CN103709306A - Nano emulsion of peroxide vulcanized fluororubber and polymerization method thereof - Google Patents
Nano emulsion of peroxide vulcanized fluororubber and polymerization method thereof Download PDFInfo
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Abstract
The invention discloses a production method of a peroxide vulcanized fluoroelastomer, which comprises the following steps: 1. preparing three fluorine-containing monomer gases, a dispersant, a peroxide vulcanization point monomer, an initiator, a chain-transfer agent, a pH regulator and deionized water; 2. regulating pH value of a dispersion solution mixed from the deionized water, dispersant solution, initiator, chain-transfer agent and pH regulator, evacuating, replacing with nitrogen until the oxygen content is acceptable, and pouring the dispersion solution into a polymerization kettle; 3. collecting the three fluorine-containing monomer gases to a pressostat to keep the pressures of the three gases constant in the pressostat; 4. respectively passing the three fluorine-containing monomer gases through an adjusting valve and a mass flowmeter, evenly mixing in a static mixer, compressing to reaction pressure by a molding press, and sending into the polymerization kettle; 5. adding the peroxide vulcanization point monomer into a measuring pump; and 6. adding the peroxide vulcanization point monomer into the polymerization kettle to perform polymerization reaction with the three fluorine-containing monomer gases in the dispersion solution.
Description
Technical field
The present invention relates to a kind of nanoemulsions and polymerization process thereof of peroxide cure viton.
Background technology
Fluoropolymer refers to the superpolymer that is connected with fluorine atom on carbon atom.The characteristics such as that fluoropolymer material has is heat-resisting, oil resistant, resistance to solvent, corrosion-resistant, powerful oxidation corrosion resistance agent, and there is good physical and mechanical properties, be widely used in many fields such as space flight and aviation, military project, national defence, automobile, petroleum and chemical industry.
At present, prepare the most frequently used method of fluoropolymer and comprise suspension polymerization and emulsion polymerization.In aqueous emulsion polymerization; polyreaction is carried out existing in situation of perfluor emulsifying agent; normally used emulsifying agent PFOS(PFO sulfonyl compound) and PFOA(ammonium perfluorocaprylate) highly stable, be difficult to degrade in environment, very big to ecosystem destructive force.European Union is formal enforcement PFOS ban in 27 days June in 2008, production and the use of restriction PFOS class material, and EPA also requires to stop producing completely for 2015 PFOA.And PFOS and PFOA when letex polymerization, it can only be dispersed into 150nm～300nm by polymerization median size, if improve stirring intensity, can cause breakdown of emulsion, therefore the preparation means of conventional fluoropolymer is restricted, nanoemulsions polymerization is as an important branch of letex polymerization, it has the not available advantage of conventional emulsion polymerization, is a technical way that substitutes conventional emulsion polymerization.
Nanoemulsions is proposed in nineteen forty-three by Hear and Schalmer the earliest.The appearance transparent being formed by water, tensio-active agent and cosurfactant, thermodynamically stable profit dispersion system.The droplet diameter of disperse phase is within the scope of 10-100nm.Wherein cosurfactant is polar organic matter, generally adopts alcohols.In nanoemulsions system, it is by one deck laminated film of emulsifying agent and assistant for emulsifying agent formation and interfacial layer, to maintain that it is stable that microballon drips.
Nanoemulsions is thermodynamic stable system, and monomers all in this system are all in micella.When surfactant concentration is higher, micella may form the micella of co-continuous network rather than dispersion.Nanoemulsions polymerization is exactly the polyreaction (adopting water-soluble or oil-soluble initiator) of the monomer in nanoemulsions.The particulate that this polymerization produces is especially little, distribution diameter 10 to 100nm.While being rich in water in system, oil phase is scattered in external phase with the uniform globule form of dripping, and forms O/W type positive nanoemulsions, and in nanoemulsions system, emulsifying agent and assistant for emulsifying agent is dense, and monomer concentration is very low.Monomer is mainly scattered in water with the microballon form of dripping, and is present in interfacial layer on a small quantity.The major part of assistant for emulsifying agent is present in interfacial layer, and some is dissolved in monomer bead and water simultaneously.Compare with conventional emulsion polymerization, the emulsion Ion Phase of nanoemulsions polymerization gained than droplet diameter at 10～100nm, appearance transparent, thermodynamically stable profit dispersion system.
