CN102108109B - Preparation method of fluorine-containing fabric finishing agent - Google Patents
Preparation method of fluorine-containing fabric finishing agent Download PDFInfo
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- CN102108109B CN102108109B CN 201010612550 CN201010612550A CN102108109B CN 102108109 B CN102108109 B CN 102108109B CN 201010612550 CN201010612550 CN 201010612550 CN 201010612550 A CN201010612550 A CN 201010612550A CN 102108109 B CN102108109 B CN 102108109B
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Abstract
The invention discloses a preparation method of a fluorine-containing fabric finishing agent. The preparation method comprises the following steps: preparing dodecafluoroheptanol methacrylate or hexadecafluorononanol methacrylate by utilizing at least one of dodecafluoroheptanol or hexadecafluorononanol and one of methacrylic acid or methyl methacrylate in the presence of a catalyst; and carrying out emulsion copolymerization on one of the dodecafluoroheptanol methacrylate or hexadecafluorononanol methacrylate and at least one of the methyl methacrylate or butyl methacrylate or styrene, so as to obtain the fluorine-containing fabric finishing agent, wherein a compound emulsifier and an initiator are added in the process. In the invention, the utilized dodecafluoroheptanol or hexadecafluorononanol is low in price, thereby being beneficial to the popularization and application of the fluorine-containing fabric finishing agent. The obtained fluorine-containing fabric finishing agent has good waterproof and oil proofing properties, can be applied to waterproof and oil proofing finishing agent for cotton, terylene, cotton or terylene mixed fabrics and paper.
Description
Technical field
The present invention relates to the preparation method of fluoropolymer monomer and fluorine-containing textile finishing agent emulsion.
Background technology
Fluorine-containing textile finishing agent is a kind of after-treating auxiliary in the textile production, and it puts on fabric face makes the surface property of fabric that huge variation take place, thereby gives the fabric specific function.Fluorine-containing textile finishing agent all demonstrates stability under various environment such as strong acid, highly basic, high temperature and high radiation, the fabric after the wherethrough reason can keep good hand feeling, good ventilation property, water vapour permeability.Owing to have the incomparable advantages of each side such as hydrophobic and lyophobic property, didirtresistance, washing fastness, rub resistance, erosion resistance, obtained paying close attention to widely.
Just begin the research of fluorine-containing textile finishing agent abroad as far back as the 1950's.Nineteen fifty, U.S. DuPont company takes the lead in ptfe emulsion as fabric finishing agent.Nineteen fifty-three, Minnesota Mining and Manufacturing Company succeeds in developing the fabric finishing agent that is the main body with the perfluorocarboxylic acid chromium complex, because washing fastness is poor, is replaced by the polymkeric substance of the better fluorinated acrylate of performance very soon.1956, it was the FC series fabric finishing agent of representative that 3M company has succeeded in developing with " ScotchgardFC-208 ", and its effective constituent consists of the polymkeric substance of fluorinated acrylate.
China's fluorine-containing textile finishing agent is since the middle nineteen sixties in last century; The common development of the upright topic of organic chemistry institute of the Chinese Academy of Sciences and Shanghai organic fluorine material institute fluorine-containing textile finishing agent has been established telomerization method, electrofluorination method and three technological lines of perfluoro acetone.The cooperation of units such as middle nineteen seventies Shanghai organic fluorine material institute and Shanghai textile scientific research institute, Shanghai No. 2 Printing and Dying Factory; Operating worker labour protection condition is a problem under the oil well to improve; Ventilative, grease proofing, the waterproof working wear material of operation under the development oil well; Through effort more than 3 years, having processed with the fluorinated acrylate is the copolymer emulsion of main body.Working wear after its is handled has satisfied requirement ventilative, grease proofing, waterproof, wears comfortablely, has improved the labour protection problem of operating worker under the oil well to a certain extent.Chinese Academy of Sciences's organic chemistry institute once cooperated with Shanghai City Mercury raincoat factory and developed water and oil repellent agent the seventies early eighties in latter stage phase.
But preparing the used fluorochemical monomer of fluorine-contained finishing agent emulsion at present is perfluoroalkyl acrylate; This perfluoroalkyl acrylate price is very expensive; Seriously restricted applying of fluorine-containing textile finishing agent, therefore, it is significant to develop fabric finishing agent of high quality and at a reasonable price.
