A prepolymer that can be used to prepare ductile PC material and its preparation method

Abstract

The present invention relates to the field of polymer materials and relates to a method for preparing a prepolymer that can be used to prepare ductile PC materials. The method comprises dissolving cyclohexene oxide and 1 mol of a catalyst in toluene under a nitrogen atmosphere and stirring the mixture at high speed in an autoclave under a CO2 atmosphere. Two mol of a dihydroxy intermediate complex are then added, the reaction continues, and finally, dichloromethane is added to terminate the reaction, resulting in the precipitation of a dihydroxy-terminated PC prepolymer in methanol. Compared to the prior art, the present invention provides a dihydroxy-terminated PC prepolymer and its preparation method, which can be used to prepare ductile PC materials. The molecular chain length of the prepolymer can be adjusted based on the molecular weight of the dihydroxy intermediate complex. By adjusting the molecular chain length of the prepolymer, the ductility (flexibility) of the PC material can be adjusted accordingly.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and in particular to a prepolymer that can be used to prepare ductile PC materials and a preparation method thereof. Background Art

[0002] Polycarbonate (PC), with its combination of high impact strength and good transparency, is a promising material that will become increasingly important in future engineering applications. For decades, numerous research groups have been investigating it, particularly as a potential replacement for polycarbonate (PC). To date, the standard for industrial PC production remains bisphenol A-based PC (BPA-PCs). However, due to the large number of benzene rings in its structure, its structure is severely affected by ultraviolet light. In recent years, researchers have considered replacing BPA-PCs with aliphatic polycarbonates, but these are unlikely to be suitable substitutes for BPA-PC in terms of thermal and mechanical properties. Polycyclohexene carbonate (PCHC) has been reported to exhibit relatively high Tg and elastic modulus. However, the main obstacle to the large-scale industrial application of PCHC is its high brittleness. Therefore, the preparation of a polycarbonate with these properties is a current research priority and will have significant implications for the future improvement of polycarbonate material performance. Summary of the Invention

[0003] In view of this, the technical problem to be solved by the present invention is to provide a prepolymer that can be used to prepare ductile PC materials, so as to achieve toughening of PCHC.

[0004] Preparation of Chromium (III) Coordination Derivative Catalysts

[0005] The present invention provides a prepolymer that can be used to prepare a ductile PC material and a preparation method thereof, wherein the catalyst preparation method of the prepolymer is as follows:

[0006] 1 mol of dimethylaminoethylamino-N,N-bis(2-methylene-4,6-tert-butylphenolate) and 4 mol of sodium hydride were placed in a Schlenk tube and cooled to -78°C. An appropriate amount of tetrahydrofuran solution was added to obtain a white suspension, which was then warmed to room temperature and stirred for 2 hours. This mixture was then transferred via a filter cannula to a suspension of 1 mol of CrCl₃(THF)₃ in tetrahydrofuran and cooled again to -78°C to obtain a pink mixture. The resulting mixture was warmed to room temperature and stirred overnight to obtain a dark purple solution. The solution was filtered and evaporated to dryness. The residue was extracted into toluene, filtered through celite, and the solvent removed under vacuum. The residue was washed with pentane and dried to obtain a purple powder of the chromium(III) coordination derivative catalyst.

[0007]

[0008] Preparation of dihydroxy intermediate ligands

[0009] The present invention provides a prepolymer that can be used to prepare a ductile PC material and a preparation method thereof, wherein the preparation method of the dihydroxy intermediate complex is as follows:

[0010] Polypropylene glycol and a chromium (III) coordination derivative catalyst were dissolved in dry toluene and stirred at 100°C under an argon atmosphere for 3 days. After cooling to room temperature, the solvent was removed by rotary evaporation to obtain a pure yellow solid, i.e., the dihydroxy intermediate complex.

[0011]

[0012] Preparation of dihydroxy-terminated PC prepolymer

[0013] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. 2 mol of the dihydroxy intermediate complex was then added, and the reaction continued for 2 hours. Finally, dichloromethane was added to terminate the reaction, and the dihydroxy-terminated PC prepolymer was precipitated in methanol.

