CN1834124A - Prepn. of PVF - Google Patents
Prepn. of PVF Download PDFInfo
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- CN1834124A CN1834124A CN 200610050411 CN200610050411A CN1834124A CN 1834124 A CN1834124 A CN 1834124A CN 200610050411 CN200610050411 CN 200610050411 CN 200610050411 A CN200610050411 A CN 200610050411A CN 1834124 A CN1834124 A CN 1834124A
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- ethylene propylene
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- fluorinated ethylene
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Abstract
This invention discloses a method to prepare polyvinyl fluoride in which vinyl fluoride is adopted as monomers for polymerization. It has the characteristics that polymerization takes place with the existence of soluble radical initiators and auxiliary reagents. The auxiliary reagents in this invention can be: A) neutral inorganic salts; B) alkali or alkali compounds; C) acid or acidic compounds. This invention has the advantages that compared to previous literature, a) polymerization time can be reduced and efficiency of catalyst and facility can be promoted without obvious change in product properties such as intrinsic viscosity, melting point and melting heat by addition of auxiliary reagent A); b) melting point and melting heat of the product can be raised by addition of auxiliary reagent B); c) melting point and melting heat of the product can be lowered by addition of auxiliary reagent C). The polyvinyl fluoride membrane by melting tape-casting extrusion with potential solvent such as N, N-dimethylformamide and biaxial orientation of vinyl fluoride has wonderful comprehensive properties.
Description
Technical field
The present invention relates to a kind of preparation method of fluorinated ethylene propylene.
Background technology
Fluoro-resin has excellent high-and low-temperature resistance, good chemically-resistant solvent, acid and alkali corrosion is arranged, anti-atmospheric aging and stress crack resistance performance; Has excellent electrical insulating property, self lubricity, not viscosity, uninflammability and self-extinguishing do not absorb water, and frictional coefficient is minimum in all plastics, and odorless, tasteless, nontoxic has been widely used in chemical industry, electric, electronics and the mechanical industry, is the industrial special engineering plastics that can not lack.Fluorinated ethylene propylene is the simplest representative in the fluoropolymer homologue, and contained number of fluorine atoms was minimum during it was formed, and therefore compared with other fluoropolymer, and its density and production cost are minimum.But the same with other fluoropolymer, fluorinated ethylene propylene has special chemical resistance, hydrophobicity and wear resistance.Remarkable ageing resistance and non-viscosity are particularly arranged.Fluorinated ethylene propylene is widely used in fields such as building, decoration, electronic circuit, sun power as film and coating.Yet the vinyl fluoride polymerization activity is low, generally is difficult to obtain the polyfluoroethylene resin of excellent property.Preparing representative art based on fluorinated ethylene propylene mainly is that some patents of E.I.Du Pont Company are (as USP 2,419,010; USP 3,129, and 207; USP 3,265, and 678 etc.).
The method of bibliographical information fluorinated ethylene propylene preparation all adopts initiator directly to cause the vinyl fluoride polymerization, mainly comes speed of reaction, viscosity (or molecular weight) and the cladodification structure of controlling polymers by control reaction temperature and reaction pressure.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, aim to provide a kind of preparation method of fluorinated ethylene propylene, by the auxiliary agent (acid, alkali or salt) that in reaction system, adds minute quantity, be issued to speed of reaction, viscosity and the cladodification structure of controlling polymers in the situation that does not change temperature of reaction and reaction pressure.
The technical solution used in the present invention is: a kind of preparation method of fluorinated ethylene propylene, and adopt fluoride monomers to carry out polyreaction as raw material, it is characterized in that this method is to carry out in the presence of water-soluble radical initiator and auxiliary agent.
Initiator among the present invention, comprise and to decompose mineral compound and the organic compound that produces free radical, as ammonium persulphate, Potassium Persulphate, antihypo, potassium superphosphate, dipropyl peroxydicarbonate, azo-bis-isobutyrate hydrochloride etc., described initiator can be a compound, also the mixture that can be made up of the compound that satisfies above-mentioned condition.
