CN110358044B - Polyurethane and preparation method and application thereof - Google Patents
Polyurethane and preparation method and application thereof Download PDFInfo
- Publication number
- CN110358044B CN110358044B CN201910412930.0A CN201910412930A CN110358044B CN 110358044 B CN110358044 B CN 110358044B CN 201910412930 A CN201910412930 A CN 201910412930A CN 110358044 B CN110358044 B CN 110358044B
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- polyurethane coating
- hour
- hydrophilic
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
-
- 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
- C08G18/65—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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a polyurethane coating based on synergy of zwitterions and hydrophilic and hydrophobic micro-areas for resisting marine organism fouling. The excellent antifouling performance is achieved by the synergistic effect of zwitterions and hydrophilic and hydrophobic heterostructure chain segments introduced into the main chain. The preparation method of the polyurethane comprises the steps of firstly forming a prepolymer by diisocyanate, a hydrophilic and hydrophobic dihydroxy compound and hydroxyl-modified zwitterions, then adding diol or diamine with small molecular weight for chain extension, and finally adding trimethylolpropane as a cross-linking agent for further reaction to form the polyurethane material containing zwitterions and hydrophilic and hydrophobic micro-areas. The novel polyurethane coating with excellent antifouling performance is successfully prepared by controlling the water resistance, the mechanical strength, the adhesive strength and the hydrophilic-hydrophobic micro-area structure of the coating, and the method has important value for developing the polyurethane marine antifouling coating.
Description
Technical Field
The invention belongs to the technical field of marine antifouling, and particularly relates to zwitterion and hydrophilic and hydrophobic micro-area cooperative antifouling-based polyurethane, and a preparation method and application thereof.
Background
Polyurethane has wide application in the fields of biomedical equipment, marine antifouling coatings and the like due to excellent biocompatibility and good mechanical properties. In recent years, polyurethane coatings have significant applications and challenges in marine engineering. Marine biofouling refers to the phenomenon of adhesion and accumulation of numerous organisms in the sea on the surfaces of ship hulls and marine equipment and the serious hazards caused by the phenomenon, such as increased weight of the ship hulls, increased surface roughness and increased oil consumption; it also accelerates corrosion and aging of hull surfaces and other marine equipment; in addition, the migration phenomenon of fouling organisms can also lead to the disturbance of the ecosystem. However, the traditional marine antifouling methods such as mechanical cleaning, ultrasound and the like have a great number of disadvantages, such as cost and expense, and the organic tin and cuprous oxide loaded antifouling paint is toxic and microbicidal and can harm human health through the enrichment effect of the biological chain. These disadvantages result in a severe limitation of the range of use. In addition, some coatings loaded with natural biological antifouling agents exist, but the coatings are still in the early development stage due to the high extraction difficulty, high cost and the like.
In recent years, the development and design of polyurethane coatings provide a more convenient, long-lasting, efficient and environment-friendly antifouling strategy for marine antifouling, but the design of the existing polyurethane antifouling coatings still has great defects. For example, chinese patent CN 108840991A reports an aqueous polyurethane material, but the document does not disclose the regulation of the hydrophilic and hydrophobic micro-domain structure, the marine antifouling performance test and the antifouling mechanism. Chinese patent CN 105732953A reports a waterborne polyurethane resistant to protein and microorganism adsorption, but the preparation process is complicated, the polyurethane needs to be prepared step by step and involves complicated purification and emulsification processes, and in addition, the polyurethane only provides application value in the biomedical field and does not research on marine antifouling. In addition, the polyurethane coating based on the toxicity and the microorganism of quaternary ammonium salt or the loaded antifouling agent has obvious antifouling effect but high hazard, so that the design and the development of a novel environment-friendly and efficient antifouling polyurethane coating are urgently required.
Disclosure of Invention
The invention provides polyurethane, which comprises the following structural units: urethane units, zwitterions, and hydrophilic-hydrophobic microdomain heterostructure segments.
According to the invention, the hydrophilic and hydrophobic micro-regions refer to amphiphilic chain segments, including hydrophilic chain segments and hydrophobic chain segments.
According to the invention, the polyurethane has the following structure:
wherein M represents a zwitterion; X-Y represents an amphiphilic chain segment, n is more than or equal to 1,
without particular limitation, it may represent any linking group, for example, any of a carbon chain, a heteroatom-containing carbon chain, an aryl group, and a heteroaryl group.
