CN114516848A

CN114516848A - Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition

Info

Publication number: CN114516848A
Application number: CN202210126906.2A
Authority: CN
Inventors: 孙永旭; 徐丹; 王磊; 耿瑞森; 刘彤彤; 张宏科
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2022-02-11
Filing date: 2022-02-11
Publication date: 2022-05-20
Anticipated expiration: 2042-02-11
Also published as: CN114516848B

Abstract

The invention provides a preparation method of a polycarbonate high-temperature degradation resistant agent and a polycarbonate composition, wherein the high-temperature degradation resistant agent prepared by adopting an indium catalyst has the following structural general formula:

Description

Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition

Technical Field

The invention relates to a polycarbonate high-temperature degradation resistant agent, in particular to a polycarbonate high-temperature degradation resistant agent, a preparation method and a polycarbonate composition, and belongs to the technical field of new chemical materials.

Background

Polycarbonate (PC for short) is a high molecular polymer containing carbonate groups in molecular chains, has the advantages of outstanding impact resistance, creep resistance, higher tensile strength, stronger heat resistance and cold resistance, excellent dielectric property, good light transmission performance and the like, is a universal engineering plastic with the highest growth speed in five engineering plastics, and has very wide application in the fields of optics, plates, automobile parts, bulletproof glass, electronics and electricity and the like.

However, in downstream application of polycarbonate, the polycarbonate product often faces a high-temperature environment in an air atmosphere, and the polycarbonate product prepared by the existing process has limited degradation resistance in the high-temperature environment, is easy to decompose and lose weight, and further causes phenomena such as yellowing and reduction of impact strength, thereby affecting the downstream application quality. Therefore, it is very important to add a certain amount of high temperature degradation resistant agent into the polycarbonate to improve the high temperature degradation resistance of the product.

At present, the industrial application is relatively pure and well-done, namely, hindered phenol antioxidants or phosphite antioxidants are added into the polycarbonate, so that the high-temperature degradation resistance of the polycarbonate is improved. In order to improve the high-temperature degradation resistance, the simultaneous addition of different antioxidants is tried by scholars to expect the synergistic effect, for example, the combination of phosphite antioxidants 627A and titanium dioxide R-TC 30 reported in the research on yellowing resistance of polycarbonate processing (engineering plastics application, Qianzuan, Wuchao, 2015,41(9):115-118) obviously improves the degradation resistance of polycarbonate under the high-temperature condition, but the dosage is 2000 ppm; the influence of phosphite antioxidants on the heat and humidity aging of polycarbonate (fine and special chemicals, Bishili, Zhang super, Zhang Qin, etc., 2020,28(8):44-46) reports that the influence of different types and different amounts of phosphite antioxidants on the molecular weight and the melt mass flow rate of polycarbonate after heat and humidity aging can obviously improve the high temperature degradation resistance of polycarbonate, but the antioxidant dosage stated in the literature is up to 3000 ppm. The addition of the high-dosage antioxidant shows that the high-temperature degradation resistance of the existing antioxidant is poor, and the production cost is undoubtedly greatly improved, so that in order to meet the high requirement of downstream application on the degradation resistance of polycarbonate under a high-temperature condition, the development of a novel high-temperature degradation resistant agent with stronger degradation resistance, particularly in a high-temperature extrusion stage, so as to improve the use efficiency becomes a problem which needs to be solved urgently by various polycarbonate manufacturers.

Disclosure of Invention

The invention aims to provide a polycarbonate high-temperature degradation resistant agent and a preparation method thereof, wherein the high-temperature degradation resistant agent contains a benzothiazole structure, and a nitrogen-carbon double bond and a benzene ring form a stable conjugated structure in space, so that the polycarbonate high-temperature degradation resistant agent has good high-temperature degradation resistance; the invention provides a preparation method of a polycarbonate high-temperature degradation resistant agent; aryl isothiocyanate is used as a raw material to prepare the high-temperature degradation resistant agent (benzothiazole compounds) under the condition that indium salt is used as a catalyst. Compared with the existing method for synthesizing the benzothiazole compounds, the preparation method has the advantages of higher yield, convenient post-treatment and purification, and capability of effectively avoiding low yield and byproducts in the preparation process. Also provides a polycarbonate composition prepared by using the high-temperature degradation resistant agent, so as to improve the degradation resistance of polycarbonate under the air atmosphere and high-temperature conditions.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides a preparation method of a polycarbonate high-temperature degradation resistant agent, which comprises the following steps:

1) dissolving aryl isothiocyanate and indium salt in a solvent;

2) and heating and stirring the mixed solution to react to obtain the arylthiazole.

