A kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane
Technical field
The present invention relates to fluorochemical urethane technical field, specially a kind of preparation of side chain type hydrophobic oleophobic fluorochemical urethane
Method.
Background technology
In recent years, fluorochemical urethane is received significant attention with its exclusive performance.Poly- ammonia is reported from nineteen forty-seven Bayer
After the chemical technology of the synthesis of ester, 1958, the research of FPU was reported earliest in a BP, and Lovelace is with non-
Fluorinated isocyanates react the broad interest that synthesis fluorochemical urethane first causes scientists from all over the world with fluorinated diol.
Fluorine has strong electronegativity, C-F bond energys high(540KJ/mol), the outer minimum van der Waals radius of dehydrogenation and fluorine are to carbochain
Shielding protection effect, the introducing due to fluorine maintaining the basis of the excellent mechanical performance of polyurethane and two-phase microstructure features
On, and the surface property and overall performance of PU are largely improved, and assign the heat-resisting weatherability of its brilliance, corrosion-resistant
Property, low-surface-energy, low frictional properties and biocompatibility etc., and low-surface-energy and low frictional properties again to have fluorochemical urethane prominent
The hydro-oleophobicity and anti-adhesion properties for going out.
At present, most of fluorochemical urethane is with the fluorinated polyether of bifunctionality or fluorination diisocyanate as Material synthesis
, contain fluorocarbon radical on this product molecule structural backbone, due to being limited by molecular backbone and stronger hydrogen bond action, it is not easy to
To surface migration and enrichment, so as to can not effectively be protected to polyurethane surface, good hydrophobic oleophobic effect is not reached, and
This fluorochemical urethane solubility property is poor.And the fluorocarbon radical of side chain type fluorochemical urethane be then restricted it is less, it is easy to table
Face migrates and is enriched with, so as to reach good hydrophobic oleophobic effect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, with hydrophobic oleophobic
Effect is good, raw material is cheap and easily-available, preparation method is simple and can industrialized production the advantages of.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, comprise the following steps:
1)The synthesis of fluorine-containing end-capping reagent
Monoethanolamine and acrylate containing fluorine monomer are dissolved in solvent orange 2 A, nitrogen deoxygenation is anti-under 25 DEG C~55 DEG C of reaction temperature
2~7 h are answered, until amido reaction is complete, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group;
2)The synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent orange 2 A, nitrogen deoxygenation under 25~55 DEG C of reaction temperature, reacts 2~5
H, after imino group reaction completely, adds ethylenediamine, at 35~55 DEG C, reacts 3~8 h, and it is complete that vacuum distillation removes unreacted
Ethylenediamine, by the metered acrylate containing fluorine monomer solution for being dissolved in solvent orange 2 A, continues to react 2~7 h, until amido is anti-
Should be complete, vacuum distillation obtains the dihydric fluorine-containing chain extender (HO-FA-OH) in end;
3)The synthesis of base polyurethane prepolymer for use as
By in equipped with agitator, thermometer, the opening reactor of air extractor, polyether Glycols are added, at 100~120 DEG C
The h of dehydrated under vacuum 2~3, is cooled to 70~90 DEG C, adds the '-diphenylmethane diisocyanate and catalyst dibutyltin cinnamic acid of metering
Dibutyl tin, reacts 2~4 h between 70~90 DEG C, obtains isocyanate-terminated performed polymer;
4)Chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, FA-OH solution is obtained, and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In, 1~2 h is reacted at 70~100 DEG C, then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue 70
The h of isothermal reaction 2~5 at~100 DEG C, until NCO reaction is complete, polymer solution is washed through methyl alcohol, water sedimentation,
Filtering, 60 DEG C of vacuum drying obtain fluorochemical urethane;
The solvent orange 2 A be selected from methyl alcohol, ethanol, toluene, acetone, ethyl acetate, tetrahydrofuran in one or more;
The solvent B is selected from dimethylformamide, dimethylacetylamide, tetrahydrofuran, butanone, 1-METHYLPYRROLIDONE
Plant or two or more.
