Self-healing copolymerized polycarbonate and preparation method therefor

Abstract

The invention relates to a self-healing copolymerized polycarbonate and a preparation method thereof. The method comprises the following steps: mixing a reducing sugar, an oxetane derivative and a first catalyst, heating and reacting at 50 to 80° C. for 0.5 to 2 h to obtain the first product; adding a diol, a diester and a second catalyst to the first product, and then heating to 180 to 220° C. for 2 to 4 h to obtain an oligomer; heating the oligomer to 230 to 270° C. and holding at the temperature and reacting for 1 to 3 h to obtain a self-healing copolymerized polycarbonate. The self-healing copolymerized polycarbonate material prepared by the method of the invention has self-healing property and biodegradability, which ensures the consistency and uniformity of the product. In addition, the block introduced into the main chain is green and environmentally friendly, and the original intention of clean production of polycarbonate has not been changed.

Claims

1. A method for preparing a self-healing copolymerized polycarbonate, comprising the following steps: S101: mixing a reducing sugar, an oxetane derivative and a first catalyst, heating the mixture to 50 to 80° C., and stirring and reacting under a protective gas condition for 0.5 to 2 h to obtain a first product, wherein: the molar ratio of the reducing sugar to the oxetane derivative is (0.5-0.8):1; and the reducing sugar is at least one of glucose, fructose, galactose, lactose and maltose; S102: adding a diol, a diester, and a second catalyst to the first product, and then heating to 180 to 220° C. for 2 to 4 h to obtain an oligomer, wherein the molar ratio of the first product, the diol and the diester is (0.07-0.13):(0.9-1.0):1; and S103: heating the oligomer to 230 to 270° C. and holding at the temperature and reacting for 1 to 3 h to obtain a self-healing copolymerized polycarbonate.

2. The method for preparing a self-healing copolymerized polycarbonate in claim 1, wherein in the step S101, the oxetane derivative is at least one of 3-(chloromethyl)-3-methyloxetane, 3-(bromomethyl)-3-methyloxetane, 3-(bromomethyl)-3-ethyloxetane, and 3-(chloromethyl)-3-ethyloxetane.

3. The method for preparing a self-healing copolymerized polycarbonate in claim 1, wherein in the step S101, the catalyst is a Lewis base.

4. The method for preparing a self-healing copolymerized polycarbonate in claim 1, wherein in the step S101, the catalyst is at least one of KOH, K.sub.2CO.sub.3, and CsCO.sub.3.

5. The method for preparing a self-healing copolymerized polycarbonate in claim 1, wherein in the step S101, the protective gas is nitrogen gas.

6. The method for preparing a self-healing copolymerized polycarbonate in claim 1, wherein in the step S102, the diol is bisphenol A, and the diester is diphenyl carbonate.

7. The method for preparing a self-healing copolymerized polycarbonate in claim 1, wherein in step S101, the mass of the first catalyst is 0.05 to 0.1% of the mass of the reducing sugar.

8. The method for preparing a self-healing copolymerized polycarbonate in claim 1, wherein in the step S102, the ratio of the total molar mass of the first product and the diol to the molar mass of the diester is 1.03:1≤n.sub.1:n.sub.2≤1.1:1, wherein n.sub.1 represents the total molar mass of the first product and the diol, and n.sub.2 represents the molar mass of the diester.

9. A self-healing copolymerized polycarbonate, prepared by a method for preparing a self-healing copolymerized polycarbonate, comprising the following steps: S101: mixing a reducing sugar, an oxetane derivative and a first catalyst, heating the mixture to 50 to 80° C., and stirring and reacting under a protective gas condition for 0.5 to 2 h to obtain a first product, wherein the molar ratio of the reducing sugar to the oxetane derivative is (0.5-0.8):1; S102: adding a diol, a diester, and a second catalyst to the first product, and then heating to 180 to 220° C. for 2 to 4 h to obtain an oligomer, wherein the molar ratio of the first product, the diol and the diester is (0.07-0.13):(0.9-1.0):1; and S103: heating the oligomer to 230 to 270° C. and holding at the temperature and reacting for 1 to 3 h to obtain a self-healing copolymerized polycarbonate.

10. The self-healing copolymerized polycarbonate in claim 9, wherein in the step S101, the reducing sugar is at least one of glucose, fructose, galactose, lactose and maltose.

11. The self-healing copolymerized polycarbonate in claim 9, wherein in the step S101, the oxetane derivative is at least one of 3-(chloromethyl)-3-methyloxetane, 3-(bromomethyl)-3-methyloxetane, 3-(bromomethyl)-3-ethyloxetane, and 3-(chloromethyl)-3-ethyloxetane.

12. The self-healing copolymerized polycarbonate in claim 9, wherein in the step S101, the catalyst is a Lewis base.

13. The self-healing copolymerized polycarbonate in claim 9, wherein in the step S101, the catalyst is at least one of KOH, K.sub.2CO.sub.3, and CsCO.sub.3.

14. The self-healing copolymerized polycarbonate in claim 9, wherein in the step S101, the protective gas is nitrogen gas.

15. The self-healing copolymerized polycarbonate in claim 9, wherein in the step S102, the diol is bisphenol A, and the diester is diphenyl carbonate.

