CN102443099A - Preparation method of (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion - Google Patents
Preparation method of (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion Download PDFInfo
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Abstract
The invention discloses a preparation method of an epoxy polyether-based (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion, which comprises the following steps of: under the effect of cationic/nonionic or anionic/nonionic surfactants, firstly carrying out seeded emulsion copolymerization on perfluoroalkyl(methyl) acrylate, aliphatic long carbon chain (methyl) acrylate, reactive vinyl monomer and alpha-alkenyl alkoxysilane in an aqueous phase so as to synthesize a silanized long carbon chain fluorinated polyacrylate emulsion; cooling to room temperature; regulating a pH value of the system to be 5.0-6.0; adding an epoxy polyether-based (sesqui) siloxane cross-linking agent and a stiffening agent; continuously stirring for 30 min; and obtaining the (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion after filtering. The modified fluorinated polyacrylate emulsion disclosed by the invention can be used for after-treatment of textiles after dilution, so that the stiff handfeel of textiles can be improved, and an excellent water-repellent and oil-repellent performance is given to the textiles.
Description
Technical field
The present invention relates to a kind of preparation method of modification fluoro polyacrylic ester emulsion, relate in particular to a kind of preparation method with epoxidized polyether base (sesquialter) silicone hybrid modification fluoro polyacrylic ester emulsion.
Background technology
Fluoro polyacrylic ester (abbreviation organic fluorine); Surface energy is low, and the water and oil repellant excellent performance is used for the aftertreatment of fiber base material; Can improve the surface property and the feel of base material; Can give water and oil repellant dirt of base material ideal and self-cleaning function again, and not influence the ventilative and water vapour permeability of health of base material, thereby can be widely used in the aspects such as functional after-finishing, paper and leather water-proof processing, fabric coating finish of various fabrics.
Emulsion copolymerization is to implement one of synthetic the most frequently used effective ways of fluoro polyacrylic ester emulsion, patent documentations such as the visible CN101148825 of this point, CN1837456, US6126849, US5242487.In addition, in organic fluorine emulsion building-up process, with the linking agent appropriateness to the emulsion major constituent---fluoro polyacrylic ester carries out cross-linking modified, further raising is arranged or improve the effect of fluoro polyacrylic ester application performance.For example, CN88108913 through adding amino acid and salt thereof, had both improved the washing fastness of the handled fabric of fluoro polyacrylic ester component in the organic fluorine emulsion is synthetic, reduced production cost again, but this reaction process with an organic solvent, is unfavorable for ecological, environmental protective.And CN1837456 is in the emulsion polymerization process of fluorochemical monomer and non-fluorochemical monomer and function monomer; Through using sticking power such as diacetone-acryloamide(DAA) or cyanogen acetyl oxygen ethyl-methyl propenoate, methylacrylic acid urea groups ester, allyl group urea groups vinyl ether to strengthen monomer, all good organic fluorine emulsions of a kind of water and oil-resistant have also been obtained.But we find in the research, and a large amount of functional sticking power strengthen monomeric use and are prone to cause the system transition crosslinked, cause emulsion package stability variation; In addition, the emulsion that this method is made directly applies to the fabric coating processing, and the stiffness of the fabric after its arrangement is not ideal enough, haves much room for improvement.
Summary of the invention
The object of the present invention is to provide the preparation method of the fluoro polyacrylic ester emulsion of a kind of epoxidized polyether base (sesquialter) silicone hybrid modification.
For this reason; The technical scheme that the present invention takes is: under the effect of sun/non-or cloudy/nonionogenic tenside; At first perfluoroalkyl (methyl) propenoate and fatty clan elder's carbochain (methyl) propenoate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane are carried out the seed emulsion copolymerization earlier at water, the long carbochain fluoro polyacrylic ester of synthesizing silaneization midbody emulsion; Reduce to room temperature then, transferring system pH is 5.0～6.0, is added into epoxidized polyether base (sesquialter) siloxane crosslinker and stiffening agent again and continues to stir 30min, through filtering the emulsion of gained, the i.e. fluoro polyacrylic ester emulsion of (sesquialter) silicone hybrid modification.
