CN100564410C - A kind of preparation method of low-molecular-weight soluble fluoro-resin - Google Patents
A kind of preparation method of low-molecular-weight soluble fluoro-resin Download PDFInfo
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- CN100564410C CN100564410C CNB2007101664461A CN200710166446A CN100564410C CN 100564410 C CN100564410 C CN 100564410C CN B2007101664461 A CNB2007101664461 A CN B2007101664461A CN 200710166446 A CN200710166446 A CN 200710166446A CN 100564410 C CN100564410 C CN 100564410C
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Abstract
The invention provides a kind of preparation method of low-molecular-weight soluble fluoro-resin, adopt the suspension polymerization mode, water is as dispersion medium, and polymerization single polymerization monomer is 70～90mol% trifluorochloroethylene and 10～30mol% vinylidene; Initiator is an organo-peroxide, and consumption is the initiator that contains 0.001～5 weight part in per 100 weight parts water media; Keep the polymerization single polymerization monomer component constant in the polymerization process, the number-average molecular weight that is polymerized to fluorine resin is till 50,000 to 450,000, and back employing freeze agglomeration is finished in reaction and the water-cooled grinding mode carries out aftertreatment.The fluoro-resin that this method obtains has very excellent chemical resistance, and good storage stability and film performance are applicable to and make various protective systems, and be easy to use, it can be dissolved in the low molecular organic solvent and directly construct.
Description
Technical field
The present invention relates to a kind of preparation method of low-molecular-weight soluble fluoro-resin, specifically, relate to the suspension polymerization that is used to produce fluorine resin, this resin is the multipolymer of vinylidene and trifluorochloroethylene, comprises adopting freeze agglomeration and water-cooled grinding mode that this resin is handled.
Background technology
Fluorine resin has excellent low temperature resistant, oil resistant and chemical-resistant, various protective systems, coatings art have been widely used in, concrete example has comprised teflon resin, polyvinylidene fluoride resin, daiflon, F26 type and F24 type fluoro-resin etc. commonly used, but its solvability is except that F24 type fluoro-resin has preferably solvability in low molecule ketone and ester class, the solvability extreme difference of other fluorine resin, even be not dissolved in any solvent, this has just limited the Application Areas of this class fluoro-resin.
Document CN1861653A discloses a kind of cross-linked water soluble fluorine resin, this resin be by comonomer trifluorochloroethylene, diacetone-acryloamide(DAA), unsaturated carboxylic acid and other non-fluorine monomers according to 15～50: 1～20: 0.1～10: 20～80 weight part ratio is polymerized, water as dispersion medium, fluorinated copolymer as the compound that contains two diazanyls groups in disperse phase and the molecule at least as solidifying agent; This cross-linked water soluble fluorine resin is the water miscible liquid that adopts letex polymerization manufactured fluoropolymer earlier, again the aqueous solution and the prepared fluoropolymer water miscible liquid of solidifying agent is carried out mixed getting.Though this water-based fluororesin also can be used as coating and uses, and is applied to numerous areas such as building, industry, woodenware, paper, weaving, leather, its preparation process more complicated, use-pattern is more single.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is dissolvable in water the fluoro-resin of low branch subclass organic solvent, the fluoro-resin of acquisition has very excellent chemical resistance, and good storage stability and film performance are easy to use.
In order to improve the solubility problem of fluoro-resin, and keep its excellent chemical-resistant, widen the Application Areas of such fluoro-resin, we are by adding the organic solubilized group in fluororesin monomer, improve its solvability, and adopted compound chain-transfer agent, pass through Molecular Structure Design, realized accurate control, obtained the fluorine resin product of excellent combination properties such as solvability, solvent resistance molecular weight and distribution, segmented structure.
In producing, the fluorine resin polymerization adopts the suspension polymerization mode usually; the product that obtains is a suspension; but the suspension that present method produces in preparation fluoro-resin process is because resin particle is too little; can't directly separate; need carry out postprocessing working procedures; adopting electrolytical mode of adding or churned mechanically form to obtain product in last handling process is method relatively more commonly used; but because the fluoro-resin of preparation requires its foreign matter content low in use; adopt and add the purity that electrolytical mode is carried out aftertreatment meeting reduction resin; simultaneously because coating is generally all lower with the molecular weight of fluoro-resin; use churned mechanically cohesion mode may change the molecular structure of chain link; cause the resin unnecessary loss; therefore adopt the mode of freeze agglomeration; by low temperature with water congeals into ice in the suspension; the formation of ice has limited the pedesis of material particles; destroyed the protective membrane of particle surface; resin particle is after thawing; under action of gravity aggegation sedimentation and water stratification; it has reduced because of adding the foreign matter content that ionogen causes; ensure the purity of resin, and reduced the unnecessary loss that mechanical cohesion causes.
