CN104893189A - Preparation method of enhanced polyvinylidene fluoride resin - Google Patents
Preparation method of enhanced polyvinylidene fluoride resin Download PDFInfo
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- CN104893189A CN104893189A CN201510271396.8A CN201510271396A CN104893189A CN 104893189 A CN104893189 A CN 104893189A CN 201510271396 A CN201510271396 A CN 201510271396A CN 104893189 A CN104893189 A CN 104893189A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/22—Vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract
The invention discloses a preparation method of enhanced polyvinylidene fluoride resin. The preparation method comprises the following steps: (a) adding fluorine-containing bromide/iodide as a chain transfer agent in a polymerization process of polyvinylidene fluoride by virtue of a polymerization method so as to introduce bromine/iodine atoms into a terminal group of a molecular chain of polyvinylidene fluoride, and carrying out condensation, washing, drying, so as to obtain a polyvinylidene fluoride polymer; and (b) mixing and dissolving the obtained polyvinylidene fluoride polymer and a solvent into a polyvinylidene fluoride solution with uniform concentration, introducing organic peroxides and a crosslinking agent into the polyvinylidene fluoride solution, reacting at 25-100 DEG C, and carrying out desolvation, washing and drying, so as to obtain the thermoplasticity-enhanced polyvinylidene fluoride resin. According to the preparation method of the enhanced polyvinylidene fluoride resin, the strength of a membrane can be increased, and the problem that an enhancement layer is peeled or damaged can be solved. The preparation method can be applied to the fields of preparation of a hollow fiber membrane for water treatment, a filtering membrane for atmospheric pollution treatment and a filter bag coating for industrial waste gas pollution treatment by virtue of processing.
Description
Technical field
The present invention relates to a kind of preparation method of enhancement type polyvinylidene fluoride resin.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) has good chemical stability, thermostability and physical strength, it is the good separation membrane material of a kind of over-all properties, but, pure pvdf membrane has tensile strength low, the shortcoming of easy fracture, people utilize fiber and cloth to strengthen film strength thus to solve this shortcoming, and as CN102784565A, CN102600733A, CN103240008A etc. have introduction, this fiber reinforcement type film then still also exists the flaky problem of enhancement layer.
The crosslinked thermostability that can improve polymkeric substance, reduces the swelling of solvent, increases film strength, and a lot of crosslinking technological has been used to fluoropolymer masking field at present.There is crosslinkable groups to provide cross-linking set in crosslinked needs, what adopt in most of document is in molecular chain, introduce bromine/iodine group in molecular chain.As the crosslinkable groups in polymer molecule prepared by patent EP2578629A1 derives from brominated or containing the bromine group of the monomeric compound of iodine or the compound of brominated and iodine and/or iodine group.Crosslinked pvdf membrane is used for two kinds of fields, one is applied to piezoelectricity field, radical initiator benzoyl peroxide (BPO) is adopted to carry out hot pressing cross-linking modified, patent CN102924732A and CN103387682A discloses this crosslinked method preparing PVDF plastics film, improve the tensile strength of film, improve the problem of fluoropolymer low temperature membrane difficulty, but, the PVDF taking this method to be formed is thermosetting resin, be difficult to reprocessing, easily formed useless solid in the course of processing, cannot recycle.
Another kind is applied to fractionation by adsorption film field, is generally to adopt crosslinkable hydrophilic polymer and the blended cross-linking modified obtained pvdf membrane again of PVDF, and patent CN103007786A, CN101203554A disclose this class methods.Although this kind of method can make pvdf membrane have certain intensity, the toughness of hydrophilic composition is obviously worse than PVDF, and along with the prolongation of time, hydrophilic composition can constantly run off, thus causes film damaged.Therefore, need to find one to strengthen film strength, enhancement layer can be solved again and peel off or the problem of breakage, and the solution of difficult processing problems, be the technical barrier needing at present to solve.
