CN111423554B - Fluorine-containing polyurethane material with water-proof, oil-proof and antifouling properties - Google Patents
Fluorine-containing polyurethane material with water-proof, oil-proof and antifouling properties Download PDFInfo
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Abstract
The invention discloses a fluorine-containing aqueous polyurethane material with water resistance, oil resistance and antifouling performance, which is prepared by synthesizing a dihydroxy fluorocarbon chain monomer through a mercapto-vinyl Michael reaction, introducing the dihydroxy fluorocarbon chain monomer into polyurethane through an addition polymerization reaction with a polyurethane prepolymer terminated by diisocyanate, and obtaining the fluorine-containing aqueous polyurethane material with water resistance, oil resistance and antifouling performance through a chain extension reaction and a neutralization reaction respectively. The fluorine-containing waterborne polyurethane material has wide application prospect in the fields of biomedicine, leather finishing agents and the like.
Description
Technical Field
The invention relates to the research field of waterproof, oil-proof and antifouling materials and the development field of polyurethane biomedical materials and leather finishing agents, in particular to a fluorine-containing polyurethane material with waterproof, oil-proof and antifouling properties.
Background
Polyurethane (PU) is a generic name of high molecular materials with characteristic groups of repeated carbamate (-NHCOO-), full-name polyurethane, which is generally prepared by reacting polydiol (polyether, polyester), polyisocyanate and micromolecule chain extender (diamine, dihydric alcohol), and is a block copolymer formed by alternating soft segments and hard segments. The soft segment is composed of polyglycol, the hard segment is composed of polyisocyanate and chain extender, phase separation exists between polyurethane chain segments due to the mutual incompatibility between the soft segment and the hard segment in thermodynamics, and a micro-region structure is formed, wherein the soft segment forms a continuous phase, and the hard segment forms micro-regions distributed in the continuous phase. In addition, because of the presence of many polar groups in the polyurethane, hydrogen bonds are likely to form within the polyurethane molecule, between molecules, between soft and hard segments, and between hard and hard segments. The polyurethane has high elasticity of rubber and high strength of plastic due to the incompatibility of soft and soft segments in a molecular chain and the existence of a large number of polar groups. Therefore, the polyurethane material can be widely applied to the fields of biomedical materials, coatings, artificial leather, adhesives, soft and hard foam plastics and the like.
However, because the polyurethane molecular chain contains a large amount of polar groups, the polyurethane molecular chain has extremely strong adhesion to a mold in the processing process, so that release agents must be introduced in the processing process, the release agents not only increase the production cost, but also are not easy to remove, and the residual materials affect the performance of the materials. On the other hand, when the soft segment is composed of polyester diol, there are a large number of ester bonds in the polyurethane at this time, and these ester bonds are easily degraded in acid and alkali. Resulting in poor thermal and chemical stability, which limits the application of polyurethane materials. In addition, because the biocompatibility of polyurethane is not good enough, when the polyurethane is used as a biomedical material and implanted into a human body for a long time, the polyurethane is easily attacked by the immune system of the human body, so that complement activation, blood coagulation and inflammatory reaction are caused.
Fluorine-containing small-molecule organic compounds have a series of excellent properties, such as excellent three-proofing properties (water, oil, stain resistance), heat resistance, chemical resistance and biostability. But compared with the fluorine-containing polymer, the tail end of the carbon chain of the fluorine-containing polymer is completely wrapped by the fluorine atom to form a hard fluorine shell, so that the fluorine-containing small molecular compound is difficult to degrade; meanwhile, the hydrophobic and oleophobic properties make the protein easily bonded with the protein, exist in blood, accumulate in tissues such as kidney, muscle, liver and the like, and affect the health of human body. Wherein the biological half-lives of the perfluorooctyl sulfonic acid (PFOS) and the perfluorooctanoic acid ammonium (PFOA) are respectively 8.7 years and 4.37 years on average, and the maximum of the PFOS can reach 21.3 years; the European Union has already placed these two substance organisms under REACH regulation and has established the content of these two substance restrictions. The fluorine-containing polymer basically keeps the characteristics of the fluorine-containing micromolecule organic compound, does not influence human health due to low chemical activity and biological activity, and has good biocompatibility. Therefore, the introduction of the fluorine-containing small-molecule organic compound into the polyurethane can compensate the defects of both the fluorine-containing material and the polyurethane material: on one hand, the thermal stability, chemical stability, biocompatibility, biological stability and stripping performance of the polyurethane material can be improved; on the other hand, the toxicity of the fluorine-containing small molecular organic compound to the human body can be obviously reduced. Greatly expands the application prospect of the fluorine-containing material and the polyurethane material in various fields.