The aryl isothiocyanate has the general structure:

wherein, the substituent R group is alkyl, alkoxy, aryl, heterocyclic radical, hydroxyl, halogen substituent; can be mono-substituent, di-substituent, tri-substituent and tetra-substituent; the mutual positioning of the disubstituent in the benzene ring is selected from ortho-position, meta-position and para-position; the mutual positioning of the three substituents in the benzene ring is selected from continuous substitution positions or interval substitution positions;

specifically, the aryl isothiocyanate is selected from the group consisting of p-methyl phenyl isothiocyanate, o-methyl phenyl isothiocyanate, m-methyl phenyl isothiocyanate, p-methoxy phenyl isothiocyanate, o-methoxy phenyl isothiocyanate, m-methoxy phenyl isothiocyanate, p-hydroxy phenyl isothiocyanate, o-hydroxy phenyl isothiocyanate, m-hydroxy phenyl isothiocyanate, piperonyl phenyl isothiocyanate, α -naphthyl isothiocyanate, β -naphthyl isothiocyanate, α -benzothiazolyl isothiocyanate, β -benzothiazolyl isothiocyanate, 5-quinolinyl isothiocyanate, 6-quinolinyl isothiocyanate, α -benzothienyl isothiocyanate, β -benzothienyl isothiocyanate, p-chlorostyrenyl isothiocyanate, o-chlorostyrenyl isothiocyanate, m-chlorostyrenyl isothiocyanate, 1, 4-dimethoxyphenyl isothiocyanate, 1, 3-dimethoxyphenyl isothiocyanate, 1, 2-dimethoxyphenyl isothiocyanate, 1, 4-dichlorophenyl isothiocyanate, 1, 3-dichlorophenyl isothiocyanate, 1, 2-dichlorophenyl isothiocyanate, 1-methoxy-2-chlorophenylisothiocyanate, 1,2, 3-trimethoxyphenyl isothiocyanate, 1,2, 4-trimethoxyphenyl isothiocyanate, 1, 2-dimethoxy-4-chlorophenylisothiocyanate, 1,2,3, 4-tetramethoxyphenyl isothiocyanate; preferably, the aryl isothiocyanate is selected from the group consisting of p-methoxyphenyl isothiocyanate, p-hydroxyphenyl isothiocyanate, piperonyl phenyl isothiocyanate, 1, 3-dimethoxyphenyl isothiocyanate, 1,2,3, 4-tetramethoxyphenyl isothiocyanate.

The indium salt is selected from one or more of indium salt corresponding to inorganic acid and indium salt corresponding to organic acid; preferably, the indium salt is selected from one of indium trichloride, indium trifluoromethanesulfonate, indium nitrate and indium sulfate.

The solvent is selected from one or more of acetonitrile, toluene, chlorobenzene, o-dichlorobenzene, N-dimethylformamide and dimethyl sulfoxide; preferably, the solvent is chlorobenzene.

The molar ratio of aryl isothiocyanate to indium salt is 1:1 to 2, preferably 1:1 to 1.5.

The solvent is used in an amount of 1 to 2L per mol of the aryl isothiocyanate.

The system reaction temperature in the step 2) is 80-189 ℃, and the highest temperature is the boiling point of the selected solvent.

The stirring speed in the step (2) is 100-^-1The stirring time is 2.5-5.5 h.

After the reaction in the step 2) is finished, a target product is obtained through separation and purification; the separation and purification method includes but is not limited to suction filtration, recrystallization, column chromatography separation and liquid-liquid extraction.

In a second aspect, the present invention provides the use of a compound in the manufacture of a polycarbonate anti-pyrolysis degradation agent having the general structural formula:

wherein the R group is alkyl, alkoxy, aryl, heterocyclic group, hydroxyl, halogen substituent; can be mono-substituent, di-substituent, tri-substituent and tetra-substituent; the mutual positioning of the disubstituent in the benzene ring is selected from ortho-position, meta-position and para-position; the mutual positioning of the trisubstituents in the benzene ring is selected from continuous substitution positions or interval substitution positions.