Summary of the invention
The object of the invention is to solve the above-mentioned technical problem existed in prior art, a kind of preparation method of enhancement type polyvinylidene fluoride resin is provided, film strength can be strengthened, enhancement layer can be solved again peel off or the problem of breakage, can be passed through the fields such as processing obtained hollow fiber membrane for water treatment, air contaminant treatment filtering membrane and industrial gaseous waste Pollution abatement filter bag coating.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of preparation method of enhancement type polyvinylidene fluoride resin, it is characterized in that preparation process comprises: (a) polyvinylidene difluoride (PVDF) adopts polymerization process, in the course of the polymerization process, add fluorine-containing bromine/iodide as chain-transfer agent, bromine/atomic iodine is introduced in polyvinylidene difluoride (PVDF) molecule segment end group, by cohesion, washing, drying, obtain polyvinylidene fluoride polymer; B the polyvinylidene fluoride polymer of acquisition and solvent are dissolved into the homogeneous polyvinylidene difluoride (PVDF) solution of concentration by (), organo-peroxide and linking agent is introduced again in polyvinylidene difluoride (PVDF) solution, react at 25 ~ 100 DEG C, through precipitation, washing, dry acquisition thermoplasticity enhancement type polyvinylidene fluoride resin.
Further, polyvinylidene difluoride (PVDF) is one or more multipolymer of vinylidene fluoride homopolymer or vinylidene and R 1216, tetrafluoroethylene, trifluoro-ethylene.
Further, polymerization process is emulsion polymerisation process or suspension polymerization.
Further, fluorine-containing bromine/iodine compound is CF
2(A) (CF
2)
ab or CF
2(CF
2)
b(CH
2)
cb or B (CF
2)
done or more of B, wherein a is 0 ~ 6, b to be 0 ~ 7, c be 1 or 2, d be 1 or 2, A be H or F, B be I or Br.
Further, solvent is one or more in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone.
Further; organo-peroxide is 2; 5-dioxy base-2; two (1-butylation) ethane of 5-or 1,3-two (t-butylperoxyisopropyl) or di-isopropyl peroxydicarbonate or tertbutyl peroxide or benzoyl peroxide or tert-butyl hydroperoxide toxilic acid, perfluoroalkyl superoxide one or more.
Further, linking agent is triallyl isonitrile urea carbon ester.
The present invention, owing to have employed technique scheme, has following beneficial effect:
The present invention is from film resin material, prepare enhancement type polyvinylidene fluoride resin, intensity through processing obtained polyvinylidene fluoride film is improved, enhancement layer can be solved peel off or the problem of breakage, difficult processing problems can be solved again, can be applicable to the fields such as hollow fiber membrane for water treatment, air contaminant treatment filtering membrane and industrial gaseous waste Pollution abatement filter bag coating.
Embodiment
The preparation method of a kind of enhancement type polyvinylidene fluoride resin of the present invention, preparation process comprises:
A () first polyvinylidene difluoride (PVDF) adopts polymerization process, polyvinylidene difluoride (PVDF) is one or more multipolymer of vinylidene fluoride homopolymer or vinylidene and R 1216, tetrafluoroethylene, trifluoro-ethylene, comonomer is because its polymerization activity in vinylidene fluoride polymerization system is not as vinylidene, molecular weight is caused to reduce, simultaneously, comonomer can destroy the crystallinity of polyvinylidene difluoride (PVDF), reduce fusing point and the thermal characteristics of material, in the present invention, preferred vinylidene fluoride homopolymer is as polyvinylidene difluoride (PVDF).Polymerization process is emulsion polymerisation process or suspension polymerization: emulsion polymerization system occurs in vinylidene fluoride monomers or vinylidene and comonomer under perfluor emulsifying agent, initiator, chain-transfer agent exist, and occurs at temperature is 40 DEG C ~ 80 DEG C; Or suspension polymerization system generation vinylidene fluoride monomers or vinylidene and comonomer are under initiator, chain-transfer agent, dispersion agent exist, occur at temperature is 15 DEG C ~ 45 DEG C.In contrast, suspension polymerization system have temperature of reaction low, containing fluorine-containing emulsifier, advantage, the preferred suspension polymerization system of the present invention such as aftertreatment is simple, resulting polymers degree of imperfection is low.In the course of the polymerization process, add fluorine-containing bromine/iodide as chain-transfer agent, by bromine/atomic iodine introducing polyvinylidene difluoride (PVDF) molecule segment end group, thus reach the object introducing reflecting point, then by cohesion, washing, drying, obtain polyvinylidene fluoride polymer.In the course of the polymerization process, fluorine-containing bromine/iodide add can before the reaction, reaction the neutralization reaction later stage add, due to the chain tra nsfer performance of fluorine-containing bromine/iodide excellence, contain the polyvinylidene fluoride resin of bromine or iodine for obtaining the larger end group of molecular weight, the reaction later stage that is added in of preferred fluorine-containing bromine/iodide adds.Fluorine-containing bromine/iodine compound is CF
2(A) (CF
2)
ab or CF
2(CF
2)
b(CH
2)
cb or B (CF
2)
done or more of B, wherein a is 0 ~ 6, b to be 0 ~ 7, c be 1 or 2, d be 1 or 2, A be H or F, B be I or Br, for introducing more terminal reactive point, be preferably B (CF
2)
done or more of B, wherein d be 1 or 2, B be I or Br.
