CN1300192C - Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent - Google Patents
Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent Download PDFInfo
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- CN1300192C CN1300192C CNB2004100665355A CN200410066535A CN1300192C CN 1300192 C CN1300192 C CN 1300192C CN B2004100665355 A CNB2004100665355 A CN B2004100665355A CN 200410066535 A CN200410066535 A CN 200410066535A CN 1300192 C CN1300192 C CN 1300192C
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Abstract
The present invention discloses a preparing method of water dispersed fine emulsion of a complete acrylic ester copolymer for an anti-oil and anti-water agent. Fine emulsion polymerizing technique is adopted; firstly, the dine emulsion of a complete acrylic ester copolymer with uniform and stable dispersing is obtained by ultrasonic fine emulsification mood, etc.; the fine emulsion polymerization of the copolymer relevant to the particle size distribution of monomer fine emulsion is obtained by the fine emulsion polymerization. The addition of an organic solvent for assisting dissolving and the addition of an assisting emulsifying agent are not required. The water dispersed fine emulsion of a complete acrylic ester copolymer prepared by the present invention has the advantages of environmental protection, small average particle diameter of emulsion particles and uniform distribution; the emulsion of a copolymer has the characteristics of good storage stability, good dilution stability and good anti-water performance and anti-oil performance of an emulsions coating film; the fine emulsion can be used as anti-oil and anti-water finishing agent for various keelson such as fabric, leather, paper, etc.
Description
Technical field
The present invention relates to the preparation method of anti-oily water repellent agent with perfluorinated acrylate multipolymer water-dispersion miniemulsion.
Background technology
Up to now, can utilize the energy characteristic of perfluoroalkyl acrylate multipolymer, give the waterproof and oilproof soil-repellent finishing effect of ground excellences such as fabric, leather, paper, the perfluoroalkyl copolymer systems comprises solution-type and emulsion-type, in recent years, consider safety problem and environmental problem, the anti-oily anti-water finishing composition of this class perfluoroalkyl multipolymer mostly is the water-dispersion emulsion-type.
When preparation perfluoroalkyl multipolymer aqueous dispersions, general all is directly to adopt the form of letex polymerization to obtain in aqueous dispersion comonomers such as perfluoroalkyl acrylate, conventional emulsion polymerization is crossed the range request monomer and is moved to micella by drop by water, because the perfluoroalkyl monomer utmost point is insoluble in water, influenced carrying out smoothly of letex polymerization, must add a certain amount of organic solvent (as acetone, Virahol etc.) at aqueous phase and come hydrotropy, (US 0173585, EP 0898011, JP-A-7-173722, JP-A-5-263070).Because the adding of these organic solvents, cause the flash-point of aqueous dispersion to descend, the water-dispersion emulsion still exists environmental problem and potential safety hazard, not emulsion stable not good enough, organic solvent also makes the emulsifying power of tensio-active agent reduce, its consumption is increased, and a large amount of emulsifying agents finally can influence the surface property of multipolymer, they present unstable to heat, light, oxygen, chemical, bring disadvantageous effect also can for the waterproof and oilproof performance of multipolymer, this is to adopt letex polymerization to obtain the common disadvantage of perfluoroalkyl multipolymer water and oil repellent agent at present.
Mini-emulsion polymerization is a kind of novel emulsion polymerisation process that latest developments are got up, it is by adopting thin emulsifying manner to obtain finely dispersed miniemulsion in certain emulsification system, add initiator then and directly in monomer droplet, cause nucleation, each monomer droplet all becomes relatively independent reactor, can avoid the problem of monomer, (US 5686518, US 6160049) in aqueous phase indissoluble and migration.A distinguishing feature of mini-emulsion polymerization will add assistant for emulsifying agent exactly, and as n-Hexadecane, hexadecanol etc., reaching the thin emulsive purpose of monomer, but the existence of assistant for emulsifying agent still can have influence on the performance of product emulsion.
Summary of the invention
Purpose of the present invention just provides the preparation method of a kind of anti-oily water repellent agent with perfluorinated acrylate multipolymer water-dispersion miniemulsion.Adopt the water and oil repellent agent of this method preparation to need not organic solvent, has Safety and Environmental Protection, prepared miniemulsion has good preservation stability and dilution stability, and the film forming properties of being filmed by this multipolymer miniemulsion that resists oily water repellent agent to form is good, waterproof and oilproof performance excellence.
