CN106700218A - Fluoropolymer heat-shrinkable sleeve and production method thereof - Google Patents
Fluoropolymer heat-shrinkable sleeve and production method thereof Download PDFInfo
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- CN106700218A CN106700218A CN201611139497.0A CN201611139497A CN106700218A CN 106700218 A CN106700218 A CN 106700218A CN 201611139497 A CN201611139497 A CN 201611139497A CN 106700218 A CN106700218 A CN 106700218A
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- Prior art keywords
- shrinkable
- fluoropolymer
- heat
- bush
- fluoropolymer heat
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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
-
- 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
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a fluoropolymer heat-shrinkable sleeve and a production method thereof. The fluoropolymer heat-shrinkable sleeve is produced by using the following components in parts by weight: 50 to 80 parts of ETFE, 5 to 50 parts of fluoropolymer, 5 to 30 parts of an acid absorbent, 0.1 to 2 parts of a copper resisting agent, 0.3 to 5 parts of sn antioxidant, 0.3 to 3 parts of a crosslinking agent and 0 to 15 parts of titanium dioxide. The heat-shrinkable sleeve with high temperature-resisting grade and softness is obtained by compounding the ETFE, the fluoropolymer and other materials, and has the characteristics of high temperature resistance and low temperature resistance; meanwhile, the fluoropolymer heat-shrinkable sleeve also has the advantages of low dielectric loss, high transmission performance, good oil resistance and solvent resistance, excellent flame retardance, higher mechanical strength and the like.
Description
Technical field
The present invention relates to cable material field.Specifically related to a kind of fluoropolymer heat-shrinkable T bush and preparation method thereof.
Background technology
Heat-shrinkable T bush also known as thermal contraction protection sleeve pipe, for electric wire, cable or wire terminal provide insulation protection.Heat-shrinkable T bush
The characteristics of with high-temperature shrinkage, fire-retardant softness, insulation corrosion protection, it is widely used in various wire harness, solder joint, the insulation protection of inductance and gold
Category pipe, the antirust of rod, corrosion protection process for protecting.Common resin has three classes in the material prescription of heat-shrinkable T bush：Polyolefin, polychlorostyrene second
Alkene, fluoropolymer.Wherein fluoropolymer has highest combination property, and high-low temperature resistant grade is high, fire-retardant, weather-proof, oil resistant, resistance to
Mill, electrical insulation capability is good, high mechanical properties, but fluororesin Costco Wholesale is high, being applied to such heat-shrinkable T bush more technical requirements it is high,
The harsh high-end market of use environment.
Existing fluorine-containing heat-shrinkable T bush mostly use ETFE resins (independent resinous principle), also have on a small quantity with ETFE resins with
Other fluoropolymer compounding uses.In addition to ETFE, market-oriented level is higher in fluoropolymer, and a variety of fluoropolymers are gathered around
There are different physical property emphasis, different temperature resistant grades, and cost of material differs, and ETFE resins are compounded from different fluoropolymers
The heat-shrinkable T bush of preparation possesses different advantages, cost and application surface.Because various fluoropolymers possess different advantage and disadvantage, with
Based on ETFE, be aided with other fluoropolymers prepare material purpose be play each component fluoropolymer performance complement feature, make
Tubing is able to be applied to specific applied environment.But most fluorine-containing heat-shrinkable T bush is generally independent resinous principle on the market,
The performance for possessing is single and production cost is too high.
The content of the invention
In order to overcome the deficiencies in the prior art, first purpose of the invention is to provide a kind of fluoropolymer thermal shrinkable sleeve
Pipe, the heat-shrinkable T bush obtains a kind of temperature resistant grade heat-shrinkable T bush high by compound the materials such as ETFE, fluoropolymer.
Second object of the present invention is to provide for a kind of preparation method of above-mentioned heat-shrinkable T bush.
Realize that the purpose of the present invention can reach by adopting the following technical scheme that：
A kind of fluoropolymer heat-shrinkable T bush, including each component by weight as follows：
In the present invention, described fluoropolymer is one or more in PVDF, PFA, PCTFE, ECTFE.