Its concrete experimental procedure is:
(1) at first; Perfluoroalkyl (methyl) propenoate, fatty clan elder's carbochain (methyl) propenoate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane is mixed composition oil phase monomer mixture; The massfraction of each component is respectively that perfluoroalkyl (methyl) propenoate is 40～75% in the oil phase monomer mixture, fatty clan elder's carbochain (methyl) propenoate is 20～45%, reaction-ity ethylene base monomer is 4.0～10%, α-alkenyl alkoxy silane is 1～5%; Secondly, press oil phase monomer mixture quality, take by weighing 0.6～3.0% molecular weight regulator, 4.0～15% sun/nonionogenic tenside or the moon/nonionogenic tenside again and measure deionized water and mix with the oil phase monomer mixture; Behind the mechanical stirring mixing; With the preparatory emulsification 30min of UW, process pre-emulsion, note is made component (I);
(2) press oil phase monomer mixture quality, take by weighing 0.5～3% initiator again, with the deionized water dissolving of 20～40 times of amounts, process initiator solution, note is made component (II);
(3) respectively get 1/4 component (I) and component (II) and place three-necked bottle, stir, logical N
2Protection, heat temperature raising to 70～80 a ℃ reaction 30min makes it to generate polymer seeds, and then is added dropwise to remaining component (I) and component (II) simultaneously; The control rate of addition makes component (I) and component (II) dropwise simultaneously at 1.5～2h, continues insulation reaction 4h; Get the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion, then, be cooled to 25～30 ℃; Accent system pH is 5.0～6.0, adds epoxidized polyether base (sesquialter) siloxanes of midbody quality of the emulsion 3.3～5% and the stiffening agent of midbody quality of the emulsion 5.3～7% again, stirs 30min; Filter with gauze; The white emulsion of gained band blue-fluorescence is (sesquialter) silicone hybrid modification fluoro polyacrylic ester emulsion, and solid content is 25～30%.
Said perfluoroalkyl (methyl) propenoate is CH
2=CRCOOCH
2CH
2R
F1Or its mixture or CH
2=CRCOOCH
2R
F2, in the formula, R=-H or-CH
3, R
F1=(CF
2)
aCF
3, a=4～12, R
F2=CF (CF
3) CHFCF (CF
3)
2Mainly comprise perfluor alkane ethyl propylene acid esters of a=4～12 and composition thereof, methylacrylic acid ten difluoro heptyl esters, dodecafluorhe-ptylacrylate.Preferentially choose the CH of a=4～12 in the reaction
2=CHCOOCH
2CH
2R
F1Mixture or methylacrylic acid ten difluoro heptyl esters.
Said fatty clan elder's carbochain (methyl) propenoate is CH
2The mixture of one or more arbitrary proportions among=CRCOOR ', in the formula R=-H or-CH
3, R '=-C
4H
9～-C
18H
37, long carbochain (methyl) propenoate of preferentially choosing is (methyl) vinylformic acid n-octyl, (methyl) ethyl acrylate, (methyl) vinylformic acid lauryl alcohol ester, (methyl) vinylformic acid tridecanol ester, (methyl) vinylformic acid tetradecyl alcohol ester, (methyl) vinylformic acid hexadecanol ester or (methyl) vinylformic acid stearyl alcohol ester.
Said reaction-ity ethylene base monomer is (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, N hydroxymethyl acrylamide, (methyl) vinylformic acid-2, the mixture of two or more arbitrary proportion in 3-dihydroxyl propoxy-propyl ester, 3-chloro-2-hydroxypropyl (methyl) propenoate or the 4-1-chloro-4-methyl-benzene.
Said α-alkenyl alkoxy silane is many organoalkoxysilanes such as vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, allyloxy propyl trimethoxy silicane or the allyloxy propyl-triethoxysilicane that contains vinyl or acryloyl-oxy propyl group in the molecule.
Said molecular weight regulator is alkyl sulfhydryl or the small molecules organic cpds that contains sulfydryl, like Dodecyl Mercaptan, mercaptoethanol or Thiovanic acid.
Said sun/nonsurfactant is the mixture of cats product and nonionogenic tenside, and described the moon/nonionogenic tenside then is the mixture of AS and nonionogenic tenside;
Said cats product is chosen dodecyl benzyl dimethyl ammonium chloride 1227, dodecyl dimethyl benzyl ammonium bromide, palmityl trimethyl ammonium chloride 1631, OTAC 1831, distearyl dimethyl ammonium chloride, N, N '-double hexadecyl tetramethyl-bromination second two ammoniums 21631 or Gemini tensio-active agent;
Said nonionogenic tenside is chosen one or more in fluorine carbon Soxylat A 25-7, AEO, polyoxyethylene nonylphenol, polyoxyethylene octylphenol ether, aliphatic acid polyethenoxy ether ester, the lipid acid anhydrous sorbitol polyoxyethylene ether-ester;
Said AS is chosen perfluoroalkyl Supragil GN FBS, polyoxyethylenated alcohol sodium sulfate AES, sodium lauryl sulphate or dodecyl sulphate potassium.
