CN100480461C - Method of preparing fluorine and silicon containing hydrophobic and oil repellent fabric finishing agent - Google Patents
Method of preparing fluorine and silicon containing hydrophobic and oil repellent fabric finishing agent Download PDFInfo
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- CN100480461C CN100480461C CNB2007100672831A CN200710067283A CN100480461C CN 100480461 C CN100480461 C CN 100480461C CN B2007100672831 A CNB2007100672831 A CN B2007100672831A CN 200710067283 A CN200710067283 A CN 200710067283A CN 100480461 C CN100480461 C CN 100480461C
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Abstract
The invention discloses a method for preparing fluorine hydrophobic oil-repellent fabric finishing agent, wherein the finishing agent is lacte emulsion with blue fluorescence. And the preparation comprises that using fluorine monometer, hydrocarbons unsaturated monometer, acid monometer and functional monometer as material, with inducer, adjusting agent, buffer agent and emulsifier, via emulsion polymerization method to be composed to obtain needed finishing agent. The inventive finishing agent has better hydrophobic oil-repellent effect, high stability and high yield, or the like.
Description
(1) technical field
The present invention relates to a kind of is raw material with fluorochemical monomer, silicon-containing monomer, hydro carbons unsaturated monomer, functional monomer, through synthetic fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent of emulsion copolymerization method and preparation method thereof.
(2) background technology
Fluorine-containing textile finishing agent is the outstanding textile finishing chaste tree of generally acknowledging in the world, and it has excellent performance and unique purposes, has development prospect and promotional value, is attracted attention by common people.Its outstanding performance show as have good hydrophobic and lyophobic property, gas permeability and washable, antifouling and easy soil release characteristics; Have high surface-activity and under various environment such as strong acid, highly basic, high temperature and high radiation, have very high stability.Because fluorine-containing textile finishing agent has low concentration, high effect, make the fabric of handling to keep the gas permeability and the poisture-penetrability of original color and luster, good hand feeling, excellence, snugness of fit, corrosion-resistant, wash resistant.Fluorine-containing textile finishing agent is compared with common finishing agents such as traditional silicone-based, pyridine system, paraffin series in each side such as hydrophobic and lyophobic property, soil resistance, washability, rub resistance, corrosion resistances all has remarkable advantages, thereby developed rapidly, become the main flow of current hydrophobic and oil repellent finishing agent.At present, fluorine-containing textile finishing agent is widely used in rainproof garment fabric, clothes, curtain and carpet etc., also is used to produce series of products such as surfactant, waterproofing agent for leather, anti-fouling agent, the grease proofing sizing agent of papermaking.
The fluorine-containing hydrophobic and oil repellent fabric finishing agent of industrial use is the polyvinyls of (methyl) esters of acrylic acid, and this base polymer is made up of the fluorine-containing alkyl that contains long-chain, main polymer chain and other non-fluoro functional monomer.The polymer of independent perfluoroalkyl (methyl) acrylate can not become practical hydrophobic and oil repellent fabric finishing agent, generally speaking, give film forming and with the associativity of fiber, can form with one or more non-fluorine monomer copolymerization.The method that is usually used in preparing fluorine-containing textile finishing agent has: (1) homopolymerization method; (2) random copolymerization method; (3) segment copolymerization method.