16. The self-healing copolymerized polycarbonate in claim 9, wherein in step S101, the mass of the first catalyst is 0.05 to 0.1% of the mass of the reducing sugar.

17. The self-healing copolymerized polycarbonate in claim 9, wherein in the step S102, the ratio of the total molar mass of the first product and the diol to the molar mass of the diester is 1.03:1≤n.sub.1:n.sub.2≤1.1:1, wherein n.sub.1 represents the total molar mass of the first product and the diol, and n.sub.2 represents the molar mass of the diester.

Description

BRIEF DESCRIPTION OF FIGURES

(1) FIG. 1a is a microscopic image of scratch made on the surface of the product of the embodiment of the present invention with a diamond tip; and

(2) FIG. 1b is a microscopic image of the scratched area of FIG. 1a after self-healing.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(3) Hereinafter, embodiments of the present invention will be described in detail. Examples of the embodiments are shown in the accompanying drawings; wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The examples described below with reference to the drawings are exemplary and are intended to explain the present invention, but should not be construed as limiting the present invention.

(4) Unless otherwise specified, the experimental methods in the following embodiments are conventional methods.

(5) Unless otherwise specified, the test materials used in the following examples are purchased from conventional reagent stores.

(6) For the quantitative tests in the following examples, three repeated experiments are set, and the data are the mean value or the mean value±standard deviation of the three repeated experiments.

Example 1

(7) (a) 1.6 mol of glucose, 2 mol of 3-chloromethyl-3-methyl-butylene oxide, and a catalyst cesium carbonate (0.1% by mass of glucose) were reacted under the protection of N.sub.2 at 80° C. for 0.5 h to obtain a product 1; (b) a diol and a diester were added to the obtained product 1 (the molar ratio of the three was 0.07:1:1), the mixture was heated up to 220° C. to react for 2 h to obtain an oligomer; and (c) the oligomer was heated up to 270° C., and the reaction was continued for 1.5 h to obtain a polycarbonate copolymer.

Example 2

(8) (a) 1 mol of glucose, 2 mol of 3-chloromethyl-3-methyl-butylene oxide, and a catalyst cesium carbonate (0.05% by mass of glucose) were reacted under the protection of N.sub.2 at 50° C. for 2 h to obtain a product 1; (b) a diol and a diester were added to the obtained product 1 (the molar ratio of the three was 0.13:0.9:1), the mixture was heated up to 180° C. to react for 4 h to obtain an oligomer; and (c) the oligomer was heated up to 230° C., and the reaction was continued for 3 h to obtain a polycarbonate copolymer.

Example 3

(9) (a) 1.8 mol of glucose, 2 mol of 3-chloromethyl-3-methyl-butylene oxide, and a catalyst cesium carbonate (0.08% by mass of glucose) were reacted under the protection of N.sub.2 at 70° C. for 1.5 h to obtain a product 1; (b) a diol and a diester were added to the obtained product 1 (the molar ratio of the three was 0.1:1:1), the mixture was heated up to 210° C. to react for 4 h to obtain an oligomer; and (c) the oligomer was heated up to 250° C., and the reaction was continued for 2 h to obtain a polycarbonate copolymer.

Example 4

(10) (a) 1.8 mol of glucose, 2 mol of 3-chloromethyl-3-methyl-butylene oxide, and a catalyst cesium carbonate (0.08% by mass of glucose) were reacted under the protection of N.sub.2 at 70° C. for 1.5 h to obtain a product 1; (b) a diol and a diester were added to the obtained product 1 (the molar ratio of the three was 0.1:1:1), the mixture was heated up to 210° C. to react for 4 h to obtain an oligomer; and (c) the oligomer was heated up to 250° C., and the reaction was continued for 2 h to obtain a polycarbonate copolymer.

(11) As shown in FIG. 1, the products obtained in Examples 1 to 4 were made into a 4 cm*4 cm film, and a scratch test was performed on the surface of the film with a diamond tip. The artificially made scratches were exposed to 120 W of fluorescent ultraviolet light having a wavelength of 302 nm for 30 minutes. It can be seen that after self-healing, the original clear scratches almost disappeared.

(12) The principle may be as shown in scheme 1:

(13) ##STR00001##

(14) In summary, the self-healing copolymerized polycarbonate material prepared by the method of the present invention has self-healing property and biodegradability. The self-healing copolymerized polycarbonate is obtained by introducing a modified reducing sugar into the main chain of polycarbonate, belonging to block copolymerization, which ensures the consistency and uniformity of the product. In addition, the block introduced into the main chain is green and environmentally friendly, and the original intention of clean production of polycarbonate has not been changed.

(15) In the specification, the description with reference to the terms “one embodiment”, “some embodiments”, “examples”, “specific examples”, or “some examples” and the like means that the specific features, structures, materials, or characteristics described in combination with the embodiments or examples are included in at least one embodiment or example of the present invention. In the specification, the schematic expressions of the above terms are not necessarily directed to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in any suitable manner. In addition, without any contradiction, those skilled in the art may combine and assemble different embodiments or examples and features of the different embodiments or examples described in the specification.

(16) Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limitations on the present invention. Those skilled in the art may carry out change, modification, substitution, and variation of the above embodiments within the scope of the invention.