[0014]

[0015] Beneficial effects

[0016] 1. Compared to the prior art, the present invention provides a dihydroxy-terminated PC prepolymer and its preparation method, which can be used to prepare ductile PC materials. The molecular chain length of the prepolymer can be adjusted based on the molecular weight of the dihydroxy intermediate complex. By adjusting the molecular chain length of the prepolymer, the ductility (flexibility) of the PC material can be adjusted accordingly.

[0017] Figures in the specification

[0018] Figure 1 The H-NMR spectrum of the dihydroxy-terminated PC prepolymer is shown;

[0019] Figure 2 Represents the NMR spectrum of dihydroxy-terminated PC prepolymer. Example

[0020] like Figure 1 、 2 Shown are the H-NMR spectrum and C-NMR spectrum of PC prepolymer, respectively.

[0021] Example 1

[0022] 1 mol of PPG (100 g / mol) and 1 mol of a chromium (III) coordination derivative catalyst were dissolved in dry toluene and stirred at 100°C under argon for 3 days. After cooling to room temperature, the solvent was removed by rotary evaporation to obtain a pure yellow solid.

[0023] Example 2

[0024] 1 mol of PPG (500 g / mol) and 1 mol of chromium (III) coordination derivative catalyst were dissolved in dry toluene and stirred at 100°C under argon atmosphere for 3 days. After cooling to room temperature, the solvent was removed by rotary evaporation to obtain a pure yellow solid.

[0025] Example 3

[0026] 1 mol of PPG (1000 g / mol) and 1 mol of chromium (III) coordination derivative catalyst were dissolved in dry toluene and stirred at 100°C under argon atmosphere for 3 days. After cooling to room temperature, the solvent was removed by rotary evaporation to obtain a pure yellow solid.

[0027] Example 4

[0028] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 1 was added, and the reaction continued for 1 hour. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0029] Example 5

[0030] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 1 was added, and the reaction continued for 2 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0031] Example 6

[0032] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 1 was added, and the reaction continued for 3 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0033] Example 7

[0034] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 1 was added, and the reaction continued for 4 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0035] Example 8

[0036] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 2 was added, and the reaction continued for 1 hour. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0037] Example 9

[0038] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 2 was added, and the reaction continued for 2 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0039] Example 10

[0040] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 2 was added, and the reaction continued for 3 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0041] Example 11

[0042] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 2 was added, and the reaction continued for 4 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0043] Example 12

[0044] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 3 was added, and the reaction continued for 1 hour. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0045] Example 13

[0046] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 3 was added, and the reaction continued for 2 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0047] Example 14

[0048] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 3 was added, and the reaction continued for 3 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0049] Example 15

[0050] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 3 was added, and the reaction continued for 4 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0051] Example 16

[0052] Under a nitrogen atmosphere, 50 mol of cyclohexene oxide and 1 mol of catalyst were dissolved in toluene and stirred at 600 rpm / min in an autoclave under a CO2 atmosphere for 6 hours. Then, 2 mol of the bishydroxy intermediate complex from Example 3 was added, and the reaction continued for 5 hours. Finally, dichloromethane was added to terminate the reaction, and a bishydroxy-terminated PC prepolymer was precipitated in methanol.

[0053] Table 1 Molecular weight of intermediate complexes prepared with different polypropylene glycols

[0054] sample Mn (g / mol) Example 1 760 Example 2 1160 Example 3 1660

[0055] The data in Table 1 prove that the catalyst can form complexes with polypropylene glycol of different molecular weights.

[0056] Table 2 Molecular weight and molecular weight distribution of reactants and intermediate complexes of Example 1 after reaction for different times

[0057] sample Mn (g / mol) Mw / Mn Example 4 6500 1.12 Example 5 7800 1.09 Example 6 7820 1.02 Example 7 7829 1.03

[0058] The data in Table 2 prove that the reactants and the intermediate complex of Example 1 have basically reached a reaction equilibrium state after 1 hour of reaction.

