CN105542046B - The preparation method of daiflon - Google Patents
The preparation method of daiflon Download PDFInfo
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- CN105542046B CN105542046B CN201511029266.XA CN201511029266A CN105542046B CN 105542046 B CN105542046 B CN 105542046B CN 201511029266 A CN201511029266 A CN 201511029266A CN 105542046 B CN105542046 B CN 105542046B
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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
- C08F114/24—Trifluorochloroethene
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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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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Abstract
The present invention relates to a kind of preparation method of daiflon, belong to fluororesin modified technical field.The preparation method of daiflon of the present invention, is to add pH buffer and molecular weight regulator in a solvent, triggers CTFE monomer to carry out polymerisation in the presence of redox initiator.Present invention process is simple, energy-conserving and environment-protective, reaction are gentle, and obtained daiflon has relatively low molecular weight distribution and higher zero strength time, and melt index is stable.
Description
Technical field
The present invention relates to a kind of preparation method of daiflon, belong to fluororesin modified technical field.
Background technology
Polytrifluorochloroethylene (PCTFE) is the homopolymer of monomer CTFE, and molecular formula is (CF2-CClF) n, is one
Low permeability, resistance to cold flow, wear-resisting and excellent radiation-resistant property transparent resin are planted, it is extensive with high mechanical properties and rigidity
In terms of coating, pump valve, packaging material (film), cable, low temperature seal, medicine instrument, electronic component, simultaneously as
Its excellent performance, equally has irreplaceable effect in terms of militaria, Aero-Space, is important fluorine-containing tree
Fat.
The A of Chinese patent application CN 103304712 disclose a kind of manufacture method of bead daiflon,
This method uses oil-soluble initiator and organic dispersing agent, is prepared using the method reaction of gradient increased temperature and control speed of agitator poly-
Trifluorochlorethylene resin, the daiflon that document report this method is produced is diameter 0.5mm~5mm bead tree
Fat, to avoid the dust from flying phenomenon in production process.However, this method complex steps (gradient increased temperature), are unfavorable for extension
Production.
U.S. Patent application US 2613202 disclose it is a kind of in high yield, the polytrifluorochloroethylene preparation side of high softening-point
Method, this method uses organic peroxide catalyst and water soluble, redox initiator, by the pH and the extension that control solution
Reaction time prepares polytrifluorochloroethylene in high yield, though this method has an advantage on yield and performance, the reaction time compared with
Long, the experiment condition needed for reaction requires that higher (polymerization time is more than 10h, pH2.2~4.0), causes the waste of the energy.
Chinese patent CN 201110440614 discloses a kind of preparation method of polytrifluorochloroethylene, and this method is with inorganic
Peroxide is initiator, triggers CTFE to carry out polymerisation, then using F2/N2To obtained polytrifluorochloroethylene
Resin carries out fluorination termination process.The daiflon that this method is obtained is non-degradable under 300 DEG C of processing temperature, no
Discoloration.The problem of although this method solves the degradable discoloration of polytrifluorochloroethylene high temperature, but use F2Mode carry out end group
Processing, adds the possibility of molecular structure destruction, and is unfavorable for energy-conserving and environment-protective, and the simultaneous reactions time is longer (10~12h), increases
Running cost is added.
Chinese patent CN 102603944A disclose a kind of CTFE emulsion polymerisation process, in the method, use
Deionized water and perfluor -4- methyl -2- pentane admixtures are reaction medium (being unfavorable for environmental protection), with fluorine-containing certain herbaceous plants with big flowers base acrylic acid fourth two
Fat is surfactant, and polymerisation is carried out to CTFE in the presence of perfluoropentyl butylperoxide initiator.Should
Substantial amounts of organic reagent has been used in method, has been unfavorable for post processing, meanwhile, course of reaction is cumbersome (interim continuous dosing), right
Operation has higher requirement.
Therefore, it is necessary to study a kind of polymerization of CTFE, performance is prepared in the way of high-efficiency environment friendly excellent
Good daiflon, solves cumbersome technological process in traditional polytrifluorochloroethylene preparation process, reaction time length, production
Moral character can it is unstable, the drawbacks of be unfavorable in the industrialized productions such as environmental protection.