The invention main points of this patent be with fabric as process object, make it have water and oil-resistant simultaneously and have flexibility again.In order to make fibre not only possess water and oil-resistant but also have flexibility, and cooperate water and oil repellent agent to be put in order application with amino modified organosilan, carboxy-modified modification softeners such as organosilan.Yet this water and oil repellent agent can satisfy the needs that the requirement of flexibility but can't be satisfied grease-proof and waterproof.Therefore, some research once attempts to make water and oil-resistant and flexibility to set up simultaneously, and the perfluoroalkyl carbamate is connected with organosilan, becomes the compound of certain molecular weight scope, and this respect has patent report.In addition, also have and use the compound reaction modifying that contains perfluoro alkyl group on the organopolysiloxane skeleton, purpose also is for water and oil-resistant is combined with flexibility.But how adapting to existing problem of producing the emulsion copolymerization operation of generally using in the water and oil repellent agent technology does not at present solve.Purpose of the present invention is just by emulsion polymerisation, the finishing agent that makes waterproof and oilproof composition in the existing water and oil repellent agent and softener composition be copolymerized into water and oil-resistant and flexibility coexistence.Research background in this respect is as follows:
CA110,194612 provide a kind of method for preparing fluorine, the soft water and oil repellent agent of silicon, with perfluoroalkyl ethyl alcohol and hexamethylene diisocyanate trimer, α, ω-two (3-hydroxypropyl) dimethyl siloxane prepares carbamate, on cotton and nylon fabrics favorable waterproof property is arranged all, feel is good, but oil preventing performance is subjected to certain influence.CA128,102912 usefulness both-ends are by the containing hydrogen silicone oil and the perfluoroolefine C of methyl blocking
8F
17CH=CH
2At chloroplatinic acid is catalyst, at EtO (CH
2CH
2O)
2Among the H, 120 ℃ through addition reaction in 6 hours, the Cl of its product 0.5%
2FCCF
2Solution can be used as the soft anti-fouling agent of cotton, polyester and nylon fabrics.CA112,79351 provide a kind of preparation method who contains the polyurethanes-silicone fabric finishing agent of perfluoroalkyl, with the polyurethanes that contains perfluoroalkyl with have 2 polysiloxane groups more than the functional group the heating under the reaction (also can in the presence of catalyst, react), the NCO/OH equivalent proportion is 1:1, and product and other auxiliary agent have good common capacitive.CA111, the 176800 both-ends amido silicon oil and the C of methyl blocking
7F
15CO
2Me at room temperature reacts, and makes amino amidatioon fully make fluorine-containing siloxanes, the Cl of its product 0.5%
2FCCF
2Solution can be used as the soft anti-fouling agent of cotton, polyester and nylon fabrics.Fluorine-containing siloxanes can be the same as with the compound siloxanes softener, but because the increase of degree of amidation, so better anti-fouling effect is arranged.CA129,17036 use 0.5% CF
3(CF
2)
7(CH
2)
2Si (NCO)
3C
2Cl
3F
3Solution is handled nylon fabrics, can obtain the excellent waterproof grease proofness, but because CFC endangers ozone layer as solvent, practical application must be sought replace solvents.CA111,136488 adopt perfluoro capryl ethyl alcohol and both-end to use the epoxy radicals silicone oil of methyl blocking at BF
3.Et
2O exists down, and 60 ℃ were reacted 8 hours, and obtained fluorine-containing siloxanes, the Cl of its product 0.5%
2FCCF
2Solution can be used as the soft anti-fouling agent of cotton, polyester and nylon fabrics.CA119,11946 adopt trimethoxy thiazolinyl silane and two (perfluor-2-methyl-3-oxa-acetyl group) peroxide at Cl
2FCCF
2In solution stirred 5 hours in 60 ℃, obtain mean molecule quantity and be 850 polymer, it is dissolved in the acetone, handle obtaining fluorosilicone, the F of this fluorosilicone in 5 hours with hydrochloric acid reflux
3CCF
2CHCl
2-ClCF
2CF
2CHClF solution can be used as polyester, cotton water-proof finish uses.CA111, contain on the side chain of 176799 usefulness both-ends by methyl blocking the silicone oil of carboxyl and perfluoroalkyl alcohol in toluene in the presence of the catalyst 1200 ℃ of reactions carried out esterification, the Cl of the fluorine-containing siloxanes 0.5% of gained in 8 hours
2FCCF
2Solution can be used as the waterproof of cotton, polyester and nylon fabrics, grease proofing and soft treatment.CA114,64196 usefulness alkenyl siloxane and perfluoroalkyl mercaptan carry out addition reaction in 100～105 ℃ in the presence of AIBN, its product can be used for the waterproof and oilproof of COTTON FABRIC to be handled, and effect is fine, and washing fastness is good.
