temperature is set as 280~340 DEG C
Melting mixing in kneading machine, it is 2~4mm that length, which is made, and diameter is the cylindric plastic pellet of 1~3mm；
Step 2: the resulting plastic pellet of step 1 is extruded into tubulose through plastic extruding forming machine；
Step 3: by tubing heat temperature raising obtained above, heating method is hot-air or glycerol, when material temperature reaches
It at 120 DEG C~180 DEG C, is deformed by air pressure or air pressure and vacuum pressure official post material expansion, deformation multiplying power is 1.8
~2.0 times, the material of deformation is quickly cooled down sizing, ETFE heat-shrinkable tube of the present invention can be obtained.
Compared with prior art, the invention has the following advantages: ETFE heat-shrinkage material of the present invention and its heat-shrink tube,
Temperature grade index is above 150 DEG C, has excellent mechanical performance, electrical insulation capability, high frequency tolerant performance, while fire retardant also
It can be made colorless and transparent high-performance heat-shrinkable tube.
Specific embodiment
The present invention proposes a kind of tetra fluoloethylene copolymer resin (ETFE) heat-shrinkage material, by it is following in parts by weight
Group be grouped as:
The ETFE resin is a kind of fluorine made of the ratio alternating polymerization of ethylene and tetrafluoroethene according to molar ratio 1:1
Plastics, fusing point are 250~280 DEG C, and melt flow rate (MFR) is 1~8g/10min, and density is 1.68~1.72g/cm3。
The ternary fluororubber is by three kinds of polymerized monomers i.e. vinylidene fluoride, perfluoro methyl vinyl ether and tetrafluoro second
Alkene, fluorubber made of binary polymerization, Mooney viscosity are 121 DEG C of 25~65ML1+10@, nominal fluorine contents 63%~68%, than
Weight is 1.86~1.90.
The acid absorbent is the mixture of one of following substance or two or more of them substance: lightweight oxidation
Magnesium (MgO), calcium hydroxide [Ca (OH)2], calcium oxide (CaO), zinc oxide (ZnO) and lead oxide (PbO), the maximum of above-mentioned substance
Particle size requirements are no more than 10 microns.
The color master batch is to confer to the auxiliary agent of ETFE material contracting with heat color, can select suitable face as desired
Color；If the requirement of ETFE material contracting with heat be it is colorless and transparent, do not need that any color master batch is added.
The present invention also proposes a kind of preparation method of tetra fluoloethylene copolymer resin (ETFE) heat-shrinkable tube, including following step
It is rapid:
Step 1: weigh according to parts by weight 95~98 parts of ETFE resin, 2~5 parts of ternary fluororubber, acid absorbent 0.1~
0.5 part, 0~10 part of color master batch are uniformly mixed with high-speed mixer, are put into the twin-screw that heating temperature is set as 280~340 DEG C
Melting mixing in kneading machine, it is 2~4mm that length, which is made, and diameter is the cylindric plastic pellet of 1~3mm；
Step 2: the resulting plastic pellet of step 1 is extruded into tubulose through plastic extruding forming machine；
Step 3: by tubing heat temperature raising obtained above, heating method is hot-air or glycerol, when material temperature reaches
It at 120 DEG C~180 DEG C, is deformed by air pressure or air pressure and vacuum pressure official post material expansion, deformation multiplying power is 1.8
~2.0 times, the material of deformation is quickly cooled down sizing, just obtains ETFE heat-shrinkable tube of the present invention.
Prepare Examples and Comparative Examples
Step 1: weighing 95~98 parts of ETFE resin according to parts by weight shown in table 1,2~5 parts of ternary fluororubber, inhale acid
0.1~0.5 part of agent, 0~10 part of color master batch are uniformly mixed with high-speed mixer and are set as 280~340 DEG C with being put into heating temperature
Twin screw compounder in melting mixing, be made length be 1.5~2.5mm, diameter be 2~3mm cylindric plastic pellet；
Step 2: the resulting plastic pellet of step 1 is extruded into tubulose through plastic extruding forming machine, is immersed in normal-temperature water,
Cooled and solidified the polyester tube parison before being expanded；Then, continue to heat the pipe in 150~180 DEG C of glycerol；
Logical compressed gas, outside vacuumize inside to tubing, and forming inside and outside differential pressure makes tubing dilatating and deformable, stretch in the longitudinal direction
1.05~1.1 times, 1.8~2.0 times of expansion in radial directions, are cooled down immediately, and obtaining internal diameter is 3.2mm, with a thickness of
The ETFE collapsible tube of 0.080mm.And Performance Evaluation is carried out to pipe obtained, the results are shown in Table 2.
Table 1: the component table of preparation embodiment 1-3 and comparative example 1-3
Remarks:
ETFE resin: derived from the Tefzel 200 of E.I.Du Pont Company；
Ternary fluororubber: derived from the Viton GLT 600S of E.I.Du Pont Company；
Acid absorbent: derived from the NICC5000 of Japanese Jing Shang lime Co., Ltd.；
Color master batch: the cool material Science and Technology Ltd. blue in Shanghai, color are free.
Table 2: preparation embodiment 1-3 and comparative example 1-3 physical and chemical performance and parameter list
Remarks:
The selection of this table test item is derived from American army mark SAE-AMS-DTL 23053/14.
By the test result of table 2 it can be seen that the present invention has clearly defined the various types effectively formed and component, because
Defect of the pure ETFE in the easy embrittlement of high temperature, it is desirable that must add fluorubber is improved；But ternary fluororubber lower temperature resistance difference
Disadvantage, and define the components range of its addition.Degradation when acid absorbent can effectively absorb fluoroplastics and fluorubber high temperature process
The fluoro free radical of generation can also inhibit the aggravation of degradation reaction while reducing poisonous and harmful substance generation.
