CN102020737B - Preparation method of high-temperature resistant and high-transparent polychlorotrifluoroethylene - Google Patents
Preparation method of high-temperature resistant and high-transparent polychlorotrifluoroethylene Download PDFInfo
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- CN102020737B CN102020737B CN2010105427274A CN201010542727A CN102020737B CN 102020737 B CN102020737 B CN 102020737B CN 2010105427274 A CN2010105427274 A CN 2010105427274A CN 201010542727 A CN201010542727 A CN 201010542727A CN 102020737 B CN102020737 B CN 102020737B
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Abstract
The invention relates to a preparation method of high-temperature resistant and high-transparent polychlorotrifluoroethylene, which comprises the steps of firstly preparing polychlorotrifluoroethylene resin in deionized water from chlorotrifluoroethylene under the action of an azo type initiator, and then using cobalt fluoride to terminate the polychlorotrifluoroethylene. The polychlorotrifluoroethylene prepared by the method has excellent mechanical properties and can be resistant to the temperature of 400 DEG C, and the color can not be changed within 10 hours at the temperature of 300 DEG C.
Description
Technical field
The present invention relates to the preparation method of voltalef, be specifically related to the preparation method of a kind of high temperature resistant and high transparent voltalef (PCTFE).
Background technology
Voltalef has good unreactiveness, resistance to chemical attack and thermotolerance, high physical strength and toughness, superior dielectric properties and optical property.Embrittlement does not take place in voltalef in liquid oxygen, liquid nitrogen and natural gas liquids, not creep, effectively use temperature wide (240 ℃-205 ℃).
But because present voltalef nearly all adopts the initiator of non-fluorine, the end that causes voltalef is non-fluorine end group, and this end group can cause chain can cause chain degradation in the course of processing, has a strong impact on the color and the performance of product.
U.S. Pat 2751376; US2863916, US2902477, the US3045000 patent adopts strong oxidizers such as chlorine or ozone that the end group of voltalef is handled; Can improve the resistance toheat of voltalef; But because the intervention of strong oxidizer makes the low-molecular-weight polymkeric substance of part in the voltalef that decomposition take place, thereby cause its colour changed into yellow of whole voltalef or become coffee-like, thereby influence the system film of voltalef.
U.S. Pat 6706803 adopts Potassium Persulphate as the synthetic voltalef of initiator; Chinese patent CN101113186 adopts persulphate or superoxide as the synthetic voltalef of initiator, and Chinese patent CN101643523 adopts peroxy dicarbonate as the synthetic voltalef of initiator.Xanthochromia has all taken place according to color after these document synthetic voltalef process high temperature process and the screw rod pelletizing.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of high temperature resistant and high transparent voltalef, and the voltalef of present method preparation has excellent mechanical property, and high temperature resistant.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of high temperature resistant and high transparent voltalef is characterized in that comprising the steps:
Trifluorochloroethylene prepares daiflon in deionized water under the azo-initiator effect, with cobaltous fluoride voltalef is carried out termination process then.
Said initiator is azo two different caprylic nitriles, azo two different pelargonitriles, azo two isodecyl nitriles, azo two different caprylic nitrile hydrochlorides, azo two different pelargonitrile hydrochlorides or azo two different certain herbaceous plants with big flowers nitrile hydrochlorides, and the consumption of said initiator accounts for 0.02～0.1% of trifluorochloroethylene weight percent.
Described de-ionized electrical conductivity of water is 0.02～0.1 μ.
The weight ratio of said trifluorochloroethylene and deionized water is 1: 5～10.
The weight ratio of said cobaltous fluoride and voltalef is 1: 50～100.
Said daiflon is 30～100 ℃ of temperature, and polymerization pressure is under 0.5～1.2Mpa environment, reacts preparation in 10～16 hours.
Said polymerization temperature is preferably 50～70 ℃, and said polymerization pressure is preferably 0.6～1.0Mpa, and the said reaction times is preferably 12～15 hours.
