CN101643523A - Polychlorotrifluoroethylene resin preparation method - Google Patents
Polychlorotrifluoroethylene resin preparation method Download PDFInfo
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- CN101643523A CN101643523A CN200910183733A CN200910183733A CN101643523A CN 101643523 A CN101643523 A CN 101643523A CN 200910183733 A CN200910183733 A CN 200910183733A CN 200910183733 A CN200910183733 A CN 200910183733A CN 101643523 A CN101643523 A CN 101643523A
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Abstract
The invention provides a polychlorotrifluoroethylene resin preparation method, belonging to the technical field of the preparation of fluoropolymer material. The method comprises the following steps:firstly purifying polytrifluorochloroethylene, then adopting deionized water as medium and using initiator to performing chlorotrifluoroethylene polymerization in the presence of surfactant and obtaining polychlorotrifluoroethylene resin. The invention has the advantage that the polymerization reaction time is shortened to less than 10h, the conversion rate of chlorotrifluoroethylene reach above 90%, the obtained polychlorotrifluoroethylene resin has good heat resistance and processability and degradation and metachromatism can not appear under the processing temperature of 240-280 DEG C. Therefore, the method can meet the demand of industrialized production.
Description
Technical field
The invention belongs to the preparing technical field of fluoro-containing macromolecule material, be specifically related to a kind of preparation method of daiflon.
Background technology
Daiflon (PCTFE) is a kind of have high added value and high performance thermoplastics.As a kind of high-end product, it usually is used under the severe environment that other material can't be suitable for.When contacting with natural gas liquids with liquid oxygen, liquid nitrogen, PCTFE has outstanding anti-fragility energy, excellent gas-barrier characteristics, and not influenced by the irradiation of ultraviolet ray and gamma ray.In refrigeration agent, PCTFE has outstanding anti-creep characteristic, therefore can be used to contact the main bearing part of refrigeration agent.
Conventional process such as PCTFE can be by injection moulding, extrude, mold pressing and transfer molding are processed.PCTFE is mainly used in part, food and drug packages film, liner and bearing and the common shaped piece etc. of making supercool refrigeration equipment part, valve (valve seat, valve rod and sealing member), sealing material (lid, O shape circle, v shaped ring and special construction sealing member), compressor and pump.
PCTFE is the thermoplastic fluoroelastomer plastics of developing the earliest and commercially producing.Nineteen thirty-seven, the preparation of PCTFE was at first reported by the Fa Ben industrial (I.G.Farbenindustrie) of Germany.Nineteen forty-six, the U.S. formally built up production equipment and the operation of PCTFE, was used for nuclear industry.Nineteen fifty-seven Minnesota ,USA mining industry Mechanology Inc. (3M) beginning is sold PCTFE in a large number with " KeI-F " trade mark.
PCTFE is formed for polymerizable raw material by trifluorochloroethylene (CTFE), for the PCTFE that obtains enough molecular weight to satisfy the needs of practical application, usually adopt redox initiation system under 0～60 ℃, to carry out polymerization, the oxygenant of this initiator system is persulphate or organo-peroxide, and reductive agent is sodium bisulfite or Sodium Metabisulfite, actual polyreaction is often above 30 hours, trifluorochloroethylene transformation efficiency 60～90%, although resulting PCTFE zero strength temperature surpasses 260 ℃ (explanation has higher molecular weight), but there is unstable end group on the molecular chain, in 240～280 ℃ of degradeds easily down of processing temperature, cause mis-behave and serious discoloration.
U.S. Pat 2613202, US2689241 and US5453477 all disclose the preparation of PCTFE, in redox initiation system, add transition metal ion such as iron ion as promotor to shorten polymerization reaction time, but actual polymerization time still reaches 20 hours, and the introducing of transition metal ion has aggravated PCTFE degraded at high temperature more.
U.S. Pat 2751376, US2902477 and US3045000 adopt solvent-strong oxidizer or ozone or chlorine that the PCTFE powder is handled, can significantly improve the resistance toheat of PCTFE under 240～280 ℃ of processing temperatures, but, these treatment process all are difficult to carry out industrial applications, and seriously polluted.
