CN109929090A - A kind of water-base resin fluorochemical and its preparation and application - Google Patents
A kind of water-base resin fluorochemical and its preparation and application Download PDFInfo
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- CN109929090A CN109929090A CN201910183818.4A CN201910183818A CN109929090A CN 109929090 A CN109929090 A CN 109929090A CN 201910183818 A CN201910183818 A CN 201910183818A CN 109929090 A CN109929090 A CN 109929090A
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Abstract
The present invention provides a kind of water-base resin fluorochemical and its preparations and application.The water-base resin fluorochemical, which is characterized in that in parts by weight, preparing raw material includes: 100~200 parts of hexafluoroisopropanol；100~200 parts of isophorone diisocyanate；60~100 parts of trimethylolpropane；0.01~0.03 part of catalyst；10~100 parts of solvent；Wherein, the solvent is the mixture of one or more of acetone or ethyl acetate composition；The catalyst is dibutyl tin dilaurate.The preparation method of water-base resin fluorochemical of the invention, preparation route is short, reaction is mild, does not need pressure consersion unit, thus there is preparation process to be simple and convenient to operate, reaction condition it is mild, be suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of water-base resin fluorochemical and its preparation
Method.
Background technique
Water-base resin has many advantages, such as inexpensive, safety and environmental protection, non-ignitable, easy to use, is applying using water as decentralized medium
The technical fields such as layer, leather finish, fabric treating, ink are widely used.However, prepared by usually water-base resin
Hydrophilic radical or surfactant are introduced in journey, are kept the water resistance of resin film forming matter poorer than solvent type resin performance, are limited
The application of water-base resin.In order to widen the application range of water-base resin, in water-base resin strand introduce functional groups with
Improving these performances becomes the research focus in the field.Wherein, fluorine element modified aqueous resin prepares the water-base resin of fluorine richness
Technology receives attention and welcome in recent years.
But current fluorinated monomer functional group is few, and it is limited to can be used for the modified kind of water-base resin.Industrially, it commonly uses outer
Directly fluorinated organic compound and water-base resin are blended for emulsification, but the two poor compatibility, are distributed not in lotion and solid film
Uniformly, modified purpose is not achieved.And the method that fluorine modified aqueous resin is prepared as raw material using fluorine-containing (methyl) acrylate, synthesis
Complex process is unfavorable for industrialized production.
Summary of the invention
The object of the present invention is to provide it is a kind of prepare conveniently, be easy to large-scale production water-base resin fluorochemical and
Preparation method, to solve the technical problems such as the fluorochemical single variety that water-base resin uses, preparation complexity.
In order to achieve the above object, the present invention provides a kind of water-base resin fluorochemicals, which is characterized in that by weight
It measures number to calculate, preparing raw material includes:
Wherein, the solvent is the mixture of one or more of acetone or ethyl acetate composition；It is described
Catalyst is dibutyl tin dilaurate.
Preferably, in parts by weight, the raw material for preparing of the water-base resin fluorochemical includes:
Wherein, the solvent is acetone；The catalyst is dibutyl tin dilaurate.
Preferably, in parts by weight, the raw material for preparing of the water-base resin fluorochemical includes:
Wherein, the solvent is ethyl acetate；The catalyst is dibutyl tin dilaurate.
The present invention also provides the preparation methods of above-mentioned water-base resin fluorochemical characterized by comprising will
100~200 parts of hexafluoroisopropanols, 100~200 parts of isophorone diisocyanate, 0.01~0.03 part of catalyst sequentially add
Into reaction vessel, 20~50 DEG C are warming up to, 10~100 parts of solvents are added to reaction vessel with the speed of 0.05-0.1mL/s
In, stir it is lower react 1~3h, 60~100 parts of trimethylolpropanes are then added, are warming up to 70~90 DEG C, stir lower reaction 1~
5h is to get water-base resin fluorochemical.
The present invention also provides above-mentioned water-base resin fluorochemicals to prepare the application in water fluoric resin.
Compared with prior art, the beneficial effects of the present invention are:
1, water-base resin fluorochemical of the invention, using the isophorone diisocyanate bridge of unique chemical moieties
Connection technology chemically reacts hexafluoroisopropanol and trimethylolpropane, has obtained a kind of fluorine-containing chemical combination containing two hydroxyls
Object, two hydroxyl structures containing fluorin radical and reactivity simultaneously in the fluorochemical molecular structure；The structure can be used directly
In preparing aqueous fluorine-containing polyurethane.
2, the preparation method of water-base resin fluorochemical of the invention, preparation route is short, reaction is mild, does not need
Pressure consersion unit, thus have preparation process be simple and convenient to operate, reaction condition it is mild, be suitable for industrialized production.
