CN105440198A - Preparation method for ethylene and tetrafluoroethylene copolymer with high bonding force - Google Patents
Preparation method for ethylene and tetrafluoroethylene copolymer with high bonding force Download PDFInfo
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- CN105440198A CN105440198A CN201510714036.0A CN201510714036A CN105440198A CN 105440198 A CN105440198 A CN 105440198A CN 201510714036 A CN201510714036 A CN 201510714036A CN 105440198 A CN105440198 A CN 105440198A
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Abstract
The present invention provides a preparation method for an ethylene (E) and tetrafluoroethylene (TFE) copolymer (ETFE) with a high bonding force. Perfluoroperoxide is taken as an initiator, a third monomer containing an active or polar functional group is added for a copolymerization reaction. According to the copolymer prepared by the present invention, the melting bonding strength test shows that the obtained ETFE copolymer has a relatively high binding force.
Description
Technical field
The present invention relates to a kind of preparation method with the ethylene-tetrafluoroethylene copolymer of high adhesion.
Background technology
Ethylene-tetrafluoroethylene copolymer (ETFE) is a kind of colourless, transparent crystalline particulate body, degree of crystallinity is about 50-60%, after tetrafluoroethylene (PTFE) and poly(perfluoropropene) (FEP), the another fluoroplastics kind developed, it has tetrafluoroethylene and poly good characteristics, there is excellent mechanical property, its tensile strength is 2 times of PTFE, creep resistance and shock resistance are all better than PTFE and FEP, there is excellent erosion resistance simultaneously, radiation resistance, weather-proof hot, dielectric properties and high light transmittance etc.
Because ETFE has above excellent properties, therefore its application widely, mainly contains the following aspects: (1) is widely used in reactor, pipeline, the chemical anticorrosion lining of storage tank etc.; (2) the extruded product electric wire of ETFE is widely used in aircraft, national defence and Highrise buildings etc., has excellent fire prevention ageing-resistant performance, also can be used as aircraft, vehicle fuel pipe etc.; (3) membrane product of ETFE is a kind of high-end material of construction, high transparency, ageing-resistant and have self-cleaning property, have also been obtained attention at heavy-duty battery and separation field simultaneously; (4) ETFE fibre product is widely used in the fields such as sewage disposal, has better acid-proof alkaline; (5) high performance fluorine plastic product.
No matter be as corrosion protective lining, or be used as mould material, or as tubing, sheet material etc., all require that ETFE and other materials have good bonding force, and as one of the general character of fluorine material, ETFE bounding force is still lower, stronger interface binding power cannot be obtained, make the application of ETFE receive certain restriction.In addition, choosing of initiator also has a significant impact the processing stability of ETFE, generally choose superoxide as initiator initiated polymerization, but when causing owing to adopting non-perfluorinated superoxide, the ETFE end of the chain obtained has unstable end-group, be unfavorable for forming process process, need to carry out end group process and just can obtain stable product.Therefore choose perfluor superoxide as initiator on the one hand, the impact of unstable end-group can be eliminated, improve the processing stability of ETFE further, on the other hand, the functional group had compared with strong adhesive power is accessed, such as polarity or active group, carboxyl, carboxylic acid anhydride, amino, amide group, itrile group, ether, ester group etc., to improve the bounding force of ETFE.
Summary of the invention
For overcoming above problem, the invention provides a kind of preparation method improving ETFE bounding force.
A preparation method for high adhesion ethylene-tetrafluoroethylene copolymer, comprises the following steps: in the polymeric kettle of 10L, adds the C of 8200g after finding time
6f
13the ethene of TFE, 26g of chain-transfer agent HCFC225,743g of H, 500g and the Third monomer of total amount 2%-5%, stirring is warmed up to 65 DEG C, add peroxidation hexafluoro propyl group two acyl fluorides of 50g as initiator initiated polymerization, mol ratio is (30-70) simultaneously: TFE and E of (70-30) continues to add to maintain pressure for 1.5MPa, after 4 hours, cooling, discharges unreacted monomer, except desolventizing obtains ETFE.