While adopting nanoemulsions polymerization technique to prepare viton, formed nanoemulsions particle diameter≤100nm, can obtain contact area by augmenting response thing, thereby improves speed of reaction, when carrying out multi-component copolymer, is more conducive to low activity monomer and participates in copolyreaction.
CN101274969B has described a kind of microemulsion polymerization method of fluoropolymer, it adopts ammonium perfluorocaprylate or perfluoro-pelargonic acid ammonium is emulsifying agent, and the alkanol of non-fluorine is co-emulsifier, and the microemulsion solid content of gained is lower than 10%, therefore cause the utilization ratio of equipment greatly to reduce, affect production efficiency.
Summary of the invention
The invention provides a kind of nanoemulsions and polymerization process thereof of peroxide cure viton, it had both realized the environmental friendliness when preparing fluoropolymer, realized again peroxide cure viton when carrying out letex polymerization, make latex particle reach nano-scale, realize peroxide cure viton and carry out nanoemulsions polymerization.Selected perfluoroalkyl ethers or perfluoro alkoxy ether are introduced in viton molecular structure, have increased the snappiness of viton molecule, have improved the winter hardiness of viton goods, have expanded the Application Areas of viton.
The present invention has adopted following technical scheme: a kind of nanoemulsions of viton of peroxide cure, comprises following component: fluorochemical monomer, peroxide cure point monomer, fluorine ether emulsifying agent, assistant for emulsifying agent, initiator, chain-transfer agent and pH adjusting agent.
Described fluorochemical monomer is vinylidene, tetrafluoroethylene, R 1216, perfluoroalkyl ethers or perfluoro alkoxy ether, and described perfluoroalkyl ethers or perfluoro alkoxy ether molecule skeleton symbol are: CF2=CFO (CF2CF2O) nRf; The integer that wherein n is 0～5, and Rf is the perfluoroalkyl of 1～6 carbon atom.Described peroxide cure point monomer is can vulcanize and put a monomer with fluorochemical monomer copolymerization containing bromine or iodine; Chain-transfer agent containing bromine or iodine.Described fluorine ether emulsifying agent is at least one fluorochemical surfactant and the PFPE that contains at least one carboxylic acid, carboxylate salt, sulfonic acid or sulfonate end group.Described assistant for emulsifying agent is that molecular-weight average is that the PFPE of 200～5000 perfluoroalkyl end groups or alkylsulfonate are if sodium octyl, alkyl-sulphate are if sodium lauryl sulphate, alkyl carboxylate are as sodium stearate; Nonionogenic tenside nonyl phenol polyethylene oxide.The PFPE molecular structure skeleton symbol of described perfluoroalkyl end group is following one or more.Described initiator (E) is for example Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen persulfate ammonium, hydrogen persulfate sodium and potassium hydrogen persulfate of water-soluble peroxide.Described chain-transfer agent is Virahol, diethyl malonate, ethyl acetate, tetracol phenixin, acetone and Dodecyl Mercaptan.Described pH adjusting agent (G) is phosphoric acid salt or acetate buffer.