B the polyvinylidene fluoride polymer of acquisition and solvent are dissolved into the homogeneous polyvinylidene difluoride (PVDF) solution that concentration is 3wt.% ~ 25wt.% by (), in this process, solvent is N, one or more in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone.Organo-peroxide and linking agent is introduced again in polyvinylidene difluoride (PVDF) solution; organo-peroxide is 2; 5-dioxy base-2; two (1-butylation) ethane of 5-or 1,3-two (t-butylperoxyisopropyl) or di-isopropyl peroxydicarbonate or tertbutyl peroxide or benzoyl peroxide or tert-butyl hydroperoxide toxilic acid, perfluoroalkyl superoxide one or more.Linking agent is triallyl isonitrile urea carbon ester.Using organic peroxide evocating agent as initiator, conventional has the peroxycarbonates class such as di-isopropyl peroxydicarbonate (IPP), peroxy dicarbonate di-n-propyl ester (NPP).Initiator amount has impact to speed of reaction and molecular weight, the few speed of response of consumption is slow, gained PVDF molecular weight is low, intensity also can reduce, consumption increase causes initiator concentration in system to increase, speed of reaction increases, but the increase of chain termination frequency causes the molecular weight of polymkeric substance to reduce, and initiator amount is preferably 0.005% ~ 0.1% of total monomer weight.Then react at 25 ~ 100 DEG C, through precipitation, washing, dry acquisition thermoplasticity enhancement type polyvinylidene fluoride resin.
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.The experimental technique of unreceipted actual conditions in the following example, conventionally selects with condition.
Comparative example 1
Adopt suspension polymerization, 60L high purity water, 20kgVDF monomer, 0.1g initiator IPP, 10g dispersion agent methylcellulose gum, 30g chain-transfer agent is added in the airtight polymeric kettle of 100L, the homopolymerization polyreaction of VDF is carried out under the polymerization temperature of 30 DEG C, reaction pressure maintains 3.8MPa, obtain PVDF suspension after reaction 8h, then obtain polyvinylidene difluoride (PVDF) after washing, drying.
Embodiment 1
The present embodiment comprises the following steps:
Step one, employing suspension polymerization, add 60L high purity water, 20kgVDF monomer, 0.1g initiator IPP, 10g dispersion agent methylcellulose gum, 30g chain-transfer agent Br (CF in the airtight polymeric kettle of 100L
2)
2br, under the polymerization temperature of 30 DEG C, carry out the homopolymerization of VDF, reaction pressure maintains 3.8MPa, obtains PVDF suspension, then obtain polyvinylidene difluoride (PVDF) after reaction 8h after washing, drying;
Step 2, in glass flask, add gained polyvinylidene difluoride (PVDF) and solvent N, dinethylformamide, the mass ratio of polyvinylidene difluoride (PVDF) and solvent is 3:97, after polyvinylidene difluoride (PVDF) fully dissolves, add organo-peroxide 2, two (1-butylation) ethane of 5-dioxy base-2,5-and linking agent triallyl isonitrile urea carbon ester, continue stirring reaction 24 hours at 25 DEG C; Precipitation, washing, dry rear acquisition enhancement type polyvinylidene fluoride resin.
Embodiment 2
The present embodiment comprises the following steps:
Step one, employing suspension polymerization, add 60L high purity water, monomer total amount be 20kgVDF and R 1216 monomer, 10g initiator IPP, 20g dispersion agent Walocel MT 20.000PV and 40g chain-transfer agent CF in the airtight polymeric kettle of 100L
2h (CF
2)
2cH
2br, obtains PVDF suspension after reacting 10h under the polymerization temperature of 25 DEG C, after washing, drying, obtain polyvinylidene fluoride resin;
Step 2, in glass flask, add gained polyvinylidene difluoride (PVDF) and solvent N, N-N,N-DIMETHYLACETAMIDE, the mass ratio of polyvinylidene difluoride (PVDF) and solvent is 10:90, after polyvinylidene difluoride (PVDF) fully dissolves, add organo-peroxide di-isopropyl peroxydicarbonate and linking agent triallyl isonitrile urea carbon ester, at 30 DEG C, continue stirring reaction 24 hours; Precipitation, washing, dry rear acquisition enhancement type polyvinylidene fluoride resin.