Described Third monomer can be below one or both:
(1) perfluorovinyl sulfide ethers R (OCFXCF
2)
mcF=CF
2, wherein R is the perfluoroalkyl of carbonatoms 1 to 6, and X is trifluoromethyl group or fluorine atom, and m is an integer in 1 to 6;
(2) easy Carboxylation or Sulfonated perfluoroolefine ethers, as CH
3oC=OCF
2cF
20CF=CF etc.;
(3) vinyl ester, as vinyl acetate etc.;
(4) allyl ether, as methallyl ether etc.
The bounding force of ethylene-tetrafluoroethylene copolymer prepared by the present invention increases significantly.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Comparative example 1
In the polymeric kettle of 10L, after finding time, add the C of 8200g
6f
13h, add the chain-transfer agent HCFC225 of 500g, the ethene of TFE and 26g of 743g, stirring is warmed up to 65 DEG C, adds peroxidation hexafluoro propyl group two acyl fluorides of 50g as initiator initiated polymerization, simultaneously mol ratio be 60/40 TFE/E continue to add to maintain pressure for 1.5MPa, after 4 hours, cooling, discharges unreacted monomer, except desolventizing obtains the ETFE of 807g; Recording its melting index is 22, and infrared spectra display is without absorption peak, and gained ETFE melting treatment and base material are bonded, then carry out peeling strength test, obtaining its bond strength is 5N/cm.
embodiment 1
Operation steps is same as Example 1, in addition adds the Third monomer CF of 5% in the feed
3oCF
2cF
2cF=CF
2, obtain the copolymerization ETFE of 849g.Recording melting index is 29, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 23N/cm.
embodiment 2
Operational condition is same as Example 1, in addition adds the Third monomer CF of 5% in the feed
3cF
2(OCF
2cF
2)
2cF=CF
2, obtain the copolymerization ETFE of 855g.Recording melting index is 30, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 23.8N/cm.
embodiment 3
Operational condition is same as Example 1, in addition adds the CF of 5% in the feed
3cF
2cF
2(OCF
2cF
2)
3cF=CF
2, obtain the copolymerization ETFE of 862g.Recording melting index is 30, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 23.9N/cm.
embodiment 4
Operational condition is same as Example 1, in addition adds the CF of 5% in the feed
3cF
2cF
2cF
2(OCF
2cF
2)
4cF=CF
2, obtain the copolymerization ETFE of 869g.Recording melting index is 31, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 24.2N/cm.
embodiment 5
Operational condition is same as Example 1, in addition at the CF adding 5%
3(CF
2)
4(OCF
2cF
2)
5cF=CF
2, obtain the copolymerization ETFE of 881g.Recording melting index is 32, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 25N/cm.
embodiment 6
Operational condition is same as Example 1, in addition at the CF adding 5%
3(CF2)
5(OCF
2cF
2)
6cF=CF
2, obtain the copolymerization ETFE of 893g.Recording melting index is 33, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 25.8N/cm.
embodiment 7
Operational condition is same as Example 1, in addition at the Third monomer CH adding 2%
3oC=OCF
2cF
20CF=CF
2, obtain the copolymerization ETFE of 847g.Recording melting index is 30, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 24N/cm.
embodiment 8
Operational condition is same as Example 1, in addition in the Third monomer methallyl ether adding 2%, obtains the copolymerization ETFE of 843g.Recording melting index is 32.9, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 23.8N/cm.
embodiment 9
Operational condition is same as Example 1, in addition at the Third monomer vinyl acetate adding 2%, obtains the copolymerization ETFE of 840g.Recording melting index is 31, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 25.7N/cm.
embodiment 10
Operational condition is same as Example 1, adds the Third monomer CH of 2 kind 5%
3oC=OCF
2cF
20CF=CF
2and methallyl ether, the mol ratio of two kinds of Third monomer is 1:1, obtains multipolymer ETFE880g; Recording melting index is 37, and infrared spectra is presented at 1600cm
-1to 1820cm
-1have obvious absorption peak, bond strength is 28.6N/cm.
