CN113105605B - UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof - Google Patents
UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material, a preparation method thereof and application thereof in manufacturing UV-cured environment-friendly solid wood furniture paint and flexible electronic devices. The preparation method comprises the steps of carrying out copolymerization reaction on hydroxyl silsesquioxane, hydroxyl-terminated/amino-terminated polysiloxane, castor oil and diisocyanate, terminating with hydroxyl acrylate, preparing an acrylate-terminated silsesquioxane modified organosilicon-castor oil polyurethane prepolymer, uniformly mixing the silsesquioxane modified organosilicon-castor oil polyurethane prepolymer with polysiloxane containing mercaptopropyl siloxane chain links in proportion, defoaming in vacuum for 10-30 min, and carrying out UV curing for 10-120 s to obtain the UV-cured high-transparency POSS modified organosilicon-castor oil polyurethane material with the light transmittance of 95% (the light wavelength range is 400-800 nm), the hardness of 3H-9H, the tensile strength of 0.5-10.5 MPa, the initial thermal decomposition temperature of 250-290 ℃ and excellent adhesion with a base material.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to a UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material and preparation and application thereof.
Background
Ultraviolet (UV) curing is a new energy-saving and environment-friendly technology, and has the advantages of fast curing, environmental friendliness and the like [ L.Xue, Y.Y.Zhang, Y.J.Zuo, et al, Preparation and characterization of novel UV-curing silicone rubber vitamin-ethylene reaction [ J ], mater.Lett.,2013,106(34): 425-. The traditional UV curing macromolecule multipurpose petrochemical raw materials are gradually consumed, and the petroleum resources are always exhausted. Therefore, when the global energy crisis is getting worse, the green and cheap bio-based raw materials are used to replace petrochemical raw materials, and the research of the UV curing materials is becoming a hot spot. As an important renewable bio-based raw material, vegetable oil has the advantages of rich source, low toxicity, biodegradability and the like, and therefore has attracted extensive attention in the research and application of new UV curing materials. Chinese patent application CN102633983A discloses a preparation method of UV-cured siloxane-terminated organosilicon block polyurethane, which comprises the steps of dripping polyester polyol or polyether polyol, hydroxyl-terminated silicone oil, castor oil and the like into aromatic or aliphatic diisocyanate to obtain an organosilicon block polyurethane prepolymer, then adding siloxane with active hydrogen into the organosilicon block polyurethane prepolymer under an organic tin catalyst to react to obtain a stable siloxane-terminated organosilicon block polyurethane prepolymer, adding a UV initiator, and carrying out UV curing to obtain an organosilicon modified UV-cured polyurethane material. The Chinese invention patent ZL201610556092.0 discloses a photocuring UV coating with strong adhesive force, which comprises a primer, a middle paint and a finish paint, wherein the coatings are prepared from castor oil-based UV curing polyurethane acrylate, organosilicon modified polyurethane acrylate, polyether modified organosilicon leveling agent and UV initiator, and the coatings have the advantages of good leveling effect, high curing speed, less emission of volatile organic substances, hydrolysis resistance, low temperature resistance, good electrical insulation and superior adhesive force. The Chinese invention patent application CN201710154932.5 takes castor oil modified polyol as chain extension to prepare the ultraviolet curing water-based polyurethane acrylate glossy leather finishing agent, and the finishing agent has the characteristics of low viscosity, environmental protection, high curing speed and the like, and is particularly suitable for being used as a finishing agent for leather or artificial leather. The invention patent ZL201710699373.6 is a dual-curing solvent-free polyurethane coil coating prepared from a diglyceryl dendritic macromolecule polyurethane prepolymer, a castor oil-based polyurethane prepolymer, a composite active monomer, an inorganic composite filler, acetyl tributyl citrate, an ultraviolet curing agent, an aliphatic polyisocyanate curing agent, hydroxyethyl methacrylate phosphate and an epoxy silane coupling agent, and the obtained coating product is a solvent-free environment-friendly coating and has the advantages of good adhesive force, MEK wiping resistance, high and low temperature resistance and the like. The Chinese invention patent application CN202010895159.X reacts castor oil, ricinoleic acid and esterification reaction products with diisocyanate, polyethylene glycol acrylate and polymerization inhibitor to obtain star castor oil based aqueous UV curing prepolymer, then the star castor oil based aqueous UV curing prepolymer is mixed with plant oil based reactive nonionic surfactant, free radical photoinitiator and cationic photoinitiator, and water is added for uniform dispersion to obtain castor oil based aqueous photocurable nonionic emulsion which can be used as a film forming base material in the fields of environment-friendly coatings, printing ink and adhesives. However, the transmittance of the above UV curable materials based on castor oil is not involved, and the thermal stability of these UV curable materials is poor.
