Summary of the invention
At the deficiencies in the prior art, the present invention starts with from solvent and initiator type, increases stability of fluorinated ethylenepropylene copolymer resin end group.
The purpose of this invention is to provide a kind of polymerization technique that increases stability of fluorinated ethylenepropylene copolymer resin end group.
Technical scheme of the present invention is as follows:
The invention provides a kind of method that increases stability of fluorinated ethylenepropylene copolymer resin end group, it is characterized in that, in organic solvent, adding fluorine-containing diacyl peroxide initiator increases stability of fluorinated ethylenepropylene copolymer resin end group.
Above-mentioned initiator is selected from perfluor methoxy propyl acyl peroxide; perfluor cyclohexyl acyl peroxide, perfluor [2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide, perfluoro propionyl superoxide; perfluor oxa-alkyloyl superoxide, or β hydroxyethyl tert-butyl peroxide etc.Perfluor [2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide most preferably.
The polymerization process of increase stability of fluorinated ethylenepropylene copolymer resin end group of the present invention, step is as follows:
1) storage tank and reactor nitrogen replacement;
2) groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 2～1: 6, and weight ratio is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 5: 1～9: 1, and weight ratio is called the feed supplement monomer mixture.
3) organic solvent and auxiliary agent are joined in the reactor; The organic solvent add-on is 2L, and auxiliary agent is 0.05～0.2% of a total monomer weight, weight ratio.
4) in the reactor of step 3), feed step 2) initial monomeric mixture 2-5kg in the initial groove, be warming up to 10-100 ℃; Stir stirring velocity 60-1000r/min; Be incorporated as the fluorine-containing diacyl peroxide initiator of the 0.2-0.8% of total monomer mixture quality, begin reaction; Reaction pressure 0.7-4.0MPa, the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of adding groove to reactor, and the reaction times is 2-9h.Adding the total dosage of groove feed supplement monomer mixture is 0.1-1.2kg.
5) reaction finishes discharging, cool off reclaim behind the unreacted monomer analyze and do after the usefulness of copolyreaction, the multipolymer that makes heat 10-12h to remove initiator and the solvent of remnants in thermostat container.
The described organic solvent of step 3) is selected from 1,2,2-three fluoro-1,1,2-trichloroethane (F113), tetrafluoroethylene (liquid state), R 1216 (liquid state), the mixture of tetrafluoroethylene and hexafluoropropylene mixture (liquid state) or 1.2.2-three fluoro-1.1.2-trichloroethane (F113) and pure water.Wherein, tetrafluoroethylene and hexafluoropropylene mixture preferred weight ratio are TFE: HFP=1: 2-1: 6.
Above-mentioned organic solvent is recyclable to be utilized again.
The described auxiliary agent of step 3) is methyl alcohol, ethanol, mercaptan, tetracol phenixin, chloroform, ethylene glycol or Virahol.Particular methanol wherein.
The described reaction conditions of step 4) is preferably as follows: stirring velocity 100-800r/min, temperature of reaction 40-80 ℃, reaction pressure 0.8-3.0Mpa, reaction times 3-8h.
The described fluorine-containing diacyl peroxide initiator of step 4) is selected from perfluor methoxy propyl acyl peroxide; perfluor cyclohexyl acyl peroxide; perfluor [2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide; the perfluoro propionyl superoxide; perfluor oxa-alkyloyl superoxide, or β hydroxyethyl tert-butyl peroxide etc.Perfluor [2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide most preferably.
Step 2) described charge weight ratio is preferably: initial monomeric mixture tetrafluoroethylene: R 1216=1: 3～1: 5; Feed supplement monomer mixture tetrafluoroethylene: R 1216=6: 1～8: 1.
The excellent results of the inventive method is as follows:
1, to adopt monomer be solvent in the present invention, and the recyclable utilization of monomer has reduced cost.
2, this initiator synthetic polymer terminal group is stable, good mechanical property, and anti-cracking, melting index is adjustable, thereby can be used on the high-end precision instrument and equipment.
