CN102108109A - Preparation method of fluorine-containing fabric finishing agent - Google Patents
Preparation method of fluorine-containing fabric finishing agent Download PDFInfo
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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 based on the perfluorocarboxylic acid chromium complex, because washing fastness is poor, very fast polymkeric substance by the better fluorinated acrylate of performance replaces.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, made copolymer emulsion based on fluorinated acrylate.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
Purpose of the present 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 solution used in the present invention is such: a kind of preparation method of fluorine-containing textile finishing agent, this preparation method utilizes a kind of under catalyst action at least a and methacrylic acid in ten difluoro enanthol or the ten hexafluoro nonyl alcohols or the methyl methacrylate, prepares methacrylic acid ten difluoro enanthol esters or methacrylic acid ten hexafluoro nonyl alcohol esters; At least a at least a and methyl methacrylate in described methacrylic acid ten difluoro enanthol esters or the methacrylic acid ten hexafluoro nonyl alcohol esters or butyl methacrylate or the vinylbenzene carries out emulsion copolymerization, prepares fluorine-containing textile finishing agent; In described said process, add compound emulsifying agent and initiator.
Described compound emulsifying agent is the mixture of sodium lauryl sulphate and polyoxyethylene nonylphenol ether; Described initiator is Potassium Persulphate or ammonium persulfate; Described catalyzer is the vitriol oil or tosic acid.
As preferably, the mass ratio of sodium lauryl sulphate and polyoxyethylene nonylphenol ether is 1: 1～2 in the described 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 methacrylic acid or methyl methacrylate 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 methacrylic acid ten difluoro enanthol esters or methacrylic 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 described methacrylic acid or methyl methacrylate 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%, the weight ratio of stopper is 0.5%～2.5%, and described stopper is a kind of in thiodiphenylamine or the Resorcinol;
(2) in methacrylic acid ten difluoro enanthol esters or methacrylic acid ten hexafluoro nonyl alcohol esters, add deionized water, add at least a in methyl methacrylate or butyl methacrylate or the vinylbenzene again, add compound emulsifying agent, initiator at last; Behind the logical nitrogen 30min, pre-emulsification 30～60min, it is standby 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 standby 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 butyl acrylate is 1.0%～20%, methyl methacrylate or cinnamic weight ratio are 1.0%～10%, the weight ratio of methacrylic acid ten difluoro enanthol esters or methacrylic 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 byproduct that is produced when producing C3-Fluoroalcohol: ten difluoro enanthol or ten hexafluoro nonyl alcohols are basic raw material, by esterification, prepare the fluoropolymer monomer: methacrylic acid ten difluoro heptyl esters or methacrylic acid ten hexafluoro esters in the ninth of the ten Heavenly Stems, and then above-mentioned fluoropolymer monomer and acrylate or vinylbenzene and composition thereof carried out emulsion copolymerization, obtain a kind of novel, inexpensive organic fluorine finishing composition emulsion, and as the byproduct 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 methacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 64.0g ten difluoro enanthol, 18.9g methacrylic 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 methacrylic acid.After the cooling, sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, 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 methacrylic acid ten difluoro enanthol esters, the purity that obtains methacrylic 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 agitator, thermometer and reflux condensing tube are housed, the mixture of adding 70g deionized water and 15g butyl acrylate, 5g vinylbenzene, 5g methacrylic acid ten difluoro heptyl esters, the sodium lauryl sulphate that the 1.2g mol ratio is 1: 2 and polyoxyethylene nonylphenol ether blended compound emulsifying agent, 0.2g ammonium persulfate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, pre-emulsification 30～60min takes out about 2/3rds pre-emulsion and is contained in the dropping 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 standby 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 methacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 64.0g ten difluoro enanthol, 30.0g methyl methacrylate, 1.5g tosic acid, 1.5g Resorcinol successively.Feed nitrogen, behind reaction 3～6h under 85 ℃, temperature is increased to 110 ℃, boil off excessive methyl methacrylate.After the cooling, sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, 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 methacrylic acid ten difluoro enanthol esters, the purity that obtains methacrylic 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 agitator, thermometer and reflux condensing tube are housed, add 60g deionized water and 10g butyl acrylate, 5g methyl methacrylate, 20g methacrylic acid ten difluoro heptyl esters, 1.2g mol ratio and be 1: 1 sodium lauryl sulphate and polyoxyethylene nonylphenol ether blended compound emulsifying agent, 0.3g Potassium Persulphate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, pre-emulsification 30～60min takes out about 2/3rds pre-emulsion and is contained in the dropping 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 standby 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 methacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 83.2g ten hexafluoro nonyl alcohols, 20.6g methyl methacrylate, 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 methyl methacrylate.After the cooling, sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, 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 methacrylic acid ten hexafluoro nonyl alcohol esters, the purity that obtains methacrylic 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 agitator, thermometer and reflux condensing tube are housed, the mixture of adding 70g deionized water and 10g butyl acrylate, 5g vinylbenzene, 10g methacrylic 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 ether blended compound emulsifying agent, 0.2g ammonium persulfate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, pre-emulsification 30～60min takes out about 2/3rds pre-emulsion and is contained in the dropping 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 standby 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 methacrylic acid fluorochemical monomer: under agitation condition, in the 250ml three-necked bottle, add 64.0g ten difluoro enanthol, 20.4g methyl methacrylate, 1.5g tosic acid, 1.5g thiodiphenylamine successively.Feed nitrogen, behind reaction 3～6h under 85 ℃, temperature is increased to 110 ℃, boil off excessive methyl methacrylate.After the cooling, sodium bicarbonate aqueous solution with 2.5% is washed till slight alkalinity, 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 methacrylic acid ten difluoro enanthol esters, the purity that obtains methacrylic 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 agitator, thermometer and reflux condensing tube are housed, add 60g deionized water and 5g butyl acrylate, 5g methyl methacrylate, 25g methacrylic acid ten difluoro heptyl esters, 1.2g mol ratio and be 1: 1 sodium lauryl sulphate and polyoxyethylene nonylphenol ether blended compound emulsifying agent, 0.3g Potassium Persulphate initiator.Behind the logical nitrogen 30min, regulate rotating speed 1000rpm, pre-emulsification 30～60min takes out about 2/3rds pre-emulsion and is contained in the dropping 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 standby 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; Placed 2 hours down for-10 ℃, slowly return to room temperature again, emulsion does not have layering or demulsifying phenomenon; Emulsion is diluted to solids content 3%, and the emulsion after the 30ml dilution is put into test tube, 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; Placed 2 hours down for-10 ℃, slowly return to room temperature again, emulsion does not have layering or demulsifying phenomenon; Emulsion is diluted to solids content 3%, and the emulsion after the 30ml dilution is put into test tube, 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 |
Good by embodiment 7-10 fluorine-containing textile finishing agent waterproof of the present invention as can be seen, oil preventing performance, cotton, terylene, cotton be can be applied to or waterproof, the anti oil agent of blending fabric and paper washed.