The common fluorine-containing organic compounds currently incorporated into polyurethanes are mainly monohydric organic fluoroalcohols and dihydric organic fluoroalcohols. However, the monoorganofluoroalcohol can only be introduced into the polyurethane in the form of an end-capping agent, for example, the monoorganofluoroalcohol introduced into the polyurethane in patent CN101435159A, which results in low fluorine content in the polyurethane, and the organofluoroalcohol can only exist at the extreme end of each polyurethane chain, thus seriously affecting the water, oil and soil resistance. Therefore, the key point for obtaining the fluorine-containing polyurethane material with excellent performance is to synthesize a binary organic fluorine alcohol chain extender, and a great deal of research work is done before the problem is solved. Patent CN 102643406 a discloses a polyester type polyurethane material with side chain containing fluorine and a preparation method thereof. And (3) synthesizing the fluorine-containing oxyalkyl dihydric alcohol by the unitary organic fluorine alcohol under the action of NaOH, epichlorohydrin and perchloric acid respectively, and then carrying out chain extension reaction on the dihydric alcohol and the polyurethane prepolymer to prepare the fluorine-containing polyurethane. However, the preparation of the fluorine-containing alkoxy diol has multiple steps, long reaction time and low yield. Patent CN 103044649 a discloses a hydroxyl-containing fluorine-containing acrylate block copolymer prepared by block copolymerization of hydroxyl-containing acrylic monomer and fluorine-containing acrylic monomer. However, the hydroxyl number of each molecular chain in the product is not easy to control due to the polymerization reaction, and when the average functionality of the hydroxyl in the block polymer is more than 2, the block polymer is easy to react with the polyurethane prepolymer to generate a gel effect, so that the reaction controllability is poor, and the difficulty of the synthesis process is increased.
In order to overcome the defects and defects of the prior art, the invention aims to synthesize a new binary organic fluoroalcohol by utilizing the mercapto-vinyl Michael reaction with mild reaction conditions, short reaction time and high yield, then introduce the new binary organic fluoroalcohol into a polyurethane main chain by carrying out addition polymerization reaction with a diisocyanate-terminated polyurethane prepolymer, and obtain the water-based polyurethane material with the performances of water resistance, oil resistance and antifouling performance by respectively carrying out chain extension reaction and neutralization reaction.
Disclosure of Invention
The invention provides a fluorine-containing polyurethane material with water resistance, oil resistance and pollution resistance, which is characterized in that the preparation method comprises the following steps:
(1) preparing a dihydroxy fluorocarbon chain monomer: dissolving fluorine-containing (methyl) acrylate and mercapto-containing dihydric alcohol in a solvent A to prepare a mixed solution, adding a certain amount of Lewis base serving as a catalyst into the mixed solution under the condition of stirring, and reacting for 2-6 hours at 30-60 ℃ under the protection of inert gas; the solvent A is tetrahydrofuran capable of completely dissolving fluorine-containing (methyl) acrylate, diol containing sulfydryl and Lewis base; the inert gas is nitrogen; fluorine-containing (meth) acrylate, based on the amount of substance: mercapto group-containing diol: lewis base ═ 1: (1.2-3): (1-4);
after the reaction is finished, removing the solvent A in the product through rotary evaporation, precipitating and separating out for multiple times to obtain a purified product, and then drying in vacuum to obtain the dihydroxy fluorocarbon chain monomer;
(2) preparing a polyurethane prepolymer: firstly, adding macromolecular dihydric alcohol into a three-neck flask, and dehydrating and drying for 2-4 hours at the temperature of 100-120 ℃ under the vacuum filtration condition; reducing the temperature to 70-85 ℃, adding a certain amount of diisocyanate, and adding the macromolecular diol: diisocyanate ═ 1: (2-9), reacting for 0.5-3 h under the conditions of inert gas protection and stirring to obtain a polyurethane prepolymer;
