CN108976346A - High stability fluoropolymer - Google Patents
High stability fluoropolymer Download PDFInfo
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- CN108976346A CN108976346A CN201810793068.8A CN201810793068A CN108976346A CN 108976346 A CN108976346 A CN 108976346A CN 201810793068 A CN201810793068 A CN 201810793068A CN 108976346 A CN108976346 A CN 108976346A
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Abstract
A kind of high stability fluoropolymer of the present invention, first step ingredient: uniformly mixes 10min for the substance comprising following mass parts in a high speed mixer；100 parts of ethylene-tetrafluoroethylene copolymer (ETFE), 4 parts of crosslinking sensitizer of the present invention, 0.2 part of 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid, N, 0.1 part of N '-ethylene bis stearamide；Wherein crosslinking sensitizer of the invention is made of component A and B, step 2: melting extrusion temperature is 240 ~ 330 DEG C by above-mentioned uniformly mixed raw material extruding pelletization in double screw extruder, obtains crosslinked fluoropolymer composition.Autohemagglutination is not easy under fluoropolymer processing temperature of the present invention, volatility is low, product stability can be improved, it is not volatile, it is not easy autohemagglutination, and improves fluoropolymer-containing melting means, therefore the ratio of A and B in adjusting crosslinking sensitizer of the present invention can be passed through, change fluoropolymer-containing melting means, to change its processing performance.
Description
Technical field
The present invention relates to crosslinking sensitizer technical field more particularly to a kind of high stability fluoropolymers.
Background technique
Fluoropolymer is crosslinked under x ray irradiation x and degrades while occurring, it is necessary to which crosslinking sensitizer is added could be in room temperature
It is lower to obtain the high degree of cross linking.Currently used for fluoropolymer-containing crosslinking sensitizer mainly by triallyl isocyanate (TAIC),
Triallyl cyanate (TAC) etc..But since fluoropolymer-containing processing temperature is substantially all at 200 DEG C or more, and TAIC,
TAC fusing point is low, and volatility is very big under fluoropolymer-containing processing temperature, or autohemagglutination, so that can generate in process big
The toxic smog of amount, and will affect product stability.
Therefore provide it is a kind of be not easy under fluoropolymer processing temperature autohemagglutination, volatility it is small be suitable for fluoropolymer
Cross-linking radiation sensitizer, be highly those skilled in the art go research.
Summary of the invention
The object of the present invention is to provide a kind of high stability fluoropolymer, which, which solves, works as
Preceding fluoropolymer crosslinking sensitizer easy autohemagglutination, volatility under fluoropolymer processing temperature is big, and generating largely has toxic smoke
Mist, the problem of product stability difference are not easy autohemagglutination under fluoropolymer processing temperature, and volatility is low, and it is steady that product can be improved
It is qualitative, it is not volatile, it is not easy autohemagglutination, and find in process, uses the sample of crosslinking sensitizer of the present invention, smoke
Measure small, the white pool of color sample, non-discolouring after irradiation, product stability is very good.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of high stability fluoropolymer passes through
Following steps obtain:
First step ingredient: the substance comprising following mass parts is uniformly mixed into 10min in a high speed mixer；
100 parts of ethylene-tetrafluoroethylene copolymer (ETFE),
4 parts of crosslinking sensitizer,
1,3,5- tri- 0.2 part of isocyanuric acid of (3,5- di-tert-butyl-4-hydroxyl benzyl),
0.1 part of N, N '-ethylene bis stearamide；
Wherein, the crosslinking sensitizer is made of component A and B, the component A: the mass ratio of component B is 0.3:1, wherein component
The structural formula of A meets following general structural formula (1):
(1)；
Wherein X is allyl, and n=2 ~ 15, the weight average molecular weight of component A is 600 ~ 5000；
The component B is 45% front three for allyl iso cyanurate, 55% triallyl isocyanate；
Step 2: melting extrusion temperature is 240 ~ 330 by above-mentioned uniformly mixed raw material extruding pelletization in double screw extruder
DEG C, obtain crosslinked fluoropolymer composition；
Step 3: by being irradiated after obtained crosslinked fluoropolymer composition tabletting, irradiation dose 15Mrad.