Said initiator is ammonium persulphate, Potassium Persulphate, water-soluble azo initiator AV-40 or AV-50;
The structure of said epoxidized polyether base (sesquialter) siloxane crosslinker is following:
EPOS-1
Or
EPOS-2
A, b=0 in the formula, 1,2 ... N, a+b=0,6,10,25, n is a positive integer.Wherein, epoxidized polyether base (sesquialter) siloxane crosslinker is with tetramethyl-ring tetrasiloxane (D
4 H) or hydrogeneous hexahedron sesquialter eight siloxanes (T
8 H) prepare with allyl polyethenoxy polyoxypropylene epoxy group(ing) ether (APEE) hydrosilylation addition reaction, temperature of reaction is 80 ℃, Si-H key and CH in the reaction raw materials
2The mol ratio of=CH-key is 1: 1.05.
In the described EPOS-1 structure, preferential selection contains a/b=7: 1, polyethers epoxy segmental molecular-weight average (M
nFour (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane (note is made EPOS-1A) of)=400 perhaps contains a=10, b=0, polyethers epoxy segmental molecular-weight average (M
nFour (2,3-glycidoxy T 46155 propyl group) tetramethyl-ring tetrasiloxane (note is made EPOS-1B) of)=500 perhaps contains a/b=7: 3, polyethers epoxy segmental molecular-weight average (M
nFour (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane (note is made EPOS-1C) of)=1000; In the described EPOS-2 structure, preferential selection contains a/b=7: 1, polyethers epoxy segmental molecular-weight average (M
n)=400 or a=10, b=0, polyethers epoxy segmental molecular-weight average (M
nPolyethers epoxy segmental eight epoxidized polyether propyl group hexahedron sesquialters eight siloxanes of)=500 (note is made EPOS-2A and EPOS-2B respectively).
Described stiffening agent is chosen the R-55 that commercially available positively charged ion etherify melamine such as FN-9000 or nonionic acrylic acid or the like stiffening agent such as the auspicious chemical industry of Shanghai tiny stream ltd produce, its ionic should be with used tensio-active agent in the letex polymerization ionic identical.
Described epoxidized polyether base (sesquialter) silicone hybrid modification fluoro polyacrylic ester emulsion, its pH is 5.0～6.0, solid content is 25～30%.
Fluoro polyacrylic ester emulsion with the modification of (sesquialter) of the present invention silicone hybrid; Amount to into solid content and be 30% emulsion; By mass ratio m (emulsion): m (water)=20～120: 1000 (g/g) dilute; Soak one with one then and roll and carry out textile finishing or spraying, fabric is through 100 ℃ of oven dry, 170 ℃ of setting 3min, with Static Contact angle measuring instrument, hand digital palpation for examination of trauma and with reference to AATCC standard etc. put in order the afterwards application performance of fabric measured or estimated then.The result finds that with emulsion fabric treated of the present invention, feel is stiff, and water can reach 153.4 ° at the contact angle of fabric face, and grease proofing grade reaches 6 grades (pressing AATCC 22-2005 standard test), has shown good water and oil repellant effect.
Description of drawings
Fig. 1 prepares route map for epoxidized polyether base (sesquialter) siloxane crosslinker, and Scheme1 is the synthetic route of EPOS-1 among Fig. 1, and Scheme 2 is the synthetic route of EPOS-2.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
The preparation of epoxidized polyether base (sesquialter) siloxane crosslinker
Referring to Fig. 1, be example with EPOS-1A.In the three-necked bottle that TM, reflux condensing tube are housed, add 24.1g tetramethyl-ring tetrasiloxane (D successively
4 H) and 168.0g a/b=7: 1, M
n=400 allyl polyethenoxy polyoxypropylene epoxy group(ing) ether (APEE) is heated with stirring to 80 ℃, adds the 50ppm platinum catalyst again, and the system of treating is changeed transparent continued stirring reaction 10min, gets transparent liquid, i.e. epoxidized polyether radical siloxane linking agent EPOS-1A.
