CN113929849A - Organic silicon modified waterborne polyurethane and preparation method and application thereof - Google Patents
Organic silicon modified waterborne polyurethane and preparation method and application thereof Download PDFInfo
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- CN113929849A CN113929849A CN202111361059.XA CN202111361059A CN113929849A CN 113929849 A CN113929849 A CN 113929849A CN 202111361059 A CN202111361059 A CN 202111361059A CN 113929849 A CN113929849 A CN 113929849A
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- 238000002360 preparation method Methods 0.000 title claims description 23
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- 239000004793 Polystyrene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 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
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides organic silicon modified waterborne polyurethane which is prepared by the following steps: s1: mixing diisocyanate and organic silicon vegetable oil-based polyol at 65-85 ℃, uniformly dispersing, adding a chain extender and a catalyst, and reacting for 10-30 min; the organic silicon vegetable oil-based polyol is prepared by carrying out an epoxy ring-opening reaction on epoxidized vegetable oil and an organic silicon monomer, wherein the structural formula of the organic silicon monomer is shown in the specification
Wherein R is methyl or ethyl, R1Is one of alkyl, substituted alkyl or heteroalkyl, R2Is one of hydroxyl, amino or carboxyl; s2: adding butanone or acetone for dilution, continuously reacting for 30-150 min, and cooling after the reaction is finishedAnd (3) neutralizing by using a neutralizing agent, adding water for emulsification, and removing butanone or acetone by rotary evaporation to obtain the organic silicon modified waterborne polyurethane emulsion which has good storage stability and excellent antifouling property. The invention also provides application of the organic silicon modified waterborne polyurethane.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to organic silicon modified waterborne polyurethane as well as a preparation method and application thereof.
Background
Biological fouling substances such as proteins, cells, microorganisms, aquatic organisms and the like are easy to adhere and aggregate on the surfaces of daily supplies, building materials, biomedical materials, marine equipment and the like, a series of problems are brought to industries such as medical treatment and health, food, shipping and the like, and the health and property safety of human beings are seriously threatened. Wherein, marine biofouling increases the ship navigation resistance, blocks the marine engineering facilities, even causes the local perforation corrosion of the base material, and influences the service performance and the service life of the marine engineering facilities. In addition, in the process of cleaning the marine fouling, biological invasion, epidemic propagation and the like can be caused, so that economic loss and social harm are caused. The antifouling paint can effectively prevent various pollutants from corroding and polluting the base material without influencing the performance of the base material, and is the most convenient and effective antifouling measure. Current antifouling coating technology also relies heavily on the use of toxic biocides, which pose a serious threat to humans and the ecological environment. Therefore, the non-release environment-friendly polymer coating replaces the traditional release coating, is used for preventing marine organism fouling and reducing the danger to the marine ecological environment, and is the future development direction of the marine antifouling coating.
TABLE 1 Main types, structural characteristics and problems of the novel environmentally friendly antifouling paints
The existing novel antifouling paint mainly comprises fouling prevention type, fouling desorption type, biocidal type, degradation self-polishing paint and the like, and the main structural characteristics and the existing problems of the existing novel antifouling paint are shown in the table 1. Among many antifouling coatings, the fouling desorption type coating with low surface energy of organosilicon becomes a hot spot of the current antifouling coating research. The fouling is difficult to attach to the surface due to the low surface energy property of the fouling, even if the fouling is not firmly attached, the fouling is easy to fall off under the action of water flow or other external force, and the fouling has great application potential in the fields of marine antifouling, medical health, public health and the like.
The low surface energy nature of the low surface energy antifouling paint reduces the adhesion between the paint and fouling substances, and also reduces the adhesion between the coating and the base material. But hydrogen bonds can be formed between the base material and polar groups such as epoxy groups, carbamate, allophanate, dopamine and the like, so that the adhesion between the coating and the base material is effectively improved, and the mechanical property of the coating is enhanced. By combining the organosilicon low-surface-energy coating and the polyurethane, the defects of poor mechanical property of an organosilicon coating and poor adhesion with a substrate can be overcome, and meanwhile, the water resistance and weather resistance of the polyurethane can be effectively improved, so that the organosilicon low-surface-energy antifouling coating becomes one of active research fields of low-surface-energy antifouling coatings.