Preferably, the acid absorbent is the one kind in the first acid absorbent, magnesia, magnesium hydroxide；First acid
Absorbent is made up of Tissuemat E and 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols).
Preferably, first acid absorbent by Tissuemat E and 4, press by 4 '-thiobis (the 6- tert-butyl group -3- methylphenols)
Weight compares 1:1 mixture is formed.
Preferably, the crosslinking agent is triallyl isonitrile urea acid fat or triallyl nitrile urea acid fat.
Preferably, the antioxidant is 2,6- di-tert-butylphenols, 4,4'- thiobis (the 6- tert-butyl group -3- methylphenols), four
One kind in [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester.
Preferably, the copper resistant agent is N- bigcatkin willows amino neighbour's benzene diimine or N, N '-bis- [β (3,5- bis- tertiary factory's base -4- hydroxyls
Base phenyl) propionyl] hydrazine.
Preferably, the fluoropolymer heat-shrinkable T bush includes following each component by weight：
Preferably, the fluoropolymer heat-shrinkable T bush includes following each component by weight：
The present invention also provides a kind of preparation method of fluoropolymer heat-shrinkable T bush, comprises the following steps：
1) ETFE, fluoropolymer, acid absorbent, copper resistant agent, antioxidant, the titanium dioxide of formula ratio are taken, single spiral shell is put into successively
It is uniform in banburying at 260-320 DEG C in the refining material room of bar banburying comminutor；
2) again to the crosslinking coagent that formula ratio is added in the refining material room of single screw rod banburying comminutor, under the conditions of 260-320 DEG C
Banburying is uniform；Obtain compound；
3) by compound mechanical feed to single screw rod banburying comminutor prilling section, at 260-360 DEG C extrude, draw
Silk, air-cooled, pelletizing；Obtain pellet；
4) use is provided with mouth mold and the screw extruder of core and pellet into pipe is extruded at 260-360 DEG C；Obtain primary tube
Material；
5) primary tubing is carried out into cross-linking radiation；Irradiation dose is 4-16Mrad；Again by cross-linking radiation after primary tubing
Thermal contraction casing tube is obtained in stretching, cooling and shaping is expanded at 280-360 DEG C；
6) thermal contraction casing tube is processed through the leveling of plastic cement evener, mark obtains heat-shrinkable T bush finished product.
Compared to existing technology, the beneficial effects of the present invention are：
1st, the present invention obtains a kind of temperature resistant grade thermal shrinkable sleeve high by compound the materials such as ETFE, fluoropolymer
Pipe；The characteristics of heat-shrinkable T bush has high temperature resistant (more than 260 DEG C), low temperature resistant (less than -75 DEG C)；Meanwhile, also with antiacid, anti-
Alkali, health organic solvent, dielectric loss are small, transmission performance is high, and oil resistant, solvent resistance are good, higher with excellent anti-flammability
The advantages of mechanical strength.
Specific embodiment
Below, with reference to specific embodiment, the present invention is described further：
Embodiment 1：
A kind of fluoropolymer heat-shrinkable T bush, including each component by weight as follows：
Described fluoropolymer is PVDF.The acid absorbent is magnesia；The copper resistant agent is N- bigcatkin willows amino neighbour's benzene
Diimine；The antioxidant is 2,6- di-tert-butylphenols；The crosslinking coagent is triallyl isonitrile urea acid fat.
