CN102443099B - 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 can be low, the water and oil repellant excellent performance, aftertreatment for fiber base material, can improve surface property and the feel of base material, can give again base material desirable water and oil repellant dirt and self-cleaning function, and not affect the ventilative and water vapour permeability of the 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, this point visible CN101148825, CN1837456, the patent documentations such as US6126849, US5242487.In addition, in organic fluorine emulsion building-up process, by 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 by 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 again production cost, 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, by using the Adhesion enhancement monomers such as diacetone-acryloamide(DAA) or cyanogen acetyl oxygen ethyl-methyl acrylate, methacrylic acid urea groups ester, allyl group urea groups vinyl ether, all good organic fluorine emulsions of a kind of water and oil-resistant have also been obtained.But in research, we find, the use of a large amount of functional Adhesion enhancement monomers easily causes the system transition crosslinked, causes 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 it arranges 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) acrylate and fatty clan elder's carbochain (methyl) acrylate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane are first carried out to the seed emulsion copolymerization at water, the long carbochain fluoro polyacrylic ester of synthesizing silaneization intermediate emulsion; Then be down to room temperature, adjusting system pH is 5.0～6.0, then is added into epoxidized polyether base (sesquialter) siloxane crosslinker and stiffening agent continuation stirring 30min, after filtration, the emulsion of gained, i.e. the fluoro polyacrylic ester emulsion of (sesquialter) silicone hybrid modification.
Its concrete experimental procedure is:
(1) at first, by perfluoroalkyl (methyl) acrylate, fat clan elder's carbochain (methyl) acrylate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane mixes and forms the oil phase monomer mixture, in the oil phase monomer mixture, to be respectively perfluoroalkyl (methyl) acrylate be 40～75% to the massfraction of each component, fat clan elder's carbochain (methyl) acrylate 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 again 0.6～3.0% molecular weight regulator, 4.0 sun/nonionogenic tenside of～15% or the moon/nonionogenic tenside and metering deionized water mix with the oil phase monomer mixture, after mechanical stirring mixes, with ultrasonic wave pre-emulsification 30min, make pre-emulsion, be denoted as component (I),
(2) press oil phase monomer mixture quality, then take 0.5～3% initiator, with the deionized water dissolving of 20～40 times of amounts, make initiator solution, be denoted as component (II);
(3) respectively get 1/4 component (I) and component (II) and be placed in three-necked bottle, stir, logical N
2protection, be heated to 70～80 ℃ of reaction 30min and make it to generate polymer seeds, and then be added dropwise to simultaneously remaining component (I) and component (II), control rate of addition, component (I) and component (II) are dropwised simultaneously at 1.5～2h, continue insulation reaction 4h, obtain the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion, then, be cooled to 25～30 ℃, tune system pH is 5.0～6.0, add again epoxidized polyether base (sesquialter) siloxanes of intermediate emulsion quality 3.3～5% and the stiffening agent of intermediate emulsion quality 5.3～7%, stir 30min, with gauze, filter, the white emulsion of gained band blue-fluorescence, be (sesquialter) silicone hybrid modification fluoro polyacrylic ester emulsion, solid content is 25～30%.
Said perfluoroalkyl (methyl) acrylate is CH
2=CRCOOCH
2CH
2R
F1Or its mixture or CH
2=CRCOOCH
2R
F2, in 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, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate.In reaction, preferentially choose the CH of a=4～12
2=CHCOOCH
2CH
2R
F1Mixture or dodecafluoroheptyl methacrylate.
Said fatty clan elder's carbochain (methyl) acrylate is CH
2The mixture of one or more arbitrary proportions in=CRCOOR ', in formula R=-H or-CH
3, R '=-C
4H
9～-C
18H
37, long carbochain (methyl) acrylate 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, chloro-2-hydroxypropyl (methyl) acrylate of 3-or 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 molecule.
Said molecular weight regulator is alkyl sulfhydryl or the small molecules organic compound that contains sulfydryl, as Dodecyl Mercaptan, mercaptoethanol or Thiovanic acid.
