CN107586389A - A kind of preparation method of fluoropolymer modifier - Google Patents
A kind of preparation method of fluoropolymer modifier Download PDFInfo
- Publication number
- CN107586389A CN107586389A CN201610533631.9A CN201610533631A CN107586389A CN 107586389 A CN107586389 A CN 107586389A CN 201610533631 A CN201610533631 A CN 201610533631A CN 107586389 A CN107586389 A CN 107586389A
- Authority
- CN
- China
- Prior art keywords
- fluoropolymer
- preparation
- reactor
- vinylidene fluoride
- modifier according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention relates to a kind of preparation method of fluoropolymer modifier.Binary fluoropolymer is synthesized by the method for emulsion polymerization; binary fluoropolymer and grafted monomers are carried out to high-energy ray radiating surface graft modification in the solution again; gained mixture is scrubbed, filters, dries, and polyethylene pipe resins processing special surface modified fluoride-containing rheological agent particulate is made through comminutor.It is characterized in that：In vinylidene fluoride/hexafluoropropylene copolymer, 65~85wt% of vinylidene fluoride, 15~35wt% of hexafluoropropene；In vinylidene fluoride/tetrafluoroethylene copolymer, 60~80wt% of vinylidene fluoride, 20~40wt% of tetrafluoroethene；In tetrafluoroethylene/hexafluoropropylene copolymer, 50~80wt% of tetrafluoroethene, 20~50wt% of hexafluoropropene；Graft modification amount of monomer is 1~6wt%.Fluoropolymer modifier surface introduces new functional groups, improve surface compatability, lubricity and with the performance such as the caking property of metal.
Description
Technical field
The present invention relates to the preparation field of fluoropolymer modifier, more particularly to a kind of fluoropolymer modifier particulate that is modified of surface
Preparation method.
Background technology
In recent years, it is also growing to the demand of low-carbon alkene with the fast development of Global Oil chemical industry.Low-carbon
Alkane catalytic dehydrogenation technology is to increase production the effective way of C3~C4 alkene.
Some manufacturing deficiencies often occur in polyethylene pipe resins during melting extrusion.Such as：Lose on extrudate surface
Frost, surface wrinkling, under higher shear stress, material operates generating period melt fracture under constant rotating speed
When, extrudate is in periodically smooth and roughened state, so as to influence the extrusion efficiency of products appearance and process equipment.It is general at present
All over the extrusion processing characteristics for improving pipe resin using fluoropolymer modifier.Fluorine-containing processing rheological agent can reduce polyvinyl piping materials
The frictional force of molecular resin interchain, so as to reduce melt viscosity, mobility is improved, and then improve its processing characteristics.
In recent years, different types of fluorine processing rheological agent is successively developed both at home and abroad：
US 03125547A provide a kind of fluorocarbon polymer processing aid, and wherein fluoropolymer is that fluorine atom and carbon are former
The ratio between son is at least 1:2 fluoroolefin homopolymer and copolymer, and fluorocarbon polymer is with similar with hydrocarbon polymer
Melt flow characteristics, it can be reduced in nonfluorinated polymers extrusion using the fluorocarbon polymer of 0.01~2.0% (weight ratio)
Die pressure.In addition rate of extrusion is also remarkably improved using the auxiliary agent, without causing melt fracture.
CN201110165285.0 is related to a kind of fluoropolymer additive, and it is averaged by what core and shell portion were formed
Particle diameter is 0.2~1um particulate, and described core is made up of fluorocarbon polymer, and the weight ratio in the core and shell portion is 20:
80~45:55.In organosilane crosslinked polyethylene extrusion, the processing aid is added, not only extruded velocity is fast, and extruded product
Surface smoothness is high.
CN201010283187.2 provides a kind of preparation method of modified fluorine-containing processing aid.By fluoroelastomer, trigger
Agent cumyl peroxide, the mixing of grafted monomers GMA, obtain being modified fluoroelastomer, then and (oxygenated hydrocarbon)
Polymer reaction obtains modified fluorine-containing processing aid；Described fluoroelastomer is tetrafluoroethene, hexafluoropropene, vinylidene fluoride
Terpolymer, or the bipolymer of vinylidene and hexafluoropropene；The modified fluorine-containing processing aid effectively increases
The tack time of fluoroelastomer and metal, reduces the usage amount of fluoroelastomer, adds fluoroelastomer and (oxygenated hydrocarbon)
The compatibility of polymer, improve well known processing characteristics.
But there is loosely organized and without problems such as good polarity for above-mentioned fluorine processing rheological agent.
The content of the invention
In order to solve problem present in background technology, it is necessary to design surface can be higher modified with polar fluorine-containing stream
Become agent so that polar group can be migrated preferentially during polyvinyl piping materials extrusion molding to resin/metal wall, so as to play
Interior addition, the effect of outer lubrication, there is positive meaning for the processing characteristics for improving polyethylene pipe resins.