On the other hand, because coating is relatively low with the molecular weight of fluoro-resin, and requires low-permeability, the carboxylate radical in the polymkeric substance is higher relatively, and this has influenced the solvability of fluoro-resin in organic solvent to a great extent.Therefore the present invention adopts organic initiators, introduces the organic solubilized group on polymer terminal group.The introducing of organic group increases polymer molecule and organic solvent Intermolecular Forces, thereby improved solvability to a great extent, reduce the end group hydrolysis problem that tradition uses no organic initiators to cause in the building-up process, reduce the acidity of resin, help improving the gas of resin hydrolysis in use generation to object generation erosion, compare with the emulsion polymerisation process that common no organic initiators causes, the polymerisate good stability, solvability improves, molecular structure and distribution have all obtained effective control, improved the regularity of molecular chain, symmetry, and reduced low molecular weight part, solve the sagging of its solvability and fluorine coating, phenomenons such as wire drawing.
In existing technology, still introduce in the polymerization process of unexposed like product and adopt suspension polymerization, and such fluoro-resin all to exist solvability relatively poor, the problem that workability is relatively poor.We have adopted following technical scheme to achieve these goals for this reason: water is as dispersion medium, fluorinated copolymer is as disperse phase, adopt organo-peroxide as initiator, use freeze agglomeration and water-cooled grinding mode to carry out aftertreatment, when using, it can be dissolved in the low molecular organic solvent and directly construct as coating.
In order to realize the object of the invention, the preparation method of a kind of low-molecular-weight soluble fluoro-resin of the present invention adopts the suspension polymerization mode, and water is as dispersion medium, and polymerization single polymerization monomer is 70～90mol% trifluorochloroethylene and 10～30mol% vinylidene; Initiator is an organo-peroxide, and consumption is the initiator that contains 0.001～5 weight part in per 100 weight parts water media; Keep the polymerization single polymerization monomer component constant in the polymerization process, the number-average molecular weight that is polymerized to fluorine resin is till 50,000 to 450,000, and back employing freeze agglomeration is finished in reaction and the water-cooled grinding mode carries out aftertreatment.
Wherein, the polymerization single polymerization monomer that contains 30～50 weight parts in per 100 weight parts water media.
Suspension system for the stable polymerization reaction adds 0～5 weight part suspension stabilizer in per 100 weight parts water dispersion medium.
The add-on of water medium of the present invention will make and leave the vapour space that is enough to receive gaseous monomer in the reactor.Generally be no more than volumetrical 2/3.
Described suspension stabilizer is selected from any one in methylcellulose gum, carboxymethyl cellulose, the talcum etc.
Described organo-peroxide is two-second month in a season of di-isopropyl peroxydicarbonate (IPP), peroxy dicarbonate-butyl ester, two-second month in a season-hexyl superoxide, two propionyl superoxide etc.
Described initiator in use needs in its water-soluble soluble hydrocarbon solvent.Hydrocarbon solvent of the present invention is not influence to polyreaction basically, because the chain transfer reaction of these hydrocarbon solvents is less, and it is soluble in the reactor water medium, in addition, in the polymerization reaction take place for the amount of initiator and reaction monomers, its content is very little.Therefore, initiator of the present invention adds with the solution form, and its concentration is 0.1～75 weight %, and solvent for use is a hydrocarbon solvent, is selected from R
1OH, R
2COOR or R
1COR
3, R wherein
1And R
3Be methyl, ethyl or the tertiary butyl, R
2With R be hydrogen, methyl, ethyl or the tertiary butyl.Be specially: methyl alcohol, methyl-formiate, tert.-butyl acetate, acetone, methyl acetate or methyl tertbutyl ketone etc.
In order to control the molecular weight of fluoro-resin, also can in polyreaction, add compound chain-transfer agent (molecular weight regulator).Its consumption is 0.001～0.01% of a mix monomer weight.