The further improved technical solution of above-mentioned technical proposal is as follows:
In above scheme, the weight average molecular weight of the component A is 4500.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
1. high stability fluoropolymer of the present invention, fluoropolymer-containing crosslinking sensitizer process temperature in fluoropolymer
Autohemagglutination is not easy under degree, volatility is low, and product stability can be improved, and it is not volatile, it is not easy autohemagglutination, and find in process,
Using the sample of crosslinking sensitizer of the present invention, smoke amount is small, the white pool of color sample, non-discolouring after irradiation, and product is stablized
Property is very good.
2. high stability fluoropolymer of the present invention, fluoropolymer-containing crosslinking sensitizer, since A and B is to fluorine-containing poly-
The plasticization effect of object is different, can change the processability of crosslinked fluoropolymer to a certain extent by the ratio of adjusting A and B
Energy.Since the viscosity of component A is larger, fluoropolymer-containing melting means can be reduced；And component B has good plasticising to fluoropolymer
Effect can be improved fluoropolymer-containing melting means, therefore can pass through the ratio of A and B in adjusting crosslinking sensitizer of the present invention
Example, to change fluoropolymer-containing melting means, to change its processing performance.
3. high stability fluoropolymer of the present invention, fluoropolymer-containing crosslinking sensitizer can be in a certain range
Change the mechanical property of crosslinked fluoropolymer composition, i.e. tensile strength and elongation at break.The analysis of causes is thought: due to this
Inventing component A in the crosslinking sensitization is long-chain macromolecule, is accordingly used in fluoropolymer, the cross-linked network formed after crosslinking
Grid is bigger, so its elongation at break can be relatively large；Component B is small molecule monomer, and strand is short, is accordingly used in fluorine-containing
The grid of polymer, the cross-linked network formed after crosslinking is smaller, so its elongation at break can be relatively small, intensity is larger.
Therefore the ratio of component A and component B is different in crosslinking sensitizer of the present invention, can influence fluoropolymer to a certain extent
Tensile strength and elongation at break after crosslinking.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment: a kind of high stability fluoropolymer, the crosslinking sensitizer in fluoropolymer are mixed by component A and component B
Close, the component A: the mass ratio of component B is 0.3:1, and wherein component A meets following general structural formula (1):
(1)；
Wherein X is vinyl, allyl, methylallyl or propargyl, and the weight average molecular weight of n=2 ~ 15, X is 600 ~ 5000；
The component B is 45% front three for allyl iso cyanurate, 55% triallyl isocyanate.
The weight average molecular weight of said components A is 850.
Described in detail below: the crosslinking sensitizer is made of component A and B, the component A: the mass ratio of component B is
0.3:1, the X are allyl, and the weight average molecular weight of the component A is 4500, and the component B is that 45% 3 methylallyl is different
Cyanate, 55% triallyl isocyanate.
A kind of crosslinked fluoropolymer using above-mentioned crosslinking sensitizer, is obtained by following steps:
First step ingredient: the substance comprising following mass parts is uniformly mixed into 10min in a high speed mixer；
100 parts of ethylene-tetrafluoroethylene copolymer (ETFE),
4 parts of crosslinking sensitizer of the present invention,
1,3,5- tri- 0.2 part of isocyanuric acid of (3,5- di-tert-butyl-4-hydroxyl benzyl),
0.1 part of N, N '-ethylene bis stearamide；
Wherein crosslinking sensitizer of the invention is made of component A and B, and the weight ratio of A and B are shown in Table 1, and wherein the structural formula of A is as follows:
Step 2: melting extrusion temperature is 240 ~ 330 by above-mentioned uniformly mixed raw material extruding pelletization in double screw extruder
DEG C, obtain crosslinked fluoropolymer composition；
Step 3: irradiation dose 15Mrad surveys its stretching by irradiating after obtained crosslinked fluoropolymer composition tabletting
Intensity and elongation at break.Test method: GJB-773A 2000, (50 ± 5) mm/min the results are shown in Table 1:
Table 1
It is stretched as can be seen from Table 1 using the crosslinked fluoropolymer tensile strength of crosslinking sensitizer of the present invention and fracture
Long rate can be adjusted by changing the content of component A and B in crosslinking agent.It is found in process, use is of the present invention
The sample of crosslinking sensitizer, smoke amount is small, and the white pool of color sample, non-discolouring after irradiation, product stability is very good.Of the invention
Crosslinking sensitizer is also used as the crosslinking agent of other high molecular polymers.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (2)
1. a kind of high stability fluoropolymer, is obtained by following steps:
First step ingredient: the substance comprising following mass parts is uniformly mixed into 10min in a high speed mixer；
100 parts of ethylene-tetrafluoroethylene copolymer (ETFE),
4 parts of crosslinking sensitizer,
1,3,5- tri- 0.2 part of isocyanuric acid of (3,5- di-tert-butyl-4-hydroxyl benzyl),
0.1 part of N, N '-ethylene bis stearamide；
Wherein, the crosslinking sensitizer is made of component A and B, the component A: the mass ratio of component B is 0.3:1, wherein component
The structural formula of A meets following general structural formula (1):
(1)；
Wherein X is allyl, and n=2 ~ 15, the weight average molecular weight of component A is 600 ~ 5000；
The component B is 45% front three for allyl iso cyanurate, 55% triallyl isocyanate；
Step 2: melting extrusion temperature is 240 ~ 330 by above-mentioned uniformly mixed raw material extruding pelletization in double screw extruder
DEG C, obtain crosslinked fluoropolymer composition；
Step 3: by being irradiated after obtained crosslinked fluoropolymer composition tabletting, irradiation dose 15Mrad.