At present, the organosilicon modified polyurethane is mainly prepared by introducing Polydimethylsiloxane Diol (PDMS) into a soft segment main chain. A great step subject group (Biomacromolecules 2020,21,4, 1460-. However, the mechanical properties of the coating are poor by the incorporation of silicon through the soft segment backbone. Moreover, the existing organosilicon modified polyurethane multi-base solvent type polyurethane contains a large amount of Volatile Organic Compounds (VOC), or the prepolymer is directly poured and then cured into a film, which is not beneficial to long-term storage and transportation. The waterborne polyurethane coating takes water as a dispersion medium, not only inherits the advantages of strong adhesion, high hardness, high wear resistance and the like of solvent type polyurethane, but also has the advantage of low VOC (volatile organic compounds), and can effectively reduce environmental pollution and harm to human health. At present, most of raw materials of the organic silicon modified polyurethane are derived from increasingly exhausted petrochemical resources, and the development of natural renewable resources to replace petrochemical resources to synthesize polyurethane becomes an important direction for realizing the sustainable development of high polymer materials. The triglyceride structure of the polyol synthesized by typical green renewable vegetable oil resources endows polyurethane with good biodegradability, and the polyhydroxy functional group structure can improve the crosslinking degree, mechanical property and water resistance of a polyurethane coating. However, the research on the silicon-fluorine modified vegetable oil-based waterborne polyurethane is relatively less at present, and the development of the organosilicon vegetable oil polyol for preparing the waterborne polyurethane antifouling paint has important research value.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a preparation method of organic silicon modified waterborne polyurethane, which has the advantages of simple preparation process, easy control and convenient realization of industrial production.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of organosilicon modified waterborne polyurethane comprises the following steps: s1: mixing diisocyanate and organic silicon vegetable oil-based polyol at 65-85 ℃, uniformly dispersing, adding a chain extender and a catalyst, and reacting for 10-30 min; the organic silicon vegetable oil-based polyol is prepared by carrying out an epoxy ring-opening reaction on epoxidized vegetable oil and an organic silicon monomer, wherein the structural formula of the organic silicon monomer is shown in the specification
Wherein R is methyl or ethyl, R1Is one of alkyl, substituted alkyl or heteroalkyl, R2Is one of hydroxyl, amino or carboxyl;
s2: adding butanone or acetone for dilution, continuing to react for 30-150 min, cooling to room temperature after the reaction is finished, neutralizing by a neutralizing agent, adding water for emulsification, and removing butanone or acetone by rotary evaporation to obtain the organic silicon modified waterborne polyurethane emulsion.
The invention has the beneficial effects that:
compared with the prior art, the method uses the organic silicon vegetable oil-based polyol to prepare the organic silicon modified waterborne polyurethane, the organic silicon can migrate to the surface, and the polyurethane side chain alkoxy is adoptedHydrolysis condensation in-situ generation of chemically bonded nano SiO2The antifouling structure with different Si concentration gradients from the surface layer to the bottom layer and the surface super-hydrophobic nano topological antifouling structure are constructed, and the coordination and unification of the degradation self-polishing and the long-acting antifouling of the coating can be realized by utilizing the biodegradability of the plant oil-based waterborne polyurethane.
And secondly, the main raw materials of the organic silicon vegetable oil polyalcohol are derived from green renewable vegetable oil resources to replace petroleum chemical products, so that the degradability and safety of the polymer prepared from the organic silicon vegetable oil polyalcohol are improved, secondary pollution is not generated, and the organic silicon vegetable oil polyalcohol contributes to relieving the global problems of excessive consumption of fossil resources, energy and environment.
In addition, the polyhydroxy structure and alkoxy hydrolysis crosslinking effect of the vegetable oil-based polyol endow the waterborne polyurethane with more excellent mechanical property and water resistance, and further the waterborne polyurethane is widely applied to the fields of textiles, daily necessities, marine antifouling and medical health.
In the preparation of polyurethanes, diisocyanates, catalysts, chain extenders and neutralizing agents conventional in the art can be used in the present invention, with the reaction conditions also being conventional controlled conditions.