3, this method has reduced treatment and finishing section, by original cohesion, sintering, oven dry, fragmentation, granulation, change into and remove solvent, screw rod granulation, simplified flow process greatly, the minimizing that equipment uses, reduce the consumption of the input of equipment purchasing fund and manpower, the energy, greatly reduced production cost, improved production efficiency, and owing to lacking of contacting with the external world, manually-operated operation is also few, has guaranteed the cleanliness factor of material, has improved the quality of material.
4, this method polymerization pressure is low, and temperature is low, has reduced energy consumption.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.Described monomer is polymerization-grade.
Embodiment 1:
Before carrying out copolyreaction, use the nitrogen gauge pressure that equals 1.5 times of reaction pressures but be not more than the reactor authorized pressure, the stopping property of check reactor.The 1h internal pressure should not reduce under agitation condition, putting nitrogen to atmosphere to 0.02-0.07MPa and be evacuated to surplus pressure afterwards is 3-9mmHg, and under vacuum condition, stop to stir and stop to vacuumize and keep 10-15min, the variation of the vacuum tightness that do not have during this period.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds each one of groove, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 2 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 8: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 2kg, feed supplement monomer mixture dosage is 0.4kg.
After check reactor stopping property, under vacuum in the 3L reactor adding 2L1.2.2-three fluoro-1.1.2-trichloroethane (F113) solvents and be the methyl alcohol auxiliary agent of monomer total mass 0.1%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 3.0MPa, closes initial groove feed valve.Open to stir, stirring velocity 400r/min adds 0.6% the initiator perfluor methoxy propyl acyl peroxide that accounts for total monomer weight after reactor is heated to 50 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 8h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to-50 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 2:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 3 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 9: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 3kg, feed supplement monomer mixture dosage is 0.6kg.
After check reactor stopping property, under vacuum, add 2L liquid state TFE and HFP mixture in the 3L reactor as solvent be the methyl alcohol auxiliary agent of monomer total mass 0.05%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 0.7MPa, closes initial groove feed valve.Open to stir, stirring velocity 60r/min adds 0.2% the initiator perfluor methoxy propyl acyl peroxide that accounts for total monomer weight after reactor is heated to 10 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 6h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to-50 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 3:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 4 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 6: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 2kg, feed supplement monomer mixture dosage is 0.2kg.
After check reactor stopping property, under vacuum in the 3L reactor mixture of adding 2L1.2.2-three fluoro-1.1.2-trichloroethane and pure water as solvent be the methyl alcohol auxiliary agent of monomer total mass 0.2%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 1.1MPa, closes initial groove feed valve.Open to stir, stirring velocity 1000r/min adds 0.3% the initiator perfluoro propionyl superoxide that accounts for total monomer weight after reactor is heated to 100 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 2h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to 30 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 4:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 5 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 5: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 4kg, feed supplement monomer mixture dosage is 1kg.
After check reactor stopping property, under vacuum in the 3L reactor adding 2L1.2.2-three fluoro-1.1.2-trichloroethane (F113) solvents and be the isopropylcarbinol auxiliary agent of monomer total mass 0.15%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 2.0MPa, closes initial groove feed valve.Open to stir, stirring velocity 800r/min adds 0.4% the initiator perfluor cyclohexyl acyl peroxide that accounts for total monomer weight after reactor is heated to 60 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 4h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to 15 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 5:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 6 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 7: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 5kg, feed supplement monomer mixture dosage is 1.2kg.
After check reactor stopping property, under vacuum, add 2L liquid state TFE and HFP mixture in the 3L reactor as solvent be the ethylene glycol auxiliary agent of monomer total mass 0.1%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 3.0MPa, closes initial groove feed valve.Open to stir, stirring velocity 100r/min adds 0.8% the initiator perfluor oxa alkyl acyl peroxide that accounts for total monomer weight after reactor is heated to 80 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 6h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to 25 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 6:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 6 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 8: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 3.5kg, feed supplement monomer mixture dosage is 0.8kg.
After check reactor stopping property, under vacuum in the 3L reactor mixture of adding 2L1.2.2-three fluoro-1.1.2-trichloroethane and pure water as solvent be the chloroform auxiliary agent of monomer total mass 0.1%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 2.0MPa, closes initial groove feed valve.Open to stir, stirring velocity 200r/min adds 0.7% the initiator perfluor cyclohexyl acyl peroxide that accounts for total monomer weight after reactor is heated to 40 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 8h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to 20 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 7:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 5 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 9: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 4.5kg, feed supplement monomer mixture dosage is 0.9kg.