The same EPOS-1A of preparation method of other epoxidized polyether base (sesquialter) siloxane crosslinkers, its raw material consumption is seen table 1.
Used raw material and the consumption thereof of table 1 preparation epoxidized polyether base (sesquialter) siloxanes EPOS
APEE
(1): a/b=7: 1, M
n=400; APEE
(2): a=10, b=0, M
n=500; APEE
(3): a/b=7: 3, M
n=1000, limit APEE when in the access EPOS molecule, can abbreviate polyethers epoxy segment as.
Embodiment 1: taking by weighing the 37.5g structure successively is CH
2=CHCOOCH
2CH
2(CF
2)
4～12CF
3Perfluor alkane ethyl propylene acid esters, 10.0g methylacrylic acid lauryl alcohol ester, 1.5g Propylene glycol monoacrylate and 0.5g 4-1-chloro-4-methyl-benzene and 0.5g vinyltriethoxysilane, it mix is formed the oil phase monomer mixture.Then; Take by weighing 0.7g mercaptoethanol, 2.5g palmityl trimethyl ammonium chloride 1631,1.5g AEO and 163.2g deionized water again and mix with the oil phase monomer mixture, the mechanical stirring mixing uses UW at 30 ± 2 ℃ of emulsification 30min then; Process stable pre-emulsion; Note is made component (I), places tap funnel (I), and is subsequent use.
Other gets the 1.5g ammonium persulphate, processes initiator solution with the 30.0g deionized water dissolving, and note is made component (II), places tap funnel (II), and is subsequent use.
Have in TM, reflux condensing tube, tap funnel (I) and the four-necked bottle (II) at device, each adds 1/4 component (I) and component (II), stirs, logical N
2Protection is warming up to 80 ℃ of reaction 30min, and then is added dropwise to remaining ingredient (I), (II), and the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h, continues insulation reaction 4h and gets the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion.Then, be cooled to 25～30 ℃, transferring system pH is 5.0～6.0, is added dropwise to 12.4g (5%, in midbody emulsion total mass) soluble epoxide polyether-based siloxanes EPOS-1A [Scheme1, a/b=7: 1, polyethers epoxy segmental molecular-weight average M again
n=400] and 17.3g (7%; In midbody emulsion total mass) stiffening agent FN-9000 stirs 30min, filters, and must have a little the white emulsion of blue-fluorescence; Be the cation fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-1A hybrid modification, solid content is about 30%.
Embodiment 2: take by weighing 20.0g methacrylic ester ten difluoro heptyl esters, 20.0g vinylformic acid lauryl alcohol ester, 2.5g Bing Xisuandingzhi, 3.0gN-NMA, 2.0g 4-1-chloro-4-methyl-benzene and 2.5g γ-methacryloxypropyl trimethoxy silane successively, it is mixed form the oil phase monomer mixture.Then; Take by weighing 0.3g Dodecyl Mercaptan, 2.0g dodecyl dimethyl benzyl ammonium bromide and 3g aliphatic acid polyethenoxy ether ester SG-10 and 211.2g deionized water again and mix with the oil phase monomer mixture, the mechanical stirring mixing, with UW at 25 ℃ of emulsification 30min; Process stable pre-emulsion; Note is made component (I), places tap funnel (I), and is subsequent use.
Other gets 0.25g water-soluble azo initiator AV-40, processes initiator solution with the 10.0g deionized water dissolving, and note is made component (II), places tap funnel (II), and is subsequent use.
In TM, reflux condensing tube, tap funnel (I) and four-necked bottle (II) were housed, each added 1/4 component (I) and component (II), stirred, logical N
2Protection is warming up to 70 ℃ of reaction 30min, and then is added dropwise to remaining ingredient (I), (II), and the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h, continues insulation reaction 4h and gets the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion.Then, be cooled to 25～30 ℃, transferring system pH is 5.0～6.0, adds 10.5g (4%, in midbody emulsion total mass) soluble epoxide polyether-based siloxanes EPOS-1B [Scheme1, a=10, b=0, polyethers epoxy segmental M again
n=500] and 15.7g (6%) stiffening agent R-55 in midbody emulsion total mass stir 30min, filter, even white emulsion, i.e. the cation fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-1B hybrid modification, solid content is about 27%.