3, hexafluoroisopropanol is prepared fluorine-containing diol compound by chemical modification technique introducing by the present invention, this contains
The diol compound of fluorine can be used for preparing the water fluoric resins such as aqueous fluorine-containing polyurethane, can be widely used for aircraft, ship, builds
It builds, the coating protection technical field of traffic and various machinery.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the resulting water-base resin fluorochemical of embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
In raw material used in various embodiments of the present invention in addition to the special producer shown and model, other raw materials be it is commercially available,
Specification is that chemistry is pure.
The model of various equipment and the information of manufacturer used in the present invention are as follows:
380 type infrared chromatographs, Nicolet company, the U.S..
Embodiment 1
A kind of water-base resin fluorochemical, in parts by weight, preparing raw material includes:
Wherein, the solvent is acetone；The catalyst is dibutyl tin dilaurate；
Above-mentioned water-base resin fluorochemical the preparation method comprises the following steps:
100 parts of hexafluoroisopropanols, 100 parts of isophorone diisocyanate, 0.01 part of catalyst are added sequentially to four mouthfuls
In flask, 20 DEG C are warming up to, 10 parts of solvents are added in four-hole boiling flask with the speed of 0.05mL/s, stirs lower reaction 1h, so
60 parts of trimethylolpropanes are added afterwards and are warming up to 70 DEG C, stir lower reaction 1h to get water-base resin fluorochemical.
Above-mentioned resulting water-base resin fluorochemical is passed through into infrared chromatograph (380 type of Nicolet company, the U.S.)
Infrared spectrum analysis is carried out, resulting infrared spectrogram is as shown in Figure 1, from figure 1 it appears that 3401.22cm-1It is O-H key
Stretching vibration absworption peak；
2960.11cm-1It is-CH3The stretching vibration absworption peak of middle c h bond；
1701.41cm-1It is C=O stretching vibration absworption peak；Illustrate to generate carbamate groups；
1466.48cm-1It is the bending vibration absorption peak of c h bond；
1260.43cm-1It is the stretching vibration absworption peak of C-F key；
It is indicated above, the resulting hexafluoroisopropanol of the present invention, isophorone diisocyanate, trimethylolpropane at
Function is reacted.
It is indicated above that embodiment 1 is successfully prepared water-base resin fluorochemical.
Embodiment 2
A kind of water-base resin fluorochemical, in parts by weight, preparing raw material includes:
Wherein, the solvent is ethyl acetate；The catalyst is dibutyl tin dilaurate；
Above-mentioned water-base resin fluorochemical the preparation method comprises the following steps:
Four mouthfuls are added sequentially to by 200 parts of hexafluoroisopropanols, 200 parts of isophorone diisocyanate, 0.03 part of catalyst
In flask, 50 DEG C are warming up to, 100 parts of solvents are added in four-hole boiling flask with the speed of 0.1ml/s, stirs lower reaction 3h, so
100 parts of trimethylolpropanes are added afterwards and are warming up to 90 DEG C, stir lower reaction 5h to get water-base resin fluorochemical.
Obtained water-base resin is dissolved in deuterated chloroform (CDCl with fluorochemical3) in solvent, measure it1H spectrum.It is used
Characterization instrument is Bruker ADVANCEIII HD 400, as a result are as follows: the outer-CH of isophorone diisocyanate compound ring3's
Proton peak is present in δ=1.11ppm ,-CH in ring2Proton peak is present in δ=1.28ppm ,-the CH that is connected with ammonia ester bond2-
For proton peak present in δ=2.90ppm, δ=0.96ppm is-CH in trimethylolpropane3Proton peak, at δ=3.50ppm
For on trimethylolpropane with the mutually o- CH of hydroxyl2Proton peak, at δ=2.9ppm on trimethylolpropane with ammonia ester bond phase
Adjacent-CH2Proton peak, be at δ=5.85ppm and the mutually o- CH of fluorocarbon chain2Proton peak, it is indicated above that 2 success of embodiment
It is prepared for water-base resin fluorochemical.
Embodiment 3
A kind of water-base resin fluorochemical, in parts by weight, preparing raw material includes:
Wherein, the solvent is acetone or the ethyl acetate mixture that 1:1 is formed by volume；The catalyst is
Dibutyl tin dilaurate；
Above-mentioned water-base resin fluorochemical the preparation method comprises the following steps:
Four mouthfuls are added sequentially to by 150 parts of hexafluoroisopropanols, 151 parts of isophorone diisocyanate, 0.02 part of catalyst
In flask, 30 DEG C are warming up to, 30 parts of solvents are added in four-hole boiling flask with the speed of 0.06ml/s, stirs lower reaction 2h, so
75 parts of trimethylolpropanes are added afterwards and are warming up to 80 DEG C, stir lower reaction 3h to get water-base resin fluorochemical.