The polymerization process of the nanoemulsions of the viton of a kind of peroxide cure of the present invention, concrete steps are as follows:
Step 1, in the polymerization process of the nanoemulsions of the viton of peroxide cure of the present invention, is pressed into required initial mixing monomer in the reactor of the water and milk dispersion being comprised of deionized water and part of auxiliary.Deionized water and auxiliary agent are filled in reactor by a certain amount of in reactor; Step 2 when initial mix monomer all adds after reactor, then is added mix monomer by compressor in reactor, now can add the required auxiliary agent of polyreaction according to polyreaction process.The copolymerization rate of every kind of fluorochemical monomer is different, therefore should set the relative content of every kind of described fluorochemical monomer, so that the ratio that fluoroelastomer keeps the copolymerization fluorochemical monomer of desired properties to have; Step 3, in polyreaction whole process, adds and adds mix monomer and can peroxide cure point monomer with controlled speed, to keep constant reactor pressure under controllable temperature.By the relative ratios who adds contained monomer in mix monomer charging be set as with gained fluoropolymer in comonomer unit required ratio about equally.The amount of the polymkeric substance generating approximately equates with the semi-invariant of incremental monomer feed.In the polymerisation process of the nanoemulsions of the viton of peroxide cure, the time of polyreaction is conventionally in 1～15 hour.
The present invention has following beneficial effect: compared with prior art, the beneficial effect of technical scheme of the present invention is as follows: the selected peroxide cure point monomer (B) of the present invention for containing bromine or iodine can with the sulfuration point monomer of fluorochemical monomer copolymerization; Chain-transfer agent containing bromine or iodine, it has guaranteed can carry out copolyreaction with fluorochemical monomer, realize the reactive group of introducing peroxide curable on fluoroelastomer molecular structure, thereby guarantee that fluoroelastomer can carry out free radical curing, realizes mechanical property and the processing characteristics of fluoroelastomer excellence.Selected fluorine ether emulsifying agent (C) is at least one fluorochemical surfactant and the PFPE that contains at least one carboxylic acid, carboxylate salt, sulfonic acid or sulfonate end group.Described assistant for emulsifying agent (D) for molecular-weight average be the PFPE of 200～5000 perfluoroalkyl end groups.Both realized the environmental friendliness when preparing fluoropolymer, realized again peroxide cure viton when carrying out letex polymerization, make latex particle reach nano-scale, realize peroxide cure viton and carry out nanoemulsions polymerization, the polyreaction of peroxide cure viton is more easy to control, reduce the requirement to polymerization equipment, more easily realized industrialization.Selected perfluoroalkyl ethers or perfluoro alkoxy ether are introduced in viton molecular structure, have increased the snappiness of viton molecule, have improved the winter hardiness of viton goods, have expanded the Application Areas of viton.
Accompanying drawing explanation
Fig. 1 is the nanoemulsions polymerization process schema of peroxide cure viton of the present invention.
Embodiment
In Fig. 1, the invention provides a kind of nanoemulsions of viton of peroxide cure, comprise following component: fluorochemical monomer, peroxide cure point monomer, fluorine ether emulsifying agent, assistant for emulsifying agent, initiator, chain-transfer agent and pH adjusting agent, described fluorochemical monomer is vinylidene, tetrafluoroethylene, R 1216, perfluoroalkyl ethers or perfluoro alkoxy ether, and described perfluoroalkyl ethers or perfluoro alkoxy ether molecule skeleton symbol are: CF2=CFO (CF2CF2O) nRf; The integer that wherein n is 0～5, and Rf is the perfluoroalkyl of 1～6 carbon atom, described peroxide cure point monomer for containing bromine or iodine can with a fluorochemical monomer copolymerization sulfuration point monomer; Chain-transfer agent containing bromine or iodine, described fluorine ether emulsifying agent is at least one fluorochemical surfactant and the PFPE that contains at least one carboxylic acid, carboxylate salt, sulfonic acid or sulfonate end group, and described assistant for emulsifying agent is that molecular-weight average is that the PFPE of 200～5000 perfluoroalkyl end groups or alkylsulfonate are if sodium octyl, alkyl-sulphate are if sodium lauryl sulphate, alkyl carboxylate are as sodium stearate; Nonionogenic tenside nonyl phenol polyethylene oxide, the PFPE molecular structure skeleton symbol of described perfluoroalkyl end group is following one or more, described initiator (E) is for example Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen persulfate ammonium, hydrogen persulfate sodium and potassium hydrogen persulfate of water-soluble peroxide, described chain-transfer agent is Virahol, diethyl malonate, ethyl acetate, tetracol phenixin, acetone and Dodecyl Mercaptan, and described pH adjusting agent (G) is phosphoric acid salt or acetate buffer.