To reach above-mentioned purpose, the present invention provides a kind of preparation method of fluoropolymer modifier, comprised the following steps：
S1 synthesizes binary fluoropolymer by the method for emulsion polymerization；
S2 by binary fluoropolymer and the solution that grafted monomers, solvent and polymerization inhibitor form by high-energy ray radiate into
Row surface graft modification, gained mixture is scrubbed, filters, dries, being granulated, and the fluoropolymer modifier particulate that surface is modified is made；
The binary fluoropolymer, grafted monomers, the ratio between the dosage of solvent and polymerization inhibitor are：10:1:50:0.01~
50:6:90:1；During the surface graft modification, high-energy ray is electron beam high-energy ray, dose of radiation is 10~
100kGy, the time of radiation is 1min~1h.
The fluoropolymer modifier particulate that above-mentioned surface is modified and polyethylene pipe resins mixing granulation formation polyvinyl piping materials are special
Materials.
The preparation method of fluoropolymer modifier of the present invention, wherein, the polymerization inhibitor is preferably inorganic metal salt, enters one
Step is preferably sulfate or chloride.
The preparation method of fluoropolymer modifier of the present invention, wherein, the solvent be preferably by deionized water, ethanol,
Isopropanol, butanol, acetone, methyl iso-butyl ketone (MIBK) and cyclohexanone form at least one of group.
The preparation method of fluoropolymer modifier of the present invention, wherein, the grafted monomers preferably at least contain a carbon
Carbon double bond or at least containing a polar monomer for being capable of function dough, enables grafted monomers to be grafted on fluoropolymer.
The preparation method of fluoropolymer modifier of the present invention, wherein, the grafted monomers are preferably carboxylate, carboxylic acyloxy
Base ester, epoxide, cyclic lactone or the polyethylene glycol containing double bond.
The preparation method of fluoropolymer modifier of the present invention, in the emulsion polymerization process, it is preferred that emulsifying agent is dense
Degree is higher than critical micelle concentration, and emulsifying agent is to be lived by APEO analog anion surfactants, sulfate anion surface
Property agent and fluorocarbon surfactant form at least one of group；Solvent be by deionized water, ethanol, isopropanol, butanol,
Acetone, methyl iso-butyl ketone (MIBK) and cyclohexanone form at least one of group；Initiator is by persulfuric acid ammonium salt, alkali sulfite
Earth metal salt, alkali pyrophosphate earth metal salt and alkali metal salts form at least one of group.Above-mentioned initiator is used
Measure preferably 0.1~5wt%, further preferred 0.1~3wt%；Further preferred 1~the 5cmc of mentioned emulsifier concentration；It is above-mentioned molten
Agent dosage is preferably 50~90wt%, further preferred 60~85wt%.
The preparation method of fluoropolymer modifier of the present invention, in the emulsion polymerization process, it is preferred that react full mistake
Journey deoxygenation, nitrogen protection, 40~120 DEG C, 3~8MPa of pressure of temperature, 1~24 hour time, 200~1000 turns of mixing speed/
Minute；It may further be preferable that 60~100 DEG C, 4~6MPa of pressure of temperature, 4~12 hours time, mixing speed 400~800
Rev/min.
The preparation method of fluoropolymer modifier of the present invention, it is preferred that fluorine-containing member in the binary fluoropolymer
Plain molecular mass is more than the 60% of binary fluoropolymer gross mass, and the molecular weight of the binary fluoropolymer is 10~100
Ten thousand.
The preparation method of fluoropolymer modifier of the present invention, these, it is preferred to, the binary fluoropolymer is served as reasons
Vinylidene fluoride/hexafluoropropylene copolymer, vinylidene fluoride/tetrafluoroethylene copolymer and tetrafluoroethylene/hexafluoropropylene copolymer
At least one of formed colony.
The preparation method of fluoropolymer modifier of the present invention, it is preferred that the vinylidene fluoride/hexafluoropropene copolymerization
In thing：65~85wt% of vinylidene fluoride, 15~35wt% of hexafluoropropene；In the vinylidene fluoride/tetrafluoroethylene copolymer：
60~80wt% of vinylidene fluoride, 20~40wt% of tetrafluoroethene；In the tetrafluoroethylene/hexafluoropropylene copolymer：Tetrafluoro second
50~80wt% of alkene, 20~50wt% of hexafluoropropene.
The preparation method of fluoropolymer modifier of the present invention, during the surface graft modification, dose of radiation is preferred
For 20~80kGy, radiated time is preferably 1~30 minute.
The preparation method of fluoropolymer modifier of the present invention, in washing process, detergent is preferably the mixture
By 1~5wt% inorganic acid, water, methanol, ethanol, acetic acid, n-butanol, tetrahydrofuran, methyl formate, tri-n-butylamine, MEK and
Ethyl acetate forms at least one of group.
The preparation method of fluoropolymer modifier of the present invention, the mixture is in the drying process：Preferably, dry
60~120 DEG C of temperature, 6~12 hours drying times；It may further be preferable that 60~100 DEG C of drying temperature, drying time 6~8
Hour.
The preparation method of fluoropolymer modifier of the present invention, wherein, the fluoropolymer modifier that final obtained surface is modified
The mean particle dia of particulate is preferably 0.5~5mm；More preferably 0.5~3mm..
The preparation method of fluoropolymer modifier of the present invention, shown in emulsion polymerization formula such as formula (I), the surface
Shown in graft modification reaction equation such as formula (II), shown in the part chemical formula such as formula (III) of the grafted monomers.