Embodiment 3: take by weighing 10.0g CH successively
2=CHCOOCH
2CH
2(CF
2)
4～12CF
3Perfluor alkane ethyl propylene acid esters, 6.0g methylacrylic acid stearyl alcohol ester, 2.0g Bing Xisuandingzhi, 0.6g Propylene glycol monoacrylate, 0.8g 4-1-chloro-4-methyl-benzene, 0.6g vinyltrimethoxy silane, it mix is formed the oil phase monomer mixture.Then, take by weighing 0.6g Dodecyl Mercaptan, 0.8g N again, N '-double hexadecyl tetramethyl-bromination second two ammoniums, 0.4g fluorine carbon Soxylat A 25-7,1.8g polyoxyethylene nonylphenol OP-10 and 82.4g deionized water mix with the oil phase monomer mixture; Behind the mechanical stirring mixing; At 30 ℃ of emulsification 30min, process stable pre-emulsion with UW, note is made component (I); Place tap funnel (I), subsequent use.
Other gets the 0.3g Potassium Persulphate, processes initiator solution with the 12.0g deionized water dissolving, and note is made component (II), places tap funnel (II), and is subsequent use.
In TM, reflux condensing tube, tap funnel (I) and four-necked bottle (II) were housed, each added 1/4 component (I) and component (II), stirred, logical N
2Protection is warming up to 80 ℃ of reaction 30min, is added dropwise to remaining ingredient (I), (II) again, and the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h, continues insulation reaction 4h and gets the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion.Then, be cooled to 25～30 ℃, transferring system pH is 5.0～6.0, adds 5.5g (4.7%, in midbody emulsion total mass) epoxidized polyether radical siloxane linking agent EPOS-1C [Scheme1, a/b=7: 3, polyethers epoxy segmental M again
n=1000] and 6.3g (5.3%) stiffening agent R-55 in midbody emulsion total mass stir 30min, filter, white emulsion, i.e. the cation fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-1C hybrid modification, solid content is about 29%.
Embodiment 4: take by weighing 15.0g methylacrylic acid ten difluoro heptyl esters, 7.5g vinylformic acid hexadecanol ester, 0.8g Hydroxyethyl acrylate, 1.2g 4-1-chloro-4-methyl-benzene, 0.5g vinyltriethoxysilane successively, it is mixed form the oil phase monomer mixture.Then, take by weighing 0.4g Dodecyl Mercaptan, 0.6g N again, N '-double hexadecyl tetramethyl-bromination second two ammoniums, 0.2g fluorine carbon Soxylat A 25-7,1.0g polyoxyethylene nonylphenol OP-10 and 89.2g deionized water mix with the oil phase monomer mixture; Behind the mechanical stirring mixing; At 30 ℃ of preparatory emulsification 30min, process stable pre-emulsion with UW, note is made component (I); Place tap funnel (I), subsequent use.
Other gets the 0.5g ammonium persulphate, processes initiator solution with the 20.0g deionized water dissolving, and note is made component (II), places tap funnel (II), and is subsequent use.
In TM, reflux condensing tube, tap funnel (I) and four-necked bottle (II) were housed, each added 1/4 component (I) and component (II), stirred, logical N
2Protection is warming up to 75 ℃ of reaction 30min, is added dropwise to remaining ingredient (I), (II) again, and the rate of addition of controlling the two makes it in 1.5～2h, to dropwise simultaneously, continues insulation reaction 4h and gets the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion.Reaction finishes, and is cooled to 25～30 ℃, and transferring system pH is 5.0～6.0, and [Scheme 2, a/b=7: 1, polyethers epoxy segmental M to add 4.5g (3.3%, in midbody emulsion total mass) eight epoxidized polyether propyl group hexahedron silsesquioxane EPOS-2A again
n=400] and 5.5g (6.7%; In midbody emulsion total mass) stiffening agent FN-9000 stirs 30min, filters, and must have a little the emulsion of blue-fluorescence; Be the cation fluoro polyacrylic ester emulsion of epoxidized polyether base silsesquioxane EPOS-2A hybrid modification, solid content is about 25%.
