PHOTO-INDUCED CATIONIC POLYMERIZED PURE VEGETABLE OIL-BASED POLYMER, PREPARATION METHOD AND USE THEREOF

Abstract

The present invention relates to a photo-induced cationic polymerized pure vegetable oil-based polymer and a preparation method and use thereof. The preparation method comprises the following steps: mixing a dry oil, an epoxy vegetable oil and an initiator uniformly, irradiating to initiate a photo-curing reaction, and then placing at ambient temperature, and continuing to a heat-curing reaction so as to obtain a photo-induced cationic polymerized pure vegetable oil-based polymer. In the present invention, vegetable oil resources which are low in price, widespread, and easy to regenerate are used to prepare the pure vegetable oil-based polymers instead of the fossil-derived monomers completely, thereby achieving the efficient use of vegetable oils. In the present invention, an unconventional photo-induced heat frontal polymerization technology is used to prepare the pure vegetable oil-based polymer, thereby achieving a photo-thermal dual curing reaction of a vegetable oil system without heating. The preparation method of the present invention is simple, mild in the conditions, energy-saving and environment-friendly, stable in the product quality, and suitable for large-scale production.

Claims

1. A method for preparing a photo-induced cationic polymerized pure vegetable oil-based polymer, characterized by comprising the following steps: a dry oil, an epoxy vegetable oil and an initiator are mixed uniformly, irradiated, and then placed at ambient temperature and continued to heat-curing reaction, so as to obtain a photo-induced cationic polymerized pure vegetable oil-based polymer.

2. The method for preparing a photo-induced cationic polymerized pure vegetable oil-based polymer according to claim 1, characterized in that the dry oil is at least one of tung oil, linseed oil and Chinese tallow tree seed oil.

3. The method for preparing a photo-induced cationic polymerized pure vegetable oil-based polymer according to claim 1, characterized in that the epoxy vegetable oil is at least one of epoxy castor oil, epoxy soybean oil, epoxy linseed oil, epoxy rapeseed oil and epoxy tung oil.

4. The method for preparing a photo-induced cationic polymerized pure vegetable oil-based polymer according to claim 1, characterized in that the initiator is a photo-thermal dual initiator, particularly at least one of 2,4,6-triphenylpyranotetrafluoroborate, diaryliodonium salt, triarylsulfonium salt and alkylsulfonium salt.

5. The method for preparing a photo-induced cationic polymerized pure vegetable oil-based polymer according to claim 1, characterized in that the irradiation time is 1-5 min, and the light source is a UV-LED point light source with a wavelength of 365 nm.

6. The method for preparing a photo-induced cationic polymerized pure vegetable oil-based polymer according to claim 1, characterized in that the heat-curing reaction time after the irradiation is 10-30 min.

7. The method for preparing a photo-induced cationic polymerized pure vegetable oil-based polymer according to claim 1, characterized in that the mass ratio of various raw materials is 15-80% of the dry oil, 15-80% of the epoxy vegetable oil, and 1-5% of the initiator.

8. A photo-induced cationic polymerized pure vegetable oil-based polymer prepared by the method of claim 1.

9. Use of a light-induced cationic polymerized pure vegetable oil-based polymer according to claim 1 in the field of polymer materials.

10. The use according to claim 9, characterized in that the photo-induced cationic polymerized pure vegetable oil-based polymer is applied in the fields of coatings, inks, adhesives, plastics, fibers, 3D printing and composites.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, the present invention will be further described in detail with reference to the examples, but the embodiments of the present invention are not limited thereto. The materials involved in the following examples are all commercial available.

Example 1

[0021] 80 g of tung oil, 19 g of epoxy soya oil and 1 g of TPP are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm, and irradiated for 1 min, and finally, continued to reaction at room temperature for 10 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 120° C., which can effectively initiate the heat-curing reaction in the late-stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

Example 2

[0022] 20 g of linseed oil, 78 g of epoxy linseed oil and 2 g of diaryliodonium salt are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm, and irradiated for 5 min, and finally placed at room temperature and continued to reaction for 20 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 119° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

Example 3

[0023] 60 g of Chinese tallow tree seed oil, 37 g of epoxy rapeseed oil and 3 g of triarylsulfonium salt are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm, and irradiated for 3 min, and finally placed at room temperature and continued to reaction for 30 min, so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 124° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

Example 4

[0024] 16 g of tung oil, 80 g of epoxy tung oil and 4 g of alkylsulfonium salt are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm, and irradiated for 3 min, and finally placed at room temperature, and continued to reaction for 15 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 118° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

