CN111892819A - Preparation method and application of UV (ultraviolet) curing transparent material - Google Patents

Preparation method and application of UV (ultraviolet) curing transparent material Download PDF

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CN111892819A
CN111892819A CN202010096439.4A CN202010096439A CN111892819A CN 111892819 A CN111892819 A CN 111892819A CN 202010096439 A CN202010096439 A CN 202010096439A CN 111892819 A CN111892819 A CN 111892819A
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杨雄发
吴于飞
刘江玲
程飞
焦晓皎
范云鑫
潘庆华
来国桥
郝超伟
华西林
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Hangzhou Normal University
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Abstract

The invention relates to the field of organic polymer materials, and provides a preparation method of a UV (ultraviolet) curing transparent material, aiming at solving the problems that an unmodified optical transparent organic silicon material has poor mechanical property, long curing time in preparation, high energy consumption and the like, and the problem that the cured material of the traditional UV curing polymer material has low hardness. The organosilicon material with higher hardness, low water absorption, good thermal stability and high light transmittance is obtained by UV curing, the material composition is simple, the cost is saved, and the material has no residual photoinitiator after curing and has good scratch resistance.

Description

Preparation method and application of UV (ultraviolet) curing transparent material
Technical Field
The invention relates to the field of organic polymer materials, in particular to a preparation method and application of a UV curing transparent material of a sulfur-containing hyperbranched copolymer based on cage-shaped polysilsesquioxane-carbosilane.
Background
At present, the traditional optical transparent high polymer materials such as polymethyl methacrylate, polycarbonate and the like have the defects of poor high and low temperature resistance, poor aging resistance, large linear expansion coefficient, easy moisture absorption, poor chemical stability and the like, and the development requirements of optical electronic components and the like are difficult to completely meet. The organic silicon optical transparent high polymer material has the advantages of good high and low temperature resistance, weather resistance, aging resistance, good electric insulation property and the like, and is widely applied to the fields of optical transparent PET release films, LED packaging, optical lenses, diffraction gratings, liquid crystal display and the like.
The curing and forming of the existing optical transparent organic silicon high polymer material are basically cured by hydrosilylation reaction or peroxide free radical reaction under the heating condition, or cured for a long time at room temperature under the catalysis of organic tin. These curing methods have a long curing time or high energy consumption. The ultraviolet curing has the advantages of high curing speed, simple processing technology, low energy consumption and no pollution, and is widely applied to a plurality of fields. In recent years, with the enhancement of environmental protection consciousness of people, the UV curing polymer material has outstanding advantages and shows strong market competitiveness.
The traditional UV curing high polymer material mainly comprises four parts, namely a photoinitiator, a matrix prepolymer, a diluent and various auxiliaries [ Chenkang, Liyao, research progress of ultraviolet curing cross-linking agents, Shandong chemical engineering, 2018, 47 and 46-49], the cost is high, the performance of a product can be degraded by the residual photoinitiator, the hardness of a cured product is low, and when the UV curing high polymer material is used as an optical device protective layer or UV curing solid wood furniture paint, the final product is easy to scratch in the transportation process.
Disclosure of Invention
In order to solve the problems of poor mechanical property, long curing time in preparation, high energy consumption and the like of an unmodified optical transparent organic silicon material and the problem of low hardness of a cured product of a traditional UV curing high polymer material, the invention provides a preparation method of a UV curing transparent material.
The invention also provides application of the UV-cured transparent material in solvent-free UV-cured solid wood furniture paint, UV-cured PET release films, UV-cured LED packaging and protective layers of optical transparent electronic devices.
The invention is realized by the following technical scheme: the preparation method of the UV curing transparent material comprises the following steps:
(1) stirring octavinyl cage polysilsesquioxane and mercaptopropyl alkoxy silane in a reaction solvent A, carrying out UV irradiation reaction, decompressing and desolventizing and residual raw materials to obtain an alkoxy-terminated sulfur-containing hyperbranched copolymer of cage polysilsesquioxane-carbosilane;
the cage-shaped polysilsesquioxane is an intramolecular organic-inorganic hybrid compound consisting of an inorganic framework consisting of silicon and oxygen and organic groups surrounding the inorganic framework, and is introduced into a polymer system, so that a strong chemical action can be formed between an inorganic phase and an organic phase, the inorganic phase and the organic phase are well compatible, a polymer matrix can be reinforced on a molecular level, and the hardness and the wear resistance of a high polymer material are improved. The hyperbranched polycarbosilane has good fluidity, solubility, thermal stability and the like.
Preferably, the molar ratio of the vinyl group to the mercaptopropyl group in the amount of the octavinyl polysilsesquioxane and the mercaptopropyl siloxane used is 1:1 to 1: 1.2. The mercaptosiloxane reacts with the octavinyl polysilsesquioxane and it does not crosslink and cure, but is allowed to react sufficiently. At the moment, the molar ratio of the vinyl group to the mercaptopropyl group is 1: 1-1: 1.2, so as to ensure that the vinyl group completely reacts and ensure the structural controllability and regularity of the obtained hyperbranched polymer.