Anti-oily water repellent agent of the present invention is characterized in that may further comprise the steps: in mass percent with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion
1) with the copolymerized monomer mixture of 10-40%, account for the emulsifying agent of monomer total mass 1.0-6.0% and the deionized water mixing stirring 10-30min of 60-90% and obtain pre-emulsion, with resulting pre-emulsion supersound process 1-10min in ultrasonic device, obtain size distribution again at the stable monomer miniemulsion of 30-150nm;
Above-mentioned copolymerized monomer mixture is made up of following four types polymerisable monomer: perfluoroalkyl acrylate, consumption are the 20-60% of monomer total mass; Alkyl acrylate soft monomer, consumption are the 10-60% of monomer total mass; Vinyl hard monomer, consumption are the 10-60% of monomer total mass; Functional monomer, consumption are the 0.5-5% of monomer total mass;
Above-mentioned emulsifying agent is made up of quaternary ammonium salt cationic type tensio-active agent and the nonionogenic tenside that has the polyoxyethylene segment, and wherein cats product accounts for the 20-80% of emulsifying agent total amount;
2) will place a reactor through the monomer miniemulsion that meticulous emulsification obtains, add respectively and account for monomer mass 0.05-1% chain-transfer agent, account for the initiator of monomer mass 0.05-1%, be warming up to 50-90 ℃ of initiated polymerization, reacted 2-6 hour, and be incubated 1-3 hour, by the time monomer conversion reaches 95.0% when above, be cooled to room temperature, obtain after filtration.
Above-mentioned steps 1) consumption of emulsifying agent is preferably the 1-3% that accounts for the monomer total mass in; Cats product preferably accounts for the 40-60% of emulsifying agent total amount; Step 2) initiator that adds in preferably accounts for the 0.2-0.8% of monomer mass.
Among the present invention, said perfluoroalkyl (methyl) acrylate is that molecular formula is CH
2=(R) C (O) CO (CH
2)
2(CF
2) nCF
3Monomer mixture, R is H, CH in the formula
3Perhaps halogen atom, n is 1,3,5,7,9,11,13,15,17.Preferably 5,7,9,11.Said alkyl acrylate soft monomer, its molecular formula are CH
2=CHCOO (CH
2)
nCH
3, wherein n is 1-20.4-17 preferably.The rigid monomer of said vinyl is selected from vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, vinylidene chloride or their mixture.Said functional monomer can be vinylformic acid, acrylamide, Hydroxyethyl acrylate, the own ester of vinylformic acid hydroxyl, methacrylic acid, itaconicacid or their mixture.
Among the present invention, the general formula of said quaternary ammonium salt cationic type tensio-active agent is: CH
3(CH
2)
nN
+(R1) (R2) (R3) X
-, wherein n is 8-18, and R1, R2 represent that carbonatoms is the alkyl of 1-6, and R3 is that carbonatoms is alkyl or the aryl of 1-6, and X represents halogen atom.The general formula that has the nonionogenic tenside of polyoxyethylene segment is: RO (CH
2CH
2O)
nH, wherein R is that carbonatoms is alkyl or the aryl of 6-10, n is 4-20.
Among the present invention, said chain-transfer agent is a lauryl mercaptan; Initiator can be water miscible persulphate, it also can be oil-soluble initiator, perhaps both use simultaneously, water miscible persulphate, can be selected from Potassium Persulphate, ammonium persulphate or Sodium Persulfate, oil-soluble initiator can be selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide.
The present invention adopts earlier, and preparation is uniformly dispersed, particle diameter in the 30-150nm scope with interior stable monomer miniemulsion, add initiator again, be warmed up to 50-90 ℃ of initiated polymerization and obtain copolymer emulsion, also can add initiator earlier and carry out thin emulsification when temperature is lower than 40 ℃, the initiated polymerization that heats up again obtains multipolymer water-dispersion emulsion.