Auxiliary agent can be A among the present invention: inorganic salt compound, neutral salt particularly, preferred halide salt, as Repone K, sodium-chlor, ammonium chloride, calcium chloride, Potcrate, potassium bromate, Potassium Iodate etc., because fluorine atom polarity long radius is little in the vinyl fluoride, make vinyl fluoride compare bigger polarity is arranged with other vinyl monomers, carry out addition reaction easily and be difficult to carry out polyreaction, inorganic salt compound as reaction promoter adds the polarity that can increase medium in the reaction medium, reduce the instantaneous dipole that is dissolved in vinyl fluoride in the medium, improve the polymerization activity of vinyl fluoride; Auxiliary agent also can be B: alkali or basic cpd, and as ammoniacal liquor, sodium hydroxide, potassium hydroxide, calcium hydroxide etc., the existence of alkaline medium has reduced on the fluorine carbon atom hydrogen by the probability of cladodification, improves product melt temperature and melting heat; Auxiliary agent can also be C: acid or acidic cpd, and example hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid etc., the existence of acidic medium has improved on the fluorine carbon atom hydrogen by the probability of cladodification, reduces product melt temperature and melting heat.
Advantage of the present invention is to compare with document in the past, and 1. the adding of auxiliary agent A can significantly reduce polymerization reaction time, improves catalyzer and equipment service efficiency, and product property (limiting viscosity, melt temperature, melting heat etc.) does not have obviously and changes; 2. the adding of auxiliary agent B can improve the melt temperature and the melting heat of product; 3. the adding of auxiliary agent C can reduce the melt temperature and the melting heat of product.Gained fluorinated ethylene propylene film forming properties is good, and fluorinated ethylene propylene has excellent comprehensive performances through two-way stretch gained polyvinyl fluoride thin film after extruding with latent solvent (as N, dinethylformamide) fusion curtain coating again.
As a further improvement on the present invention, the preparation method of fluorinated ethylene propylene of the present invention is by carrying out with step:
1) a certain amount of distilled water is added polymerization reaction kettle and is stirred and heated to 30～90 ℃; 2) a certain amount of distilled water, initiator and auxiliary agent are mixed the back in the batching still and add polymerization reaction kettle; 3) in polymerization reaction kettle, import fluoride monomers after polymerization reaction kettle is heated to 50～150 ℃, and keep the polymerization reaction kettle internal pressure, can generate polyvinyl fluoride polymer in 5.0～50.0MPa scope with volume pump.The mass ratio of described initiator and auxiliary agent is 100: 1～1: 100.Described polymerization reaction time is 2.5 hours.
Embodiment
The present invention is monomer with the vinyl fluoride, intermittently or in the successive reaction still is carrying out polymerization with distilled water, initiator, auxiliary agent, makes the fluorinated ethylene propylene of white bubble powder or tiny spheroidal particle.After extruding with latent solvent fusion curtain coating, prepared fluorinated ethylene propylene has excellent comprehensive performances through two-way stretch gained polyvinyl fluoride thin film again.
Concrete operation method and processing condition are as follows: step 1) adds distilled water polymerization reaction kettle and is heated to assigned temperature, and preferable temperature is 30～90 ℃; Step 2) under the room temperature distilled water, initiator and auxiliary agent are mixed the back in the batching still and add in the polymerization reaction kettle, the mass ratio of initiator and auxiliary agent is 100: 1～1: 100; Step 3) is heated to assigned temperature with polymerization reaction kettle, and preferable temperature is 50～150 ℃, imports fluoride monomers with volume pump in polymerization reaction kettle, and keeps the polymerization reaction kettle internal pressure in certain limit, and preferable pressure is 5.0～50.0MPa.The polymerization certain hour was lowered the temperature after 2～15 hours, and transformation efficiency is generally 40～90%, reclaims unreacted monomer, discharging, and product is white bubble powder or white tiny spheroidal particle.
Embodiment 1) 6000 parts of distilled water of adding in 10 liters of polymerization reaction kettles, be stirred and heated to 30 ℃, in the batching still, add 1000 parts of distilled water, 1 part of azo-bis-isobutyrate hydrochloride and 25 parts of Repone K, back adding polymerization reaction kettle stirs, the polymerization reaction kettle temperature is risen to 100 ℃ rapidly, and import fluoride monomers with volume pump, keep the polymerization reaction kettle internal pressure between 25.0～28.0MPa, react cooling in 2.5 hours, reclaim unreacted monomer, discharging obtains white bubble end, filter, wash, dry 985 parts of white powders.Product is dissolved in N in 110 ℃, dinethylformamide, and recording polymer property viscosity is 1.51dL/g.