Preferably, the high temperature degradation resistant agent is

The third aspect of the present invention provides a method for preparing a polycarbonate composition using a polycarbonate high temperature degradation resistant agent, comprising: and adding one or more of the high-temperature degradation resistant agents into the polycarbonate powder, and uniformly mixing to obtain the polycarbonate composition.

The mixing mode is high mixing machine mixing.

In a fourth aspect, the present invention provides a polycarbonate composition comprising a polycarbonate resistance to high temperature degradation.

The invention has the beneficial effects that:

1) the preparation method of the polycarbonate high-temperature degradation resistant agent uses indium salt as a catalyst. The indium salt has a d-electron empty orbit, the sulfur atom of the aryl isothiocyanate has a lone pair electron, and the sulfur atom has reversed polarity after coordination, so that intramolecular cyclization reaction is easy to occur to generate the benzothiazole compound. Therefore, the preparation method is simple, convenient and feasible, is convenient to operate and has wide industrial applicability;

2) the polycarbonate prepared by the method has high yield of the high-temperature degradation resistant agent, is convenient to purify after treatment, and can effectively avoid low yield and byproducts in the preparation process, thereby avoiding introducing other impurities into the polycarbonate composition;

3) the polycarbonate high-temperature degradation resistant agent prepared by the invention contains a benzothiazole structure, wherein nitrogen-carbon double bonds and benzene rings form a stable conjugated structure in space, so that the polycarbonate high-temperature degradation resistant agent has good high-temperature degradation resistance;

4) under the condition of the same addition amount of the high-temperature degradation resistant agent, the product has more excellent high-temperature degradation resistance than the existing high-temperature degradation resistant agent, and is specifically embodied in that the injection molding product has higher molecular weight and narrower molecular weight distribution, lower yellowness and haze, and higher impact strength and tensile strength;

5) under the same high-temperature degradation resistance effect, the addition amount of the high-temperature degradation resistant agent is obviously smaller than that of the traditional high-temperature degradation resistant agent, which shows that the high-temperature degradation resistant agent has stronger high-temperature degradation resistance and higher efficiency, and the addition amount of the high-temperature degradation resistant agent can be obviously reduced in practical industrial application, so that the production cost is effectively saved.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.

The raw materials and sources are detailed in table 1.

TABLE 1

Example 1

Acetonitrile (40ml) and phenyl isothiocyanate (2.70g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (8.85g, 40mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of acetonitrile, the temperature is refluxed at 80 ℃, after the indium trichloride is completely dissolved, the reflux reaction is carried out for 4 hours, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 2.62g of the polycarbonate high-temperature degradation resistant agent, wherein the yield is 97%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.23(s,1H),7.53-7.57(m,2H),8.23-8.33(m,1H),8.09-8.13(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent A are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent A.

Note: ppm is used in the present invention to express the content of the component in the solid, 1ppm ═ 1 μ g/g.

Example 2

Adding toluene (40ml) and p-methyl phenyl isothiocyanate (2.98g, 20mmol) into a reactor provided with a thermometer and a reflux condenser tube in sequence, adding indium trichloride (6.64g, 30mmol) into the reactor at one time, raising the temperature of a reaction system to the boiling point of the toluene at 110 ℃ for reflux, after the indium trichloride is completely dissolved, carrying out reflux reaction for 4 hours, filtering to obtain filtrate, and removing a solvent in the filtrate by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering to obtain a white solid, wherein the white solid is 2.80g of the polycarbonate high-temperature degradation resistant agent B, and the yield is 94%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.11(s,1H),7.89-8.02(m,1H),7.79(s,1H),7.21-7.35(s,1H),2.52(s,3H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent B are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent B.

Example 3

Chlorobenzene (40ml) and o-methyl phenyl isothiocyanate (2.98g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (4.43g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene and refluxed at 132 ℃, after the indium trichloride is completely dissolved, the reflux reaction is carried out for 3.5h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product by using ethyl acetate, and filtering out white solid in the crude product by suction to obtain 2.68g of the polycarbonate high-temperature degradation resistant agent C, wherein the yield is 90%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.17(s,1H),7.78-7.87(m,1H),7.30-7.47(m,1H),7.01-7.16(m,1H),2.02(s,3H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent C are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent C.