Described compound chain-transfer agent is two or more mixing such as methyl acetate, ethyl acetate, butylacetate, diethyl malonate, acetone or tetracol phenixin.Preferred compound chain-transfer agent is two kinds of mix reagents of ethyl acetate and diethyl malonate, and its weight proportion is 1: 1～5, most preferably is 1: 4.
Described chain-transfer agent can add before reaction, also can be in adding down in various degree that reaction is carried out, but require narrow molecular weight distribution when using as coating, so generally all be chosen at the preceding adding of reaction.
Pressure-controlling is at 1.0～5.0MPa in the polymerization process of the present invention.
Temperature of reaction is controlled at 30～100 ℃.
The emulsion of the present invention after with polymerization carried out aftertreatment, in order to reduce the impurity in the resin, adopts the mode of freeze agglomeration, and the emulsion that makes is congealed into ice in-35 ℃ of chilled brines, and when through after thawing, water and resin are with regard to natural separation.
When pulverizing, adopts resin the water-cooled crushing technology.Because the Tg and the Tm of this resin are lower, general mechanical disintegration produces that heat is bigger, and as no special measure, the temperature during pulverizing is higher than Tm, the resin deliquescing of will being heated, melt bond again agglomerating.Therefore by selecting the disintegrating apparatus of cooling jacket for use, pulverize being lower than under 60 ℃, such as pulverizing in logical tap water or-35 ℃ of salt solution.Granularity is below 100 orders.
Specifically, the preparation method of a kind of low-molecular-weight soluble fluoro-resin of the present invention comprises the steps:
1) add the water medium that contains suspension stabilizer in reactor, the amount of water medium makes and leaves the vapour space that is enough to receive gaseous monomer in the reactor;
2) in reactor, add the mixture of 70～90mol% trifluorochloroethylene and 10～30mol% vinylidene gaseous monomer, mix and form uniform dispersion;
3) by adding organic peroxide evocating agent to described dispersion, polymerization at 30～100 ℃ of following trigger monomers, the amount of described organo-peroxide is to contain 0.001～5 weight part in per 100 weight parts water media, the described organo-peroxide that adds is 0.1～75 weight % concentration, be the solution of solvent with the hydrocarbon, described organo-peroxide is two-second month in a season of di-isopropyl peroxydicarbonate (IPP), peroxy dicarbonate-butyl ester, two-second month in a season-hexyl superoxide, two propionyl superoxide etc., described hydrocarbon is R
1OH, R
2COOR or R
1COR
3, R wherein
1And R
3Be methyl, ethyl or the tertiary butyl, R
2With R be hydrogen, methyl, ethyl or the tertiary butyl;
4) in polymerization process, regulate the supply polymerization single polymerization monomer, make that gas phase component keeps constant relatively in the still, up to the number-average molecular weight of fluorine resin output till 50,000 to 450,000;
5) then the emulsion that makes is adopted the mode of freeze agglomeration, congeals into ice, again through after thawing, separate fluorine resin;
6) at last fluorine resin being carried out water-cooled pulverizes.
The number-average molecular weight of the described fluorine resin that obtains is 50,000 to 450,000, and considers that it uses as coating, and preferred number-average molecular weight is 5～200,000.
Viton of the present invention is in application of paints, and the solvent that is used for dissolving viton comprises one or more the mixing of ethanol, acetone, ether, chloroform, acetylene, methyl acetate, ethyl acetate, butylacetate, benzene equal solvent.
When fluoro-resin of the present invention is used for coating,, add certain amount of dispersant and dispersion aids because its construction and dispersiveness have certain difficulty during as coating for this reason.Dispersion agent generally is an inorganic filler, and as one or more the mixing in lime carbonate, talcum powder, barium sulfate, sal epsom, the titanium dioxide etc., its consumption is 1～20Wt%, is preferably 5～10wt%.Dispersion aids is an organic dispersing agent, and as carbonates or stearic acid, consumption is 1/10～1/12 of a dispersion agent.