Summary of the invention
The object of the invention just is to provide a kind of preparation method of fluorine-containing textile finishing agent, and the production cost of this method is low, can produce the good fluorine-containing textile finishing agent of waterproof oil-proof result.
To achieve these goals; The technical scheme that the present invention adopts is such: a kind of preparation method of fluorine-containing textile finishing agent; This preparation method is a kind of under catalyst action at least a and methylacrylic acid or the TEB 3K that utilizes in ten difluoro enanthol or the ten hexafluoro nonyl alcohols, prepares methylacrylic acid ten difluoro enanthol esters or methylacrylic acid ten hexafluoro nonyl alcohol esters; At least a at least a and TEB 3K in said methylacrylic acid ten difluoro enanthol esters or the methylacrylic acid ten hexafluoro nonyl alcohol esters or NSC 20956 or the vinylbenzene carries out emulsion copolymerization, prepares fluorine-containing textile finishing agent; In said said process, add compound emulsifying agent and initiator.
Said compound emulsifying agent is the mixture of sodium lauryl sulphate and polyoxyethylene nonylphenol; Said initiator is Potassium Persulphate or ammonium persulfate; Said catalyzer is the vitriol oil or tosic acid.
As preferably, the mass ratio of sodium lauryl sulphate and polyoxyethylene nonylphenol is 1: 1～2 in the said compound emulsifying agent.
The preparation method of fluorine-containing textile finishing agent carries out as follows:
(1) under agitation condition, add a kind of among both of ten difluoro enanthol or ten hexafluoro nonyl alcohols, a kind of among both of methylacrylic acid or TEB 3K adds catalyzer, stopper again, feeds nitrogen at last; React 3～6h down at 80～140 ℃, after the cooling, divide disacidify; Organic phase is washed till slight alkalinity with 2.5% sodium bicarbonate aqueous solution; Be washed till neutrality with deionized water again, tell organic layer, use the anhydrous magnesium sulfate drying after-filtration; Reaction mixture is carried out underpressure distillation, obtain methylacrylic acid ten difluoro enanthol esters or methylacrylic acid ten hexafluoro nonyl alcohol esters; Wherein: the quality with ten difluoro enanthol or ten hexafluoro nonyl alcohols is a benchmark; The mol ratio of said methylacrylic acid or TEB 3K is 1: 1～1.5; The weight ratio of the vitriol oil is 10%～150%; The weight ratio of tosic acid is 1.0%～5.0%, and the weight ratio of stopper is 0.5%～2.5%, and said stopper is a kind of in thiodiphenylamine or the Resorcinol;
(2) in methylacrylic acid ten difluoro enanthol esters or methylacrylic acid ten hexafluoro nonyl alcohol esters, add deionized water, add at least a in TEB 3K or NSC 20956 or the vinylbenzene again, add compound emulsifying agent, initiator at last; Behind the logical nitrogen 30min, emulsification 30～60min in advance, it is subsequent use to take out about 2/3rds pre-emulsion, remaining 1/3rd pre-emulsions heating; When temperature reaches 75～85 ℃, stop to heat up, when treating that emulsion is blueness, begin to drip above-mentioned subsequent use pre-emulsion; Pre-emulsion 2～6h dropwises, and keeps temperature 1～2h then, cools off the emulsion that gets product; Wherein: the gross weight with pre-emulsion is a benchmark; The weight ratio of deionized water is 50%～80%; The weight ratio of Bing Xisuandingzhi is 1.0%～20%; TEB 3K or cinnamic weight ratio are 1.0%～10%, and the weight ratio of methylacrylic acid ten difluoro enanthol esters or methylacrylic acid ten hexafluoro nonyl alcohol esters is 5.0%～30%, and the weight ratio of compound emulsifying agent is 0.5%～2.0%, the initiator weight/power ratio is 0.2%～2%.
Compared with prior art, the invention has the advantages that:
1, the present invention utilizes the sub product that is produced when producing C3-Fluoroalcohol: ten difluoro enanthol or ten hexafluoro nonyl alcohols are basic raw material; Through esterification; Prepare the fluoropolymer monomer: methylacrylic acid ten difluoro heptyl esters or methylacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems; And then above-mentioned fluoropolymer monomer and propenoate or vinylbenzene and composition thereof carried out emulsion copolymerization, obtain a kind of novel, inexpensive organic fluorine finishing composition emulsion, and as the sub product that is produced in the C3-Fluoroalcohol production---ten difluoro enanthol or ten hexafluoro nonyl alcohols are cheap; Turn waste into wealth, help applying of fluorine-containing textile finishing agent.