Preferably, the mercaptopropylalkoxysilane is one or more selected from mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane and mercaptopropylmethyldiethoxysilane.
Preferably, the reaction solvent A is one or more selected from tetrahydrofuran, diethyl ether, toluene, xylene and petroleum ether. The amount used is an amount that dissolves the solute, and is preferably 1 to 2 times the total mass of octavinyl polysilsesquioxane and mercaptopropyl siloxane.
The reaction conditions of UV irradiation are as follows: the light source power is 100W-1000W, the main peak wavelength is 365nm or 405nm, the distance from the light source is 20cm, and the irradiation reaction is carried out for 0.5-6 h.
Preferably, the solvent and the residual raw material are removed under reduced pressure at 80-120 ℃/130 mmHg.
The reaction formula is (taking the synthesis of the sulfur-containing hyperbranched copolymer of 24 methoxy-terminated cage polysilsesquioxane-carbosilane as an example):
Figure BDA0002385365940000021
(2) performing Grignard reaction on the product obtained in the step (1) under anhydrous and oxygen-free conditions to obtain a polyhedral oligomeric silsesquioxane-carbosilane allyl terminated hyperbranched copolymer; the reaction formula is (taking the synthesis of the liquid polyhedral oligomeric silsesquioxane-carbosilane allyl terminated hyperbranched copolymer containing 24 allyl groups as an example):
Figure BDA0002385365940000031
the preparation method comprises the following steps:
(a) placing 60g of Mg scraps (2.500mol) and one to two pieces of iodine into a clean three-necked bottle under anhydrous and anaerobic conditions, then adding 400-3000 ml of solvent B, cooling the mixed system to-5-20 ℃ by using an ice bath, slowly dropwise adding a mixed solution of 50-600 ml of solvent B and 252.0g of allyl bromide (2.100mol, 5% excess), and reacting at-5-20 ℃ for 1-24 hours to obtain a solvent B solution of the allyl magnesium bromide Grignard reagent.
The solvent B is one or a mixture of two of tetrahydrofuran and diethyl ether.
(b) Dissolving the dried alkoxy-terminated polyhedral oligomeric silsesquioxane-carbosilane sulfur-containing hyperbranched copolymer in 20ml of solvent B, slowly dropwise adding the solvent B into the allyl bromide Grignard reagent B solution, and after the addition is finished, maintaining the reaction mixture at the temperature of-5-40 ℃ for reacting for 8-24 h. Adding the reaction mixture into 50-500 ml of saturated NH at-5-40 DEG C4Aqueous solution of Cl (saturated NH)4The amount of the aqueous Cl solution is preferably such that no bubbles are emitted after the mixture is stirred and mixed), and the mixture is filtered by a Buchner funnel. Extracting the water phase with 30-300 mL of solvent B for three times, washing the combined organic phase with 30-300 mL of deionized water for three times, washing with 50-200 mL of saturated NaCl aqueous solution for one time, and then with 20-50 g of anhydrous MgSO4And (3) after drying, removing the solvent and unreacted raw materials at the temperature of 80-120 ℃/130mmHg under reduced pressure to obtain a crude product. And then pouring the crude product into 50-500 mL of ethanol, precipitating the crude product, and drying for 12-24 h at 40-80 ℃/130mmHg to obtain the cage polysilsesquioxane-carbosilane allyl terminated hyperbranched copolymer.
(3) Mixing the allyl-terminated hyperbranched copolymer of cage-shaped polysilsesquioxane-carbosilane with polysiloxane containing sulfydryl, removing bubbles, and carrying out UV curing for 10-120 s to obtain the UV-cured transparent material.
Preferably, the molar ratio of sulfydryl to allyl in the polyhedral oligomeric silsesquioxane-carbosilane allyl terminated hyperbranched copolymer to the sulfydryl-containing organosilicon polymer is 0.6: 1-1.3: 1. Preferably, the polyhedral oligomeric silsesquioxane-carbosilane allyl terminated hyperbranched copolymer and the organosilicon polymer containing sulfydryl are uniformly mixed according to the molar ratio of allyl to sulfydryl of 0.8: 1-1.2: 1. In this case, the system undergoes a crosslinking reaction under UV radiation.
Preferably, the bubble is degassed under reduced pressure at 130 mmHg/25-40 deg.C for 5-30 min.
Preferably, the power of the UV curing light source is 500-.
The preparation method of the organosilicon polymer containing sulfydryl comprises the following steps: the method comprises the steps of cohydrolyzing and condensing alkoxy silane containing sulfhydryl groups, other alkoxy siloxane and end-capping agent hexamethyldisiloxane in an organic solvent C under the catalysis of an acid catalyst, washing the mixture to be neutral, and removing the organic solvent C, residual raw materials and low molecular products under reduced pressure to obtain the polysiloxane containing sulfhydryl groups, wherein each molecule at least contains three mercaptopropyl functional groups.
The alkoxy silane containing sulfydryl is selected from one or more of mercaptopropyl methyldimethoxysilane, mercaptopropyl methyldiethoxysilane, mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane.
The other alkoxy silane is selected from one or more of dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, methyl orthosilicate and ethyl orthosilicate; preferably, the other alkoxy silane is selected from one or more of dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, methyl trimethoxy silane, phenyl trimethoxy silane and ethyl orthosilicate.