The prepared perfluorinated acrylate multipolymer water-dispersion miniemulsion blueing light of the present invention is translucent.Its molecular weight is 10
3-10
6, the molecular weight polydispersity coefficient is 1.0-2.0, and size distribution accounts for 90% of total amount at the particle of 50-110nm, and the second-order transition temperature of multipolymer is 0-60 ℃, is preferably 5-30 ℃,
The multipolymer water-dispersion emulsion of the present invention's preparation, it is characterized in that adopting the way of mini-emulsion polymerization, because conventional emulsion polymerization is crossed the range request monomer and is moved to micella by drop by water, the perfluoroalkyl monomer utmost point is insoluble in water, influenced carrying out smoothly of letex polymerization, cause in the letex polymerization the monomeric transformation efficiency of perfluoroalkyl low, add the environmental problem that to bring again behind the organic solvent hydrotropy, Ying Xiang emulsion property also, adopt the method for mini-emulsion polymerization, do not require the migration of monomer at aqueous phase, direct initiated polymerization in monomer droplet can be avoided the indissoluble problem of perfluorinated monomers.
The prepared perfluoroalkyl copolymer emulsion that is used for the fabric waterproof anti oil agent of the present invention, its preparation method is characterised in that only needs to add a spot of emulsifying agent, the assistant for emulsifying agent that does not need mini-emulsion polymerization often to add, as n-Hexadecane, hexadecanol etc., because had the strong hydrophobic monomer perfluoroalkyl acrylate of long-chain in this polymerization system, can play the effect of assistant for emulsifying agent, make the monomer emulsion that obtains through meticulous emulsification in polymerization process, keep stable.
The prepared anti-oily water repellent agent of the present invention perfluorinated acrylate multipolymer water-dispersion miniemulsion, its feature also is not with an organic solvent, environmental friendliness, safe in utilization, the emulsifying agent consumption is few, do not need assistant for emulsifying agent, can be reduced to minimum to the disadvantageous effect of multipolymer surface performance emulsifying agent, because almost be all monomer droplet while initiated polymerizations, speed of response is fast, even molecular weight distribution, the latex particle median size is little, size distribution is even, and the stability in storage of the emulsion that polymerization obtains, dilution stability are good, the waterproof and oilproof performance excellence of emulsion.The waterproof oil-proof finishing that can be used for wide variety of substrates such as fabric, leather, paper, carpet.
Anti-oily water repellent agent of the present invention perfluorinated acrylate multipolymer water-dispersion miniemulsion, be used for fabric waterproof oil resistant finish processing condition for being: polymer emulsion is diluted, make polymer ratio account for the 0.5-5% of total system quality, the most handy 1-3%, the fluorine that adheres on the fabric accounts for the 0.05-2% of fabric gross weight according to mass ratio, 0.1-1% preferably, with can be under 100-200 ℃ temperature drying treatment 1-10 minute after dipping, the extruding drying in the fabric waterproof oil-proofing agent aqueous dispersions, waterproof oil-proof result there be good promoter action.
Embodiment
Embodiment 1
Perfluoroalkyl acrylate (the perfluor carbon number is 6,8,10) 12g, lauryl methacrylate(LMA) 4g, lauryl mercaptan 0.1g, Potassium Persulphate 0.1g, vinylbenzene 6g, acrylamide 0.2g, dodecyl-3-methyl brometo de amonio 0.3g, OP-9 0.2g are mixed with the 45g deionized water, stir pre-emulsification 10 minutes at 40 ℃, under this temperature pre-emulsion is carried out ultrasonic thin emulsification 5 minutes then, the monomer miniemulsion median size that obtains is at 121nm.
Again monomer emulsion is placed the 100ml four-hole boiling flask that has stirring rake, thermometer, return line, logical nitrogen device, gas displacement in the bottle is become nitrogen, be warming up to 65 ℃ under stirring, initiated polymerization 6 hours, obtain the translucent emulsion of blueing light, median size is 117nm, and molecular weight is 110000, the solid content of emulsion is 32%, and monomer conversion is 97%.
Embodiment 2
Perfluoroalkyl acrylate (the perfluor carbon number is 6,8,10) 10g, methacrylic acid cetyl ester 6g, lauryl mercaptan 0.1g, Diisopropyl azodicarboxylate 0.1g, vinylbenzene 4g, acrylic acid 0.2g, hexadecyl-3-methyl brometo de amonio 0.21g, NP-40 0.24g are mixed with the 45g deionized water, stir pre-emulsification 10 minutes at 40 ℃, under this temperature pre-emulsion is carried out ultrasonic thin emulsification 5 minutes then, the monomer miniemulsion median size that obtains is at 128nm.