2, the resulting fluorine-containing textile finishing agent waterproof of the present invention, oil preventing performance are good, can be applied to cotton, terylene, cotton or wash waterproof, the anti oil agent of blending fabric and paper.
Embodiment
Embodiment 1
The preparation of methylacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 64.0g ten difluoro enanthol, 18.9g methylacrylic acid, the 6.4g vitriol oil, 1.5g thiodiphenylamine successively.Feed nitrogen, behind reaction 3～6h under 85 ℃, temperature is increased to 110 ℃, boil off excessive methylacrylic acid.After the cooling; Sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, is washed till neutrality with deionized water again, tells organic layer; Use the anhydrous magnesium sulfate drying after-filtration; Reaction mixture is carried out underpressure distillation, obtain methylacrylic acid ten difluoro enanthol esters, the purity that obtains methylacrylic acid ten difluoro enanthol esters can be analyzed with vapor-phase chromatography.
The preparation of fluorine-containing textile finishing agent emulsion: in the four-hole boiling flask of the 250ml that whisking appliance, TM and reflux condensing tube are housed, the mixture of adding 70g deionized water and 15g Bing Xisuandingzhi, 5g vinylbenzene, 5g methylacrylic acid ten difluoro heptyl esters, the sodium lauryl sulphate that the 1.2g mol ratio is 1: 2 and polyoxyethylene nonylphenol blended compound emulsifying agent, 0.2g ammonium persulfate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, emulsification 30～60min in advance takes out about 2/3rds pre-emulsion and is contained in the tap funnel remaining pre-emulsion heating in water bath.When fluid temperature in the flask reaches 75～85 ℃, stop to heat up and attention maintenance constant temperature, when emulsion is blueness in the bottle, begin to drip above-mentioned subsequent use pre-emulsion; Pre-emulsion 2～6h dropwises, and keeps temperature 1～2h then, cools off the emulsion that gets product.
Embodiment 2
The preparation of methylacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 64.0g ten difluoro enanthol, 30.0g TEB 3K, 1.5g tosic acid, 1.5g Resorcinol successively.Feed nitrogen, behind reaction 3～6h under 85 ℃, temperature is increased to 110 ℃, boil off excessive TEB 3K.After the cooling; Sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, is washed till neutrality with deionized water again, tells organic layer; Use the anhydrous magnesium sulfate drying after-filtration; Reaction mixture is carried out underpressure distillation, obtain methylacrylic acid ten difluoro enanthol esters, the purity that obtains methylacrylic acid ten difluoro enanthol esters can be analyzed with vapor-phase chromatography.
The preparation of fluorine-containing textile finishing agent emulsion: in the four-hole boiling flask of the 250ml that whisking appliance, TM and reflux condensing tube are housed, add 60g deionized water and 10g Bing Xisuandingzhi, 5g TEB 3K, 20g methylacrylic acid ten difluoro heptyl esters, 1.2g mol ratio and be 1: 1 sodium lauryl sulphate and polyoxyethylene nonylphenol blended compound emulsifying agent, 0.3g Potassium Persulphate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, emulsification 30～60min in advance takes out about 2/3rds pre-emulsion and is contained in the tap funnel remaining pre-emulsion heating in water bath.When fluid temperature in the flask reaches 75～85 ℃, stop to heat up and attention maintenance constant temperature, when emulsion is blueness in the bottle, begin to drip above-mentioned subsequent use pre-emulsion; Pre-emulsion 2～6h dropwises, and keeps temperature 1～2h then, cools off the emulsion that gets product.
Embodiment 3
The preparation of methylacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 83.2g ten hexafluoro nonyl alcohols, 20.6g TEB 3K, the 16.5g vitriol oil, 1.5g thiodiphenylamine successively.Feed nitrogen, behind reaction 3～6h under 85 ℃, temperature is increased to 110 ℃, boil off excessive TEB 3K.After the cooling; Sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, is washed till neutrality with deionized water again, tells organic layer; Use the anhydrous magnesium sulfate drying after-filtration; Reaction mixture is carried out underpressure distillation, obtain methylacrylic acid ten hexafluoro nonyl alcohol esters, the purity that obtains methylacrylic acid ten hexafluoro nonyl alcohol esters can be analyzed with vapor-phase chromatography.