The beneficial effects of the invention are as follows：Redesigned by molecular structure and fluoropolymer progress surface modified synthesis is gathered
Ethene pipe resin processes special surface modified fluoride-containing rheological agent particulate.Surface molecule structure is redesigned can be in polymer
Surface introduces new feature, improve surface compatability, lubricity and with the performance such as the caking property of metal.It is it is possible to prevente effectively from mixed
The drawbacks of compound separation is caused in polyethylene pipe resins extrusion, improves processing characteristics, reduces or eliminates die orifice buildup and show
As shortening the supply delay time, improving surface gloss, reduce extrusion pressure；
Modified fluoropolymer modifier has excellent physical and chemical performance, the processing for improving polyethylene pipe resins
Performance has positive meaning.
Brief description of the drawings
Fig. 1 is binary fluoropolymer polyvinylidene fluoride-tetrafluoroethene (- (C in embodiment 3 and 42F4)-(C2H2F2)-)
Nucleus magnetic hydrogen spectrum；
Fig. 2 is the nucleus magnetic hydrogen spectrum that polyvinylidene fluoride-tetrafluoroethene is grafted polyethyleneglycol diacrylate in embodiment 3；
Fig. 3 is the nucleus magnetic hydrogen spectrum that polyvinylidene fluoride-tetrafluoroethene is grafted ethyl acetoacetate in embodiment 4.
Embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as the limit to the present invention
System.
Embodiment 1
In 250mL stainless steel cauldrons, 150mL deionized waters are sequentially added, 0.114g perfluorooctanoic acid emulsifying agents are consolidated
Body.
Connection experiment pipeline, closes all valves.Wherein, reactor charging aperture connection nitrogen, reactor exhaust outlet is successively
Connect wide-mouth bottle and vavuum pump.The thermocouple of reactor, belt, test the speed circle, condensed water are connected, open condensed water.
With nitrogen pump drainage 3 times：The ball-type funnel cock on wide-mouth bottle is opened, starts vavuum pump, opens reactor exhaust outlet,
Ball-type funnel cock is closed, after continuing 1~2min, reactor exhaust outlet is closed, opens ball-type funnel cock, close vavuum pump；
Nitrogen valve is slowly opened, nitrogen is passed through into kettle, lasts about half a minute.So operate 3 times repeatedly.
Slowly the gas in nitrogen pipeline is discharged, nitrogen pipeline is unloaded from reactor charging aperture；Feed pump is discharged
Mouth is connected with reactor charging aperture.
Reactor controller is opened, rotating speed 550rpm, 90 DEG C of temperature are set.
After temperature is increased to 90 DEG C and stabilization, two kinds of gaseous state lists of vinylidene fluoride and hexafluoropropene are passed through into reactor
Body, charging rate are respectively 209.0g/h and 112.5g/h, and the two mass ratio is 65：35, until pressure reaches in kettle
4.5MPa。
12.1g ammonium persulfate solutions (ammonium persulfate concentrations 0.21g/mL) are added in reactor；Ammonium persulfate is molten
The addition speed of liquid is 12.1g/h.
Two kinds of gaseous monomers are continually fed into according to the above ratio, system is maintained 4.5MPa, polymerization time 4h.
After stopping charging 30 minutes, reactor controller and feed pump are closed, but ensures that condensed water is always maintained at what is opened
State.
Test the speed circle, thermocouple, belt on reactor is taken down rapidly, reactor is taken out rapidly from heating mantle, put
In screw clamp, rinsed with running water on the outside of reactor, system is cooled.
Treat that temperature drops to room temperature, after reactor pressure keeps 20min constant, close condensed water.
Plastic bottle equipped with ethanol is connected to reactor exhaust outlet, pressure gauge registration is observed, slowly opens exhaust outlet, make
Pressure gauge reading is zero；Reactor inlet valve is opened, pressure in pipeline is reduced to zero.The valve closed on reactor.
Gained emulsion will be polymerize, use MgCl2Solution is demulsified, and obtains solid product；Solid product is washed with deionized, and
It is dried in vacuo at 100 DEG C, produces poly- (vinylidene fluoride-hexafluoropropene) solid i.e. binary fluoropolymer.
Poly- (vinylidene fluoride-hexafluoropropene) solid 72g is added in irradiation tube, while adds the poly- second of polarity grafted monomers
Omega-diol diacrylate (molecular weight 700) 40g, ethanol 320g, 0.12% six ferrous sulfate hydrate ammonium salt solution 72g, by 10
Sealed after minute logical nitrogen deoxygenation.
At room temperature using electron radiation accelerator carry out co segregation polymerisation, to setting dose of radiation 20kGy,
Irradiation stops after 4 minutes.
Obtained graft modification rheological agent is repeatedly washed with deionized water, 3% watery hydrochloric acid, places into 80 DEG C of vacuum drying chamber
Dry to constant weight.
Above-mentioned products therefrom is granulated (0.5~3mm) surface modified fluoride-containing rheological agent particulate is made.
Embodiment 2：
In 250mL stainless steel cauldrons, 150mL deionized waters, 0.114g perfluorooctanoic acid solids are sequentially added.