After check reactor stopping property, under vacuum in the 3L reactor adding 2L1.2.2-three fluoro-1.1.2-trichloroethane (F113) solvents and be the tetracol phenixin auxiliary agent of monomer total mass 0.1%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 3.0MPa, closes initial groove feed valve.Open to stir, stirring velocity 400r/min adds 0.6% initiator perfluor [the 2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide that accounts for total monomer weight after reactor is heated to 20 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 7h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to 10 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 8:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 3 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 6: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 3kg, feed supplement monomer mixture dosage is 0.8kg.
After check reactor stopping property, under vacuum, add 2L liquid state TFE and HFP mixture in the 3L reactor as solvent be the mercaptan auxiliary agent of monomer total mass 0.1%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 2.0MPa, closes initial groove feed valve.Open to stir, stirring velocity 600r/min adds 0.5% initiator perfluor [the 2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide that accounts for total monomer weight after reactor is heated to 70 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction adds the feed supplement monomer mixture of groove to reactor.Reaction times 5h.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to 20 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Embodiment 9:
The reactor stopping property detects with example 1.
The batching of groove is mixed: the groove that is mixed is divided into initial groove and adds two of grooves, and tetrafluoroethylene in the initial groove: the R 1216 ratio is 1: 4 (weight ratio), is called initial monomeric mixture; Add tetrafluoroethylene in the groove: the R 1216 ratio is 7: 1 (weight ratio), is called the feed supplement monomer mixture.Dosage: initial monomeric mixture 4kg, feed supplement monomer mixture are 1kg.
After check reactor stopping property, under vacuum in the 3L reactor mixture of adding 2L1.2.2-three fluoro-1.1.2-trichloroethane and pure water as solvent be the methyl alcohol auxiliary agent of monomer total mass 0.1%.Adding initial monomeric mixture to pressure then is 0.01-0.07MPa, and sampling analysis oxygen level, when oxygen level is not more than 0.002% (volume ratio), reactor cooling is to certain temperature, and stopping under the stirring condition, adding initial monomeric mixture to pressure once more is 3.0MPa, closes initial groove feed valve.Open to stir, stirring velocity 800r/min adds 0.4% initiator perfluor [the 2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide that accounts for total monomer weight after reactor is heated to 60 ℃.Begin reaction, copolyreaction begins to be accompanied by the decline of pressure, and the every decline 0.1MPa of pressure in copolyreaction replenishes the feed supplement monomer mixture of adding groove in right amount, reaction times 6h to reactor.
After certain feed supplement monomer mixture runs out of, the heating of stopped reaction device stops to add the feed supplement monomer mixture, stops to stir, reaction mass is cooled to 20 ℃, cool off behind the unreacted monomer it collect analyze in the withdrawing can and do after the usefulness of copolyreaction.After the reactor displacement, open reactor cap, draw off the multipolymer that makes, and in the thermostat container of certain temperature, heat 10-12h to remove remaining initiator and solvent.
Polymerization velocity was moderate when comparative example 1, embodiment 2 and embodiment 3 found to use monomer as medium, and polymkeric substance has the preferable performance index.Next is that F113 also is the material that damages the ozone layer.Comparative example 4, embodiment 5 and embodiment 6 and comparative example 7, embodiment 8 and embodiment 9 obtain similar result.
When comparative example 2, embodiment 5 and embodiment 8 find to use monomer as medium; adopt perfluor cyclohexyl acyl peroxide and perfluor [2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] when superoxide is initiator; polymerization velocity is moderate, and polymer terminal group stabilizing mechanical performance is good.Next is that the peroxide breakdown temperature is low, and raw material makes easily for perfluor [2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl].Therefore perfluor [2.5.8 trimethylammonium 3.6.9 three oxygen base lauroyl] superoxide is preferred initiator.
Embodiment 10:
Concrete operations are with embodiment 9, and the different tetrafluoroethylene that are to use are solvent.
Embodiment 11:
Concrete operations are with embodiment 9, and the different R 1216s that are to use are solvent.
Embodiment 12:
Concrete operations are with embodiment 9, and the different ethanol that are to use are auxiliary agent.