Preferably, the acrylate containing fluorine monomer is selected from acrylic acid trifluoro ethyl ester, hexafluoro isopropyl acrylate, third
It is olefin(e) acid hexafluoro butyl ester, ten difluoro heptyl methacrylates, perfluorooctylethyl group acrylate, perfluoro decyl ethyl propylene acid esters, complete
Fluorine dodecyl ethyl propylene acid esters one or more.
Preferably, the mol ratio of the monoethanolamine and acrylate containing fluorine monomer is 1:2.
Preferably, the diethanol amine, methyl acrylate, the mol ratio of acrylate containing fluorine monomer are 1:1:2.
Preferably, the diethanol amine and the mol ratio of ethylenediamine are 1:1.2~1:1.5.
Preferably, the polyether Glycols are molecular weight M=5.0 × 102~2.0 × 104Polyethylene glycol, polypropylene glycol,
Polytetrahydrofuran diol, PEO-propylene oxide copolymer glycol.
Preferably, the polyether Glycols and the mol ratio of '-diphenylmethane diisocyanate are 1:1.5~1:2.
Preferably, the mass concentration of the fluorine-containing end-capping reagent FA-OH is 5%~12%, and its addition is polyurethane prepolymer
The 2%~8% of weight.
Preferably, the chain extender and polyether Glycols and the mol ratio of diisocyanate are 1:1, wherein fluorine-containing chain extender
The mol ratio of HO-FA-OH and chain extender BDO is 1:2~20:1.
A kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane of the present invention, with following beneficial effect:
The present invention is realized and introduces fluorine carbon simultaneously from polyurethane backbone end and side chain by fluorine-containing end-capping reagent and fluorine-containing chain extender
Group, has prepared side chain type fluorochemical urethane, because fluorine carbon teminal base and side base have what is be sent to material surface migration certainly and assemble
Trend, forms the convex tactile and low-surface-energy interface of fluorine carbon, so with good hydrophobic oleophobic effect.Raw material used in the present invention
Cheap and easily-available, preparation method is simple, can industrialized production, with larger practicality.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment and to this
Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, comprise the following steps:
1)The synthesis of fluorine-containing end-capping reagent
Monoethanolamine and acrylate containing fluorine monomer are dissolved in solvent orange 2 A, nitrogen deoxygenation reacts 3.5 under 35 DEG C of reaction temperature
H, until amido reaction is complete, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group;
2)The synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent orange 2 A, nitrogen deoxygenation under 25 DEG C of reaction temperature, reacts 5 h, imido
After base reaction completely, ethylenediamine is added, at 35 DEG C, react 5 h, vacuum distillation removes the complete ethylenediamine of unreacted, by metering
Addition is dissolved in the acrylate containing fluorine monomer solution of solvent orange 2 A, continues to react 4 h, until amido reaction is complete, vacuum distillation is obtained
To the dihydric fluorine-containing chain extender (HO-FA-OH) in end;
3)The synthesis of base polyurethane prepolymer for use as
By in equipped with agitator, thermometer, the opening reactor of air extractor, polyether Glycols are added, under 100 DEG C of vacuum
3 h are dehydrated, 75 DEG C are cooled to, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering are added, 75
3.5 h are reacted at DEG C, isocyanate-terminated performed polymer is obtained;
4)Chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, FA-OH solution is obtained, and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In, 1.5 h are reacted at 80 DEG C, then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue permanent at 80 DEG C
Temperature 3.5 h of reaction, until NCO reaction is complete, polymer solution is through methyl alcohol, water sedimentation, washing, filtering, 60 DEG C of vacuum
It is dried to obtain fluorochemical urethane;
In the present embodiment, the solvent orange 2 A is methyl alcohol;The solvent B is dimethylformamide;The acrylate containing fluorine list
Body is acrylic acid trifluoro ethyl ester;The mol ratio of the monoethanolamine and acrylate containing fluorine monomer is 1:2;The diethanol amine,
Methyl acrylate, the mol ratio of acrylate containing fluorine monomer are 1:1:2;The diethanol amine is 1 with the mol ratio of ethylenediamine:
1.2;The polyether Glycols are polypropylene glycol that molecular weight is 500;The polyether Glycols and '-diphenylmethane diisocyanate
Mol ratio be 1:2;The mass concentration of the fluorine-containing end-capping reagent FA-OH is 12%, and addition accounts for polyurethane prepolymer weight
8%;The chain extender is 1 with the mol ratio of polyether Glycols:1, wherein fluorine-containing chain extender HO-FA-OH and chain extender BDO
Mol ratio is 1:2.