(3) adding a dihydroxyl fluorocarbon chain monomer and a catalyst accounting for 1-9 wt% of the total material into a three-neck flask, wherein the molar ratio of the dihydroxyl fluorocarbon chain monomer to diisocyanate is (0.01-0.6): 1, adding a solvent B to completely dissolve the mixture, and then carrying out condensation reflux reaction for 2-5 h under the conditions that the temperature is 60-110 ℃, the inert gas is used for protection and stirring;
(4) adding a hydrophilic chain extender into a three-neck flask, wherein the molar ratio of the hydrophilic chain extender to diisocyanate is (0.05-0.8): 1, and reacting for 1-3 hours at the temperature of 65-85 ℃ under the protection of inert gas and under the stirring condition; then, reducing the temperature to 40-55 ℃, adding triethylamine with the same molar weight as the hydrophilic chain extender, and carrying out neutralization reaction for 0.5-1 h;
(5) after the reaction is finished, adding the reaction product into a certain amount of deionized water, stirring for 0.5-1 h under the condition of high-speed stirring, wherein the stirring speed is 6000-10000 rpm, then stirring for 1-2 h at low speed, wherein the stirring speed is 2000-5000 rpm, and concentrating the product until the solid content is 15% -45%, thus obtaining the fluorine-containing aqueous polyurethane emulsion with the performances of water resistance, oil resistance and pollution resistance.
The fluorine-containing (methyl) acrylate is one of 2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluoroheptyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl acrylate, 2,3,4,4, 4-hexafluorobutyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, 2,3, 3-tetrafluoropropyl methacrylate and pentafluorophenol acrylate.
The dihydric alcohol containing the sulfhydryl is one of 3-sulfhydryl-1, 2-propanediol and 4-sulfhydryl-1, 2-butanediol; the solvent B is one or a mixture of more of tetrahydrofuran, acetone and petroleum ether.
The fluorine-containing waterborne polyurethane material with the water-proof, oil-proof and antifouling properties is characterized in that the macroglycol is one or a mixture of more of polytetrahydrofuran ether glycol with the number average molecular weight of 1000-12000, polysiloxane diol, polyhexamethylene adipate diol, polycarbonate diol, polycaprolactone diol and polyethylene glycol.
The fluorine-containing polyurethane material with the performances of water resistance, oil resistance and stain resistance is characterized in that the diisocyanate is one or a mixture of more of isophorone diisocyanate, hexamethylene diisocyanate, 2, 6-toluene diisocyanate, 1, 4-benzene diisocyanate and 1, 4-cyclohexane diisocyanate.
The invention discloses a preparation method of a fluorine-containing polyurethane material with water resistance, oil resistance and antifouling performance, which comprises the steps of firstly synthesizing a dihydroxy fluorocarbon chain monomer through a mercapto-vinyl Michael reaction, then introducing the dihydroxy fluorocarbon chain monomer into polyurethane through an addition polymerization reaction with a diisocyanate-terminated polyurethane prepolymer, and then obtaining the polyurethane material with the water resistance, the oil resistance and the antifouling performance through a chain extension reaction and a neutralization reaction respectively. The fluorine-containing micromolecule organic compound has the characteristics of water resistance, oil resistance, pollution resistance, heat resistance and the like, but is easy to be bonded with protein in blood, is enriched in human bodies and influences the health of the human bodies; the fluorine-containing polymer still basically keeps the characteristics of fluorine-containing small molecular organic compounds and has good biocompatibility; meanwhile, the chemical activity and the biological activity of the compound are low, so that the compound does not affect the health of human bodies. The fluorine-containing micromolecule organic compound is introduced into the polyurethane material, so that the water resistance, biocompatibility and other properties of the polyurethane can be well improved, and the toxicity of the fluorine-containing micromolecule organic compound can be remarkably reduced. The fluorine-containing polyurethane has wide application prospect in the fields of biomedical materials, leather finishing agents and the like.