Example 4

Sequentially adding o-dichlorobenzene (40ml) and m-methyl phenyl isothiocyanate (2.98g, 20mmol) into a reactor provided with a thermometer and a reflux condenser tube, adding indium trifluoromethanesulfonate (16.86g, 30mmol) into the reactor at one time, raising the temperature of a reaction system to the boiling point of o-dichlorobenzene and refluxing, after the indium trifluoromethanesulfonate is completely dissolved, carrying out reflux reaction for 4.5 hours, filtering to obtain filtrate, and removing the solvent in the filtrate by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is obtained by suction filtration, thus obtaining 2.53g of polycarbonate high temperature resistant degradation agent D with the yield of 85 percent. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.33(s,1H),7.89(s,1H),7.69-7.81(m,1H),7.21-7.37(m,1H),2.16(s,3H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent D are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent D.

Example 5

Sequentially adding N, N-dimethylformamide (40ml) and p-methoxy phenyl isothiocyanate (3.30g, 20mmol) into a reactor provided with a thermometer and a reflux condenser tube, adding indium nitrate (4.10g, 20mmol) into the reactor at one time, raising the temperature of a reaction system to 153 ℃ of the boiling point of the N, N-dimethylformamide for reflux, after the indium nitrate is completely dissolved, carrying out reflux reaction for 4 hours, filtering to obtain filtrate, and evaporating the solvent in the filtrate by using a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is filtered out by suction, so that 3.27g of polycarbonate high-temperature degradation resistant agent E is obtained, and the yield is 99%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.42(s,1H),7.63(s,1H),7.47-7.58(m,1H),6.89-7.12(m,1H)，3.78(s,3H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent E are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent E.

Example 6

Sequentially adding dimethyl sulfoxide (40ml) and o-methoxy phenyl isothiocyanate (3.30g, 20mmol) into a reactor provided with a thermometer and a reflux condenser tube, adding indium sulfate (15.53g, 30mmol) into the reactor at one time, raising the temperature of a reaction system to 189 ℃ of the boiling point of the dimethyl sulfoxide for reflux, after the indium sulfate is completely dissolved, carrying out reflux reaction for 3.5 hours, filtering to obtain filtrate, and evaporating to remove the solvent in the filtrate by using a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.20g of polycarbonate high-temperature degradation resistant agent F with the yield of 97%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.56(s,1H),7.67-7.89(m,1H),7.43-7.56(m,1H),7.02-7.15(m,1H),3.82(s,3H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent F are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent F.

Example 7

Chlorobenzene (40ml) and m-methoxy phenyl isothiocyanate (3.30g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (4.43g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 2.5h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is filtered out by suction, so that 3.07G of polycarbonate high-temperature degradation resistant agent G is obtained, and the yield is 93%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.64(s,1H),8.26(s,1H),7.87-8.01(m,1H),7.20-7.28(m,1H),3.88(s,3H)。

then, 12kg of polycarbonate powder and 0.12G of polycarbonate high temperature degradation resistant agent G are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent G.

Example 8

Chlorobenzene (40ml) and p-hydroxyisorhodanate (3.02g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene and refluxed at 132 ℃, after the indium trichloride is completely dissolved, the reflux reaction is carried out for 3.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product by using ethyl acetate, and filtering out white solid in the crude product by suction to obtain 2.96g of the polycarbonate high-temperature degradation resistant agent H, wherein the yield is 98%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.30(s,1H),7.40-7.59(m,1H),7.13(s,1H),6.92-7.06(m,1H),5.12(s,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate anti-high temperature degradation agent H are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the anti-high temperature degradation agent H.

Example 9

Chlorobenzene (40ml) and o-hydroxy phenyl isothiocyanate (3.02g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 4.5h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product by using ethyl acetate, and filtering out white solid in the crude product by suction to obtain 2.81g of the polycarbonate high-temperature degradation resistant agent I with the yield of 93 percent. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.38(s,1H),7.44-7.57(m,1H),7.22-7.35(m,1H),6.90-7.01(m,1H),5.25(s,1H)。

then, taking 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent I, and uniformly stirring and mixing by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent I.

