CN103387633A - Preparation method of ultrahigh-molecular-weight polyvinylidene fluoride material - Google Patents
Preparation method of ultrahigh-molecular-weight polyvinylidene fluoride material Download PDFInfo
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- CN103387633A CN103387633A CN2012101396473A CN201210139647A CN103387633A CN 103387633 A CN103387633 A CN 103387633A CN 2012101396473 A CN2012101396473 A CN 2012101396473A CN 201210139647 A CN201210139647 A CN 201210139647A CN 103387633 A CN103387633 A CN 103387633A
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Abstract
The invention provides a preparation method of an ultrahigh-molecular-weight polyvinylidene fluoride material. The polyvinylidene fluoride material is prepared from monomer vinylidene fluoride through an emulsification polymerization method. An adopted fluorine-containing surfactant emulsion polymerization system comprises a fluorine-containing surfactant or a mixed emulsion polymerization system composed of the fluorine-containing surfactant and an anionic or nonionic emulsifier. An initiation system adopts nitroxide radicals, and polymerization is initiated through high temperature. The initiation polymerization system adopted by the invention has active free radical polymerization characters. The prepared polyvinylidene fluoride high-molecular material has the advantages of large molecular weight, controllable molecular weight, narrow molecular weight distribution, excellent mechanical performance, good melt fluidity, and excellent processing performance. The preparation method provided by the invention is an ultrahigh-molecular-weight polyvinylidene fluoride material preparation method with high efficiency and controllability.
Description
Technical field
The invention belongs to the fluoro-resin technical field, be specifically related to a kind of preparation method of ultra-high molecular weight poly (vinylidene fluoride) material.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF or PVF
2) be the homopolymer of vinylidene (VDF), molecular weight 400,000～600,000, degree of crystallinity 60%～80%, fluorine content 59%, its repeating unit is-CH
2-CF
2-, CH
2-and CF
2The alternative arrangement of-primitive, make PVDF except having good chemical resistance, high thermal resistance, scale resistance, weathering resistance, UV resistant, radiation resistance, also has the properties such as piezoelectricity, pyroelectricity, and its range of application constantly enlarges.Up to now, the PVDF resin has developed into the fluoro-resin kind that is only second in the world tetrafluoroethylene, is widely used in the aspects such as robot calculator, aerospace, information processing, sound appliances, medicine equipment, robot, physical testing, opticinstrument, weapon industry.
China from the beginning of the sixties in last century, starts the R﹠D work of PVDF resin material, and so far, R ﹠ D Level improves little, and technical progress is slow, and production technique falls behind.Seldom, annual production is only hundred tons in the manufacturing enterprise of present domestic PVDF resin, and kind is single, and quality is unstable, can not meet the demand of domestic market to high-quality PVDF resin far away, the main dependence on import of goods level PVDF resin.From the technical information of present disclosed polyvinylidene fluoride material, production method and technique are more backward.
CN101508749A discloses the preparation method of a kind of polyvinylidene difluoride (PVDF) (PVDF), adopting ketone or alcohols is molecular weight regulator, superoxide or azo are initiator, method by solution polymerization prepares the polyvinylidene difluoride (PVDF) macromolecular material, use fluothane hydrocarbon medium to be solvent, cost is higher, and relates to the recovery of solvent, and the feature of environmental protection is poor.
CN101824122A discloses a kind of in-situ preparation method of hydrophilic PVDF material, this hydrophilic PVDF material is comprised of the raw material of following weight percent: PVDF 43-84%, hydrophilic modifying monomer 16-45%, SAN 0-19%, the material modified 0-5% of inorganic hydrophilic, peroxide initiator 0.2-1%, wherein SAN is vinyl cyanide and cinnamic multipolymer.The preparation method of this material be with raw material under solution state, use in-situ polymerization, realize completing the abundant blend between molecular chain in polymerization.
CN101319081A discloses a kind of hydrophilic PVDF material blend preparation method, this hydrophilic PVDF material, this material is made by the raw material of following mass percent: PVDF 60-90%, SAN 10-40%, PMMA 0-30%, PTFE 0-1%, kaolin 0-1%, wherein SAN is vinyl cyanide and cinnamic multipolymer.The preparation method is for carrying out the raw material of different proportionings blend under molten state.
CN1532212A discloses a kind of method of emulsion polymerizing preparation vinylidene material, use chain-transfer agent, radical initiator and dispersion agent, vinylidene or optional comonomer are disperseed in water, then carry out radical polymerization and prepare PVDF homopolymer or multipolymer.