Preferably, the molar ratio of the hydroxyl groups of the organic silicon vegetable oil-based polyol, the diisocyanate and the chain extender is 1.0: 1.8-2.6: 0.5-1.5.
Preferably, the solid content of the organosilicon modified waterborne polyurethane emulsion is 5-50%.
Preferably, the solid content of the catalyst is 0.1-1% by mass of the total mass of the diisocyanate and the organic silicon vegetable oil-based polyol.
Preferably, the reaction temperature in the step S1 is 50-90 ℃, and the reaction time is 20-30 min; in the step S2, the reaction temperature is 70-80 ℃, and the reaction time is 60-90 min.
Preferably, the epoxy group in the epoxidized vegetable oil and the R in the silicone monomer2The molar ratio of (A) to (B) is 1.0: 1.2-5.
Preferably, the epoxidized vegetable oil is one or more of epoxidized soybean oil, castor oil, tung oil, sunflower seed oil, linseed oil, cottonseed oil or olive oil.
Preferably, the epoxidized vegetable oil has not less than 3 epoxy groups, and the silicone monomer can be modified on either side of the epoxy group after the ring opening.
Preferably, in the structural formula of the organosilicon monomer, n is an integer of 0-3.
The following description is given by way of example of an epoxidized vegetable oil of the formula:
the structural formula of the epoxy vegetable oil is as follows:
after the ring opening of the epoxy, the epoxy groups at the 1, 2, 3, 4, 5, 6 and 7, 8 positions in the formula (1) are opened, and at the moment
Modifications may be made at any of positions 1 and 2, at any of positions 3 and 4, at any of positions 5 and 6 and at any of positions 7 and 8. The organic silicon vegetable oil-based polyol shown as a formula (2),
modifications at positions 1, 3, 5, 8:
wherein R is methyl or ethyl, R1Is one of alkyl, substituted alkyl or heteroalkyl, and R' is one of-O-, ester, -N-or-NH-.
Preferably, the epoxy ring-opening reaction in step S1 requires no catalyst or selects one or more of the following catalysts: the catalyst comprises tetrafluoroboric acid, sodium ethoxide and boron trifluoride diethyl etherate, and the dosage of the catalyst is 0.1-5% of the total mass of the epoxidized vegetable oil and the organosilicon monomer. Specifically, in the epoxy ring-opening reaction, when R is2When the carboxyl is adopted, a catalyst is not adopted; when R is2When the catalyst is amino or hydroxyl, the selected catalyst is one or more of tetrafluoroboric acid, sodium ethoxide or boron trifluoride diethyl etherate.
Preferably, the temperature of the epoxy ring-opening reaction in the step S1 is 45-120 ℃, and the time is 20-120 min; before the epoxy ring-opening reaction, the epoxy vegetable oil, the organic silicon monomer and the initiator are mixed and dissolved in an organic solvent; the method also comprises the steps of extraction, drying, filtration, evaporation and drying after the ring opening reaction of the epoxy resin. Specifically, the treatment process after the epoxy ring-opening reaction is as follows: the reacted product was extracted with ethyl acetate, then dried over anhydrous magnesium sulfate, filtered and rotary evaporated to remove ethyl acetate, then dried under vacuum at 45 ℃ overnight.
More preferably, the time for the epoxy ring-opening reaction is 30 min.
Preferably, the organic solvent is one or more of ethyl acetate, dichloromethane, petroleum ether, diethyl ether or tetrachloromethane.
On the other hand, the invention also provides organosilicon modified waterborne polyurethane which is prepared by the preparation method.
In addition, the application of the organosilicon modified waterborne polyurethane in preparing waterborne polyurethane coating films, coatings, sealants, adhesives, foams or composite materials is also within the protection scope of the invention.