Example 10

Chlorobenzene (40ml) and m-hydroxy phenyl isothiocyanate (3.02g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 2.87g of polycarbonate high-temperature degradation resistant agent J, wherein the yield is 95%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.22(s,1H),8.12(s,1H),7.78-7.92(m,1H),6.90-7.01(m,1H),5.32(s,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent J are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent J.

Example 11

Chlorobenzene (40ml) and piperonyl phenyl isothiocyanate (3.58g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trifluoromethanesulfonate (16.86g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trifluoromethanesulfonate is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.51g of polycarbonate high-temperature degradation resistant agent K with the yield of 98%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.78(s,1H),7.88(s,1H),7.41(s,1H),6.07(s,2H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent K are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent K.

Example 12

Chlorobenzene (40ml) and alpha-naphthyl isothiocyanate (3.70g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trifluoromethanesulfonate (16.86g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene for reflux, after the indium trifluoromethanesulfonate is completely dissolved, reflux reaction is carried out for 5.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.40g of the polycarbonate high-temperature degradation resistant agent L with the yield of 92%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.01(s,1H),8.51-8.63(m,1H),8.16-8.27(m,1H),8.01-8.12(m,1H),7.52-7.68(m,2H),7.31-7.42(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent L are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent L.

Example 13

Chlorobenzene (40ml) and beta-naphthyl isothiocyanate (3.70g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trifluoromethanesulfonate (16.86g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene for reflux, after the indium trifluoromethanesulfonate is completely dissolved, reflux reaction is carried out for 5.5 hours, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is filtered out by suction, so that 3.29g of polycarbonate high-temperature degradation resistant agent M is obtained, and the yield is 89%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.05(s,1H),8.12-8.23(m,2H),8.11(s,1H),8.07(s,1H),7.53-7.69(m,2H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent M are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent M.

Example 14

Chlorobenzene (40ml) and alpha-benzothiazole isothiocyanate (3.85g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium nitrate (4.10g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.70g of the polycarbonate high-temperature degradation resistant agent N, wherein the yield is 96%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.22(s,2H),7.72-7.89(m,2H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent N are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent N.

Example 15

Chlorobenzene (40ml) and beta-benzothiazole isothiocyanate (3.85g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium nitrate (4.10g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.77g of polycarbonate high-temperature degradation resistant agent, wherein the yield is 98%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.32(s,2H),8.23(s,1H),8.12(s,1H).

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent O are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent O.

Example 16

Chlorobenzene (40ml) and 5-quinolinisothiocyanate (3.72g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium sulfate (15.53g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium sulfate is completely dissolved, reflux reaction is carried out for 5.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized from ethyl acetate, and the white solid was filtered off by suction to give 3.46g of polycarbonate anti-pyrolysis agent P in 93% yield. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.11(s,1H),8.78-8.91(m,1H),8.12-8.23(m,1H),7.92-8.02(m,1H),7.71-7.82(m,1H),7.46-7.58(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent P are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent P.

Example 17

Chlorobenzene (40ml) and 6-quinoline isothiocyanate (3.72g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium sulfate (15.53g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium sulfate is completely dissolved, reflux reaction is carried out for 5.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is filtered out by suction, so that 3.39g of polycarbonate high-temperature degradation resistant agent Q is obtained, and the yield is 91%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.12(s,1H),8.77-8.93(m,1H),8.26-8.41(m,1H),8.05(s,1H),7.68(s,1H),7.29-7.38(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent Q are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent Q.

Example 18

Chlorobenzene (40ml) and alpha-benzothiophene isothiocyanate (3.83g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is filtered out by suction, so that 3.39g of polycarbonate high-temperature degradation resistant agent is obtained, and the yield is 88.5%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.10(s,1H),8.26-8.41(m,1H),7.78-7.86(m,2H),7.32-7.45(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent R are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300R/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent R.