The peroxide cure viton being made by method of the present invention includes but not limited to comprise following comonomer and combines: (1) vinylidene, R 1216, tetrafluoroethylene and 4-are bromo-3,3,4,4-tetrafluoro-1-butylene; (2) vinylidene, R 1216, tetrafluoroethylene and 4-are iodo-3,3,4,4-tetrafluoro-1-butylene; (3) vinylidene, perfluor (methyl ethylene) ether, tetrafluoroethylene and 4-are bromo-3,3,4,4-tetrafluoro-1-butylene; (4) vinylidene, perfluor (methyl ethylene) ether, tetrafluoroethylene and 4-are iodo-3,3,4,4-tetrafluoro-1-butylene; (5) tetrafluoroethylene, perfluor (methyl ethylene) ether and 4-are bromo-3,3,4,4-tetrafluoro-1-butylene.Described peroxide cure point monomer (B) is can vulcanize and put a monomer with fluorochemical monomer copolymerization containing bromine or iodine; Chain-transfer agent containing bromine or iodine.The preferred bromotrifluoethylene of peroxide cure point monomer; 4-is bromo-3,3,4,4-tetrafluoro-1-butylene; Bromine ethene; 1-is bromo-2,2-difluoroethylene; Hexafluoropropylene-based bromine; 4-is bromo-1,1, the fluoro-1-butylene of 2-tri-; 4-is bromo-1,1,3,3,4,4-hexafluoro butylene; The bromo-3-of 4-is chloro-1,1,3,4,4-five fluorine butylene; 6-is bromo-5,5,6,6-tetrafluoro hexene; 4-bromine perfluor-1-butylene and 3,3-difluoro propenyl bromine; Iodoethylene, 4-are iodo-3,3,4,4-tetrafluoro-1-butylene; 3-chlorine-4-iodine-3,4,4-trifluoro butylene; 2-is iodo-1,1,2,2-tetrafluoro-1-(vinyloxy group) ethane; Methylene iodide; Isosorbide-5-Nitrae-diiodo perfluo-normal butane; 1,6-bis-is iodo-3,3,4,4-tetrafluoro hexane; The bromo-2-iodine of 1-R 116; The bromo-3-iodine of 1-perfluoropropane; The iodo-2-of 1-is bromo-1,1-C2H4F2 C2H4F2.Described fluorine ether emulsifying agent (C) is at least one fluorochemical surfactant and the PFPE that contains at least one carboxylic acid, carboxylate salt, sulfonic acid or sulfonate end group.
Wherein fluorine ether emulsifying agent (C) molecular structure skeleton symbol is:
Rf-[OCF
2CF(CF
3)]
n-OCF
2COOM
The integer that wherein n is 2～5;
M is H, NH
4, basic metal;
Rf is 2～8 perfluoro alkane.
Described assistant for emulsifying agent (D) for molecular-weight average be that the PFPE of 200～5000 perfluoroalkyl end groups or alkylsulfonate are if sodium octyl, alkyl-sulphate are if sodium lauryl sulphate, alkyl carboxylate are as sodium stearate; Nonionogenic tenside nonyl phenol polyethylene oxide.
The PFPE molecular structure skeleton symbol of perfluoroalkyl end group is following one or more:
(1)?RfO[CF(CF
3)CF
2O]
x[CF(CF
3)O]
y(OCF
2)
z?Rf
‘
Wherein x, y, z is the numerical value that meets molecular-weight average;
Rf and Rf
'for identical or different CF
3, C
2f
5, C
3f
7group.
