CN101735381A - Organic fluorine waterproof oilproof finishing agent emulsion and preparation thereof - Google Patents
Organic fluorine waterproof oilproof finishing agent emulsion and preparation thereof Download PDFInfo
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- CN101735381A CN101735381A CN200810159983A CN200810159983A CN101735381A CN 101735381 A CN101735381 A CN 101735381A CN 200810159983 A CN200810159983 A CN 200810159983A CN 200810159983 A CN200810159983 A CN 200810159983A CN 101735381 A CN101735381 A CN 101735381A
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Abstract
The invention discloses an organic fluorine waterproof oilproof finishing agent emulsion and a preparation method thereof. The organic fluorine waterproof oilproof finishing agent is polymerized from impurity-oxygen perfluoro-alkyl (methyl) acrylate monomer used as the principal monomer, and higher fatty alcohol acroleic acid and hydroxyethyl (methyl) acrylate used as the auxiliary monomer. The organic fluorine waterproof oilproof finishing agent emulsion can be used for waterproof and oilproof finishing of paper sheets and paper boards.
Description
Technical field
The invention belongs to paper, paperboard surface finishing field.Relate to a kind of organic fluorine waterproof oil resistant finish agent emulsion and preparation method thereof.
Background technology
Organic fluorine treatment agent product have lower interfacial tension, good thermotolerance and chemical stability, thereby can give the waterproof and the oil preventing performance of base material excellences such as woven fabric, leather, paper and cardboard.
(methyl) acrylic ester high molecular type has good film-forming property, characteristics that the cured article snappiness is good, with its as finishing composition handler woven fabric, paper etc. after, the item for disposal good permeability, good hand feeling is arranged.Though poly-(methyl) acrylate has better waterproof, and raw material is easy to get, cost is low, does not possess oil preventing performance.If fluorochemical monomer with the common polymerization of (methyl) acrylic ester monomer, then can be prepared not only waterproof but also grease proofing surface finishing agent.
Although fluorochemicals has important use in waterproof, aspect grease proofing, fluorochemicals need use a large amount of auxiliary agents usually.This analog assistant be in water and fluorine monomer in the organic solvent of high-dissolvability is all arranged, the use of solvent helps monomer to have monomer droplet to spread in polyalcohol emulsion particle.As U.S. Pat 08/048,350 add acetone as the polymerization used additives when polymerization, Japanese Patent JP309562/1999 proposes water miscible high viscosity auxiliary agent (25 ℃ time viscosity more than 3cP) is added to the water as triethylene glycol, dipropylene glycol dme etc. and forms compound water-medium.But the use of solvent can cause the decline of aqueous dispersion burning-point, perhaps remains in the object being treated, and this is very disadvantageous.No matter use which kind of solvent, all can increase the VOC value (volatile organic matter) of system, unfavorable to environment.And the present invention is a kind of waterproof oil-proof finishing agent emulsion that is used for paper and cardboard, and it is a kind of waterproof oil-proof finishing agent of aqueous dispersion type, does not wherein contain those unwelcome organic solvents.Therefore use not only safety performance height, also very little to the influence of environment.
Because the proportion of (methyl) acrylic ester monomer and fluorochemical monomer differs bigger, when obtaining multipolymer by emulsion polymerization, suspension polymerization etc., be difficult to make above-mentioned two kinds can gather monomer and be dispersed in uniformly in the polymerisation medium, therefore before polymerization, want by the high speed mechanical stirring it is dispersed in the polymerisation medium uniformly earlier.
The present invention is assorted oxygen perfluoroalkyl (methyl) acrylate monomer, high fatty alcohol (methyl) Acrylic Acid Monomer, (methyl) crylic acid hydroxy ester class monomer, the fluorinated copolymer emulsion that letex polymerization obtains in the presence of emulsifying agent, chain-transfer agent, initiator.The present invention has excellent water and oil repellant performance, and emulsion particle diameter is little, and does not wherein contain those unwelcome organic solvents, therefore uses not only safety performance height, and is also very little to the influence of environment.Working method of the present invention is simple simultaneously, and reaction conditions requires simple.Compare not only waterproof oil-proof result with product of the same type good but also cost is low.
Summary of the invention
The invention discloses a kind of organic fluorine waterproof oil resistant finish agent emulsion.By assorted oxygen perfluoroalkyl (methyl) acrylate monomer, high fatty alcohol (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester class monomer, copolymerization obtains in the presence of emulsifying agent, chain-transfer agent, initiator.This waterproof oil-proof finishing agent emulsion does not contain organic solvent, and makes it have excellent waterproof, grease proofness on the ventilation property that guarantees paper and cardboard, pliability, elastic foundation.This emulsion is the oyster white water miscible liquid, stable performance, and solid content is 20～25%.