The transparent organic silicon polymer material has wide application in the fields of flexible display, wearable equipment, wireless communication, man-machine interaction, biological medical treatment and the like [ Chengyo, a new mode for realizing remote intelligent medical treatment by flexible electronic technology products [ J ], the robot industry, 2018,6,82-83 ]. However, the tensile strength of the pure organosilicon transparent material without reinforcement is very low (not higher than 0.5MPa), which restricts the application of organosilicon optical transparent high molecular material in the field of flexible transparent electronic devices. Although the nano silicon dioxide (white carbon black) or MQ resin is adopted to reinforce the organosilicon material, the transmittance of the material reinforced by the white carbon black is very low, the controllability of the preparation of the MQ resin is poor, and the pollution is great.
The applicant adopts a series of silicon-containing hyperbranched sulfhydryl polymer and acrylate terminated polyurethane to cure in the presence of a UV photoinitiator, so as to obtain a temperature-sensitive fluorescent material (Chinese patent application CN202010096440.7) with the pencil hardness of 4B-2B, the light transmittance of 75.0-98% at 25 ℃ and the tensile strength of 0.5 MPa-3.0 MPa; a silicon-containing hyperbranched sulfhydryl polymer is adopted to react with acrylate-terminated polyurethane to obtain a flexible organosilicon material (Chinese patent application CN202010096461.9) with the light transmittance of more than 95 percent (the light wavelength range is 400-800 nm), the hardness of more than or equal to 4B and the tensile strength of 1 MPa-3.5 MPa. Although these materials have high tensile strength, their thermal stability is to be improved. The applicant also reacts isocyanate-terminated hyperbranched organosilicon-modified polyurethane with hydroxyl acrylate to obtain organosilicon-modified polyurethane containing acrylate groups, and the organosilicon-modified polyurethane and polysiloxane containing mercaptopropyl are subjected to UV curing to obtain a material with the light transmittance of more than 90% and the hardness of 4B-9H, wherein the mechanical property of the material is poor although the initial thermal decomposition temperature is as high as 290-350 ℃ (Chinese patent application CN 201910775983.9).
The silsesquioxane is an intramolecular organic-inorganic hybrid compound consisting of an inorganic framework consisting of silicon and oxygen and organic groups surrounding the periphery of the inorganic framework, has a hexahedral cubic structure, has the size of 1-3 nm and the average size of about 1.5nm, is close to the sizes of chain segments and random coils of most other polymers, is introduced into a polymer system, can form stronger chemical action between an inorganic phase and an organic phase, and is well compatible with the inorganic phase and the organic phase, so that a polymer matrix can be reinforced on the molecular level. The invention Chinese patent ZL200510028254.5 reports an ultraviolet curing coating containing POSS and a preparation method thereof, and particularly the ultraviolet curing coating is prepared by mixing white solid powder POSS with double bonds with diisocyanate, polyol and catalyst-based reactive diluent to prepare polyurethane acrylate according to a certain proportion. A transparent flexible silicone material having a light transmittance of 95% or more, a tensile strength of about 1.5MPa and an elongation of 17% [ Y.T.Liao, Y.C.Lin, S.W.Kuo, high thermal stable, transparent, and flexible silicone nanocomposites by combining of double-decker-shaped polymeric silicones and polydimethysilnoloxanes [ J ], Macromolecules,2017,50(15):5739-5747] can be obtained by Y.T.Liao et al. However, the organosilicon polymer raw materials with special structures required by the materials have long synthesis time and low yield, and are difficult to meet the industrial requirements. The applicant previously applied Chinese patent CN202010096439.4 prepares liquid silsesquioxane with silsesquioxane as a core and polycarbosilane as an arm, and then carries out UV curing on the silsesquioxane and mercapto-group silicone resin to obtain an organic silicon coating with light transmittance of over 90 percent in a light wave range of 400-800 nm, pencil hardness of B-7H and initial thermal decomposition of 260-360 ℃, but the material is brittle.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a preparation method of a UV-cured high-transparency POSS modified organosilicon-castor oil polyurethane material, which comprises the steps of selecting silsesquioxane containing hydroxyl to carry out copolymerization reaction with diisocyanate and hydroxyl/amino-terminated polysiloxane to prepare a silsesquioxane modified acrylate-based organosilicon-castor oil polyurethane copolymer with a silsesquioxane chain segment in a main chain, uniformly mixing the silsesquioxane modified acrylate-based organosilicon-castor oil polyurethane copolymer with polysiloxane containing mercaptopropyl siloxane chain segments in proportion, carrying out vacuum defoamation for 5-30 min, carrying out UV curing for 10-120 s, the UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material