(2)?RfO[CF
2CF
2O]?
x[CF(CF
3)?O]
y(OCF
2)
z[CF(CF
3)CF
2O]?
wRf
‘
Wherein x, y, z, w are the numerical value that meets molecular-weight average;
Rf and Rf
'for identical or different CF
3, C
2f
5, C
3f
7group.
(3)?RfO[CF(CF
3)CF
2O]
xRf
‘
Wherein x is the numerical value that meets molecular-weight average;
Rf and Rf
'for identical or different C
2f
5, C
3f
7group.
(4)?RfO[CF
2CF
2O]?
x(OCF
2)
yRf
‘
Wherein x, y are the numerical value that meets molecular-weight average;
Rf and Rf
'for identical or different CF
3, C
2f
5, C
3f
7group.
Described initiator (E) is for example Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen persulfate ammonium, hydrogen persulfate sodium and potassium hydrogen persulfate of water-soluble peroxide.
Described chain-transfer agent (F) is Virahol, diethyl malonate, ethyl acetate, tetracol phenixin, acetone and Dodecyl Mercaptan.Described pH adjusting agent (G) is phosphoric acid salt or acetate buffer.
The polymerization process of the nanoemulsions of the viton of a kind of peroxide cure of the present invention, concrete steps are as follows:
Step 1, in the polymerization process of the nanoemulsions of the viton of peroxide cure of the present invention, is pressed into required initial mixing monomer in the reactor of the water and milk dispersion being comprised of deionized water and part of auxiliary.Deionized water and auxiliary agent are filled in reactor by a certain amount of in reactor;
Step 2 when initial mix monomer all adds after reactor, then is added mix monomer by compressor in reactor, now can add the required auxiliary agent of polyreaction according to polyreaction process.The copolymerization rate of every kind of fluorochemical monomer is different, therefore should set the relative content of every kind of described fluorochemical monomer, so that the ratio that fluoroelastomer keeps the copolymerization fluorochemical monomer of desired properties to have;
Step 3, in polyreaction whole process, adds and adds mix monomer and can peroxide cure point monomer with controlled speed, to keep constant reactor pressure under controllable temperature.By the relative ratios who adds contained monomer in mix monomer charging be set as with gained fluoropolymer in comonomer unit required ratio about equally.The amount of the polymkeric substance generating approximately equates with the semi-invariant of incremental monomer feed.In the polymerisation process of the nanoemulsions of the viton of peroxide cure, the time of polyreaction is conventionally in 1～15 hour.
Further illustrate the polymerization process of nanoemulsions of the viton of peroxide cure of the present invention below:
Step 1, in the polymerization process of the nanoemulsions of the viton of peroxide cure of the present invention, is pressed into required initial mixing monomer in the reactor of the water and milk dispersion being comprised of deionized water and part of auxiliary.Deionized water and auxiliary agent are filled in reactor by a certain amount of in reactor, and one or more in a certain amount of vinylidene, tetrafluoroethylene, R 1216, perfluoroalkyl ethers or perfluoro alkoxy ether of described initial mixing monomer form.Control initial mixing monomer amount so that the pressure of reactor between 1～8MPa, the fluorine ether emulsifying agent (C) that described water and milk dispersion comprises at least one the above-mentioned type and assistant for emulsifying agent (D).For controlling the pH value of polyreaction emulsion, described water and milk dispersion pH adjusting agent (G), as phosphoric acid salt or acetate buffer.According to the nanoemulsions of the viton of prepared peroxide cure, pH value is controlled between 3～7.PH adjusting agent (G) also can join at the different time of polyreaction whole process in reactor, can add separately or add together with other component, described water and milk dispersion also comprises above-mentioned initiator (E) as Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen persulfate ammonium, hydrogen persulfate sodium and potassium hydrogen persulfate, described concrete operation step is: open and stir, pass into heating medium, material in reactor is risen to the temperature of regulation, temperature remains on 25 ℃～130 ℃, in the scope of preferably 50 ℃～100 ℃; Start compressor to the initial monomer that is pressed into specified amount in still, when the group of initiator thermolysis gained reacts with the fluorochemical monomer of dispersion, now polyreaction starts to carry out, and the pressure declining in reactor, by the continuous supply of compressor, makes polyreaction continue to carry out.