The content of the invention
It is an object of the invention to provide a kind of preparation method of daiflon, its technique is simple, energy-saving ring
Protect, react gentle, obtained daiflon has relatively low molecular weight distribution and higher zero strength time, and melting refers to
Number is stable.
The preparation method of daiflon of the present invention, is to add pH buffer and molecular weight in a solvent
Conditioning agent, triggers CTFE monomer to carry out polymerisation in the presence of redox initiator.
The solvent is high purity water, and its electrical conductivity is not more than 0.1 μ Scm-1, its consumption is CTFE monomer mass
0.2~10 times.
The pH buffer is dihydric phosphate, preferably sodium dihydrogen phosphate or potassium dihydrogen phosphate.Its consumption is trifluoro chlorine
The 0.01~20% of vinyl monomer quality, preferably 0.1~10%, more preferably 1~5%.
The molecular weight regulator is dithiocar-bamate, preferably SDD, diethyl
Base nabam, dibenzyl aminodithioformic acid sodium, PZ, the sulphur of di-n-butyl two
For carbamic acid sodium, ammonium dithiocarbamate, APDC, ferric dimethyl dithiocarbamate,
Diethylammonium diethyldithiocarbamate.The consumption of molecular weight regulator for CTFE monomer mass 0.01~
20%, preferably 0.1~10%, more preferably 1~5%.
The redox initiator is the mixture of persulfate and bisulfites, and mixing quality ratio is 1:5~5:
1；The consumption of redox initiator is the 0.1~10% of CTFE monomer mass, preferably 1~8%, more preferably 4
~6%.
The reaction temperature is 10 DEG C~70 DEG C, preferably 20 DEG C~60 DEG C, more preferably 30 DEG C~50 DEG C.
The reaction time is 3~9h, more preferably preferably 4~8h, 5~7h.
The polymerisation is carried out under spontaneous pressure, and reaction pressure is 0.2~2Mpa.
Speed of agitator is 300~800r/min, preferably 400r/min~600r/min during the reaction, is more preferably
500r/min~600r/min.
The preparation method of described daiflon, comprises the following steps：
(1) it is 10 DEG C~15 DEG C to control high-purity coolant-temperature gage, by high purity water, pH adjusting agent, initiator and molecular weight regulator
It is deployed into initial soln；
(2) under negative pressure, initial soln is mixed and be transferred in reactor；CTFE is disposably passed through under agitation
Gas；
(3) adjust and control reactor temperature to required temperature and keep constant, finally give powder or bead is poly-
Trifluorochlorethylene resin.
Melt and refer to assay method according to the method implementation described in standard ASTM D-1238；
This patent is carried out using zero strength time assay method according to the method described in standard ASTM D-1430-03.
The present invention compared with prior art, has the advantages that：
(1) using disposably feeding intake, reaction is gentle, and easy temperature control, process is simple；
(2) by adding molecular weight regulator, zero strength time and the mechanical performance of PCTFE resins are effectively improved；
(3) by controlling the addition of molecular weight regulator and pH adjusting agent, it is allowed to the daiflon prepared
Melt index be 0.1g/10min~30g/10min, the demand of different purposes can be met；
(4) high purity water is used as reaction medium, using inorganic salts as initiator, pH adjusting agent and molecular-weight adjusting
Agent, it is to avoid the environmental problem brought using organic solvent or dispersant；
(5) according to the preparation method of the present invention, the reaction time is typically smaller than 9 hours, the poly- trifluoro obtained by the present invention
Vinyl chloride, with higher conversion ratio (being more than 90%) and yield (being more than 80%), effectively shortens polymerization time, improves poly-
Close efficiency；
(6) according to the implementation of the present invention, alternative obtains powdered or bead resin, meets product difference and adds
The demand of work technique；Obtained polytrifluorochloroethylene has stronger high-temperature stability, in 240 DEG C~280 DEG C not degradable changes
Color, the section bars such as transparent bar, tubing are can obtain by being molded extrusion.
Embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the implementation of the present invention.