Example 19

Chlorobenzene (40ml) and beta-benzothiophene isothiocyanate (3.83g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is filtered out by suction, so that 3.42g of polycarbonate high-temperature degradation resistant agent S is obtained, and the yield is 89.3%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.11(s,1H),8.23(s,1H),8.12(s,1H),7.65-7.78(m,2H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent S are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent S.

Example 20

Chlorobenzene (40ml) and p-chloro phenyl isothiocyanate (3.39g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.5 hours, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 2.78g of the polycarbonate high-temperature degradation resistant agent T, wherein the yield is 82.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.79(s,1H),8.13(s,1H),7.65-7.78(m,1H)，7.43-7.57(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent T are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent T.

Example 21

Chlorobenzene (40ml) and o-chloro phenyl isothiocyanate (3.39g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized by ethyl acetate, and white solid in the crude product is filtered out by suction, so that 2.72g of polycarbonate high-temperature degradation resistant agent U is obtained, and the yield is 81.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.81(s,1H),7.92-8.13(m,1H),7.47-7.56(m,2H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent U are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent U.

Example 22

Chlorobenzene (40ml) and m-chloro phenyl isothiocyanate (3.39g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 2.88g of polycarbonate high-temperature degradation resistant agent V, wherein the yield is 85.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.82(s,1H),8.24(s,1H),7.81-7.95(m,1H)，7.42-7.56(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent V are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent V.

Example 23

Chlorobenzene (40ml) and 1, 4-dimethoxy phenylisothiocyanate (3.90g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene and refluxed at 132 ℃, after the indium trichloride is completely dissolved, the reflux reaction is carried out for 3.5h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.86g of polycarbonate high-temperature degradation resistant agent W with the yield of 99.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.12(s,1H),6.89-7.12(m,2H),3.86(s,6H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent W are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent W.

Example 24

Chlorobenzene (40ml) and 1, 3-dimethoxy phenylisothiocyanate (3.90g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.86g of the polycarbonate high-temperature degradation resistant agent X, wherein the yield is 99.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.22(s,1H),7.08(s,1H),6.57(s，1H)，3.87(s,6H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent X are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent X.

Example 25

Chlorobenzene (40ml) and 1, 2-dimethoxy phenylisothiocyanate (3.90g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene at 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.86g of the polycarbonate high-temperature degradation resistant agent Y with the yield of 99.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.31(s,1H),7.08-7.22(m,1H),6.57-6.81(m，1H)，3.82(s,3H)，3.75(s，3H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent Y are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent Y.

Example 26

Chlorobenzene (40ml) and 1, 4-dichloro phenyl isothiocyanate (4.08g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.5 hours, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product by using ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.22g of the polycarbonate high-temperature degradation resistant agent Z with the yield of 79.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.89(s,1H),7.34-7.50(m,2H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent Z are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent Z.

Example 27

Chlorobenzene (40ml) and 1, 3-dichloro phenyl isothiocyanate (4.08g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.5 hours, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.14g of the polycarbonate high-temperature degradation resistant agent alpha, wherein the yield is 77.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.81(s,1H),8.01(s,1H),7.57(s,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent alpha are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent alpha.

Example 28

Chlorobenzene (40ml) and 1, 2-dichloro phenyl isothiocyanate (4.08g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium trichloride (6.65g, 30mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to 132 ℃ for reflux, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.5 hours, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.06g of polycarbonate high-temperature degradation resistant agent beta, wherein the yield is 75.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ10.72(s,1H),7.83-8.01(m,1H),7.57-7.62(m,1H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate anti-high temperature degradation agent beta are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the anti-high temperature degradation agent beta.

Example 29

Chlorobenzene (40ml) and 1-methoxy-2-chloro phenyl isothiocyanate (4.00g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium nitrate (4.10g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to 132 ℃ for reflux, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 3.70g of the polycarbonate high-temperature degradation resistant agent gamma, wherein the yield is 92.5%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.25(s,1H),7.45-7.76(m,2H),4.02(s,3H)。

then, taking 12kg of polycarbonate powder and 0.12g of polycarbonate anti-high temperature degradation agent gamma, and uniformly stirring and mixing by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition containing 10ppm of the anti-high temperature degradation agent gamma.

