CN102351974A - Fluorocarbon resin and its preparation method - Google Patents
Fluorocarbon resin and its preparation method Download PDFInfo
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- CN102351974A CN102351974A CN201110200623XA CN201110200623A CN102351974A CN 102351974 A CN102351974 A CN 102351974A CN 201110200623X A CN201110200623X A CN 201110200623XA CN 201110200623 A CN201110200623 A CN 201110200623A CN 102351974 A CN102351974 A CN 102351974A
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Abstract
The invention relates to a fluorocarbon resin and its preparation method. The fluorocarbon resin is prepared by the following method: 1) fully mixing vinyl acetate, hexone and xylene in a reaction vessel; 2) adding azodiisobutyronitrile, undecylenic acid and ethylene glycol monoallyl ether into the reaction vessel; 3) driving a proper amount of tetrafluoroethene gas phase monomer into the reaction vessel after enclosed vacuum-pumping of the reaction vessel; 4) driving residual tetrafluoroethene gas phase monomer into the reaction vessel by the use of a pump, maintaining proper reaction pressure, heating the reaction vessel, and controlling the temperature inside the reaction vessel; 5) reducing reaction pressure inside the vessel, stopping reaction, recovering the tetrafluoroethene gas phase monomer, and discharging. The method provided by the invention can be used to easily obtain the room temperature curing fluororesin with high fluorine-containing amount, and is suitable for large scale production at low cost.
Description
Technical field
The present invention relates to a kind of fluorocarbon resin and preparation method thereof, belong to the synthetic field of resin.
Background technology
From the synthetic teflon resin of The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, in 1938 so far, fluorocarbon resin has the history of six more than ten years, and oneself is diversified for the development of resin kind.And the exploitation of fluorocarbon coating starts from the pvdf coating that gathers fluorine vinylchlorid coating and Japan of E.I.Du Pont Company, and the history of three more than ten years is also arranged so far.Because its excellent properties, fluorocarbon coating more and more receives domestic and international coating personage's concern.Fluorocarbon coating grows out of nothing, and to many, oneself becomes huge fresh combatants the research and development of fluorine coating, production, application from few.
Because fluorocarbon resin such as percent crystallinity such as tetrafluoroethylene, pvdf and voltalef are very high; So solubleness is very low in organic solvent; Therefore usually add some monomers that contain functional group and carry out polymerization and increase its solubleness, adjust its performance such as hardness, pigment-dispersing, intermiscibility, resistance to marring simultaneously and, can introduce usually like-OH with the base material tack;-COOH;-O-,-COOR etc. carry out modification, and used solidifying agent has trimeric cyanamide, isocyanic ester and amine resin etc.
Utilize the molecule copolymerization technique, Japan AGC company has developed fluoroolefin-vinyl ether co-polymer (FEVE) resin nineteen eighty-two, has released the thermosetting fluoro carbon resin of the Lumiflon trade mark.This resin is applied in the fluorocarbon coating, can normal temperature and intermediate temperature setting, and glossiness is high.Be mainly used in building, bridge, TV tower etc. and be difficult to the ornamental protection of large scale structure etc. of often maintenance, have that construction is simple, protection effect is good and characteristics such as protection life-span length.The range of application of fluorine coating has greatly been expanded in the appearance of FEVE fluorine coating, and fluorine coating is applied in daily life.Year history surplus the employing FEVE fluorine paint sprayings existing 20 such as All Nippon Airways' aircraft of Japan, alum bridge spanning the sea, Nissan bridge car.After nineteen eighty-two, Elf Alt Chem company studies successful vinylidene fluoride one tetrafluoroethylene, one hexafluoropropylene copolymer (VDF-TFE-HEP) and contains the functional polymer of vinylidene fluoride, and it can ambient cure, but poor solvent resistance.Thereafter, successful terminal hydroxy group PFPE resin is studied by Ausimont SPA company, can prepare the self-cleaning paint of ambient cure.The nineties in 20th century, the Robert FB of Washington state naval research department studies successful tetrafluoroethylene one fluorine-containing polyvalent alcohol coating, also can ambient cure.