with the light transmittance of 95 percent (the light wavelength range is 400-800 nm), the hardness of 3H-9H, the tensile strength of 0.5-10.5 MPa, the initial thermal decomposition temperature of 250-290 ℃ and excellent adhesion with a base material can be obtained. In the preparation method, the hydroxyl silsesquioxane participates in copolymerization reaction, so that the hydroxyl silsesquioxane is bonded on the main chain of the copolymer through a covalent bond and cannot be precipitated from a copolymer system, thereby retaining the advantages of the silsesquioxane and overcoming the defects of poor thermal stability, poor mechanical property, low light transmittance and the like of the UV curing material. Meanwhile, the system adopts a bio-based raw material of castor oil, and utilizes hydroxyl in the castor oil molecule to participate in copolymerization reaction, so that the mechanical property of the organic silicon material is improved, and the application field of the bio-based material is expanded. The optical transparent organic silicon modified material has very high light transmittance and excellent tensile strength after being cured, has the advantages of rapid curing process, low energy consumption, environmental protection, no need of adding a photoinitiator, and cost saving. The material can be used for UV curing high-grade environment-friendly solid wood furniture paint, and is expected to be used in the field of flexible electronic devices and the like.
A preparation method of a UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material comprises the following steps:
(1) mixing hydroxyl silsesquioxane, amino-terminated/hydroxyl-terminated (namely amino-terminated or hydroxyl-terminated) polysiloxane and castor oil, heating to 100-120 ℃, decompressing, dehydrating, cooling to 30-60 ℃, adding diisobutyl tin laurate under the protection of inert atmosphere, dropwise adding diisocyanate into the mixture under mechanical stirring to react to obtain an isocyanate-terminated polyurethane prepolymer, then adding hydroxyl acrylate into the obtained prepolymer at 20-80 ℃, and obtaining acrylate-terminated silsesquioxane-modified organosilicon-polyurethane after the reaction is finished;
the diisocyanate is one or a mixture of more of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate isomer mixture (TDI), diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI);
the addition amount of the castor oil accounts for 30-40 wt% of the total mass (the total mass of the hydroxyl silsesquioxane, the amino-terminated/hydroxyl-terminated polysiloxane, the castor oil, the diisocyanate and the hydroxyl acrylate) of the raw materials for preparing the acrylate-terminated silsesquioxane-modified organosilicon-polyurethane;
(2) carrying out cohydrolysis-condensation reaction on mercaptopropyl alkoxysilane, difunctional alkoxysilane and trifunctional alkoxysilane in an organic solvent at the temperature of 30-80 ℃ for 0.5-12 h under the catalysis of an acid catalyst, washing with water to neutrality, reducing the pressure at 130mmHg/170 ℃ to 5min, and obtaining clear and transparent polysiloxane containing mercaptopropyl siloxane chain links;
the mercaptopropyl alkoxysilane is one or a mixture of more of mercaptopropyl methyldimethoxysilane, mercaptopropyl methyldiethoxysilane, mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane;
the difunctional alkoxy silane is one or a mixture of dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dimethoxy silane and diphenyl diethoxy silane;
the trifunctional alkoxy silane is one or a mixture of more of methyltrimethoxy silane, methyltriethoxy silane, phenyl trimethoxy silane and phenyl triethoxy silane;
the organic solvent is one or a mixture of more of toluene, xylene, petroleum ether, tetrahydrofuran and butyl acetate, and the dosage of the organic solvent is 0.5-4 times of the total mass of the mercaptopropyl alkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane;
the acid catalyst is one or a mixture of more of hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, and the dosage of the acid catalyst is 0.05-5 wt% of the total mass of the mercaptopropyl alkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane; the acid catalyst is added in the form of aqueous solution, wherein the amount of water is 1-2.5 times of the sum of the mole numbers of alkoxy groups of the mercaptopropylalkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane;
the ratio of the mole number of the mercaptopropylalkoxysilane to the sum of the mole numbers of other alkoxysilanes is 0.05-0.65: 1, and the mole ratio R/Si of all organic groups in the mercaptopropylalkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane to silicon atoms is 1.3-2.0: 1;
(3) uniformly mixing the acrylate-terminated silsesquioxane-modified organosilicon-polyurethane obtained in the step (1) and the mercaptopropyl siloxane chain link-containing polysiloxane obtained in the step (2) according to the molar ratio of acrylate groups to mercapto groups of 1-5: 1, then carrying out vacuum degassing on the mixture for 5-30 min at the temperature of 130 mmHg/25-40 ℃, and carrying out UV curing for 10-120 s to obtain the UV-cured high-transparency POSS-modified organosilicon-castor oil polyurethane material.