Embodiment 3
The present embodiment comprises the following steps:
Step one, employing suspension polymerization, add 65L high purity water, 15kgVDF monomer, 15g dispersion agent, 8g initiator NPP and 50g chain-transfer agent BrCF in the airtight polymeric kettle of 100L
2br, obtains the homopolymer of PVDF under the polymerization temperature of 35 DEG C again after washing, drying after reacting 12h;
Step 2, in glass flask, add gained polyvinylidene difluoride (PVDF) and solvent N-methyl pyrilidone, the mass ratio of polyvinylidene difluoride (PVDF) and solvent is 15:85, after polyvinylidene difluoride (PVDF) fully dissolves, add organo-peroxide benzoyl peroxide and linking agent triallyl isonitrile urea carbon ester, at 40 DEG C, continue stirring reaction 24 hours; Precipitation, washing, dry rear acquisition enhancement type polyvinylidene fluoride resin.
Embodiment 4
The present embodiment comprises the following steps:
Step one, adopt emulsion polymerisation process, in the airtight polymeric kettle of 100L, add 65L high purity water, VDF that monomer total amount is 15kg and R 1216 monomer (HFP), 12g initiator NPP, 30g perfluor ethers emulsifying agent and 100g chain-transfer agent CF
3(CF
2) I, obtain PVDF-HFP emulsion react 3h under the polymerization temperature of 80 DEG C after, after cohesion, washing, drying, obtain polyvinylidene fluoride resin;
Step 2, in glass flask, add gained polyvinylidene difluoride (PVDF) and solvent N, N-N,N-DIMETHYLACETAMIDE, the mass ratio of polyvinylidene difluoride (PVDF) and solvent is 20:80, after polyvinylidene difluoride (PVDF) fully dissolves, add organo-peroxide tert-butyl hydroperoxide toxilic acid and linking agent triallyl isonitrile urea carbon ester, at 30 DEG C, continue stirring reaction 24 hours; Precipitation, washing, dry rear acquisition enhancement type polyvinylidene fluoride resin.
Embodiment 5
The present embodiment comprises the following steps:
Step one, adopt suspension polymerization, in the airtight polymeric kettle of 100L, add 60L high purity water, VDF that monomer total amount is 20kg and tetrafluoroethylene (TFE) monomer, 28g dispersion agent, 15g initiator NPP and 250g chain-transfer agent CF
2h (CF
2)
3(CH
2)
2br, obtains the multipolymer of PVDF under the polymerization temperature of 40 DEG C again after washing, drying after reacting 10h;
Step 2, in glass flask, add resulting polymers resin and solvent N-methyl pyrilidone, the mass ratio of polyvinylidene difluoride (PVDF) and solvent is 25:75, after resin to be polymerized fully dissolves, add organo-peroxide 1,3-two (t-butylperoxyisopropyl) and linking agent triallyl isonitrile urea carbon ester, continue stirring reaction 24 hours at 40 DEG C; Precipitation, washing, dry rear acquisition enhancement type polyvinylidene fluoride resin.
Embodiment 6
Step one, adopt suspension polymerization, in the airtight polymeric kettle of 100L, add 60L high purity water, VDF that monomer total amount is 20kg and trifluoro-ethylene (TrFE) monomer, 36g dispersion agent, 20g initiator NPP and 460g chain-transfer agent CF
3(CF
2)
3(CH
2)
2br, obtains the multipolymer of PVDF under the polymerization temperature of 45 DEG C again after washing, drying after reacting 10h;
The method that step 2, employing mixing are extruded is to prepare enhancement type polyvinylidene fluoride resin, pvdf resin step one obtained and organo-peroxide tert-butyl hydroperoxide toxilic acid and linking agent triallyl isonitrile urea carbon ester are after 50 DEG C of high-speed mixing, add twin screw extruder, twin-screw extrusion temperature controls at 160 ~ 190 DEG C, extrude, granulation, obtains enhancement type polyvinylidene fluoride resin.