The output and the offshore company of domestic fluorine coating are close, but home products quality and offshore company have a long way to go.The subject matter that domestic solvent-borne type FEVE fluorocarbon resin exists is exactly unstable product quality; This is the main reason that many national key construction projects and government's landmark are suspected when calling for tenders of project is selected homemade fluorine resin coating, and domestic a lot of fluorine resin coating manufacturing enterprise lacks the virtual mass control to product.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high normal temperature solidifying fluorine carbon resin of fluorine content that can be easier to obtain.
The technical scheme that the present invention solves the problems of the technologies described above is following: a kind of fluorocarbon resin, adopt each composition of raw materials of following weight percent synthetic: YLENE 22.0～23.0%, vinyl acetate 20.0～21.0%, ethylene glycol monoallyl ether 6.0～7.0%, Diisopropyl azodicarboxylate 0.75～0.8%, undecylenic acid 0.94～0.98%, hexone 9.5～9.8%, tetrafluoroethylene gas phase monomer 38.5～39.0%.
The invention has the beneficial effects as follows: in said fluorocarbon resin, added tetrafluoroethylene gas phase monomer (PTFE monomer) raw material; The PTFE monomer has characteristics such as fluorine content height, the as easy as rolling off a log polymerization of little, the two key of molecular radius; Compare with other Fluorine containing olefine class monomers; It can be easier to obtain the high ambient cure fluoro-resin of fluorine content, and industrial scale is big, and is with low cost; And adopt synthetic fluorocarbon resin (FEVE) polymerization time of PTFE monomer short; Effect is better; And the TFE monomer adopts the monomer technology of dynamically adding; The ratio of strict control PTFE monomer in whole polymerization process is in constant all the time, reduces the generation of homopolymerization as far as possible, makes that the PTFE chain link is evenly distributed in the product; Adopt the alkane alkenyl esters as comonomer, through adjusting process prescription and polymerizing condition, realized the accurate control to the molecular chain-end structure basically, gained copolymer molecule alternating structure is more regular.Film performance is good, and the FEVE excellent storage stability can ambient cure.
Further, it is synthetic that said fluorocarbon resin preferably adopts each composition of raw materials of following weight percent: YLENE 22.8%, vinyl acetate 21.0%, ethylene glycol monoallyl ether 6.06%, Diisopropyl azodicarboxylate 0.79%, undecylenic acid 0.95%, hexone 9.8%, tetrafluoroethylene gas phase monomer 38.6%.
The another technical scheme that the present invention solves the problems of the technologies described above is following: also there was a preliminary preparation in a kind of preparation method of fluorocarbon resin before the preparation fluorocarbon resin.
Preliminary preparation is following:
A. polymeric kettle is carried out bulge test, pressure 0.9Mpa, behind the pressurize 4h, release is subsequent use;
B. inspection
1. stir machine oil window oil level;
2. vacuum pump oil window oil level;
3. surge tank oil window oil level and N
2Bottle and polymeric kettle correctly connect;
4. N
2Bottle pressure is answered＞3Mpa;
5. cistern water level;
6. valve such as bleeder valve, vent valve cuts out;
7. the feed compartment material returning valve is closed.