Embodiment 2) 6000 parts of distilled water of adding in 10 liters of polymerization reaction kettles, be stirred and heated to 30 ℃, in the batching still, add 1000 parts of distilled water, 1 part of azo-bis-isobutyrate hydrochloride and 25 parts of potassium hydroxide, back adding polymerization reaction kettle stirs, the polymerization reaction kettle temperature is risen to 100 ℃ rapidly, and import fluoride monomers with volume pump, keep the polymerization reaction kettle internal pressure between 25.0～28.0MPa, react cooling in 2.5 hours, reclaim unreacted monomer, discharging obtains white tiny spheroidal particle, filter, wash, dry 1320 parts of white powders.Product is dissolved in N in 110 ℃, dinethylformamide, and recording polymer property viscosity is 1.35dL/g.
Embodiment 3) 6000 parts of distilled water of adding in 10 liters of polymerization reaction kettles, be stirred and heated to 30 ℃, in the batching still, add 1000 parts of distilled water, 1 part of azo-bis-isobutyrate hydrochloride and 25 parts of hydrochloric acid, back adding polymerization reaction kettle stirs, the polymerization reaction kettle temperature is risen to 100 ℃ rapidly, and import fluoride monomers with volume pump, keep the polymerization reaction kettle internal pressure between 25.0～28.0MPa, react cooling in 2.5 hours, reclaim unreacted monomer, discharging obtains white bubble end, filter, wash, dry 311 parts of white powders.Product is dissolved in N in 110 ℃, dinethylformamide, and recording polymer property viscosity is 1.82dL/g.
Fluorinated ethylene propylene is through latent solvent N, and dinethylformamide melt extrudes tests result such as table 1 according to GB530-88, GB13022-91, GB/T2410-1980 after two-way stretch becomes film.
Embodiment 4) 6000 parts of distilled water of adding in 10 liters of polymerization reaction kettles, be stirred and heated to 30 ℃, in the batching still, add 1000 parts of distilled water, 1 part of ammonium persulphate and 25 parts of potassium hydroxide, back adding polymerization reaction kettle stirs, the polymerization reaction kettle temperature is risen to 100 ℃ rapidly, and import fluoride monomers with volume pump, keep the polymerization reaction kettle internal pressure between 25.0～28.0MPa, react cooling in 2.5 hours, reclaim unreacted monomer, discharging obtains white bubble end, filter, wash, dry 1081 parts of white powders.Product is dissolved in N in 110 ℃, dinethylformamide, and recording polymer property viscosity is 2.42dL/g.
Table 1 two-way stretch polyvinyl fluoride thin film The performance test results
1)
Wherein: the thick 1.8mil of film.
What should be understood that is: the foregoing description is just to explanation of the present invention, rather than limitation of the present invention, and any innovation and creation that do not exceed in the connotation scope of the present invention all fall within protection scope of the present invention.
Claims (12)
1, a kind of preparation method of fluorinated ethylene propylene adopts fluoride monomers to carry out polyreaction as raw material, it is characterized in that this method is to carry out in the presence of water-soluble radical initiator and auxiliary agent.
2, the preparation method of fluorinated ethylene propylene as claimed in claim 1 is characterized in that described initiator is to decompose the inorganic salt that produce free radical.
3, the preparation method of fluorinated ethylene propylene as claimed in claim 2 is characterized in that described initiator is any or multiple combination wherein of ammonium persulphate, Potassium Persulphate, antihypo, potassium superphosphate.
4, the preparation method of fluorinated ethylene propylene as claimed in claim 1 is characterized in that described initiator is to decompose the organic compound that produces free radical.
5, the preparation method of fluorinated ethylene propylene as claimed in claim 4 is characterized in that described initiator is di-isopropyl peroxydicarbonate and/or azo-bis-isobutyrate hydrochloride.
6, the preparation method of fluorinated ethylene propylene as claimed in claim 1 is characterized in that described auxiliary agent is an inorganic salt compound.
7, the preparation method of fluorinated ethylene propylene as claimed in claim 6 is characterized in that described auxiliary agent is a halide salt.
8, the preparation method of fluorinated ethylene propylene as claimed in claim 1 is characterized in that described auxiliary agent is an alkali.