Embodiment 2
The invention discloses a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, comprise the following steps:
1)The synthesis of fluorine-containing end-capping reagent
Monoethanolamine and acrylate containing fluorine monomer are dissolved in solvent orange 2 A, nitrogen deoxygenation reacts 3.5 under 35 DEG C of reaction temperature
H, until amido reaction is complete, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group;
2)The synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent orange 2 A, nitrogen deoxygenation under 25 DEG C of reaction temperature, reacts 5 h, imido
After base reaction completely, ethylenediamine is added, at 35 DEG C, react 5 h, vacuum distillation removes the complete ethylenediamine of unreacted, by metering
Addition is dissolved in the acrylate containing fluorine monomer solution of solvent orange 2 A, continues to react 4 h, until amido reaction is complete, vacuum distillation is obtained
To the dihydric fluorine-containing chain extender (HO-FA-OH) in end;
3)The synthesis of base polyurethane prepolymer for use as
By in equipped with agitator, thermometer, the opening reactor of air extractor, polyether Glycols are added, under 110 DEG C of vacuum
2.5 h are dehydrated, 80 DEG C are cooled to, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering is added,
3 h are reacted at 80 DEG C, isocyanate-terminated performed polymer is obtained;
4)Chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, FA-OH solution is obtained, and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In, 1.5 h are reacted at 80 DEG C, then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue permanent at 100 DEG C
Temperature 2 h of reaction, until NCO reaction is complete, polymer solution is done through methyl alcohol, water sedimentation, washing, filtering, 60 DEG C of vacuum
It is dry to obtain fluorochemical urethane;
In the present embodiment, the solvent orange 2 A is methyl alcohol;The solvent B is dimethylacetylamide;The acrylate containing fluorine list
Body is hexafluorobutyl acrylate, ten difluoro heptyl methacrylates;The mol ratio of the monoethanolamine and acrylate containing fluorine monomer
It is 1:2;The diethanol amine, methyl acrylate, the mol ratio of acrylate containing fluorine monomer are 1:1:2;The diethanol amine
It is 1 with the mol ratio of ethylenediamine:1.2;The polyether Glycols are the polypropylene glycol of molecular weight 2000;The polyether Glycols with
The mol ratio of '-diphenylmethane diisocyanate is 1:1.6;The mass concentration of the fluorine-containing end-capping reagent FA-OH is 8%, addition
Account for the 6% of polyurethane prepolymer weight;The chain extender is 0.6 with the mol ratio of polyether Glycols:1, wherein fluorine-containing chain extender
The mol ratio of HO-FA-OH and chain extender BDO is 20:1.
Embodiment 3
The invention discloses a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, comprise the following steps:
1)The synthesis of fluorine-containing end-capping reagent
Monoethanolamine and acrylate containing fluorine monomer are dissolved in solvent orange 2 A, nitrogen deoxygenation reacts 2.5 under 45 DEG C of reaction temperature
H, until amido reaction is complete, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group;
2)The synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent orange 2 A, nitrogen deoxygenation under 35 DEG C of reaction temperature, reacts 3.5 h, sub-
After amino reaction completely, ethylenediamine is added, at 45 DEG C, react 4 h, vacuum distillation removes the complete ethylenediamine of unreacted, based on
Amount adds the acrylate containing fluorine monomer solution for being dissolved in solvent orange 2 A, continues to react 3.5 h, until amido reaction is complete, decompression is steamed
Evaporate and obtain the dihydric fluorine-containing chain extender (HO-FA-OH) in end;
3)The synthesis of base polyurethane prepolymer for use as
By in equipped with agitator, thermometer, the opening reactor of air extractor, polyether Glycols are added, under 120 DEG C of vacuum
2 h are dehydrated, 90 DEG C are cooled to, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering are added, 90
2 h are reacted at DEG C, isocyanate-terminated performed polymer is obtained;
4)Chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, FA-OH solution is obtained, and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In, 1.5 h are reacted at 90 DEG C, then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue permanent at 90 DEG C
Temperature 3 h of reaction, until NCO reaction is complete, polymer solution is done through methyl alcohol, water sedimentation, washing, filtering, 60 DEG C of vacuum
It is dry to obtain fluorochemical urethane;
In the present embodiment, the solvent orange 2 A is methyl alcohol/tetrahydrofuran(v/v;2:1);The solvent B is dimethylformamide/fourth
Ketone(v/v;1:1);The acrylate containing fluorine monomer is perfluorooctylethyl group acrylate, perfluoro decyl ethylacrylic acid
Ester;The mol ratio of the monoethanolamine and acrylate containing fluorine monomer is 1:2;The diethanol amine, methyl acrylate, fluorine-containing third
The mol ratio of olefin(e) acid esters monomer is 1:1:2;The diethanol amine is 1 with the mol ratio of ethylenediamine:1.5;The polyethers binary
Alcohol is the polypropylene glycol of molecular weight 5000;The polyether Glycols are 1 with the mol ratio of '-diphenylmethane diisocyanate:2;It is described
The mass concentration of fluorine-containing end-capping reagent FA-OH is 6%, and addition accounts for the 2% of polyurethane prepolymer weight;The chain extender and polyethers
The mol ratio of dihydroxylic alcohols is 1:1, wherein the mol ratio of fluorine-containing chain extender HO-FA-OH and chain extender BDO is 2:1.
Embodiment 4
The invention discloses a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, comprise the following steps:
1)The synthesis of fluorine-containing end-capping reagent
Monoethanolamine and acrylate containing fluorine monomer are dissolved in solvent orange 2 A, nitrogen deoxygenation reacts 2.5 under 45 DEG C of reaction temperature
H, until amido reaction is complete, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group;
2)The synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent orange 2 A, nitrogen deoxygenation under 35 DEG C of reaction temperature, reacts 3.5 h, sub-
After amino reaction completely, ethylenediamine is added, at 45 DEG C, react 4 h, vacuum distillation removes the complete ethylenediamine of unreacted, based on
Amount adds the acrylate containing fluorine monomer solution for being dissolved in solvent orange 2 A, continues to react 3.5 h, until amido reaction is complete, decompression is steamed
Evaporate and obtain the dihydric fluorine-containing chain extender (HO-FA-OH) in end;
3)The synthesis of base polyurethane prepolymer for use as
By in equipped with agitator, thermometer, the opening reactor of air extractor, polyether Glycols are added, under 120 DEG C of vacuum
2 h are dehydrated, 90 DEG C are cooled to, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering are added, 90
2 h are reacted at DEG C, isocyanate-terminated performed polymer is obtained;
4)Chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, FA-OH solution is obtained, and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In, 1.2 h are reacted at 90 DEG C, then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue permanent at 90 DEG C
Temperature 3 h of reaction, until NCO reaction is complete, polymer solution is done through methyl alcohol, water sedimentation, washing, filtering, 60 DEG C of vacuum
It is dry to obtain fluorochemical urethane;
In the present embodiment, the solvent orange 2 A is methanol/acetone(v/v;1:1)Mixture;The solvent B is N- methylpyrroles
Alkanone;The acrylate containing fluorine monomer is perfluorododecyl ethyl propylene acid esters;The monoethanolamine and fluorine-containing
The mol ratio of esters monomer is 1:2;The diethanol amine, methyl acrylate, the mol ratio of acrylate containing fluorine monomer are 1:
1:2;The diethanol amine is 1 with the mol ratio of ethylenediamine:1.2;The polyether Glycols are the poly- tetrahydrochysene furan of molecular weight 2000
Mutter glycol;The polyether Glycols are 1 with the mol ratio of '-diphenylmethane diisocyanate:1.5;The fluorine-containing end-capping reagent FA-OH
Mass concentration be 10%, addition accounts for the 5% of polyurethane prepolymer weight;The chain extender and polyether Glycols mole
Than being 0.5:1, wherein the mol ratio of fluorine-containing chain extender HO-FA-OH and chain extender BDO is 10:1.