After preliminary preparation is ready, carry out the preparation of fluorocarbon resin again, specifically may further comprise the steps:
1) opens the polymerization exhaust-valve; Pipeline is reinforced goes up valve, valve down, drives charging valve, with the vinyl acetate that accounts for said synthetic fluorocarbon resin raw material weight per-cent 20.0～21.0%, 9.5～9.8% MIBK and YLENE thorough mixing in reaction kettle of 22.0～23.0%; Open material returning valve; Weighing feed back amount is added, and closes polymerization pipeline charging valve;
2) drive the hopper charging valve; In reaction kettle, add the Diisopropyl azodicarboxylate account for said synthetic fluorocarbon resin raw material weight per-cent 0.75～0.8%, 0.94～0.98% undecylenic acid and 6.0～7.0% ethylene glycol monoallyl ether more successively; Close the hopper charging valve, do charge book;
3) closed reactor is vacuumized, squeeze into 50～80% the tetrafluoroethylene gas phase monomer that accounts for synthetic fluorocarbon resin formulation weight per-cent 38.5～39.0% again with pump;
4) with pump remaining tetrafluoroethylene gas phase monomer is squeezed in the reaction kettle, reinforced finishing closed the monomer charging valve again, balances a jar feeding N
2Stirring is opened in pressure regulation, keeps reaction pressure 0.4～0.8MPa; Stirring velocity is 50～80 rev/mins, stirs 1～4 hour, uses the slow reacting by heating still of chuck in the reaction process; And the control reactor temperature, keep opening big water coolant after 5～20 hours; Observe still temperature still and press, adjustment is seen pressure at any time;
5) after tetrafluoroethylene gas phase monomer added, stopped reaction when still internal reaction pressure drops to 0.8～1.0MPa reclaimed tetrafluoroethylene gas phase monomer, return mechanism behind the desolventizing;
6) after the tetrafluoroethylene gas phase MONOMER RECOVERY, use N
2Gas in the displacement still cools to the slow exhaust-valve of opening below 30 ℃, and step-down is 0MPa in the polymeric kettle, closes stirrer, closes equilibrium still temperature still and presses, and discharging promptly gets product.
Further, the airtight concrete steps that vacuumize are in the said step 3): drive the polymeric kettle vacuum valve, open polymeric kettle unit price material valve N
2Vacuum pump left by valve, observes still and presses, and earlier closed reactor is evacuated to vacuum tightness and is-0.1MPa～-0.08 MPa, keeps 5～30min, charges into nitrogen and makes and reach 0.1～1.0MPa in the said reaction kettle, closes the N2 bottle, closes polymeric kettle N
2Valve vacuumizes once more, closes the polymkeric substance vacuum valve, closes vacuum pump.
Further, after airtight the vacuumizing, oxygen level is 17～18ppm in the reaction kettle in the said step 3).
Further, in the said step 4), reactor temperature is 69～73 ℃.
Further, the concrete steps of control reactor temperature are in the said step 4): adjustment surge tank pressure, press 0.05～0.1MPa greater than still; When the still temperature reaches 68 ℃, close hot water valve, open cold valves slightly; Be raised to 71 ℃ so that the still temperature is slow, control 71 ± 2 ℃ of still temperature at any time, 71 ± 2 ℃ of constant temperature; Still is pressed greater than 1.1MPa, when still uncontrollable, through emptying, make pressure drop to the follow-up supervention of 0.8MPa should to keep 5～20 hours.
Further, said in step 6), cool to below 30 ℃ and delay when opening exhaust-valve, product must not be taken exhaust-valve out of.
Description of drawings
The fluorocarbon resin coating that Fig. 1 makes for the present invention and the artificial accelerated aging gloss velocity of variation comparative result synoptic diagram of trifluorochloroethylene-vinyl acetate copolymer coating;
The fluorocarbon resin coating that Fig. 2 makes for the present invention and the artificial accelerated aging value of chromatism changing conditions of trifluorochloroethylene-vinyl acetate copolymer coating be synoptic diagram as a result.
In the accompanying drawing, the material of each serial representative is following:
Embodiment
Below in conjunction with accompanying drawing principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
1. prepare
A. polymeric kettle is carried out bulge test, pressure 0.9Mpa, behind the pressurize 4h, release is subsequent use;
B. inspection
1. stir machine oil window oil level;
2. vacuum pump oil window oil level;
3. surge tank oil window oil level and N
2Bottle and polymeric kettle correctly connect;
4. N
2Bottle pressure is answered＞3Mpa;
5. cistern water level;
6. valve such as bleeder valve, vent valve cuts out;
7. the feed compartment material returning valve is closed.