Connection experiment pipeline, closes all valves.Wherein, reactor charging aperture connection nitrogen, reactor exhaust outlet is successively
Connect wide-mouth bottle and vavuum pump.The thermocouple of reactor, belt, test the speed circle, condensed water are connected, open condensed water.
With nitrogen pump drainage 3 times：The ball-type funnel cock on wide-mouth bottle is opened, starts vavuum pump, opens reactor exhaust outlet,
Ball-type funnel cock is closed, after continuing 1~2min, reactor exhaust outlet is closed, opens ball-type funnel cock, close vavuum pump；
Nitrogen valve is slowly opened, nitrogen is passed through into kettle, lasts about half a minute.So operate 3 times repeatedly.
Slowly the gas in nitrogen pipeline is discharged, nitrogen pipeline is unloaded from reactor charging aperture；Feed pump is discharged
Mouth is connected with reactor charging aperture.
Reactor controller is opened, rotating speed 800rpm, 80 DEG C of temperature are set.
After temperature is increased to 80 DEG C and stabilization, two kinds of gaseous state lists of vinylidene fluoride and hexafluoropropene are passed through into reactor
Body, charging rate are respectively 209.0g/h and 112.5g/h, and the two mass ratio is 65：35, until pressure reaches in kettle
4.5MPa。
12.1g ammonium persulfate solutions (ammonium persulfate concentrations 0.21g/mL) are added in reactor；Ammonium persulfate is molten
The addition speed of liquid is 12.1g/h.
Two kinds of gaseous monomers are continually fed into according to the above ratio, system is maintained 4.5MPa, polymerization time 4h.
After stopping charging 30 minutes, reactor controller and feed pump are closed, but ensures that condensed water is always maintained at what is opened
State.
Test the speed circle, thermocouple, belt on reactor is taken down rapidly, reactor is taken out rapidly from heating mantle, put
In screw clamp, rinsed with running water on the outside of reactor, system is cooled.
Treat that temperature drops to room temperature, after reactor pressure keeps 20min constant, close condensed water.
Plastic bottle equipped with ethanol is connected to reactor exhaust outlet, pressure gauge registration is observed, slowly opens exhaust outlet, make
Pressure gauge reading is zero；Reactor inlet valve is opened, pressure in pipeline is reduced to zero.The valve closed on reactor.
Gained emulsion will be polymerize, use MgCl2Solution is demulsified, and obtains solid product；Solid product is washed with deionized, and
It is dried in vacuo at 100 DEG C, produces poly- (vinylidene fluoride-hexafluoropropene) solid.
Poly- (vinylidene fluoride-hexafluoropropene) solid 72g is added in irradiation tube, while adds polarity grafted monomers acetyl
Ethyl acetate 33g, ethanol 467g and 0.12% copper-bath 86g, sealed after logical nitrogen deoxygenation in 10 minutes.
At room temperature using electron radiation accelerator carry out co segregation polymerisation, to setting dose of radiation 20kGy,
Irradiation stops after 4 minutes.
Obtained graft modification rheological agent is repeatedly washed with deionized water, 3% watery hydrochloric acid, places into 80 DEG C of vacuum drying chamber
Dry to constant weight.
Above-mentioned products therefrom is granulated (0.5~5mm) surface modified fluoride-containing rheological agent particulate is made.
Embodiment 3：
In 250mL stainless steel cauldrons, 150mL deionized waters, 0.114g perfluorooctanoic acid solids are sequentially added.
Connection experiment pipeline, closes all valves.Wherein, reactor charging aperture connection nitrogen, reactor exhaust outlet is successively
Connect wide-mouth bottle and vavuum pump.The thermocouple of reactor, belt, test the speed circle, condensed water are connected, open condensed water.
With nitrogen pump drainage 3 times：The ball-type funnel cock on wide-mouth bottle is opened, starts vavuum pump, opens reactor exhaust outlet,
Ball-type funnel cock is closed, after continuing 1~2min, reactor exhaust outlet is closed, opens ball-type funnel cock, close vavuum pump；
Nitrogen valve is slowly opened, nitrogen is passed through into kettle, lasts about half a minute.So operate 3 times repeatedly.
Slowly the gas in nitrogen pipeline is discharged, nitrogen pipeline is unloaded from reactor charging aperture；Feed pump is discharged
Mouth is connected with reactor charging aperture.
Reactor controller is opened, rotating speed 700rpm, 80 DEG C of temperature are set.
After temperature is increased to 80 DEG C and stabilization, two kinds of gaseous state lists of vinylidene fluoride and tetrafluoroethene are passed through into reactor
Body, charging rate are respectively 209.0g/h and 112.5g/h, and the two mass ratio is 65：35, until pressure reaches in kettle
4.5MPa。
12.1g ammonium persulfate solutions (ammonium persulfate concentrations 0.21g/mL) are added in reactor；Ammonium persulfate is molten
The addition speed of liquid is 12.1g/h.
Two kinds of gaseous monomers are continually fed into according to the above ratio, system is maintained 4.5MPa, polymerization time 4h.
After stopping charging 30 minutes, reactor controller and feed pump are closed, but ensures that condensed water is always maintained at what is opened
State.