(3) summary of the invention
The purpose of this invention is to provide and a kind ofly have good hydrophobic, hate oil, soft effect, good appearance and stability and have fluorine-containing, the silicon polymer hydrophobic and oil repellent fabric finishing agent of good compatibility and a kind of technology is simple, productive rate is high, do not have the preparation method of fluorine-containing, the silicon polymer hydrophobic and oil repellent fabric finishing agent of " three wastes " substantially with other printing and dyeing assistant.
Fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent of the present invention is the emulsion of milky white colour band blue-fluorescence, be to be raw material with fluorochemical monomer, hydro carbons unsaturated monomer, silicon-containing monomer and functional monomer, in the presence of initator, conditioning agent, buffer and emulsifying agent, synthetic through the emulsion copolymerization method; Described fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent is to be made by the raw material of weight components:
6～12 parts of fluorochemical monomers
4～10 parts of hydro carbons unsaturated monomers
1～5 part of silicon-containing monomer
1～5 part of functional monomer
0.1～0.5 part of initator
4～12 parts of emulsifying agents
0.1～1 part of buffer
0.1～1 part of conditioning agent
50～150 parts of deionized waters
Wherein, described fluorochemical monomer is one of following compounds or arbitrarily several combination: 1. perfluoro hexyl ethyl propylene acid esters, 2. perfluoro capryl ethyl propylene acid esters, 3. perfluor decyl ethyl propylene acid esters, 4. perfluoro hexyl ethyl-methyl acrylate, 5. perfluoro capryl ethyl-methyl acrylate, 6. perfluor decyl ethyl-methyl acrylate;
Described hydro carbons unsaturated monomer is one of following: 1. (methyl) acrylic ester compound, 2. vinyl compound;
Described silicon-containing monomer is one of following compounds: mono-vinyl silicone oil, (methyl) acryloxy trimethoxy silane, (methyl) acryloxy triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, D
4(octamethylcy-clotetrasiloxane), DMC (dimethyl-silicon alkylene oxide);
Described functional monomer is for having the unsaturated compound of a functional group at least;
Described initator is one of following: 1. water-soluble persulfate, 2. oil-soluble azo compound or organic peroxide, the 3. water soluble compound of azo class;
Described buffer is water-soluble phosphoric acid hydrogen salt, dihydric phosphate, bicarbonate, carbonate etc.;
Described conditioning agent is a sulfur alcohol compound;
Described emulsifying agent is one of following compounds or any several combination: 1. quaternary cationic surfactant; 2. fatty alcohol-polyoxyethylene ether series non-ionic surfactants; 3. polyalcohol series non-ionic surfactants.
Specifically, described hydro carbons unsaturated monomer is one of following: (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid laurate, (methyl) stearyl acrylate acid esters, (methyl) acrylamide, acrylonitrile, acrolein, vinylacetate, styrene, ethene, vinyl chloride, vinylidene chloride etc.
Described functional monomer is (methyl) acrylic acid, itaconic acid, maleic acid, N hydroxymethyl acrylamide, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) glycidyl acrylate etc.
Described initator is one of following: potassium peroxydisulfate, ammonium persulfate etc., azodiisobutyronitrile (AIBN), azo 2,4-nitrile dimethyl, benzoyl peroxide (BPO), azo diisobutyl amidine hydrochloride (AIBA) etc.
Described conditioning agent is positive lauryl mercaptan, acetic acid n-dodecyl mercaptan ester, succinic acid list-n-dodecyl mercaptan ester, ethanedioic acid two-n-dodecyl mercaptan ester etc.
Described quaternary cationic surfactant is 1231,1631,1831,1227,1627,1827 etc.;
Described fatty alcohol-polyoxyethylene ether series non-ionic surfactants is paregal O, paregal O-10, paregal O-25, paregal O-35, peregal A-20, SG-10, LAE-9, AEO
8, AEO
9Deng;
Described polyalcohol series non-ionic surfactants is Arlacel-60, Arlacel-80, Arlacel-83, Tween-60, Tween-80, Tween-81, Tween-85 etc.
Optimum emulsifying agent is the mixture of cationic surfactant and non-ionic surface active agent.