Again monomer emulsion is placed the 100ml four-hole boiling flask that has stirring rake, thermometer, return line, logical nitrogen device, gas displacement in the bottle is become nitrogen, be warming up to 75 ℃ under stirring, initiated polymerization 6 hours, obtain the translucent emulsion of blueing light, median size is 100000 for the 125nm molecular weight, and the solid content of emulsion is 30%, and monomer conversion is 96%.
Embodiment 3
Perfluoroalkyl acrylate (the perfluor carbon number is 6,8,10) 8g, methacrylic acid stearyl 6g, lauryl mercaptan 0.1g, ammonium persulphate 0.12g, methyl methacrylate 4g, acrylamide 0.3g, dodecyl-3-methyl brometo de amonio 0.18g, OP-10 0.36g are mixed with the 40g deionized water, stir pre-emulsification 10 minutes at 40 ℃, under this temperature pre-emulsion is carried out ultrasonic thin emulsification 3 minutes then, the monomer miniemulsion median size that obtains is at 116nm.
Again monomer emulsion is placed the 100ml four-hole boiling flask that has stirring rake, thermometer, return line, logical nitrogen device, gas displacement in the bottle is become nitrogen, be warming up to 70 ℃ under stirring, initiated polymerization 6 hours, obtain the translucent emulsion of blueing light, median size is 113nm, and molecular weight is 98000, the solid content of emulsion is 30%, and monomer conversion is 95%.
Embodiment 4
Perfluoroalkyl acrylate (the perfluor carbon number is 6,8,10) 9g, lauryl methacrylate(LMA) 8g, lauryl mercaptan 0.15g, 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.14g, methyl methacrylate 6g, acrylamide 0.2g, octadecyl-3-methyl-benzyl ammonium chloride 0.18g, NP-40 0.24g are mixed with the 50g deionized water, stir pre-emulsification 10 minutes at 40 ℃, under this temperature pre-emulsion is carried out ultrasonic thin emulsification 5 minutes then, the monomer miniemulsion median size that obtains is at 131nm.
Again monomer emulsion is placed the 100ml four-hole boiling flask that has stirring rake, thermometer, return line, logical nitrogen device, gas displacement in the bottle is become nitrogen, be warming up to 70 ℃ under stirring, initiated polymerization 6 hours, obtain the translucent emulsion of blueing light, median size is 120000 for the 128nm molecular weight, and the solid content of emulsion is 31%, and monomer conversion is 97%.
Embodiment 5
Perfluoroalkyl acrylate (the perfluor carbon number is 6,8,10) 9g, lauryl methacrylate(LMA) 8g, lauryl mercaptan 0.15g, Potassium Persulphate 0.14g, methyl acrylate 6g, Hydroxyethyl acrylate 0.5g, octadecyl-3-methyl-benzyl ammonium chloride 0.35g, NP-40 0.24g are mixed with the 50g deionized water, stir pre-emulsification 30 minutes at 40 ℃.
The monomer emulsion that will not pass through supersound process again places the 100ml four-hole boiling flask that has stirring rake, thermometer, return line, logical nitrogen device, gas displacement in the bottle is become nitrogen, be warming up to 70 ℃ under stirring, initiated polymerization 6 hours obtains white emulsion, and emulsion has more gel, median size is 155nm, molecular weight is 140000, and the solid content of emulsion is 25%, and monomer conversion is 75%
Embodiment 6
With perfluoroalkyl acrylate (the perfluor carbon number is 6,8,10) 12g, lauryl methacrylate(LMA) 4g, lauryl mercaptan 0.12g, Diisopropyl azodicarboxylate 0.12g, this ethene 4g, acetone 8g, vinylformic acid 0.18g, hexadecyl-2-methyl-benzyl ammonium chloride 0.3g, NP-40 0.28g mix with the 50g deionized water, stir pre-emulsification 30 minutes at 40 ℃.
The monomer emulsion that will not pass through supersound process again places the 100ml four-hole boiling flask that has stirring rake, thermometer, return line, logical nitrogen device, gas displacement in the bottle is become nitrogen, be warming up to 75 ℃ under stirring, initiated polymerization 6 hours obtains white emulsion, and emulsion has small amount of gel, median size is 135nm, molecular weight is 120000, and the solid content of emulsion is 27%, and monomer conversion is 90%
Emulsion particle diameter and size distribution adopt the laser light scattering particle size analyzer determination; Molecular weight adopts the GPC method to measure.