Test the speed circle, thermocouple, belt on reactor is taken down rapidly, reactor is taken out rapidly from heating mantle, put
In screw clamp, rinsed with running water on the outside of reactor, system is cooled.
Treat that temperature drops to room temperature, after reactor pressure keeps 20min constant, close condensed water.
Plastic bottle equipped with ethanol is connected to reactor exhaust outlet, pressure gauge registration is observed, slowly opens exhaust outlet, make
Pressure gauge reading is zero；Reactor inlet valve is opened, pressure in pipeline is reduced to zero.The valve closed on reactor.
Gained emulsion will be polymerize, use MgCl2Solution is demulsified, and obtains solid product；Solid product is washed with deionized, and
It is dried in vacuo at 100 DEG C, produces poly- (vinylidene fluoride-tetrafluoroethene) solid.
Gained binary fluoropolymer product 100g is added in irradiation tube, while adds polarity grafted monomers polyethylene glycol dipropyl
Olefin(e) acid ester (molecular weight 700) 56g, ethanol 400g, 0.12% six ferrous sulfate hydrate ammonium salt solution 90g, by 10 minutes logical nitrogen
Sealed after gas deoxygenation.
At room temperature using electron radiation accelerator carry out co segregation polymerisation, to setting dose of radiation 40kGy,
Irradiation stops after 2 minutes.
Obtained graft modification rheological agent is repeatedly washed with deionized water, 3% watery hydrochloric acid, places into 80 DEG C of vacuum drying chamber
Dry to constant weight.
Above-mentioned products therefrom is granulated (0.5~3mm) surface modified fluoride-containing rheological agent particulate is made.
Embodiment 4：
In 250mL stainless steel cauldrons, 150mL deionized waters, 0.114g perfluorooctanoic acid solids are sequentially added.
Connection experiment pipeline, closes all valves.Wherein, reactor charging aperture connection nitrogen, reactor exhaust outlet is successively
Connect wide-mouth bottle and vavuum pump.The thermocouple of reactor, belt, test the speed circle, condensed water are connected, open condensed water.
With nitrogen pump drainage 3 times：The ball-type funnel cock on wide-mouth bottle is opened, starts vavuum pump, opens reactor exhaust outlet,
Ball-type funnel cock is closed, after continuing 1~2min, reactor exhaust outlet is closed, opens ball-type funnel cock, close vavuum pump；
Nitrogen valve is slowly opened, nitrogen is passed through into kettle, lasts about half a minute.So operate 3 times repeatedly.
Slowly the gas in nitrogen pipeline is discharged, nitrogen pipeline is unloaded from reactor charging aperture；Feed pump is discharged
Mouth is connected with reactor charging aperture.
Reactor controller is opened, rotating speed 700rpm, 80 DEG C of temperature are set.
After temperature is increased to 80 DEG C and stabilization, two kinds of gaseous state lists of vinylidene fluoride and tetrafluoroethene are passed through into reactor
Body, charging rate are respectively 209.0g/h and 112.5g/h, and the two mass ratio is 65：35, until pressure reaches in kettle
4.5MPa。
12.1g ammonium persulfate solutions (ammonium persulfate concentrations 0.21g/mL) are added in reactor；Ammonium persulfate is molten
The addition speed of liquid is 12.1g/h.
Two kinds of gaseous monomers are continually fed into according to the above ratio, system is maintained 4.5MPa, polymerization time 4h.
After stopping charging 30 minutes, reactor controller and feed pump are closed, but ensures that condensed water is always maintained at what is opened
State.
Test the speed circle, thermocouple, belt on reactor is taken down rapidly, reactor is taken out rapidly from heating mantle, put
In screw clamp, rinsed with running water on the outside of reactor, system is cooled.
Treat that temperature drops to room temperature, after reactor pressure keeps 20min constant, close condensed water.
Plastic bottle equipped with ethanol is connected to reactor exhaust outlet, pressure gauge registration is observed, slowly opens exhaust outlet, make
Pressure gauge reading is zero；Reactor inlet valve is opened, pressure in pipeline is reduced to zero.The valve closed on reactor.
Gained emulsion will be polymerize, use MgCl2Solution is demulsified, and obtains solid product；Solid product is washed with deionized, and
It is dried in vacuo at 100 DEG C, produces poly- (vinylidene fluoride-tetrafluoroethene) solid.
Gained binary fluoropolymer product 100g is added in irradiation tube, while adds polarity grafted monomers ethyl acetoacetate
33g, ethanol 467g and 0.12% copper-bath 86g, sealed after logical nitrogen deoxygenation in 10 minutes.
At room temperature using electron radiation accelerator carry out co segregation polymerisation, to setting dose of radiation 40kGy,
Irradiation stops after 2 minutes.
Obtained graft modification rheological agent is repeatedly washed with deionized water, 3% watery hydrochloric acid, places into 80 DEG C of vacuum drying chamber
Dry to constant weight.
Above-mentioned products therefrom is granulated (0.5~3mm) surface modified fluoride-containing rheological agent particulate is made.
Embodiment 5：
In 250mL stainless steel cauldrons, 150mL deionized waters, 0.114g perfluorooctanoic acid solids are sequentially added.