Said sun/nonsurfactant is the mixture of cats product and nonionogenic tenside, and described the moon/nonionogenic tenside is the mixture of anion surfactant and nonionogenic tenside;
Said cats product is chosen dodecyl benzyl dimethyl ammonium chloride 1227, dodecyl dimethyl benzyl ammonium bromide, palmityl trimethyl ammonium chloride 1631, octadecyl trimethyl ammonium chloride 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, fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, aliphatic acid polyethenoxy ether ester, lipid acid anhydrous sorbitol polyoxyethylene ether-ester;
Said anion surfactant is chosen perfluoroalkyl benzene sulfonic acid sodium salt 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 as follows:
EPOS-1
Or
EPOS-2
A, b=0 in formula, 1,2 ... n, a+b=0,6,10,25, n are positive integer.Wherein, epoxidized polyether base (sesquialter) siloxane crosslinker 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 reaction raw materials
2The mol ratio of=CH-key is 1: 1.05.
In described EPOS-1 structure, preferential selection contains a/b=7: 1, the molecular-weight average (M of polyethers epoxy segment
nFour (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane (being denoted as EPOS-1A) of)=400, or contain the molecular-weight average (M of a=10, b=0, polyethers epoxy segment
nFour (2,3-glycidoxy polyoxyethylene propyl group) tetramethyl-ring tetrasiloxane (being denoted as EPOS-1B) of)=500, or contain a/b=7: 3, the molecular-weight average (M of polyethers epoxy segment
nFour (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane (being denoted as EPOS-1C) of)=1000; In described EPOS-2 structure, preferential selection contains a/b=7: 1, the molecular-weight average (M of polyethers epoxy segment
nMolecular-weight average (the M of)=400 or a=10, b=0, polyethers epoxy segment
nEight epoxidized polyether propyl group hexahedron sesquialter eight siloxanes (being denoted as respectively EPOS-2A and EPOS-2B) of the polyethers epoxy segment of)=500.
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 chemical industry as auspicious as Shanghai tiny stream company limited produces, its ionic should be with tensio-active agent used in 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 by the modification of (sesquialter) of the present invention silicone hybrid, amount to into solid content and be 30% emulsion, m (emulsion): m (water)=20～120 in mass ratio: 1000 (g/g) dilute, then with one, soaking one rolls and carries out textile finishing or spraying, fabric is through 100 ℃ of oven dry, 170 ℃ of setting 3min, then with Static Contact angle measuring instrument, hand digital palpation for examination of trauma and with reference to AATCC standard etc., the arrange application performance of fabric afterwards measured or estimated.Found that, with the fabric that emulsion of the present invention is processed, 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.
The accompanying drawing explanation
Fig. 1 is epoxidized polyether base (sesquialter) siloxane crosslinker syntheti c route figure, and in Fig. 1, Scheme1 is the synthetic route of EPOS-1, and Scheme 2 is the synthetic route of EPOS-2.
Embodiment
The present invention will be further described below in conjunction with embodiment.
The preparation of epoxidized polyether base (sesquialter) siloxane crosslinker
Referring to Fig. 1, the EPOS-1A of take is example.In the three-necked bottle that thermometer, reflux condensing tube are housed, add successively 24.1g tetramethyl-ring tetrasiloxane (D
4 H) and 168.0g a/b=7: 1, M
n=400 allyl polyethenoxy polyoxypropylene epoxy group(ing) ether (APEE), be heated with stirring to 80 ℃, then add the 50ppm platinum catalyst, turn after transparent and continue stirring reaction 10min until system, obtain 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 in Table 1.
Table 1 prepares epoxidized polyether base (sesquialter) siloxanes EPOS raw material and consumption thereof used
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 in accessing the EPOS molecule time, can be referred to as polyethers epoxy segment.
Embodiment 1: taking successively the 37.5g structure is CH
2=CHCOOCH
2CH
2(CF
2)
4～12CF
3Perfluor alkane ethyl propylene acid esters, 10.0g methacrylic 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 to the oil phase monomer mixture.Then, taking 0.7g mercaptoethanol, 2.5g palmityl trimethyl ammonium chloride 1631,1.5g fatty alcohol-polyoxyethylene ether and 163.2g deionized water mixes with the oil phase monomer mixture again, mechanical stirring mixes, then use ultrasonic wave at 30 ± 2 ℃ of emulsification 30min, make stable pre-emulsion, be denoted as component (I), be placed in dropping funnel (I), standby.