2. the preparation of fluorocarbon resin
1) opens the polymerization exhaust-valve; Pipeline is reinforced goes up valve, valve down, drives charging valve, with the vinyl acetate that accounts for synthetic fluorocarbon resin formulation weight per-cent 20.0%, 9.5% MIBK and YLENE thorough mixing in reaction kettle of 22.0%; Open material returning valve; Weighing feed back amount is added, and closes polymerization pipeline charging valve;
2) drive the hopper charging valve, in reaction kettle, add the Diisopropyl azodicarboxylate account for synthetic fluorocarbon resin formulation weight per-cent 0.75%, 0.94% undecylenic acid and 6.0% ethylene glycol monoallyl ether more successively, close the hopper charging valve, do charge book;
3) closed reactor is vacuumized after, make that oxygen level is 17ppm in the reaction kettle, squeeze into 50% the tetrafluoroethylene gas phase monomer that accounts for synthetic fluorocarbon resin formulation weight per-cent 38.5% again with pump.The said airtight concrete steps that vacuumize are: drive the polymeric kettle vacuum valve, open polymeric kettle unit price material valve N
2Vacuum pump left by valve, observes still and presses, and earlier closed reactor is evacuated to vacuum tightness and is-0.1MPa, keeps 5min, charges into nitrogen and makes and reach 0.1MPa in the said reaction kettle, closes N
2Bottle closes polymeric kettle N
2Valve vacuumizes once more, closes the polymkeric substance vacuum valve, closes vacuum pump;
4) with pump remaining 50% tetrafluoroethylene gas phase monomer is squeezed in the reaction kettle, reinforced finishing closed the monomer charging valve again, balances a jar feeding N
2Stirring is opened in pressure regulation, and to keep reaction pressure be 0.4MPa, and stirring velocity is 50 rev/mins, stirs 1 hour; Use the slow reacting by heating still of chuck in the reaction process, the observation still is pressed, the still temperature keeps a record, and the balancing pressure tank is pressed 0.05MPa greater than still, when the still temperature reaches 68 ℃ at any time; Close hot water valve, open cold valves slightly, be raised to 71 ℃, control 71 ℃ of still temperature at any time so that the still temperature is slow; 71 ℃ of constant temperature, still are pressed greater than 1.1MPa, when still uncontrollable, and can emptying, making pressure drop to the follow-up supervention of 0.8MPa should; Behind the constant temperature 5h, open big water coolant, observe still temperature still and press, adjustment is seen pressure at any time;
5) after tetrafluoroethylene gas phase monomer added, stopped reaction when still internal reaction pressure drops to 0.8MPa reclaimed tetrafluoroethylene gas phase monomer, return mechanism behind the desolventizing;
6) after the tetrafluoroethylene gas phase MONOMER RECOVERY, use N
2Gas in the displacement still cools to below 30 ℃
Delay and open exhaust-valve (can not take product out of), step-down is 0MPa, closes stirrer, closes equilibrium still temperature still and presses, and discharging promptly gets product.
1. prepare with embodiment 1.
2. the preparation of fluorocarbon resin
1) opens the polymerization exhaust-valve; Pipeline is reinforced goes up valve, valve down, drives charging valve, with the vinyl acetate that accounts for synthetic fluorocarbon resin formulation weight per-cent 21.0%, 9.8% MIBK and YLENE thorough mixing in reaction kettle of 22.8%; Open material returning valve; Weighing feed back amount is added, and closes polymerization pipeline charging valve;
2) drive the hopper charging valve, in reaction kettle, add the Diisopropyl azodicarboxylate account for synthetic fluorocarbon resin formulation weight per-cent 0.79%, 0.95% undecylenic acid and 6.06% ethylene glycol monoallyl ether more successively, close the hopper charging valve, do charge book;
3) closed reactor is vacuumized after, make that oxygen level is 17ppm in the reaction kettle, squeeze into 70% the tetrafluoroethylene gas phase monomer that accounts for synthetic fluorocarbon resin formulation weight per-cent 38.6% again with pump.The said airtight concrete steps that vacuumize are: drive the polymeric kettle vacuum valve, open polymeric kettle unit price material valve N
2Vacuum pump left by valve, observes still and presses, and earlier closed reactor is evacuated to vacuum tightness and is-0.09 MPa, keeps 20min, charges into nitrogen and makes and reach 0.1MPa in the said reaction kettle, closes N
2Bottle closes polymeric kettle N
2Valve vacuumizes once more, closes the polymkeric substance vacuum valve, closes vacuum pump;