2. high stability fluoropolymer according to claim 1, it is characterised in that: the weight average molecular weight of the component A
It is 4500.
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| CN201810793068.8A CN108976346B (en) | 2015-08-06 | 2015-08-06 | High stability fluoropolymers |
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| CN201510476936.6A CN105037797B (en) | 2015-08-06 | 2015-08-06 | For fluoropolymer-containing crosslinking sensitizer |
| CN201810793068.8A CN108976346B (en) | 2015-08-06 | 2015-08-06 | High stability fluoropolymers |
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| CN201810792366.5A Active CN109206819B (en) | 2015-08-06 | 2015-08-06 | High crosslinking degree sensitizer applied to fluorine-containing polymer |
| CN201810793068.8A Active CN108976346B (en) | 2015-08-06 | 2015-08-06 | High stability fluoropolymers |
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| CN106674579B (en) * | 2016-11-29 | 2019-08-09 | 中广核高新核材科技（苏州）有限公司 | The preparation method of engineering plastics cross-linked accelerating agent for irradiation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456991A (en) * | 2008-12-25 | 2009-06-17 | 临海市亚东特种电缆料厂 | Halogen-free flame retardant sheath material |
| CN102617923A (en) * | 2012-03-28 | 2012-08-01 | 天津市普立泰高分子科技有限公司 | Irradiation cross-linking low-smoke zero-halogen high flame-retarding polyolefin insulation material and preparing method thereof |
| CN103360675A (en) * | 2013-07-31 | 2013-10-23 | 深圳瑞亚达科技有限公司 | Crosslinkable oil-resistant low-smoke zero-halogen flame retardant electric wire and cable material and preparation method |
| CN104629159A (en) * | 2015-02-05 | 2015-05-20 | 中广核三角洲（江苏）塑化有限公司 | Crosslinked ethylene-tetrafluoroethylene copolymer insulating material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176027A (en) * | 1977-09-13 | 1979-11-27 | Raychem Corporation | Shaped article of radiation crosslinked triazine-trione polymeric composition |
| US8697291B2 (en) * | 2010-10-07 | 2014-04-15 | Uchicago Argonne, Llc | Non-aqueous electrolyte for lithium-ion battery |
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2015
- 2015-08-06 CN CN201510476936.6A patent/CN105037797B/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456991A (en) * | 2008-12-25 | 2009-06-17 | 临海市亚东特种电缆料厂 | Halogen-free flame retardant sheath material |
| CN102617923A (en) * | 2012-03-28 | 2012-08-01 | 天津市普立泰高分子科技有限公司 | Irradiation cross-linking low-smoke zero-halogen high flame-retarding polyolefin insulation material and preparing method thereof |
| CN103360675A (en) * | 2013-07-31 | 2013-10-23 | 深圳瑞亚达科技有限公司 | Crosslinkable oil-resistant low-smoke zero-halogen flame retardant electric wire and cable material and preparation method |
| CN104629159A (en) * | 2015-02-05 | 2015-05-20 | 中广核三角洲（江苏）塑化有限公司 | Crosslinked ethylene-tetrafluoroethylene copolymer insulating material |
Also Published As
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| CN109206819B (en) | 2021-02-23 |
| CN105037797A (en) | 2015-11-11 |
| CN105037797B (en) | 2018-07-20 |
| CN109206819A (en) | 2019-01-15 |
| CN108976346B (en) | 2021-06-04 |
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