The preparation method comprises the steps of carrying out copolymerization reaction on hydroxyl silsesquioxane, hydroxyl-terminated/amino-terminated polysiloxane, castor oil and diisocyanate, terminating with hydroxyl acrylate, preparing an acrylate-terminated silsesquioxane modified organosilicon-castor oil polyurethane prepolymer, uniformly mixing the silsesquioxane modified organosilicon-castor oil polyurethane prepolymer with polysiloxane containing mercaptopropyl siloxane chain links in proportion, defoaming in vacuum for 5-30 min, and carrying out UV curing for 10-120 s to obtain the UV-cured high-transparency POSS modified organosilicon-castor oil polyurethane material with the light transmittance of 95% (the light wavelength range is 400-800 nm), the hardness of 3H-9H, the tensile strength of 0.5-10.5 MPa, the initial thermal decomposition temperature of 250-290 ℃ and excellent adhesion with a base material.
Preferably, in step (1), the hydroxyl silsesquioxane is one or a mixture of silsesquioxanes represented by the following formulas (I) to (III):
(I) denoted silsesquioxane 1;
(II) as silsesquioxane 2;
(III), noted as silsesquioxane 3.
Preferably, in the step (1), the amino-terminated/hydroxyl-terminated polysiloxane is one or a mixture of more of dimethylpolysiloxane with amino groups at both ends, methylphenylpolysiloxane with amino groups at both ends, dimethylpolysiloxane with hydroxyl groups at both ends, and methylphenylpolysiloxane with hydroxyl groups at both ends.
In the step (1), the molecular weight of the amino-terminated/hydroxyl-terminated polysiloxane is preferably 800-15000, and more preferably 1000-5000.
In the step (1), the mass of the hydroxyl silsesquioxane is preferably 0.5% to 20% of the mass of the amino terminated/hydroxyl terminated polysiloxane, and more preferably 1% to 10%.
Preferably, in step (1), the diisobutyl tin laurate is added in an amount of 0.1 to 0.4 wt% based on the total mass of the raw materials for preparing the acrylate-terminated, silsesquioxane-modified silicone-polyurethane (which means the sum of the mass of the hydroxyl silsesquioxane, amino-terminated/hydroxyl-terminated polysiloxane, castor oil, diisocyanate, and hydroxyl acrylate).
In the step (1), the diisocyanate is preferably added in a molar amount of 1.05 to 3.5 times, more preferably 1.5 to 2.5 times, the molar amount of the isocyanate group of the diisocyanate is the sum of the molar amounts of all amino groups and hydroxyl groups in the hydroxyl silsesquioxane, the amino-terminated/hydroxyl-terminated polysiloxane, and the castor oil.
Preferably, in the step (1), the hydroxy acrylate is one or a mixture of more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxyphenyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and 4-hydroxybutyl acrylate.
Preferably, in step (1), the hydroxyl acrylate is added in a molar amount equal to the molar amount of isocyanate groups of the prepolymer when no hydroxyl acrylate is added.
Preferably, in the step (2), the reaction temperature of the cohydrolysis-condensation reaction is 30-78 ℃, and the reaction time is 0.5-8 h.
The invention also provides the UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material prepared by the preparation method. The UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material has the light transmittance of 95 percent, the hardness of 3H-9H, the tensile strength of 0.5-10.5 MPa, the initial thermal decomposition temperature of 250-290 ℃, the water absorption rate of not more than 2.80wt percent and the water contact angle of 105.0-109.8 degrees in the light wavelength range of 400-800 nm.
The optically transparent organic silicon modified material obtained by the invention has very high light transmittance and excellent tensile strength, is rapid in curing process, low in energy consumption, environment-friendly, free of adding a photoinitiator and capable of saving cost. The material can be used for UV curing high-grade environment-friendly solid wood furniture paint, and is expected to be used in the field of flexible electronic devices and the like.