4) with pump remaining 30% tetrafluoroethylene gas phase monomer is squeezed in the reaction kettle, reinforced finishing closed the monomer charging valve again, balances a jar feeding N
2Stirring is opened in pressure regulation, and to keep reaction pressure be 0.6MPa, and stirring velocity is 70 rev/mins, stirs 3 hours; Use the slow reacting by heating still of chuck in the reaction process, the observation still is pressed, the still temperature keeps a record, and the balancing pressure tank is pressed 0.07MPa greater than still, when the still temperature reaches 68 ℃ at any time; Close hot water valve, open cold valves slightly, be raised to 71 ℃, control 72 ℃ of still temperature at any time so that the still temperature is slow; 72 ℃ of constant temperature, still are pressed greater than 1.1MPa, when still uncontrollable, and can emptying, making pressure drop to the follow-up supervention of 0.8MPa should; Behind the constant temperature 15h, open big water coolant, observe still temperature still and press, adjustment is seen pressure at any time;
5) after tetrafluoroethylene gas phase monomer added, stopped reaction when still internal reaction pressure drops to 0.9MPa reclaimed tetrafluoroethylene gas phase monomer, return mechanism behind the desolventizing;
6) after the tetrafluoroethylene gas phase MONOMER RECOVERY, use N
2Gas in the displacement still cools to below 30 ℃
Delay and open exhaust-valve (can not take product out of), step-down is 0MPa, closes stirrer, closes equilibrium still temperature still and presses, and discharging promptly gets product.
1. prepare with embodiment 1.
2. the preparation of fluorocarbon resin
1) opens the polymerization exhaust-valve; Pipeline is reinforced goes up valve, valve down, drives charging valve, with the vinyl acetate that accounts for synthetic fluorocarbon resin formulation weight per-cent 21.0%, 9.8% MIBK and YLENE thorough mixing in reaction kettle of 23.0%; Open material returning valve; Weighing feed back amount is added, and closes polymerization pipeline charging valve;
2) drive the hopper charging valve, in reaction kettle, add the Diisopropyl azodicarboxylate account for synthetic fluorocarbon resin formulation weight per-cent 0.8%, 0.98% undecylenic acid and 7.0% ethylene glycol monoallyl ether more successively, close the hopper charging valve, do charge book;
3) closed reactor is vacuumized after; Making the interior oxygen level of reaction kettle is 17ppm; Squeeze into 80% the tetrafluoroethylene gas phase monomer that accounts for synthetic fluorocarbon resin formulation weight per-cent 39.0% again with pump, the said airtight concrete steps that vacuumize are: drive the polymeric kettle vacuum valve, open polymeric kettle unit price material valve N
2Vacuum pump left by valve, observes still and presses, and earlier closed reactor is evacuated to vacuum tightness and is-0.08 MPa, keeps 30min, charges into nitrogen and makes and reach 1.0MPa in the said reaction kettle, closes N
2Bottle closes polymeric kettle N
2Valve vacuumizes once more, closes the polymkeric substance vacuum valve, closes vacuum pump;
4) with pump remaining 20% tetrafluoroethylene gas phase monomer is squeezed in the reaction kettle, reinforced finishing closed the monomer charging valve again, balances a jar feeding N
2Stirring is opened in pressure regulation, and to keep reaction pressure be 0.8MPa, and stirring velocity is 80 rev/mins, stirs 4 hours; Use the slow reacting by heating still of chuck in the reaction process, the observation still is pressed, the still temperature keeps a record, and the balancing pressure tank is pressed 0.1MPa greater than still, when the still temperature reaches 68 ℃ at any time; Close hot water valve, open cold valves slightly, be raised to 71 ℃, control 73 ℃ of still temperature at any time so that the still temperature is slow; 73 ℃ of constant temperature, still are pressed greater than 1.1MPa, when still uncontrollable, and can emptying, making pressure drop to the follow-up supervention of 0.8MPa should; Behind the constant temperature 20h, open big water coolant, observe still temperature still and press, adjustment is seen pressure at any time;
5) after tetrafluoroethylene gas phase monomer added, stopped reaction when still internal reaction pressure drops to 1.0MPa reclaimed tetrafluoroethylene gas phase monomer, return mechanism behind the desolventizing;
6) after the tetrafluoroethylene gas phase MONOMER RECOVERY, use N
2Gas in the displacement still cools to below 30 ℃
Delay and open exhaust-valve (can not take product out of), step-down is 0MPa, closes stirrer, closes equilibrium still temperature still and presses, and discharging promptly gets product.