Embodiment 5: taking by weighing the 13.5g structure successively is CH
2=CHCOOCH
2CH
2(CF
2)
4～12CF
3Perfluor alkane ethyl propylene acid esters, 8.0g vinylformic acid stearyl alcohol ester, 1.5g N hydroxymethyl acrylamide, 1.0g 4-1-chloro-4-methyl-benzene, 1.0g γ-methacryloxypropyl triethoxyl silane, it mix is formed the oil phase monomer mixture.Then; Take by weighing 0.5g Dodecyl Mercaptan, 0.5g perfluoroalkyl Supragil GN, 0.5g AEO and 92.0g deionized water again and mix with the oil phase monomer mixture, the mechanical stirring mixing, with UW at 30 ℃ of emulsification 30min; Process stable pre-emulsion; Note is made component (I), places tap funnel (I), and is subsequent use.
Other gets 0.4g water-soluble azo initiator AV-50, processes initiator solution with the 14.0g deionized water dissolving, and note is made component (II), places tap funnel (II), and is subsequent use.
In TM, reflux condensing tube, tap funnel (I) and four-necked bottle (II) were housed, each added 1/4 component (I) and component (II), stirred, logical N
2Protection is warming up to 80 ℃ of reaction 30min, is added dropwise to remaining ingredient (I), (II) again, and the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h, continues insulation reaction 4h then, gets the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion.Then, be cooled to 25～30 ℃, transferring system pH is 5.0～6.0, adds 5.0g (3.8%, in midbody emulsion total mass) epoxidized polyether radical siloxane EPOS-1A [Scheme1 (1), a/b=7: 1, polyethers epoxy segmental M again
n=400] and 8.2g (6.2%; In midbody emulsion total mass) stiffening agent FN-9000 stir 30min, filter, must have a little the emulsion of blue-fluorescence; Be the negatively charged ion fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-1A hybrid modification, solid content is about 27%.
Embodiment 6: take by weighing 14.5g methacrylic ester ten difluoro heptyl esters, 7.5g vinylformic acid stearyl alcohol ester, 1.5g Propylene glycol monoacrylate, 0.8g 3-chloro-2-hydroxypropylmethyl propenoate, 0.7g vinyltrimethoxy silane successively, it is mixed form the oil phase monomer mixture.Then; Take by weighing 0.5g Dodecyl Mercaptan, 0.8g sodium lauryl sulphate, 1.2g lipid acid anhydrous sorbitol polyoxyethylene ether-ester Tween-80 and 95.0g deionized water again and mix with the oil phase monomer mixture, behind the mechanical stirring mixing, with UW at 30 ℃ of emulsification 30min; Process stable pre-emulsion; Note is made component (I), places tap funnel (I), and is subsequent use.
Other gets the 0.6g Potassium Persulphate, uses 15.0g H
2The O deionized water dissolving is processed initiator solution, and note is made component (II), places tap funnel (II), and is subsequent use.
In TM, reflux condensing tube, tap funnel (I) and four-necked bottle (II) were housed, each added 1/4 component (I) and component (II), stirred, logical N
2Protection is warming up to 75 ℃ of reaction 30min, is added dropwise to remaining ingredient (I), (II) again, and the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h, continues insulation reaction 4h, gets the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion.Then, be cooled to 25～30 ℃, transferring system pH is 5.0～6.0, and [Scheme 2, a=10, b=0, polyethers epoxy segment M to add 6.1g (4.4%, in midbody emulsion total mass) epoxidized polyether base silsesquioxane EPOS-2B again
n=500] and 7.7g (5.4%) stiffening agent R-55 in midbody emulsion total mass stir 30min, filter, white emulsion, i.e. the negatively charged ion fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-2B hybrid modification, solid content is about 27%.
Getting the fluoro polyacrylic ester emulsion of (sesquialter) silicone hybrid modification of embodiment 1～6 preparation, be converted into solid content and be 30% emulsion, is that 20～80: 1000 (g/g) dilute by emulsion and quality ratio, is made into arrangement and uses the work body lotion.Other gets polyester piece good, it is impregnated into soaks a roll process with one in this body lotion and put in order, and pick-up is about 70%.Fabric in 170 ℃ of setting 3min, places moisture eliminator equilibrium at room temperature 24h more then in 100 ℃ of baking 5min, estimates stiff feel with the hand digital palpation for examination of trauma, and carries out performance measurement with reference to related standards.Wherein, the hydrophobic performance of fabric face, θ representes with static contact angle, measures with JC2000 type static contact angle determinator; The oil repellent of fabric face is measured with reference to the AATCC118-2007 standard, and its result sees table 2.