The carbon fluorine monomer that arrives wherein involved in the present invention is assorted oxygen perfluoroalkyl (methyl) acrylate monomer.It is by dimerization of hexafluoropropene oxide body, tripolymer, the tetramer and contain (methyl) Acrylic Acid Monomer reactant of esterification of free hydroxyl group, preferably tripolymer.
The monomeric general formula of (methyl) crylic acid hydroxy ester class is:
CH
2＝CH(R
1)-COO-C
nH
2n-OH
Wherein, R
1Be hydrogen or methyl, n is an integer 2,3,4,5 or 6; Preferably 3.
Hydrocarbon monomer is the high fatty alcohol esters of acrylic acid, comprise (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Octyl acrylate, (methyl) dodecyl acrylate, (methyl) Process Conditions of Cetane Acrylate, (methyl) octadecyl acrylate, preferred (methyl) octadecyl acrylate.
The monomeric general formula of (methyl) crylic acid hydroxy ester class is:
CH
2＝CH(R
1)-COO-C
nH
2n-OH
Wherein, R
1Be hydrogen or methyl, n is an integer 2,3,4,5 or 6; Preferably 2,3.
Used fluoro-acrylate monomer, high fatty alcohol acrylic ester monomer, the monomeric mass ratio of (methyl) crylic acid hydroxy ester class are 20～80: 75～15: 5, and preferably 55: 40: 5.
Used emulsifying agent is cats product and nonionogenic tenside complexed surfactant, and compound emulsifying agent HLB value is 8.0～15.0, and preferred HLB value is 12.0 compound emulsifying agent.
The emulsifying agent consumption is 7～10% of a total monomer quality, preferred 8%.
Chain-transfer agent is alkyl sulfhydryl, preferably lauryl mercaptan.
The chain-transfer agent consumption is 1 of total monomer quality～3 ‰, preferably 2 ‰.
What initiator used is water soluble starter, preferred azo diisobutyl ether.
Initiator amount is 7 of total monomer quality～10 ‰, preferably 8 ‰.
Its preparation method is that principal monomer, auxiliary body, emulsifying agent, chain-transfer agent are added container successively, and the mode that drips water and stirring is gradually carried out pre-emulsification, and initiator drips into pre-emulsion in the mode of solution, carries out under the 50-80 degree letex polymerization 6-10 hour.
The organic fluorine waterproof oil resistant finish agent emulsion that wherein is used for paper and cardboard is diluted to solid content as requested after polymerization be 15～30% emulsion, and preferred solid content is 20% emulsion.
When base materials such as paper are handled, 20% emulsion is become the required concentration of base material such as paper by 6% dilution proportion.With soaking the pool in the emulsion of paper after dilution 1～3 minute, then at 120 ℃ of oven dry, cool to room temperature.Base materials such as treated paper have promptly possessed the performance of water and oil repellant.
Embodiment
Embodiment 1
With 120g stearyl methacrylate, 165g Propylene oxide hexafluoride tripolymer Rocryl 410,15g Rocryl 410, HLB value is that 12.0 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; heating makes its fusing and carries out the emulsion that pre-emulsification forms O/W with continuous Dropwise 5 50g water under 50 ℃, drips initiator (the 2.4g Potassium Persulphate initiator 50g aqueous solution) polymerization at last under the inert conditions of nitrogen protection and promptly gets the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard in 5.5 hours.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 90 fens.
Embodiment 2
With 150g stearyl methacrylate, 135g Propylene oxide hexafluoride tripolymer Rocryl 410,15g Rocryl 410, HLB value is that 12.0 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; heating makes its fusing and carries out the emulsion that pre-emulsification forms O/W with continuous Dropwise 5 50g water under 50 ℃, drips initiator (the 2.6g over cure is to the ammonium initiator 50g aqueous solution) polymerization at last under the inert conditions of nitrogen protection and promptly gets the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard in 5 hours.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, under 120 ℃ of conditions, dries then, and cool to room temperature,
Embodiment 3
With 80g stearyl methacrylate, 80 gram Process Conditions of Cetane Acrylate, 135g Propylene oxide hexafluoride tripolymer hydroxyethyl methylacrylates, 15g Rocryl 410, HLB value is that 12.0 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; heating makes its fusing and carries out the emulsion that pre-emulsification forms 0/W with continuous Dropwise 5 50g water under 50 ℃, drips initiator (the 2.5g Potassium Persulphate 50g aqueous solution) polymerization at last under the inert conditions of nitrogen protection and promptly gets the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard in 6 hours.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 90 fens.