The invention also provides application of the UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material in manufacturing UV-cured environment-friendly solid wood furniture paint and flexible electronic devices.
Compared with the prior art, the invention has the main advantages that:
1. the unreinforced pure organic silicon transparent material has very low tensile strength (not higher than 0.5MPa) and basically has no practical value except for being used as a filling material, and the UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material prepared by the invention has the advantages of 0.5-10.5 MPa of tensile strength, 95% of light transmittance (the light wavelength range is 400-800 nm), 3H-9H of hardness and very excellent mechanical property.
(2) The thermal stability of the existing UV curing material is poor, and the thermal stability of the UV curing material is improved after the silsesquioxane is copolymerized and modified.
(3) The novel high polymer material is prepared by copolymerizing the hydroxyl silsesquioxane with the castor oil and the polyurethane, and the problem of material performance deterioration caused by precipitation and uneven dispersion of solid silsesquioxane when the existing silsesquioxane is blended and modified with the UV curing material is solved.
Drawings
FIG. 1 is a graph of light transmittance for different acrylate-based to mercapto mole ratio cured materials of example 3;
FIG. 2 is a thermogravimetric TGA (N) of different acrylate-to-mercapto molar ratios of cured materials of example 3 2 ) A graph;
FIG. 3 is a stress-strain plot of cured materials of example 3 with different acrylate-to-mercapto molar ratios;
FIG. 4 is a photograph of a UV-cured solid wood furniture paint of example 3 having a molar ratio of acrylate groups to thiol groups of 3: 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
In the present invention, the analytical test method is as follows:
the molecular structure and purity of the raw material were measured by Brucker Advance-400NMR (Brucker, Germany) nuclear magnetic resonance apparatus and polarimeter (Autopol II);
and (3) testing light transmittance: an Evolution 300 type ultraviolet-visible spectrophotometer of the American Thermo Fisher company tests the light transmittance of the polymer, the test wavelength range is 300-800 nm, and the sample thickness is 10 mm;
tensile strength test: the experimental equipment is a UH6503D microcomputer controlled electronic tension-compression cycle reciprocating testing machine manufactured by Yoghong measurement and control technology (Shanghai) Limited company, the stretching speed is 2mm/min, each film is measured for 3 times, and the average value is taken.
Pencil hardness: the measurement is carried out according to GB/T6739-2006 paint film hardness measurement by a colored paint and varnish pencil method.
Water contact angle: an IL4200 type contact angle measuring instrument, KRUSS, Germany, drops 2 microliters of water on the surface of a sample to be measured from a micro syringe with a needle tube containing deionized water, measures the contact angle of distilled water and a solid coating film in the air, and measures the value by an internal contact method. The mean values were taken 5 times in parallel.
Water absorption: cutting the coating into square blocks with certain shapes, soaking in deionized water at room temperature for 24h, sucking water on the surface of the coating by using filter paper, and calculating the water absorption of the coating according to the following formula:
wherein B represents the water absorption (%), m 1 Denotes the mass of the coating film before immersion, m 2 The mass of the coating film after soaking was measured by blotting the liquid on the surface of the coating film with filter paper.
Example 1
1) Adding 5g of silsesquioxane 1, 50g of castor oil and 10g of polydimethylsiloxane with two hydroxyl end capping ends and molecular weight 4000 into a clean 250mL four-neck flask with a thermometer inserted, heating to 100-120 ℃, reducing the pressure to 130mmHg, dehydrating for 2h, cooling to 60 ℃, stirring under the protection of nitrogen, adding 0.127g of diisobutyl tin dilaurate, slowly adding 40g of HDI, heating to 80 ℃, reacting for 3h, adding 22.305g of hydroxyethyl methacrylate, and continuing to react for 3h to obtain yellowish transparent liquid, namely the organic silicon-polyurethane modified by the silsesquioxane with the end capping of acrylate.
2) A mixture of 56.2g of deionized water and 3.5g of 36.5% by weight of concentrated hydrochloric acid was added dropwise to a mixture of 78.54g of 3-mercaptopropyltrimethoxysilane, 48.75g of dimethyldiethoxysilane, 47.98g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (in a proportion of 0.004mol/g of mercapto group and 1.3 of organic group/silicon atom) and 175g of toluene at 50 ℃ with mechanical stirring, and after 0.5h of dropwise addition, the reaction was continued at 50 ℃ for 8h, followed by washing with water until neutrality, and the solvent, the residual starting materials and the low-molecular-weight products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 70.5g of colorless transparent mercapto-containing polysiloxane.
