CN102504074A - Preparation method for tetrafluoroethylene-vinyl copolymer - Google Patents
Preparation method for tetrafluoroethylene-vinyl copolymer Download PDFInfo
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- CN102504074A CN102504074A CN2011103498392A CN201110349839A CN102504074A CN 102504074 A CN102504074 A CN 102504074A CN 2011103498392 A CN2011103498392 A CN 2011103498392A CN 201110349839 A CN201110349839 A CN 201110349839A CN 102504074 A CN102504074 A CN 102504074A
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Abstract
The invention relates to a preparation method for a tetrafluoroethylene-vinyl copolymer, which belongs to the technical field of organic chemical synthesis of novel materials. The preparation method comprises the following steps of: adding an initial monomer into a solvent under a vacuum condition, heating to 55-60 DEG C; and adding a supplemented monomer and an initiator for reacting at the temperature of 55-60 DEG C under the pressure of 0.7-0.8 MPa for 3-5 hours, wherein the molar ratio of an initial monomer to the supplemented monomer is (7-10):1. A polymerization monomer is partitioned into the initial monomer and the supplemented monomer with different constitutions, so that the uniformity and completeness of a polymerization reaction are facilitated; the molecular weight of a ternary body in the copolymer is adjusted, so that an optimal pertinent point can be reached, and the comprehensive performance of a product is enhanced; and the selected initiator is stable and has high adjustability.
Description
Technical field
The present invention relates to organic chemistry synthetic new material technology field, particularly a kind of preparation method of tetrafluoroethylene-ethylene copolymer.
Background technology
Tetrafluoroethylene-ethylene copolymer has tetrafluoroethylene and poly advantage concurrently; Have on tetrafluoroethylene high-weatherability, high chemical stability, the high dielectric property basis; Has poly excellent processability again; Overcome can only mold pressing processing shortcoming, available common thermoplastics method for processing carries out machine-shaping, as extrude, mold pressing, injection moulding, spraying etc.Contain C-H because of tetrafluoroethylene-ethylene copolymer simultaneously; Have only the fluorine material of carbon-fluorine bond different with other; So the influence of irradiation Paratetrafluoroethylene-ethylene copolymer is obviously different, so tetrafluoroethylene-ethylene copolymer is used more extensive at nuclear power and field of aerospace.
The patent No. is that 200810138051.5 Chinese invention patent discloses a kind of ethylene-tetrafluoroethylene copolymer; Its structure is by ethene, tetrafluoroethylene, R 1216 and 1; 2, four kinds of monomer copolymerizations of 2-trifluorostyrene make, and ethene and tetrafluoroethylene shared molar ratio sum in multipolymer is 90-99.9%; All the other monomers shared molar ratio sum in multipolymer is 0.1 ~ 10%; The ethylene-tetrafluoroethylene copolymer that obtains at high temperature has heat-resisting cracking ability, has excellent mechanical property.The R 1216 that the present invention relates to and 1,2,2-trifluorostyrene cost is high, toxicity is big, is not most economical, safe starting material.
Application number is the method for manufacture that 200910095877.2 Chinese invention patent application discloses a kind of ethene and TFE copolymer; Comprise the steps: 1) adding solvent perfluor-4-methyl-2-amylene in polymerization reactor; Remove chlorine; Be heated to 40-85 ℃ of temperature, charge into the mixed gas of polymerization single polymerization monomer tetrafluoroethylene and ethene, reaction pressure is 0.5-2.0Mpa; 2) in reactor drum, add the chain-transfer agent cyclohexane, the 3rd monomer, initiator peroxo-perfluor naphthenic base formyl, and the mixed gas of additional polymerization single polymerization monomer tetrafluoroethylene and ethene obtain polymer powders through the recovery solvent, after having neither part nor lot in the auxiliary agent of reaction.3) polymer powders that obtains is got final product after handling 1-10h in oven dry under the 100-200 ℃ of condition.New initiator that the present invention selected for use and polymer solvent efficiency of initiation are stable, side reaction is few, produce the ethene and the tetrafluoroethylene copolymer resins excellent product performance that obtain, and high temperature resistant cracking performance is excellent.The reaction pressure that the present invention relates to be 0.5-2.0Mpa than higher, polymerization procedure is more loaded down with trivial details, is not suitable for large-scale application in suitability for industrialized production.
Summary of the invention
For used material cost height more than solving, complex process, problem that polymerization pressure is high, the invention provides that a kind of raw materials used cost is low, technology is easy to operate, the preparation method of the tetrafluoroethylene-ethylene copolymer of products obtained therefrom good combination property.