The molar ratio of the mercapto group-containing siloxane to other alkoxysilanes is 0.05-0.65: 1, the molar ratio of all organic groups to silicon atoms is 1.3-2.0: 1, preferably the molar ratio of the mercapto group-containing siloxane to other alkoxysilanes is 0.1-0.45: 1, and the molar ratio of all organic groups to silicon atoms is 1.4-1.8: 1.
The organic solvent C is selected from one or more of toluene, xylene, petroleum ether, tetrahydrofuran and butyl acetate; the dosage of the additive is 0.5-4 times of the total mass of the raw materials. Preferably, the organic solvent is one or more selected from toluene, xylene and petroleum ether, and the dosage of the organic solvent is 0.8-2 times of the total mass of the raw materials.
The acidic catalyst is selected from one or more of hydrochloric acid, sulfuric acid, acetic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, the dosage of the catalyst is 0.05-5 wt% of the total mass of the raw materials, and preferably, the dosage of the acidic catalyst is 0.1-3 wt% of the total mass of the raw materials.
The dosage of water in the hydrolysis-condensation reaction is 1-2.5 times of the mole number of all alkoxy groups in the raw materials, and preferably, the dosage of water is 1-1.8 times of the mole number of all alkoxy groups in the raw materials.
The temperature of the cohydrolysis-condensation reaction is 30-80 ℃, and the reaction time is 0.5-48 h. Preferably, the temperature of the co-hydrolysis-condensation reaction is 40-70 ℃, and the reaction time is 2-18 h.
In the preparation method of the UV curing transparent material, the light curing conditions are as follows: the power of the UV curing light source is 500-1000W, the main peak wavelength is 365nm or 405nm, the distance from the light source is 20cm, and the microwave radio UV curing machine is preferably a ZB-T150-UV1000 type microwave radio UV curing machine.
The invention synthesizes the allyl-terminated hyperbranched copolymer of cage-shaped polysilsesquioxane-carbosilane, and the allyl-terminated hyperbranched copolymer and the organosilicon polymer containing sulfydryl are subjected to sulfydryl-vinyl (thiol-ene) click reaction and UV curing to obtain the organosilicon material with higher hardness, low water absorption, good thermal stability and high light transmittance. The preparation process of the material does not need to use a photoinitiator, a diluent and various auxiliaries, the material composition is simple, the cost is saved, the industrialization is facilitated, and the material has good scratch resistance after being cured.
The prepared UV curing transparent material has the light transmittance of more than 90 percent in the light wave range of 400-800nm, the pencil hardness of controllable in the range of B-7H, the water absorption of 0.02-0.25 wt percent and the initial thermal decomposition of 260-360 ℃. The obtained transparent organic silicon coating material is expected to be used for solvent-free UV-cured solid wood furniture paint, UV-cured PET release films, UV-cured LED packaging and optical transparent electronic device protective layers.
Compared with the prior art, the invention has the beneficial effects that:
(1) the problems of longer curing time, high energy consumption and the like in the preparation process of the conventional organic silicon optical transparent material are solved; the method does not need to add a photoinitiator, a diluent and other auxiliary agents, and solves the problems that the existing UV curing high polymer material is complex in composition (mainly comprises four parts, namely the photoinitiator, a matrix prepolymer, the diluent and various auxiliary agents), high in cost, high in product quality influenced by residual photoinitiator and the like;
(2) the organosilicon material with higher hardness, low water absorption, good thermal stability and high light transmittance is obtained by UV curing, and has good scratch resistance.
Drawings
FIG. 1 is a diagram of the preparation of the allyl-terminated hyperbranched copolymer of polyhedral oligomeric silsesquioxane-carbosilane having 24 allyl groups of example 11H NMR spectrum;
FIG. 2 is the allyl terminated hyperbranched copolymer POSS-Vi of cage polysilsesquioxane-carbosilane containing 24 allyl groups of example 124IR spectrograms of the mercapto resin and the cured film;
FIG. 3 is a photograph of cured products of the allyl-terminated hyperbranched copolymer of polyhedral oligomeric silsesquioxane-carbosilane having 24 allyl groups and a mercapto-polysiloxane having a mercapto content of 0.004% mol/g and different R/Si in example 1;
FIG. 4 is a photograph of the allyl terminated hyperbranched copolymer of 24 allyl polyhedral oligomeric silsesquioxane-carbosilane and cured products with 0.004% mol/g mercapto content and different mercapto to allyl molar ratios of example 1;
FIG. 5 is a graph showing the transmittance of a cured product of 12 in Table 1.
Detailed Description
The present invention is further illustrated by the following examples, in which the starting materials are either commercially available or prepared by conventional methods.
Nuclear magnetic resonance: deuterated chloroform (CDCl)3) MakingSolvent, hydrogen spectrum at room temperature by Brucker Advance-400NMR Nuclear magnetic resonance apparatus (Brucker, Germany) ((R))1H-NMR)。
Fourier infrared (FT-IR): when the Nicolet700 type Fourier transform infrared spectrometer (provided with ATR accessory) of Nicolet company in America is used for testing, a sample is directly placed in the ATR accessory of the infrared spectrometer, and the test is carried out at 4000-700 cm-1Fourier ir spectrum within the range.