Example 30

Chlorobenzene (40ml) and 1,2, 3-trimethoxy phenyl isothiocyanate (4.50g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium nitrate (4.10g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to 132 ℃ for reflux, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 4.41g of polycarbonate high-temperature degradation resistant agent delta with the yield of 98.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.01(s,1H),6.78(s,1H),3.78(s,9H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent delta are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent delta.

Example 31

Chlorobenzene (40ml) and 1,2, 4-trimethoxy phenyl isothiocyanate (4.50g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium nitrate (4.10g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to 132 ℃ for reflux, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain 4.41g of the polycarbonate high-temperature degradation resistant agent epsilon, wherein the yield is 98.0%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.07(s,1H),6.82(s,1H),3.88(s,9H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent epsilon are taken, stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, and the polycarbonate composition containing 10ppm of high temperature degradation resistant agent epsilon is prepared.

Example 32

Chlorobenzene (40ml) and 1, 2-dimethoxy-4-chloro phenyl isothiocyanate (4.60g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium nitrate (4.10g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to be refluxed at 132 ℃, after the indium nitrate is completely dissolved, the reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product with ethyl acetate, and filtering out white solid in the crude product by suction to obtain zeta 4.40g of the polycarbonate high-temperature degradation resistant agent with the yield of 95.5%. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ9.23(s,1H),7.12(s,1H),3.99(s,6H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent zeta are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent zeta.

Example 33

Chlorobenzene (40ml) and 1,2,3, 4-tetramethoxyphenyl isothiocyanate (5.11g, 20mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser tube, indium nitrate (4.10g, 20mmol) is added into the reactor at one time, the temperature of a reaction system is raised to the boiling point of chlorobenzene to be refluxed at 132 ℃, after the indium nitrate is completely dissolved, the reflux reaction is carried out for 4.0h, filtrate is obtained by filtration, and a solvent in the filtrate is removed by evaporation through a rotary evaporator to obtain a crude product. And recrystallizing the obtained crude product by using ethyl acetate, and filtering out white solid in the crude product by suction to obtain 5.06g of the polycarbonate high-temperature degradation resistant agent eta with the yield of 99.0 percent. The reaction formula is as follows:

¹H NMR(CDCl₃,500MHz):δ8.78(s,1H),3.52(s,12H)。

then, 12kg of polycarbonate powder and 0.12g of polycarbonate high temperature degradation resistant agent eta are taken, and stirred and mixed uniformly by a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent eta.

Example 34

Taking 12kg of polycarbonate powder, 0.06g of polycarbonate high temperature degradation resistant agent E and 0.06g of polycarbonate high temperature degradation resistant agent H, and uniformly stirring and mixing by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition containing 5ppm of the high temperature degradation resistant agent E and 5ppm of the high temperature degradation resistant agent H.

Example 35

Taking 12kg of polycarbonate powder, 0.06g of polycarbonate high temperature degradation resistant agent K and 0.06g of polycarbonate high temperature degradation resistant agent X, and stirring and mixing uniformly by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition containing 5ppm of the high temperature degradation resistant agent K and 5ppm of the high temperature degradation resistant agent X.

Example 36

Taking 12kg of polycarbonate powder, 0.12g of polycarbonate high-temperature degradation resistant agent X and 0.12g of polycarbonate high-temperature degradation resistant agent eta, and uniformly stirring and mixing by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition containing 10ppm of the high-temperature degradation resistant agent X and 10ppm of the high-temperature degradation resistant agent eta.

To verify the technical effect of the present invention, comparative analysis was performed by setting the following comparative examples:

comparative example 1

12kg of polycarbonate powder was taken without adding any high temperature degradation resistant agent.

Comparative example 2

Taking 12kg of polycarbonate blank powder and 0.12g of antioxidant 1010, and uniformly stirring and mixing by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition added with 10ppm of antioxidant 1010.

Comparative example 3

Taking 12kg of polycarbonate blank powder and 0.12g of benzothiazoline, and uniformly stirring and mixing the polycarbonate blank powder and the benzothiazoline by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition added with 10ppm of antioxidant benzothiazoline.

Comparative example 4

Taking 12kg of polycarbonate blank powder and 0.12g of 2-methylbenzothiazoline, and stirring and mixing uniformly by using a high-speed mixer under the working conditions that the rotating speed is 300r/min and the mixing time is 10min to prepare the polycarbonate composition added with 10ppm of antioxidant 2-methylbenzothiazoline.