Drawings
FIG. 1 is an infrared spectrum (FT-IR) of bishydroxy fluorocarbon chain monomer A prepared in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum (1H-NMR) of bishydroxy fluorocarbon chain monomer A prepared in example 1.
FIG. 3 is a Mass Spectrum (MS) of bishydroxy fluorocarbon chain monomer A prepared in example 1.
FIG. 4 is an infrared spectrum (FT-IR) of the fluorine-containing polyurethane prepared in example 1.
FIG. 5 shows NMR spectra of fluorinated polyurethane prepared in example 1: (1H-NMR)。
FIG. 6 shows the results of water contact angle experiments for polyurethane films of different fluorine contents prepared in example 1.
Detailed Description
Four specific examples of the present invention are given below to specifically illustrate the preparation of the fluorine-containing polyurethane having water-repellent, oil-repellent, and stain-repellent properties.
Example 1: the specific process of the preparation reaction of the dihydroxyl fluorocarbon chain monomer is as follows: 2.16g of 3-mercapto-1, 2-propanediol, 7.92g of 2- (perfluorooctyl) ethyl methacrylate and 0.9g of triethylamine catalyst and 40mL of tetrahydrofuran were added to a three-necked flask, respectively, and reacted for 4 hours at 35 ℃ under nitrogen protection and magnetic stirring. After the reaction is finished, performing rotary evaporation on the mixed solution to remove most of the solvent, precipitating the concentrated reaction product in water for 2 times, each time for 4 hours, pouring out the supernatant, and performing vacuum drying for 4 hours to obtain the dihydroxy fluorocarbon chain extender monomer A.
20g of polytetrahydrofuran ether (M) are weighed outn2000) was added to a 250mL three-necked flask, vacuum-dried at 110 ℃ for 2 hours, the temperature was reduced to 80 ℃, 19.980g of isophorone diisocyanate and 150mL of tetrahydrofuran solvent were added, and the mixture was mechanically stirred under nitrogen protection and reacted at 60 ℃ for 1 hour. 6.26g of the bishydroxy fluorocarbon chain monomer A and 1.701g of dimethylolpropionic acid were added, and the mixture was stirred at 80 ℃ to conduct catalytic reaction for 2 hours. 4.599g of 1, 4-butanediol were added and the reaction was continued for 1 h. After the reaction is finished, adding reactants into high-purity deionized water, firstly stirring and emulsifying at a high speed of 10000rpm for 30min, and then stirring and emulsifying at a low speed for 1h to obtain the fluorine-containing polyurethane aqueous emulsion with the performances of water resistance, oil resistance and pollution resistance.
Example 2: the specific process of the preparation reaction of the dihydroxyl fluorocarbon chain monomer is as follows: 2.44g of 4-mercapto-1, 2-butanediol, 7.92g of 2- (perfluorooctyl) ethyl methacrylate and 1.8g of the catalyst triethylamine, 40mL of tetrahydrofuran were added to a three-necked flask and reacted for 4h at 35 ℃ under nitrogen protection and magnetic stirring. After the reaction is finished, performing rotary evaporation on the mixed solution to remove most of the solvent, precipitating the concentrated reaction product in water for 2 times, each time for 4 hours, pouring out the supernatant, and performing vacuum drying for 4 hours to obtain the dihydroxy fluorocarbon chain extender monomer B.
20g of polycarbonate diol (M) are weighed outn2000) was added to a 250mL three-necked flask, vacuum-dried at 110 ℃ for 2 hours, cooled to 80 ℃, added with 19.99g of toluene diisocyanate and 150mL of tetrahydrofuran solvent, mechanically stirred under nitrogen, and reacted at 60 ℃ for 1 hour. 2.84g of the bishydroxy fluorocarbon chain monomer B and 2.52g of dimethylolpropionic acid were added, and the mixture was stirred at 80 ℃ to conduct catalytic reaction for 2 hours. 6.849g of 1, 4-butanediol were added, at 80 ℃ in the presence of a catalystReacting for 24 hours under the conditions. Adding the reactant into high-purity deionized water, firstly stirring and emulsifying at high speed of 10000rpm for 15min, and then stirring and emulsifying at low speed for 0.5h to obtain the fluorine-containing polyurethane water-based emulsion with the properties of water resistance, oil resistance and pollution resistance.