Embodiment 4
With 120g methacrylic dodecyl gallate, 165g Propylene oxide hexafluoride tripolymer hydroxyethyl methylacrylate, 15g hydroxyethyl methylacrylate, HLB value is that 12.0 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; 50 ℃ down heating make its fusing and carry out the emulsion that pre-emulsification forms O/W with continuous Dropwise 5 50g water, last initiator (the 2.2g azo two NSC 18620 50g aqueous solution) polymerase 17 that drips under the inert conditions of nitrogen protection hour promptly gets the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 80 fens.
Embodiment 5
With 140g methacrylic acid hexadecyl ester; 20 gram stearyl methacrylates; 150g Propylene oxide hexafluoride tripolymer hydroxyethyl methylacrylate; the 15g hydroxyethyl methylacrylate; the HLB value is 12.0 compound emulsifying agent 24g; lauryl mercaptan 0.4g joins in the flask of 2000ml; 50 ℃ down heating make its fusing and carry out the emulsion that pre-emulsification forms O/W with continuous Dropwise 5 50g water, last initiator (the 2.4g azo two NSC 18620 50g aqueous solution) polymerase 17 that drips under the inert conditions of nitrogen protection hour promptly gets the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 80 fens.
Embodiment 6
With 130g methacrylic acid hexadecyl ester, 40 gram octadecyl acrylates, 150g Propylene oxide hexafluoride tripolymer Rocryl 410s, 15g Rocryl 410, HLB value is that 12.0 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; 50 ℃ down heating make its fusing and carry out pre-emulsification formation emulsion with continuous Dropwise 5 50ml water, under inert conditions, drip initiator (the 2.4g azo two NSC 18620 50g aqueous solution) polymerase 17 hour then in nitrogen protection.Promptly get the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 80 fens.
Embodiment 7
With 100g stearyl methacrylate, 40 gram methacrylic acids 20 diester, 150g Propylene oxide hexafluoride tripolymer Rocryl 410,15g Rocryl 410, HLB value is that 11.5 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; heating makes its fusing and carries out pre-emulsification with continuous Dropwise 5 50ml water and forms emulsion under 50 ℃, drips initiator (the 2.5g Potassium Persulphate 50g aqueous solution) polymerization 8 hours then under the inert conditions of nitrogen protection.Promptly get the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 90 fens.
Embodiment 8
With 120g methacrylic dodecyl gallate, 30 gram methacrylic acids, 20 diester; 165g Propylene oxide hexafluoride tripolymer Rocryl 410,15g Rocryl 410, HLB value are that 11.5 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; heating makes its fusing and carries out pre-emulsification with continuous Dropwise 5 50ml water and forms emulsion under 50 ℃, drips initiator (the 2.5g Potassium Persulphate 50g aqueous solution) polymerization 6 hours then under the inert conditions in nitrogen protection.Promptly get the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 90 fens.
Embodiment 9
With 140g stearyl methacrylate, 165g Propylene oxide hexafluoride tripolymer Rocryl 410,15g hydroxyethyl methylacrylate, HLB value is that 11.5 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; heating makes its fusing and carries out pre-emulsification with continuous Dropwise 5 50ml water and forms emulsion under 50 ℃, drips initiator (the 2.4 ammonium persulphate 50g aqueous solution) polymerization 6 hours then under the inert conditions in nitrogen protection.Promptly get the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches the 80+ branch.
Embodiment 10
With 120g stearyl methacrylate, 40 gram Process Conditions of Cetane Acrylate; 165g Propylene oxide hexafluoride tripolymer Rocryl 410,15g hydroxyethyl methylacrylate, HLB value are that 11.5 compound emulsifying agent 24g, lauryl mercaptan 0.4g join in the flask of 2000ml; 50 ℃ down heating make its fusing and carry out pre-emulsification formation emulsion with continuous Dropwise 5 50ml water, under inert conditions, drip initiator (the 50g aqueous solution of 2.4g azo two NSC 18620) polymerase 17 hour then in nitrogen protection.Promptly get the waterproof oil-proof finishing agent emulsion that is used for paper and cardboard.
Solid content is that about 20% emulsion is diluted to 3%, with soaking the pool in the emulsion of paper after dilution 1～3 minute, dries under 120 ℃ of conditions then, and cool to room temperature detects water repellency and reaches 80 fens.