Claims (11)
1. anti-oily water repellent agent is characterized in that may further comprise the steps: in mass percent with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion
1) with the copolymerized monomer mixture of 10-40%, account for the emulsifying agent of monomer total mass 1.0-6.0% and the deionized water mixing stirring 10-30min of 60-90% and obtain pre-emulsion, with resulting pre-emulsion supersound process 1-10min in ultrasonic device, obtain size distribution again at the stable monomer miniemulsion of 30-150nm;
Above-mentioned copolymerized monomer mixture is made up of following four types polymerisable monomer: perfluoroalkyl acrylate, consumption are the 20-60% of monomer total mass; Alkyl acrylate soft monomer, consumption are the 10-60% of monomer total mass; Vinyl hard monomer, consumption are the 10-60% of monomer total mass; Functional monomer, consumption are the 0.5-5% of monomer total mass;
Above-mentioned emulsifying agent is made up of quaternary ammonium salt cationic type tensio-active agent and the nonionogenic tenside that has the polyoxyethylene segment, and wherein cats product accounts for the 20-80% of emulsifying agent total amount;
2) will place a reactor through the monomer miniemulsion that meticulous emulsification obtains, add respectively and account for monomer mass 0.05-1% chain-transfer agent, account for the initiator of monomer mass 0.05-1%, be warming up to 50-90 ℃ of initiated polymerization, reacted 2-6 hour, and be incubated 1-3 hour, by the time monomer conversion reaches 95.0% when above, cooling is cooled to room temperature, obtains after filtration.
2. anti-oily water repellent agent according to claim 1 is characterized in that with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion said perfluoroalkyl acrylate is that molecular formula is CH
2=CH (O) CO (CH
2)
2(CF
2)
nCF
3Monomer mixture, n is 1,3,5,7,9,11,13,15,17 in the formula.
3. the anti-oily water repellent agent according to claim 1 preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion, the molecular formula that it is characterized in that the alkyl acrylate soft monomer is CH
2=CHCOO (CH
2)
nCH
3, wherein n is 1-20.
4. anti-oily water repellent agent according to claim 1 is characterized in that with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion the rigid monomer of said vinyl is selected from vinylbenzene, methyl methacrylate, Jia Jibingxisuanyizhi, vinylidene chloride or their mixture.
5. anti-oily water repellent agent according to claim 1 is characterized in that with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion said functional monomer is vinylformic acid, acrylamide, Hydroxyethyl acrylate, the own ester of vinylformic acid hydroxyl, methacrylic acid, itaconicacid or their mixture.
6. anti-oily water repellent agent according to claim 1 is characterized in that the general formula of said quaternary ammonium salt cationic type tensio-active agent is: CH with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion
3(CH
2)
nN
+(R1) (R2) (R3) X
-, wherein n is 8-18, and R1, R2 represent that carbonatoms is the alkyl of 1-6, and R3 is that carbonatoms is alkyl or the aryl of 1-6, and X represents halogen atom.
7. anti-oily water repellent agent according to claim 1 is characterized in that with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion the said general formula that has the nonionogenic tenside of polyoxyethylene segment is: RO (CH2CH2O)
nH, wherein R is that carbonatoms is alkyl or the aryl of 6-10, n is 4-20.
8. anti-oily water repellent agent according to claim 1 is with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion, it is characterized in that cats product in the emulsifying agent accounts for the 40-60% of emulsifying agent total amount.
9. anti-oily water repellent agent according to claim 1 is characterized in that with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion said chain-transfer agent is a lauryl mercaptan.
10. anti-oily water repellent agent according to claim 1 is characterized in that with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion said initiator is water miscible persulphate, is selected from Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
11. anti-oily water repellent agent according to claim 1 is characterized in that with the preparation method of perfluorinated acrylate multipolymer water-dispersion miniemulsion said initiator is oil-soluble initiator, is selected from azo diethyl butyronitrile, azo diethyl heptonitrile or benzoyl peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100665355A CN1300192C (en) | 2004-09-17 | 2004-09-17 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
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|---|---|---|---|
| CNB2004100665355A CN1300192C (en) | 2004-09-17 | 2004-09-17 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
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| CN1300192C true CN1300192C (en) | 2007-02-14 |
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