And (3) testing light transmittance: an Evolution 300 type ultraviolet-visible spectrophotometer of the United states Thermo Fisher company tests the light transmittance of the polymer, the test wavelength range is 400-800nm, and the sample thickness is 10 mm;
pencil hardness: the measurement is carried out according to GB/T6739-2006 determination of paint film hardness by the pencil method for color paint and varnish.
Thermogravimetric analysis (TGA): thermogravimetric analysis is carried out by a TG209 thermogravimetric analyzer manufactured by German Steady instruments manufacturing company Limited, and the temperature rise rate is 10 ℃/min under the protection of nitrogen, and the temperature range is between room temperature and 800 ℃.
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 formula.
Figure BDA0002385365940000061
Wherein B represents water absorption (%); m is1Represents the quality of the coating film before soaking; m is2The 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) 1.0g of octavinyl polysilsesquioxane (POSS-Vi)81.58mmol), 2.48g (3-mercaptopropyl) trimethoxysilane (12.64mmol) and 30mL of THF were added to a 50mL single neck round bottom equipped with a stir barIn a flask. And irradiating the reaction mixture by using UV light with the main peak wavelength of 405nm and 500W for reaction for 3h, and then removing the solvent and residual raw materials by using 120 ℃/130mmHg under reduced pressure to obtain the 24 methoxy-terminated cage polysilsesquioxane-carbosilane sulfur-containing hyperbranched copolymer.
(2) Under the anhydrous and oxygen-free conditions, 60g of Mg scraps (2.500mol) and two pieces of iodine are placed in a clean three-necked bottle, 1000ml of diethyl ether is added, the temperature of a mixed system is reduced to 0-5 ℃ by using an ice bath, and then a mixed solution of 200ml of diethyl ether and 252.0g of allyl bromide (2.100mol) is slowly dropped. And after the dropwise addition is finished, reacting for 2 hours at the temperature of 0-5 ℃ to obtain an ether solution of the allyl magnesium bromide Grignard reagent.
20ml of dry diethyl ether and the resulting sulfur-containing hyperbranched copolymer mixture of 24 methoxy-terminated cage polysilsesquioxane-carbosilane were slowly added dropwise to allyl bromide Grignard reagent, and after the addition, the reaction mixture was stirred overnight at room temperature. The reaction mixture was added to cooled 100mL of saturated NH4And (4) carrying out suction filtration on the Cl aqueous solution. The aqueous layer was extracted three times with ether 50mL, and the combined organic layers were washed three times with deionized water 50mL, once with 50mL saturated aqueous NaCl, followed by 20g anhydrous MgSO4After drying, most of the volatiles were removed and the crude product was then precipitated as an oil by pouring the concentrated solution into 100mL of methanol. Vacuum drying the pure product to obtain 6g of flowable viscous liquid, namely, the allyl terminated hyperbranched copolymer of the cage polysilsesquioxane-carbosilane containing 24 allyl groups,1the H NMR spectrum is shown in FIG. 1.
1HNMR(400MHz，CDCl3，ppm)：＝0.63-0.92(-SiCH2CH2-)，0.93-0.1.14(-SiCH2-)，1.18-1.39(-CH2CH2CH2-)，1.51-1.84(-SiCH2CH＝CH2)，2.38-2.80(-CH2SCH2-)，4.68-5.01(-CH2CH＝CH2)，5.60-5.95(-CH2CH＝CH2) A is the residual Si-O-CH3B is CDCl3Solvent peak.
The double bond content calculated from the hydrogen spectrum is: 7.41 mmol/g.
(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 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 18h, followed by washing with water until neutral, 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.
And (3) taking 3.0g of the liquid polyhedral oligomeric silsesquioxane-carbosilane allyl terminated hyperbranched copolymer and 5.76g of the mercapto-polysiloxane in the step (2), uniformly mixing, carrying out vacuum defoaming at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 30s to form a film with the main peak wavelength of 405nm to obtain the UV cured transparent material 1.
The UV-curable transparent material 1 has a light transmittance of 90.5%, a pencil hardness of 3H, and a thermal decomposition temperature of 330 ℃.
As shown in FIG. 2, the cured film was found to be 1627cm-1The characteristic peak of the stretching vibration of the carbon-carbon double bond almost disappears; at 2550cm-1The characteristic peak of the mercapto group disappears. It can be seen that the mercapto group and allyl group in the curing system react well, which can prove the success of the preparation of the curing system.
Example 2
(1) 1.0g of octavinyl polysilsesquioxane (POSS-Vi)81.58mmol), 3.014g (3-mercaptopropyl) triethoxysilane (12.64mmol) and 100mL diethyl ether were added to a 250mL single neck round bottom flask equipped with a stir bar. After the reaction mixture is irradiated by UV light with the main peak wavelength of 365nm of 100W for reaction for 6h, the solvent and residual raw materials are removed under the reduced pressure of 80 ℃/130mmHg, and the 24 ethoxy-terminated caged polysilsesquioxane-carbosilane sulfur-containing hyperbranched copolymer is obtained.