The temperature of reaction of said termination process is 160～170 ℃, and reaction pressure is 0.6～1.5Mpa, and the residence time is 1～3 hour.
The voltalef of the present invention preparation has excellent mechanical property, and heatproof reaches 400 ℃, 300 ℃ of nondiscolorations in following 10 hours.
Embodiment:
Through following examples the present invention is further specified.Embodiment adopts the standard of ASTM D-1430 to detect.
Embodiment 1
In the autoclave of 50L 304SS Stainless Steel Band chuck and stirring, drop into specific conductivity and be 40 kilograms of 0.02 deionized waters; In polymeric kettle, add 8 kilograms of trifluorochloroethylene monomers then; Start whipping appts; Logical people's short steam in chuck, the temperature in the controlled polymerization still is 58 ℃, the pressure of polymeric kettle is 0.69Mpa.When the polymerization system temperature reaches 58 ℃, pump into 4 gram azos, two different caprylic nitriles with volume pump, keep 58 ℃ of system temperatures then; System pressure 0.69Mpa, 12 hours, the emptying system pressure; The bottom from polymeric kettle of voltalef powder and water is emitted; Adopt plate filter with voltalef powder and water sepn, the voltalef powder in oven for drying, is obtained 6 kilograms voltalef dried powder.
With 6 kilograms of voltalef powder add 15L have stir and add cover alloy material fluoridize still; Add 120 gram cobaltous fluorides then; Start the stirring of fluoridizing still, in chuck, feed the steam of 0.9Mpa pressure, the system temperature that still is fluoridized in control is 160 ℃; Fluoridize the pressure 0.8Mpa of still, kept this temperature and pressure 2 hours.
To fluoridize voltalef powder behind the end-blocking with the washing body, drying obtains 5.8 kilograms voltalef powder, the voltalef powder is processed corresponding sample strip according to ASTM D-1430 detect, and detected result is seen table 1.
Embodiment 2
In the autoclave of 50L 304SS Stainless Steel Band chuck and stirring, drop into specific conductivity and be 35 kilograms of the deionized waters of 0.06 μ; In polymeric kettle, add 5 kilograms of trifluorochloroethylene monomers then; Start whipping appts; Logical people's short steam in chuck, the temperature in the controlled polymerization still is 70 ℃, the pressure of polymeric kettle is 0.9Mpa.When the polymerization system temperature reaches 70 ℃, pump into 5 gram azos, two different pelargonitriles with volume pump, keep 70 ℃ of system temperatures then; System pressure 0.9Mpa, 13 hours, the emptying system pressure; The bottom from polymeric kettle of voltalef powder and water is emitted; Adopt plate filter with voltalef powder and water sepn, the voltalef powder in oven for drying, is obtained 4 kilograms voltalef dried powder.
With 4 kilograms of voltalef powder add 15L have stir and add cover alloy material fluoridize still; Add 67 gram cobaltous fluorides then; Start the stirring of fluoridizing still, in chuck, feed the steam of 0.9Mpa pressure, the system temperature that still is fluoridized in control is 170 ℃; Fluoridize the pressure 1.0Mpa of still, kept this temperature and pressure 1 hour.
To fluoridize voltalef powder behind the end-blocking with the washing body, drying obtains 3.7 kilograms voltalef powder, the voltalef powder is processed corresponding sample strip according to ASTM D-1430 detect, and detected result is seen table 1.
Embodiment 3
In the autoclave of 50L 304SS Stainless Steel Band chuck and stirring, drop into specific conductivity and be 40 kilograms of the deionized waters of 0.08 μ; In polymeric kettle, add 5 kilograms of trifluorochloroethylene monomers then; Start whipping appts; Logical people's short steam in chuck, the temperature in the controlled polymerization still is 58 ℃, the pressure of polymeric kettle is 0.69Mpa.When the polymerization system temperature reaches 58 ℃, pump into 4 gram azos, two isodecyl nitriles with volume pump, keep 58 ℃ of system temperatures then; System pressure 0.69Mpa, 15 hours, the emptying system pressure; The bottom from polymeric kettle of voltalef powder and water is emitted; Adopt plate filter with voltalef powder and water sepn, the voltalef powder in oven for drying, is obtained 3.5 kilograms voltalef dried powder.