The preparation of fluorine-containing textile finishing agent emulsion: in the four-hole boiling flask of the 250ml that whisking appliance, TM and reflux condensing tube are housed, the mixture of adding 70g deionized water and 10g Bing Xisuandingzhi, 5g vinylbenzene, 10g methylacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems, the sodium lauryl sulphate that the 1.2g mol ratio is 1: 2 and polyoxyethylene nonylphenol blended compound emulsifying agent, 0.2g ammonium persulfate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, emulsification 30～60min in advance takes out about 2/3rds pre-emulsion and is contained in the tap funnel remaining pre-emulsion heating in water bath.When fluid temperature in the flask reaches 75～85 ℃, stop to heat up and attention maintenance constant temperature, when emulsion is blueness in the bottle, begin to drip above-mentioned subsequent use pre-emulsion; Pre-emulsion 2～6h dropwises, and keeps temperature 1～2h then, cools off the emulsion that gets product.
Embodiment 4
The preparation of methylacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 64.0g ten difluoro enanthol, 20.4g TEB 3K, 1.5g tosic acid, 1.5g thiodiphenylamine successively.Feed nitrogen, behind reaction 3～6h under 85 ℃, temperature is increased to 110 ℃, boil off excessive TEB 3K.After the cooling; Sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, is washed till neutrality with deionized water again, tells organic layer; Use the anhydrous magnesium sulfate drying after-filtration; Reaction mixture is carried out underpressure distillation, obtain methylacrylic acid ten difluoro enanthol esters, the purity that obtains methylacrylic acid ten difluoro enanthol esters can be analyzed with vapor-phase chromatography.
The preparation of fluorine-containing textile finishing agent emulsion: in the four-hole boiling flask of the 250ml that whisking appliance, TM and reflux condensing tube are housed, add 60g deionized water and 5g Bing Xisuandingzhi, 5g TEB 3K, 25g methylacrylic acid ten difluoro heptyl esters, 1.2g mol ratio and be 1: 1 sodium lauryl sulphate and polyoxyethylene nonylphenol blended compound emulsifying agent, 0.3g Potassium Persulphate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, emulsification 30～60min in advance takes out about 2/3rds pre-emulsion and is contained in the tap funnel remaining pre-emulsion heating in water bath.When fluid temperature in the flask reaches 75～85 ℃, stop to heat up and attention maintenance constant temperature, when emulsion is blueness in the bottle, begin to drip above-mentioned subsequent use pre-emulsion; Pre-emulsion 2～6h dropwises, and keeps temperature 1～2h then, cools off the emulsion that gets product.
Embodiment 5
Fluorine-containing waterproof oil-proof finishing agent emulsion stability is measured: get an amount of embodiment 1-4 gained emulsion, pour in the wide-necked bottle, build, at room temperature 20 ℃ static 3 months, no breakdown of emulsion or demixing phenomenon generation; 60 ℃ of insulations 120 hours, naturally cooling to room temperature did not have breakdown of emulsion or demixing phenomenon generation;-10 ℃ of held 2 hours slowly return to room temperature again, and emulsion does not have layering or demulsifying phenomenon; Emulsion is diluted to solids content 3%, puts into test tube to the emulsion after the 30ml dilution, and the high 20cm of fluid column placed 72 hours, and no breakdown of emulsion or demixing phenomenon take place; In the scale test tube of 20ml, add the 16ml emulsion, add the CaCl2 solution of 4ml0.5% (wt%) again, shake up, left standstill 48 hours, no breakdown of emulsion or demixing phenomenon take place.
Embodiment 6
Fluorine-containing waterproof oil-proof finishing agent emulsion stability is measured: get an amount of embodiment 1-4 gained emulsion, pour in the wide-necked bottle, build, at room temperature 20 ℃ static 3 months, no breakdown of emulsion or demixing phenomenon generation; 60 ℃ of insulations 120 hours, naturally cooling to room temperature did not have breakdown of emulsion or demixing phenomenon generation;-10 ℃ of held 2 hours slowly return to room temperature again, and emulsion does not have layering or demulsifying phenomenon; Emulsion is diluted to solids content 3%, puts into test tube to the emulsion after the 30ml dilution, and the high 20cm of fluid column placed 72 hours, and no breakdown of emulsion or demixing phenomenon take place; In the scale test tube of 20ml, add the 16ml emulsion, add the CaCl2 solution of 4ml0.5% (wt%) again, shake up, left standstill 48 hours, no breakdown of emulsion or demixing phenomenon take place.
