CN106750077B - 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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CN106750077B
CN106750077B CN201611003725.1A CN201611003725A CN106750077B CN 106750077 B CN106750077 B CN 106750077B CN 201611003725 A CN201611003725 A CN 201611003725A CN 106750077 B CN106750077 B CN 106750077B
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fluorine
acrylate
fluorochemical urethane
preparation
solvent
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CN106750077A (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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract

The invention discloses a kind of preparation methods of side chain type hydrophobic oleophobic fluorochemical urethane, comprising the following steps: 1) synthesis of fluorine-containing end-capping reagent；2) synthesis of fluorine-containing chain extender；3) 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 that.

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 technique
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 British patent, and Lovelace is with non- Fluorinated isocyanates react the broad interest that synthesis fluorochemical urethane for the first time causes scientists from all over the world with fluorinated diol.
Fluorine has a strong electronegativity, high C-F bond energy (540KJ/mol), and the smallest van der Waals radius and fluorine are to carbochain outside dehydrogenation Shielding protection effect, since the introducing of fluorine is on the basis for maintaining polyurethane excellent mechanical performance and two-phase microstructure features On, and the surface property and overall performance of PU is largely improved, and assign its brilliant heat-resisting weatherability, corrosion-resistant Property, low-surface-energy, low frictional properties and biocompatibility etc., and again to have fluorochemical urethane prominent for low-surface-energy and low frictional properties Hydro-oleophobicity and anti-adhesion properties out.
Currently, most of fluorochemical urethane is using 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, is not easy to To surface migration and enrichment, so that effective protection cannot be carried out to polyurethane surface, good hydrophobic oleophobic effect is not achieved, 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 migration and enrichment, to reach good hydrophobic oleophobic effect.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of side chain type hydrophobic oleophobic fluorochemical urethane, have hydrophobic oleophobic Effect is good, raw material is cheap and easily-available, preparation method is simple and can industrialized production the advantages that.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of preparation methods of side chain type hydrophobic oleophobic fluorochemical urethane, comprising the following steps:
1) synthesis of fluorine-containing end-capping reagent
Ethanol amine and acrylate containing fluorine monomer are dissolved in solvent A, nitrogen deoxygenation, in 25 DEG C~55 DEG C of reaction temperature 2~7 h of lower reaction, until amido fully reacting, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group；
2) synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent A, nitrogen deoxygenation reacts 2 under 25~55 DEG C of reaction temperature After imino group fully reacting, ethylenediamine is added in~5 h, at 35~55 DEG C, reacts 3~8 h, vacuum distillation removes unreacted Complete ethylenediamine, by the metered acrylate containing fluorine monomer solution for being dissolved in solvent A, the reaction was continued 2~7 h, until amine Base fully reacting, vacuum distillation obtain holding dihydric fluorine-containing chain extender (HO-FA-OH)；
3) synthesis of base polyurethane prepolymer for use as
By equipped with blender, thermometer, air extractor opening reaction kettle in, polyether Glycols are added, 100~ 120 DEG C of 2~3 h of dehydrated under vacuum, are cooled to 70~90 DEG C, and the '-diphenylmethane diisocyanate and catalyst dibutyltin of metering is added Dilaurylate 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, obtains FA-OH solution, and it is pre- to be slowly dropped to above-mentioned polyurethane In aggressiveness, 1~2 h is reacted at 70~100 DEG C, and then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue 2~5 h of isothermal reaction at 70~100 DEG C, until isocyanate group fully reacting, polymer solution are washed through methanol, water sedimentation It washs, filters, 60 DEG C of vacuum drying obtain fluorochemical urethane；
The solvent A is selected from one or more of methanol, ethyl alcohol, toluene, acetone, ethyl acetate, tetrahydrofuran；
The solvent B is in dimethylformamide, dimethyl acetamide, tetrahydrofuran, butanone, N-Methyl pyrrolidone One 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 The one or more of fluorine dodecyl ethyl propylene acid esters.