Step 2 all adds after reactor when initial mix monomer, then in reactor, adds mix monomer by compressor, now can add the required auxiliary agent of polyreaction according to polyreaction process.The copolymerization rate of every kind of fluorochemical monomer is different, therefore should set the relative content of every kind of described fluorochemical monomer, so that the ratio that fluoroelastomer keeps the copolymerization fluorochemical monomer of desired properties to have.
Step 3, in polyreaction whole process, adds and adds mix monomer and can peroxide cure point monomer with controlled speed, to keep constant reactor pressure under controllable temperature.By the relative ratios who adds contained monomer in mix monomer charging be set as with gained fluoropolymer in comonomer unit required ratio about equally.The amount of the polymkeric substance generating approximately equates with the semi-invariant of incremental monomer feed.In the polymerisation process of the nanoemulsions of the viton of peroxide cure, the time of polyreaction is conventionally in 1～15 hour.
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only for further illustrating of the present invention; can not be interpreted as limiting the scope of the invention, these those skilled in the art can content make some nonessential improvement and adjustment to the present invention according to the present invention.
Embodiment 1
In 10L reactor, add 6kg deionization, 60g fluorine ether emulsifying agent (C
2f
5[OCF
2cF (CF
3)]
3oCF
2cOONH
4), 3g Sodium phosphate dibasic, 10g molecular weight be 600 molecular structure is (1) assistant for emulsifying agent, opens steam regulating valve, and deionized water in reactor is warming up to 80 ℃, pass into high pure nitrogen and vacuumize oxygen level displacement in reactor to≤30ppm.Subsequently by compressor under 3.5MPa pressure, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 45% by massfraction, massfraction are 5%, massfraction are 50%.Adding massfraction is 10% potassium persulfate solution 300g, initiated polymerization, polymerization pressure declines, add again mix monomer, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 55% by massfraction, massfraction are 10%, massfraction are 35% is pressed into reactor by compressor, keeps this pressure and temperature reaction.After reaction 30min, bromo-3,3,4 by the volume pump 4-that to add containing massfraction be 10%, 4-tetrafluoro-1-butylene, containing massfraction, be the aqueous solution 10g of 1% fluorine ether emulsifying agent.Every 2 hours, adding massfraction is 10% potassium persulfate solution 100g, when adding mix monomer amount, reaches 3kg, reaction times 10h.Gained nanoemulsions polymer solids level 30%.
Embodiment 2
In 20L reactor, add 12kg deionization, 130g fluorine ether emulsifying agent (C
2f
5[OCF
2cF (CF
3)]
3oCF
2cOONH
4), 6g Sodium phosphate dibasic, 20g molecular weight be 600 molecular structure is (1) assistant for emulsifying agent, opens steam regulating valve, and deionized water in reactor is warming up to 80 ℃, pass into high pure nitrogen and vacuumize oxygen level displacement in reactor to≤30ppm.Subsequently by compressor under 3.5MPa pressure, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 45% by massfraction, massfraction are 5%, massfraction are 50%.Adding massfraction is 10% potassium persulfate solution 600g, initiated polymerization, polymerization pressure declines, add again mix monomer, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 55% by massfraction, massfraction are 10%, massfraction are 35% is pressed into reactor by compressor, keeps this pressure and temperature reaction.After reaction 30min, bromo-3,3,4 by the volume pump 4-that to add containing massfraction be 10%, 4-tetrafluoro-1-butylene, containing massfraction, be the aqueous solution 20g of 1% fluorine ether emulsifying agent.Every 2 hours, adding massfraction is 10% potassium persulfate solution 200g, when adding mix monomer amount, reaches 6kg, reaction times 10h.Gained nanoemulsions polymer solids level 28.5%.
