CN103709304A - Preparation method of high-strength fluorine-containing polymer - Google Patents
Preparation method of high-strength fluorine-containing polymer Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-strength fluorine-containing polymer. The method comprises the following steps: 1) adding water and an emulsifier to a reactor, and evacuating until the oxygen content is smaller than or equal to 50ppm; 2) continuing to add a pH regulator and a chain transfer agent; 3) heating the reactor to 40-60 DEG C, and adding a mixed monomer composed of 1,1-difluoroethylene, tetrafluoroethylene and trifluorochloroethylene; 4) adding an initiator, beginning polymerization reaction, and lastingly adding the mixed monomer to maintain the pressure inside the reactor constant in the polymerization reaction; and 5) finishing the polymerization reaction when the solid content of a polymer emulsion achieves 25-35% by mass, freezing and condensing the emulsion, washing and drying, so as to obtain the fluorine-containing polymer which is relatively high in strength, good in ageing resistance, and good in mechanical property and has the molecular weight of 150,000-300,000. The preparation method of the fluorine-containing polymer, which is disclosed by the invention, is fewer in raw materials, simple in technology, and applicable to large-scale popularization.
Description
Technical field
The preparation method who the present invention relates to a kind of high strength fluoropolymer, belongs to polymeric material field.
Background technology
Fluoropolymer is due to its good ageing resistance, higher density and mechanical property preferably, at home and abroad in Nuclear weapons explosive formulation, as main caking agent or coated application of paints, as the PBX-9502 of the U.S., LX-17 explosive.Fluoropolymer mainly plays bonding coating function to single chmical compound explosive, and performance all has considerable influence to performances such as the moulding of explosive, mechanics, processing and environmental compatibilities, belongs to the critical material of Nuclear weapons Explosive Parts.
CN1692132A discloses a kind of fluoropolymer, and the fluoropolymer that it comprises the repeating unit that derives from tetrafluoroethylene (TFE), R 1216 (HFP), difluoroethylene (VDF), trifluorochloroethylene (CTFE), has good adhesive property.But it need further raising at aspects such as intensity, elongations.
Summary of the invention
In order to overcome above-mentioned defect, the present invention, by existing technique, starting material are improved, obtains a kind of fluoropolymer with higher-strength, good ageing resistance and mechanical property.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for high strength fluoropolymer, comprises the steps:
1) in reactor, add water, emulsifying agent, be evacuated to oxygen level≤50ppm;
2) continue to add pH adjusting agent, chain-transfer agent;
3) reactor heating, to 40-60 ℃, adds by vinylidene fluoride, tetrafluoroethylene, the mix monomer that trifluorochloroethylene forms;
4) add initiator, start polyreaction; Continue to add mix monomer constant to maintain reactor pressure therebetween;
5) treat that polymerized emulsion solid content reaches mass percent 25-35%, finish polyreaction, emulsion freeze agglomeration, washing and dry, obtains fluoropolymer.
In above-mentioned preparation method, in step 1), described emulsifying agent is long-chain perfluorocarboxylic acid salt, preferably ammonium perfluorocaprylate and/or Sodium perfluorooctanoate; The dosage of described emulsifying agent is to add 0.01-5 weight part emulsifying agent in every 100 weight parts water media.
In order to be conducive to the decomposition of initiator, in step 2) in, described PH conditioning agent is borax, dipotassium hydrogen phosphate or its sodium salt.
In step 2) in, described chain-transfer agent is diethyl malonate, diethyl succinate, chloroform, tetracol phenixin, normal hexane, acetone or ethyl acetate; The input amount of chain-transfer agent is the 0.01-5% of mix monomer weight.
In step 3), vinylidene fluoride, tetrafluoroethylene, the mol ratio of trifluorochloroethylene is 10-12:1-3:5-8.
In step 4), described initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate; The dosage of initiator is the 0.001-5% of mix monomer weight;
In order to guarantee certain polymerization velocity, avoid again too high the caused emulsion breaking of efficiency of initiation, and to equipment and system, pipeline build-up of pressure, polymeric reaction temperature of the present invention is controlled at 40-100 ℃ simultaneously, pressure-controlling is at 3.0-3.5MPa.
In step 4), can also, according to reaction needed, add chain-transfer agent.
The present invention is by adjusting content and the component proportion of comonomer, polymerization technique is improved, control ph value of emulsion, adjust the auxiliary agent joining day, obtain thering is higher-strength, good ageing resistance, better mechanical property, the fluoropolymer of molecular weight between 15-30 ten thousand.The preparation method of fluoropolymer of the present invention, raw material is few, technique is simple, be applicable to large-scale promotion.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
In the reactor of 10L, prepare fluoropolymer.
In reactor, add 5L deionized water and 2g ammonium perfluorocaprylate.Reactor should carry out evacuation processes, when its oxygen level≤50ppm, adds borax 5g, propanedioic acid diethyl fat (chain-transfer agent) 5ml.Content in reactor is heated to 56 ℃.With containing 55mol%1,1-difluoroethylene (VDF), 10mol% tetrafluoroethylene (TFE), the mix monomer of 35mol% trifluorochloroethylene (CTFE) rises to 3.2MPa by reactor pressure.With 88r/min speed, stir, reactor pressure is controlled in 3.2 ± 0.02MPa.
Add Potassium Persulphate 1g to start reaction, after polyreaction starts, by supplementing mix monomer, absolute pressure in reactor is maintained between 3.2 ± 0.02MPa, reaction times is about 10h, emulsion solid content reaches 30%(mass percent) left and right, finish polyreaction, reclaim unreacted monomer, emit emulsion, by emulsion freeze agglomeration, with deionized water wash, 100 ℃ of left and right vacuum-dryings, produce polymkeric substance and surpass 2Kg, its characteristic is listed in table 1.