Embodiment 7
Fluorine-containing waterproof oil-proof finishing agent waterproof and oilproof performance test: different fabrics are immersed in the embodiment 1 gained emulsion; Carry out waterproofing tests according to the 3M-II-1988 method; Carry out grease proofness by test according to AATCC 118-1992 method, gained waterproof and oilproof grade such as following table.
| Fabric | Classification of waterproof | Grease proofing grade |
| Cotton | 5 | 2 |
| Terylene | 6 | 2 |
| Wash/cotton 64/35 | 5 | 2 |
Embodiment 8
Fluorine-containing waterproof oil-proof finishing agent waterproof and oilproof performance test: different fabrics are immersed in the embodiment 2 gained emulsions; Carry out waterproofing tests according to the 3M-II-1988 method; Carry out grease proofness by test according to AATCC 118-1992 method, gained waterproof and oilproof grade such as following table.
| Fabric | Classification of waterproof | Grease proofing grade |
| Cotton | 6 | 3 |
| Terylene | 7 | 3 |
| Wash/cotton 64/35 | 6 | 3 |
Embodiment 9
Fluorine-containing waterproof oil-proof finishing agent waterproof and oilproof performance test: different fabrics are immersed in the embodiment 3 gained emulsions; Carry out waterproofing tests according to the 3M-II-1988 method; Carry out grease proofness by test according to AATCC 118-1992 method, gained waterproof and oilproof grade such as following table.
| Fabric | Classification of waterproof | Grease proofing grade |
| Cotton | 5 | 3 |
| Terylene | 6 | 3 |
| Wash/cotton 64/35 | 6 | 3 |
Embodiment 10
Fluorine-containing waterproof oil-proof finishing agent waterproof and oilproof performance test: different fabrics are immersed in the embodiment 4 gained emulsions; Carry out waterproofing tests according to the 3M-II-1988 method; Carry out grease proofness by test according to AATCC 118-1992 method, gained waterproof and oilproof grade such as following table.
| Fabric | Classification of waterproof | Grease proofing grade |
| Cotton | 6 | 3 |
| Terylene | 7 | 3 |
| Wash/cotton 64/35 | 7 | 3 |
Can find out that by embodiment 7-10 fluorine-containing textile finishing agent waterproof of the present invention, oil preventing performance are good, can be applied to cotton, terylene, cotton or wash waterproof, the anti oil agent of blending fabric and paper.
The above only is a preferred implementation of the present invention, and protection scope of the present invention also not only is confined to the foregoing description, and all technical schemes that belongs under the thinking of the present invention all belong to protection scope of the present invention.Should be pointed out that for those skilled in the art some improvement and retouching not breaking away under the principle of the invention prerequisite also should be regarded as protection scope of the present invention.