The disclosed method for preparing polyvinylidene difluoride (PVDF) of CN101434670A, use redox initiation system, and its oxygenant is cumene peroxide, and reductive agent is clorox, and its mol ratio is 1:1-1:3; Polymerizing condition is gentle, the relatively high and end group stabilization of polymerisate amylose regularity.
The preparation method of above-mentioned disclosed PVDF material, adopts traditional free radical R﹠D mode more, and the polymericular weight of preparation can not reach ultra-high molecular weight, and the molecular weight distribution friendship is wide, can't adapt to the demand of market to the high-performance polyvinylidene fluoride material.The present invention has adopted new polymerization technique, when preparing the PVDF material of ultra-high molecular weight, can regulate and control the molecular weight of polymkeric substance, and the polyvinylidene difluoride (PVDF) of preparation has excellent mechanical property, good fluidity of molten and the higher transparency.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of ultra-high molecular weight poly (vinylidene fluoride) material.
The invention provides a kind of preparation method of ultra-high molecular weight poly (vinylidene fluoride) material, the method is under emulsifying agent, and vinylidene fluoride monomers and acrylic ester monomer obtain the ultra-high molecular weight poly (vinylidene fluoride) material by nitroxyl free radical active free radical polymerization mode.System adjustment by tensio-active agent, change the latex particle size of letex polymerization material, change concentration and the polymerisation conversion of nitroxyl free radical, adjust the molecular weight of polymkeric substance, thereby adjust the processing characteristicies such as melting index of material, and the mechanical properties such as impact, stretching.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, with vinylidene, acrylic ester monomer adds in reactor, add water, emulsifying agent and nitroxyl free radical, use the air in the nitrogen replacement reactor, polymerization temperature remains on 80-150 ℃, reaction pressure 3.0-6.0Mpa, reaction times 4-10 hour.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, described emulsifying agent is fluorochemical surfactant, or the mixture of fluorochemical surfactant and other negatively charged ion or nonionogenic tenside.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, described fluorochemical surfactant is perfluoroalkyl acid ammonium, perfluoroalkyl wherein is C
3F
7, C
4F
9, C
5F
11C
6F
13, C
7F
15, C
8F
17, C
9F
19, C
10F
21, C
11F
23, C
12F
25In a kind of.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, described anion surfactant is disproportionation rosin acid potassium or sodium salt anion surfactant.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, described nonionogenic tenside is one or both in alkylbenzene Soxylat A 25-7, fatty alcohol-polyoxyethylene ether.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, the Soxylat A 25-7 in described alkylbenzene Soxylat A 25-7 or fatty alcohol-polyoxyethylene ether is polyoxyethylene (2～20) ether.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, the alkyl in described alkylbenzene or fatty alcohol or fatty group are a kind of in octyl group, nonyl, decyl, undecyl, dodecyl.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, described nitroxyl free radical are the oxygen amine compound of cycloaliphatic hydrocarbon tertiary amine, specifically as shown in Figure 1.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material provided by the invention, described acrylic ester monomer is methyl acrylate, ethyl ester, propyl ester, butyl ester, pentyl ester and monooctyl ester, one or more in methyl methacrylate, ethyl ester, propyl ester, butyl ester, pentyl ester and monooctyl ester.
One of content of the present invention is to design the emulsion polymerization system that a class and high molecular polyvinylidene difluoride (PVDF) Polymer materialspreparation are complementary, the emulsifying agent that adopts is independent fluorochemical surfactant, or the mixture of fluorochemical surfactant and other negatively charged ion or nonionogenic tenside.The initiator system of initiated polymerization adopts alkyl oxygen amine free radical, has the characteristics of living polymerization.
Two of content of the present invention is the above-mentioned emulsion polymerization system, and the poly-inclined to one side fluorine vinyl polymer material of preparation has the constitutional features of ultra-high molecular weight, narrow molecular weight distributions, and mechanical properties of polymer is excellent.
The preparation method of ultra-high molecular weight poly (vinylidene fluoride) material of the present invention, can adopt separately the vinylidene fluoride monomers polymerization, also can use vinylidene and acrylic ester monomer to obtain by nitroxyl free radical active free radical polymerization mode.System adjustment by tensio-active agent, change the latex particle size of letex polymerization material, change concentration and the polymerisation conversion of nitroxyl free radical, adjust the molecular weight of polymkeric substance, thereby adjust the processing characteristicies such as melting index of material, and the mechanical properties such as impact, stretching.
The polyvinylidene difluoride (PVDF) that method of the present invention prepares has excellent mechanical property, good fluidity of molten and the higher transparency and obvious price advantage; In addition, having reduced the pollution to environment, is a kind of method of environmental protection.