As can be seen from above embodiment and comparative example, bond strength of the present invention obtains significant raising.
Claims (2)
1. a preparation method for high adhesion ethylene-tetrafluoroethylene copolymer, is characterized in that, comprises the following steps: in the polymeric kettle of 10L, adds the C of 8200g after finding time
6f
13the ethene of TFE, 26g of chain-transfer agent HCFC225,743g of H, 500g and the Third monomer of total amount 2%-5%, stirring is warmed up to 65 DEG C, add peroxidation hexafluoro propyl group two acyl fluorides of 50g as initiator initiated polymerization, mol ratio is (30-70) simultaneously: TFE and E of (70-30) continues to add to maintain pressure for 1.5MPa, after 4 hours, cooling, discharges unreacted monomer, except desolventizing obtains ETFE.
2. preparation method according to claim 1, is characterized in that, described Third monomer is perfluorovinyl sulfide ethers R (OCFXCF
2)
mcF=CF
2, perfluoroolefine ethers, vinyl ester, one or both in methallyl ether.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510714036.0A CN105440198A (en) | 2015-10-29 | 2015-10-29 | Preparation method for ethylene and tetrafluoroethylene copolymer with high bonding force |
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|---|---|---|---|
| CN201510714036.0A CN105440198A (en) | 2015-10-29 | 2015-10-29 | Preparation method for ethylene and tetrafluoroethylene copolymer with high bonding force |
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|---|---|
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084113A (en) * | 2016-06-27 | 2016-11-09 | 山东华氟化工有限责任公司 | A kind of ethylene tetrafluoroethylene copolymer and preparation method and application |
| CN109721675A (en) * | 2018-12-18 | 2019-05-07 | 浙江巨化技术中心有限公司 | A kind of ethylene-tetrafluoroethylene copolymer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1292643A (en) * | 1968-11-19 | 1972-10-11 | Du Pont | Ethylene/tetrafluoroethylene copolymers |
| JPH06298809A (en) * | 1993-04-16 | 1994-10-25 | Asahi Glass Co Ltd | Production of ethylene-tetrafluoroethylene copolymer |
| CN101508753A (en) * | 2009-02-16 | 2009-08-19 | 巨化集团公司 | Preparation of ethylene and tetrafluoroethylene copolymer |
| CN102504074A (en) * | 2011-11-08 | 2012-06-20 | 山东华氟化工有限责任公司 | Preparation method for tetrafluoroethylene-vinyl copolymer |
-
2015
- 2015-10-29 CN CN201510714036.0A patent/CN105440198A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1292643A (en) * | 1968-11-19 | 1972-10-11 | Du Pont | Ethylene/tetrafluoroethylene copolymers |
| JPH06298809A (en) * | 1993-04-16 | 1994-10-25 | Asahi Glass Co Ltd | Production of ethylene-tetrafluoroethylene copolymer |
| CN101508753A (en) * | 2009-02-16 | 2009-08-19 | 巨化集团公司 | Preparation of ethylene and tetrafluoroethylene copolymer |
| CN102504074A (en) * | 2011-11-08 | 2012-06-20 | 山东华氟化工有限责任公司 | Preparation method for tetrafluoroethylene-vinyl copolymer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084113A (en) * | 2016-06-27 | 2016-11-09 | 山东华氟化工有限责任公司 | A kind of ethylene tetrafluoroethylene copolymer and preparation method and application |
| CN106084113B (en) * | 2016-06-27 | 2018-06-12 | 山东华氟化工有限责任公司 | A kind of ethylene-tetrafluoroethylene copolymer and preparation method and application |
| CN109721675A (en) * | 2018-12-18 | 2019-05-07 | 浙江巨化技术中心有限公司 | A kind of ethylene-tetrafluoroethylene copolymer and preparation method thereof |
| CN109721675B (en) * | 2018-12-18 | 2021-01-08 | 浙江巨化技术中心有限公司 | Ethylene-tetrafluoroethylene copolymer and preparation method thereof |
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Application publication date: 20160330 |