9, the preparation method of fluorinated ethylene propylene as claimed in claim 1 is characterized in that described auxiliary agent is acid.
10, as the preparation method of any one described fluorinated ethylene propylene of claim 1-9, it is characterized in that carrying out according to the following steps: 1) a certain amount of distilled water is added polymerization reaction kettle and is stirred and heated to 30～90 ℃; 2) a certain amount of distilled water, initiator and auxiliary agent are mixed the back in the batching still and add polymerization reaction kettle; 3) in polymerization reaction kettle, import fluoride monomers after polymerization reaction kettle is heated to 50～150 ℃, and keep the polymerization reaction kettle internal pressure, can generate polyvinyl fluoride polymer in 5.0～50.0MPa scope with volume pump.
11, the preparation method of fluorinated ethylene propylene as claimed in claim 10, the mass ratio that it is characterized in that described initiator and auxiliary agent is 100: 1～1: 100.
12, the preparation method of fluorinated ethylene propylene as claimed in claim 11 is characterized in that described polymerization reaction time is 1-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100504117A CN100500710C (en) | 2006-04-17 | 2006-04-17 | Preparation of PVF |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100504117A CN100500710C (en) | 2006-04-17 | 2006-04-17 | Preparation of PVF |
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| CN1834124A true CN1834124A (en) | 2006-09-20 |
| CN100500710C CN100500710C (en) | 2009-06-17 |
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| CNB2006100504117A Active CN100500710C (en) | 2006-04-17 | 2006-04-17 | Preparation of PVF |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820034A (en) * | 2010-04-30 | 2010-09-01 | 浙江日月旺光能科技有限公司 | Production process of solar cell back film and device thereof |
| CN102276948A (en) * | 2010-09-03 | 2011-12-14 | 中化蓝天集团有限公司 | Preparation method of biaxially stretched polyvinyl fluoride film |
| CN104448148A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of modified polyvinyl fluoride and the prepared modified polyvinyl fluoride |
| CN104448147A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of modified graft polyvinyl fluoride and the prepared modified graft polyvinyl fluoride |
| CN105504116A (en) * | 2014-10-20 | 2016-04-20 | 浙江蓝天环保氟材料有限公司 | Preparation method of polyfluoroethylene resin with high chain regularity |
| CN106280143A (en) * | 2016-08-10 | 2017-01-04 | 吴迪 | A kind of preparation method of nano combined polyvinyl fluoride thin film |
| CN106432565A (en) * | 2015-08-06 | 2017-02-22 | 浙江蓝天环保高科技股份有限公司 | Anticorrosive polyfluoroethylene resin, and preparation method and application thereof |
-
2006
- 2006-04-17 CN CNB2006100504117A patent/CN100500710C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820034A (en) * | 2010-04-30 | 2010-09-01 | 浙江日月旺光能科技有限公司 | Production process of solar cell back film and device thereof |
| CN102276948A (en) * | 2010-09-03 | 2011-12-14 | 中化蓝天集团有限公司 | Preparation method of biaxially stretched polyvinyl fluoride film |
| CN104448148A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of modified polyvinyl fluoride and the prepared modified polyvinyl fluoride |
| CN104448147A (en) * | 2013-09-13 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of modified graft polyvinyl fluoride and the prepared modified graft polyvinyl fluoride |
| CN104448147B (en) * | 2013-09-13 | 2017-02-15 | 中国石油化工股份有限公司 | Preparation method of modified graft polyvinyl fluoride and the prepared modified graft polyvinyl fluoride |
| CN104448148B (en) * | 2013-09-13 | 2017-02-15 | 中国石油化工股份有限公司 | Preparation method of modified polyvinyl fluoride and the prepared modified polyvinyl fluoride |
| CN105504116A (en) * | 2014-10-20 | 2016-04-20 | 浙江蓝天环保氟材料有限公司 | Preparation method of polyfluoroethylene resin with high chain regularity |
| CN106432565A (en) * | 2015-08-06 | 2017-02-22 | 浙江蓝天环保高科技股份有限公司 | Anticorrosive polyfluoroethylene resin, and preparation method and application thereof |
| CN106280143A (en) * | 2016-08-10 | 2017-01-04 | 吴迪 | A kind of preparation method of nano combined polyvinyl fluoride thin film |
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| Publication number | Publication date |
|---|---|
| CN100500710C (en) | 2009-06-17 |
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