Separately get the 1.5g ammonium persulphate, make initiator solution with the 30.0g deionized water dissolving, be denoted as component (II), be placed in dropping funnel (II), standby.
At device, have in thermometer, reflux condensing tube, dropping funnel (I) and four-necked bottle (II), respectively add 1/4 component (I) and component (II), stir, logical N
2Protection; be warming up to 80 ℃ of reaction 30min; and then being added dropwise to remaining ingredient (I), (II), the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h, continues insulation reaction 4h and obtains the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion.Then, be cooled to 25～30 ℃, adjusting system pH is 5.0～6.0, then is added dropwise to 12.4g (5%, in the intermediate emulsion total mass) soluble epoxide polyether-based siloxanes EPOS-1A[Scheme1, a/b=7: 1, the molecular-weight average M of polyethers epoxy segment
n=400] and 17.3g (7%, in the intermediate emulsion total mass) stiffening agent FN-9000 stirs 30min, filter, the white emulsion of blue-fluorescence slightly, be the cation fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-1A hybrid modification, solid content is about 30%.
Embodiment 2: take successively 20.0g methacrylic ester ten difluoro heptyl esters, 20.0g vinylformic acid lauryl alcohol ester, 2.5g butyl acrylate, 3.0gN-n-methylolacrylamide, 2.0g 4-1-chloro-4-methyl-benzene and 2.5g γ-methacryloxypropyl trimethoxy silane, it is mixed and forms the oil phase monomer mixture.Then, taking 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 mixes with the oil phase monomer mixture again, mechanical stirring mixes, by ultrasonic wave at 25 ℃ of emulsification 30min, make stable pre-emulsion, be denoted as component (I), be placed in dropping funnel (I), standby.
Separately get 0.25g water-soluble azo initiator AV-40, make initiator solution with the 10.0g deionized water dissolving, be denoted as component (II), be placed in dropping funnel (II), standby.
In thermometer, reflux condensing tube, dropping funnel (I) and four-necked bottle (II) are housed, respectively add 1/4 component (I) and component (II), stir logical N
2Protection; be warming up to 70 ℃ of reaction 30min; and then being added dropwise to remaining ingredient (I), (II), the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h, continues insulation reaction 4h and obtains the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion.Then, be cooled to 25～30 ℃, adjusting system pH is 5.0～6.0, then adds 10.5g (4%, in the intermediate emulsion total mass) soluble epoxide polyether-based siloxanes EPOS-1B[Scheme1, the M of a=10, b=0, polyethers epoxy segment
n=500] and 15.7g (6%, in the intermediate emulsion total mass) stiffening agent R-55 stirs 30min, filters, and obtains even white emulsion, be the cation fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-1B hybrid modification, solid content is about 27%.
Embodiment 3: take successively 10.0g CH
2=CHCOOCH
2CH
2(CF
2)
4～12CF
3Perfluor alkane ethyl propylene acid esters, 6.0g methacrylic acid stearyl alcohol ester, 2.0g butyl acrylate, 0.6g Propylene glycol monoacrylate, 0.8g 4-1-chloro-4-methyl-benzene, 0.6g vinyltrimethoxy silane, it mix is formed to the oil phase monomer mixture.Then, take again 0.6g Dodecyl Mercaptan, 0.8g N, N '-double hexadecyl tetramethyl-bromination second two ammoniums, 0.4g fluorine carbon Soxylat A 25-7,1.8g polyoxyethylene nonylphenol ether OP-10 and 82.4g deionized water mix with the oil phase monomer mixture, after mechanical stirring mixes, by ultrasonic wave, at 30 ℃ of emulsification 30min, make stable pre-emulsion, be denoted as component (I), be placed in dropping funnel (I), standby.
Separately get the 0.3g Potassium Persulphate, make initiator solution with the 12.0g deionized water dissolving, be denoted as component (II), be placed in dropping funnel (II), standby.