[0059] Table 3 Molecular weight and molecular weight distribution of reactants and intermediate complexes of Example 2 after reaction for different times

[0060] sample Mn (g / mol) Mw / Mn Example 8 8600 1.33 Example 9 11600 1.25 Example 10 13200 1.02 Example 11 13210 1.03

[0061] The data in Table 3 prove that the reactants and the intermediate complex of Example 2 have basically reached a reaction equilibrium state after 3 hours of reaction.

[0062] Table 4 Molecular weight and molecular weight distribution of the reactants and the intermediate complex of Example 3 after reaction for different times

[0063] sample Mn (g / mol) Mw / Mn Example 12 9700 1.27 Example 13 13500 1.21 Example 14 16800 1.16 Example 15 17500 1.09 Example 16 17510 1.03

[0064] The data in Table 4 prove that the reactants and the intermediate complex of Example 3 have basically reached a reaction equilibrium state after 4 hours of reaction.

[0065] Based on the data in Table 2-4, we can see that when the molecular weight is 100 g / mol, the time required to reach equilibrium is 1 hour; when the molecular weight is 500 g / mol, the time required to reach equilibrium is 3 hours; and when the molecular weight is 500 g / mol, the time required to reach equilibrium is 4 hours. From the above data, we can conclude that as the molecular weight of polypropylene glycol increases, the time required for the reaction of the complex to reach equilibrium increases accordingly.

[0066] The foregoing description is merely a preferred embodiment of the present invention. It should be understood that the present invention is not limited to the form disclosed herein and should not be construed as excluding other embodiments. Rather, the present invention can be used in various other combinations, modifications, and environments and can be modified within the scope of the concept described herein through the above teachings or techniques or knowledge in the relevant field. Modifications and variations made by those skilled in the art that do not depart from the spirit and scope of the present invention are intended to be protected by the appended claims.

Claims

1. A method for preparing a prepolymer for preparing ductile PC material, characterized in that: The preparation method comprises the following steps: dissolving cyclohexene oxide and 1 mol of a catalyst in toluene under a nitrogen atmosphere, and stirring the mixture at high speed in a high-pressure reactor under a CO2 atmosphere; then adding 2 mol of a dihydroxy intermediate complex, continuing the reaction, and finally adding dichloromethane to terminate the reaction, thereby precipitating a dihydroxy-terminated PC prepolymer in methanol; The preparation method of the dihydroxy intermediate complex comprises dissolving polypropylene glycol and a chromium (III) coordination derivative catalyst in dry toluene and stirring the mixture under an argon atmosphere at 100° C.; cooling the mixture to room temperature and removing the solvent by rotary evaporation to obtain a pure yellow solid, namely the dihydroxy intermediate complex.

2. The method for preparing a prepolymer for preparing a ductile PC material according to claim 1, characterized in that: The molar ratio of the polypropylene glycol to the chromium (III) coordination derivative catalyst is 1:1, and the molecular weight of the polypropylene glycol is 100-2000 g / mol.

3. The method for preparing a prepolymer for preparing a ductile PC material according to claim 1, characterized in that: The molar ratio of the cyclohexene oxide, the dihydroxy intermediate complex and the catalyst is 50:2:

1.

4. The method for preparing a prepolymer for preparing a ductile PC material according to claim 1, characterized in that: Preparation method of chromium (III) coordination derivative catalyst: Dimethylaminoethylamino-N, N-bis(2-methylene-4,6-tert-butylphenolate) and sodium hydride are placed in a Schlenk tube and cooled to -78°C; an appropriate amount of tetrahydrofuran solution is added to obtain a white suspension, which is heated to room temperature and stirred for 2 hours; the mixture is transferred to a tetrahydrofuran suspension of CrCl3(THF)3 through a filter cannula, and cooled to -78°C again to obtain a pink mixture; the resulting mixture is warmed to room temperature and stirred overnight to obtain a dark purple solution; the solution is filtered and evaporated to dryness; the residue is extracted into toluene, filtered through diatomaceous earth and the solvent is removed under vacuum; the residue is washed with pentane and dried to obtain a purple powder chromium (III) coordination derivative catalyst.

5. A prepolymer for preparing ductile PC material, characterized in that: The prepolymer is obtained by the preparation method according to any one of claims 1 to 4.

Images