The present invention realizes through following measure:
A kind of preparation method of tetrafluoroethylene-ethylene copolymer adds initial monomer in solvent under vacuum condition, be warming up to 55-60 ℃ in 30 minutes, adds to add monomer and initiator, and reaction is 3-5 hour under 55-60 ℃, 0.7-0.8MPa condition;
The molecular fraction of each raw material is tetrafluoroethylene 45-50% in the said initial monomer, and ethene 44-55%, the 3rd monomer are 2-6%, and the said molecular fraction of adding each raw material in the monomer is tetrafluoroethylene 39-43%, and ethene 51-55%, the 3rd monomer are 2-6%;
Said initial monomer is 7-10:1 with adding monomeric mol ratio;
Said the 3rd monomer is a propylene.
Preferred said solvent is 1,2,2-trifluoro hexane, and the concentration of initial monomer in solvent is to contain 0.15-0.25 mole initial monomer in every liter of solvent.
Preferred initiator is the superoxide of peroxy dicarbonate two-(4 tert-butyl cyclohexyl) ester or acyl fluorides.
The superoxide of preferred said acyl fluorides is perfluor (2-positive propoxy propionyl) superoxide (C
12F
22O
4).
The add-on of preferred initiator is to add the 1.25-1.8g initiator in every mole of initial monomer.
The molecular fraction of each raw material is a tetrafluoroethylene 50% in the preferred said initial monomer; Ethene 44%, the three monomer is 6%, and the molecular fraction of adding each raw material in the monomer is a tetrafluoroethylene 43%; Ethene 51%; The 3rd monomer is 6%, and initial monomer is 7:1 with adding monomeric mol ratio, and initiator is perfluor (2-positive propoxy propionyl) superoxide; The concentration of initial monomer in solvent is to contain 0.16 mole of initial monomer in every liter of solvent, and the add-on of initiator is to add the 1.786g initiator in every mole of initial monomer.
Multipolymer distillating recovering solvent after the preferred reaction obtains the pellet of multipolymer after washing, the oven dry.
Preferably in 30 minutes, be warming up to 55-60 ℃.
Though content is seldom in multipolymer for the 3rd monomer among the present invention; But the performance impact to multipolymer is very big; Particularly melt and irreplaceable effect is arranged aspect the index range enlarging multipolymer; Regulate the molecular weight of the triplet in the multipolymer through efficient ways, reach best corresponding point, melt the exponential controlled range and bring up to 16-36g/10min (the reached 1-100 g/10min of divine boat).Except keeping good flowability, have high-weatherability, high chemical stability, high medium property, good radiation resistance and metal is had stronger tackiness.Polymerization technique provided by the invention has adopted solution polymerization process; Be different from and suspend or dispersion polymerization; Add the 3rd monomer in a small amount in the dimerization system, thereby make under the mechanical performance of products situation that great changes will take place, change its fusing point; Make it have superior processing characteristics, its finished product is divided into granulation material and powder according to different purposes.The granulation material mainly is used in the making of the insulation layer of doing cable, optical cable and film, and powder mainly is used in to be done spray material and make the base-material that some have the formulation material of special purpose.
Beneficial effect of the present invention:
1, polymerization single polymerization monomer is divided into initial monomer and adds monomer two portions; And two-part composition is different, helps the homogeneity and the sufficient reacting of polyreaction, regulates the molecular weight of the triplet in the multipolymer; Reach best corresponding point, help improving The comprehensive performance;
2, the 3rd monomeric adding, very big to the performance impact of multipolymer, particularly irreplaceable effect is arranged aspect the stable high fusion index multipolymer producing;
3, the initiator of selecting for use is stable, and Modulatory character is strong.
Embodiment
For a better understanding of the present invention, further specify below in conjunction with specific embodiment.
Embodiment 1
In the 500L polymeric kettle, add 1,2 of 350L, 2-Freon 113 solvent is under the condition of 0.01Mpa in absolute pressure; Add 80 moles of initial monomers, the mole of initial monomer consists of tetrafluoroethylene 45%, ethene 53%, propylene 2%; Rose to 55-60 ℃ in 30 minutes in the polymeric kettle temperature, add 8 moles and add monomer and 100 gram initiator peroxy dicarbonate 21 (4 tert-butyl cyclohexyl) esters carry out polyreaction, add monomeric mole and consist of tetrafluoroethylene 43%; Ethene 55%, propylene 2% keeps 55-60 ℃ of temperature and pressure under the 0.7-0.8Mpa condition, to react; Reacted 3 hours, reacted multipolymer is put into the washing still, reclaim solvent through Distallation systm; With the pellet that obtains multipolymer after the washing of multipolymer process, the oven dry, detect performance index again, the result is following: weight: 25kg; Molten index: 16 g/10min, tensile strength: 48Mpa, elongation: 466%.