In thermometer, reflux condensing tube, dropping funnel (I) and four-necked bottle (II) are housed, respectively add 1/4 component (I) and component (II), stir logical N
2Protection, be warming up to 80 ℃ of reaction 30min, then be 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 obtain the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion.Then, be cooled to 25～30 ℃, adjusting system pH is 5.0～6.0, then adds 5.5g (4.7%, in the intermediate emulsion total mass) epoxidized polyether radical siloxane linking agent EPOS-1C[Scheme1, a/b=7: 3, the M of polyethers epoxy segment
n=1000] and 6.3g (5.3%, in the intermediate emulsion total mass) stiffening agent R-55 stirs 30min, filters, and obtains white emulsion, be the cation fluoro polyacrylic ester emulsion of epoxidized polyether radical siloxane EPOS-1C hybrid modification, solid content is about 29%.
Embodiment 4: take successively 15.0g dodecafluoroheptyl methacrylate, 7.5g vinylformic acid hexadecanol ester, 0.8g Hydroxyethyl acrylate, 1.2g 4-1-chloro-4-methyl-benzene, 0.5g vinyltriethoxysilane, it is mixed and forms the oil phase monomer mixture.Then, take again 0.4g Dodecyl Mercaptan, 0.6g N, N '-double hexadecyl tetramethyl-bromination second two ammoniums, 0.2g fluorine carbon Soxylat A 25-7,1.0g polyoxyethylene nonylphenol ether OP-10 and 89.2g deionized water mix with the oil phase monomer mixture, after mechanical stirring mixes, by ultrasonic wave, at 30 ℃ of pre-emulsification 30min, make stable pre-emulsion, be denoted as component (I), be placed in dropping funnel (I), standby.
Separately get the 0.5g ammonium persulphate, make initiator solution with the 20.0g deionized water dissolving, be denoted as component (II), be placed in dropping funnel (II), standby.
In thermometer, reflux condensing tube, dropping funnel (I) and four-necked bottle (II) are housed, respectively add 1/4 component (I) and component (II), stir logical N
2Protection; be warming up to 75 ℃ of reaction 30min; be added dropwise to remaining ingredient (I), (II), the rate of addition of controlling the two makes it to dropwise simultaneously in 1.5～2h again, continues insulation reaction 4h and obtains the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion.React complete, be cooled to 25～30 ℃, adjusting system pH is 5.0～6.0, then adds 4.5g (3.3%, in the intermediate emulsion total mass) eight epoxidized polyether propyl group hexahedron silsesquioxane EPOS-2A[Scheme 2, a/b=7: 1, the M of polyethers epoxy segment
n=400] and 5.5g (6.7%, in the intermediate emulsion total mass) stiffening agent FN-9000 stirs 30min, filter, the emulsion of blue-fluorescence slightly, be the cation fluoro polyacrylic ester emulsion of epoxidized polyether base silsesquioxane EPOS-2A hybrid modification, solid content is about 25%.
Embodiment 5: taking successively the 13.5g structure 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 to the oil phase monomer mixture.Then, taking 0.5g Dodecyl Mercaptan, 0.5g perfluoroalkyl benzene sulfonic acid sodium salt, 0.5g fatty alcohol-polyoxyethylene ether and 92.0g deionized water mixes with the oil phase monomer mixture again, mechanical stirring mixes, by ultrasonic wave at 30 ℃ of emulsification 30min, make stable pre-emulsion, be denoted as component (I), be placed in dropping funnel (I), standby.
Separately get 0.4g water-soluble azo initiator AV-50, make initiator solution with the 14.0g deionized water dissolving, be denoted as component (II), be placed in dropping funnel (II), standby.
In thermometer, reflux condensing tube, dropping funnel (I) and four-necked bottle (II) are housed, respectively add 1/4 component (I) and component (II), stir logical N
2Protection; be warming up to 80 ℃ of reaction 30min, then be added dropwise to remaining ingredient (I), (II), the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h; then continue insulation reaction 4h, obtain the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion.Then, be cooled to 25～30 ℃, adjusting system pH is 5.0～6.0, then adds 5.0g (3.8%, in the intermediate emulsion total mass) epoxidized polyether radical siloxane EPOS-1A[Scheme1 (1), a/b=7: 1, the M of polyethers epoxy segment
n=400] and 8.2g (6.2%, in the intermediate emulsion total mass) stiffening agent FN-9000 stir 30min, filter, the emulsion of blue-fluorescence slightly, 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 successively 14.5g methacrylic ester ten difluoro heptyl esters, 7.5g vinylformic acid stearyl alcohol ester, 1.5g Propylene glycol monoacrylate, the chloro-2-HPMA of 0.8g 3-, 0.7g vinyltrimethoxy silane, it is mixed and forms the oil phase monomer mixture.Then, taking 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 mixes with the oil phase monomer mixture again, after mechanical stirring mixes, by ultrasonic wave at 30 ℃ of emulsification 30min, make stable pre-emulsion, be denoted as component (I), be placed in dropping funnel (I), standby.