According to the invention, the zwitterion can be selected from any one of a carboxyl ammonium group, a sulfoammonium group, a betaine group, a quaternary ammonium pyridine sulfonate and a quaternary ammonium imidazole sulfonate; illustratively, the zwitterion is derived from a hydroxyl-modified zwitterionic compound, such as from 3- (tris (2-hydroxyethyl) ammonio) propane-1-sulfonate (THEAPS).
According to the invention, the amphiphilic chain segment comprises a hydrophilic group and a hydrophobic group; for example, the amphiphilic chain segment is obtained by reacting the following A-type compounds and B-type compounds with diisocyanate:
(A) at least one of polypropylene glycol and polyethylene glycol,
(B) at least one of bisphenol A, hydroxyl-terminated polyformaldehyde, polycaprolactone diol, polycarbonate diol, polyester diol and polysiloxane diol.
According to the invention, the molecular weight of the class a compound may be 200 to 6000, for example 600, 1000; the molecular weight of the B compound can be 200-2000, such as 1000.
According to the invention, the reaction raw materials of the polyurethane comprise diisocyanate, the A-type compound, the B-type compound and hydroxyl-modified zwitterionic compound.
The invention also provides a preparation method of the polyurethane material, which comprises the following steps: firstly, diisocyanate, a dihydroxy compound and a hydroxyl-modified zwitterionic compound react to form a prepolymer, then a chain extender is added for chain extension, and finally a cross-linking agent is added to obtain the polyurethane material.
According to the invention, the hydroxyl-modified zwitterionic compound is prepared from any one of 1, 3-propane sultone, ethyl bromoacetate and ethyl 3-bromopropionate and C containing terminal hydroxyl1-6Alkyl amine compounds.
According to the invention, said C containing terminal hydroxyl groups1-6The alkylamine compound is preferably any one of triethanolamine, N-methyldiethanolamine, and N-ethyldiethanolamine.
As an example, the hydroxyl-modified zwitterionic compound may be the compound 3- (tris (2-hydroxyethyl) ammonio) propane-1-sulfonate (THEAPS) shown below:
according to the present invention, the dihydroxy compound includes a hydrophilic group and a hydrophobic group.
According to the invention, the dihydroxy compound is a combination of at least one of the following compounds of class a and at least one of the following compounds of class B:
(A) at least one of polypropylene glycol and polyethylene glycol,
(B) at least one of bisphenol A, hydroxyl-terminated polyformaldehyde, polycaprolactone diol, polycarbonate diol, polyester diol and polysiloxane diol.
According to the invention, the molecular weight of the class a compound may be 200 to 6000, for example 600, 1000; the molecular weight of the B compound can be 200-2000, such as 1000.
According to the present invention, the diisocyanate may be any one or more of aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate, preferably any one or more of hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane dimethylene diisocyanate, 1, 4-cyclohexane diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate.
According to the invention, the mass ratio of the diisocyanate, the dihydroxy compound and the hydroxyl modified zwitterionic compound can be 1 (1-5) to (0.1-2), preferably 1 (1-4) to (0.3-1), such as 1:2: 0.6.
According to the present invention, the mass ratio of the A-based compound to the B-based compound in the dihydroxy compound may be (5-10): 1, preferably (8-10): 1, for example, 9: 1.
According to the invention, the molecular weight of the chain extender is not more than 200, and the chain extender can be any one of dihydric alcohol or diamine, such as ethylene glycol and ethylenediamine.
According to the invention, the crosslinking agent may be trimethylolpropane.
According to the invention, the molar ratio of the chain extender to the cross-linking agent to the diisocyanate can be (0.1-0.5): 1, preferably (0.1-0.3): 1.
According to an exemplary embodiment of the present invention, the method for preparing the polyurethane material comprises the steps of:
(1) adding diisocyanate, a dihydroxy compound and a hydroxyl modified zwitterionic compound into a reactor, and adding a proper amount of catalyst and solvent to react to obtain a prepolymer;
(2) and (2) adding a chain extender into the prepolymer obtained in the step (1) for chain extension, and then adding a cross-linking agent to obtain the polyurethane material.