Conveniently testing method, lists in table 1 by the resin property of comparative example and embodiment, and the limiting viscosity of the polyvinylidene fluoride resin obtained increases, and tensile strength improves, and elongation at break reduces.
| Sequence number | Limiting viscosity (dl/g) | Tensile strength (MPa) | Elongation at break (%) |
| Comparative example | 1.02 | 44.2 | 175.4 |
| Embodiment 1 | 1.39 | 54.8 | 159.6 |
| Embodiment 2 | 1.31 | 52.6 | 161.2 |
| Embodiment 3 | 1.42 | 55.8 | 158.4 |
| Embodiment 4 | 1.20 | 46.1 | 170.1 |
| Embodiment 5 | 1.15 | 45.4 | 171.2 |
| Embodiment 6 | 1.17 | 47.1 | 169.3 |
Table 1 performance comparison table
The present invention can strengthen film strength, can solve again enhancement layer and peel off or the problem of breakage, can be passed through the fields such as processing obtained hollow fiber membrane for water treatment, air contaminant treatment filtering membrane and industrial gaseous waste Pollution abatement filter bag coating.
These are only specific embodiments of the invention, but technical characteristic of the present invention is not limited thereto.Any based on the present invention, for solving substantially identical technical problem, realize substantially identical technique effect, done simple change, equivalent replacement or modification etc., be all covered by among protection scope of the present invention.
Claims (7)
1. the preparation method of an enhancement type polyvinylidene fluoride resin, it is characterized in that preparation process comprises: (a) polyvinylidene difluoride (PVDF) adopts polymerization process, in the course of the polymerization process, add fluorine-containing bromine/iodide as chain-transfer agent, bromine/atomic iodine is introduced in polyvinylidene difluoride (PVDF) molecule segment end group, by cohesion, washing, drying, obtain polyvinylidene fluoride polymer; B the polyvinylidene fluoride polymer of acquisition and solvent are dissolved into the homogeneous polyvinylidene difluoride (PVDF) solution of concentration by (), organo-peroxide and linking agent is introduced again in polyvinylidene difluoride (PVDF) solution, react at 25 ~ 100 DEG C, through precipitation, washing, dry acquisition thermoplasticity enhancement type polyvinylidene fluoride resin.
2. the preparation method of a kind of enhancement type polyvinylidene fluoride resin according to claim 1, is characterized in that: described polyvinylidene difluoride (PVDF) is one or more multipolymer of vinylidene fluoride homopolymer or vinylidene and R 1216, tetrafluoroethylene, trifluoro-ethylene.
3. the preparation method of a kind of enhancement type polyvinylidene fluoride resin according to claim 1, is characterized in that: described polymerization process is emulsion polymerisation process or suspension polymerization.
4. the preparation method of a kind of enhancement type polyvinylidene fluoride resin according to claim 1, is characterized in that: described fluorine-containing bromine/iodine compound is CF
2(A) (CF
2)
ab or CF
2(CF
2)
b(CH
2)
cb or B (CF
2)
done or more of B, wherein a is 0 ~ 6, b to be 0 ~ 7, c be 1 or 2, d be 1 or 2, A be H or F, B be I or Br.
5. the preparation method of a kind of enhancement type polyvinylidene fluoride resin according to claim 1, is characterized in that: described solvent is one or more in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone.
6. the preparation method of a kind of enhancement type polyvinylidene fluoride resin according to claim 1; it is characterized in that: described organo-peroxide is 2; 5-dioxy base-2; two (1-butylation) ethane of 5-or 1,3-two (t-butylperoxyisopropyl) or di-isopropyl peroxydicarbonate or tertbutyl peroxide or benzoyl peroxide or tert-butyl hydroperoxide toxilic acid, perfluoroalkyl superoxide one or more.
7. the preparation method of a kind of enhancement type polyvinylidene fluoride resin according to claim 1, is characterized in that: described linking agent is triallyl isonitrile urea carbon ester.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150203A (en) * | 2021-04-07 | 2021-07-23 | 浙江巨化技术中心有限公司 | Vinylidene fluoride copolymer and preparation method thereof |
| CN113441018A (en) * | 2021-08-06 | 2021-09-28 | 苏州富淼膜科技有限公司 | Preparation method of polyvinylidene fluoride hollow fiber ultrafiltration membrane |
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| 刘国杰等: "《氟碳树脂涂料及施工应用》", 31 January 2005, 中国石化出版社 * |
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| CN113150203A (en) * | 2021-04-07 | 2021-07-23 | 浙江巨化技术中心有限公司 | Vinylidene fluoride copolymer and preparation method thereof |
| CN113441018A (en) * | 2021-08-06 | 2021-09-28 | 苏州富淼膜科技有限公司 | Preparation method of polyvinylidene fluoride hollow fiber ultrafiltration membrane |
| CN113441018B (en) * | 2021-08-06 | 2023-08-04 | 苏州富淼膜科技有限公司 | Preparation method of polyvinylidene fluoride hollow fiber ultrafiltration membrane |
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