CN101161930A - Organic water-proof oil-resist finishing agent for paper and cardboard and preparation thereof - Google Patents
Organic water-proof oil-resist finishing agent for paper and cardboard and preparation thereof Download PDFInfo
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- CN101161930A CN101161930A CN 200710017129 CN200710017129A CN101161930A CN 101161930 A CN101161930 A CN 101161930A CN 200710017129 CN200710017129 CN 200710017129 CN 200710017129 A CN200710017129 A CN 200710017129A CN 101161930 A CN101161930 A CN 101161930A
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Abstract
The invention provides an emulsion for waterproofing and oilproofing finishing aspect of paper or cardboard and the preparation method thereof, wherein, the emulsion comprises a) a copolymer of repeated unit formed by oxa-perfluoroalkyl group (methyl) acrylate monomer, higher fatty alcohol (methyl) acrylate monomer, (methyl) hydroxyl acrylate monomer; b) an emulsifier; c) a chain transfer agent; d) an initiator. The invention is used for waterproofing and oilproofing finishing of paper. The emulsion for waterproofing and oilproofing finishing aspect of paper or cardboard of the invention does not contain organic solvent, so not only safety performance is high, but also small affect to environment is provided when used.
Description
Technical field
The invention belongs to paper, paperboard surface finishing field.Relate to emulsion of a kind of fluorine-containing waterproof oil-proof finishing agent and preparation method thereof.This emulsion is mainly used in the anti-oil processing of surface waterproofing of paper and cardboard.
Background technology
After use after a while, base material (as woven fabric, leather, paper, cardboard etc.) is understood dirty and is tarnished.For woven fabric, the base material of leather one class can also make it recover former state by washing repeatedly; But it is obviously impracticable with the method for washing for paper and cardboard.This just need handle the surface of paper and cardboard before using, and made it avoid staining of water-based and oiliness.Organic fluoride finishing agent product have lower interfacial tension, good heat resistance 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 solidfied material pliability is good, with its as finishing agent processor 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.
CN1408753 discloses and has comprised as the compound with following structural formula of necessary component and the water and oil repellant composition of thermoplastic materials polymer, and wherein, the symbol in the following formula has following implication: R
f: C
1-20Poly-fluoro-alkyl, X:(CH
2)
m, m is the integer of 1-10 in the formula, A, A
1, A
2: represent O independently of one another, S or N (Z
3), Z in the formula
3Be hydrogen atom or alkyl, Z
1: octadecyl, Z
2: alkyl, or have a hydrogen atom substituted alkyl at least, W: trivalent organic group, and a, b: represent 1 or 2 independently of one another, its condition is that a+b is 2 or 3.
CN1493601 discloses fluorine-containing water-repellent oil-repellent agent of a kind of emulsion type and preparation method thereof, the fluorine-containing water-repellent oil-repellent agent of emulsion type be by monomer, emulsifying agent and water through the pre-emulsification of ultrasonic technology, initiated polymerization and the emulsion of fluorinated copolymer in aqueous medium that obtain under initator then.
CN1927894 discloses the preparation method and the application of a kind of fluorine-containing carbon chain acrylate and copolymer thereof, and the product main component is a kind of fluorine-containing carbon chain acrylate, and its general formula is:
This compound can be used for the water and oil repellant on surfaces such as textiles, metal, paper, glass, plastics, rubber, pottery to be handled.
CN101016696 and CN101016697 disclose a kind of fluorine-containing hydrophobic and oil repellent fabric finishing agent and preparation method thereof respectively, described fluorine-containing hydrophobic and oil repellent fabric finishing agent is the emulsion of milky white colour band blue-fluorescence, its preparation method is: the quaternary monomer of forming with fluorochemical monomer, hydro carbons unsaturated monomer, acid monomer and functional monomer is a raw material, in the presence of initator, conditioning agent, buffer and emulsifying agent, obtain described fluorine-containing hydrophobic and oil repellent fabric finishing agent with the emulsion copolymerization method is synthetic.
Although fluorochemical has important use in waterproof, aspect grease proofing, fluorochemical 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, Japan 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 dimethyl ether 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.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of Organic fluoride fabric water-refusing oil-refusing finishing agent that is used for paper and cardboard.