Description of drawings
The structure iron of the oxygen amine compound of cycloaliphatic hydrocarbon tertiary amine in Fig. 1 the present invention.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1:
With vinylidene (VDF) 8.5g, 2,2 ' dimethyl-5,5 ' dimethylcyclopentane oxygen amine 0.25g, ammonium chloride 0.15g, ammonium perfluorocaprylate 0.15g join in appropriate water, air in use nitrogen replacement reactor three times, rising temperature to 120 ℃, reaction pressure are 5.0Mpa, carry out polyreaction 7 hours, and obtained polyvinylidene difluoride (PVDF) (PVDF) macromolecular material.
Embodiment 2:
With vinylidene (VDF) 6.5g, methyl methacrylate 2g, 2,2 ' dimethyl-5,5 ' dimethylcyclopentane oxygen amine 0.25g, ammonium chloride 0.15g, ammonium perfluorocaprylate 0.15g join in appropriate water, air in use nitrogen replacement reactor three times, rising temperature to 120 ℃, reaction pressure are 5.0Mpa, carry out polyreaction 7 hours, and obtained polyvinylidene difluoride (PVDF) (PVDF) macromolecular material.
Embodiment 3:
With vinylidene (VDF) 6.5g, methyl methacrylate 2g, 2,2 ' dimethyl-5,5 ' dimethylcyclopentane oxygen amine 0.25g, ammonium chloride 0.15g, ammonium perfluorocaprylate 0.10g, disproportionation rosin acid potassium 0.05g join in appropriate water, air in use nitrogen replacement reactor three times, rising temperature to 120 ℃, reaction pressure are 5.0Mpa, carry out polyreaction 7 hours, and obtained polyvinylidene difluoride (PVDF) (PVDF) macromolecular material.
Embodiment 4:
With vinylidene (VDF) 6.5g, methyl methacrylate 2g, 2,2 ' dimethyl-5,5 ' dimethylcyclopentane oxygen amine 0.25g, ammonium chloride 0.15g, ammonium perfluorocaprylate 0.10g, polyoxyethylene nonylphenol ether (n=10) 0.05g join in appropriate water, air in use nitrogen replacement reactor three times, rising temperature to 120 ℃, reaction pressure are 5.0Mpa, carry out polyreaction 7 hours, and obtained polyvinylidene difluoride (PVDF) (PVDF) macromolecular material.
Comparative Examples 1
Vinylidene (VDF) 7g, Potassium Persulphate 1.0g, ammonium perfluorocaprylate 0.2g raw material are joined appropriate water, and polyreaction is 4 hours under 120 ℃ of temperature of reaction, reaction pressure 5.0Mpa condition, aggregates into polyvinylidene difluoride (PVDF) (PVDF).
Comparative Examples 2
Vinylidene (VDF) 7g, Potassium Persulphate 0.1g, ferrous sulfate 0.2g, ammonium perfluorocaprylate 0.2g raw material are joined in the vinylformic acid medium, polyreaction is 4 hours under 80 ℃ of temperature of reaction, reaction pressure 5.0Mpa condition, aggregates into polyvinylidene difluoride (PVDF) (PVDF).
Polymerization rate, polymer output, polymericular weight and molecular weight in embodiment 1-3 and Comparative Examples 1-2 polyreaction are carried out evaluation comparison.The results are shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | |
| Polymerization rate (g/h) | 6.0 | 5.5 | 5.0 | 8.0 | 4.3 |
| Polymer yield (%) | 89 | 90 | 93 | 80 | 75 |
| Polymericular weight (Mn x10 -5gmol) | 13.10 | 12.50 | 12.30 | 4.60 | 4.50 |
| Molecular weight distribution (Mw/Mn) | 1.28 | 1.30 | 1.29 | 3.32 | 2.31 |
Can see from the result of table 1, the letex polymerization initiator system has a great impact polymerization rate and polymericular weight and molecular weight distribution, and alkyl oxygen amine free radical has the active free radical polymerization feature, and polymerization rate is very fast, the molecular weight of polymkeric substance is large, and molecular weight distribution is narrower.
Claims (10)
1. the preparation method of a ultra-high molecular weight poly (vinylidene fluoride) material, it is characterized in that: under emulsifying agent, vinylidene fluoride monomers and acrylic ester monomer obtain the ultra-high molecular weight poly (vinylidene fluoride) material by nitroxyl free radical active free radical polymerization mode.
2. according to the preparation method of ultra-high molecular weight poly (vinylidene fluoride) material claimed in claim 1, it is characterized in that: with vinylidene, acrylic ester monomer adds in reactor, add water, emulsifying agent and nitroxyl free radical, use the air in the nitrogen replacement reactor, polymerization temperature remains on 80-150 ℃, reaction pressure 3.0-6.0Mpa, reaction times 4-10 hour.