Preparation method fluorine-containing, the silicon hydrophobic and oil repellent fabric finishing agent is as follows:
At room temperature fluorochemical monomer, hydro carbons unsaturated monomer, silicon-containing monomer, functional monomer, emulsifying agent, buffer, conditioning agent and deionized water in the component are placed mulser, pre-emulsification forms stable white pre-emulsion; Pre-emulsion is transferred in the reaction vessel; under nitrogen protection; stir, be warming up to 50～80 ℃; add initator; reaction is when having obvious blue fluorescence to occur; continue insulation 0.5～2.0 hour, cooling, the white emulsion that obtains having blue-fluorescence is described fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent.
Concrete recommendation is preparation method fluorine-containing, the silicon hydrophobic and oil repellent fabric finishing agent carry out according to following steps:
(1) at room temperature with perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, the mixture of perfluor decyl ethyl propylene acid esters (weight ratio is 1:3:1) 6.0～12.0 grams, stearyl acrylate acid esters 4.0～10.0 grams, allyltrimethoxysilanis 1.0～5.0 grams, glycidyl methacrylate 1.0～5.0 grams, cationic surfactant 1,231 1.0～3.0 grams, the non-ionic surface active agent Arlacel-80, Tween-80 (weight ratio 1:2) 3.0～9.0 grams, positive lauryl mercaptan 0.1～1.0g, potassium dihydrogen phosphate 0.1～1.0 gram and deionized water 50～150 grams place mulser, pre-emulsification 0.5 hour forms stable white pre-emulsion;
(2) above-mentioned pre-emulsion is transferred in the container; under nitrogen protection; stir, heat up; at 50～80 ℃, add ammonium persulfate 0.1～0.5 gram, react after 5～15 minutes; when obvious blue fluorescence occurs; continue insulation 0.5～2.0 hour, cool off, obtain having the white emulsion of blue-fluorescence at last.
Fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent provided by the invention is the emulsion of milky white colour band blue-fluorescence, have good waterproof, grease proofing, antifouling property, make fabric sofetening, washable, and have good penetration and a film forming ability, and good stable, at room temperature place 1 year, not stratified, no obvious sediment.The waterproof ability of emulsion reaches 100 fens (AATTC22-1-1989 standard, terylene), and grease proofing ability reaches 4 grades (AATTC118-1983 standard, nylon), with other printing and dyeing assistant excellent compatibility is arranged.Preparation technology is simple, productive rate is high, do not have " three wastes " substantially.
(4) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not restricted to this.Hydrophobicity performance of gained hydrophobic and oleophobic agent (terylene) and oil preventing performance (nylon) are pressed AATTC22-1-1989 standard A ATTC118-1983 standard testing.
Embodiment 1
With 6.0 gram perfluoro hexyl ethyl propylene acid esters, 4.0 gram (methyl) ethyl acrylate, 1.0 gram methacryloxy trimethoxy silane, 1.0 gram N hydroxymethyl acrylamides, 1.0 gram cationic surfactants 1231,3.4 gram non-ionic surface active agent paregal O, 0.1 restrain positive lauryl mercaptan, 0.1 gram sodium bicarbonate, 50 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 50 ℃, add ammonium persulfate 0.10 gram, reacting has obvious blue fluorescence to occur after 15 minutes, can lower the temperature after 2.0 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 70 minutes, and grease proofing have 3 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 2
With 7.2 gram perfluoro capryl ethyl propylene acid esters, 4.5 gram (methyl) Isooctyl acrylate monomer, 1.5 gram acryloxy trimethoxy silane, 1.5 gram acrylamides, 2.0 gram cationic surfactants 1631,3.4 gram non-ionic surface active agent paregal O-25,0.2 gram acetic acid n-dodecyl mercaptan ester, 0.2 gram saleratus, 60 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 55 ℃, add potassium peroxydisulfate 0.15 gram, reacting has obvious blue fluorescence to occur after 12 minutes, can lower the temperature after 2.0 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 70 minutes, and grease proofing have 3 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 3
With 12.0 gram perfluoro capryl ethyl propylene acid esters, 8.2 gram stearyl acrylate acid esters, 4.5 the gram allyltrimethoxysilanis, 1.7 gram glycidyl methacrylate, 2.0 gram cationic surfactants 1627,8.0 gram non-ionic surfactant Tween-80,0.2 restrain positive lauryl mercaptan, 0.1 gram potassium dihydrogen phosphate, 120 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.30 gram, reacting has obvious blue fluorescence to occur after 6 minutes, can lower the temperature after 1.0 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 90 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 4