According to the present invention, the solvent in step (1) may be an amide-based organic solvent, preferably any one or more of N, N-dimethylacetamide, N-dimethylformamide, N-diethylformamide, and N, N-diethylacetamide.
According to the invention, the temperature of the reaction in step (1) may be between 50 ℃ and 100 ℃, for example 80 ℃; the reaction time is 0.5-4 h, such as 1 h.
According to the present invention, the reaction in step (1) may be performed under an inert atmosphere, which may be any one or more of nitrogen, argon, helium.
According to the invention, a solvent, preferably acetone, may be added in step (2) to adjust the viscosity of the system.
The invention also provides polyurethane prepared by the method.
The invention also provides the application of the polyurethane in the field of marine antifouling; preferably, the polyurethane is useful for marine antifouling coatings.
The invention also provides a coating or film comprising said polyurethane.
According to the invention, the coating can be obtained by spraying the polyurethane on the surface of the substrate in a spraying manner.
According to the present invention, the base material may be any one of PVC, nylon, and non-woven fabric.
The invention has the beneficial effects that:
the polyurethane material containing zwitterions and hydrophilic and hydrophobic micro-regions provided by the invention shows outstanding algae adhesion resistance on the premise that the water absorption and the bonding strength meet the practical application conditions. On one hand, the polyurethane material can be endowed with self-emulsifying property and protein adsorption resistance due to the existence of zwitterions to prevent the formation of biological fouling, on the other hand, the polyurethane material can also show excellent anti-biological fouling performance due to the existence of hydrophilic and hydrophobic micro-areas, and the polyurethane material has more excellent antifouling performance based on the synergistic effect of the hydrophilic and hydrophobic micro-areas, so that the invention has better application prospect in a marine antifouling coating.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of THEAPS;
FIG. 2 is an optical photograph of the anti-algal adhesion test of the polyurethane materials obtained in example 1 and comparative examples 1 to 4 against Navicula;
FIG. 3 is an optical photograph of an anti-algae adhesion test for Nitzschia closterium obtained in example 1 and comparative examples 1 to 4;
FIG. 4 is a statistical chart of the results of the algae adhesion resistance test of the polyurethane materials obtained in example 1 and comparative examples 1 to 4;
FIG. 5 shows the results of the swelling test in water of the polyurethane materials obtained in example 1 and comparative examples 1 to 4;
FIG. 6 shows the results of the tensile breaking strength test of the polyurethane material bonded PVC obtained in example 1 and comparative examples 1 to 4;
FIG. 7 shows the results of the water contact angle test in air for the polyurethane materials obtained in example 1 and comparative examples 1 to 4;
FIG. 8 is a confocal laser photograph of the polyurethane materials obtained in example 1 and comparative examples 1 to 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation process of THEAPS is as follows: weighing 10g of 1, 3-propane sultone, adding the 1, 3-propane sultone into a 100mL round-bottom flask, then pouring 30mL of ethyl acetate solvent, heating and stirring the mixture in a water bath at 40 ℃, slowly dripping 10g of triethanolamine into the system by using a separating funnel, fully reacting the mixture for 24 hours, then carrying out vacuum filtration, washing the mixture for three times by using ethyl acetate to obtain white THEAPS crystals, and drying the white THEAPS crystals by using a vacuum oven, wherein a nuclear magnetic hydrogen spectrum diagram of the crystals is shown in figure 1.
1.5g of THEAPS, 4.5g of polyethylene glycol (PEG) (Mn 600) and 0.5g of polycaprolactone diol (PCL) (Mn 1000) are weighed into a 100mL round-bottomed flask and dehydrated in vacuum at 120 ℃ for 2 hours, then 20mL of DMF solvent which is dried and dehydrated is added and heated and stirred at 40 ℃ to dissolve, then 2.5g of hexamethylene diisocyanate is added, the temperature is raised to 80 ℃ and the reaction is stirred under the protection of nitrogen for 1 hour to form a polyurethane prepolymer. Then, 0.145g of ethylene glycol was added to conduct a chain extension reaction for 1 hour. Finally, 0.299g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the polyurethane coating, the polyurethane coating is obtained by uniformly spraying the polyurethane coating on the surface of the base material PVC in a spraying mode and finally reacting for 1 hour at 80 ℃.