The organic silicon vegetable oil-based polyol in the polyurethane raw material is derived from green renewable vegetable oil resources, replaces petrochemical products, increases the degradability and safety of the polymer prepared from the organic silicon vegetable oil-based polyol, does not generate secondary pollution, and is favorable for reducing the problems of excessive consumption of global fossil resources, energy and environment; the organic silicon vegetable oil-based polyol has a cross-linking polyhydroxy structure and a side chain suspended low-surface-energy antifouling chain, is liquid at normal temperature and has the advantage of obvious compatibility; when the polyol is used for preparing waterborne polyurethane, the good storage stability can be endowed to waterborne polyurethane emulsion, the crosslinking degree of the waterborne polyurethane is improved, and the mechanical property and the resistance of the waterborne polyurethane are further improvedWater-based, organic silicon is quantitatively introduced into water-based polyurethane, the organic silicon can migrate to the surface, and the polyurethane side chain alkoxy is hydrolyzed and condensed to generate chemically bonded nano SiO in situ2The antifouling structure with different Si concentration gradients from the surface layer to the bottom layer and the surface super-hydrophobic nano topological structure are constructed, and the coordination and unification of the degradation self-polishing and the long-acting antifouling of the coating can be realized by utilizing the biodegradability of the plant oil-based water-based polyurethane.
Drawings
FIG. 1 is a reaction scheme for the preparation of silicone vegetable oil based polyols of examples 1 and 2;
FIG. 2 is a reaction scheme for the preparation of silicone vegetable oil based polyols for examples 3 and 4;
FIG. 3 is a reaction scheme for the preparation of silicone vegetable oil based polyols for examples 5 and 6;
FIG. 4 is a gel permeation chromatogram of the silicone vegetable oil-based polyols prepared in examples 1-6;
FIG. 5 is a bar graph of the antibacterial adhesion ratios of the silicone-modified aqueous polyurethane emulsions obtained in examples 7, 9, 10, and 11.
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative of the present invention only, and are not intended to limit the scope of the present invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as recommended by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The organosilicon vegetable oil-based polyol, the organosilicon modified aqueous polyurethane emulsion or the aqueous polyurethane coating material provided in each example are characterized as follows.
(1) Gel Permeation Chromatography (GPC)
The molecular weight of the sample was measured by using the Prominence GPC system of Shimadzu corporation. The system was equipped with a RID-10A differential refractometer and Shodex KF804L and KF802.5 chromatography columns. Tetrahydrofuran was used as the mobile phase, and the flow rate and column temperature were 0.3 mL/min and 30 ℃ respectively. Polystyrene standards were used.
(2) Determination of hydroxyl number
The carboxyl group in the chain extender was measured according to AOCS Official Method Te 1a-64 Method. The specific operation is as follows: adding 1g of chain extender and 15g of absolute ethyl alcohol into an erlenmeyer flask, dissolving, adding 3-5 drops of phenolphthalein indicator, and adding 0.5mol L of phenolphthalein indicator-1Titration of potassium hydroxide solution.
The hydroxyl group content of the sample was measured according to the Unilever method. The specific operation is as follows: 10g of a mixture of acetic anhydride and pyridine (mass ratio 1:9) and 1.0g of polyol were added to the Erlenmeyer flask. After the mixture was reacted at 90-100 ℃ for 1 hour, 25mL of pyridine and 10mL of deionized water were added. After further reaction for 20min, the product is reacted with 0.5mol L of phenolphthalein as an indicator-1Titration of potassium hydroxide solution. Blank assays were performed in a similar procedure.
(3) Stability of aqueous polyurethane emulsion
Aqueous polyurethane emulsion stability characterized by centrifuging the sample at 3000rpm for 30min using a Tomos 3-18 centrifuge from Shanghai Tomo scientific instruments.
(4) Particle size distribution and Zeta potential
The particle size distribution and Zeta potential of the aqueous polyurethane emulsion were measured with a Zeta-sizer Nano ZSE from malvern instruments ltd, u.k. the sample was diluted to about 0.01% by weight before the test.
(5) Contact angle
Using the water drop shape analysis system DSA100 (Kruss, Hamburg, Germany), 3. mu.L of distilled water was used at room temperature. The test results are the average of three replicates after 10s exposure to water.