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 the some improvements and modifications not breaking away under the principle of the invention prerequisite also should be considered as protection scope of the present invention.
Claims (4)
1. the preparation method of a fluorine-containing textile finishing agent, it is characterized in that: this preparation method utilizes a kind of under catalyst action at least a and methacrylic acid in ten difluoro enanthol or the ten hexafluoro nonyl alcohols or the methyl methacrylate, prepares methacrylic acid ten difluoro enanthol esters or methacrylic acid ten hexafluoro nonyl alcohol esters; At least a at least a and methyl methacrylate in described methacrylic acid ten difluoro enanthol esters or the methacrylic acid ten hexafluoro nonyl alcohol esters or butyl methacrylate or the vinylbenzene carries out emulsion copolymerization, prepares fluorine-containing textile finishing agent; In described said process, add compound emulsifying agent and initiator.
2. the preparation method of a kind of fluorine-containing textile finishing agent according to claim 1, it is characterized in that: described compound emulsifying agent is the mixture of sodium lauryl sulphate and polyoxyethylene nonylphenol ether; Described initiator is Potassium Persulphate or ammonium persulfate; Described catalyzer is the vitriol oil or tosic acid.
3. the preparation method of a kind of fluorine-containing textile finishing agent according to claim 2, it is characterized in that: the mol ratio of sodium lauryl sulphate and polyoxyethylene nonylphenol ether is 1: 1～2 in the described compound emulsifying agent.
4. the preparation method of a kind of fluorine-containing textile finishing agent according to claim 2 is characterized in that: carry 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 methacrylic acid or methyl methacrylate 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 methacrylic acid ten difluoro enanthol esters or methacrylic 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 described methacrylic acid or methyl methacrylate 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%, the weight ratio of stopper is 0.5%～2.5%, and described stopper is a kind of in thiodiphenylamine or the Resorcinol;
(2) in methacrylic acid ten difluoro enanthol esters or methacrylic acid ten hexafluoro nonyl alcohol esters, add deionized water, add at least a in methyl methacrylate or butyl methacrylate or the vinylbenzene again, add compound emulsifying agent, initiator at last; Behind the logical nitrogen 30min, pre-emulsification 30～60min, it is standby 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 standby 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 butyl acrylate is 1.0%～20%, methyl methacrylate or cinnamic weight ratio are 1.0%～10%, the weight ratio of methacrylic acid ten difluoro enanthol esters or methacrylic 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%.
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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 |
| CN103938451A (en) * | 2014-03-25 | 2014-07-23 | 福州大学 | Fluorine-silicon-containing core-shell type fabric finishing agent and preparation method thereof |
| CN105061666A (en) * | 2015-08-07 | 2015-11-18 | 陕西科技大学 | Preparation method for organic-phosphorus-modified fluorine-containing polyacrylate flame retarding finishing agent |
| CN105111358A (en) * | 2015-08-07 | 2015-12-02 | 陕西科技大学 | Preparation method for phosphorus-containing polyacrylate/nano Mg(OH)2 composite emulsion |
| CN110982009A (en) * | 2019-12-18 | 2020-04-10 | 中国石油大学(华东) | Fluoropolymer microemulsion wetting reversal agent and preparation method and application thereof |
| CN113527239A (en) * | 2021-06-29 | 2021-10-22 | 安徽三宝棉纺针织投资有限公司 | Preparation method of ketoanhydride-polyphenolic acid active oxygen molecule finishing agent |
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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 |
| CN103938451A (en) * | 2014-03-25 | 2014-07-23 | 福州大学 | Fluorine-silicon-containing core-shell type fabric finishing agent and preparation method thereof |
| 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 |
| CN105061666A (en) * | 2015-08-07 | 2015-11-18 | 陕西科技大学 | Preparation method for organic-phosphorus-modified fluorine-containing polyacrylate flame retarding finishing agent |
| CN105111358A (en) * | 2015-08-07 | 2015-12-02 | 陕西科技大学 | Preparation method for phosphorus-containing polyacrylate/nano Mg(OH)2 composite emulsion |
| 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 |
| CN110982009A (en) * | 2019-12-18 | 2020-04-10 | 中国石油大学(华东) | Fluoropolymer microemulsion wetting reversal agent and preparation method and application thereof |
| CN113527239A (en) * | 2021-06-29 | 2021-10-22 | 安徽三宝棉纺针织投资有限公司 | Preparation method of ketoanhydride-polyphenolic acid active oxygen molecule finishing agent |
| 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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