The electrical conductivity of high purity water used is 0.05 μ Scm in embodiment-1。
Embodiment 1
High purity water 500g accurately is weighed in the beaker of clean dried, is controlled 12 DEG C ± 1 DEG C of water temperature, is weighed 3.2g di(2-ethylhexyl)phosphates
Hydrogen potassium, 5.0g sodium hydrogensulfites and 7.8g potassium peroxydisulfates are added in the beaker containing high purity water, while accurately weighing and adding
4.8g SDDs, are thoroughly mixed the reactor that mixed solution is transferred to cleaning by negative pressure
In, reactor is carried out using high-purity argon gas to vacuumize displacement deoxygenation.Magnetic stirring apparatus is opened to 500r/min, by reactor with
CTFE gas cylinder is connected, and the addition 980g CTFE monomers into reactor.Reactor is warming up to 30 DEG C, control
Reaction temperature is 30 DEG C ± 1 DEG C, and stirring reaction stops reaction after 6 hours, and powdered daiflon is taken out in release.
Through high-purity water washing, drying, weigh and obtain 872g products, yield 89%.
Test result shows that the product melt index is 5.2g/10min, and the zero strength time is 341s.
Comparative example 1
High purity water 500g accurately is weighed in the beaker of clean dried, is controlled 12 DEG C ± 1 DEG C of water temperature, is weighed 3.2g di(2-ethylhexyl)phosphates
Hydrogen potassium, 5.0g sodium hydrogensulfites and 7.8g potassium peroxydisulfates are added in the beaker containing high purity water, stirring mixture to completely it is molten
In solution, the reactor that mixed solution is transferred to cleaning by negative pressure, reactor is carried out using high-purity argon gas to vacuumize displacement
Deoxygenation.Magnetic stirring apparatus is opened to 500r/min, reactor is connected with CTFE gas cylinder, and is added into reactor
990g CTFE monomers.Reactor is warming up to 30 DEG C, controlling reaction temperature is 30 DEG C ± 1 DEG C, stirring reaction 7 hours
Afterwards, reaction is stopped, powdered daiflon is taken out in release.
Through high-purity water washing, drying, weigh and obtain 690g products, yield 69.7%.
Test result shows that the product melt index is 2.6g/10min, and the zero strength time is 278s.
Embodiment 2
High purity water 650g accurately is weighed in the beaker of clean dried, is controlled 12 DEG C ± 1 DEG C of water temperature, is weighed 5.0g di(2-ethylhexyl)phosphates
Hydrogen potassium, 3.6g potassium bisulfites and 8g potassium peroxydisulfates are added in the beaker containing high purity water, are thoroughly mixed to completely molten
Solution, while accurately weighing and adding 6.0g dibenzyl aminodithioformic acid sodium, cleaning is transferred to by mixed solution by negative pressure
Reactor in, using high-purity argon gas to reactor carry out vacuumize displacement deoxygenation.Magnetic stirring apparatus is opened to 800r/min,
Reactor is connected with CTFE gas cylinder, and the addition 1020g CTFE monomers into reactor.Reactor is heated up
To 35 DEG C, controlling reaction temperature is 35 DEG C ± 1 DEG C, and stirring reaction stops reaction after 3 hours, and the poly- trifluoro of bead is taken out in release
Vinyl chloride resin, a diameter of 1~2mm.
Through high-purity water washing, drying, weigh and obtain 877g products, yield 86%.
Test result shows that the product melt index is 8.5g/10min, and the zero strength time is 311s.
Embodiment 3
High purity water 600g accurately is weighed in the beaker of clean dried, is controlled 12 DEG C ± 1 DEG C of water temperature, is weighed 4.4g di(2-ethylhexyl)phosphates
Hydrogen potassium, 8g sodium hydrogensulfites and 4.8g ammonium persulfates are added in the beaker containing high purity water, are thoroughly mixed, while accurately
Weigh and add 6.7g di-n-butyl dithiocarbamate sodiums, mixed solution is transferred to the reactor of cleaning by negative pressure
In, reactor is carried out using high-purity argon gas to vacuumize displacement deoxygenation.Magnetic stirring apparatus is opened to 300r/min, by reactor with
CTFE gas cylinder is connected, and the addition 850g CTFE monomers into reactor.Reactor is warming up to 50 DEG C, control
Reaction temperature is 50 DEG C ± 1 DEG C, and stirring reaction stops reaction after 7 hours, and powdered daiflon is taken out in release.
Through high-purity water washing, drying, weigh and obtain 773g products, yield 91%.
Test result shows that the product melt index is 9g/10min, and the zero strength time is 302s.