Preferably, the molar ratio of the ethanol amine and acrylate containing fluorine monomer is 1:2.
Preferably, the diethanol amine, methyl acrylate, acrylate containing fluorine monomer molar ratio be 1:1:2.
Preferably, the molar ratio of the diethanol amine and ethylenediamine is 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, polyethylene oxide-propylene oxide copolymer glycol.
Preferably, the molar ratio of the polyether Glycols and '-diphenylmethane diisocyanate is 1:1.5~1:2.
Preferably, the mass concentration of the fluorine-containing end-capping reagent FA-OH is 5%~12%, and additional amount is polyurethane prepolymer The 2%~8% of weight.
Preferably, the molar ratio of the chain extender and polyether Glycols and diisocyanate is 1:1, wherein fluorine-containing chain extender The molar 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, have it is following the utility model has the advantages that
The present invention is realized through fluorine-containing end-capping reagent and fluorine-containing chain extender from polyurethane backbone end and side chain while being introduced Fluorocarbon group has prepared side chain type fluorochemical urethane, since fluorine carbon teminal base and side group have oneself to be sent to material surface migration and gather The trend of collection forms the convex touching of fluorine carbon and low-surface-energy interface, so having good hydrophobic oleophobic effect.It is used in the present invention Raw material is cheap and easily-available, and preparation method is simple, can industrialized production, have biggish practicability.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below with reference to embodiment and to this Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of preparation methods of side chain type hydrophobic oleophobic fluorochemical urethane, comprising the following steps:
1) synthesis of fluorine-containing end-capping reagent
Ethanol amine and acrylate containing fluorine monomer are dissolved in solvent A, nitrogen deoxygenation is reacted under 35 DEG C of reaction temperature 3.5 h, until amido fully reacting, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group；
2) synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent A, nitrogen deoxygenation reacts 5 h under 25 DEG C of reaction temperature, After imino group fully reacting, ethylenediamine is added, at 35 DEG C, reacts 5 h, vacuum distillation removes the complete ethylenediamine of unreacted, presses The metered acrylate containing fluorine monomer solution for being dissolved in solvent A, the reaction was continued, and 4 h are depressurized and are steamed up to amido fully reacting It evaporates to obtain and holds dihydric fluorine-containing chain extender (HO-FA-OH)；
3) synthesis of base polyurethane prepolymer for use as
By in the opening reaction kettle that blender, thermometer, air extractor are housed, polyether Glycols are added, it is true at 100 DEG C Sky is lower to be dehydrated 3 h, is cooled to 75 DEG C, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering is added, 3.5 h are reacted at 75 DEG C, obtain isocyanate-terminated performed polymer；
4) chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, obtains FA-OH solution, and it is pre- to be slowly dropped to above-mentioned polyurethane In aggressiveness, 1.5 h are reacted at 80 DEG C, and then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue at 80 DEG C Lower 3.5 h of isothermal reaction, until isocyanate group fully reacting, polymer solution is washed through methanol, water sedimentation, filtering, and 60 DEG C Vacuum drying obtains fluorochemical urethane；
In the present embodiment, the solvent A is methanol；The solvent B is dimethylformamide；The fluorinated acrylate Class monomer is acrylic acid trifluoro ethyl ester；The molar ratio of the ethanol amine and acrylate containing fluorine monomer is 1:2；The diethanol Amine, methyl acrylate, acrylate containing fluorine monomer molar ratio be 1:1:2；The molar ratio of the diethanol amine and ethylenediamine For 1:1.2；The polyether Glycols are the polypropylene glycol that molecular weight is 500；The polyether Glycols and two isocyanide of diphenyl-methane The molar ratio of acid esters is 1:2；The mass concentration of the fluorine-containing end-capping reagent FA-OH is 12%, and additional amount accounts for base polyurethane prepolymer for use as The 8% of quality；The molar ratio of the chain extender and polyether Glycols is 1:1, wherein fluorine-containing chain extender HO-FA-OH and chain extender The molar ratio of BDO is 1:2.