Heat-shrinkable T bush described in the present embodiment is adopted and is prepared from the following method：
1) take the ETFE of formula ratio, fluoropolymer, acid absorbent, copper resistant agent, antioxidant, successively input single screw rod banburying make
It is uniform in banburying at 260 DEG C in the refining material room of grain machine；-
2) again to the crosslinking coagent that formula ratio is added in the refining material room of single screw rod banburying comminutor, banburying under the conditions of 260 DEG C
Uniformly；Obtain compound；-
3) by compound mechanical feed to single screw rod banburying comminutor prilling section, at 260-360 DEG C extrude, draw
Silk, air-cooled, pelletizing；Obtain pellet；
4) use is provided with mouth mold and the screw extruder of core and pellet into pipe is extruded at 260-360 DEG C；Obtain primary tube
Material；
5) primary tubing is carried out into cross-linking radiation；Irradiation dose is 4Mrad；Again by cross-linking radiation after primary tubing in
Stretching, cooling and shaping are expanded at 280-360 DEG C and obtains thermal contraction casing tube；
6) thermal contraction casing tube is processed through the leveling of plastic cement evener, mark obtains heat-shrinkable T bush finished product.
Embodiment 2：
A kind of fluoropolymer heat-shrinkable T bush, including each component by weight as follows：
The acid absorbent is magnesium hydroxide；The copper resistant agent is N, N '-bis- [β (3,5- bis- tertiary factory's base -4- hydroxy phenyls)
Propionyl] hydrazine；The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；The crosslinking is helped
Agent is triallyl isonitrile urea acid fat.Described fluoropolymer is PFA.
Heat-shrinkable T bush described in the present embodiment is adopted and is prepared from the following method：
1) ETFE, fluoropolymer, acid absorbent, copper resistant agent, antioxidant, the titanium dioxide of formula ratio are taken, single spiral shell is put into successively
It is uniform in banburying at 320 DEG C in the refining material room of bar banburying comminutor；
2) again to the crosslinking coagent that formula ratio is added in the refining material room of single screw rod banburying comminutor, banburying under the conditions of 320 DEG C
Uniformly；Obtain compound；
3) by compound mechanical feed to single screw rod banburying comminutor prilling section, at 260-360 DEG C extrude, draw
Silk, air-cooled, pelletizing；Obtain pellet；
4) use is provided with mouth mold and the screw extruder of core and pellet into pipe is extruded at 260-360 DEG C；Obtain primary tube
Material；
5) primary tubing is carried out into cross-linking radiation；Irradiation dose is 16Mrad；Again by cross-linking radiation after primary tubing in
Stretching, cooling and shaping are expanded at 280-360 DEG C and obtains thermal contraction casing tube；
6) thermal contraction casing tube is processed through the leveling of plastic cement evener, mark obtains heat-shrinkable T bush finished product.
Embodiment 3：
A kind of fluoropolymer heat-shrinkable T bush, including each component by weight as follows：
The acid absorbent is magnesium hydroxide；The copper resistant agent is N, N '-bis- [β (3,5- bis- tertiary factory's base -4- hydroxy phenyls)
Propionyl] hydrazine；The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；The crosslinking is helped
Agent is triallyl nitrile urea acid fat.Described fluoropolymer is PCTFE.
Heat-shrinkable T bush described in the present embodiment is adopted and is prepared from the following method：
1) ETFE, fluoropolymer, acid absorbent, copper resistant agent, antioxidant, the titanium dioxide of formula ratio are taken, single spiral shell is put into successively
It is uniform in banburying at 300 DEG C in the refining material room of bar banburying comminutor；
2) again to the crosslinking coagent that formula ratio is added in the refining material room of single screw rod banburying comminutor, banburying under the conditions of 300 DEG C
Uniformly；Obtain compound；
3) by compound mechanical feed to single screw rod banburying comminutor prilling section, at 260-360 DEG C extrude, draw
Silk, air-cooled, pelletizing；Obtain pellet；
4) use is provided with mouth mold and the screw extruder of core and pellet into pipe is extruded at 260-360 DEG C；Obtain primary tube
Material；
5) primary tubing is carried out into cross-linking radiation；Irradiation dose is 10Mrad；Again by cross-linking radiation after primary tubing in
Stretching, cooling and shaping are expanded at 280-360 DEG C and obtains thermal contraction casing tube；
6) thermal contraction casing tube is processed through the leveling of plastic cement evener, mark obtains heat-shrinkable T bush finished product.