(6) Antifouling properties
The antifouling properties were carried out according to the shake flask method in the literature, as follows: bacteria capable of producing biofilm (S.aureus M4, S.aureus S45, E.coli DH5 alpha/p 253) stored in this laboratory were cultured to the logarithmic phase of growth (OD)600About 0.5) post-dilution by 100 times to obtain 106CFU/mL bacterial liquid. Adding 5mL of each bacterial solution into each well of 6-well kangning plate, carefully placing 1cm of each bacterial solution with sterile forceps2Adding different vegetable oil-based waterborne polyurethane membrane materials and Nylon (a 0.22 micron Nylon microporous filter membrane used in a joint transfer experiment in a laboratory is used as a control sample) into corresponding bacteria liquid, and performing static culture at 37 ℃ for 24 hours. The 4 materials were washed 3 times with sterile PBS buffer and transferred to another sterile EP tube, 5mL sterile PBS was added, ultraclean 30min, bacteria adhered to each material were eluted to PBS and after 10-fold dilution, each gradient dilution was plated on MH agar medium. The plates were incubated in a 37 ℃ incubator for 15h, observed and counted.
The percent of adhesion resistance (viable cell number adhered to the nylon membrane-viable cell number adhered to the polyurethane membrane)/viable cell number adhered to the nylon membrane x 100%.
In the following embodiments, embodiments 1 to 6 are organic silicon vegetable oil-based polyols and a preparation method thereof, and the preparation steps are that epoxidized vegetable oil and an organic silicon monomer are subjected to an epoxy ring-opening reaction to obtain the organic silicon vegetable oil-based polyols; the structural formula of the organic silicon monomer is
Wherein R is methyl or ethyl, R1Is one of alkyl, substituted alkyl or heteroalkyl, R2Is one of hydroxyl, amino or carboxyl. The preparation conditions of examples 1 to 6 are shown in Table 2.
TABLE 2 preparation conditions of vegetable oil-based antifouling polyol
Examples 1 to 2:
embodiments 1-2 provide a series of silicone vegetable oil-based polyols, which are prepared by respectively adopting silicone ring-opening epoxidized soybean oil containing carboxyl groups with different structures, and the specific process is as follows.
Adding the organosilicon monomer containing carboxyl into a reaction bottle, introducing nitrogen for protection, heating to 80-120 ℃, dripping epoxidized vegetable oil according to a proportion, extracting a product by using ethyl acetate, and drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate. The product was filtered and rotary evaporated to remove ethyl acetate and then dried under vacuum at 45 ℃ overnight to give a vegetable oil based polyol with low surface energy silicone in the side chain. Specific preparation conditions are shown in table 2, and the reaction scheme is shown in fig. 1.
Examples 3 to 4:
embodiments 3 to 4 provide a series of silicone vegetable oil-based polyols, which are prepared by ring-opening reactions of epoxidized vegetable oil and hydroxyl-containing silicones of different structures, respectively, and the specific process is as follows.
Adding the hydroxyl-containing organosilicon monomer and a catalyst into a reaction bottle, uniformly mixing, heating to 40-80 ℃, dripping epoxidized vegetable oil in proportion, continuing to react for 20-120min, extracting a product with ethyl acetate, and drying with anhydrous magnesium sulfate or anhydrous sodium sulfate. The product was filtered and rotary evaporated to remove ethyl acetate and then dried under vacuum at 45 ℃ overnight to give a vegetable oil based polyol with low surface energy silicone in the side chain. Specific reaction conditions are shown in table 1, and the reaction scheme is shown in fig. 2.
Examples 5 to 6:
embodiments 5-6 provide a series of silicone vegetable oil-based polyols, which are prepared by ring-opening reactions of epoxidized soybean oil and amino-containing silicones of different structures, respectively, in the following specific process.
Adding the hydroxyl-containing organosilicon monomer and a catalyst into a reaction bottle, uniformly mixing, heating to 40-80 ℃, dripping epoxidized vegetable oil in proportion, continuing to react for 60min, extracting a product with ethyl acetate, and drying with anhydrous magnesium sulfate or anhydrous sodium sulfate. The product was filtered and rotary evaporated to remove ethyl acetate and then dried under vacuum at 45 ℃ overnight to give a vegetable oil based polyol with low surface energy silicone in the side chain. The specific reaction conditions are shown in Table 1, and the reaction scheme is shown in FIG. 3.