3) Taking 10g of the acrylate-terminated silsesquioxane-modified organosilicon-polyurethane obtained in the step 1) and 1.8g of the mercapto-silicone resin in the step 2), uniformly mixing, carrying out vacuum defoamation at 130mmHg/30 ℃ for 20min, and carrying out UV curing to obtain the material with the properties shown in Table 1.
TABLE 1 Properties of materials prepared at different UV curing times
Example 2
1) Adding 3g of silsesquioxane 1, 5g of silsesquioxane 2, 50g of castor oil, 5g of double-end hydroxyl-terminated polydimethylsiloxane with the molecular weight of 1000 and 10g of double-end hydroxyl-terminated polydimethylsiloxane with the molecular weight of 15000 into a clean 250mL four-neck flask inserted with a thermometer, heating to 100-120 ℃, reducing the pressure to 130mmHg, dehydrating for 2h, cooling to 30 ℃, stirring under the protection of nitrogen, adding 0.225g of diisobutyl tin dilaurate, slowly adding 45g of IPDI, heating to 60 ℃, reacting for 8h, adding 26.850g of hydroxypropyl methacrylate, and continuing to react for 8h to obtain yellowish transparent liquid, namely the acrylate-terminated silsesquioxane-modified organosilicon-polyurethane.
2) Under the condition of 50 ℃ and mechanical stirring, a mixture of 56.2g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid is dropwise added into a mixture of 39.27g of 3-mercaptopropyltrimethoxysilane, 48.75g of dimethyldiethoxysilane, 74.38g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (the proportion of 0.002mol/g of mercapto group and 1.3 of organic group/silicon atom) and 175g of toluene, the reaction is continued at 50 ℃ for 8 hours after 0.5 hour of dropwise addition, then the reaction is washed to be neutral, and the solvent, residual raw materials and low molecular weight products are removed under reduced pressure at 130mmHg/170 ℃ to obtain 65.5g of colorless and transparent mercapto polysiloxane, and the mark is silicon resin 1.
A mixture of 56.2g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid was added dropwise to a mixture of 58.905g of 3-mercaptopropyltrimethoxysilane, 48.75g of dimethyldiethoxysilane, 61.18g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (in a proportion of 0.003mol/g of mercapto group and 1.3 of organic group/silicon atom) and 175g of toluene at 50 ℃ with mechanical stirring, and after 0.5h of dropwise addition, the reaction was continued at 50 ℃ for 8h, and then the mixture was washed with water to neutrality, and the solvent, the residual starting materials and the low-molecular-weight products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 38.4g of colorless transparent mercapto-containing polysiloxane, which was labeled as Silicone 2.
Under the condition of 50 ℃ and mechanical stirring, a mixture of 56.2g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid is dropwise added into a mixture of 78.54g of 3-mercaptopropyltrimethoxysilane, 48.75g of dimethyldiethoxysilane, 47.98g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (the proportion of 0.004mol/g of mercapto group and 1.3 of organic group/silicon atom) and 175g of toluene, the reaction is continued at 50 ℃ for 8 hours after 0.5 hour of dropwise addition, then the mixture is washed to be neutral, and the solvent, residual raw materials and low molecular weight products are removed under reduced pressure at 130mmHg/170 ℃ to obtain 70.5g of colorless and transparent mercapto polysiloxane, which is marked as silicone resin 3.
A mixture of 56.2g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid was added dropwise to a mixture of 98.18g of 3-mercaptopropyltrimethoxysilane, 48.75g of dimethyldiethoxysilane, 34.76g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (in a proportion of 0.005mol/g of mercapto group and 1.3 of organic group/silicon atom) and 175g of toluene at 50 ℃ with mechanical stirring, and after 0.5h of dropwise addition, the reaction was continued at 50 ℃ for 8h, and then the mixture was washed with water to neutrality, and the solvent, the residual starting materials and the low-molecular products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 78.4g of colorless transparent mercapto-containing polysiloxane, which was labeled as Silicone resin 4.
A mixture of 56.2g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid was added dropwise to a mixture of 117.81g of 3-mercaptopropyltrimethoxysilane, 48.75g of dimethyldiethoxysilane, 34.78g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (in a proportion of 0.006mol/g of mercapto group content and 1.3 of organic group/silicon atom) and 175g of toluene at 50 ℃ with mechanical stirring, and after 0.5h of dropwise addition, the reaction was continued at 50 ℃ for 8h, and then the mixture was washed with water to neutrality, and the solvent, the residual starting materials and the low-molecular-weight products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 81.5g of colorless transparent mercapto-containing polysiloxane, which was labeled as silicone resin 5.