The preparation method of low-molecular-weight soluble fluoro-resin of the present invention, by in fluororesin monomer, adding the organic solubilized group, improve its solvability, and adopted compound chain-transfer agent, in the product aftertreatment, adopt freeze agglomeration and water-cooled grinding mode, thus obtained fluorine resin good stability, solvability improves, molecular structure and distribution have all obtained effective control, regularity, the symmetry of molecular chain have been improved, and reduced low molecular weight part, solve the phenomenon such as sagging, wire drawing of its solvability and fluorine coating.When using, it can be dissolved in the low molecular organic solvent and directly construct as coating.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
In the autoclave of 50L, carry out intermittent type suspension polymerization of the present invention, with the preparation fluorine resin.Add the 30L deionized water in reactor, the air of the vapour space use earlier nitrogen replacement in the reactor, replaces with the trifluorochloroethylene monomer mixture that contains 70mol% with the vinylidene fluoride monomers of 30mol% then, with the interior temperature rise to 70 of reactor ℃.With membrane compressor above-mentioned monomer mixture is added in the reactor to pressure and to rise to 2.0MPa.After reaching 2.0MPa, the reactor pressure controller is set in the automatic operational stage under the 2.0MPa.
During monomer adds, prepare two kinds of solution that are used for the polymerization phase: a kind of is solution at the 30wt% di-isopropyl peroxydicarbonate (IPP) that is dissolved in methyl-formiate, a kind of is with ethyl acetate and diethyl malonate, and its weight ratio is that 1: 4 uniform mixing uses as compound chain-transfer agent.
Open when reactor pressure reaches 2.0MPa and stir, with the mix monomer thorough mixing in the reactor, the compound chain-transfer agent with 200g adds in the reactor then, adds the initiator solution (IPP that is equivalent to 24g) of 80g behind the several minutes, begins reaction.In reaction process, keep 70 ℃ of reactor pressure 2.0MPa, temperature always.
According to the difference of various reactivity ratio of monomer and the variation of each stage gas phase composite of reaction, dynamically regulate supply monomer component, make gas phase component maintenance constant relatively (vinylidene 30mol% and trifluorochloroethylene 70mol%) in the still, speed of reaction be the 1000g polymkeric substance/hour, when speed of reaction is lower than this speed, should add the hydrocarbon solution that contains 6g IPP30wt% in reactor, stopped reaction when producing polymkeric substance above 15Kg reclaims monomer.The polymkeric substance that obtains is carried out freeze agglomeration in-35 ℃ of chilled brines, the after scouring that thaws then, vacuum-drying ,-35 ℃ of salt carry out water-cooled with disintegrating apparatus under water and pulverize.Its product performance sees Table 2.
By similar above-mentioned polymerization process, post-treating method keeps auxiliary agent content unanimity, adjusts the monomer whose proportioning respectively and sees Table 1 (being respectively embodiment 2-embodiment 4), obtains the fluorine resin of different physicochemical characteristics, and its detected result sees Table 2.
The monomeric proportioning of table 1 vinylidene fluoride monomers and trifluorochloroethylene
| Embodiment | Vinylidene fluoride monomers, mol% | The trifluorochloroethylene monomer, mol% |
| 2 | 25 | 75 |
| 3 | 20 | 80 |
| 4 | 15 | 85 |
Table 2 fluorine resin performance test results
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Solvability | Molten entirely | Molten entirely | Molten entirely | Insoluble |
| Cl content, % | 21 | 23 | 25 | 27 |
| Intrinsic viscosity, 100ml/g | 0.78 | 0.83 | 0.82 | 0.85 |
| Number-average molecular weight, ten thousand | 7.2 | 7.5 | 8.0 | 9.2 |
| Water tolerance | Aluminium sheet played vesicle in 3 days | The 5d aluminium sheet is non-foaming | The 10d aluminium sheet is non-foaming | - |
Remarks: 1, solvability is that the fluorine resin that drying is good is dissolved in the ethyl acetate, and its mass percent is 8%.
2, will evenly be coated in the surface of aluminum plate of 40mm * 40mm by the good solution of above-mentioned 1 dissolving, be positioned in the water 25 ℃ of constant temperature.
Comparative Examples 1
By the same polymeric method with embodiment 1, initiator and chain-transfer agent that it adopts are different.Open when reactor pressure reaches 2.0MPa and stir, with the mix monomer thorough mixing in the reactor, the ethyl acetate with 200g adds in the reactor then, adds the persulfate aqueous solution that 1000ml contains 3Wt% behind the several minutes, begins reaction.Keep reactor pressure 2.0MPa and temperature in reaction process is 80 ℃ always.
According to the difference of various reactivity ratio of monomer and the variation of each stage gas phase composite of reaction, dynamically regulate supply monomer component, make gas phase component maintenance constant relatively (vinylidene 20mol% and trifluorochloroethylene 80mol%) in the still, should send out speed and be the 1000g polymkeric substance/hour, when speed of reaction is lower than this speed, should add the persulfate aqueous solution that 200m contains 3Wt% in reactor, stopped reaction when producing polymkeric substance above 15Kg reclaims monomer.The polymkeric substance that obtains is carried out the freeze agglomeration after scouring, vacuum-drying, water-cooled is pulverized.Its characteristic is listed in table 3.