The application performance of the fluoro polyacrylic ester emulsion of table 2 (sesquialter) silicone hybrid modification
* water is at the static contact angle of fabric face
Claims (9)
1. the preparation method of (sesquialter) silicone hybrid modification fluoro polyacrylic ester emulsion; It is characterized in that: under the effect of sun/non-or cloudy/nonionogenic tenside; At first perfluoroalkyl (methyl) propenoate and fatty clan elder's carbochain (methyl) propenoate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane are carried out the seed emulsion copolymerization earlier at water; The long carbochain fluoro polyacrylic ester of synthesizing silaneization midbody emulsion is reduced to room temperature then, and transferring system pH is 5.0～6.0; Be added into epoxidized polyether base (sesquialter) siloxane crosslinker and stiffening agent again and continue to stir 30min; Through filtering the emulsion of gained, the i.e. fluoro polyacrylic ester emulsion of (sesquialter) silicone hybrid modification.
2. the preparation method of (sesquialter) according to claim 1 silicone hybrid modification fluoro polyacrylic ester emulsion is characterized in that concrete experimental procedure is:
(1) at first; Perfluoroalkyl (methyl) propenoate, fatty clan elder's carbochain (methyl) propenoate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane is mixed composition oil phase monomer mixture; The massfraction of each component is respectively that perfluoroalkyl (methyl) propenoate is 40～75% in the oil phase monomer mixture, fatty clan elder's carbochain (methyl) propenoate is 20～45%, reaction-ity ethylene base monomer is 4.0～10%, α-alkenyl alkoxy silane is 1～5%; Secondly, press oil phase monomer mixture quality, take by weighing 0.6～3.0% molecular weight regulator, 4.0～15% sun/nonionogenic tenside or the moon/nonionogenic tenside again and measure deionized water and mix with the oil phase monomer mixture; Behind the mechanical stirring mixing; With the preparatory emulsification 30min of UW, process pre-emulsion, note is made component (I);
(2) press oil phase monomer mixture quality, take by weighing 0.5～3% initiator again, with the deionized water dissolving of 20～40 times of amounts, process initiator solution, note is made component (II);
(3) respectively get 1/4 component (I) and component (II) and place three-necked bottle, stir, logical N
2Protection, heat temperature raising to 70～80 a ℃ reaction 30min generates polymer seeds, and then is added dropwise to remaining component (I) and component (II) simultaneously; The control rate of addition makes component (I) and component (II) dropwise simultaneously at 1.5～2h, continues insulation reaction 4h; Get the long carbochain fluoro polyacrylic ester of silylanization midbody emulsion, then, be cooled to 25～30 ℃; Transferring pH is 5.0～6.0, adds epoxidized polyether base (sesquialter) siloxanes of midbody quality of the emulsion 3.3～5% and the stiffening agent of midbody quality of the emulsion 5.3～7% again, stirs 30min; Filter with gauze; The white emulsion of gained band blue-fluorescence is (sesquialter) silicone hybrid modification fluoro polyacrylic ester emulsion, and solid content is 25～30%.
3. the preparation method of (sesquialter) according to claim 1 and 2 silicone hybrid modification fluoro polyacrylic ester emulsion is characterized in that:
Said perfluoroalkyl (methyl) propenoate is CH
2=CRCOOCH
2CH
2R
F1Or its mixture or CH
2=CRCOOCH
2R
F2, in the formula, R=-H or-CH
3, R
F1=(CF
2)
aCF
3, a=4～12, R
F2=CF (CF
3) CHFCF (CF
3)
2
Said fatty clan elder's carbochain (methyl) propenoate is CH
2The mixture of one or more arbitrary proportions among=CRCOOR ', in the formula R=-H or-CH
3, R '=-C
4H
9～-C
18H
37, fatty clan elder's carbochain (methyl) propenoate of preferentially choosing is (methyl) vinylformic acid n-octyl, (methyl) ethyl acrylate, (methyl) vinylformic acid lauryl alcohol ester, (methyl) vinylformic acid tridecanol ester, (methyl) vinylformic acid tetradecyl alcohol ester, (methyl) vinylformic acid hexadecanol ester or (methyl) vinylformic acid stearyl alcohol ester;
Said reaction-ity ethylene base monomer is (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, N hydroxymethyl acrylamide, (methyl) vinylformic acid-2, the mixture of two or more arbitrary proportion in 3-dihydroxyl propoxy-propyl ester, 3-chloro-2-hydroxypropyl (methyl) propenoate or the 4-1-chloro-4-methyl-benzene;
Said α-alkenyl alkoxy silane is many organoalkoxysilanes such as vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, allyloxy propyl trimethoxy silicane or the allyloxy propyl-triethoxysilicane that contains vinyl or acryloyl-oxy propyl group in the molecule.