With 10.0 gram perfluoro capryl ethyl propylene acid esters, 8.2 gram stearyl acrylate acid esters, 4.5 the gram allyltrimethoxysilanis, 1.7 gram glycidyl methacrylate, 2.0 gram cationic surfactants 1827,8.0 gram non-ionic surface active agent Arlacel-80,0.2 restrain positive lauryl mercaptan, 0.1 gram potassium dihydrogen phosphate, 120 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.30 gram, reacting has obvious blue fluorescence to occur after 6 minutes, can lower the temperature after 1.0 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 80 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 5
With 8.5 gram perfluor decyl ethyl propylene acid esters, 5.0 gram (methyl) acrylic acid laurate, 2.0 gram methacryloxy triethoxysilane, 1.7 gram hydroxy-ethyl acrylates, 3.0 gram cationic surfactants 1831,3.4 gram non-ionic surface active agent peregal A-20,0.5 gram succinic acid list-n-dodecyl mercaptan ester, 0.5 gram sodium carbonate, 70 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 60 ℃, add AIBN 0.20 gram, reacting has obvious blue fluorescence to occur after 11 minutes, can lower the temperature after 1.8 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 70～80 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 6
With 9.7 gram perfluoro hexyl ethyl-methyl acrylate, 5.7 gram (methyl) stearyl acrylate acid esters, 2.5 gram acryloxy front three ethylsilane, 2.7 gram hydroxypropyl acrylates, 2.0 gram cationic surfactants 1227,6.0 gram non-ionic surface active agent SG-10,0.2 gram ethanedioic acid two-n-dodecyl mercaptan ester, 0.8 gram potash, 80 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 65 ℃, add 0.20 gram BPO, reacting has obvious blue fluorescence to occur after 10 minutes, can lower the temperature after 1.6 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 70～80 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 7
With 10.2 gram perfluoro capryl ethyl-methyl acrylate, 6.2 gram acrylonitrile, 3.0 gram methacryloxy trimethoxy silane, 3.7 gram hydroxyethyl methylacrylate, 1.0 gram cationic surfactant 1231 and 1631 (weight ratio 1:1), 6.0 gram non-ionic surface active agent LAE-9, AEO8 (weight ratio 1:1), 0.8 restrain positive lauryl mercaptan, 1.0 gram dibastic sodium phosphate, 90 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add azo (2, the 4-nitrile dimethyl) 0.20 gram, reacting has obvious blue fluorescence to occur after 10 minutes, can lower the temperature after 1.5 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 80 minutes, and grease proofing have 5 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 8
With 11.2 gram perfluor decyl ethyl-methyl acrylate, 7.3 gram vinylacetate, 3.5 gram vinyltrimethoxy silane, 4.7 gram hydroxy propyl methacrylate, 3.0 gram cationic surfactant 1231 and 1831 (weight ratio 1:1), 6.0 gram non-ionic surface active agent Arlacel-60, Tween-60 (weight ratio 1:1), 1.0 restrain positive lauryl mercaptan, 0.1 gram potassium hydrogen phosphate, 100 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 75 ℃, add AIBA 0.20 gram, reacting has obvious blue fluorescence to occur after 9 minutes, can lower the temperature after 1.2 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 80～90 minutes, and grease proofing have 5 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 9
With 12.0 gram perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, the mixture of perfluor decyl ethyl propylene acid esters (weight ratio is 1:3:1), 7.5 gram styrene, 4.0 gram vinyltriethoxysilane, 5.0 gram glycidyl acrylate, 1.0 gram cationic surfactant 1231 and 1227 (weight ratio 1:1), 8.0 gram non-ionic surface active agent paregal O-25, paregal O-35 (weight ratio 1:1), 0.2 restrain positive lauryl mercaptan, 0.1 gram sodium dihydrogen phosphate, 110 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 80 ℃, add ammonium persulfate 0.25 gram, reacting has obvious blue fluorescence to occur after 8 minutes, can lower the temperature after 1.0 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 90 minutes, and grease proofing have 3 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 10