Embodiment 2
According to the method for embodiment 1, prepare fluoropolymer.Difference is, emulsifying agent is Sodium perfluorooctanoate.Vinylidene fluoride, tetrafluoroethylene, the mol ratio of trifluorochloroethylene is 10:1:5.Polymeric reaction temperature of the present invention is controlled at 60 ℃, and pressure-controlling is at 3.5MPa.Chain-transfer agent is Diethyl succinate.
Embodiment 3
According to the method for embodiment 1, prepare fluoropolymer.Difference is, emulsifying agent is Sodium perfluorooctanoate.Vinylidene fluoride, tetrafluoroethylene, the mol ratio of trifluorochloroethylene is 12:3:8.Polymeric reaction temperature of the present invention is controlled at 70 ℃, and pressure-controlling is at 3.3MPa.Chain-transfer agent is Diethyl succinate.
Experimental example
Take CN1692132A as reference examples, embodiment 1-3 gained fluoropolymer and reference examples are carried out to characteristic present.The results are shown in Table 1.
Table 1 characteristic present data
Although 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 (7)
1. a preparation method for high strength fluoropolymer, is characterized in that, comprises the steps:
1) in reactor, add water, emulsifying agent, be evacuated to oxygen level≤50ppm;
2) continue to add pH adjusting agent, chain-transfer agent;
3) reactor heating, to 40-60 ℃, adds by vinylidene fluoride, tetrafluoroethylene, the mix monomer that trifluorochloroethylene forms;
4) add initiator, start polyreaction; Continue to add mix monomer constant to maintain reactor pressure therebetween;
5) treat that polymerized emulsion solid content reaches mass percent 25-35%, finish polyreaction, emulsion freeze agglomeration, washing and dry, obtains fluoropolymer.
2. preparation method according to claim 1, is characterized in that, in step 1), described emulsifying agent is perfluorocarboxylic acid salt, preferably ammonium perfluorocaprylate and/or Sodium perfluorooctanoate; The dosage of described emulsifying agent is to add 0.01-5 weight part emulsifying agent in every 100 weight parts water media.
3. preparation method according to claim 1, is characterized in that, in step 2) in, described pH adjusting agent is borax, dipotassium hydrogen phosphate or its sodium salt.
4. preparation method according to claim 1, is characterized in that, in step 2) in, described chain-transfer agent is diethyl malonate, diethyl succinate, chloroform, tetracol phenixin, normal hexane, acetone or ethyl acetate; The input amount of described chain-transfer agent is the 0.01-5% of mix monomer weight.
5. preparation method according to claim 1, is characterized in that, in step 3), and described vinylidene fluoride, tetrafluoroethylene, the mol ratio of trifluorochloroethylene is 10-12:1-3:5-8.
6. preparation method according to claim 1, is characterized in that, in step 4), described initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate; The dosage of initiator is the 0.001-5% of mix monomer weight.
7. preparation method according to claim 1, is characterized in that, in step 4), described polymeric reaction temperature is controlled at 40-100 ℃, and pressure-controlling is at 3.0-3.5MPa.
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| CN201310731172.1A CN103709304A (en) | 2013-12-26 | 2013-12-26 | Preparation method of high-strength fluorine-containing polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193854A (en) * | 2014-09-28 | 2014-12-10 | 无锡市新颖密封材料厂 | Fluororubber preparation method |
| CN110078856A (en) * | 2019-04-22 | 2019-08-02 | 中昊晨光化工研究院有限公司 | A kind of tetrafluoroethene modified polyvinilidene fluoride resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1026202A1 (en) * | 1997-10-24 | 2000-08-09 | Daikin Industries, Ltd. | Aqueous resin dispersion composition |
| JP2010280103A (en) * | 2009-06-03 | 2010-12-16 | Daikin Ind Ltd | Laminate, molding, fuel hose and method for manufacturing the laminate |
| CN102482632A (en) * | 2009-09-03 | 2012-05-30 | 株式会社尼康 | Agitation method, cell culture method, agitation apparatus, and cell culture apparatus |
| CN103351446A (en) * | 2013-07-25 | 2013-10-16 | 中昊晨光化工研究院有限公司 | Preparation method of high-tensile-strength polyvinylidene fluoride |
-
2013
- 2013-12-26 CN CN201310731172.1A patent/CN103709304A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1026202A1 (en) * | 1997-10-24 | 2000-08-09 | Daikin Industries, Ltd. | Aqueous resin dispersion composition |
| JP2010280103A (en) * | 2009-06-03 | 2010-12-16 | Daikin Ind Ltd | Laminate, molding, fuel hose and method for manufacturing the laminate |
| CN102482632A (en) * | 2009-09-03 | 2012-05-30 | 株式会社尼康 | Agitation method, cell culture method, agitation apparatus, and cell culture apparatus |
| CN103351446A (en) * | 2013-07-25 | 2013-10-16 | 中昊晨光化工研究院有限公司 | Preparation method of high-tensile-strength polyvinylidene fluoride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193854A (en) * | 2014-09-28 | 2014-12-10 | 无锡市新颖密封材料厂 | Fluororubber preparation method |
| CN110078856A (en) * | 2019-04-22 | 2019-08-02 | 中昊晨光化工研究院有限公司 | A kind of tetrafluoroethene modified polyvinilidene fluoride resin and preparation method thereof |
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Application publication date: 20140409 |