Polymerization time in the PCTFE preparation process is long, the transformation efficiency workability low and resulting PCTFE of trifluorochloroethylene is poor, being present industry common concern and technical problem that always wish to solve the 240-280 ℃ of variable color of easily degrading down for example, also is simultaneously the bottleneck that restriction PCTFE is able to suitability for industrialized production.In recent years, in view of remarkable increase and the continuous expansion of purposes and day by day harsh (require 240-280 ℃ scope in keep do not degrade and nondiscoloration) of physicals of China to the PCTFE consumption, therefore, be necessary further to explore from the autonomous angle of industry the preparation technology of more rational PCTFE, technical scheme described below produces under this background.
Summary of the invention
Task of the present invention is to provide a kind of and helps to shorten polymerization time and help improving the transformation efficiency of trifluorochloroethylene and use and satisfy suitability for industrialized production and require and can ensure that PCTFE is that 240-280 ℃ of scope do not degraded and the preparation method of the daiflon of the workability that embodies product is used in nondiscoloration in processing temperature.
Task of the present invention is finished like this, a kind of preparation method of daiflon, it is earlier to the voltalef purification process, be medium then with the deionized water, in the presence of tensio-active agent, adopt initiator to cause the trifluorochloroethylene polyreaction, obtain daiflon.
In a specific embodiment of the present invention, the weight part ratio of described trifluorochloroethylene, deionized water, tensio-active agent and initiator is 100: 250-1000: 0.02-2: 0.1-2.
In another specific embodiment of the present invention, the processing mode of described purification process for adopt in suction type and the mode of washing any one mode remove impurity in the described trifluorochloroethylene.
In another specific embodiment of the present invention, described suction type is for using the impurity in gac, molecular sieve or the porous silica gel absorption removal trifluorochloroethylene; Described mode of washing is for adopting the impurity in the basic solution washing removal trifluorochloroethylene.
In another specific embodiment of the present invention, described basic solution is sodium hydroxide solution or potassium hydroxide solution, and the mass percent concentration of described sodium hydroxide and potassium hydroxide solution respectively is 1-15%.
Go back in the specific embodiment of the present invention, described tensio-active agent is perfluorinated surfactant or partially fluorinated tensio-active agent.
More of the present invention and in specific embodiment, described perfluorinated surfactant is perfluoroalkyl carboxylate, fluorinated alkyl sulfonate or perfluoroalkyl oxa-carboxylate salt; Described partially fluorinated tensio-active agent is the perfluoro alkoxy benzene sulfonate.
In of the present invention and then specific embodiment, the transformation period when described initiator is 10-50 ℃ is the organic initiators of 0.1-10h.
Of the present invention again more and in specific embodiment, described organic initiators is dialkyl acyl class, new decanoate ester peroxide class, peroxy dicarbonates or perfluor superoxide.
In again of the present invention and then specific embodiment, the temperature of described polyreaction is 0-70 ℃, the pressure of polyreaction is 0.2-0.8MPa, the time of polyreaction is 4-9.5h, and the feeding mode of described trifluorochloroethylene is that disposable input or add continuously drops into or disposable input combines with adding continuously.
Technical scheme provided by the invention can shorten to the reaction times of polyreaction＜10h; The transformation efficiency of trifluorochloroethylene reaches more than 90%, and resulting daiflon resistance toheat is good, has good workability, can not occur degraded and metachromatism under 240-280 ℃ processing temperature.Therefore, can be suitable for the suitability for industrialized production requirement.
Embodiment
Embodiment 1-11:
In the vertical stainless steel polymerization reaction kettle of the 10L that has stirring, carry out polyreaction, deionized water, trifluorochloroethylene (CTFE), the consumption of tensio-active agent and initiator, polymerization temperature, polymerization pressure and polymerization time, the CTFE transformation efficiency, the mass loss of the ZST numerical value of PCTFE and degradation property test sees Table 1, in embodiment 1-11, tensio-active agent is a perfluorinated surfactant, the concrete perfluoro butyl potassium sulfonate (KFBS) that adopts, transformation period when initiator adopts 10-50 ℃ is the organic initiators of 0.1-10h, specifically selects peroxy dicarbonate diisopropyl ester (IPP) for use.