(2) Under the anhydrous and oxygen-free conditions, 60g of Mg scraps (2.500mol) and two pieces of iodine are placed in a clean three-necked bottle, 400ml of tetrahydrofuran is added, the temperature of a mixed system is reduced to 0-5 ℃ by using an ice bath, and then a mixed solution of 50ml of tetrahydrofuran and 252.0g of allyl bromide (2.100mol) is slowly dropped. And reacting for 24 hours at the temperature of-5 ℃ after the dripping is finished to obtain a tetrahydrofuran solution of the allyl magnesium bromide Grignard reagent.
20ml of a mixture of dry diethyl ether and 24 ethoxy-terminated, sulfur-containing hyperbranched copolymers of polyhedral oligomeric silsesquioxane-carbosilane were slowly added dropwise to the allyl bromide Grignard reagent, and after the addition was complete, the reaction mixture was stirred overnight at room temperature. The reaction mixture was added to cooled 200mL of saturated NH4And (4) carrying out suction filtration on the Cl aqueous solution. The aqueous layer was extracted three times with 300mL tetrahydrofuran, and the combined organic layers were washed three times with 300mL deionized water, once with 200mL saturated aqueous NaCl, followed by 30g anhydrous MgSO4After drying, most of the volatiles were removed and the crude product was then precipitated as an oil by pouring the concentrated solution into 500mL ethanol. The pure product was dried under vacuum to give 6.8g of a flowable viscous liquid, i.e., a 24 allyl-containing polyhedral oligomeric silsesquioxane-carbosilane allyl-terminated hyperbranched copolymer.
(3) A mixture of 109.2g of deionized water and 8.785g of p-toluenesulfonic acid was added dropwise to a mixture of 78.54g of 3-mercaptopropyltrimethoxysilane, 64.34g of dimethyldiethoxysilane, 32.83g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (in a proportion of 0.004mol/g of mercapto group and 1.4 of organic group/silicon atom) and 351.4g of xylene at 40 ℃ with mechanical stirring, the reaction was continued at 40 ℃ for 24 hours after 0.5 hour of dropping, and then the mixture was washed with water to neutrality and the solvent, residual starting materials and low-molecular-weight products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 75.8g of colorless transparent mercaptopolysiloxane containing 75.8 g.
According to the mixture ratio in the following table, the mercapto polysiloxane and the allyl terminated hyperbranched copolymer of the cage polysilsesquioxane-carbosilane in 1 are respectively taken, uniformly mixed, subjected to vacuum defoamation at 130mmHg/30 ℃ for 20min, and subjected to UV curing on the transparent materials from 2-1 to 2-17.
The results of UV curing the UV-curable transparent materials 2-1 to 2-17 with a main peak wavelength of 365nm are shown in Table 1.
TABLE 1 List of UV-cured Material Properties of allyl-terminated hyperbranched copolymers of mercaptopolysiloxane and cage-polysilsesquioxane-carbosilane at different mercapto to allyl molar ratios
Figure BDA0002385365940000091
The transmittance curve for the cured product of 12 in Table 1 is shown in FIG. 5, which illustrates that the cured product has a very high transmittance in the visible range (400-800 nm).
Example 3
(1) 1.0g of octavinyl polysilsesquioxane (POSS-Vi)81.58mmol), 2.28g (3-mercaptopropyl) methyldimethoxysilane (12.64mmol), 50mL tetrahydrofuran and 50mL diethyl ether were added to a 250mL single neck round bottom flask equipped with a stir bar. And (3) irradiating the reaction mixture by using 1000W of UV light with the main peak wavelength of 365nm for reaction for 0.5h, and then removing the solvent and residual raw materials at the reduced pressure of 80 ℃/130mmHg to obtain the sulfur-containing hyperbranched copolymer of 8 methyl dimethoxy terminated cage-shaped polysilsesquioxane-carbosilane.
(2) Putting 60g of Mg scraps (2.500mol) and two pieces of iodine into a clean three-necked bottle under anhydrous and anaerobic conditions, then adding 1000ml of tetrahydrofuran, 1000ml of xylene and 1000ml of diethyl ether, cooling the mixed system to 20-30 ℃ by using an ice bath, and slowly dropwise adding a mixed solution of 100ml of tetrahydrofuran, 200ml of xylene, 200ml of diethyl ether and 252.0g of allyl bromide (2.100 mol). And after the dropwise addition is finished, reacting for 12 hours at the temperature of 20-30 ℃ to obtain a solution of the allyl magnesium bromide Grignard reagent.