Example 3: the specific process of the preparation reaction of the dihydroxyl fluorocarbon chain monomer is as follows: 2.16g of 3-mercapto-1, 2-propanediol, 6.48g of 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl methacrylate and 1.8g of triethylamine catalyst, 40mL of tetrahydrofuran are added into a three-neck flask and reacted for 4 hours under the conditions of 35 ℃, nitrogen protection and magnetic stirring. After the reaction is finished, performing rotary evaporation on the mixed solution to remove most of the solvent, precipitating the concentrated reaction product in water for 2 times, each time for 4 hours, pouring out the supernatant, and performing vacuum drying for 4 hours to obtain the dihydroxy fluorocarbon chain extender monomer C.
20g of polycaprolactone diol (Mn 2000) is weighed into a 250mL three-neck flask, vacuum dehydration drying is carried out at 110 ℃ for 2h, the temperature is reduced to 80 ℃, 7.92g of 1, 4-cyclohexane diisocyanate and 150mL of tetrahydrofuran solvent are added, mechanical stirring is carried out under the protection of nitrogen, and reaction is carried out at 60 ℃ for 1 h. 3.408g of the above bishydroxy fluorocarbon chain monomer C and 1.53g of dimethylolpropionic acid were added thereto, and the mixture was stirred at 80 ℃ to conduct catalytic reaction for 2 hours. 7.974g of 1, 4-butanediol were added and the mixture was reacted at 80 ℃ in the presence of a catalyst for 24 hours. Adding the reactant into high-purity deionized water, firstly stirring and emulsifying at high speed of 10000rpm for 15min, and then stirring and emulsifying at low speed for 0.5h to obtain the fluorine-containing polyurethane water-based emulsion with the properties of water resistance, oil resistance and pollution resistance.
Example 4: the specific process of the preparation reaction of the dihydroxyl fluorocarbon chain monomer is as follows: 2.44g of 4-mercapto-1, 2-butanediol, 3.75g of hexafluorobutyl methacrylate and 1.8g of triethylamine catalyst, 30mL of tetrahydrofuran were added to a three-necked flask and reacted for 4 hours at 35 ℃ under nitrogen protection and magnetic stirring. After the reaction is finished, performing rotary evaporation on the mixed solution to remove most of the solvent, precipitating the concentrated reaction product in water for 2 times, each time for 4 hours, pouring out the supernatant, and performing vacuum drying for 4 hours to obtain the dihydroxy fluorocarbon chain extender monomer D.
20g of polyethylene glycol (Mn 2000) was weighed into a 250mL three-necked flask, dehydrated and dried under vacuum at 110 ℃ for 2 hours, cooled to 80 ℃, added with 19.2g of hexamethylene diisocyanate and 150mL of tetrahydrofuran solvent, mechanically stirred under nitrogen protection, and reacted at 60 ℃ for 1 hour. 4.544g of the above bishydroxy fluorocarbon chain monomer D and 1.26g of dimethylolpropionic acid were added thereto, and the mixture was stirred at 80 ℃ to conduct catalytic reaction for 2 hours. 9.0g of 1, 4-butanediol was added and the reaction was carried out at 80 ℃ in the presence of a catalyst for 24 hours. Adding the reactant into high-purity deionized water, firstly stirring and emulsifying at high speed of 10000rpm for 15min, and then stirring and emulsifying at low speed for 0.5h to obtain the fluorine-containing polyurethane water-based emulsion with the properties of water resistance, oil resistance and pollution resistance.