3., according to the preparation method of the described ultra-high molecular weight poly (vinylidene fluoride) material of claim 1-2, it is characterized in that: described emulsifying agent is fluorochemical surfactant, or the mixture of fluorochemical surfactant and other negatively charged ion or nonionogenic tenside.
4., according to the preparation method of ultra-high molecular weight poly (vinylidene fluoride) material claimed in claim 3, it is characterized in that: described fluorochemical surfactant is perfluoroalkyl acid ammonium, and perfluoroalkyl wherein is C
3F
7, C
4F
9, C
5F
11C
6F
13, C
7F
15, C
8F
17, C
9F
19, C
10F
21, C
11F
23, C
12F
25In a kind of.
5., according to the preparation method of ultra-high molecular weight poly (vinylidene fluoride) material claimed in claim 3, it is characterized in that: described anion surfactant is disproportionation rosin acid potassium or sodium salt anion surfactant.
6., according to the preparation method of ultra-high molecular weight poly (vinylidene fluoride) material claimed in claim 3, it is characterized in that: described nonionogenic tenside is one or both in alkylbenzene Soxylat A 25-7, fatty alcohol-polyoxyethylene ether.
7., according to the preparation method of ultra-high molecular weight poly (vinylidene fluoride) material claimed in claim 6, it is characterized in that: the Soxylat A 25-7 in described alkylbenzene Soxylat A 25-7 or fatty alcohol-polyoxyethylene ether is polyoxyethylene (2～20) ether.
8., according to the preparation method of ultra-high molecular weight poly (vinylidene fluoride) material claimed in claim 6, it is characterized in that: the alkyl in described alkylbenzene or fatty alcohol or fatty group are a kind of in octyl group, nonyl, decyl, undecyl, dodecyl.
9., according to the preparation method of the described ultra-high molecular weight poly (vinylidene fluoride) material of claim 1-2, it is characterized in that: described nitroxyl free radical is the oxygen amine compound of cycloaliphatic hydrocarbon tertiary amine.
10. according to the preparation method of the described ultra-high molecular weight poly (vinylidene fluoride) material of claim 1-2, it is characterized in that: described acrylic ester monomer is methyl acrylate, ethyl ester, propyl ester, butyl ester, pentyl ester and monooctyl ester, one or more in methyl methacrylate, ethyl ester, propyl ester, butyl ester, pentyl ester and monooctyl ester.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672368A (en) * | 2015-03-09 | 2015-06-03 | 河北工业大学 | Preparation method of form-adjustable anisotropic asymmetric emulsion particles |
| CN105153603A (en) * | 2006-07-06 | 2015-12-16 | 阿科玛股份有限公司 | Ultra-high molecular weight poly(vinylidene fluoride) and manufacturing method thereof |
| CN109065811A (en) * | 2018-08-20 | 2018-12-21 | 湖南烁普新材料有限公司 | Aqueous PVDF coating diaphragm and its preparation method and application |
| CN115867625A (en) * | 2022-06-16 | 2023-03-28 | 宁德时代新能源科技股份有限公司 | Adhesive, preparation method and application thereof |
-
2012
- 2012-05-08 CN CN2012101396473A patent/CN103387633A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 聂俊等: "《光聚合技术与应用》", 31 January 2009, 化学工业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153603A (en) * | 2006-07-06 | 2015-12-16 | 阿科玛股份有限公司 | Ultra-high molecular weight poly(vinylidene fluoride) and manufacturing method thereof |
| CN104672368A (en) * | 2015-03-09 | 2015-06-03 | 河北工业大学 | Preparation method of form-adjustable anisotropic asymmetric emulsion particles |
| CN104672368B (en) * | 2015-03-09 | 2016-12-21 | 河北工业大学 | A kind of preparation method of the asymmetric latex particle of the adjustable anisotropy of form |
| CN109065811A (en) * | 2018-08-20 | 2018-12-21 | 湖南烁普新材料有限公司 | Aqueous PVDF coating diaphragm and its preparation method and application |
| CN109065811B (en) * | 2018-08-20 | 2021-08-27 | 湖南烁普新材料有限公司 | Water-based PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof |
| CN115867625A (en) * | 2022-06-16 | 2023-03-28 | 宁德时代新能源科技股份有限公司 | Adhesive, preparation method and application thereof |
| WO2023240543A1 (en) * | 2022-06-16 | 2023-12-21 | 宁德时代新能源科技股份有限公司 | Binder, and preparation method therefor and use thereof |
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Application publication date: 20131113 |