With 3.5 kilograms of voltalef powder add 15L have stir and add cover alloy material fluoridize still; Add 35 gram cobaltous fluorides then; Start the stirring of fluoridizing still, in chuck, feed the steam of 0.9Mpa pressure, the system temperature that still is fluoridized in control is 160 ℃; Fluoridize the pressure 0.8Mpa of still, kept this temperature and pressure 2 hours.
To fluoridize voltalef powder behind the end-blocking with the washing body, drying obtains 3.4 kilograms voltalef powder, the voltalef powder is processed corresponding sample strip according to ASTM D-1430 detect, and detected result is seen table 1.
Embodiment 4
In the autoclave of 50L 304SS Stainless Steel Band chuck and stirring, drop into specific conductivity and be 45 kilograms of the deionized waters of 0.1 μ; In polymeric kettle, add 4.5 kilograms of trifluorochloroethylene monomers then; Start whipping appts; Logical people's short steam in chuck, the temperature in the controlled polymerization still is 70 ℃, the pressure of polymeric kettle is 0.9Mpa.When the polymerization system temperature reaches 70 ℃, pump into 4.5 gram azos, two different caprylic nitrile hydrochlorides with volume pump, keep 70 ℃ of system temperatures then; System pressure 0.9Mpa 15 hours; The emptying system pressure is emitted the bottom from polymeric kettle of voltalef powder and water, adopts plate filter with voltalef powder and water sepn; The voltalef powder in oven for drying, is obtained 4.3 kilograms voltalef dried powder.
With 4.3 kilograms of voltalef powder add 15L have stir and add cover alloy material fluoridize still; Add 86 gram cobaltous fluorides then; Start the stirring of fluoridizing still, in chuck, feed the steam of 0.9Mpa pressure, the system temperature that still is fluoridized in control is 170 ℃; Fluoridize the pressure 0.9Mpa of still, kept this temperature and pressure 2 hours.
To fluoridize voltalef powder behind the end-blocking with the washing body, drying obtains 4.1 kilograms voltalef powder, the voltalef powder is processed corresponding sample strip according to ASTM D-1430 detect, and detected result is seen table 1.
Embodiment 5
In the autoclave of 50L 304SS Stainless Steel Band chuck and stirring, drop into specific conductivity and be 45 kilograms of the deionized waters of 0.1 μ; In polymeric kettle, add 5 kilograms of trifluorochloroethylene monomers then; Start whipping appts; Logical people's short steam in chuck, the temperature in the controlled polymerization still is 58 ℃, the pressure of polymeric kettle is 0.69Mpa.When the polymerization system temperature reaches 58 ℃, pump into 5 gram azos, two different pelargonitrile hydrochlorides with volume pump, keep 58 ℃ of system temperatures then; System pressure 0.69Mpa, 12 hours, the emptying system pressure; The bottom from polymeric kettle of voltalef powder and water is emitted; Adopt plate filter with voltalef powder and water sepn, the voltalef powder in oven for drying, is obtained 4.5 kilograms voltalef dried powder.
With 4.5 kilograms of voltalef powder add 15L have stir and add cover alloy material fluoridize still; Add 90 gram cobaltous fluorides then; Start the stirring of fluoridizing still, in chuck, feed the steam of 0.9Mpa pressure, the system temperature that still is fluoridized in control is 170 ℃; Fluoridize the pressure 0.9Mpa of still, kept this temperature and pressure 2 hours.
To fluoridize voltalef powder behind the end-blocking with the washing body, drying obtains 4.4 kilograms voltalef powder, the voltalef powder is processed corresponding sample strip according to ASTM D-1430 detect, and detected result is seen table 1.