3) Taking 10g of the acrylate-terminated silsesquioxane-modified organosilicon-polyurethane obtained in the step 1) and 10g of the mercapto-silicone obtained in the step 2), uniformly mixing, carrying out vacuum defoamation at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 90s to obtain the material with the properties shown in the table 2.
TABLE 2 Effect of mercapto content of mercapto-silicones
Example 3
1) Adding 4g of silsesquioxane 3, 50g of castor oil, 3g of polydimethylsiloxane with two hydroxyl end caps and a molecular weight of 800 and 10g of polydimethylsiloxane with two hydroxyl end caps and a molecular weight of 10000 into a clean 250mL four-neck flask with a thermometer inserted, heating to 100-120 ℃, reducing the pressure to 130mmHg, dewatering for 2h, cooling to 30 ℃, stirring under the protection of nitrogen, adding 0.592g of diisobutyl tin dilaurate, slowly adding 48.5g of MDI, heating to 70 ℃, reacting for 6h, adding 32.456g of 4-hydroxyphenyl methacrylate, and continuing to react for 6h to obtain yellowish transparent liquid, namely the organic silicon-polyurethane modified by the silsesquioxane with the end caps.
2) A mixture of 56.2g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid was added dropwise to a mixture of 78.54g of 3-mercaptopropyltrimethoxysilane, 48.75g of dimethyldiethoxysilane, 47.98g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (in a proportion of 0.004mol/g of mercapto group and 1.3 of organic group/silicon atom) and 175g of toluene at 50 ℃ with mechanical stirring, and after 0.5h of dropwise addition, the reaction was continued at 50 ℃ for 8h, and then the reaction was washed with water to neutrality, and the solvent, the residual starting materials and the low-molecular-weight products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 70.5g of colorless transparent mercapto-containing polysiloxane.
3) Taking 1.8g of the acrylate-terminated silsesquioxane-modified silicone-polyurethane obtained in the step 1) and 1.8g of the mercapto-silicone resin obtained in the step 2), uniformly mixing, performing vacuum defoamation at 130mmHg/30 ℃ for 20min, and performing UV curing for 90s to obtain the material with the properties shown in the table 3 and the figures 1-3. The decomposition temperature of the UV curing material is higher than 290 ℃ when the thermal weight loss is 5%, and the carbon residue rate is 3.4-15.3% at 800 ℃, which shows that the thermal stability of the UV curing material is good; the tensile strength of the obtained material can reach 10.5MPa to the maximum and is far higher than that of an unreinforced pure organosilicon material.
TABLE 3 Effect of different acrylate-to-mercapto molar ratios
The material with the molar ratio of acrylate group to mercapto group being 3:1 is used as the UV-cured solid wood furniture paint (as shown in figure 4), the cured material has excellent adhesion with solid wood furniture, and the solid wood furniture has clear texture and smooth surface. This indicates that the obtained UV curable material has a very good use in UV curing solid wood furniture lacquers.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material is characterized by comprising the following steps:
(1) mixing hydroxyl silsesquioxane, amino-terminated/hydroxyl-terminated polysiloxane and castor oil, heating to 100-120 ℃, decompressing, dehydrating, cooling to 30-60 ℃, adding diisobutyl tin laurate under the protection of inert atmosphere, dropwise adding diisocyanate into the mixture under mechanical stirring, reacting to obtain an isocyanate-terminated polyurethane prepolymer, then adding hydroxyl acrylate into the obtained prepolymer at 20-80 ℃, and obtaining acrylate-terminated silsesquioxane-modified organosilicon-polyurethane after the reaction is finished;
the diisocyanate is one or a mixture of more of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate isomer mixture, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate;
the addition amount of the castor oil accounts for 30-40 wt% of the total mass of the raw materials for preparing the acrylate-terminated silsesquioxane-modified organosilicon-polyurethane;
the hydroxyl silsesquioxane has a structure shown as the following formula (III):
(2) carrying out cohydrolysis-condensation reaction on mercaptopropyl alkoxysilane, difunctional alkoxysilane and trifunctional alkoxysilane in an organic solvent at the temperature of 30-80 ℃ for 0.5-12 h under the catalysis of an acid catalyst, washing with water to neutrality, reducing the pressure at 130mmHg/170 ℃ to 5min, and obtaining clear and transparent polysiloxane containing mercaptopropyl siloxane chain links;