Claims (3)
1. A fluorine-containing waterborne polyurethane material with waterproof, oil-proof and antifouling properties is characterized in that the preparation method comprises the following steps:
(1) preparing a dihydroxy fluorocarbon chain monomer: dissolving fluorine-containing (methyl) acrylate and mercapto-containing dihydric alcohol in a solvent A to prepare a mixed solution, adding a certain amount of Lewis base serving as a catalyst into the mixed solution under the condition of stirring, and under the protection of inert gas, adding 30-60% of Lewis base serving as a catalystoC, reacting for 2-6 h; the solvent A is tetrahydrofuran capable of completely dissolving fluorine-containing (methyl) acrylate, diol containing sulfydryl and Lewis base; the inert gas is nitrogen; fluorine-containing (meth) acrylate, based on the amount of substance: mercapto group-containing diol: lewis base = 1: (1.2-3): (1-4);
after the reaction is finished, removing the solvent A in the product through rotary evaporation, precipitating and separating out for multiple times to obtain a purified product, and then drying in vacuum to obtain the dihydroxy fluorocarbon chain monomer;
(2) preparing a polyurethane prepolymer: firstly, adding macromolecular diol into a three-neck flask at 100-120 DEG CoC, dehydrating and drying for 2-4 hours under the condition of vacuum filtration; reducing the temperature to 70-85 DEG CoC, adding a certain amount of diisocyanate, wherein the mass ratio of the macrodiol: diisocyanate = 1: (2-9), reacting for 0.5-3 h under the conditions of inert gas protection and stirring to obtain a polyurethane prepolymer;
(3) three-neck flaskAdding a dihydroxyl fluorocarbon chain monomer and a catalyst accounting for 1-9 wt% of the total material, wherein the molar ratio of the dihydroxyl fluorocarbon chain monomer to diisocyanate is (0.01-0.6): 1, adding a solvent B to completely dissolve the mixture, and then, at the temperature of 60-110 DEG CoC. Under the conditions of inert gas protection and stirring, carrying out condensation reflux reaction for 2-5 h;
(4) adding a hydrophilic chain extender into a three-neck flask, wherein the mole ratio of the hydrophilic chain extender to diisocyanate is (0.05-0.8): 1, and the temperature is 65-85oC. Reacting for 1-3 h under the conditions of inert gas protection and stirring; then, the temperature is reduced to 40-55 DEGoAdding triethylamine in an equimolar amount with the hydrophilic chain extender, and carrying out a neutralization reaction for 0.5-1 h;
(5) after the reaction is finished, adding the reaction product into a certain amount of deionized water, stirring for 0.5-1 h under the condition of high-speed stirring, wherein the stirring speed is 6000-10000 rpm, then stirring for 1-2 h at low speed, wherein the stirring speed is 2000-5000 rpm, and concentrating the product until the solid content is 15% -45%, so as to obtain the fluorine-containing aqueous polyurethane emulsion with the performances of water resistance, oil resistance and pollution damage resistance;
the fluorine-containing (methyl) acrylate is one of 2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluoroheptyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl acrylate, 2,3,4,4, 4-hexafluorobutyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, 2,3, 3-tetrafluoropropyl methacrylate and pentafluorophenol acrylate;
the dihydric alcohol containing the sulfhydryl is one of 3-sulfhydryl-1, 2-propanediol and 4-sulfhydryl-1, 2-butanediol; the solvent B is one or a mixture of more of tetrahydrofuran, acetone and petroleum ether.
2. The fluorine-containing aqueous polyurethane material with the water-proof, oil-proof and stain-proof properties according to claim 1, wherein the macrodiol is one or a mixture of several of polytetrahydrofuran ether diol, polysiloxane diol, polyhexamethylene adipate diol, polycarbonate diol, polycaprolactone diol and polyethylene glycol with the number average molecular weight of 1000-12000.
3. The fluorine-containing aqueous polyurethane material with water-proof, oil-proof and stain-proof properties according to claim 1, wherein the diisocyanate is one or a mixture of isophorone diisocyanate, hexamethylene diisocyanate, 2, 6-toluene diisocyanate, 1, 4-benzene diisocyanate and 1, 4-cyclohexane diisocyanate.
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| CN112876643A (en) * | 2021-02-03 | 2021-06-01 | 四川大学 | Preparation method of waterborne polyurethane with waterproof and self-extinction functions |
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