Embodiment 3
In 50L reactor, add 30kg deionization, 300g fluorine ether emulsifying agent (C
2f
5[OCF
2cF (CF
3)]
3oCF
2cOONH
4), 15g Sodium phosphate dibasic, 50g molecular weight be 600 molecular structure is (1) assistant for emulsifying agent, opens steam regulating valve, and deionized water in reactor is warming up to 80 ℃, pass into high pure nitrogen and vacuumize oxygen level displacement in reactor to≤30ppm.Subsequently by compressor under 3.5MPa pressure, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 45% by massfraction, massfraction are 5%, massfraction are 50%.Adding massfraction is 10% potassium persulfate solution 1500g, initiated polymerization, polymerization pressure declines, add again mix monomer, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 55% by massfraction, massfraction are 10%, massfraction are 35% is pressed into reactor by compressor, keeps this pressure and temperature reaction.After reaction 30min, bromo-3,3,4 by the volume pump 4-that to add containing massfraction be 10%, 4-tetrafluoro-1-butylene, containing massfraction, be the aqueous solution 50g of 1% fluorine ether emulsifying agent.Every 2 hours, adding massfraction is 10% potassium persulfate solution 500g, when adding mix monomer amount, reaches 15kg, reaction times 10h.Gained nanoemulsions polymer solids level 30%.
Embodiment 4
In 100L reactor, add 60kg deionization, 600g fluorine ether emulsifying agent (C
2f
5[OCF
2cF (CF
3)]
3oCF
2cOONH
4), 30g Sodium phosphate dibasic, 100g molecular weight be 600 molecular structure is (1) assistant for emulsifying agent, opens steam regulating valve, and deionized water in reactor is warming up to 80 ℃, pass into high pure nitrogen and vacuumize oxygen level displacement in reactor to≤30ppm.Subsequently by compressor under 3.5MPa pressure, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 45% by massfraction, massfraction are 5%, massfraction are 50%.Adding massfraction is 10% potassium persulfate solution 3000g, initiated polymerization, polymerization pressure declines, add again mix monomer, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 55% by massfraction, massfraction are 10%, massfraction are 35% is pressed into reactor by compressor, keeps this pressure and temperature reaction.After reaction 30min, bromo-3,3,4 by the volume pump 4-that to add containing massfraction be 10%, 4-tetrafluoro-1-butylene, containing massfraction, be the aqueous solution 100g of 1% fluorine ether emulsifying agent.Every 2 hours, adding massfraction is 10% potassium persulfate solution 1000g, when adding mix monomer amount, reaches 30kg, reaction times 10h.Gained nanoemulsions polymer solids level 30%.
Embodiment 5
In 100L reactor, add 60kg deionization, 600g fluorine ether emulsifying agent (C
2f
5[OCF
2cF (CF
3)]
3oCF
2cOONH
4), 30g Sodium phosphate dibasic, 100g molecular weight be 600 molecular structure is (1) assistant for emulsifying agent, opens steam regulating valve, and deionized water in reactor is warming up to 80 ℃, pass into high pure nitrogen and vacuumize oxygen level displacement in reactor to≤30ppm.Subsequently by compressor under 3.5MPa pressure, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 45% by massfraction, massfraction are 5%, massfraction are 50%.Adding massfraction is 10% potassium persulfate solution 3000g, initiated polymerization, polymerization pressure declines, add again mix monomer, the perfluorinated methyl ethylene ether that the tetrafluoroethylene that the vinylidene that is 55% by massfraction, massfraction are 10%, massfraction are 35% is pressed into reactor by compressor, keeps this pressure and temperature reaction.After reaction 30min, bromo-3,3,4 by the volume pump 4-that to add containing massfraction be 10%, 4-tetrafluoro-1-butylene, containing massfraction, be the aqueous solution 100g of 1% fluorine ether emulsifying agent.Every 2 hours, adding massfraction is 10% potassium persulfate solution 1000g, when adding mix monomer amount, reaches 30kg, reaction times 10h.Gained nanoemulsions polymer solids level 30.