Obtained water-base resin is dissolved in deuterated chloroform (CDCl with fluorochemical3) in solvent, measure it1H spectrum.It is used
Characterization instrument is Bruker ADVANCEIII HD 400, as a result are as follows: the outer-CH of isophorone diisocyanate compound ring3's
Proton peak is present in δ=1.11ppm ,-CH in ring2Proton peak is present in δ=1.28ppm ,-the CH that is connected with ammonia ester bond2-
For proton peak present in δ=2.90ppm, δ=0.96ppm is-CH in trimethylolpropane3Proton peak, at δ=3.50ppm
For on trimethylolpropane with the mutually o- CH of hydroxyl2Proton peak, at δ=2.9ppm on trimethylolpropane with ammonia ester bond phase
Adjacent-CH2Proton peak, be at δ=5.85ppm and the mutually o- CH of fluorocarbon chain2Proton peak, it is indicated above that 3 success of embodiment
It is prepared for water-base resin fluorochemical.
Using the water-base resin fluorochemical of above-mentioned preparation, it is prepared for a kind of water-base resin, in parts by weight,
Its raw material includes:
Concentration is 30 parts of persulfate aqueous solution of 5%；
The preparation method of above-mentioned water-base resin characterized by comprising polyether Glycols PTMG1000 is placed in and is had
Blender, thermometer, N2In the four-hole boiling flask of protective device, vacuum dehydration 2h at 110 DEG C under nitrogen protection.It is cooled to 80 DEG C
Afterwards, isophorone diisocyanate and dibutyl tin dilaurate is added, is stirred to react 2h under nitrogen protection, dihydroxy first is added
Base propionic acid, water-base resin are continued to be stirred to react 1h under nitrogen protection with fluorochemical, are cooled to 60 DEG C, and acrylic acid hydroxyl is added
Ethyl ester stirs under nitrogen protection carries out end capping reaction 1h, is cooled to 30 DEG C of addition triethylamines and is stirred to react under nitrogen protection
0.5h adds deionized water and disperses to form lotion, MS-1 multi-functional emulsifier is added, 70 DEG C are warming up to, with the speed of 1ml/min
The mixed solution of methyl methacrylate, ethyl acrylate is added dropwise in degree, while 5% concentration is added dropwise with the speed of 0.3ml/min
Persulfate aqueous solution is stirred to react 2 hours under nitrogen protection to get resin aqueous emulsion.
The resulting 8 parts of modified aqueous resins of above-mentioned steps are taken, are coated on tetrafluoroethene plate, are dried in 50 DEG C to constant weight,
Up to the modified aqueous resin latex film of thickness about 0.03mm；
By above-mentioned resulting modified aqueous resin latex film by infrared chromatograph (380 type of Nicolet company, the U.S.) into
Row infrared spectrum analysis, as a result as follows:
2933cm-1It is-CH3The stretching vibration absworption peak of middle c h bond；
1701cm-1For the stretching vibration absworption peak of-C=O- in carbamate structures；
1237cm-1It is C-F stretching vibration absworption peak；
1447cm-1It is the bending vibration absorption peak of c h bond；
Indicated above, the present invention is resulting successfully to have occurred polymerization reaction, generates water-base resin.
Above said content is only the basic explanation under present inventive concept, and is appointed made by technical solution according to the present invention
What equivalent transformation, is within the scope of protection of the invention.
Claims (5)
1. a kind of water-base resin fluorochemical, which is characterized in that in parts by weight, preparing raw material includes:
Wherein, the solvent is the mixture of one or more of acetone or ethyl acetate composition；The catalysis
Agent is dibutyl tin dilaurate.
2. water-base resin fluorochemical as described in claim 1, which is characterized in that in parts by weight, described
The raw material for preparing of water-base resin fluorochemical includes:
Wherein, the solvent is acetone；The catalyst is dibutyl tin dilaurate.
3. water-base resin fluorochemical as described in claim 1, which is characterized in that in parts by weight, described
The raw material for preparing of water-base resin fluorochemical includes:
Wherein, the solvent is ethyl acetate；The catalyst is dibutyl tin dilaurate.
4. the preparation method of water-base resin fluorochemical of any of claims 1-3, which is characterized in that packet
It includes: successively by 100~200 parts of hexafluoroisopropanols, 100~200 parts of isophorone diisocyanate, 0.01~0.03 part of catalyst
It is added in reaction vessel, is warming up to 20~50 DEG C, 10~100 parts of solvents are added to reaction with the speed of 0.05-0.1mL/s
In container, stir it is lower react 1~3h, 60~100 parts of trimethylolpropanes are then added, are warming up to 70~90 DEG C, it is anti-under stirring
Answer 1~5h to get water-base resin fluorochemical.
5. water-base resin fluorochemical of any of claims 1-3 is preparing answering in water fluoric resin
With.
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| CN113651923A (en) * | 2021-08-20 | 2021-11-16 | 上海应用技术大学 | Damping water-based resin |
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