Embodiment 2
In the 500L polymeric kettle, add 1,2 of 350L, 2-Freon 113 solvent is under the condition of 0.01Mpa in absolute pressure; Add 56 moles of initial monomers, the mole of initial monomer consists of tetrafluoroethylene 50%, ethene 44%, propylene 6%; Rose to 40-45 ℃ in 30 minutes in the polymeric kettle temperature, add 8 moles and add monomer and 100 gram initiator perfluor (2-positive propoxy propionyl) superoxide carry out polyreaction, add monomeric mole and consist of tetrafluoroethylene 43%; Ethene 51%, propylene 6% keeps 55-60 ℃ of temperature and pressure under the 0.7-0.8Mpa condition, to react; Reacted 5 hours, reacted multipolymer is put into the washing still, reclaim solvent through Distallation systm; With the pellet that obtains multipolymer after the washing of multipolymer process, the oven dry, detect performance index again, the result is following: weight: 23kg; Molten index: 36g/10min, tensile strength: 55Mpa, elongation: 512%.
Embodiment 3
In the 500L polymeric kettle, add 1,2 of 350L, 2-Freon 113 solvent is under the condition of 0.01Mpa in absolute pressure; Add 64 moles of initial monomers, the mole of initial monomer consists of tetrafluoroethylene 50%, ethene 46%, propylene 4%; Rose to 55-60 ℃ in 30 minutes in the polymeric kettle temperature, add 8 moles and add monomer and 100 gram initiator peroxy dicarbonate 21 (4 tert-butyl cyclohexyl) esters carry out polyreaction, add monomeric mole and consist of tetrafluoroethylene 43%; Ethene 53%, propylene 4% keeps 55-60 ℃ of temperature and pressure under the 0.7-0.8Mpa condition, to react; Reacted 3 hours, reacted multipolymer is put into the washing still, reclaim solvent through Distallation systm; With the pellet that obtains multipolymer after the washing of multipolymer process, the oven dry, detect performance index again, the result is following: weight: 22kg; Molten index: 18g/10min, tensile strength: 47Mpa, elongation: 484%.
The comparative example 1
With embodiment 1 contrast, initial monomer removes propylene with adding in the monomer, and shared molar ratio is all assigned in tetrafluoroethylene and the ethene, and other conditions are constant, obtain tetrafluoroethylene-ethylene copolymer, detect performance index, and the result is following:
Weight: 25kg, molten index: 1g/10min, tensile strength: 22Mpa elongation: 213%.
The comparative example 2
With embodiment 1 contrast, with initial monomer with add monomer and before heating up, add together, other conditions are constant, obtain tetrafluoroethylene-ethylene copolymer, detect performance index, the result is following:
Weight: 25kg, molten index: 0.5g/10min, tensile strength: 24Mpa elongation: 226%.
Through embodiment 1 contrast with comparative example 1, comparative example 2, adding, the initial monomer of visible the 3rd monomer propylene brought into play important effect with the performance raising of adding two factor Paratetrafluoroethylene-ethylene copolymers of monomeric reinforced form.
Claims (8)
1. the preparation method of a tetrafluoroethylene-ethylene copolymer; It is characterized in that under absolute pressure is the condition of 0.01Mpa, in solvent, adding initial monomer; Be warming up to 55-60 ℃, add and to add monomer and initiator, reaction is 3-5 hour under 55-60 ℃, 0.7-0.8MPa condition;
The molecular fraction of each raw material is tetrafluoroethylene 45-50% in the said initial monomer, and ethene 44-55%, the 3rd monomer are 2-6%, and the said molecular fraction of adding each raw material in the monomer is tetrafluoroethylene 39-43%, and ethene 51-55%, the 3rd monomer are 2-6%;
Said initial monomer is 7-10:1 with adding monomeric mol ratio;
Said the 3rd monomer is a propylene.
2. preparation method according to claim 1 is characterized in that said solvent is 1,2, and 2-Freon 113, the initial monomer concentration in solvent is to contain 0.15-0.25 mole initial monomer in every liter of solvent.