Example 2
The preparation process of THEAPS is as follows: weighing 10g of 1, 3-propane sultone, adding the weighed 1, 3-propane sultone into a 100mL round-bottom flask, then pouring 30mL of ethyl acetate solvent, heating and stirring the mixture in a water bath at 40 ℃, slowly dripping 10g of triethanolamine into the system by using a separating funnel, fully reacting the mixture for 24 hours, then performing reduced pressure suction filtration, washing the mixture for three times by using ethyl acetate to obtain white crystals, and drying the white crystals by using a vacuum oven.
1.5g of THEAPS, 4.5g of polyethylene glycol (PEG) (Mn 1000) and 0.5g of polycarbonate diol (PCDL) (Mn 1000) were weighed into a 100mL round-bottomed flask, vacuum-dehydrated at 120 ℃ for 2 hours, then 20mL of DMF solvent which had been dehydrated was added and dissolved by heating with stirring at 40 ℃, then 2.5g of hexamethylene diisocyanate was added, the temperature was raised to 80 ℃ and the reaction was stirred under nitrogen for 1 hour to form a polyurethane prepolymer. Then, 0.184g of ethylene glycol was added to conduct a chain extension reaction for 1 hour. Finally, 0.239g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the polyurethane coating, the polyurethane coating is uniformly sprayed on the surface of the base material PVC by a spraying mode, and finally the polyurethane coating is obtained after the reaction is carried out for 1 hour at 80 ℃.
Comparative example 1
The specific preparation method of the polyurethane coating containing only zwitterions is as follows: the preparation process of THEAPS is as follows: weighing 10g of 1, 3-propane sultone, adding the 1, 3-propane sultone into a 100mL round-bottom flask, then pouring 30mL of ethyl acetate solvent, heating and stirring the mixture in a water bath at 40 ℃, slowly dripping 10g of triethanolamine into the system by using a separating funnel, fully reacting the mixture for 24 hours, then carrying out vacuum filtration, washing the mixture for three times by using ethyl acetate to obtain white THEAPS crystals, and drying the white THEAPS crystals by using a vacuum oven.
Weighing 5g of THEAPS, placing the weighed materials into a 100mL round-bottom flask, dehydrating the materials in vacuum at 120 ℃ for 2 hours, adding 20mL of DMF solvent which is dried and dehydrated, heating and stirring the mixture to dissolve the materials at 40 ℃, adding 2g of hexamethylene diisocyanate, raising the temperature to 80 ℃, and stirring the mixture to react the mixture for 1 hour under the protection of nitrogen to form a polyurethane prepolymer. Then, 0.155g of ethylene glycol was added to conduct a chain extension reaction for 1 hour. Finally, 0.255g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the polyurethane coating, the polyurethane coating is uniformly sprayed on the surface of the base material PVC by a spraying mode, and finally the polyurethane coating is obtained after the reaction is carried out for 1 hour at the temperature of 80 ℃.
Comparative example 2
The specific preparation method of the polyurethane coating only containing hydrophilic and hydrophobic micro-regions comprises the following steps: 4.5g of polyethylene glycol (PEG) (Mn 1000) and 0.5g of Polycaprolactone (PCL) (Mn 1000) are weighed and put into a 100mL round-bottom flask for vacuum dehydration at 120 ℃ for 2 hours, then 20mL of DMF solvent which is dried and dehydrated is added for heating and stirring dissolution at 40 ℃, then 2g of hexamethylene diisocyanate is added, the temperature is raised to 80 ℃ and stirring reaction is carried out for 1 hour under the protection of nitrogen, and then the polyurethane prepolymer is formed. Then, 0.184g of ethylene glycol was added to conduct a chain extension reaction for 1 hour. Finally, 0.223g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the polyurethane coating, the polyurethane coating is uniformly sprayed on the surface of the PVC substrate by a spraying mode, and finally the polyurethane coating is obtained after the reaction is carried out for 1 hour at the temperature of 80 ℃.