Embodiment 4
High purity water 498g is weighed in the beaker of clean dried, 12 DEG C ± 1 DEG C of water temperature is controlled, weighs 6.3g biphosphates
Potassium, 4.5g potassium bisulfites and 7.2g potassium peroxydisulfates are added in the beaker containing high purity water, are thoroughly mixed, while accurately
Weigh and add 7g ammonium dithiocarbamates, in the reactor that mixed solution is transferred to cleaning by negative pressure, using high-purity
Argon gas carries out vacuumizing displacement deoxygenation to reactor.Magnetic stirring apparatus is opened to 500r/min, by reactor and CTFE
Gas cylinder is connected, and the addition 926g CTFE monomers into reactor.Reactor is warming up to 68 DEG C, controlling reaction temperature is
68 DEG C ± 1 DEG C, stirring reaction stops reacting, release after 9 hours, taking-up bead daiflon, a diameter of 1~
2mm。
Through high-purity water washing, drying, weigh and obtain 825g products, yield 89%.
Test result shows that the product melt index is 7.1g/10min, and the zero strength time is 330s.
Claims (7)
1. a kind of preparation method of daiflon, it is characterised in that：PH buffer and molecular weight are added in a solvent
Conditioning agent, triggers CTFE monomer to carry out polymerisation in the presence of redox initiator；
The solvent is high purity water；
Redox initiator is the mixture of persulfate and bisulfites；
The mass ratio of solvent, pH buffer, molecular weight regulator and redox initiator and CTFE monomer be 20~
1000:0.01~20:0.01~20:0.1~10:100；
Comprise the following steps：
(1) it is 10 DEG C~15 DEG C to control high-purity coolant-temperature gage, and high purity water, pH adjusting agent and initiator are deployed into initial soln；
(2) under negative pressure, initial soln and molecular weight regulator are mixed and are transferred in reactor；Disposably it is passed through under agitation
CTFE gas；
(3) adjust and control reactor temperature to required temperature and keep constant, finally give powder or the poly- trifluoro of bead
Vinyl chloride resin；
Reaction temperature is 10 DEG C~70 DEG C.
2. the preparation method of daiflon according to claim 1, it is characterised in that：High-purity water conductivity is not
More than 0.1 μ Scm-1。
3. the preparation method of daiflon according to claim 1, it is characterised in that：PH buffer is phosphoric acid
Dihydric salt.
4. the preparation method of daiflon according to claim 1, it is characterised in that：Molecular weight regulator is
Dithiocar-bamate.
5. the preparation method of daiflon according to claim 1, it is characterised in that：Persulfate and sulfurous
The mixing quality ratio of sour hydrogen salt is 1:5~5:1.
6. the preparation method of daiflon according to claim 1, it is characterised in that：Reaction time be 3~
9h。
7. the preparation method of daiflon according to claim 1, it is characterised in that：Speed of agitator during reaction
For 300~800r/min.
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| CN105542046B true CN105542046B (en) | 2017-11-07 |
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| CN112979857B (en) * | 2019-12-16 | 2022-09-02 | 浙江省化工研究院有限公司 | Modified polychlorotrifluoroethylene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2569524A (en) * | 1949-06-16 | 1951-10-02 | Du Pont | Polymerization of trifluorochloroethylene in the presence of silver ion, bisulfite ion and persulfate |
| JPH05170811A (en) * | 1991-12-25 | 1993-07-09 | Daikin Ind Ltd | Improvement of heat resistance of chlorotrifluoroethylene polymer |
| CN102603944A (en) * | 2012-03-14 | 2012-07-25 | 常熟市新华化工有限公司 | Method for preparing polychlorotrifluoroethylene resin |
| CN103304712A (en) * | 2013-05-07 | 2013-09-18 | 山东森福新材料有限公司 | Manufacturing method of beaded polytrifluorochloroethylene resins |
| CN103755850B (en) * | 2013-12-30 | 2016-04-27 | 山东华夏神舟新材料有限公司 | A kind of preparation method of the polyvinylidene fluoride resin for sun power backboard membrane |
| CN103755858B (en) * | 2013-12-30 | 2016-04-27 | 山东华夏神舟新材料有限公司 | A kind of solution polymerization process of polyvinylidene fluoride copolymer |
| CN104448079B (en) * | 2014-11-14 | 2017-06-16 | 东莞市长安东阳光铝业研发有限公司 | A kind of method for preparing polytrifluorochloroethylene |
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