Concrete test example
1. the fluorocarbon resin that embodiment of the invention 1-3 is made is measured its index according to relevant national standard, shown in the table 1 specific as follows.
The technical indicator of the fluorocarbon resin that table 1 embodiment of the invention 1-3 makes
2. fluorocarbon resin of the present invention can be made into fluorocarbon resin coating, and fluorocarbon resin coating that is made into and trifluorochloroethylene-vinyl acetate copolymer coating is done simultaneous test, with its people that films, compares aging speed.Series 1 is tetrafluoroethylene-vinyl ether co-polymer, and series 2 is trifluorochloroethylene-vinyl acetate copolymer.Can find out that from Fig. 1, Fig. 2 in artificial accelerated aging 5000h scope, tetrafluoroethylene-vinyl ether is filmed to have kept and protected light, tint retention ability preferably.And the fluorocarbon coating of trifluorochloroethylene-vinyl acetate type has been kept and has been protected light, tint retention ability preferably in 3000h, begins obvious decline but surpass guarantor's light rate of filming behind 3000 h, protects the light rate during to 5000 h and is merely about 60%.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. fluorocarbon resin; It is characterized in that said fluorocarbon resin is synthetic by following raw materials by weight percent: YLENE 22.0～23.0%, vinyl acetate 20.0～21.0%, ethylene glycol monoallyl ether 6.0～7.0%, Diisopropyl azodicarboxylate 0.75～0.8%, undecylenic acid 0.94～0.98%, hexone 9.5～9.8%, tetrafluoroethylene gas phase monomer 38.5～39.0%.
2. fluorocarbon resin according to claim 1; It is characterized in that the weight proportion of each raw material of said fluorocarbon resin is: YLENE 22.8%, vinyl acetate 21.0%, ethylene glycol monoallyl ether 6.06%, Diisopropyl azodicarboxylate 0.79%, undecylenic acid 0.95%, hexone 9.8%, tetrafluoroethylene gas phase monomer 38.6%.
3. the preparation method of a fluorocarbon resin is characterized in that, said preparing method's concrete technical process is:
1) opens the polymerization exhaust-valve; Pipeline is reinforced goes up valve, valve down, drives charging valve, with the vinyl acetate that accounts for said synthetic fluorocarbon resin raw material weight per-cent 20.0～21.0%, 9.5～9.8% MIBK and YLENE thorough mixing in reaction kettle of 22.0～23.0%; Open material returning valve; Weighing feed back amount is added, and closes polymerization pipeline charging valve;
2) drive the hopper charging valve; In reaction kettle, add the Diisopropyl azodicarboxylate account for said synthetic fluorocarbon resin raw material weight per-cent 0.75～0.8%, 0.94～0.98% undecylenic acid and 6.0～7.0% ethylene glycol monoallyl ether more successively; Close the hopper charging valve, do charge book;
3) closed reactor is vacuumized after, squeeze into 50～80% the tetrafluoroethylene gas phase monomer that accounts for synthetic fluorocarbon resin formulation weight per-cent 38.5～39.0% again with pump;
4) with pump remaining tetrafluoroethylene gas phase monomer is squeezed in the reaction kettle, reinforced finishing closed the monomer charging valve again, balances a jar feeding N
2Stirring is opened in pressure regulation, keeps reaction pressure 0.4～0.8MPa; Stirring velocity is 50～80 rev/mins, and churning time is 1～4 hour, uses the slow reacting by heating still of chuck in the reaction process; And the control reactor temperature, keep opening big water coolant after 5～20 hours; Observe still temperature still and press, adjustment is seen pressure at any time;
5) after tetrafluoroethylene gas phase monomer added, stopped reaction when still internal reaction pressure drops to 0.8～1.0MPa reclaimed tetrafluoroethylene gas phase monomer, return mechanism behind the desolventizing;
6) after the tetrafluoroethylene gas phase MONOMER RECOVERY, use N
2Gas in the displacement still cools to the slow exhaust-valve of opening below 30 ℃, and step-down is 0MPa in the polymeric kettle, closes stirrer, closes equilibrium still temperature still and presses, and discharging promptly gets product.