Embodiment 6
In the autoclave of 50L 304SS Stainless Steel Band chuck and stirring, drop into specific conductivity and be 42 kilograms of the deionized waters of 0.06 μ; In polymeric kettle, add 7 kilograms of trifluorochloroethylene monomers then; Start whipping appts; Logical people's short steam in chuck, the temperature in the controlled polymerization still is 58 ℃, the pressure of polymeric kettle is 0.69Mpa.When the polymerization system temperature reaches 58 ℃, pump into 7 gram azos, two isodecyl nitrile hydrochlorides with volume pump, keep 58 ℃ of system temperatures then; System pressure 0.69Mpa, 13 hours, the emptying system pressure; The bottom from polymeric kettle of voltalef powder and water is emitted; Adopt plate filter with voltalef powder and water sepn, the voltalef powder in oven for drying, is obtained 6.3 kilograms voltalef dried powder.
With 6.3 kilograms of voltalef powder add 15L have stir and add cover alloy material fluoridize still; Add 63 gram cobaltous fluorides then; Start the stirring of fluoridizing still, in chuck, feed the steam of 0.9Mpa pressure, the system temperature that still is fluoridized in control is 160 ℃; Fluoridize the pressure 0.8Mpa of still, kept this temperature and pressure 2 hours.
To fluoridize voltalef powder behind the end-blocking with the washing body, drying obtains 6.1 kilograms voltalef powder, the voltalef powder is processed corresponding sample strip according to ASTM D-1430 detect, and detected result is seen table 1.
The performance of the voltalef that table 1 instance is prepared
The foregoing description does not limit the present invention in any way, and every employing is equal to the technical scheme that replacement or the mode of equivalent transformation obtain and all drops in protection scope of the present invention.
Claims (8)
1. the preparation method of a high temperature resistant and high transparent voltalef is characterized in that comprising the steps:
Trifluorochloroethylene prepares daiflon in deionized water under the azo-initiator effect, with cobaltous fluoride voltalef is carried out termination process then; Said azo-initiator is azo two different caprylic nitriles, azo two different pelargonitriles, azo two isodecyl nitriles, azo two different caprylic nitrile hydrochlorides, azo two different pelargonitrile hydrochlorides or azo two isodecyl nitrile hydrochlorides.
2. the preparation method of a kind of high temperature resistant and high transparent voltalef according to claim 1, it is characterized in that: the consumption of said initiator accounts for 0.02～0.1% of trifluorochloroethylene weight percent.
3. the preparation method of a kind of high temperature resistant and high transparent voltalef according to claim 1, it is characterized in that: described de-ionized electrical conductivity of water is 0.02～0.1 μ.
4. the preparation method of a kind of high temperature resistant and high transparent voltalef according to claim 3, it is characterized in that: the weight ratio of said trifluorochloroethylene and deionized water is 1: 5～10.
5. the preparation method of voltalef according to claim 1, it is characterized in that: the weight ratio of said cobaltous fluoride and voltalef is 1: 50～100.
6. the preparation method of voltalef according to claim 1, it is characterized in that: said daiflon is 30～100 ℃ of temperature, and polymerization pressure is under 0.5～1.2MPa environment, reacts preparation in 10～16 hours.
7. the preparation method of voltalef according to claim 6, it is characterized in that: said polymerization temperature is 50～70 ℃, and said polymerization pressure is 0.6～1.0MPa, and the said reaction times is 12～15 hours.
8. the preparation method of a kind of high temperature resistant and high transparent voltalef according to claim 1, it is characterized in that: the temperature of reaction of said termination process is 160～170 ℃, and reaction pressure is 0.6～1.5MPa, and the residence time is 1～3 hour.
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| DE3368269D1 (en) * | 1982-05-03 | 1987-01-22 | Occidental Chem Co | CHLOROTRIFLUOROETHYLENE TELOMERIZATION PROCESS |
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