Embodiment 4：
A kind of fluoropolymer heat-shrinkable T bush, including each component by weight as follows：
First acid absorbent by Tissuemat E and 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols) by weight
1:1 mixture is formed.Described fluoropolymer is ECTFE.
Heat-shrinkable T bush described in the present embodiment is adopted and is prepared from the following method：
1) ETFE of formula ratio, fluoropolymer, the first acid absorbent, N- bigcatkin willows amino neighbour's benzene diimine, 4,4'- are taken thio
Double (the 6- tert-butyl group -3- methylphenols), titanium dioxide, successively in close at 300 DEG C in the refining material room of input single screw rod banburying comminutor
Refining is uniform；-
2) again to the triallyl nitrile urea acid fat that formula ratio is added in the refining material room of single screw rod banburying comminutor, 300 DEG C of bars
Banburying is uniform under part；Obtain compound；-
3) by compound mechanical feed to single screw rod banburying comminutor prilling section, at 260-360 DEG C extrude, draw
Silk, air-cooled, pelletizing；Obtain pellet；
4) use is provided with mouth mold and the screw extruder of core and pellet into pipe is extruded at 260-360 DEG C；Obtain primary tube
Material；
5) primary tubing is carried out into cross-linking radiation；Irradiation dose is 14Mrad；Again by cross-linking radiation after primary tubing in
Stretching, cooling and shaping are expanded at 280-360 DEG C and obtains thermal contraction casing tube；
6) thermal contraction casing tube is processed through the leveling of plastic cement evener, mark obtains heat-shrinkable T bush finished product.
Checking embodiment
The fluoropolymer heat-shrinkable T bush prepared by embodiment 1-4 is chosen, tensile strength, fracture is carried out to the heat-shrinkable T bush and is stretched
The projects such as rate long, heat ageing after-drawing strength retention, anti-flammability are detected, as a result as shown in table 1 below, selected by embodiment 4
Material and preparation method obtain the heat-shrinkable T bush of best performance.
The properties testing result of table 1, embodiment 1-4 heat-shrinkable T bush
For a person skilled in the art, technical scheme that can be as described above and design, make other each
Plant corresponding change and deform, and all these changes and deforms the protection model that should all belong to the claims in the present invention
Within enclosing.
Claims (9)
1. a kind of fluoropolymer heat-shrinkable T bush, it is characterised in that including each component as follows by weight：
2. fluoropolymer heat-shrinkable T bush according to claim 1, it is characterised in that：The acid absorbent is that the first acid absorbs
One kind in agent, magnesia, magnesium hydroxide；First acid absorbent by Tissuemat E and 4,4 '-thiobis (the 6- tert-butyl groups-
3- methylphenols) composition.
3. fluoropolymer heat-shrinkable T bush according to claim 1, it is characterised in that：First acid absorbent is by polyethylene
Wax and 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols) are by weight 1:1 mixture is formed.
4. fluoropolymer heat-shrinkable T bush according to claim 1, it is characterised in that：The crosslinking agent is triallyl isonitrile
Urea acid fat or triallyl nitrile urea acid fat.
5. fluoropolymer heat-shrinkable T bush according to claim 1, it is characterised in that：The antioxidant is 2,6- di-t-butyls
Phenol, 4,4'- thiobis (the 6- tert-butyl group -3- methylphenols), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] Ji Wusi
One kind in alcohol ester.
6. fluoropolymer heat-shrinkable T bush according to claim 1, it is characterised in that：The copper resistant agent is adjacent N- bigcatkin willows amino
Benzene diimine or N, N '-bis- [β (3,5- bis- tertiary factory's base -4- hydroxy phenyls) propionyl] hydrazines.