The performance test results of the fluorine resin of table 3 Comparative Examples 1
| Performance | Comparative Examples 1 |
| Solvability | Insoluble |
| Cl content, % | 24.8 |
| Intrinsic viscosity, 100ml/g | 0.83 |
| Number-average molecular weight, ten thousand | 7.9 |
| Water tolerance | - |
Remarks: 1, solvability is that the fluorine resin that drying is good is dissolved in the ethyl acetate, and its mass percent is 8%.
2, will evenly be coated in the surface of aluminum plate of 40mm * 40mm by the good solution of 1 dissolving, be positioned in the water 25 ℃ of constant temperature.
Basic polymerization process is with embodiment 3, and that has carried out respectively that replica test obtains the results are shown in Table 4.
Table 4 performance test results
| Performance | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Solvability | Molten entirely | Jin Rong | Molten entirely | Molten entirely |
| Cl content, % | 24.8 | 25.3 | 25.0 | 25.2 |
| Intrinsic viscosity, 100ml/g | 0.8 | 0.83 | 0.82 | 0.85 |
| Number-average molecular weight, ten thousand | 7.9 | 8.5 | 8.0 | 8.3 |
| Water tolerance | Aluminium sheet was non-foaming in 10 days | The 15d aluminium sheet is non-foaming | The 10d aluminium sheet is non-foaming | The 10d aluminium sheet is non-foaming |
Embodiment 5-8
Basic polymerization process is with embodiment 1, and different is:
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Suspension stabilizer | Methylcellulose gum | Carboxymethyl cellulose | Talcum | - |
| Consumption | Contain 2 parts in 100 parts of water | Contain 1 part in 100 parts of water | Contain 5 parts in 100 parts of water | |
| Monomer | 30mol% vinylidene and 70mol% trifluorochloroethylene | 10mol% vinylidene and 90mol% trifluorochloroethylene | 20mol% vinylidene and 80mol% trifluorochloroethylene | 25mol% vinylidene and 75mol% trifluorochloroethylene |
| Initiator | IPP | Two-second month in a season of peroxy dicarbonate-butyl ester | Two propionyl superoxide | Two-second month in a season-hexyl superoxide |
| Consumption | Contain 5 parts in 100 parts of water | Contain 1 part in 100 parts of water | Contain 0.001 part in 100 parts of water | Contain 0.05 part in 100 parts of water |
| Hydrocarbon solvent | Methyl alcohol | Methyl acetate | Acetone | Tert.-butyl acetate |
| Initiator concentration | 10％ | 75％ | 50％ | 0.1％ |
| Compound chain-transfer agent | Methyl acetate and acetone (1: 3) | Ethyl acetate and diethyl malonate (1: 1) | Methyl acetate, ethyl acetate and tetracol phenixin (1: 2: 1) | Ethyl acetate and diethyl malonate (1: 3) |
| Consumption | Contain 5 parts in 100 parts of water | Contain 2 parts in 100 parts of water | Contain 3 parts in 100 parts of water | Contain 1 part in 100 parts of water |
| Temperature | 80℃ | 120℃ | 200℃ | 30℃ |
| Pressure | 1.0MPa | 2.0MPa | 3.0MPa | 5.0MPa |
| Freeze agglomeration | -35℃ | -35℃ | -35℃ | -35℃ |
| Water-cooled is pulverized | -35 ℃ of salt solution | -35 ℃ of salt solution | -35 ℃ of salt solution | -35 ℃ of salt solution |
| The number-average molecular weight of fluorine resin | 10.2 ten thousand | 50,000 | 19.8 ten thousand | 150,000 |
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the preparation method of a low-molecular-weight soluble fluoro-resin adopts the suspension polymerization mode, and water is characterized in that as dispersion medium polymerization single polymerization monomer is 70～90mol% trifluorochloroethylene and 10～30mol% vinylidene; Initiator is an organo-peroxide, and consumption is the initiator that contains 0.001～5 weight part in per 100 weight parts water dispersion medium; Keep the polymerization single polymerization monomer component constant in the polymerization process, the number-average molecular weight that is polymerized to fluorine resin is till 50,000 to 200,000, and back employing freeze agglomeration is finished in reaction and the water-cooled grinding mode carries out aftertreatment; Described freeze agglomeration is for to congeal into ice in-35 ℃ of chilled brines, again through thawing water and resin isolation; Described water-cooled is pulverized to adopt to be lower than under 60 ℃ and is pulverized.