Claims (5)
1. organic fluorine waterproof oil resistant finish agent emulsion is the multipolymer of the repeating unit that is made of monomer a, monomer b and monomer c.Monomer a is a kind of assorted oxygen perfluoroalkyl (methyl) acrylate monomer, and monomer b is high fatty alcohol (methyl) acrylate monomer, and monomer c is a kind of (methyl) crylic acid hydroxy ester class monomer.It is characterized in that assorted oxygen perfluoroalkyl (methyl) acrylate monomer is as principal monomer, it is by dimerization of hexafluoropropene oxide body, tripolymer, the tetramer and contain (methyl) Acrylic Acid Monomer reactant of esterification of free hydroxyl group, and high fatty alcohol vinylformic acid and (methyl) crylic acid hydroxy ester are as auxiliary monomer.
2. a kind of organic fluorine waterproof oil resistant finish agent emulsion as claimed in claim 1 is characterized in that used fluorinated acrylate monomer, high fatty alcohol acrylate monomer, the monomeric mass ratio of (methyl) crylic acid hydroxy ester class are 20～80: 75～15: 5.
3. the preparation method of a kind of organic fluorine waterproof oil resistant finish agent emulsion as claimed in claim 1, it is characterized in that principal monomer, auxiliary monomer, emulsifying agent, chain-transfer agent are added container successively, the mode that drips water gradually and stir is carried out pre-emulsification, initiator drips into pre-emulsion in the mode of solution, carries out under the 50-80 degree letex polymerization 6-10 hour.
4. the preparation method of a kind of organic fluorine waterproof oil resistant finish agent emulsion as claimed in claim 3, it is characterized in that used emulsifying agent is cats product and nonionogenic tenside complexed surfactant, compound emulsifying agent HLB value is 8.0～15.0, and consumption is 7～10% of a total monomer quality; Chain-transfer agent is an alkyl sulfhydryl, and consumption is 1 of total monomer quality～3 ‰.
5. the preparation method of a kind of organic fluorine waterproof oil resistant finish agent emulsion as claimed in claim 3 is characterized in that using water soluble starter, and consumption is 7 of total monomer quality～10 ‰.
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| CN200810159983A CN101735381A (en) | 2008-11-14 | 2008-11-14 | Organic fluorine waterproof oilproof finishing agent emulsion and preparation thereof |
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| CN200810159983A CN101735381A (en) | 2008-11-14 | 2008-11-14 | Organic fluorine waterproof oilproof finishing agent emulsion and preparation thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102587141A (en) * | 2012-01-18 | 2012-07-18 | 常州化工研究所有限公司 | Fluoride-contained textile finishing agent and preparation method thereof |
| CN102660871A (en) * | 2012-04-13 | 2012-09-12 | 江苏嘉业氟材料科技有限公司 | Fluorine containing water repellent oil repellent composition and its preparation method |
| CN105568690A (en) * | 2016-01-08 | 2016-05-11 | 湖州市千金丝织厂 | Novel antistatic water-resistant oil-resistant finishing agent and preparation method thereof |
| CN108018718A (en) * | 2016-11-04 | 2018-05-11 | 中昊晨光化工研究院有限公司 | A kind of cation fluoride fabric finishing agent and preparation method |
| CN109594422A (en) * | 2017-09-30 | 2019-04-09 | 王慧丽 | A kind of multifunctional food packaging and processing paper and its manufacturing method |
-
2008
- 2008-11-14 CN CN200810159983A patent/CN101735381A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102587141A (en) * | 2012-01-18 | 2012-07-18 | 常州化工研究所有限公司 | Fluoride-contained textile finishing agent and preparation method thereof |
| CN102660871A (en) * | 2012-04-13 | 2012-09-12 | 江苏嘉业氟材料科技有限公司 | Fluorine containing water repellent oil repellent composition and its preparation method |
| CN102660871B (en) * | 2012-04-13 | 2014-09-03 | 无锡市恒创嘉业纳米材料科技有限公司 | Fluorine containing water repellent oil repellent composition and its preparation method |
| CN105568690A (en) * | 2016-01-08 | 2016-05-11 | 湖州市千金丝织厂 | Novel antistatic water-resistant oil-resistant finishing agent and preparation method thereof |
| CN108018718A (en) * | 2016-11-04 | 2018-05-11 | 中昊晨光化工研究院有限公司 | A kind of cation fluoride fabric finishing agent and preparation method |
| CN109594422A (en) * | 2017-09-30 | 2019-04-09 | 王慧丽 | A kind of multifunctional food packaging and processing paper and its manufacturing method |
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Open date: 20100616 |