Characterization of Silicone vegetable oil-based polyols
The hydroxyl number of the silicone vegetable oil-based polyol was determined by titrating the hydroxyl number and acid number of the product, and the results are shown in table 3, while the structure of the product vegetable oil-based polyol was characterized by GPC, and the results are shown in fig. 4.
TABLE 3 hydroxyl number and molecular weight of vegetable oil based polyols
As shown in Table 3, the hydroxyl number of the vegetable oil base obtained was from 123 to 147mg KOH/g, indicating that the product obtained, after ring opening with silicone, produced a large amount of hydroxyl functional groups.
FIG. 4 is a Gel Permeation Chromatography (GPC) chart of the silicone vegetable oil-based polyols obtained in examples 1-6. As can be seen from the figure, the retention time of the obtained product is shifted to the left (the retention time is between 17 and 18.5 min) compared with the original epoxidized vegetable oil, which indicates that the molecular weight of the product is increased and the organosilicon successfully opens the epoxidized vegetable oil.
Examples 7 to 15 preparation of organosilicon-modified waterborne polyurethane
The organic silicon vegetable oil-based polyol prepared in the embodiments 1-6 is applied to the preparation of waterborne polyurethane to obtain a series of antifouling organic silicon modified waterborne polyurethane emulsions.
Specifically, the organosilicon modified waterborne polyurethane emulsion is prepared by the following steps: the silicone vegetable oil-based polyol prepared in examples 1 to 6 and diisocyanate were respectively charged into a two-necked flask equipped with a mechanical stirrer, and stirred and mixed at a temperature of 50 to 90 ℃ for 10 to 30 minutes (reaction stage 1). Then, a catalyst (1% by mass of the polyol) and a chain extender are added to continue the reaction for 10 to 30 minutes (reaction stage 2). And then, adding Methyl Ethyl Ketone (MEK) with the solid content of 20-50% to reduce the viscosity of the system and continuously reacting for 30-150 minutes. Then, when the temperature is cooled to room temperature, the system is neutralized by a neutralizing agent and stirred for about 5 to 60 minutes (neutralization time). Finally, the mixture is emulsified with distilled water at a speed of 400 to 1000rpm for 30 to 120 minutes (emulsification time), and then excess MEK is removed by rotary evaporation to obtain an aqueous Polyurethane (PU) having a solid content of 15 to 35%. Tables 4 and 5 show the specific parameter conditions of the examples.
Table 4 Experimental parameters for the aqueous polyurethane emulsions of examples 7-15
TABLE 5 Experimental conditions for examples 7-15 of aqueous polyurethane emulsions
Note: a, hydroxyl molar equivalent of organosilicon vegetable oil-based antifouling polyalcohol; and b, hydroxyl molar equivalent of the chain extender.
Comparative example
The comparative example provides an aqueous polyurethane emulsion prepared from silicone-free vegetable oil polyol, and the specific preparation process is as follows.
Castor oil polyol (available as such, CAS: 8001-79-4) and IPDI were added to a two-necked flask equipped with mechanical stirring and mixed with stirring at a temperature of 78 ℃ for 10 minutes. Then, DBTDL (1% mass fraction of polyol) was added to the mixture, followed by reaction for 10 to 30 minutes. After a subsequent DMPA chain extension reaction for 30min, 40 wt.% butanone was added to reduce the viscosity of the system. The reaction was then continued for 2h and the system was neutralized with TEA and stirred for about 30 min. Wherein the molar ratio of OH (polyol): NCO: OH (chain extender) is 1: 2: 0.99: finally, water was added to emulsify for 2 hours at a speed of 600rpm, and then excess MEK was removed by rotary evaporation to obtain an aqueous polyurethane emulsion having a solid content of 15%.
Test analysis
Pouring the aqueous polyurethane emulsion obtained in the comparative example and the organic silicon modified antifouling aqueous polyurethane emulsion obtained in examples 7-15 into a silica gel mold, and drying at room temperature to obtain a film for further analysis. All samples were dried at 60 ℃ for more than 12h prior to testing.
The measurement results are shown in Table 6.