Separately get the 0.6g Potassium Persulphate, use 15.0g H
2The O deionized water dissolving is made initiator solution, is denoted as component (II), is placed in dropping funnel (II), standby.
In thermometer, reflux condensing tube, dropping funnel (I) and four-necked bottle (II) are housed, respectively add 1/4 component (I) and component (II), stir logical N
2Protection; be warming up to 75 ℃ of reaction 30min, then be added dropwise to remaining ingredient (I), (II), the rate of addition of controlling the two makes it to dropwise simultaneously at 1.5～2h; continue insulation reaction 4h, obtain the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion.Then, be cooled to 25～30 ℃, adjusting system pH is 5.0～6.0, then adds 6.1g (4.4%, in the intermediate emulsion total mass) epoxidized polyether base silsesquioxane EPOS-2B[Scheme 2, a=10, b=0, polyethers epoxy segment M
n=500] and 7.7g (5.4%, in the intermediate emulsion total mass) stiffening agent R-55 stir 30min, filter, obtain 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 to arrange and uses the work body lotion.Separately get polyester piece good, it is impregnated into and in this body lotion, soaks a roll process with one and arrange, pick-up is about 70%.Fabric dries 5min in 100 ℃, then, in 170 ℃ of setting 3min, then is placed in moisture eliminator equilibrium at room temperature 24h, by the hand digital palpation for examination of trauma, estimates stiff feel, and carries out performance measurement with reference to related standards.Wherein, the hydrophobic performance of fabric face, θ means with static contact angle, measures with JC2000 type static contact angle determinator; The oil repellent of fabric face, measure with reference to the AATCC118-2007 standard, and it the results are shown in 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 (10)
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 will contain fluoroalkyl (methyl) acrylate and fatty clan elder's carbochain (methyl) acrylate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane first carry out the seed emulsion copolymerization at water, the long carbochain fluoro polyacrylic ester of synthesizing silaneization intermediate emulsion, then be down to room temperature, adjusting system pH is 5.0～6.0, be added into again epoxidized polyether base (sesquialter) siloxane crosslinker and stiffening agent and continue to stir 30min, after filtration, the emulsion of gained, the fluoro polyacrylic ester emulsion of i.e. (sesquialter) silicone hybrid modification, said fatty clan elder's carbochain (methyl) acrylate is CH
2the mixture of one or more arbitrary proportions in=CRCOOR', in formula R=-H or-CH
3, R'=-C
4H
9～-C
18H
37
Said sun/nonsurfactant is the mixture of cats product and nonionogenic tenside, and described the moon/nonionogenic tenside is the mixture of anion surfactant and nonionogenic tenside.