Example 5

[0025] 15 g of linseed oil, 80 g of epoxy castor oil and 5 g of TPP are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm, and irradiated for 3 min, and finally placed at room temperature, and continued to reaction for 20 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 120° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system

Example 6

[0026] 80 of Chinese tallow tree seed oil, 15 g of epoxy soybean oil and 5 g of diaryliodonium salt are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm and irradiated for 3 min, and finally placed at room temperature and continued to reaction for 30 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 119° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

Example 7

[0027] 40 g of tung oil, 57 g of epoxy castor oil and 3 g of triarylsulfonium salt are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm and irradiated for 3 min, and finally placed at room temperature and continued to reaction for 10 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 121° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

Example 8

[0028] 50 g of linseed oil, 48 g of epoxy linseed oil and 2 g of alkyl sulfonium salt are added to a transparent glass reactor, stirred uniformly, then placed under a UV-LED point light source with a wavelength of 365 nm and irradiated for 3 min, and finally placed at room temperature and continued to reaction for 20 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 122° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

Example 9

[0029] 29 g of Chinese tallow tree seed oil, 70 g of epoxy rapeseed oil and 1 g of TPP are added to a transparent glass reactor, stirred uniformly, and then placed under a UV-LED point light source with a wavelength of 365 nm and irradiated for 3 min, and finally placed at room temperature and continued to reaction for 30 min so as to obtain a pure vegetable oil-based polymer. During the reaction, a thermometer is used to monitor the temperature change of the reaction system. As shown in the tests by means of thermometer, the reaction temperature in the system at the end of the irradiation reaches 118° C., which can effectively initiate the heat-curing reaction in the late stage, indicating that the initiator can successfully initiate the photo-induced heat frontal polymerization in the system.

[0030] Performance tests of the pure vegetable oil-based polymer prepared in each example.

[0031] The degree of crosslinking is characterized by the gel rate, wherein the higher the gel rate, the higher the degree of crosslinking. The gel content of the cured coating is determined by an acetone method, wherein each cured coating is immersed in 20 mL acetone-containing glass vial at room temperature for 48 h, then dried at 60° C. until constant weight. Gel rate=W.sub.1/W.sub.0×100%, wherein W.sub.0 and W.sub.1 represent the mass before soaking and after soaking and drying, respectively.

[0032] Hardness tests are carried out according to Paints and varnishes-Determination of film hardness by pencil test (GB/T 6739-2006).

[0033] Thermal Stability Analysis (TGA analysis) is carried out by using Thermogravimetric Analyzer Type STA 449C from Netzsch Corporation, Germany, to test the abovementioned cured films, with heating rate: 10° C./min; atmosphere: nitrogen; temperature range: 35-660° C. The initial decomposition temperature when the mass loss of each example reaches 5% is recorded in Table 1.

[0034] Dynamic Thermal Mechanical Analysis (DMA) is carried out by using Dynamic Mechanical Analyzer DMA 242C, from Netzsch Corporation, Germany, to test the abovementioned cured films, with sample holder: stretch holder; oscillation frequency: 1 Hz; sample size: 20 mm×6 mm×0.5 mm; heating rate: 3° C./min; temperature range: −80-180° C. The measured glass transition temperature (Tg) of the cured film is reported in Table 1.

[0035] Mechanical Performance Analysis is carried out by using Universal Testing Machine type AGS-X 1 kN, from Shimadzu Corporation, Japan, to test the abovementioned cured films, with cross head speed: 10 mm/min; sample size: 40 mm×10 mm×0.5 mm.

TABLE-US-00001 TABLE 1 Comprehensive performance test results of the final product of each example Initial Degree of Decomposition Tensile Elongation Example Crosslinking/% Hardness TemperatureT.sub.5%/° C. T.sub.g/° C. Strength/MPa at Break/% 1 98.6 6H 362.8 56.2 38.46 2.45 2 98.8 6H 367.5 54.6 38.34 2.66 3 99.0 6H 366.8 55.6 37.99 2.62 4 98.5 6H 365.7 54.4 38.21 2.21 5 98.6 6H 366.5 55.8 38.36 2.56 6 98.7 6H 367.6 54.2 38.87 2.62 7 98.8 6H 366.6 55.9 38.35 2.44 8 98.6 6H 362.8 55.4 37.90 2.34 9 98.9 6H 368.4 56.0 38.11 2.78

[0036] The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited thereto. Any other changes, modifications, alternatives, combinations, and simplifications, made without departing from the spirit and principles of the present invention, which should be equivalent replacements, all fall in the scope of protection of the present invention.