4. the preparation method of fluorocarbon resin according to claim 3 is characterized in that, the airtight concrete steps that vacuumize are in the said step 3): drive the polymeric kettle vacuum valve, open polymeric kettle unit price material valve N
2Vacuum pump left by valve, observes still and presses, and earlier closed reactor is evacuated to vacuum tightness and is-0.1MPa～-0.08 MPa, keeps 5～30min, charges into nitrogen and makes and reach 0.1～1.0MPa in the said reaction kettle, closes N
2Bottle closes polymeric kettle N
2Valve vacuumizes once more, closes the polymkeric substance vacuum valve, closes vacuum pump.
5. according to the preparation method of claim 3 or 4 described fluorocarbon resins, it is characterized in that after airtight the vacuumizing, oxygen level is 17～18ppm in the reaction kettle in the said step 3).
6. the preparation method of fluorocarbon resin according to claim 3 is characterized in that, in step 4), said reactor temperature is 69～73 ℃.
7. according to the preparation method of claim 3 or 6 described fluorocarbon resins, it is characterized in that the concrete steps of control reactor temperature are: adjustment surge tank pressure, press 0.05～0.1MPa greater than still; When the still temperature reaches 68 ℃, close hot water valve, open cold valves slightly, be raised to 71 ℃ so that the still temperature is slow; At any time control 71 ± 2 ℃ of still temperature, 71 ± 2 ℃ of constant temperature, still are pressed greater than 1.1MPa; When still uncontrollable, through emptying, make pressure drop to 0.8MPa continued reaction, kept 5～20 hours.
8. the preparation method of fluorocarbon resin according to claim 3 is characterized in that, in said step 6), cools to below 30 ℃ and delays when opening exhaust-valve, and product must not be taken exhaust-valve out of.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102698691A (en) * | 2012-05-25 | 2012-10-03 | 南京长江涂料有限公司 | Production facility of normal temperature solidified fluorine-contained coating |
| CN106311082A (en) * | 2015-06-29 | 2017-01-11 | 中昊晨光化工研究院有限公司 | Mechanical sealed balance tank auxiliary structure applied to reactor |
| JP2017165958A (en) * | 2016-03-10 | 2017-09-21 | ダイキン工業株式会社 | Polymer, composition, coated film, laminate, back sheet and solar cell module |
| CN107383264A (en) * | 2017-08-04 | 2017-11-24 | 安徽博泰氟材料科技有限公司 | Solvent-borne type F-C paint resin copolymerization technique |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698691A (en) * | 2012-05-25 | 2012-10-03 | 南京长江涂料有限公司 | Production facility of normal temperature solidified fluorine-contained coating |
| CN106311082A (en) * | 2015-06-29 | 2017-01-11 | 中昊晨光化工研究院有限公司 | Mechanical sealed balance tank auxiliary structure applied to reactor |
| JP2017165958A (en) * | 2016-03-10 | 2017-09-21 | ダイキン工業株式会社 | Polymer, composition, coated film, laminate, back sheet and solar cell module |
| JP2017190461A (en) * | 2016-03-10 | 2017-10-19 | ダイキン工業株式会社 | Polymer, composition, coating, laminate, back sheet and solar cell module |
| CN107383264A (en) * | 2017-08-04 | 2017-11-24 | 安徽博泰氟材料科技有限公司 | Solvent-borne type F-C paint resin copolymerization technique |
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