Embodiment 5
The invention discloses a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, comprise the following steps:
1)The synthesis of fluorine-containing end-capping reagent
Monoethanolamine and acrylate containing fluorine monomer are dissolved in solvent orange 2 A, nitrogen deoxygenation reacts 3.5 under 35 DEG C of reaction temperature
H, until amido reaction is complete, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group;
2)The synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent orange 2 A, nitrogen deoxygenation under 35 DEG C of reaction temperature, reacts 3.5 h, sub-
After amino reaction completely, ethylenediamine is added, at 55 DEG C, react 3 h, vacuum distillation removes the complete ethylenediamine of unreacted, based on
Amount adds the acrylate containing fluorine monomer solution for being dissolved in solvent orange 2 A, continues to react 2 h, until amido reaction is complete, vacuum distillation
Obtain the dihydric fluorine-containing chain extender (HO-FA-OH) in end;
3)The synthesis of base polyurethane prepolymer for use as
By in equipped with agitator, thermometer, the opening reactor of air extractor, polyether Glycols are added, under 120 DEG C of vacuum
2 h are dehydrated, 90 DEG C are cooled to, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering are added, 90
2 h are reacted at DEG C, isocyanate-terminated performed polymer is obtained;
4)Chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, FA-OH solution is obtained, and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In, 1.5 h are reacted at 90 DEG C, then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue permanent at 90 DEG C
Temperature 3 h of reaction, until NCO reaction is complete, polymer solution is done through methyl alcohol, water sedimentation, washing, filtering, 60 DEG C of vacuum
It is dry to obtain fluorochemical urethane;
In the present embodiment, the solvent orange 2 A is toluene;The solvent B is dimethylformamide/butanone(v/v;1:1);It is described to contain
Perfluoroalkyl acrylate esters monomer is acrylic acid trifluoro ethyl ester;The mol ratio of the monoethanolamine and acrylate containing fluorine monomer is 1:2;
The diethanol amine, methyl acrylate, the mol ratio of acrylate containing fluorine monomer are 1:1:2;The diethanol amine and second two
The mol ratio of amine is 1:1.2;The polyether Glycols are the PEO-propylene oxide copolymer glycol of molecular weight 2000;Institute
It is 1 that polyether Glycols are stated with the mol ratio of '-diphenylmethane diisocyanate:1.8;The quality of the fluorine-containing end-capping reagent FA-OH is dense
It is 7% to spend, and addition accounts for the 3% of polyurethane prepolymer weight;The chain extender is 0.8 with the mol ratio of polyether Glycols:1, its
In the mol ratio of fluorine-containing chain extender HO-FA-OH and chain extender BDO be 10:1.
In order to verify the technique effect obtained by the present invention, the products obtained therefrom of embodiment 1~5 is tested respectively, specific knot
Fruit is as shown in table 1:
The different embodiment properties of product test results of table 1
|
Surface energy |
Static water contact |
Static oil contact |
Embodiment 1 |
23.8 |
105° |
92° |
Embodiment 2 |
18.3 |
152° |
131° |
Embodiment 3 |
20.5 |
116° |
109° |
Embodiment 4 |
19.1 |
138° |
122° |
Embodiment 5 |
19.6 |
129° |
114° |
Conventional polyurethanes |
28~35 |
65 °~77 ° |
55 °~63 ° |
As can be seen from Table 1, the present invention is realized by fluorine-containing end-capping reagent and fluorine-containing chain extender from polyurethane backbone end and side
Chain introduces fluorocarbon group simultaneously, has prepared side chain type fluorochemical urethane, and material list is sent to certainly because fluorine carbon teminal base and side base have
The trend that face migrates and assembles, forms the convex tactile and low-surface-energy interface of fluorine carbon, so with good hydrophobic oleophobic effect.This hair
Bright used raw material is cheap and easily-available, and preparation method is simple, can industrialized production, with larger practicality.
The above, only presently preferred embodiments of the present invention not makees any formal limitation to the present invention;It is all
The those of ordinary skill of the industry can described in by specification and the above and swimmingly implement the present invention;But, it is all to be familiar with
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be Equivalent embodiments of the invention;Meanwhile, it is all according to reality of the invention
Variation, modification and evolution of any equivalent variations that matter technology is made to above example etc., still fall within technology of the invention
Within the protection domain of scheme.