Connection experiment pipeline, closes all valves.Wherein, reactor charging aperture connection nitrogen, reactor exhaust outlet is successively
Connect wide-mouth bottle and vavuum pump.The thermocouple of reactor, belt, test the speed circle, condensed water are connected, open condensed water.
With nitrogen pump drainage 3 times：The ball-type funnel cock on wide-mouth bottle is opened, starts vavuum pump, opens reactor exhaust outlet,
Ball-type funnel cock is closed, after continuing 1~2min, reactor exhaust outlet is closed, opens ball-type funnel cock, close vavuum pump；
Nitrogen valve is slowly opened, nitrogen is passed through into kettle, lasts about half a minute.So operate 3 times repeatedly.
Slowly the gas in nitrogen pipeline is discharged, nitrogen pipeline is unloaded from reactor charging aperture；Feed pump is discharged
Mouth is connected with reactor charging aperture.
Reactor controller is opened, rotating speed 700rpm, 80 DEG C of temperature are set.
After temperature is increased to 80 DEG C and stabilization, two kinds of gaseous state lists of tetrafluoroethene and hexafluoropropene are passed through into reactor
Body, charging rate are respectively 209.0g/h and 112.5g/h, and the two mass ratio is 65：35, until pressure reaches in kettle
4.5MPa。
12.1g ammonium persulfate solutions (ammonium persulfate concentrations 0.21g/mL) are added in reactor；Ammonium persulfate is molten
The addition speed of liquid is 12.1g/h.
Two kinds of gaseous monomers are continually fed into according to the above ratio, system is maintained 4.5MPa, polymerization time 4h.
After stopping charging 30 minutes, reactor controller and feed pump are closed, but ensures that condensed water is always maintained at what is opened
State.
Test the speed circle, thermocouple, belt on reactor is taken down rapidly, reactor is taken out rapidly from heating mantle, put
In screw clamp, rinsed with running water on the outside of reactor, system is cooled.
Treat that temperature drops to room temperature, after reactor pressure keeps 20min constant, close condensed water.
Plastic bottle equipped with ethanol is connected to reactor exhaust outlet, pressure gauge registration is observed, slowly opens exhaust outlet, make
Pressure gauge reading is zero；Reactor inlet valve is opened, pressure in pipeline is reduced to zero.The valve closed on reactor.
Gained emulsion will be polymerize, use MgCl2Solution is demulsified, and obtains solid product；Solid product is washed with deionized, and
It is dried in vacuo at 100 DEG C, produces poly- (hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)) solid.
Gained binary fluoropolymer product 100g is added in irradiation tube, while adds polarity grafted monomers polyethylene glycol dipropyl
Olefin(e) acid ester (molecular weight 700) 40g, ethanol 320g, 0.12% six ferrous sulfate hydrate ammonium salt solution 90g, by 10 minutes logical nitrogen
Sealed after gas deoxygenation.
At room temperature using electron radiation accelerator carry out co segregation polymerisation, to setting dose of radiation 80kGy,
Irradiation stops after 1 minute.
Obtained graft modification rheological agent is repeatedly washed with deionized water, 3% watery hydrochloric acid, places into 80 DEG C of vacuum drying chamber
Dry to constant weight.
Above-mentioned products therefrom is granulated (0.5~3mm) surface modified fluoride-containing rheological agent particulate is made.
Embodiment 6：
In 250mL stainless steel cauldrons, 150mL deionized waters, 0.114g perfluorooctanoic acid solids are sequentially added.
Connection experiment pipeline, closes all valves.Wherein, reactor charging aperture connection nitrogen, reactor exhaust outlet is successively
Connect wide-mouth bottle and vavuum pump.The thermocouple of reactor, belt, test the speed circle, condensed water are connected, open condensed water.
With nitrogen pump drainage 3 times：The ball-type funnel cock on wide-mouth bottle is opened, starts vavuum pump, opens reactor exhaust outlet,
Ball-type funnel cock is closed, after continuing 1~2min, reactor exhaust outlet is closed, opens ball-type funnel cock, close vavuum pump；
Nitrogen valve is slowly opened, nitrogen is passed through into kettle, lasts about half a minute.So operate 3 times repeatedly.
Slowly the gas in nitrogen pipeline is discharged, nitrogen pipeline is unloaded from reactor charging aperture；Feed pump is discharged
Mouth is connected with reactor charging aperture.
Reactor controller is opened, rotating speed 700rpm, 80 DEG C of temperature are set.
After temperature is increased to 80 DEG C and stabilization, two kinds of gaseous state lists of tetrafluoroethene and hexafluoropropene are passed through into reactor
Body, charging rate are respectively 209.0g/h and 112.5g/h, and the two mass ratio is 65：35, until pressure reaches in kettle
4.5MPa。
12.1g ammonium persulfate solutions (ammonium persulfate concentrations 0.21g/mL) are added in reactor；Ammonium persulfate is molten
The addition speed of liquid is 12.1g/h.
Two kinds of gaseous monomers are continually fed into according to the above ratio, system is maintained 4.5MPa, polymerization time 4h.