Comparative example 3
The specific preparation method of the polyurethane coating only containing the positive ions and the hydrophilic and hydrophobic micro-areas comprises the following steps: the positive ion refers to methyl triethanolammonium p-toluenesulfonate (MTEA-OTs). Firstly, adding a proper amount of methyl p-toluenesulfonate dissolved by ethyl acetate into a round-bottom flask provided with magnetons, slowly dropwise adding triethanolamine into a system, wherein the molar ratio of the methyl p-toluenesulfonate to the triethanolamine is 1.2:1, heating and stirring in a water bath at 40 ℃, performing reduced pressure suction filtration after reacting for 24 hours, washing with ethyl acetate for three times to obtain MTEA-OTs which is white crystalline powder, and drying by using a vacuum oven.
5g of MTEA-OTs and 4.5g of polyethylene glycol (PEG) (Mn 600) and 0.5g of Polycaprolactone (PCL) (Mn 1000) are weighed into a 100mL round-bottomed flask and dehydrated under vacuum at 120 ℃ for 2 hours, then 20mL of DMF solvent which is dried and dehydrated is added, heated and stirred at 40 ℃ to dissolve, then 2.5g of hexamethylene diisocyanate is added, the temperature is raised to 80 ℃ and the reaction is stirred under the protection of nitrogen for 1 hour to form prepolymer polyurethane. Then, 0.194g of ethylene glycol was added to conduct a chain extension reaction for 1 hour. Finally, 0.219g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the polyurethane coating, the polyurethane coating is uniformly sprayed on the surface of the PVC substrate by a spraying mode, and finally the polyurethane coating is obtained after the reaction is carried out for 1 hour at 80 ℃.
Comparative example 4
The specific preparation method of the polyurethane coating only containing negative ions and hydrophilic and hydrophobic micro-areas comprises the following steps: the anion is potassium hydroquinone sulfate (HDS)
5g of HDS and 4.5g of polyethylene glycol (PEG) (Mn 600) and 0.5g of polycaprolactone diol (PCL) (Mn 1000) are weighed into a 100mL round-bottomed flask and dehydrated under vacuum at 120 ℃ for 2 hours, then 20mL of DMF solvent which is dried and dehydrated is added, heated and stirred at 40 ℃ to dissolve, then 3.75g of hexamethylene diisocyanate is added, the temperature is raised to 80 ℃ and the reaction is stirred under the protection of nitrogen for 1 hour to form a polyurethane prepolymer. Then, 0.276g of ethylene glycol was added to conduct a chain extension reaction for 1 hour. Finally, 0.358g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the polyurethane coating, the polyurethane coating is uniformly sprayed on the surface of the PVC substrate by a spraying mode, and finally the polyurethane coating is obtained after the reaction is carried out for 1 hour at 80 ℃.
Test example
The polyurethane coatings prepared in example 1 and comparative examples 1 to 4 were subjected to an algae adhesion resistance test, a swelling test, an adhesion PVC tensile strength test and an air water contact angle test, respectively, and laser confocal photographs were taken of the polyurethane materials of example 1 and comparative examples 1 to 2. Wherein the anti-algae attachment test was for Nitzschia closterium and Navicula, and the results are shown in FIGS. 2-4; the swelling test results are shown in fig. 5; the bonded PVC tensile strength test is shown in fig. 6; the water contact angle test result is shown in fig. 7, and the polyurethane coating prepared in example 1 has moderate hydrophilicity in air, so that a better antifouling effect can be achieved; the laser confocal photograph is shown in fig. 8, and confirms that hydrophilic and hydrophobic domains with uniform size exist in the polyurethane coating prepared in example 1.