4. the preparation method of (sesquialter) according to claim 2 silicone hybrid modification fluoro polyacrylic ester emulsion; It is characterized in that: said molecular weight regulator is alkyl sulfhydryl or the small molecules organic cpds that contains sulfydryl, like Dodecyl Mercaptan, mercaptoethanol or Thiovanic acid.
5. the preparation method of (sesquialter) according to claim 1 and 2 silicone hybrid modification fluoro polyacrylic ester emulsion; It is characterized in that: said sun/nonsurfactant is the mixture of cats product and nonionogenic tenside, and described the moon/nonionogenic tenside then is the mixture of AS and nonionogenic tenside;
Said cats product is chosen dodecyl benzyl dimethyl ammonium chloride 1227, dodecyl dimethyl benzyl ammonium bromide, palmityl trimethyl ammonium chloride 1631, OTAC 1831, distearyl dimethyl ammonium chloride, N, N '-double hexadecyl tetramethyl-bromination second two ammoniums 21631 or Gemini tensio-active agent;
Said nonionogenic tenside is chosen one or more in fluorine carbon Soxylat A 25-7, AEO, polyoxyethylene nonylphenol, polyoxyethylene octylphenol ether, aliphatic acid polyethenoxy ether ester, the lipid acid anhydrous sorbitol polyoxyethylene ether-ester;
Said AS is chosen perfluoroalkyl Supragil GN FBS, polyoxyethylenated alcohol sodium sulfate AES, sodium lauryl sulphate or dodecyl sulphate potassium.
6. the preparation method of (sesquialter) according to claim 2 silicone hybrid modification fluoro polyacrylic ester emulsion, it is characterized in that: said initiator is ammonium persulphate, Potassium Persulphate, water-soluble azo initiator AV-40 or AV-50;
7. the preparation method of (sesquialter) according to claim 1 and 2 silicone hybrid modification fluoro polyacrylic ester emulsion, it is characterized in that: the structure of said epoxidized polyether base (sesquialter) siloxane crosslinker is following:
EPOS-1
Or
EPOS-2
A, b=0 in the formula, 1,2 ... N, n are positive integer.Wherein, epoxidized polyether base (sesquialter) siloxane crosslinker is with tetramethyl-ring tetrasiloxane (D
4 H) or hydrogeneous hexahedron sesquialter eight siloxanes (T
8 H) prepare with allyl polyethenoxy polyoxypropylene epoxy group(ing) ether (APEE) hydrosilylation addition reaction, temperature of reaction is 80 ℃, Si-H key and CH in the reaction raw materials
2The mol ratio of=CH-key is 1: 1.05.
8. the preparation method of (sesquialter) according to claim 1 and 2 silicone hybrid modification fluoro polyacrylic ester emulsion; It is characterized in that: said stiffening agent is positively charged ion etherify melamine or nonionic acrylic acid or the like stiffening agent, its ionic should be with used tensio-active agent in the letex polymerization ionic identical.
9. epoxidized polyether base according to claim 7 (sesquialter) siloxane crosslinker is characterized in that:
In the said EPOS-1 structure, preferential selection contains a/b=7: 1, polyethers epoxy segmental molecular-weight average (M
nWater-soluble four (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane of)=400; Perhaps contain a=10, b=0, polyethers epoxy segmental molecular-weight average (M
nWater-soluble four (2,3-glycidoxy T 46155 propyl group) tetramethyl-ring tetrasiloxane of)=500; Perhaps contain a/b=7: 3, polyethers epoxy segmental molecular-weight average (M
nWater-soluble four (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane of)=1000; In the said EPOS-2 structure, preferential selection contains a/b=7: 1, polyethers epoxy segmental molecular-weight average (M
n)=400 or a=10, b=0, polyethers epoxy segmental molecular-weight average (M
nEight epoxidized polyether propyl group hexahedron sesquialters, eight siloxanes of)=500.
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