40ml of a mixture of dry diethyl ether and 8 methyldimethoxy-terminated cage polysilsesquioxane-carbosilane-containing hyperbranched copolymers containing sulphur were slowly added dropwise to allyl bromide Grignard reagent and, after the addition, the reaction mixture was stirred overnight at room temperature. The reaction mixture was added to cooled 500mL of saturated NH4And (4) carrying out suction filtration on the Cl aqueous solution. The aqueous layer was extracted three times with 100mL of tetrahydrofuran, 200mL of diethyl ether, and the combined organic layers were washed three times with 100mL of deionized water, once with 100mL of saturated aqueous NaCl solution, and then with 40g of anhydrous MgSO4After drying, most of the volatiles were removed and the crude product was then precipitated as an oil by pouring the concentrated solution into 200mL methanol and 100mL isopropanol. The pure product was dried under vacuum to give 7.0g of a flowable viscous liquid, i.e., an allyl-terminated hyperbranched copolymer of 8 methyldiallylpropyl-terminated polyhedral oligomeric silsesquioxane-carbosilane.
(3) A mixture of 132.48g of deionized water and 8.785g of trifluoromethanesulfonic acid was added dropwise to a mixture of 78.54g of 3-mercaptopropyltrimethoxysilane, 79.63g of dimethyldiethoxysilane, 17.97g of methyltrimethoxysilane, 1.62g of hexamethyldisiloxane (in a proportion of 0.004mol/g of mercapto group, organic group/silicon atom of 1.5) and 744.6g of tetrahydrofuran at 30 ℃ with mechanical stirring, the reaction was continued at 30 ℃ for 48 hours after 0.5 hour of dropping, and then the mixture was washed with water to neutrality and the solvent, residual starting materials and low-molecular-weight products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 68.5g of colorless transparent mercapto-containing polysiloxane.
6.669g of mercaptopolysiloxane and 3.0g of allyl-terminated hyperbranched copolymer of 8 methyl diallyl-terminated polyhedral oligomeric silsesquioxane-carbosilane are uniformly mixed, vacuum defoamed at 130mmHg/30 ℃ for 20min, and then cured by UV with the main peak wavelength of 405nm for 30s to form a film, so that the UV-cured transparent material 3 is obtained.
The UV-curable transparent material 3 has the light transmittance of 90.8 percent, the pencil hardness of 5H and the thermal decomposition temperature of 354.5 ℃.
Example 4
(1) 1.0g of octavinyl polysilsesquioxane (POSS-Vi)81.58mmol), 2.456g (3-mercaptopropyl) methyldiethoxysilane (12.64mmol), 50mL tetrahydrofuran and 50mL diethyl ether were charged to a 250mL single neck round bottom flask equipped with a stir bar. After the reaction mixture is irradiated by UV light with the main peak wavelength of 405nm of 200W for reaction for 4h, the solvent and residual raw materials are removed under the reduced pressure of 80 ℃/130mmHg, and 8 methyl diethoxy methoxyl-terminated cage polysilsesquioxane-carbosilane sulfur-containing hyperbranched copolymers are obtained.
(2) 60g of Mg scraps (2.500mol) and two pieces of iodine are placed in a clean three-necked bottle under anhydrous and oxygen-free conditions, then 1000ml of tetrahydrofuran and 1000ml of toluene are added, and after the mixed system is cooled to 20-30 ℃ by using an ice bath, a mixed solution of 300ml of tetrahydrofuran, 200ml of toluene and 252.0g of allyl bromide (2.100mol) is slowly dropped. After the dropwise addition, reacting for 6h at 30-40 ℃ to obtain a solution of the allyl magnesium bromide Grignard reagent.
40ml of dry diethyl ether and 8 methyldiethoxymethoxy-terminated cage polysilsesquioxane-carbosilane containing sulfur hyperbranched copolymerThe mixture was slowly added dropwise to allyl bromide grignard reagent and after addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was added to cooled 200mL of saturated NH4And (4) carrying out suction filtration on the Cl aqueous solution. The aqueous layer was extracted three times with 100mL of tetrahydrofuran and 200mL of toluene, and the combined organic layers were washed three times with 100mL of deionized water, once with 100mL of saturated aqueous NaCl solution, and then with 40g of anhydrous MgSO4After drying, most of the volatiles were removed and the crude product was then precipitated as an oil by pouring the concentrated solution into 200mL methanol and 100mL isopropanol. The pure product was dried under vacuum to give 6.5g of a flowable viscous liquid, i.e., an allyl-terminated hyperbranched copolymer of 8 methyldiallylpropyl-terminated polyhedral oligomeric silsesquioxane-carbosilane.
(3) Under the condition of 70 ℃ and mechanical stirring, a mixture of 132.48g of deionized water and 1.1157g of concentrated sulfuric acid is dropwise added into a mixture of 78.54g of 3-mercaptopropyltrimethoxysilane, 36.6g of mercaptopropylmethyldimethoxysilane, 79.63g of dimethyldiethoxysilane, 17.97g of methyltrimethoxysilane, 10.4g of ethyl orthosilicate and 1.62g of hexamethyldisiloxane (according to the proportion that the mercapto content is 0.0065mol/g and the organic group/silicon atom is 2.0) and 224.2g of butyl acetate, after 0.5h of dropwise addition, the reaction is continued for 4h at 70 ℃, then the mixture is washed to be neutral by water, and the solvent, residual raw materials and low-molecular products are removed under reduced pressure at 130mmHg/170 ℃ to obtain 89.2g of colorless and transparent mercapto polysiloxane.