The results show that: the polyurethane with the synergistic effect of the zwitterion and the hydrophilic and hydrophobic micro-area in the embodiment 1 of the invention shows good hydrophilicity while basically maintaining the tensile strength of the bonded PVC and ensuring the water resistance of the polyurethane coating, and the algae attachment resistance of the polyurethane is obviously superior to that of the products in the comparative examples 1-4.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A polyurethane coating, characterized in that it is prepared by the following steps:
weighing 10g of 1, 3-propane sultone, adding the weighed 1, 3-propane sultone into a 100mL round-bottom flask, then pouring 30mL of ethyl acetate solvent, heating and stirring the mixture in a water bath at 40 ℃, slowly dripping 10g of triethanolamine into the system by using a separating funnel, carrying out full reaction for 24 hours, then carrying out reduced pressure suction filtration, washing the mixture for three times by using ethyl acetate to obtain white THEAPS crystals, and drying the white THEAPS crystals by using a vacuum oven;
weighing 1.5g of THEAPS, 4.5g of polyethylene glycol and 0.5g of polycaprolactone diol, putting the materials into a 100mL round-bottom flask, carrying out vacuum dehydration for 2 hours at 120 ℃, adding 20mL of DMF solvent which is dried and dehydrated, heating and stirring the mixture at 40 ℃ to dissolve the DMF solvent, adding 2.5g of hexamethylene diisocyanate, raising the temperature to 80 ℃, and carrying out stirring reaction for 1 hour under the protection of nitrogen to form a polyurethane prepolymer; then adding 0.145g of ethylene glycol to carry out chain extension reaction for 1 hour; finally, 0.299g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the polyurethane coating, the polyurethane coating is uniformly sprayed on the surface of the base material PVC in a spraying mode, and finally the polyurethane coating is obtained after the reaction is carried out for 1 hour at the temperature of 80 ℃;
wherein the molecular weight Mn of the polyethylene glycol is 600, and the molecular weight Mn of the polycaprolactone diol is 1000.
2. A polyurethane coating, characterized in that it is prepared by the following steps:
weighing 10g of 1, 3-propane sultone, adding the weighed 1, 3-propane sultone into a 100mL round-bottom flask, then pouring 30mL of ethyl acetate solvent, heating and stirring the mixture in a water bath at 40 ℃, slowly dripping 10g of triethanolamine into the system by using a separating funnel, carrying out full reaction for 24 hours, then carrying out reduced pressure suction filtration, washing the mixture for three times by using ethyl acetate to obtain white crystals, and drying the white crystals by using a vacuum oven;
weighing 1.5g of THEAPS, 4.5g of polyethylene glycol and 0.5g of polycarbonate diol, putting the materials into a 100mL round-bottom flask, dehydrating the materials in vacuum at 120 ℃ for 2 hours, adding 20mL of DMF (dimethyl formamide) solvent which is dehydrated, heating and stirring the materials at 40 ℃ to dissolve the materials, adding 2.5g of hexamethylene diisocyanate, raising the temperature to 80 ℃, and stirring the materials under the protection of nitrogen to react for 1 hour to form a polyurethane prepolymer; then adding 0.184g of ethylene glycol to carry out chain extension reaction for 1 hour; finally, 0.239g of trimethylolpropane diluted by acetone is used as a cross-linking agent to adjust the viscosity of the cross-linking agent, the cross-linking agent is uniformly sprayed on the surface of the base material PVC in a spraying mode, and finally the polyurethane coating is obtained after the reaction is carried out for 1 hour at 80 ℃;
wherein the molecular weight Mn of the polyethylene glycol is 1000, and the molecular weight Mn of the polycarbonate diol is 1000.
3. Use of the polyurethane coating according to claim 1 or 2 in the field of marine antifouling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910412930.0A CN110358044B (en) | 2019-05-17 | 2019-05-17 | Polyurethane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910412930.0A CN110358044B (en) | 2019-05-17 | 2019-05-17 | Polyurethane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110358044A CN110358044A (en) | 2019-10-22 |
| CN110358044B true CN110358044B (en) | 2020-09-22 |
Family
ID=68215260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910412930.0A Active CN110358044B (en) | 2019-05-17 | 2019-05-17 | Polyurethane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110358044B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358039B (en) * | 2019-08-28 | 2021-05-04 | 盐城工学院 | Preparation method of self-coloring polyurethane based on zwitterion, product and application thereof |
| CN111116865B (en) * | 2020-01-06 | 2022-02-18 | 万华化学集团股份有限公司 | High-water-resistance and hydrophilic polyisocyanate curing agent and preparation method and application thereof |