Table 6 shows particle diameters, zeta potentials, and water contact angles of the aqueous polyurethane emulsions obtained in examples 7 to 15 and comparative examples
| Sample (I) | Particle size (nm) | Zeta potential (mV) | Storage stability (moon) | Water contact Angle (°) |
| Example 7 | 422.6±0.1 | -42.7±5.2 | ＞24 | 136.2±2.4 |
| Example 8 | 329.8±0.8 | -41.2±2.8 | ＞24 | 130.1±2.9 |
| Example 9 | 347.6±1.3 | -48.3±9.6 | ＞24 | 121.9±1.8 |
| Example 10 | 346.6±2.2 | -49.4±4.8 | ＞24 | 140.6±4.7 |
| Example 11 | 319.8±0.4 | -51.6±3.3 | ＞24 | 134.4±4.2 |
| Example 12 | 249.9±6.4 | -48.3±9.6 | ＞24 | 128.1±3.6 |
| Example 13 | 245.4±1.8 | 51.6±2.2 | ＞24 | 142.2±3.4 |
| Example 14 | 263.4±1.2 | 53.5±1.9 | ＞24 | 135.7±2.4 |
| Example 15 | 197.4±1.4 | 44.1±43.2 | ＞24 | 130.4±6.2 |
| Comparative example | 20.3±12.6 | -40.4±1.5 | ＞24 | 62.3±1.4 |
As can be seen from Table 6, the particle sizes of the organosilicon modified antifouling waterborne polyurethane emulsions obtained in examples 7-15 are 163.4-422.6 nm, which are higher than those of the comparative example (20.3nm), and the introduction of organosilicon reduces the hydrophilicity of the waterborne polyurethane. In the structure of the waterborne polyurethane obtained in the embodiments 7 to 12, as the content of the hydrophilic chain extender increases, the content of the silicone vegetable oil-based antifouling polyol decreases, and the particle size of the polyurethane emulsion gradually increases, which is caused by the decrease of the overall hydrophilicity of the polyurethane; next, as the degree of neutralization of the aqueous polyurethane increases, the content of the hydrophilic quaternary ammonium salt formed during the emulsification increases, and the hydrophilicity of the aqueous polyurethane is promoted, and therefore, the particle diameter of the resulting aqueous polyurethane emulsion gradually decreases (examples 13 to 15).
Pouring the obtained waterborne polyurethane emulsion into a polytetrafluoroethylene or silicified glass mold, standing at room temperature for water volatilization, and drying in a common oven at 60 ℃ for 2 days after the surface of the film is dry and not sticky to hands to obtain the antifouling vegetable oil-based waterborne polyurethane coating film for testing contact angle and antifouling performance. The contact angle results are shown in table 6. We can see that the water contact angle (121.0-142.2 ℃) of the water-based polyurethane coating film prepared by the organic silicon polyol is far higher than that (62.3 ℃) of a comparative example without silicon, and the introduction of the organic silicon greatly improves the hydrophobicity of the coating film, thereby being beneficial to the antifouling property of the coating film. This is because, during the film formation process, the low surface energy organosilicon migrates to the gas-liquid interface (i.e., the surface of the coating film), resulting in the accumulation of a large amount of hydrophobic organosilicon structures on the surface of the coating film, thereby improving the hydrophobicity of the coating film.