With 12.0 gram perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, the mixture of perfluor decyl ethyl propylene acid esters (weight ratio is 3:1:1), 8.2 gram stearyl acrylate acid esters, 4.5 gram allyltrimethoxysilanis, 1.7 gram glycidyl methacrylate, 2.0 gram cationic surfactant 1231,8.0 gram non-ionic surface active agent Arlacel-80, Tween-80 (weight ratio 1:2), 0.2 restrain positive lauryl mercaptan, 0.1 gram potassium dihydrogen phosphate, 120 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.30 gram, reacting has obvious blue fluorescence to occur after 6 minutes, can lower the temperature after 1.0 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 100 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 11
With 12.0 gram perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, the mixture of perfluor decyl ethyl propylene acid esters (weight ratio is 1:3:1), 8.2 gram stearyl acrylate acid esters, 4.5 gram allyltrimethoxysilanis, 1.7 gram glycidyl methacrylate, 2.0 gram cationic surfactant 1231,8.0 gram non-ionic surface active agent Arlacel-80, Tween-80 (weight ratio 1:2), 0.2 restrain positive lauryl mercaptan, 0.1 gram potassium dihydrogen phosphate, 120 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.30 gram, reacting has obvious blue fluorescence to occur after 6 minutes, can lower the temperature after 1.0 hours in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 100 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 12
With 12.0 gram perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, the mixture of perfluor decyl ethyl propylene acid esters (weight ratio is 1:1:3), 8.8 gram acrylic acid laurate, 5.0 gram allyltriethoxysilane, 1.7 gram acrylamide, 3.0 gram cationic surfactant 1631,8.0 gram non-ionic surface active agent Arlacel-80, Tween-80 (weight ratio 1:3), 0.2 restrain positive lauryl mercaptan, 0.1 gram sodium bicarbonate, 130 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.35 gram, reacting has obvious blue fluorescence to occur after 5 minutes, can lower the temperature after 0.8 hour in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 90 minutes, and grease proofing have 5 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 13
With the mixture (weight ratio is 1:3:1) of 12.0 gram perfluoro hexyl ethyl-methyl acrylate, perfluoro capryl ethyl-methyl acrylate, perfluor decyl ethyl-methyl acrylate, 9.2 gram alkyl acrylates, 2.5 gram D
41.7 gram N hydroxymethyl acrylamide, 1.2 gram cationic surfactant 1831,3.4 gram non-ionic surface active agent Arlacel-83, Tween-85 (weight ratio is 1:4), 0.2 restrain positive lauryl mercaptan, 0.1 gram sodium bicarbonate, 140 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.40 gram, reacting has obvious blue fluorescence to occur after 5 minutes, can lower the temperature after 0.8 hour in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 90 minutes, and grease proofing have 3 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 14
With 12.0 gram perfluoro hexyl ethyl-methyl acrylate, perfluoro capryl ethyl-methyl acrylate, the mixture of perfluor decyl ethyl-methyl acrylate (weight ratio is 3:1:1), 9.6 gram Isooctyl acrylate monomer, 3.5 gram DMC, 1.7 gram hydroxy-ethyl acrylate, 1.2 gram cationic surfactant 1231,1831 (weight ratio is 1:4), 3.4 gram non-ionic surface active agent Arlacel-83, Tween-85 (weight ratio is 1:4), 0.2 restrain positive lauryl mercaptan, 0.1 gram sodium bicarbonate, 150 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.4 gram, reacting has obvious blue fluorescence to occur after 5 minutes, can lower the temperature after 0.6 hour in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 90 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Embodiment 15
With 12.0 gram perfluoro hexyl ethyl-methyl acrylate, perfluoro capryl ethyl-methyl acrylate, the mixture of perfluor decyl ethyl-methyl acrylate (weight ratio is 1:1:3), 10.0 gram ethyl acrylate, 1.5 gram mono-vinyl silicone oil, 1.7 gram hydroxy-ethyl acrylate, 1.2 gram cationic surfactant 1227,3.4 gram non-ionic surface active agent Arlacel-60, paregal O (weight ratio is 1:4), 0.2 restrain positive lauryl mercaptan, 0.1 gram sodium bicarbonate, 90 gram deionized waters place the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5 hour, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle of devices such as stirring, logical nitrogen, condensation, thermometric are housed.Under the nitrogen protection, stir, heat up, and under 70 ℃, add ammonium persulfate 0.4 gram, reacting has obvious blue fluorescence to occur after 5 minutes, can lower the temperature after 0.5 hour in insulation, obtains having the white emulsion of blue-fluorescence.This emulsion is pressed AATTC22-1-1989 standard and its hydrophobic and oil repellent performance of AATTC118-1983 standard test, and measurement result shows that its waterproof effect is 90 minutes, and grease proofing have 4 grades.