Embodiment 2
The invention discloses a kind of preparation methods of side chain type hydrophobic oleophobic fluorochemical urethane, comprising the following steps:
1) synthesis of fluorine-containing end-capping reagent
Ethanol amine and acrylate containing fluorine monomer are dissolved in solvent A, nitrogen deoxygenation is reacted under 35 DEG C of reaction temperature 3.5 h, until amido fully reacting, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group；
2) synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent A, nitrogen deoxygenation reacts 5 h under 25 DEG C of reaction temperature, After imino group fully reacting, ethylenediamine is added, at 35 DEG C, reacts 5 h, vacuum distillation removes the complete ethylenediamine of unreacted, presses The metered acrylate containing fluorine monomer solution for being dissolved in solvent A, the reaction was continued, and 4 h are depressurized and are steamed up to amido fully reacting It evaporates to obtain and holds dihydric fluorine-containing chain extender (HO-FA-OH)；
3) synthesis of base polyurethane prepolymer for use as
By in the opening reaction kettle that blender, thermometer, air extractor are housed, polyether Glycols are added, it is true at 110 DEG C Sky is lower to be dehydrated 2.5 h, is cooled to 80 DEG C, the '-diphenylmethane diisocyanate and catalyst dibutyltin cinnamic acid dibutyl of metering is added Tin reacts 3 h at 80 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, obtains FA-OH solution, and it is pre- to be slowly dropped to above-mentioned polyurethane In aggressiveness, 1.5 h are reacted at 80 DEG C, and then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue at 100 DEG C Lower 2 h of isothermal reaction, until isocyanate group fully reacting, polymer solution is washed through methanol, water sedimentation, filtering, and 60 DEG C true Sky is dried to obtain fluorochemical urethane；
In the present embodiment, the solvent A is methanol；The solvent B is dimethyl acetamide；The fluorinated acrylate Class monomer is hexafluorobutyl acrylate, ten difluoro heptyl methacrylates；The ethanol amine and acrylate containing fluorine monomer rub You are than being 1:2；The diethanol amine, methyl acrylate, acrylate containing fluorine monomer molar ratio be 1:1:2；The diethyl The molar ratio of hydramine and ethylenediamine is 1:1.2；The polyether Glycols are the polypropylene glycol of molecular weight 2000；The polyethers binary The molar ratio of alcohol and '-diphenylmethane diisocyanate is 1:1.6；The mass concentration of the fluorine-containing end-capping reagent FA-OH is 8%, is added Enter amount accounts for polyurethane prepolymer weight 6%；The molar ratio of the chain extender and polyether Glycols is 0.6:1, wherein fluorine-containing chain extension The molar ratio of agent HO-FA-OH and chain extender BDO is 20:1.