Polymerization reaction kettle is through after the deoxidation treatment, add deionized water, tensio-active agent, the stirring velocity of polymerization reaction kettle is 350n/min, temperature in the control reactor is to setting (appointment) temperature, add through the CTFE gas after the porous silica gel adsorption treatment, gauge pressure reaches setting pressure in still, disposable adding initiator (IPP) beginning polyreaction.In reactor, replenish the CTFE gas that adding is crossed through the porous silica gel adsorption treatment, satisfy specified pressure with the gauge pressure of keeping in the reactor.The temperature of reaction of control reactor in the polymerization process.When CTFE monomer add-on reaches appointment numerical value, stop to add CTFE, finish reaction behind the 1h, blow away CTFE gas residual in the still with nitrogen, pressure in the reactor is reduced to normal pressure, material is isolated daiflon (PCTFE) wet feed after coagulating through calcium chloride in the still, through washing, drying, obtains finished product PCTFE powder again.
Table 1
| Embodiment | The H2O gram | The CTFE gram | The KFBS gram | The IPP gram | Temperature ℃ | Pressure MPa | Time hour | Transformation efficiency % | ZST second | Degradation property % |
| ??1 | ??7000 | ??700 | ??7 | ??35 | ??40 | ??0.7 | ??4 | ??95 | ??352 | ??0.04 |
| ??2 | ??7000 | ??1400 | ??7 | ??35 | ??40 | ??0.7 | ??6 | ??94 | ??370 | ??0.02 |
| ??3 | ??7000 | ??2800 | ??7 | ??35 | ??40 | ??0.7 | ??8 | ??92 | ??410 | ??0.01 |
| ??4 | ??7000 | ??1400 | ??1.4 | ??35 | ??40 | ??0.7 | ??6.5 | ??92 | ??375 | ??0.02 |
| ??5 | ??7000 | ??1400 | ??140 | ??35 | ??40 | ??0.7 | ??5.5 | ??96 | ??365 | ??0.03 |
| ??6 | ??7000 | ??1400 | ??7 | ??7 | ??40 | ??0.7 | ??9.5 | ??91 | ??368 | ??0.04 |
| ??7 | ??7000 | ??1400 | ??7 | ??140 | ??40 | ??0.7 | ??4 | ??97 | ??340 | ??0.05 |
| ??8 | ??7000 | ??1400 | ??7 | ??35 | ??0 | ??0.7 | ??9.5 | ??91 | ??450 | ??0.01 |
| ??9 | ??7000 | ??1400 | ??7 | ??35 | ??70 | ??0.7 | ??5 | ??96 | ??270 | ??0.03 |
| ??10 | ??7000 | ??1400 | ??7 | ??35 | ??40 | ??0.2 | ??10 | ??91 | ??302 | ??0.02 |
| ??11 | ??7000 | ??1400 | ??7 | ??35 | ??40 | ??0.8 | ??5.5 | ??95 | ??390 | ??0.01 |
Can be seen by the embodiment 1-11 shown in the above-mentioned table 1: the polymerization time of the present invention's preparation is 4-9.5h, significantly shortens than prior art (20h); Trifluorochloroethylene (CTFE) transformation efficiency is 91-98%; The PCTFE that obtains does not degrade under processing temperature 240-280 ℃, nondiscoloration.Because the foregoing description 1-11 carried out purification process to CTFE, under the effect of organic initiators and fluorochemical surfactant, carry out radical polymerization, can obtain more than zero strength time (ZST)＞300 second, thereby under 240-280 ℃, guarantee not degrade and nondiscoloration.
Because of CTFE can contain impurity in process of production, some impurity is the artificial stablizer that adds, some then is the acidic impurities that trace water among the CTFE and CTFE reaction are produced, these impurity all are unfavorable for the radical polymerization of CTFE, and consume initiator on the one hand, cause speed of response to be slowed down, can form more low molecular organic material on the other hand, comprise low-molecular-weight PCTFE, cause the PCTFE variable color of in the time of processing temperature 240-280 ℃, degrading.The inventive method is carried out purification process to CTFE, can eliminate aforesaid defective.
Embodiment 1-11 adopts porous silica gel to CTFE absorption (absorption) impurity, also can be with diluted alkaline solution to the CTFE gas scrubbing.Per kilogram gac, molecular sieve or porous silica gel are 0.1-10 ton CTFE to the treatment capacity of CTFE, are preferably 0.5-2 ton CTFE.If use sig water washing CTFE gas, the mass percent concentration of sig water is 1-15% so, is preferably 5-10%, and sig water is NaOH or KOH, can determine whether needing to change alkali lye by the monitoring concentration of lye.Certainly suction type also can mix use with mode of washing.
Zero strength time (ZST) test: the ZST value has been represented the molecular weight size of PCTFE, and the inventive method is carried out the ZST DATA REASONING of PCTFE according to USS ASTMD1430-03.