Claims (1)
1. the preparation method of a fluorine-containing textile finishing agent; It is characterized in that: this preparation method is a kind of under catalyst action at least a and methylacrylic acid or the TEB 3K that utilizes in ten difluoro enanthol or the ten hexafluoro nonyl alcohols, prepares methylacrylic acid ten difluoro heptyl esters or methylacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems; At least a at least a and TEB 3K in said methylacrylic acid ten difluoro heptyl esters or the methylacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems or NSC 20956 or the vinylbenzene carries out emulsion copolymerization, prepares fluorine-containing textile finishing agent; In said said process, add compound emulsifying agent and initiator;
Said compound emulsifying agent is the mixture of sodium lauryl sulphate and polyoxyethylene nonylphenol; Said initiator is Potassium Persulphate or ammonium persulfate; Said catalyzer is the vitriol oil or tosic acid;
The mol ratio of sodium lauryl sulphate and polyoxyethylene nonylphenol is 1: 1～2 in the said compound emulsifying agent;
The preparation method of said fluorine-containing textile finishing agent carries out as follows:
(1) under agitation condition, add a kind of among both of ten difluoro enanthol or ten hexafluoro nonyl alcohols, a kind of among both of methylacrylic acid or TEB 3K adds catalyzer, stopper again, feeds nitrogen at last; React 3～6h down at 80～140 ℃, after the cooling, divide disacidify; Organic phase is washed till slight alkalinity with 2.5% sodium bicarbonate aqueous solution; Be washed till neutrality with deionized water again, tell organic layer, use the anhydrous magnesium sulfate drying after-filtration; Reaction mixture is carried out underpressure distillation, obtain methylacrylic acid ten difluoro heptyl esters or methylacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems; Wherein: the quality with ten difluoro enanthol or ten hexafluoro nonyl alcohols is a benchmark; The mol ratio of said methylacrylic acid or TEB 3K is 1: 1～1.5; The weight ratio of the vitriol oil is 10%～150%; The weight ratio of tosic acid is 1.0%～5.0%, and the weight ratio of stopper is 0.5%～2.5%, and said stopper is a kind of in thiodiphenylamine or the Resorcinol;
(2) in methylacrylic acid ten difluoro heptyl esters or methylacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems, add deionized water, add at least a in TEB 3K or NSC 20956 or the vinylbenzene again, add compound emulsifying agent, initiator at last; Behind the logical nitrogen 30min, emulsification 30～60min in advance, it is subsequent use to take out about 2/3rds pre-emulsion, remaining 1/3rd pre-emulsions heating; When temperature reaches 75～85 ℃, stop to heat up, when treating that emulsion is blueness, begin to drip above-mentioned subsequent use pre-emulsion; Pre-emulsion 2～6h dropwises, and keeps temperature 1～2h then, cools off the emulsion that gets product; Wherein: the gross weight with pre-emulsion is a benchmark; The weight ratio of deionized water is 50%～80%; The weight ratio of Bing Xisuandingzhi is 1.0%～20%; TEB 3K or cinnamic weight ratio are 1.0%～10%, and the weight ratio of methylacrylic acid ten difluoro heptyl esters or methylacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems is 5.0%～30%, and the weight ratio of compound emulsifying agent is 0.5%～2.0%, the initiator weight/power ratio is 0.2%～2%.
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| CN103628316A (en) * | 2013-10-25 | 2014-03-12 | 王以元 | Novel preparation method of paper fiber fabric coating finishing agent microemulsion |
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| CN103938451B (en) * | 2014-03-25 | 2015-11-18 | 福州大学 | A kind of fluorine silicon core-shell type fabric finishing agent and preparation method thereof |
| CN105061666B (en) * | 2015-08-07 | 2017-04-12 | 陕西科技大学 | Preparation method for organic-phosphorus-modified fluorine-containing polyacrylate flame retarding finishing agent |
| CN105111358B (en) * | 2015-08-07 | 2017-09-22 | 陕西科技大学 | A kind of phosphorous polyacrylate/nanometer Mg (OH)2The preparation method of complex emulsions |
| CN110982009B (en) * | 2019-12-18 | 2022-05-17 | 中国石油大学(华东) | Fluoropolymer microemulsion wetting reversal agent and preparation method and application thereof |
| CN113527239B (en) * | 2021-06-29 | 2023-01-13 | 安徽三宝棉纺针织投资有限公司 | Preparation method of ketone anhydride-polyphenol acid active oxygen molecule finishing agent |
| CN116285407A (en) * | 2022-12-26 | 2023-06-23 | 韩山师范学院 | High-fluidity tea residue/polypropylene composite material and preparation method thereof |
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| US6207782B1 (en) * | 1998-05-28 | 2001-03-27 | Cromption Corporation | Hydrophilic siloxane latex emulsions |
| US6833418B2 (en) * | 2002-04-05 | 2004-12-21 | 3M Innovative Properties Company | Dispersions containing perfluorovinyl ether homopolymers and use thereof |
| CN100523078C (en) * | 2006-04-29 | 2009-08-05 | 广州市白云化工实业有限公司 | Low fluorine content material and synthesizing process thereof |
| CN101293940B (en) * | 2007-04-29 | 2012-11-21 | 上海远东氟材料技术有限公司 | Method for preparing water-proof, oil-proof fluorine acrylic acid containing cation/non-tonic surface active agent emulsions |
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