CN106750077A - A kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane - Google Patents

A kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane Download PDF

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CN106750077A
CN106750077A CN201611003725.1A CN201611003725A CN106750077A CN 106750077 A CN106750077 A CN 106750077A CN 201611003725 A CN201611003725 A CN 201611003725A CN 106750077 A CN106750077 A CN 106750077A
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fluorine
preparation
acrylate
fluorochemical urethane
side chain
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CN106750077B (en
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袁琴
陈旭东
魏珊珊
唐孝芬
朱永祥
张奇
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Guangdong Juhang Institute For Advanced Materials Co ltd
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Guangdong Nanfang Fountain Plastic Technology Co Ltd
Guangdong New Material Research Institute Co Ltd
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    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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Abstract

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;2)The synthesis of fluorine-containing chain extender;3)The synthesis of base polyurethane prepolymer for use as;4)Chain extension end capping reaction.Preparation method hydrophobic oleophobic effect of the invention is good, raw material is cheap and easily-available, preparation method is simple and can industrialized production the advantages of.

Description

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.

Claims (9)

1. a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, it is characterised in that 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.
2. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that:It is described to contain Perfluoroalkyl acrylate esters monomer is selected from acrylic acid trifluoro ethyl ester, hexafluoro isopropyl acrylate, hexafluorobutyl acrylate, ten difluoro heptan Base acrylate, perfluorooctylethyl group acrylate, perfluoro decyl ethyl propylene acid esters, perfluorododecyl ethyl propylene acid esters One or more.
3. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1 and 2, it is characterised in that:Step Rapid 1)The monoethanolamine is 1 with the mol ratio of acrylate containing fluorine monomer:2.
4. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1 and 2, it is characterised in that:Step Rapid 2)The diethanol amine, methyl acrylate, the mol ratio of acrylate containing fluorine monomer are 1:1:2.
5. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that:Step 2) The diethanol amine is 1 with the mol ratio of ethylenediamine:1~1:2.
6. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that:Step 3) The polyether Glycols are molecular weight M=5.0 × 102~2.0 × 104Polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol Or PEO-propylene oxide copolymer glycol.
7. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that:Step 3) The polyether Glycols are 1 with the mol ratio of '-diphenylmethane diisocyanate:1.5~1:2.
8. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that:Step 4) The mass concentration of the fluorine-containing end-capping reagent FA-OH be 5%~12%, its addition for polyurethane prepolymer weight 2%~ 8%。
9. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that:Step 4) The chain extender and polyether Glycols and the mol ratio of diisocyanate are 1:1, wherein fluorine-containing chain extender HO-FA-OH and chain extension The mol ratio of agent BDO is 1:2~20:1.
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CN107141440A (en) * 2017-06-16 2017-09-08 北京化工大学 Aqueous oligomer of organosilicon polyurethane acrylate that a kind of stiffening ring is modified and preparation method thereof
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CN109880055A (en) * 2019-02-27 2019-06-14 黑龙江省科学院石油化学研究院 A kind of comb shaped structure urethane acrylate and preparation method thereof of perfluoroalkyl chain sealing end
CN109880055B (en) * 2019-02-27 2022-01-28 黑龙江省科学院石油化学研究院 Preparation method of perfluoroalkyl chain terminated polyurethane acrylate with comb-shaped structure
CN109749048A (en) * 2019-02-28 2019-05-14 陕西科技大学 Hold fluoroalkyl and the double modified polyurethane emulsions of side chain fluoroalkyl and preparation method thereof
CN110437416A (en) * 2019-08-19 2019-11-12 美瑞新材料股份有限公司 A kind of fluorine silication method for preparing polyurethane elastic body of comb shaped structure
CN110437416B (en) * 2019-08-19 2021-08-10 美瑞新材料股份有限公司 Preparation method of fluorosilicated polyurethane elastomer with comb-shaped structure
CN113387825A (en) * 2021-06-10 2021-09-14 福州大学 Long-chain alkyl ester amine compound or fluorine-containing long-chain alkyl ester amine compound and kilogram-level preparation method thereof
CN113429871A (en) * 2021-07-06 2021-09-24 吴江市汉塔纺织整理有限公司 Novel waterborne polyurethane bionic super-hydrophobic coating and preparation method thereof

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