Another object of the present invention provides the preparation method of described Organic fluoride fabric water-refusing oil-refusing finishing agent.
The invention provides a kind of organic fluorine waterproof anti oil agent.By assorted oxygen perfluoroalkyl (methyl) acrylate monomer, higher aliphatic (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester class monomer, copolymerization obtains in the presence of emulsifying agent, chain-transferring agent, initator.This waterproof oil-proof finishing agent emulsion does not contain organic solvent, and makes it have excellent waterproof, grease proofness on the gas permeability that guarantees paper and cardboard, pliability, elastic foundation.This emulsion is the oyster white aqueous emulsion, stable performance, and solid content is 20～25%.
The invention provides a kind of organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard, comprise in the emulsion:
A) copolymer of the repetitive of assorted oxygen perfluoroalkyl (methyl) acrylate monomer, higher aliphatic (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester monomer formation;
B) a kind of emulsifying agent;
C) a kind of chain-transferring agent;
D) initator;
Wherein:
The general structure of described assorted oxygen perfluoroalkyl (methyl) acrylate monomer is:
R wherein
1Be hydrogen or methyl, m is 0,1,2,3; Preferably 1.
The general structure of described higher aliphatic (methyl) acrylic monomers is:
Wherein, R
2Be hydrogen or methyl, p is the integer of integer 11-21; Preferably 17.
Described emulsifying agent is cationic surfactant and non-ionic surface active agent complexed surfactant.
Described chain-transferring agent is an alkyl hydrosulfide;
Described initator is a water soluble starter.
Preferably, assorted oxygen perfluoroalkyl (methyl) acrylate monomer described in a) is by dimerization of hexafluoropropene oxide body, tripolymer or the tetramer and contain free hydroxyl group (methyl) acrylic monomers esterification and obtain.Preferred, assorted oxygen perfluoroalkyl (methyl) acrylate monomer by the hexafluoropropylene oxide tripolymer with contain free (methyl) crylic acid hydroxy ester monomer esterification and obtain, be i.e. hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate.
The higher aliphatic acrylate is selected from one or more in (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecyl acrylate, (methyl) Process Conditions of Cetane Acrylate and/or (methyl) octadecyl acrylate; Preferably, higher aliphatic acrylate (methyl) octadecyl acrylate.
Preferably, the mass ratio of assorted oxygen perfluoroalkyl (methyl) acrylate monomer a), higher aliphatic (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester monomer is 20～80: 75～15: 3～8, and the mass ratio of preferred fluorinated acrylate monomer, higher aliphatic acrylate monomer, (methyl) crylic acid hydroxy ester class monomer is 55: 40: 5.
Total monomer quality is the quality sum of assorted oxygen perfluoroalkyl (methyl) acrylate monomer, higher aliphatic (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester monomer.
Preferably, b) emulsifying agent described in is cationic surfactant and non-ionic surface active agent complexed surfactant, and compound emulsifying agent HLB value is 8.0～15.0, and preferred HLB value is 12.0 compound emulsifying agent.
Cationic surfactant is selected from 1831,1631, two 1821, rope Luo Ming A etc.
Non-ionic surface active agent is selected from AEO class, LAE class, class of department series, OP class, 6502,6501 etc.
The emulsifying agent consumption is 7～10% of a total monomer quality, preferred 8%.
C) chain-transferring agent described in is alkyl hydrosulfide, preferably lauryl mercaptan.
The chain-transferring agent consumption is 1 of total monomer quality～3 ‰, preferably 2 ‰.
What initator used is water soluble starter; Preferably, water soluble starter is selected from ammonium persulfate, potassium peroxydisulfate or azo diisobutyl ether; Preferred, water soluble starter is the azo diisobutyl ether.
Initiator amount is 7 of total monomer quality～10 ‰, preferably 8 ‰.
The present invention also provides the described organic fluorine waterproof anti oil agent emulsion preparation method that is used for paper and cardboard, it is characterized in that, to mix oxygen perfluoroalkyl (methyl) acrylate monomer, higher aliphatic (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester monomer, emulsifying agent, chain-transferring agent adds container successively, the mode that drips water gradually and stir is carried out pre-emulsification, forms pre-emulsion; Initator drips into pre-emulsion in the mode of solution, carries out under 50-80 ℃ emulsion polymerisation 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.
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 water-dispersion type, does not wherein contain those unwelcome organic solvents.Therefore use not only security 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 copolymer 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 mechanical agitation at a high speed it is dispersed in the polymerisation medium uniformly earlier.
The present invention is assorted oxygen perfluoroalkyl (methyl) acrylate monomer, higher aliphatic (methyl) acrylic monomers, (methyl) crylic acid hydroxy ester class monomer, the fluorinated copolymer emulsion that emulsion polymerisation obtains in the presence of emulsifying agent, chain-transferring agent, initator.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 security performance height, and is also very little to the influence of environment.Method of operating of the present invention is simple simultaneously, and reaction condition requires simple.Compare not only waterproof oil-proof result with product of the same type good but also cost is low.
The specific embodiment
Following examples are to further specify of the present invention, but the present invention is not limited thereto.
Embodiment 1
With 120g octadecyl methacrylate, 165g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 15g hydroxy propyl methacrylate, 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 initator (the 2.4g potassium peroxydisulfate initator 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 octadecyl methacrylate, 135g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 15g hydroxy propyl methacrylate, 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 initator (the 2.6g over cure is to the 50g aqueous solution of ammonium initator) 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 octadecyl methacrylate, 80 gram Process Conditions of Cetane Acrylate, 135g hexafluoropropylene oxide tripolymer hydroxyethyl methylacrylates, 15g hydroxy propyl methacrylate, 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 initator (the 50g aqueous solution of 2.5g potassium peroxydisulfate) 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 metering system dodecyl gallate, 165g hexafluoropropylene oxide 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 initator (the 2.2g azo two NSC 18620s 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 octadecyl methacrylates; 150g hexafluoropropylene oxide 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 initator (the 50g aqueous solution of the 2.4g azo two NSC 18620s) 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 hexafluoropropylene oxide tripolymer hydroxy propyl methacrylates, 15g hydroxy propyl methacrylate, 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 initator (the 50g aqueous solution of 2.4g azo two NSC 18620s) 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 octadecyl methacrylate, 40 gram methacrylic acids 20 diester, 150g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 15g hydroxy propyl methacrylate, 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 initator (the 50g aqueous solution of 2.5g potassium peroxydisulfate) 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 metering system dodecyl gallate, 30 gram methacrylic acids, 20 diester; 165g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 15g hydroxy propyl methacrylate, 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 initator (the 50g aqueous solution of 2.5g potassium peroxydisulfate) 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 octadecyl methacrylate, 165g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 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 initator (the 50g aqueous solution of 2.4 ammonium persulfates) 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 80
+Divide.
Embodiment 10
With 120g octadecyl methacrylate, 40 gram Process Conditions of Cetane Acrylate; 165g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 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 initator (the 50g aqueous solution of 2.4g azo two NSC 18620s) 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 10
With 120g propyl methacrylate, 40 gram Process Conditions of Cetane Acrylate; 40g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 15g hydroxyethyl methylacrylate, HLB value are that 8 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 initator (the 50g aqueous solution of 2.4g azo two NSC 18620s) 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 10
With 40g butyl methacrylate, 165g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 15g hydroxyethyl methylacrylate, HLB value is that 15 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 initator (the 50g aqueous solution of 2.4g azo two NSC 18620s) 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 10
With 40 gram Process Conditions of Cetane Acrylate; 165g hexafluoropropylene oxide tripolymer hydroxy propyl methacrylate, 15g hydroxyethyl methylacrylate, HLB value are that 10 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 initator (the 50g aqueous solution of 2.4g azo two NSC 18620s) 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 (10)
1. organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard comprises in the emulsion:
A) copolymer of the repetitive of assorted oxygen perfluoroalkyl (methyl) acrylate monomer, higher aliphatic (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester monomer formation;
B) a kind of emulsifying agent;
C) a kind of chain-transferring agent;
D) initator;
Wherein:
The general structure of described assorted oxygen perfluoroalkyl (methyl) acrylate monomer is:
The general structure of described higher aliphatic (methyl) acrylic monomers is:
The general formula of described (methyl) crylic acid hydroxy ester class monomer 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.
Described emulsifying agent is cationic surfactant and non-ionic surface active agent complexed surfactant.
Described chain-transferring agent is an alkyl hydrosulfide;
Described initator is a water soluble starter.
2. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1, it is characterized in that a) assorted oxygen perfluoroalkyl (methyl) acrylate monomer described in is by dimerization of hexafluoropropene oxide body, tripolymer or the tetramer and contain free hydroxyl group (methyl) acrylic monomers esterification and obtain.
3. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1, it is characterized in that the higher aliphatic acrylate is selected from one or more in (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecyl acrylate, (methyl) Process Conditions of Cetane Acrylate and/or (methyl) octadecyl acrylate; Preferably, higher aliphatic acrylate (methyl) octadecyl acrylate.
4. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1, it is characterized in that a) mass ratio of the fluoro-acrylate monomer described in, higher aliphatic acrylic ester monomer, (methyl) crylic acid hydroxy ester class monomer is 20～80: 75～15: 3～8.
5. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1, it is characterized in that, b) emulsifying agent described in is cationic surfactant and non-ionic surface active agent complexed surfactant, compound emulsifying agent HLB value is 8.0～15.0, and the emulsifying agent consumption is 7～10% of a total monomer quality.
6. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1 is characterized in that c) chain-transferring agent described in is an alkyl hydrosulfide, and the chain-transferring agent consumption is 1 of total monomer quality～3 ‰.
7. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1 is characterized in that c) chain-transferring agent described in is a lauryl mercaptan.
8. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1 is characterized in that described initator is a water soluble starter, and initiator amount is 7 of total monomer quality～10 ‰.
9. the organic fluorine waterproof oil resistant finish agent emulsion that is used for paper and cardboard as claimed in claim 1 is characterized in that described initator is selected from ammonium persulfate, potassium peroxydisulfate or azo diisobutyl ether.
10. the preparation method who is used for the organic fluorine waterproof oil resistant finish agent emulsion of paper and cardboard as claimed in claim 1, it is characterized in that, to mix oxygen perfluoroalkyl (methyl) acrylate monomer, higher aliphatic (methyl) acrylate monomer, (methyl) crylic acid hydroxy ester monomer, emulsifying agent, chain-transferring agent adds container successively, the mode that drips water gradually and stir is carried out pre-emulsification, forms pre-emulsion; Initator drips into pre-emulsion in the mode of solution, carries out under 50-80 ℃ emulsion polymerisation 6-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710017129 CN101161930A (en) | 2007-09-04 | 2007-09-04 | Organic water-proof oil-resist finishing agent for paper and cardboard and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710017129 CN101161930A (en) | 2007-09-04 | 2007-09-04 | Organic water-proof oil-resist finishing agent for paper and cardboard and preparation thereof |
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| CN101161930A true CN101161930A (en) | 2008-04-16 |
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| CN 200710017129 Pending CN101161930A (en) | 2007-09-04 | 2007-09-04 | Organic water-proof oil-resist finishing agent for paper and cardboard and preparation thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677469A (en) * | 2012-06-01 | 2012-09-19 | 王峥轲 | Ultramicron three-proofing finishing agent and preparation method thereof |
| CN104903515A (en) * | 2012-10-12 | 2015-09-09 | 佐治亚-太平洋化工品有限公司 | Greaseproof paper with lower content of fluorochemicals |
-
2007
- 2007-09-04 CN CN 200710017129 patent/CN101161930A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677469A (en) * | 2012-06-01 | 2012-09-19 | 王峥轲 | Ultramicron three-proofing finishing agent and preparation method thereof |
| CN104903515A (en) * | 2012-10-12 | 2015-09-09 | 佐治亚-太平洋化工品有限公司 | Greaseproof paper with lower content of fluorochemicals |
| CN104903515B (en) * | 2012-10-12 | 2018-04-13 | 佐治亚-太平洋化工品有限公司 | Anti- lipid paper with relatively low fluorine-containing chemical content |
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