4.104g of mercapto polysiloxane and 3.0g of 8 methyl diallyl end-capped allyl end-capped hyperbranched copolymer of polyhedral oligomeric silsesquioxane-carbosilane are uniformly mixed, and the mixture is subjected to vacuum defoamation at 130mmHg/30 ℃ for 30min and then subjected to UV curing for 30s to form a film with the main peak wavelength of 365nm, so that the UV-cured transparent material 4 is obtained.
The UV-curable transparent material 4 has a light transmittance of 91.5%, a pencil hardness of 3H, and a thermal decomposition temperature of 334.5 ℃.
Example 5
The steps (1) and (2) are the same as in example 1.
(3) A mixture of 155.5g of deionized water and 3.5g of acetic acid was added dropwise to a mixture of 39.27g of 3-mercaptopropyltrimethoxysilane, 18.3g of mercaptopropylmethyldimethoxysilane, 79.63g of dimethyldiethoxysilane, 39.6g of methylphenyldimethoxysilane, 17.97g of methyltrimethoxysilane, 19.8g of phenyltrimethoxysilane, 10.4g of ethyl orthosilicate, and 1.62g of hexamethyldisiloxane (in a ratio of 0.002mol/g of mercapto group, 1.3 of organic group/silicon atom) and 350g of petroleum ether at 70 ℃ with mechanical stirring, and after 0.5h of dropping, the reaction was continued at 75 ℃ for 12h, followed by washing with water to neutrality, and the solvent, residual starting materials and low-molecular weight products were removed under reduced pressure at 130mmHg/170 ℃ to obtain 98.5g of colorless transparent mercapto-containing polysiloxane.
13.338g of mercaptopolysiloxane and 3.0g of the allyl-terminated hyperbranched copolymer of 24 allyl polyhedral oligomeric silsesquioxane-carbosilane in example 1 were uniformly mixed, subjected to vacuum deaeration at 130mmHg/30 ℃ for 5min, and subjected to UV curing with a main peak wavelength of 405nm for 30s to form a film, so as to obtain the UV-cured transparent material 5.
The UV-curable transparent material 5 has a light transmittance of 92.5%, a pencil hardness of 3H, and a thermal decomposition temperature of 338.5 ℃.
Example 6
The steps (1) and (2) are the same as in example 1.
(3) A mixture of 155.5g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid was added dropwise to a mixture of 42.56g of 3-mercaptopropyltriethoxysilane, 22.8g of mercaptopropylmethyldiethoxysilane, 79.63g of dimethyldiethoxysilane, 39.6g of diphenyldiethoxysilane, 17.97g of methyltriethoxysilane, 19.8g of phenyltriethoxysilane, 11.8g of methyl orthosilicate, 1.62g of hexamethyldisiloxane (ratio of 0.3mol/g of mercapto group content, organic group/silicon atom: 1.5) and 350g of petroleum ether at 80 ℃ with mechanical stirring, and after 0.5h of dropping, the reaction was continued at 80 ℃ for 0.5h, followed by washing with water to neutrality and removal of the solvent, residual starting materials and low molecular weight products at 130 ℃/170 ℃ under reduced pressure to obtain 98.5g of colorless transparent mercaptopolylsiloxane.
8.892g of mercaptopolysiloxane and 3.0g of the allyl-terminated hyperbranched copolymer of 24 allyl polyhedral oligomeric silsesquioxane-carbosilane in example 1 were uniformly mixed, subjected to vacuum deaeration at 130mmHg/30 ℃ for 5min, and subjected to UV curing with a main peak wavelength of 405nm for 30s to form a film, so as to obtain the UV-cured transparent material 6.
The UV-curable transparent material 6 has the light transmittance of 91.8 percent, the pencil hardness of 4H and the thermal decomposition temperature of 346.0 ℃.
Example 7
The steps (1) and (2) are the same as in example 1.
(3) A mixture of 155.5g of deionized water and 3.5g of 36.5% concentrated hydrochloric acid was added dropwise to a mixture of 52.85g of 3-mercaptopropyltriethoxysilane, 32.8g of mercaptopropylmethyldiethoxysilane, 79.63g of dimethyldiethoxysilane, 39.6g of diphenyldiethoxysilane, 17.97g of methyltriethoxysilane, 19.8g of phenyltriethoxysilane, 11.8g of methyl orthosilicate, and 1.62g of hexamethyldisiloxane (in a proportion of 0.45mol/g of mercapto group content and 1.5 of organic group/silicon atom), 100g of toluene and 150g of xylene, at 80 ℃ and with mechanical stirring, and after 0.5h of dropping, the reaction was continued at 80 ℃ for 0.5h, followed by washing with water to neutrality and removal of the solvent, residual starting materials and low molecular weight products under reduced pressure at 130/170 ℃ to obtain 98.5g of colorless transparent mercaptopolysiloxane-containing 98.5 g.
5.928g of mercaptopolysiloxane and 3.0g of the allyl-terminated hyperbranched copolymer of 24 allyl polyhedral oligomeric silsesquioxane-carbosilane in example 1 were uniformly mixed, subjected to vacuum defoaming at 130mmHg/30 ℃ for 5min, and subjected to UV curing with a main peak wavelength of 365nm for 30s to form a film, so as to obtain a UV-cured transparent material 7.