Claims (10)
1. a nanoemulsions for the viton of peroxide cure, comprises following component: fluorochemical monomer, peroxide cure point monomer, fluorine ether emulsifying agent, assistant for emulsifying agent, initiator, chain-transfer agent and pH adjusting agent.
2. the nanoemulsions of the viton of peroxide cure according to claim 1, it is characterized in that described fluorochemical monomer is vinylidene, tetrafluoroethylene, R 1216, perfluoroalkyl ethers or perfluoro alkoxy ether, described perfluoroalkyl ethers or perfluoro alkoxy ether molecule skeleton symbol are: CF2=CFO (CF2CF2O) nRf; The integer that wherein n is 0～5, and Rf is the perfluoroalkyl of 1～6 carbon atom.
3. the nanoemulsions of the viton of peroxide cure according to claim 1, it is characterized in that described peroxide cure point monomer for containing bromine or iodine can with a fluorochemical monomer copolymerization sulfuration monomer; Chain-transfer agent containing bromine or iodine.
4. the nanoemulsions of the viton of peroxide cure according to claim 1, is characterized in that described fluorine ether emulsifying agent is at least one fluorochemical surfactant and the PFPE that contains at least one carboxylic acid, carboxylate salt, sulfonic acid or sulfonate end group.
5. the nanoemulsions of the viton of peroxide cure according to claim 1, is characterized in that described assistant for emulsifying agent is that molecular-weight average is that the PFPE of 200～5000 perfluoroalkyl end groups or alkylsulfonate are if sodium octyl, alkyl-sulphate are if sodium lauryl sulphate, alkyl carboxylate are as sodium stearate; Nonionogenic tenside nonyl phenol polyethylene oxide.
6. the nanoemulsions of the viton of peroxide cure according to claim 1, the PFPE molecular structure skeleton symbol that it is characterized in that described perfluoroalkyl end group is following one or more.
7. the nanoemulsions of the viton of peroxide cure according to claim 1, is characterized in that described initiator (E) is for example Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen persulfate ammonium, hydrogen persulfate sodium and potassium hydrogen persulfate of water-soluble peroxide.
8. the nanoemulsions of the viton of peroxide cure according to claim 1, is characterized in that described chain-transfer agent is Virahol, diethyl malonate, ethyl acetate, tetracol phenixin, acetone and Dodecyl Mercaptan.
9. the nanoemulsions of the viton of peroxide cure according to claim 1, is characterized in that described pH adjusting agent (G) is for phosphoric acid salt or acetate buffer.
10. the polymerization process of the nanoemulsions of the viton of a kind of peroxide cure of the present invention, concrete steps are as follows:
Step 1, in the polymerization process of the nanoemulsions of the viton of peroxide cure of the present invention, is pressed into required initial mixing monomer in the reactor of the water and milk dispersion being comprised of deionized water and part of auxiliary;
Deionized water and auxiliary agent are filled in reactor by a certain amount of in reactor;
Step 2 when initial mix monomer all adds after reactor, then is added mix monomer by compressor in reactor, now can add the required auxiliary agent of polyreaction according to polyreaction process;
The copolymerization rate of every kind of fluorochemical monomer is different, therefore should set the relative content of every kind of described fluorochemical monomer, so that the ratio that fluoroelastomer keeps the copolymerization fluorochemical monomer of desired properties to have;
Step 3, in polyreaction whole process, adds and adds mix monomer and can peroxide cure point monomer with controlled speed, to keep constant reactor pressure under controllable temperature;
By the relative ratios who adds contained monomer in mix monomer charging be set as with gained fluoropolymer in comonomer unit required ratio about equally;
The amount of the polymkeric substance generating approximately equates with the semi-invariant of incremental monomer feed;
In the polymerisation process of the nanoemulsions of the viton of peroxide cure, the time of polyreaction is conventionally in 1～15 hour.
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