The aqueous solutions obtained in examples 7, 9, 10 and 11 were selectedThe antifouling performance of the polyurethane film is represented by a table shaking method, the proportion is used as a control sample, and the influence rule of the content of organic silicon in the coating on the antifouling performance of the coating is researched. The polyurethane coating films obtained in examples 7, 9, 10 and 11 and comparative example and Nylon (0.22 μm Nylon microporous filter membrane used in the bonding transfer experiment in the laboratory) were cut into pieces of 1X 1cm2And (5) placing the large and small samples into a sterile 6-hole plate, and carrying out ultraviolet sterilization for 2 hours for later use. The laboratory-stored bacteria capable of producing biofilm, staphylococcus aureus (S. aureus M4, S. aureus S45) and gram-negative bacteria (e.coli ATCC 25922) were cultured to logarithmic phase (OD600 value of 0.5) and diluted to obtain 106CFU/mL bacterial liquid. 5mL of the bacterial liquid is added into a 6-well plate containing the coating sample, and the mixture is subjected to static culture at 37 ℃ for 24 hours. The 4 materials were washed 3 times with sterile PBS buffer and transferred to another sterile EP tube, 5mL sterile PBS was added, ultraclean 30min, bacteria adhered to each material were eluted to PBS and after 10-fold dilution, each gradient dilution was plated on MH agar medium. The plates were incubated in a 37 ℃ incubator for 15h, observed and counted. As shown in fig. 5, the anti-adhesion effect of the coating film on gram-positive bacteria (s.aureus M4, s.aureus S45) and gram-negative bacteria e.coli ATCC 25922 was obtained by plate counting, wherein s.aureus S45 is very likely to form a biofilm. The two kinds of bacteria can be adhered to the surfaces of the nylon membrane and the polyurethane without organic silicon at higher adhesion rates, and after the organic silicon polyol is introduced, the number of the bacteria adhered to the surface of the polyurethane membrane is obviously reduced, the adhesion rate is over 90 percent, and the highest antibacterial adhesion performance reaches 99 percent (figure 5). The introduction of the low surface energy organosilicon antifouling polyol can effectively improve the antibacterial adhesion capability of the polyurethane film.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the scope of the present invention, and that those skilled in the art can make other variations or modifications based on the above description and ideas, and all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of organosilicon modified waterborne polyurethane is characterized by comprising the following steps:
s1: mixing diisocyanate and organic silicon vegetable oil-based polyol at 65-85 ℃, uniformly dispersing, adding a chain extender and a catalyst, and reacting for 10-30 min; the organic silicon vegetable oil-based polyol is prepared by carrying out an epoxy ring-opening reaction on epoxidized vegetable oil and an organic silicon monomer, wherein the structural formula of the organic silicon monomer is shown in the specification
Wherein R is methyl or ethyl, R1Is one of alkyl, substituted alkyl or heteroalkyl, R2Is one of hydroxyl, amino or carboxyl;
s2: adding butanone or acetone for dilution, continuing to react for 30-150 min, cooling to room temperature after the reaction is finished, neutralizing by a neutralizing agent, adding water for emulsification, and removing butanone or acetone by rotary evaporation to obtain the organic silicon modified waterborne polyurethane emulsion.
2. The method according to claim 1, wherein the molar ratio of the hydroxyl groups of the silicone vegetable oil-based polyol, the diisocyanate and the chain extender is 1.0: 1.8-2.6: 0.5-1.5.
3. The preparation method of claim 1, wherein the solid content of the organosilicon modified aqueous polyurethane emulsion is 5-50%.
4. The method according to claim 1, wherein the catalyst has a solid content of 0.1 to 1% by mass based on the total mass of the diisocyanate and the silicone vegetable oil-based polyol.
5. The method according to claim 1, wherein the reaction temperature in step S1 is 50-90 ℃, and the reaction time is 20-30 min; in the step S2, the reaction temperature is 70-80 ℃, and the reaction time is 60-90 min.
6. The method according to claim 1, wherein the epoxy group in the epoxidized vegetable oil and the R in the silicone monomer2The molar ratio of (A) to (B) is 1.0: 1.2-5.
7. The method of claim 1, wherein the epoxy ring-opening reaction in step S1 is carried out without a catalyst or with one or more of the following catalysts: the catalyst comprises tetrafluoroboric acid, sodium ethoxide and boron trifluoride diethyl etherate, and the dosage of the catalyst is 0.1-5% of the total mass of the epoxidized vegetable oil and the organosilicon monomer.
8. The method according to claim 1, wherein the temperature of the epoxy ring-opening reaction in step S1 is 45-120 ℃ and the time is 20-120 min; before the ring-opening reaction of epoxy, mixing and dissolving the epoxy vegetable oil, the organic silicon monomer and the initiator in an organic solvent; the method also comprises the steps of extraction, drying, filtration, evaporation and drying after the ring opening reaction of the epoxy resin.
9. An organosilicon-modified waterborne polyurethane, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the silicone-modified aqueous polyurethane of claim 9 for the preparation of aqueous polyurethane coating films, coatings, sealants, adhesives, foams or composites.
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