Embodiment 3
The invention discloses a kind of preparation methods of side chain type hydrophobic oleophobic fluorochemical urethane, comprising the following steps:
1) synthesis of fluorine-containing end-capping reagent
Ethanol amine and acrylate containing fluorine monomer are dissolved in solvent A, nitrogen deoxygenation is reacted under 45 DEG C of reaction temperature 2.5 h, until amido fully reacting, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group；
2) synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent A, nitrogen deoxygenation reacts 3.5 under 35 DEG C of reaction temperature After imino group fully reacting, ethylenediamine is added in h, at 45 DEG C, reacts 4 h, and vacuum distillation removes the complete ethylenediamine of unreacted, By the metered acrylate containing fluorine monomer solution for being dissolved in solvent A, the reaction was continued, and 3.5 h subtract up to amido fully reacting Pressure distillation obtains holding dihydric fluorine-containing chain extender (HO-FA-OH)；
3) synthesis of base polyurethane prepolymer for use as
By in the opening reaction kettle that blender, thermometer, air extractor are housed, polyether Glycols are added, it is true at 120 DEG C Sky is lower to be dehydrated 2 h, is cooled to 90 DEG C, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering is added, 2 h are reacted at 90 DEG C, obtain isocyanate-terminated performed polymer；
4) chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, obtains FA-OH solution, and it is pre- to be slowly dropped to above-mentioned polyurethane In aggressiveness, 1.5 h are reacted at 90 DEG C, and then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue at 90 DEG C Lower 3 h of isothermal reaction, until isocyanate group fully reacting, polymer solution is washed through methanol, water sedimentation, filtering, and 60 DEG C true Sky is dried to obtain fluorochemical urethane；
In the present embodiment, the solvent A is methanol/tetrahydrofuran (v/v；2:1)；The solvent B is dimethyl formyl Amine/butanone (v/v；1:1)；The acrylate containing fluorine monomer is perfluorooctylethyl group acrylate, perfluoro decyl ethyl third Olefin(e) acid ester；The molar ratio of the ethanol amine and acrylate containing fluorine monomer is 1:2；The diethanol amine, contains methyl acrylate The molar ratio of perfluoroalkyl acrylate esters monomer is 1:1:2；The molar ratio of the diethanol amine and ethylenediamine is 1:1.5；The polyethers Dihydric alcohol is the polypropylene glycol of molecular weight 5000；The molar ratio of the polyether Glycols and '-diphenylmethane diisocyanate is 1:2； The mass concentration of the fluorine-containing end-capping reagent FA-OH is 6%, and additional amount accounts for the 2% of polyurethane prepolymer weight；The chain extender with The molar ratio of polyether Glycols is 1:1, wherein the molar 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 methods of side chain type hydrophobic oleophobic fluorochemical urethane, comprising the following steps:
1) synthesis of fluorine-containing end-capping reagent
Ethanol amine and acrylate containing fluorine monomer are dissolved in solvent A, nitrogen deoxygenation is reacted under 45 DEG C of reaction temperature 2.5 h, until amido fully reacting, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group；
2) synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent A, nitrogen deoxygenation reacts 3.5 under 35 DEG C of reaction temperature After imino group fully reacting, ethylenediamine is added in h, at 45 DEG C, reacts 4 h, and vacuum distillation removes the complete ethylenediamine of unreacted, By the metered acrylate containing fluorine monomer solution for being dissolved in solvent A, the reaction was continued, and 3.5 h subtract up to amido fully reacting Pressure distillation obtains holding dihydric fluorine-containing chain extender (HO-FA-OH)；
3) synthesis of base polyurethane prepolymer for use as
By in the opening reaction kettle that blender, thermometer, air extractor are housed, polyether Glycols are added, it is true at 120 DEG C Sky is lower to be dehydrated 2 h, is cooled to 90 DEG C, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering is added, 2 h are reacted at 90 DEG C, obtain isocyanate-terminated performed polymer；
4) chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, obtains FA-OH solution, and it is pre- to be slowly dropped to above-mentioned polyurethane In aggressiveness, 1.2 h are reacted at 90 DEG C, and then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue at 90 DEG C Lower 3 h of isothermal reaction, until isocyanate group fully reacting, polymer solution is washed through methanol, water sedimentation, filtering, and 60 DEG C true Sky is dried to obtain fluorochemical urethane；
In the present embodiment, the solvent A is methanol/acetone (v/v；Mixture 1:1)；The solvent B is N- methyl Pyrrolidones；The acrylate containing fluorine monomer is perfluorododecyl ethyl propylene acid esters；The ethanol amine and fluorine-containing third The molar ratio of olefin(e) acid esters monomer is 1:2；The molar ratio of the diethanol amine, methyl acrylate, acrylate containing fluorine monomer For 1:1:2；The molar ratio of the diethanol amine and ethylenediamine is 1:1.2；The polyether Glycols are poly- the four of molecular weight 2000 Hydrogen furans glycol；The molar ratio of the polyether Glycols and '-diphenylmethane diisocyanate is 1:1.5；The fluorine-containing end-capping reagent The mass concentration of FA-OH is 10%, and additional amount accounts for the 5% of polyurethane prepolymer weight；The chain extender and polyether Glycols Molar ratio is 0.5:1, wherein the molar 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 methods of side chain type hydrophobic oleophobic fluorochemical urethane, comprising the following steps:
1) synthesis of fluorine-containing end-capping reagent
Ethanol amine and acrylate containing fluorine monomer are dissolved in solvent A, nitrogen deoxygenation is reacted under 35 DEG C of reaction temperature 3.5 h, until amido fully reacting, vacuum distillation obtains the fluorine-containing end-capping reagent (FA-OH) of terminal hydroxy group；
2) synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent A, nitrogen deoxygenation reacts 3.5 under 35 DEG C of reaction temperature After imino group fully reacting, ethylenediamine is added in h, at 55 DEG C, reacts 3 h, and vacuum distillation removes the complete ethylenediamine of unreacted, By the metered acrylate containing fluorine monomer solution for being dissolved in solvent A, the reaction was continued, and 2 h are depressurized up to amido fully reacting Distillation obtains holding dihydric fluorine-containing chain extender (HO-FA-OH)；
3) synthesis of base polyurethane prepolymer for use as
By in the opening reaction kettle that blender, thermometer, air extractor are housed, polyether Glycols are added, it is true at 120 DEG C Sky is lower to be dehydrated 2 h, is cooled to 90 DEG C, the '-diphenylmethane diisocyanate and catalyst dibutyltin dilaurylate of metering is added, 2 h are reacted at 90 DEG C, obtain isocyanate-terminated performed polymer；
4) chain extension end capping reaction
Fluorine-containing end-capping reagent FA-OH is dissolved in solvent B, obtains FA-OH solution, and it is pre- to be slowly dropped to above-mentioned polyurethane In aggressiveness, 1.5 h are reacted at 90 DEG C, and then by metering, two kinds of chain extenders of HO-FA-OH and BDO are added, continue at 90 DEG C Lower 3 h of isothermal reaction, until isocyanate group fully reacting, polymer solution is washed through methanol, water sedimentation, filtering, and 60 DEG C true Sky is dried to obtain fluorochemical urethane；
In the present embodiment, the solvent A is toluene；The solvent B is dimethylformamide/butanone (v/v；1:1)；Institute Stating acrylate containing fluorine monomer is acrylic acid trifluoro ethyl ester；The molar ratio of the ethanol amine and acrylate containing fluorine monomer is 1:2；The diethanol amine, methyl acrylate, acrylate containing fluorine monomer molar ratio be 1:1:2；The diethanol amine with The molar ratio of ethylenediamine is 1:1.2；The polyether Glycols are polyethylene oxide-propylene oxide copolymer two of molecular weight 2000 Alcohol；The molar ratio of the polyether Glycols and '-diphenylmethane diisocyanate is 1:1.8；The fluorine-containing end-capping reagent FA-OH's Mass concentration is 7%, and additional amount accounts for the 3% of polyurethane prepolymer weight；The molar ratio of the chain extender and polyether Glycols is 0.8:1, wherein the molar ratio of fluorine-containing chain extender HO-FA-OH and chain extender BDO is 10:1.