| CN115003723B (en) * | 2020-01-07 | 2023-12-05 | 诠达化学股份有限公司 | Thermoplastic polyurethane with high tensile strength, preparation formula and manufacturing method thereof |
| CN112760023B (en) * | 2021-01-25 | 2022-04-26 | 四川大学 | Mixed-charge polyurethane coating material and preparation method and application thereof |
| CN113135846A (en) * | 2021-04-07 | 2021-07-20 | 吉和昌新材料(荆门)有限公司 | Preparation method of sulfobetaine type waterborne polyurethane chain extender |
| CN115746244B (en) * | 2022-11-23 | 2024-09-17 | 北京奥科瑞检测技术开发有限公司 | Super-impregnating resin composition and preparation method thereof |
| CN117050724A (en) * | 2023-07-26 | 2023-11-14 | 山东润兴环保科技有限公司 | Radioactive decontamination material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483574A (en) * | 2013-09-18 | 2014-01-01 | 广州秀珀化工股份有限公司 | Polyether hydrophilic modifier with zwitter-ion group and preparation method thereof, and water dispersible polyisocyanate composition |
| CN104262597A (en) * | 2014-10-10 | 2015-01-07 | 泉州三欣新材料科技有限公司 | Zwitterionic polyester diol and preparation method thereof |
| CN104371085A (en) * | 2014-10-29 | 2015-02-25 | 泉州三欣新材料科技有限公司 | Preparation method of zwitterionic waterborne polyurethane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140235811A1 (en) * | 2010-12-14 | 2014-08-21 | Industrial Technology Research Institute | Raw materials and methods of manufacturing bio-based epoxy resins |
-
2019
- 2019-05-17 CN CN201910412930.0A patent/CN110358044B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483574A (en) * | 2013-09-18 | 2014-01-01 | 广州秀珀化工股份有限公司 | Polyether hydrophilic modifier with zwitter-ion group and preparation method thereof, and water dispersible polyisocyanate composition |
| CN104262597A (en) * | 2014-10-10 | 2015-01-07 | 泉州三欣新材料科技有限公司 | Zwitterionic polyester diol and preparation method thereof |
| CN104371085A (en) * | 2014-10-29 | 2015-02-25 | 泉州三欣新材料科技有限公司 | Preparation method of zwitterionic waterborne polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110358044A (en) | 2019-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110358044B (en) | Polyurethane and preparation method and application thereof | |
| CN109337565B (en) | Block polyether ester polyol and preparation method and application thereof | |
| CN107163224B (en) | Biodegradable high-molecular marine antifouling material and preparation and application thereof | |
| CA1093722A (en) | Aqueous film-forming dispersions, films formed therefrom and methods of producing such films | |
| CN115074008A (en) | Organic silicon antifouling coating and preparation method thereof | |
| CN112961594B (en) | Hydrolysis-controllable marine antifouling paint and preparation method thereof | |
| CN103254397A (en) | Waterproof and weather-resistant polyester-type waterborne polyurethane emulsion and preparation method | |
| CN112794975A (en) | Organic silicon modified polyurea for ocean non-toxic antifouling and preparation method thereof | |
| WO2004076517A1 (en) | Aqueous polyurethane resin dispersion and sheet material obtained from the same | |
| CN109929088B (en) | Disulfide bond polyurethane and preparation method and application thereof | |
| CN110511347A (en) | A kind of side chain degradable polyurethane and its preparation method and application | |
| US11859099B2 (en) | Amphiphilic siloxane-polyurethane fouling-release coatings and uses thereof | |
| CN109912772A (en) | A kind of preparation method of the shape memory polyurethane of novel response quickly | |
| CN118085692A (en) | Bi-component main chain degradation and side chain hydrolysis type marine antifouling paint and preparation method thereof | |
| AU2018448389B2 (en) | Curable film-forming compositions demonstrating decreased cure time with stable pot life | |
| CN113968951A (en) | Fluorine-containing modified waterborne polyurethane and preparation method and application thereof | |
| CN112375494A (en) | Silicon-based coating material and preparation method thereof | |
| JPH06305913A (en) | Resin composition and structure produced by using the same composition | |
| CN115850646B (en) | Waterborne polyurethane for marine antifouling and preparation method thereof | |
| CN113105816B (en) | Side chain epoxy functionalized polyurethane coating and preparation method and application thereof | |
| EP3621999A2 (en) | Curable film-forming compositions demonstrating decreased cure time with stable pot life | |
| CN107857866A (en) | A kind of high solid content water EU resin and preparation method thereof | |
| JPS6284167A (en) | Film-forming composition for aquatic antifouling use | |
| CN116240728B (en) | Water-based bionic environment-friendly antifouling paint and preparation method and application thereof | |
| JPS6335888A (en) | Finish processing agent of fiber belts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |