CN106084117B - A kind of environment-friendly type fluorinated acrylate emulsion and preparation method with beveled structure - Google Patents
A kind of environment-friendly type fluorinated acrylate emulsion and preparation method with beveled structure Download PDFInfo
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- CN106084117B CN106084117B CN201510224554.4A CN201510224554A CN106084117B CN 106084117 B CN106084117 B CN 106084117B CN 201510224554 A CN201510224554 A CN 201510224554A CN 106084117 B CN106084117 B CN 106084117B
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Abstract
The invention discloses a kind of environment-friendly type fluorinated acrylate emulsion and preparation method with beveled structure.It is introduced primarily into a kind of short chain fluorochemical with beveled structure, and is applied to the emulsion polymerization of fluorinated acrylate.Due to the presence of multiple fluorocarbon chains in this short-chain fluorine-containing acrylate monomer, beveled structure is formed, steric hindrance increases, so that fluorine chain is stablized and be covered in surface, play effective shielding action；Meanwhile the presence of multiple fluorine chains, the fluorinated volume on surface can be effectively improved, to improve the water repellent of entire polymer, refuse oil, soil repellency energy.The short-chain fluorine-containing acrylic acid ester emulsion had both solved the problem of environmental pollution of long chain fluorine-containing acrylic acid ester emulsion, the disadvantage of common environment-friendly type fluorinated acrylate emulsion water and oil repellant performance deficiency is overcome again, it can be used as novel environment friendly polymer emulsion, assign product surface excellent water and oil repellant performance.
Description
Technical field
The invention belongs to fluorinated acrylate resin arts, in particular to fluorinated acrylate emulsion and preparation method.
Background technique
Acrylate containing fluorine polymer is the copolymer of perfluoropropene ester monomer Yu Conventional acrylic ester monomer, due to it
With the excellent transparency, film forming, oil resistivity, weatherability, mechanical stability and adhesiveness, especially there is excellent water repellent
Refuse oil and refuse dirty characteristic, be now widely used for textile finishing, building and antifouling paint, paper product processing, electronic device, optical fiber,
The fields such as optical element, electric appliance and electronic coating, it has also become one of functional material being most widely used in fluoropolymer.And mesh
Before, the fluorinated acrylate industrially used is mainly polymerize by the acrylate or methyl acrylic ester of long fluorocarbon chain (C >=8)
Object structure composition.It is due to longer fluorocarbon chain section, crystallization easy to form, to make fluorine chain can be perpendicular to surface alignment, surface
The minimum CF of energy3Group is exposed in outermost, is easy to obtain good water repellent, oil repellency.
But with fluoropolymer-containing a large amount of uses, its bring environmental problem causes the extensive concern of people.?
There is high persistence, degradation cycle was constantly assembled and accumulated in environment, human body and animal tissue up to 100 years or more in environment
It is tired, potential danger is generated to human health and environment, therefore the substitute for developing long fluorocarbon chain acrylate seems especially urgent
It cuts.The study found that the fluorinated acrylate polymer of short fluorocarbon chain (C≤6) is due to fluorocarbon chain with long fluorocarbon chain polymer phase ratio
It is shorter, there is good degradability, without bioconcentration, problem of environmental pollution is not present, therefore has become and research and develop at present
Hot spot.External some major companies have carried out more research to short fluorocarbon chain fluorinated acrylate, as 3M company have developed with
The perfluorochemical of this short fluorocarbon chain of perfluoro butyl sulfonic acid (PFBS) is fluorinated acrylate polymer (the patent US of fluorocarbon source
7659351), but with long fluorocarbon chain polymer phase ratio, the water repellency of short fluorocarbon chain polymer is substantially suitable, but refusing oil, refuse
It is also significantly less than long fluorocarbon chain polymer in the performances such as dirty and water pressure resistance, if long fluorocarbon chain polymer oil repellency is up to 5 grades, and
Short fluorocarbon chain also fails to reach 3 grades.
From the point of view of fluoropolymer-containing water and oil repellant mechanism, whether long chain fluorine-containing polymer or short-chain fluorine-containing polymerization
Object, there is fluorine chain being critical that with excellent water and oil repellant performance shielding action to improve fluorine-containing groups in the stabilization on surface
Property aggregation.Therefore, this project is quasi- assigns short-chain fluorine-containing polymer excellent shielding action by Molecular Design, make its
While meeting environmental requirements, there is outstanding water and oil repellant performance.And pass through literature survey: (the Advanced such as Caliceti
Drug Delivery Reviews, 2003,55,10,1261) once in the research of the pharmacokinetics of PEG- protein conjugate
In, the PEG polymer of beveled structure is prepared, better protective effect can be improved compared with linear structure in this umbrella shape polymer,
It effectively prevent interfering with each other and influencing for itself and other biological structure, tissue etc..
Based on the inspiration of beveled structure shielding action, the present invention proposes that count a kind of short fluorocarbon chain with beveled structure fluorine-containing
Acrylate polymer, wherein forming beveled structure due to the presence of multiple fluorocarbon chains, steric hindrance increases, and keeps fluorine chain steady
Surely it is covered in surface, plays effective shielding action (such as attached drawing 1).
Meanwhile the presence of multiple fluorine chains, the fluorinated volume on surface can be effectively improved, thus improve the water repellent of entire polymer,
Refuse oil, soil repellency energy.
Summary of the invention
The present invention provides the environment-friendly type fluorinated acrylate emulsion with beveled structure, the environment which has had is friendly
Good property and excellent water and oil repellant performance.
Water and oil repellant fluorinated acrylate fabric finishing agent provided by the invention, the content of component and each component are as follows: table
Face activating agent: 0.1%-8%；The short-chain fluorine-containing monomer of beveled structure: 4%-25%；Acrylic ester monomer: 5%-15%；Draw
Send out agent: 0.1%-2%；Cosolvent: 2%-20%；Water: 50%-70%.The above score is weight fraction.
Fluorochemical monomer used by environment-friendly type fluorinated acrylate emulsion provided by the invention with beveled structure has
The environment-friendly type short chain fluorochemical of beveled structure (see formula 1).
Emulsifier used by environment-friendly type fluorinated acrylate emulsion provided by the invention with beveled structure is this Pan
60, the nonionic surfactants such as this Pan 80, this Pan 85, peregal, polysorbas20, polysorbate40 and dodecyl (double) quaternary ammonium salt
Class, cetyl (double) quaternary ammonium salt, octadecyl (double) quaternary cationic surfactant it is one or more.
Esters of acrylic acid list used by environment-friendly type fluorinated acrylate emulsion provided by the invention with beveled structure
Body is methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, metering system
Sour hydroxyl ethyl ester, hydroxy propyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, third
Olefin(e) acid hydroxyl ethyl ester, hydroxypropyl acrylate, long-chain (methyl) acrylate (C10~C18) one or more.
Initiator used by environment-friendly type fluorinated acrylate emulsion provided by the invention with beveled structure is azo
A series of azo-initiators of bis-isobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, V50 it is one or more.
Cosolvent used by environment-friendly type fluorinated acrylate emulsion provided by the invention with beveled structure is second two
The one or more of alcohol methyl ether, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether, tripropylene glycol equal solvent.
Environment-friendly type fluorinated acrylate emulsion provided by the invention with beveled structure the preparation method is as follows:
All monomers are put into surfactant, deionized water, in initiator mixed liquor, high speed emulsifies, and pre-emulsion is made.
Part pre-emulsion is placed in flask, 40 DEG C -85 DEG C, is stirred at reflux reaction 0.5-2h；Remaining pre-emulsion is added dropwise to reactant
System, 1-5h；Insulation reaction 1-4h；Cooling, filtering, obtain final lotion.
Characteristic of the invention is: using the fluorochemical with beveled structure of environment-friendly type, this compound is used
Degradable short fluorocarbon chain (C≤6) in environment is conducive to increase on the one hand due to forming beveled structure with multiple fluorocarbon chains
Steric hindrance, fluorine chain, which can be stablized, is covered in surface, plays effective shielding action；On the other hand, depositing due to multiple fluorine chains
The fluorinated volume on surface can be being effectively improved, to still maintain refusing for entire polymer while with environmentally friendly
Water refuses oil, soil repellency energy.
Detailed description of the invention
Fig. 1 is fluorinated acrylate polymer structural schematic diagram.
Specific embodiment
(1) 1g Si Pan 80,0.5g octadecyl trimethyl chlorine (bromine) are changed into ammonia, 0.7g peregal, 6.1g methacrylic acid
Methyl esters, 2.5g butyl acrylate, 6.7g octadecyl methacrylate, 1.5g hydroxy-ethyl acrylate, the short chain of 16.7g beveled structure contain
Fluorine compounds 1., 0.8g azodiisobutyronitrile, 72g deionized water mix jointly, high-speed stirred, be made pre-emulsion；Later, it takes
35g pre-emulsion in a round bottom flask, 75 DEG C, reacts 1h；Divide 2h to instill in flask remaining pre-emulsion, keeps the temperature 2h；Cooling；Filtering
Obtain product.
(2) by 0.8g dodecylbenzyl quaternary ammonium salt, 1.2g Si Pan 85,2.3g methyl acrylate, 2.9g methacrylic acid
Butyl ester, 3.1g ethyl acrylate, 5.1g octadecyl methacrylate, 2.3g lauryl methacrylate, 2.0g acrylic acid hydroxypropyl
Ester, 13.5g beveled structure short chain fluorochemical 1., 0.7gV50,70g deionized water mix jointly, high-speed stirred is made pre-
Lotion；Later, it takes 50g pre-emulsion in a round bottom flask, 70 DEG C, reacts 1h；1h is divided to instill in flask remaining pre-emulsion, heat preservation
1h；Cooling；Filter to obtain product.
(3) by 0.8g polysorbas20,0.5g Si Pan 85,0.5g hexadecanyl trimethyl quaternary ammonium salt, 5.3g methyl methacrylate
Ester, 8.5g butyl methacrylate, 1g Process Conditions of Cetane Acrylate, 3g octadecyl acrylate, 3.5g hydroxyethyl methacrylate,
17.6g beveled structure short chain fluorochemical 1., 0.2g azobisisoheptonitrile, 0.4gV50,71g deionized water mix jointly, it is high
Speed stirring, is made pre-emulsion；Later, it takes 20g pre-emulsion in a round bottom flask, 80 DEG C, reacts 2h；Divide remaining pre-emulsion to 3h drop
Enter in flask, keeps the temperature 3h；Cooling；Filter to obtain product.
(4) by 0.3g Si Pan 80,1.2g hexadecanyl trimethyl quaternary ammonium salt, 0.9g polysorbate40,2.5g methyl acrylate,
4.1g butyl methacrylate, 5g isobornyl acrylate, 3g Process Conditions of Cetane Acrylate, 1.6g hydroxypropyl acrylate, 16g umbrella shape knot
Structure short chain fluorochemical 2., 0.5g azobisisoheptonitrile, 80g deionized water mix jointly, high-speed stirred, be made pre-emulsion；
Later, pre-emulsion is put into round-bottomed flask, 75 DEG C, reacts 6h；Cooling；Filter to obtain product.
Claims (6)
1. a kind of environment-friendly type fluorinated acrylate emulsion with beveled structure, it is characterised in that it includes that surface is living that it, which prepares component,
Property agent, the short chain fluorochemical of beveled structure, acrylic ester monomer, initiator, cosolvent, water, the weight hundred of each component
Divide and compare content are as follows:
Surfactant: 0.1%-8%
The short chain fluorochemical of beveled structure: 4%-25%
Acrylic ester monomer: 5%-15%
Initiator: 0.1%-2%
Cosolvent: 2%-20%
Water: 50%-70%
Wherein, the short chain fluorochemical of beveled structure be structural formula 1. with structural formula 2. shown in one of compound or two
Kind:
Wherein, 1. in Rf be CnF2n+1, n=2~6；N=1~20 in 2..
2. a kind of environment-friendly type fluorinated acrylate emulsion with beveled structure according to claim 1, it is characterised in that
The surfactant is this Pan 60, this Pan 80, this Pan 85, peregal, polysorbas20 or polysorbate40 nonionic surfactant
With dodecyl quaternary ammonium salt, cetyl quaternary ammonium salt or octadecyl quaternary cationic surfactant.
3. a kind of environment-friendly type fluorinated acrylate emulsion with beveled structure according to claim 1, it is characterised in that
The initiator be azodiisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, one kind of V50 azo-initiator or
It is a variety of.
4. a kind of environment-friendly type fluorinated acrylate emulsion with beveled structure according to claim 1, it is characterised in that
The acrylic ester monomer is methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid
Isobornyl thiocyanoacetate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate,
Isobornyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, C10~C18Long-chain (methyl) acrylate one kind or
It is several.
5. a kind of environment-friendly type fluorinated acrylate emulsion with beveled structure according to claim 1, it is characterised in that
The cosolvent is ethylene glycol monomethyl ether, the one or more of butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether, tripropylene glycol.
6. a kind of environment-friendly type fluorinated acrylate emulsion with beveled structure according to claim 1, it is characterised in that
The preparation method is as follows:
All monomers are put into surfactant, water, in initiator mixed liquor, high speed emulsifies, and pre-emulsion is made, by the pre- cream in part
Liquid is placed in flask, 40 DEG C -85 DEG C, is stirred at reflux reaction 0.5-2h；Remaining pre-emulsion is added dropwise to reaction system, 1-5h；It protects
Temperature reaction 1-4h；Cooling, filtering, obtain final lotion.
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| CN108658736A (en) * | 2017-04-01 | 2018-10-16 | 中国科学院成都有机化学有限公司 | One kind having the short fluorocarbon chain fluorochemical monomer and preparation method of " tree-like " structure |
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