After stopping charging 30 minutes, reactor controller and feed pump are closed, but ensures that condensed water is always maintained at what is opened
State.
Test the speed circle, thermocouple, belt on reactor is taken down rapidly, reactor is taken out rapidly from heating mantle, put
In screw clamp, rinsed with running water on the outside of reactor, system is cooled.
Treat that temperature drops to room temperature, after reactor pressure keeps 20min constant, close condensed water.
Plastic bottle equipped with ethanol is connected to reactor exhaust outlet, pressure gauge registration is observed, slowly opens exhaust outlet, make
Pressure gauge reading is zero；Reactor inlet valve is opened, pressure in pipeline is reduced to zero.The valve closed on reactor.
Gained emulsion will be polymerize, use MgCl2Solution is demulsified, and obtains solid product；Solid product is washed with deionized, and
It is dried in vacuo at 100 DEG C, produces poly- (hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)) solid.
Gained binary fluoropolymer product 50g is added in irradiation tube, while adds polarity grafted monomers ethyl acetoacetate
40g, ethanol 460g and 0.12% copper-bath 86g, sealed after logical nitrogen deoxygenation in 10 minutes.
At room temperature using electron radiation accelerator carry out co segregation polymerisation, to setting dose of radiation 80kGy,
Irradiation stops after 1 minute.
Obtained graft modification rheological agent is repeatedly washed with deionized water, 3% watery hydrochloric acid, places into 80 DEG C of vacuum drying chamber
Dry to constant weight.
Above-mentioned products therefrom is granulated (0.5~3mm) surface modified fluoride-containing rheological agent particulate is made.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (14)
1. a kind of preparation method of fluoropolymer modifier, it is characterised in that comprise the following steps：
S1 synthesizes binary fluoropolymer by the method for emulsion polymerization；
The solution of binary fluoropolymer and grafted monomers, solvent and polymerization inhibitor composition is radiated and carries out table by S2 by high-energy ray
Face graft modification, gained mixture is scrubbed, filters, dries, being granulated, and the fluoropolymer modifier particulate that surface is modified is made；
The binary fluoropolymer, grafted monomers, the ratio between the dosage of solvent and polymerization inhibitor are：10:1:50:0.01~50:6:
90:1；During the surface graft modification, high-energy ray is electron beam high-energy ray, and dose of radiation is 10~100kGy, spoke
The time penetrated is 1min~1h.
2. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that the polymerization inhibitor is inorganic metal
Salt.
3. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that the solvent is by deionization
Water, ethanol, isopropanol, butanol, acetone, methyl iso-butyl ketone (MIBK) and cyclohexanone form at least one of group.
4. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that the grafted monomers at least contain
One carbon-carbon double bond or at least containing a polar monomer for being capable of function dough, enables grafted monomers to be grafted on fluoropolymer
On thing.
5. the preparation method of fluoropolymer modifier according to claim 4, it is characterised in that the grafted monomers are carboxylic acid
Ester, carboxylic acyloxy base ester, epoxide, cyclic lactone or the polyethylene glycol containing double bond.
6. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that in the emulsion polymerization process,
Emulsifier concentration is higher than critical micelle concentration, emulsifying agent be by APEO analog anion surfactants, sulfate the moon from
Sub- surfactant and fluorocarbon surfactant form at least one of group；Solvent is by deionized water, ethanol, isopropyl
Alcohol, butanol, acetone, methyl iso-butyl ketone (MIBK) and cyclohexanone form at least one of group；Initiator be by persulfuric acid ammonium salt,
Alkali sulfite earth metal salt, alkali pyrophosphate earth metal salt and alkali metal salts form at least one of group.
7. the preparation method of fluoropolymer modifier according to claim 6, it is characterised in that in the emulsion polymerization process,
The deoxygenation of reaction overall process, nitrogen protection, 40~120 DEG C, 3~8MPa of pressure of temperature, 1~24 hour time, mixing speed 200~
1000 revs/min.
8. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that in the binary fluoropolymer
Molecular mass containing fluorine element is more than the 60% of binary fluoropolymer gross mass, and the molecular weight of the binary fluoropolymer is 10
~100 ten thousand.
9. the preparation method of fluoropolymer modifier according to claim 8, it is characterised in that the binary fluoropolymer is
It is copolymerized by vinylidene fluoride/hexafluoropropylene copolymer, vinylidene fluoride/tetrafluoroethylene copolymer and tetrafluoroethylene/hexafluoropropylene
Thing forms at least one of colony.
10. the preparation method of fluoropolymer modifier according to claim 9, it is characterised in that the vinylidene fluoride/hexafluoro
In propylene copolymer：65~85wt% of vinylidene fluoride, 15~35wt% of hexafluoropropene；Vinylidene fluoride/the tetrafluoroethene
In copolymer：60~80wt% of vinylidene fluoride, 20~40wt% of tetrafluoroethene；The tetrafluoroethylene/hexafluoropropylene copolymer
In：50~80wt% of tetrafluoroethene, 20~50wt% of hexafluoropropene.
11. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that the surface graft modification mistake
Cheng Zhong, dose of radiation are 20~80kGy, and radiated time is 1~30 minute.
12. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that the mixture is washed
Cheng Zhong, detergent are by 1~5wt% inorganic acid, water, methanol, ethanol, acetic acid, n-butanol, tetrahydrofuran, methyl formate, three
Butylamine, MEK and ethyl acetate form at least one of group.
13. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that the mixture is dried
Cheng Zhong：60~120 DEG C of drying temperature, 6~12 hours drying times.
14. the preparation method of fluoropolymer modifier according to claim 1, it is characterised in that final obtained surface is modified
The mean particle dia of fluoropolymer modifier particulate be 0.5~5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610533631.9A CN107586389A (en) | 2016-07-07 | 2016-07-07 | A kind of preparation method of fluoropolymer modifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610533631.9A CN107586389A (en) | 2016-07-07 | 2016-07-07 | A kind of preparation method of fluoropolymer modifier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107586389A true CN107586389A (en) | 2018-01-16 |
Family
ID=61046499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610533631.9A Pending CN107586389A (en) | 2016-07-07 | 2016-07-07 | A kind of preparation method of fluoropolymer modifier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107586389A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021129336A1 (en) * | 2019-12-26 | 2021-07-01 | 浙江佳华精化股份有限公司 | Method for preparing fluorine-containing polymer processing aid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286157A (en) * | 2011-06-20 | 2011-12-21 | 上海鲁聚聚合物技术有限公司 | Fluoropolymer processing aid, silane cross-linked polyethylene composition containing fluoropolymer processing aid and application of fluoropolymer processing aid |
| CN102399407A (en) * | 2010-09-15 | 2012-04-04 | 中国石油天然气股份有限公司 | Method for preparing modified fluorine-containing processing aid |
-
2016
- 2016-07-07 CN CN201610533631.9A patent/CN107586389A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399407A (en) * | 2010-09-15 | 2012-04-04 | 中国石油天然气股份有限公司 | Method for preparing modified fluorine-containing processing aid |
| CN102286157A (en) * | 2011-06-20 | 2011-12-21 | 上海鲁聚聚合物技术有限公司 | Fluoropolymer processing aid, silane cross-linked polyethylene composition containing fluoropolymer processing aid and application of fluoropolymer processing aid |
Non-Patent Citations (1)
| Title |
|---|
| 李晓，等: "γ射线共辐照接枝聚偏氟乙烯超滤膜表面亲水性研究", 《辐射研究与辐射工艺学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021129336A1 (en) * | 2019-12-26 | 2021-07-01 | 浙江佳华精化股份有限公司 | Method for preparing fluorine-containing polymer processing aid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1904539B1 (en) | Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant | |
| EP1392744B1 (en) | Emulsifier free aqueous emulsion polymerization process for making fluoropolymers | |
| EP1556426B1 (en) | Emulsifier free aqueous emulsion polymerization to produce copolymers of a fluorinated olefin and hydrocarbon olefin | |
| EP3500603B1 (en) | Fluoropolymers comprising tetrafluoroethylene and one or more perfluorinated alkyl allyl ether comonomers | |
| US20070072985A1 (en) | Method of making a fluoropolymer | |
| JP2013542308A5 (en) | ||
| WO1995008598A1 (en) | Aqueous dispersion of vinylidene fluoride polymer and process for producing the same | |
| JP3640415B2 (en) | Polytetrafluoroethylene micropowder and methods for producing and using them | |
| EP2310430B1 (en) | Melt-flowable fluoropolymer comprising repeating units arising from tetrafluoroethylene and a hydrocarbon monomer having a functional group and a polymerizable carbon-carbon double bond | |
| WO2014088820A1 (en) | Highly fluorinated polymers | |
| CN110713564A (en) | Wide-temperature-range perfluoroether rubber and synthesis method thereof | |
| US4186121A (en) | Process for obtaining colloidal dispersion of polymeric tetrafluoroethylene | |
| CN115677936A (en) | Preparation method of perfluoropolymer emulsion, perfluoroelastomer and preparation method of perfluoroelastomer | |
| EP2310429B1 (en) | Non-melt-flowable perfluoropolymer comprising repeating units arising from tetrafluoroethylene and a monomer having a functional group and a polymerizable carbon-carbon double bond | |
| CN107586389A (en) | A kind of preparation method of fluoropolymer modifier | |
| TW553956B (en) | Aqueous emulsion polymerization process for the manufacturing of fluoropolymers | |
| EP0774473B1 (en) | Tetrafluoroethylene polymer for improved paste extrusion | |
| US4189551A (en) | Process for reducing adhesions during suspension polymerization | |
| CN106543371A (en) | A kind of tube material modified fluoride-containing rheological agent and its application | |
| CN115678180B (en) | Preparation method of high-impact polyvinyl chloride | |
| CN106543370A (en) | The preparation method of fluoropolymer modifier microgranule | |
| KR102132753B1 (en) | Vinyl chloride polymer and preparation method thereof | |
| JPS61205A (en) | Production of vinyl chloride resin for paste technique | |
| CN104693337A (en) | Synthetic method for tetrafluoroethylene-propylene copolymer crude rubber | |
| JPS61206A (en) | Production of vinyl chloride resin for paste technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180116 |
|
| WD01 | Invention patent application deemed withdrawn after publication |