the mercaptopropyl alkoxysilane is one or a mixture of more of mercaptopropyl methyldimethoxysilane, mercaptopropyl methyldiethoxysilane, mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane;
the difunctional alkoxy silane is one or a mixture of dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dimethoxy silane and diphenyl diethoxy silane;
the trifunctional alkoxy silane is one or a mixture of more of methyltrimethoxy silane, methyltriethoxy silane, phenyl trimethoxy silane and phenyl triethoxy silane;
the organic solvent is one or a mixture of more of toluene, xylene, petroleum ether, tetrahydrofuran and butyl acetate, and the dosage of the organic solvent is 0.5-4 times of the total mass of the mercaptopropyl alkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane;
the acid catalyst is one or a mixture of more of hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, and the dosage of the acid catalyst is 0.05-5 wt% of the total mass of the mercaptopropyl alkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane; the acid catalyst is added in the form of aqueous solution, wherein the amount of water is 1-2.5 times of the sum of the mole numbers of alkoxy groups of the mercaptopropylalkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane;
the ratio of the mole number of the mercaptopropylalkoxysilane to the sum of the mole numbers of other alkoxysilanes is 0.05-0.65: 1, and the mole ratio R/Si of all organic groups in the mercaptopropylalkoxysilane, the difunctional alkoxysilane and the trifunctional alkoxysilane to silicon atoms is 1.3-2.0: 1;
(3) uniformly mixing the acrylate-terminated silsesquioxane-modified organosilicon-polyurethane obtained in the step (1) and the polysiloxane containing mercaptopropyl siloxane chain links obtained in the step (2) according to the molar ratio of acrylate groups to mercapto groups of 3:1, then carrying out vacuum degassing on the mixture for 5-30 min at the temperature of 130 mmHg/25-40 ℃, and carrying out UV curing for 10-120 s to obtain the UV-cured high-transparency POSS-modified organosilicon-castor oil polyurethane material;
the UV-cured high-transparency POSS modified organic silicon-castor oil polyurethane material has the light transmittance of 95 percent, the hardness of 3H-9H, the tensile strength of 0.5-10.5 MPa, the initial thermal decomposition temperature of 250-290 ℃, the water absorption rate of not more than 2.80wt percent and the water contact angle of 105.0-109.8 degrees in the light wavelength range of 400-800 nm.
2. The method according to claim 1, wherein in the step (1), the amino-terminated/hydroxy-terminated polysiloxane is one or more of dimethylpolysiloxane having amino groups at both ends, methylphenylpolysiloxane having amino groups at both ends, dimethylpolysiloxane having hydroxy groups at both ends, and methylphenylpolysiloxane having hydroxy groups at both ends.
3. The method according to claim 1, wherein the amino-terminated/hydroxy-terminated polysiloxane in step (1) has a molecular weight of 800 to 15000.
4. The method according to claim 1, wherein in the step (1), the mass of the hydroxyl silsesquioxane is 0.5 to 20% of the mass of the amino terminated/hydroxyl terminated polysiloxane.
5. The method according to claim 1, wherein in the step (1), the diisobutyl tin laurate is added in an amount of 0.1 to 0.4 wt% based on the total mass of the raw materials for preparing the acrylate-terminated silsesquioxane-modified silicone-polyurethane.
6. The method according to claim 1, wherein in the step (1), the diisocyanate is added in a molar ratio of isocyanate groups to the sum of the molar ratios of all amino groups and hydroxyl groups in the hydroxyl silsesquioxane, the amino-terminated/hydroxyl-terminated polysiloxane, and the castor oil, which is 1.05 to 3.5 times.
7. The preparation method according to claim 1, wherein in the step (1), the hydroxy acrylate is one or a mixture of more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxyphenyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and 4-hydroxybutyl acrylate;
the hydroxyl acrylate is added in a molar amount equal to the molar amount of isocyanate groups of the prepolymer when no hydroxyl acrylate is added.
8. The UV-cured high-transparency POSS modified organosilicon-castor oil polyurethane material prepared by the preparation method according to any one of claims 1-7.
9. The use of the UV-curable high-transparency POSS modified silicone-castor oil polyurethane material according to claim 8 in the manufacture of UV-curable environment-friendly solid wood furniture paint and flexible electronic devices.
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