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, to contain fluoroalkyl (methyl) acrylate, fat clan elder's carbochain (methyl) acrylate, reaction-ity ethylene base monomer and α-alkenyl alkoxy silane mixes and forms the oil phase monomer mixture, in the oil phase monomer mixture, the massfraction of each component is respectively that to contain fluoroalkyl (methyl) acrylate be 40～75%, fat clan elder's carbochain (methyl) acrylate 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 again 0.6～3.0% molecular weight regulator, 4.0 sun/nonionogenic tenside of～15% or the moon/nonionogenic tenside and metering deionized water mix with the oil phase monomer mixture, after mechanical stirring mixes, with ultrasonic wave pre-emulsification 30min, make pre-emulsion, be denoted as component (I),
(2) press oil phase monomer mixture quality, then take 0.5～3% initiator, with the deionized water dissolving of 20～40 times of amounts, make initiator solution, be denoted as component (II);
(3) respectively get 1/4 component (I) and component (II) and be placed in three-necked bottle, stir, logical N
2protection, be heated to 70～80 ℃ of reaction 30min and generate polymer seeds, and then be added dropwise to simultaneously remaining component (I) and component (II), control rate of addition, component (I) and component (II) are dropwised simultaneously at 1.5～2h, continue insulation reaction 4h, obtain the long carbochain fluoro polyacrylic ester of silanization intermediate emulsion, then, be cooled to 25～30 ℃, adjusting pH is 5.0～6.0, add again epoxidized polyether base (sesquialter) siloxanes of intermediate emulsion quality 3.3～5% and the stiffening agent of intermediate emulsion quality 5.3～7%, stir 30min, with gauze, filter, the white emulsion of gained band blue-fluorescence, be (sesquialter) silicone hybrid modification fluoro polyacrylic ester emulsion, 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:
It is said that to contain fluoroalkyl (methyl) acrylate be CH
2=CRCOOCH
2CH
2R
F1Or its mixture or CH
2=CRCOOCH
2R
F2, in formula, R=-H or-CH
3, R
F1=(CF
2)
aCF
3, a=4～12, R
F2=CF (CF
3) CHFCF (CF
3)
2
Fat clan elder's carbochain (methyl) acrylate 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, chloro-2-hydroxypropyl (methyl) acrylate of 3-or 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 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 compound that contains sulfydryl.
5. the preparation method of (sesquialter) according to claim 4 silicone hybrid modification fluoro polyacrylic ester emulsion, it is characterized in that: said alkyl sulfhydryl is Dodecyl Mercaptan, and the said small molecules organic compound that contains sulfydryl is mercaptoethanol or Thiovanic acid.
6. the preparation method of (sesquialter) according to claim 1 and 2 silicone hybrid modification fluoro polyacrylic ester emulsion, it is characterized in that: said cats product is chosen dodecyl benzyl dimethyl ammonium chloride 1227, dodecyl dimethyl benzyl ammonium bromide, palmityl trimethyl ammonium chloride 1631, octadecyl trimethyl ammonium chloride 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, fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, aliphatic acid polyethenoxy ether ester, lipid acid anhydrous sorbitol polyoxyethylene ether-ester;
Said anion surfactant is chosen perfluoroalkyl benzene sulfonic acid sodium salt FBS, polyoxyethylenated alcohol sodium sulfate AES, sodium lauryl sulphate or dodecyl sulphate potassium.
7. 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 or Potassium Persulphate.
8. 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 as follows:
EPOS-1
Or
EPOS-2
A, b=0 in formula, 1,2 ... n, n are positive integer, wherein, and epoxidized polyether base (sesquialter) siloxane crosslinker 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 reaction raw materials
2The mol ratio of=CH-key is 1:1.05.
9. 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 tensio-active agent used in letex polymerization ionic identical.
10. the preparation method of (sesquialter) according to claim 8 silicone hybrid modification fluoro polyacrylic ester emulsion is characterized in that:
In described EPOS-1 structure, the preferential molecular-weight average M that selects to contain a/b=7:1, polyethers epoxy segment
nWater-soluble four (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane of=400; The molecular-weight average M that perhaps contains a=10, b=0, polyethers epoxy segment
nWater-soluble four (2,3-glycidoxy polyoxyethylene propyl group) tetramethyl-ring tetrasiloxane of=500; The molecular-weight average M that perhaps contains a/b=7:3, polyethers epoxy segment
nWater-soluble four (2,3-glycidoxy polyoxyethylene polyoxypropylene propyl group) tetramethyl-ring tetrasiloxane of=1000; In described EPOS-2 structure, the preferential molecular-weight average M that selects to contain a/b=7:1, polyethers epoxy segment
n=400 or the molecular-weight average M of a=10, b=0, polyethers epoxy segment
n=500 eight epoxidized polyether propyl group hexahedron sesquialter eight siloxanes.
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| CN104262639B (en) * | 2014-09-05 | 2016-11-23 | 陕西科技大学 | The preparation method of super-hydrophobic cross linking polysiloxane-polysilsesquioxane nanosphere hybrid material |
| CN105780471A (en) * | 2014-12-22 | 2016-07-20 | 常熟市虹桥印染有限公司 | Antistatic finishing agent for fabric |
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