Above-mentioned test data can be effectively prepared out it can be proved that technical method through the invention and meet American army mark
The ETFE heat-shrinkage material of 23053/14 performance requirement of SAE-AMS-DTL.
Claims (3)
1. a kind of ethylene and tetra fluoloethylene copolymer resin heat-shrinkable tube are grouped as by following group in parts by weight:
The ETFE resin is a kind of fluorine modeling made of the ratio alternating polymerization of ethylene and tetrafluoroethene according to molar ratio 1:1
Material；
The ternary fluororubber is the Viton GLT 600S of E.I.Du Pont Company；
The acid absorbent is the mixture of one of following substance or two or more of them substance: light magnesium oxide, hydrogen
Calcium oxide, calcium oxide, zinc oxide and lead oxide, the maximum particle diameter of above-mentioned substance require to be no more than 10 microns.
2. a kind of ethylene according to claim 1 and tetra fluoloethylene copolymer resin heat-shrinkable tube, it is characterised in that: described
The fusing point of ETFE resin is 250~280 DEG C, and melt flow rate (MFR) is 1~8g/10min, and density is 1.68~1.72g/cm3。
3. a kind of preparation method of ethylene as claimed in claim 1 or 2 and tetra fluoloethylene copolymer resin heat-shrinkable tube, feature
It is comprising following steps:
Step 1: weigh according to parts by weight 95~98 parts of ETFE resin, 2~5 parts of ternary fluororubber, 0.1~0.5 part of acid absorbent,
It 0~10 part of color master batch, is uniformly mixed with high-speed mixer, is put into the twin screw compounder that heating temperature is set as 280~340 DEG C
Middle melting mixing, it is 2~4mm that length, which is made, and diameter is the cylindric plastic pellet of 1~3mm；
Step 2: the resulting plastic pellet of step 1 is extruded into tubulose through plastic extruding forming machine；
Step 3: by tubing heat temperature raising obtained above, heating method is hot-air or glycerol, when material temperature reaches 120 DEG C
It at~180 DEG C, is deformed by air pressure or air pressure and vacuum pressure official post material expansion, deformation multiplying power is 1.8~2.0
Times, the material of deformation is quickly cooled down sizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611237585.4A CN106633356B (en) | 2016-12-28 | 2016-12-28 | A kind of ethylene and tetra fluoloethylene copolymer resin heat-shrinkage material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611237585.4A CN106633356B (en) | 2016-12-28 | 2016-12-28 | A kind of ethylene and tetra fluoloethylene copolymer resin heat-shrinkage material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106633356A CN106633356A (en) | 2017-05-10 |
| CN106633356B true CN106633356B (en) | 2019-03-05 |
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| CN201611237585.4A Active CN106633356B (en) | 2016-12-28 | 2016-12-28 | A kind of ethylene and tetra fluoloethylene copolymer resin heat-shrinkage material and preparation method thereof |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724503A (en) * | 2020-12-31 | 2021-04-30 | 深圳市沃尔核材股份有限公司 | Heat-shrinkable sleeve and manufacturing method thereof |
| CN115490952A (en) * | 2022-10-09 | 2022-12-20 | 道恩高材(北京)科技有限公司 | Fluorine rubber/fluoroplastic thermoplastic vulcanized rubber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02195668A (en) * | 1989-01-24 | 1990-08-02 | Sumitomo Electric Ind Ltd | Heat-contractile tube containing solder |
| CN101065440A (en) * | 2004-11-26 | 2007-10-31 | 大金工业株式会社 | Thermoplastic polymer composition and process for production thereof |
| CN103756202A (en) * | 2014-01-10 | 2014-04-30 | 长园电子（集团）有限公司 | Elastic polyvinylidene fluoride heat-shrinkable sleeve and preparation method thereof |
| CN104693650A (en) * | 2011-11-21 | 2015-06-10 | 株式会社润工社 | Heat-shrinkable tube having tearability |
-
2016
- 2016-12-28 CN CN201611237585.4A patent/CN106633356B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02195668A (en) * | 1989-01-24 | 1990-08-02 | Sumitomo Electric Ind Ltd | Heat-contractile tube containing solder |
| CN101065440A (en) * | 2004-11-26 | 2007-10-31 | 大金工业株式会社 | Thermoplastic polymer composition and process for production thereof |
| CN104693650A (en) * | 2011-11-21 | 2015-06-10 | 株式会社润工社 | Heat-shrinkable tube having tearability |
| CN103756202A (en) * | 2014-01-10 | 2014-04-30 | 长园电子（集团）有限公司 | Elastic polyvinylidene fluoride heat-shrinkable sleeve and preparation method thereof |
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| CN106633356A (en) | 2017-05-10 |
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Effective date of registration: 20190321 Address after: 523000 Po Po Industrial Zone, two industrial park, Fumin industrial estate, Dalang Town, Dongguan, Guangdong Co-patentee after: Changyuan electronic (Group) Co., Ltd. Patentee after: Changyuan Electronics (Dongguan) Co., Ltd. Co-patentee after: Shanghai Changyuan Electronic Material Co., Ltd. Co-patentee after: Tianjin Changyuan Electronic Material Co., Ltd. Address before: 523000 Po Po Industrial Zone, two industrial park, Fumin industrial estate, Dalang Town, Dongguan, Guangdong Co-patentee before: Changyuan electronic (Group) Co., Ltd. Patentee before: Changyuan Electronics (Dongguan) Co., Ltd. Co-patentee before: Shanghai Changyuan Electronic Material Co., Ltd. Co-patentee before: Tianjin Changyuan Electronic Material Co., Ltd. Co-patentee before: ChangYuan Group Ltd. |
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