In order to verify the resulting technical effect of the present invention, Examples 1 to 5 products obtained therefrom 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 through fluorine-containing end-capping reagent and fluorine-containing chain extender from polyurethane backbone end Fluorocarbon group is introduced simultaneously with side chain, has prepared side chain type fluorochemical urethane, since fluorine carbon teminal base and side group have oneself to be sent to material Expect the trend of surface migration and aggregation, the convex touching of fluorine carbon and low-surface-energy interface is formed, so having good hydrophobic oleophobic effect. Raw material used in the present invention is cheap and easily-available, and preparation method is simple, can industrialized production, have biggish practicability.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the present invention in any form；It is all The those of ordinary skill of the industry can be described in by specification and described above and swimmingly implement the present invention；But it is all familiar 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 embodiment of the invention；Meanwhile all realities according to the present invention The variation, modification and evolution etc. of matter technology any equivalent variations to the above embodiments, still fall within technology of the invention Within the protection scope of scheme.

Claims (7)

1. a kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane, it is characterised in that the following steps are included:
1) synthesis of fluorine-containing end-capping reagent
Ethanol amine and acrylate containing fluorine monomer are dissolved in solvent A, nitrogen deoxygenation is anti-under 25 DEG C~55 DEG C of reaction temperature 2~7h is answered, until amido fully reacting, vacuum distillation obtains the fluorine-containing end-capping reagent of terminal hydroxy group；
2) synthesis of fluorine-containing chain extender
Diethanol amine and methyl acrylate are dissolved in solvent A, nitrogen deoxygenation, under 25~55 DEG C of reaction temperature, reaction 2~ After imino group fully reacting, ethylenediamine is added in 5h, at 35~55 DEG C, reacts 3~8h, it is complete that vacuum distillation removes unreacted Ethylenediamine, by the metered acrylate containing fluorine monomer solution for being dissolved in solvent A, the reaction was continued 2~7h, until amido reacts Completely, vacuum distillation obtains holding dihydric fluorine-containing chain extender；
3) synthesis of base polyurethane prepolymer for use as
By in the opening reaction kettle that blender, thermometer, air extractor are housed, polyether Glycols are added, at 100~120 DEG C 2~3h of dehydrated under vacuum is cooled to 70~90 DEG C, and the '-diphenylmethane diisocyanate and catalyst dibutyltin cinnamic acid two of metering is added Butyl tin reacts 2~4h between 70~90 DEG C, obtains isocyanate-terminated performed polymer；
4) chain extension end capping reaction
Fluorine-containing end-capping reagent is dissolved in solvent B, obtains fluorine-containing end capper solution, and is slowly dropped to above-mentioned base polyurethane prepolymer for use as In, 1~2h is reacted at 70~100 DEG C, and then by metering, two kinds of chain extenders of fluorine-containing chain extender and BDO are added, continue 70 2~5h of isothermal reaction at~100 DEG C, until isocyanate group fully reacting, polymer solution is through methanol, water sedimentation, washing, mistake Filter, 60 DEG C of vacuum drying obtain fluorochemical urethane；
The solvent A is selected from one or more of methanol, ethyl alcohol, toluene, acetone, ethyl acetate, tetrahydrofuran；
The solvent B in dimethylformamide, dimethyl acetamide, tetrahydrofuran, butanone, N-Methyl pyrrolidone one Kind is two or more；
Wherein, the molar ratio of the step 1) ethanol amine and acrylate containing fluorine monomer is 1:2；
Step 2) the diethanol amine, methyl acrylate, acrylate containing fluorine monomer molar ratio be 1:1:2.
2. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that: 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, it is characterised in that: step 2) The molar ratio of the diethanol amine and ethylenediamine is 1:1~1:2.
4. 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 polyethylene oxide-propylene oxide copolymer glycol.
5. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that: step 3) The molar ratio of the polyether Glycols and '-diphenylmethane diisocyanate is 1:1.5~1:2.
6. 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 is 5%~12%, and additional amount is the 2%~8% of polyurethane prepolymer weight.
7. the preparation method of side chain type hydrophobic oleophobic fluorochemical urethane according to claim 1, it is characterised in that: step 4) The molar ratio of the chain extender and polyether Glycols and diisocyanate is 1:1, wherein fluorine-containing chain extender and chain extender BDO's rubs You are than being 1:2~20:1.
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