The degradation property test: the inventive method behind 270 ± 1 ℃ of heating 5h, is measured the mass loss of test piece with the ZST test piece.ZST numerical value＞300 of PCTFE obtained by the method for the present invention second; The mass loss of degradation property test is＜0.1%.
Embodiment 12-14:
Tensio-active agent perfluoro butyl potassium sulfonate (KFBS) among the embodiment 1-11 is replaced by perfluor caproic acid ammonium (embodiment 12), perfluoroalkyl oxa-n-nonanoic acid ammonium (embodiment 13) and nona oxy benzene sulfonic acid sodium salt of perfluoro (embodiment 14), the quality numerical value of the ZST numerical value of polymerization reaction time, CTFE transformation efficiency, PCTFE and degradation property test sees Table 2, all the other conditions are with the embodiment 1-3 among the real 1-11 of table 1, i.e. corresponding embodiment 3 of all the other conditions of the corresponding embodiment 2 of all the other conditions of all the other conditions corresponding embodiment 1, the embodiment 13 of embodiment 12 and embodiment 14.NM content is all with the description to embodiment 1-11 among the present embodiment 12-14.
Table 2
| Embodiment | Tensio-active agent | Time hour | Transformation efficiency % | ZST second | Degradation property % |
| ??12 | Perfluor caproic acid ammonium | ??5.5 | ??96 | ??392 | ??0.03 |
| ??13 | Perfluoroalkyl oxa-n-nonanoic acid ammonium | ??5 | ??97 | ??380 | ??0.02 |
| ??14 | Nona oxy benzene sulfonic acid sodium salt of perfluoro | ??7 | ??92 | ??375 | ??0.04 |
Embodiment 15-17:
Initiator di-isopropyl peroxydicarbonate (IPP) among the embodiment 1-11 is replaced by by the diisobutyryl peroxide shown in the table 3 (embodiment 15), peroxidation neodecanoic acid isobutyl ester (embodiment 16) and peroxidation two perfluor propionyl (embodiment 17), the time of polyreaction, the CTFE transformation efficiency, the quality numerical value of the ZST numerical value of PCTFE and degradation property test sees Table 3, all the other conditions are with the embodiment 4-6 among the embodiment 1-11 shown in the table 1, that is: all the other conditions of embodiment 15 are corresponding to embodiment 4, all the other conditions of embodiment 16 are corresponding to the corresponding embodiment 6 of all the other conditions of embodiment 5 and embodiment 17.The content of not describing among the embodiment 15 to 17 is all with the description to embodiment 1-11.
Table 3
| Embodiment | Initiator | Time hour | Transformation efficiency % | ZST second | Degradation property % |
| ??15 | Diisobutyryl peroxide | ??7 | ??92 | ??350 | ??0.03 |
| ??16 | Peroxidation neodecanoic acid isobutyl ester | ??8 | ??91 | ??380 | ??0.04 |
| ??17 | Peroxidation two perfluor propionyl | ??5 | ??98 | ??405 | ??0.01 |
Comparative Examples 1:
Except CTFE gas does not carry out the adsorption treatment, other are identical with embodiment 2.CTFE transformation efficiency 74%, polymerization time 16 hours.The ZST of this PCTFE is 332s, and the mass loss of degradation property test is 0.35%.
Comparative Examples 2:
Restrain the ferrous sulfate except initiator changes tertbutanol peroxide 5 gram and Sodium Metabisulfite 5 grams into and adds 1, other are identical with embodiment 2.CTFE transformation efficiency 83.3%, polymerization time 10 hours.The ZST of this PCTFE is 332s, and the mass loss of thermotolerance test is 0.65%.
Comparative Examples 3:
Except not adding the tensio-active agent, other are identical with embodiment 2.CTFE transformation efficiency 70%, polymerization time 30 hours.The ZST of this PCTFE is 376s, and the mass loss of thermotolerance test is 0.07%.Attached: the present invention and the contrast of similar technique both at home and abroad.
| The item description | Domestic and international similar technique US2613202 US2689241 US5453477 | The embodiment of the invention 1～17 |
| The CTFE monomer | Be untreated | Adsorb or carrying out washing treatment, to remove impurity |
| Initiator | Redox initiator | Organic initiators |
| Tensio-active agent | Do not adopt | Use perfluorinated surfactant or partially fluorinated tensio-active agent |
| Polymerization reaction time | ＞20 hours | ＜10 hours |
| The CTFE transformation efficiency | ??＜90％ | ??＞90％ |
| ??ZST | ＞200 seconds | ＞300 seconds |
| The mass loss of degradation property test | ??＞0.1％ | ??＜0.1％ |
Claims (10)
1, a kind of preparation method of daiflon, it is characterized in that it is earlier to the voltalef purification process, be medium with the deionized water then, in the presence of tensio-active agent, adopt initiator to cause the trifluorochloroethylene polyreaction, obtain daiflon.