2. the preparation method of low-molecular-weight soluble fluoro-resin according to claim 1, it is characterized in that, described organo-peroxide is two-second month in a season of di-isopropyl peroxydicarbonate, peroxy dicarbonate-butyl ester, two-second month in a season-hexyl superoxide or two propionyl superoxide.
3. the preparation method of low-molecular-weight soluble fluoro-resin according to claim 1 and 2 is characterized in that, described organo-peroxide is to add with the solution form, and its concentration is 0.1～75 weight %, and solvent for use is a hydrocarbon solvent, is selected from R
1OH, R
2COOR or R
1COR
3, R wherein
1And R
3Be methyl, ethyl or the tertiary butyl, R
2With R be hydrogen, methyl, ethyl or the tertiary butyl.
4. the preparation method of low-molecular-weight soluble fluoro-resin according to claim 3 is characterized in that, described hydrocarbon solvent is methyl alcohol, methyl-formiate, tert.-butyl acetate, acetone, methyl acetate or methyl tertbutyl ketone.
5. according to the preparation method of claim 1,2 or 4 any described low-molecular-weight soluble fluoro-resins, it is characterized in that, also contain suspension stabilizer in the described water dispersion medium, consumption is to add 0～5 weight part in per 100 weight parts water dispersion medium; Described suspension stabilizer is selected from any one in methylcellulose gum, carboxymethyl cellulose, the talcum.
6. according to the preparation method of claim 1,2 or 4 any described low-molecular-weight soluble fluoro-resins, it is characterized in that, also add compound chain-transfer agent in the polymerization process, described compound chain-transfer agent is the two or more mixture of methyl acetate, ethyl acetate, butylacetate, diethyl malonate, acetone or tetracol phenixin, and its consumption is 0.001～0.01% of a mix monomer weight.
7. according to the preparation method of the described low-molecular-weight soluble fluoro-resin of claim 5, it is characterized in that, also add compound chain-transfer agent in the polymerization process, described compound chain-transfer agent is the two or more mixture of methyl acetate, ethyl acetate, butylacetate, diethyl malonate, acetone or tetracol phenixin, and its consumption is 0.001～0.01% of a mix monomer weight.
8. according to the preparation method of the described low-molecular-weight soluble fluoro-resin of claim 1, it is characterized in that pressure-controlling is at 1.0～5.0MPa in the polymerization process.
9. the preparation method of low-molecular-weight soluble fluoro-resin according to claim 1 is characterized in that, polymeric reaction temperature is controlled at 30～100 ℃.
10. the preparation method of low-molecular-weight soluble fluoro-resin according to claim 1 is characterized in that, it comprises the steps:
1) add the water medium that contains suspension stabilizer in reactor, the amount of water medium makes and leaves the vapour space that is enough to receive gaseous monomer in the reactor;
2) in reactor, add the mixture of 70～90mol% trifluorochloroethylene and 10～30mol% vinylidene gaseous monomer, mix and form uniform dispersion;
3) by adding organic peroxide evocating agent to described dispersion, polymerization at 30～100 ℃ of following trigger monomers, the amount of described organo-peroxide is to contain 0.001～5 weight part in per 100 weight parts water media, the described organo-peroxide that adds is 0.1～75 weight % concentration, be the solution of solvent with the hydrocarbon, described organo-peroxide is two-second month in a season of di-isopropyl peroxydicarbonate, peroxy dicarbonate-butyl ester, two-second month in a season-hexyl superoxide or two propionyl superoxide, described hydrocarbon is R
1OH, R
2COOR or R
1COR
3, R wherein
1And R
3Be methyl, ethyl or the tertiary butyl, R
2With R be hydrogen, methyl, ethyl or the tertiary butyl;
4) in polymerization process, regulate the supply polymerization single polymerization monomer, make that gas phase component keeps constant relatively in the still, up to the number-average molecular weight of fluorine resin output till 50,000 to 200,000;
5) then the emulsion that makes is adopted the mode of freeze agglomeration, congeals into ice, again through after thawing, separate fluorine resin;
6) at last fluorine resin being carried out water-cooled pulverizes.
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