7. fluoropolymer heat-shrinkable T bush according to claim 1, it is characterised in that：The fluoropolymer heat-shrinkable T bush includes
Following each component by weight：
8. fluoropolymer heat-shrinkable T bush according to claim 1, it is characterised in that：The fluoropolymer heat-shrinkable T bush includes
Following each component by weight：
9. a kind of preparation method of fluoropolymer heat-shrinkable T bush as claimed in claim 1, it is characterised in that comprise the following steps：
1) ETFE, fluoropolymer, acid absorbent, copper resistant agent, antioxidant, the titanium dioxide of formula ratio are taken, single screw rod is put into successively close
It is uniform in banburying at 260-320 DEG C in the refining material room of refining comminutor；
2) again to the crosslinking coagent that formula ratio is added in the refining material room of single screw rod banburying comminutor, banburying under the conditions of 260-320 DEG C
Uniformly；Obtain compound；
3) by compound mechanical feed to single screw rod banburying comminutor prilling section, in extrusion, wire drawing, wind at 260-360 DEG C
Cold, pelletizing；Obtain pellet；
4) use is provided with mouth mold and the screw extruder of core and pellet into pipe is extruded at 260-360 DEG C；Obtain primary tubing；
5) primary tubing is carried out into cross-linking radiation；Irradiation dose is 4-16Mrad；Again by cross-linking radiation after primary tubing in
Stretching, cooling and shaping are expanded at 280-360 DEG C and obtains thermal contraction casing tube；
6) thermal contraction casing tube is processed through the leveling of plastic cement evener, mark obtains heat-shrinkable T bush finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611139497.0A CN106700218A (en) | 2016-12-12 | 2016-12-12 | Fluoropolymer heat-shrinkable sleeve and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611139497.0A CN106700218A (en) | 2016-12-12 | 2016-12-12 | Fluoropolymer heat-shrinkable sleeve and production method thereof |
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| CN106700218A true CN106700218A (en) | 2017-05-24 |
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| CN201611139497.0A Pending CN106700218A (en) | 2016-12-12 | 2016-12-12 | Fluoropolymer heat-shrinkable sleeve and production method thereof |
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Cited By (4)
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| CN110256762A (en) * | 2019-07-19 | 2019-09-20 | 长园电子（东莞）有限公司 | A kind of radiation crosslinking modified ECTFE thermal contraction casing tube and preparation method thereof |
| CN110511517A (en) * | 2019-08-16 | 2019-11-29 | 郑州海太克高分子技术有限公司 | A kind of antistatic Teflon special material for tube and preparation method thereof |
| WO2022181142A1 (en) * | 2021-02-24 | 2022-09-01 | 住友電工ファインポリマー株式会社 | Heat-shrinkable tubing, heat-shrinkable coupling component, production method for heat-shrinkable tubing, and production method for heat-shrinkable coupling component |
| CN116082740A (en) * | 2022-11-01 | 2023-05-09 | 广州敬信高聚物科技有限公司 | Irradiation crosslinking foaming PFA/ETFE cable insulating material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256762A (en) * | 2019-07-19 | 2019-09-20 | 长园电子（东莞）有限公司 | A kind of radiation crosslinking modified ECTFE thermal contraction casing tube and preparation method thereof |
| CN110511517A (en) * | 2019-08-16 | 2019-11-29 | 郑州海太克高分子技术有限公司 | A kind of antistatic Teflon special material for tube and preparation method thereof |
| WO2022181142A1 (en) * | 2021-02-24 | 2022-09-01 | 住友電工ファインポリマー株式会社 | Heat-shrinkable tubing, heat-shrinkable coupling component, production method for heat-shrinkable tubing, and production method for heat-shrinkable coupling component |
| JP7406043B2 (en) | 2021-02-24 | 2023-12-26 | 住友電工ファインポリマー株式会社 | Heat-shrinkable tube, heat-shrinkable connecting parts, manufacturing method of heat-shrinkable tube, and manufacturing method of heat-shrinkable connecting parts |
| CN116082740A (en) * | 2022-11-01 | 2023-05-09 | 广州敬信高聚物科技有限公司 | Irradiation crosslinking foaming PFA/ETFE cable insulating material and preparation method thereof |
| CN116082740B (en) * | 2022-11-01 | 2023-11-28 | 广州敬信高聚物科技有限公司 | Irradiation crosslinking foaming PFA/ETFE cable insulating material and preparation method thereof |
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