The UV-cured transparent material 7 has the light transmittance of 90.4 percent, the pencil hardness of 6H and the thermal decomposition temperature of 356.0 ℃.
Test example
In example 1, the photo of cured products of the 24 allyl polyhedral oligomeric silsesquioxane-carbosilane allyl terminated hyperbranched copolymer and the mercaptopolysiloxane with 0.004mol/g of mercapto group content and different R/Si are shown in FIG. 3, and the photo of cured products of the 24 allyl polyhedral oligomeric silsesquioxane-carbosilane terminated hyperbranched copolymer and the mercaptol group content of 0.004mol/g and the molar ratio of mercapto group to allyl group are shown in FIG. 4. Therefore, the UV curing transparent material has good transparency.
Comparative example
The procedure of example 2 was followed, and the curing time in step (3) was 5 seconds.
Figure BDA0002385365940000131
Indicating that too short a curing time will affect the pencil hardness of the UV cured transparent material.
The UV curing transparent material prepared by the embodiment has the light transmittance of more than 90 percent in a light wave range of 400-800nm, the pencil hardness of controllable in a range of B-7H, the water absorption of 0.02-0.25 wt percent and the initial thermal decomposition of 260-360 ℃. The obtained transparent organic silicon coating material has better scratch resistance, and is expected to be used for solvent-free UV-cured solid wood furniture paint, UV-cured PET release films, UV-cured LED packaging and protective layers of optical transparent electronic devices.

Claims (10)

1. A preparation method of a UV curing transparent material is characterized by comprising the following steps:
(1) stirring octavinyl cage polysilsesquioxane and mercaptopropyl alkoxy silane in a reaction solvent A, carrying out UV irradiation reaction, decompressing and desolventizing and residual raw materials to obtain an alkoxy-terminated sulfur-containing hyperbranched copolymer of cage polysilsesquioxane-carbosilane;
(2) performing Grignard reaction on the product obtained in the step (1) under anhydrous and oxygen-free conditions to obtain a polyhedral oligomeric silsesquioxane-carbosilane allyl terminated hyperbranched copolymer;
(3) mixing the allyl-terminated hyperbranched copolymer of cage-shaped polysilsesquioxane-carbosilane with polysiloxane containing sulfydryl, removing bubbles, and carrying out UV curing for 10-120 s to obtain the UV-cured transparent material.
2. The method for preparing a UV-curable transparent material according to claim 1, wherein the molar ratio of vinyl groups to mercaptopropyl groups in the amount of octavinyl polysilsesquioxane to mercaptopropyl siloxane used in step (1) is 1:1 to 1: 1.2.
3. The method for preparing a UV curable transparent material according to claim 1 or 2, wherein in step (1), the mercaptopropylalkoxysilane is one or more selected from the group consisting of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane and mercaptopropylmethyldiethoxysilane, and the reaction solvent A is one or more selected from the group consisting of tetrahydrofuran, diethyl ether, toluene, xylene and petroleum ether.
4. The method for preparing a UV curable transparent material according to claim 1, wherein the reaction conditions of UV irradiation in step (1) are as follows: the light source power is 100W-1000W, the main peak wavelength is 365nm or 405nm, the distance from the light source is 20cm, and the irradiation reaction is carried out for 0.5-6 h.
5. The method for preparing the UV-curable transparent material according to claim 1, wherein the molar ratio of the mercapto group to the allyl group in the allyl-terminated hyperbranched copolymer of cage-shaped polysilsesquioxane-carbosilane and the mercapto group-containing organosilicon polymer in step (3) is 0.6:1 to 1.3: 1.
6. The method as claimed in claim 1, wherein the power of the UV curing light source in step (3) is 500-1000W, the wavelength of the main peak is 365nm or 405nm, and the distance from the light source is 20 cm.
7. The method for preparing a UV-curable transparent material according to claim 1 or 5, wherein the mercapto group-containing polysiloxane in step (3) is prepared by: the preparation method comprises the steps of cohydrolyzing and condensing hydrosulfide-containing alkoxy silane, other alkoxy siloxane and end-capping agent hexamethyldisiloxane in an organic solvent C under the catalysis of an acid catalyst, washing the mixture to be neutral, and removing the organic solvent C, residual raw materials and low-molecular products under reduced pressure to obtain the product.
8. The method of claim 7, wherein the amount of the acidic catalyst is 0.05 to 5wt% of the total mass of the raw materials, the amount of water is 1 to 2.5 times the mole number of all alkoxy groups in the raw materials, the mole ratio of the mercaptosiloxane to other alkoxysilanes is 0.05 to 0.65, and the mole ratio of all organic groups to silicon atoms is 1.3 to 2.0.
9. The method for preparing the UV-curable transparent material according to claim 7, wherein the temperature of the cohydrolysis-condensation reaction is 30-80 ℃ and the reaction time is 0.5-48 h.
10. Use of the UV cured transparent material obtained by the method of any one of claims 1 to 9 in UV cured solid wood furniture lacquer, UV cured PET release film, UV cured LED packaging, protective layers for optically transparent electronics.
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