3. preparation method according to claim 1 is characterized in that initiator is the superoxide of peroxy dicarbonate two-(4 tert-butyl cyclohexyl) ester or acyl fluorides.
4. preparation method according to claim 3, the superoxide that it is characterized in that said acyl fluorides is perfluor (2-positive propoxy propionyl) superoxide.
5. preparation method according to claim 1, the add-on that it is characterized in that initiator add the 1.25-1.8g initiator in every mole of initial monomer.
6. according to each described preparation method among the claim 1-5, the molecular fraction that it is characterized in that each raw material in the said initial monomer is a tetrafluoroethylene 50%, ethene 44%; The 3rd monomer is 6%; The molecular fraction of adding each raw material in the monomer is a tetrafluoroethylene 43%, and ethene 51%, the three monomer is 6%; Initial monomer is 7:1 with adding monomeric mol ratio; Initiator is perfluor (2-positive propoxy propionyl) superoxide, and the concentration of initial monomer in solvent is to contain 0.16 mole of initial monomer in every liter of solvent, and the add-on of initiator is to add the 1.786g initiator in every mole of initial monomer.
7. according to each described preparation method among the claim 1-5, it is characterized in that reacted multipolymer distillating recovering solvent, obtain the pellet of multipolymer after washing, the oven dry.
8. according to each described preparation method among the claim 1-5, it is characterized in that in 30 minutes, being warming up to 55-60 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524659A (en) * | 2013-09-29 | 2014-01-22 | 山东华氟化工有限责任公司 | Tetrafluoroethylene and vinyl copolymer emulsion and preparation method thereof |
| CN104926979A (en) * | 2015-06-18 | 2015-09-23 | 巨化集团技术中心 | Ethylene/tetrafluoroethylene copolymer powder and method for preparing same |
| CN105440198A (en) * | 2015-10-29 | 2016-03-30 | 山东华氟化工有限责任公司 | Preparation method for ethylene and tetrafluoroethylene copolymer with high bonding force |
| CN108440702A (en) * | 2018-03-19 | 2018-08-24 | 浙江巨化技术中心有限公司 | A kind of preparation method of high thermal stability ethylene-tetrafluoroethylene copolymer |
| 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 |
| WO2024046494A1 (en) * | 2022-10-12 | 2024-03-07 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretch film and preparation method therefor |
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| CN101033277A (en) * | 2007-03-27 | 2007-09-12 | 上海三爱富新材料股份有限公司 | Tetrafluoroethylene-propylene fluorine-containing elastic body and preparing method thereof |
| CN101508753A (en) * | 2009-02-16 | 2009-08-19 | 巨化集团公司 | Preparation of ethylene and tetrafluoroethylene copolymer |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033277A (en) * | 2007-03-27 | 2007-09-12 | 上海三爱富新材料股份有限公司 | Tetrafluoroethylene-propylene fluorine-containing elastic body and preparing method thereof |
| CN101508753A (en) * | 2009-02-16 | 2009-08-19 | 巨化集团公司 | Preparation of ethylene and tetrafluoroethylene copolymer |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524659A (en) * | 2013-09-29 | 2014-01-22 | 山东华氟化工有限责任公司 | Tetrafluoroethylene and vinyl copolymer emulsion and preparation method thereof |
| CN103524659B (en) * | 2013-09-29 | 2016-06-08 | 山东华氟化工有限责任公司 | A kind of tetrafluoroethene and ethylene copolymer emulsion and preparation method thereof |
| CN104926979A (en) * | 2015-06-18 | 2015-09-23 | 巨化集团技术中心 | Ethylene/tetrafluoroethylene copolymer powder and method for preparing same |
| CN104926979B (en) * | 2015-06-18 | 2017-05-10 | 巨化集团技术中心 | Ethylene/tetrafluoroethylene copolymer powder and method for preparing same |
| CN105440198A (en) * | 2015-10-29 | 2016-03-30 | 山东华氟化工有限责任公司 | Preparation method for ethylene and tetrafluoroethylene copolymer with high bonding force |
| CN108440702A (en) * | 2018-03-19 | 2018-08-24 | 浙江巨化技术中心有限公司 | A kind of preparation method of high thermal stability ethylene-tetrafluoroethylene copolymer |
| CN108440702B (en) * | 2018-03-19 | 2020-10-20 | 浙江巨化技术中心有限公司 | Preparation method of ethylene-tetrafluoroethylene copolymer with high thermal stability |
| 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 |
| WO2024046494A1 (en) * | 2022-10-12 | 2024-03-07 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretch film and preparation method therefor |
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