2, the preparation method of daiflon according to claim 1, the weight part ratio that it is characterized in that described trifluorochloroethylene, deionized water, tensio-active agent and initiator is 100: 250-1000: 0.02-2: 0.1-2.
3, the preparation method of daiflon according to claim 1, the processing mode that it is characterized in that described purification process for adopt in suction type and the mode of washing any one mode remove impurity in the described trifluorochloroethylene.
4, the preparation method of daiflon according to claim 3 is characterized in that described suction type is for using the impurity in gac, molecular sieve or the porous silica gel absorption removal trifluorochloroethylene; Described mode of washing is for adopting the impurity in the basic solution washing removal trifluorochloroethylene.
5, the preparation method of daiflon according to claim 4 is characterized in that described basic solution is sodium hydroxide solution or potassium hydroxide solution, and the mass percent concentration of described sodium hydroxide and potassium hydroxide solution respectively is 1-15%.
6, the preparation method of daiflon according to claim 1 and 2 is characterized in that described tensio-active agent is perfluorinated surfactant or partially fluorinated tensio-active agent.
7, the preparation method of daiflon according to claim 6 is characterized in that described perfluorinated surfactant is perfluoroalkyl carboxylate, fluorinated alkyl sulfonate or perfluoroalkyl oxa-carboxylate salt; Described partially fluorinated tensio-active agent is the perfluoro alkoxy benzene sulfonate.
8, the preparation method of daiflon according to claim 1 and 2 is characterized in that the transformation period when described initiator is 10-50 ℃ is the organic initiators of 0.1-10h.
9, the preparation method of daiflon according to claim 8 is characterized in that described organic initiators is dialkyl acyl class, new decanoate ester peroxide class, peroxy dicarbonates or perfluor superoxide.
10, the preparation method of daiflon according to claim 1, the temperature that it is characterized in that described polyreaction is 0-70 ℃, the pressure of polyreaction is 0.2-0.8MPa, the time of polyreaction is 4-9.5h, and the feeding mode of described trifluorochloroethylene is that disposable input or add continuously drops into or disposable input combines with adding continuously.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101955560A (en) * | 2010-04-01 | 2011-01-26 | 青岛宏丰氟硅科技有限公司 | Method for preparing chlorotrifluor ethylene homopolymer emulsion |
| CN102020737A (en) * | 2010-11-12 | 2011-04-20 | 司林旭 | Preparation method of high-temperature resistant and high-transparent polychlorotrifluoroethylene |
| CN102304306A (en) * | 2011-10-17 | 2012-01-04 | 北京联创佳艺影像新材料技术有限公司 | Water-based dye ink for jet printing of black and white images |
| JPWO2021024797A1 (en) * | 2019-08-07 | 2021-02-11 | ||
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
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2009
- 2009-08-07 CN CN200910183733A patent/CN101643523A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955560A (en) * | 2010-04-01 | 2011-01-26 | 青岛宏丰氟硅科技有限公司 | Method for preparing chlorotrifluor ethylene homopolymer emulsion |
| CN102020737A (en) * | 2010-11-12 | 2011-04-20 | 司林旭 | Preparation method of high-temperature resistant and high-transparent polychlorotrifluoroethylene |
| CN102304306A (en) * | 2011-10-17 | 2012-01-04 | 北京联创佳艺影像新材料技术有限公司 | Water-based dye ink for jet printing of black and white images |
| JPWO2021024797A1 (en) * | 2019-08-07 | 2021-02-11 | ||
| WO2021024797A1 (en) * | 2019-08-07 | 2021-02-11 | ダイキン工業株式会社 | Method for producing fluoropolymer |
| JP7453559B2 (en) | 2019-08-07 | 2024-03-21 | ダイキン工業株式会社 | Fluoropolymer manufacturing method |
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
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Open date: 20100210 |