Hydrophobic and oil repellent agent emulsion that is synthesized and waterproof crosslinking agent, antistatic additive, crease-shedding finishing agent etc. all have excellent compatibility, can be with bathe using, and be that hydrophobic and oleophobic agent is compared the fabric of handling and had softness and plentiful feel with fluorine.
Claims (8)
1. fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent, it is characterized in that described fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent is the emulsion of milky white colour band blue-fluorescence, be to be raw material with fluorochemical monomer, hydro carbons unsaturated monomer, silicon-containing monomer and functional monomer, in the presence of initator, conditioning agent, buffer and emulsifying agent, synthetic through the emulsion copolymerization method; Described fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent is to be made by the raw material of weight components:
6～12 parts of fluorochemical monomers
4～10 parts of hydro carbons unsaturated monomers
1～5 part of silicon-containing monomer
1～5 part of functional monomer
0.1～0.5 part of initator
4～12 parts of emulsifying agents
0.1～1 part of buffer
0.1～1 part of conditioning agent
50～150 parts of deionized waters
Wherein, described fluorochemical monomer is one of following compounds or arbitrarily several combination: 1. perfluoro hexyl ethyl propylene acid esters, 2. perfluoro capryl ethyl propylene acid esters, 3. perfluor decyl ethyl propylene acid esters, 4. perfluoro hexyl ethyl-methyl acrylate, 5. perfluoro capryl ethyl-methyl acrylate, 6. perfluor decyl ethyl-methyl acrylate;
Described hydro carbons unsaturated monomer is one of following: 1. (methyl) acrylic ester compound, 2. vinyl compound specifically is selected from one of following: (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid laurate, (methyl) stearyl acrylate acid esters, (methyl) acrylamide, acrylonitrile, acrolein, vinylacetate, styrene, ethene, vinyl chloride, vinylidene chloride;
Described silicon-containing monomer is one of following compounds: mono-vinyl silicone oil, (methyl) acryloxy trimethoxy silane, (methyl) acryloxy triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, D
4(octamethylcy-clotetrasiloxane), DMC (dimethyl-silicon alkylene oxide);
Described functional monomer is specially (methyl) acrylic acid, itaconic acid, maleic acid, N hydroxymethyl acrylamide, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate or (methyl) glycidyl acrylate for having the unsaturated compound of a functional group at least;
Described initator is one of following compounds: 1. water-soluble persulfate, 2. oil-soluble azo compound or organic peroxide, the 3. water soluble compound of azo class;
Described buffer is water-soluble phosphoric acid hydrogen salt, dihydric phosphate, bicarbonate or carbonate;
Described conditioning agent is a sulfur alcohol compound;
Described emulsifying agent is one of following compounds or any several combination: 1. quaternary cationic surfactant; 2. fatty alcohol-polyoxyethylene ether series non-ionic surfactants; 3. polyalcohol series non-ionic surfactants.
2. fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent as claimed in claim 1, it is characterized in that described initator is one of following: potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile (AIBN), azo 2,4-nitrile dimethyl, benzoyl peroxide (BPO), azo diisobutyl amidine hydrochloride (AIBA).
3. fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent as claimed in claim 1 is characterized in that described conditioning agent is positive lauryl mercaptan, acetic acid n-dodecyl mercaptan ester, succinic acid list-n-dodecyl mercaptan ester or ethanedioic acid two-n-dodecyl mercaptan ester.
4. fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent as claimed in claim 1 is characterized in that described quaternary cationic surfactant is 1231,1631,1831,1627,1827 or 1227.
5. fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent as claimed in claim 1, it is characterized in that described fatty alcohol-polyoxyethylene ether series non-ionic surfactants is paregal O, paregal O-10, paregal O-25, paregal O-35, peregal A-20, SG-10, LAE-9, AEO
8Or AEO
9
6. fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent as claimed in claim 1 is characterized in that described polyalcohol series non-ionic surfactants is Arlacel-60, Arlacel-80, Arlacel-83, Tween-60, Tween-80, Tween-81 or Tween-85.
7. method for preparing fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent as claimed in claim 1 is characterized in that described fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent is to be made by the raw material of weight components:
6～12 parts of fluorochemical monomers
4～10 parts of hydro carbons unsaturated monomers
1～5 part of silicon-containing monomer
1～5 part of functional monomer
0.1～0.5 part of initator
4～12 parts of emulsifying agents
0.1～1 part of buffer
0.1～1 part of conditioning agent
50～150 parts of deionized waters
Its preparation method is as follows:
At room temperature fluorochemical monomer, hydro carbons unsaturated monomer, silicon-containing monomer, functional monomer, emulsifying agent, buffer, conditioning agent and deionized water in the component are placed mulser, pre-emulsification forms stable white pre-emulsion; Pre-emulsion is transferred in the reaction vessel; under nitrogen protection; stir, be warming up to 50～80 ℃; add initator; reaction is when having obvious blue light to occur; continue insulation 0.5～2.0 hour, cooling, the white emulsion that obtains having blue-fluorescence is described fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent.
8. the preparation method of fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent as claimed in claim 7 is characterized in that described fluorine-containing, silicon hydrophobic and oil repellent fabric finishing agent is to be made by the raw material of weight components:
Weight ratio is 6～12 parts in the mixture of perfluoro hexyl ethyl propylene acid esters, perfluoro capryl ethyl propylene acid esters, the perfluor decyl ethyl propylene acid esters of 1:3:1
4～10 parts of stearyl acrylate acid esters
1～5 part of allyltrimethoxysilanis
1～5 part of glycidyl methacrylate
0.1～0.5 part of ammonium persulfate
1,231 1～3 parts of cationic surfactants
Weight ratio is 3～9 parts of non-ionic surface active agent Arlacel-80, the Tween-80 of 1:2
0.1～1 part of positive lauryl mercaptan
0.1～1 part of potassium dihydrogen phosphate
50～150 parts of deionized waters
Its preparation method carries out according to following steps:
(1) at room temperature is the perfluoro hexyl ethyl propylene acid esters of 1:3:1 with weight ratio, perfluoro capryl ethyl propylene acid esters, mixture 6.0～12.0 grams of perfluor decyl ethyl propylene acid esters, stearyl acrylate acid esters 4.0～10.0 grams, allyltrimethoxysilanis 1.0～5.0 grams, glycidyl methacrylate 1.0～5.0 grams, cationic surfactant 12311.0～3.0 grams, weight ratio is the non-ionic surface active agent Arlacel-80 of 1:2, Tween-80 3.0～9.0 grams, positive lauryl mercaptan 0.1～1.0g, potassium dihydrogen phosphate 0.1～1.0 gram and deionized water 50～150 grams place mulser, pre-emulsification 0.5 hour forms stable white pre-emulsion;
(2) above-mentioned pre-emulsion is transferred in the container; under nitrogen protection; stir, heat up; at 50～80 ℃, add ammonium persulfate 0.1～0.5 gram, react after 5～15 minutes; when obvious blue fluorescence occurs; continue insulation 0.5～2.0 hour, cool off, obtain having the white emulsion of blue-fluorescence at last.
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