Comparative example 5

Polyphosphoric acid (40ml) and 2-aminothiophenol (2.50g, 20mmol) were sequentially added to a reactor equipped with a thermometer and a reflux condenser, after the temperature of the reaction system was raised to 150 ℃, formic acid (1.01g, 22mmol) was added dropwise to the reactor using a dropping funnel with a constant pressure, and the reaction was continued for 24 hours after completion of the dropwise addition within about 2 minutes. And after the reaction is finished, filtering the system to obtain filtrate, and evaporating the solvent in the filtrate by using a rotary evaporator to obtain a crude product. Using ethyl acetate: the crude product obtained was purified by silica gel column chromatography using a mixed solution of petroleum ether 4:1 (volume ratio) as an eluent, and the target fraction was collected and subjected to rotary evaporation to obtain 1.485g of a white solid (polycarbonate anti-pyrolysis degradation agent a) with a yield of 55%. The reaction formula is as follows:

comparative example 6

Toluene (20ml), 2-aminothiophenol (2.50g, 20mmol) and phosphorus trichloride (27.47mg, 0.2mmol) were successively charged into a reactor equipped with a thermometer and a reflux condenser, and after the temperature of the reaction system was raised to 111 ℃, formic acid (1.01g, 22mmol) was dropwise added to the reactor through a dropping funnel having a constant pressure, and the dropwise addition was completed within about 1min, and the reaction was continued for 4 hours. And after the reaction is finished, filtering the system to obtain filtrate, and evaporating the solvent in the filtrate by using a rotary evaporator to obtain a crude product. Using ethyl acetate: the crude product obtained was purified by silica gel column chromatography using a mixed solution of petroleum ether 4:1 (volume ratio) as an eluent, and the target fraction was collected and subjected to rotary evaporation to obtain 2.106g of a white solid (polycarbonate anti-pyrolysis agent a) in 78% yield. The reaction formula is as follows:

the polycarbonate compositions prepared in the above examples and comparative examples were subjected to property testing after injection molding. Wherein the injection temperature is 300 ℃, the residence time in the machine barrel is 30min, and the use parameters and the processing equipment of each example and comparative example are consistent.

The test results of the properties of the injection molded articles prepared in the examples and comparative examples are shown in Table 2, in which:

molecular weight and molecular weight distribution: the molecular weight and molecular weight distribution were measured according to ASTM D3593-80 using a 1515 gel chromatograph from waters corporation.

Yellowness of test piece: the yellowness YI of the 3mm test pieces was measured according to ASTM E313, the measuring instrument being a VIS color difference meter from HUNTER LAB.

Light transmittance: the test piece thickness was 3mm and the test apparatus was a HAZE meter of HAZE-GARP PLUS from BYK, measured according to ASTM D1003.

Notched impact strength was measured according to ASTM D256 under 23 ℃ and with a tester of the type CEAST9050 pendulum impact tester.

The tensile strength was measured according to ASTM D638 under the test conditions of a tensile speed of 50mm/min and a test apparatus of a CMT4104-BZ microcomputer-controlled electronic universal tester available from MTS.

TABLE 2 Performance test Table

It is well known to those skilled in the art that the resistance of polycarbonates to high temperature degradation can be expressed in terms of molecular weight, molecular weight distribution, light transmittance, yellowness, impact strength, tensile strength, and is further explained as: after being degraded at high temperature, polycarbonate has smaller molecular weight, wider molecular weight distribution, lower light transmittance and higher yellowness, and the impact strength and the tensile strength are reduced.

According to the test results, under the same addition amount (10ppm) of the high-temperature degradation resistant agent, compared with the comparative example, each example in the invention has higher molecular weight, narrower molecular weight distribution, higher light transmittance and lower yellowness, and the impact strength and the tensile strength are higher, which shows that under the same addition amount, the technical scheme of the invention has more excellent high-temperature degradation resistance than that of the prior art;

further, the polycarbonate composition (with the addition of 10ppm of the high-temperature degradation resistant agent) prepared in each embodiment of the invention is compared with the high-temperature degradation resistance of the polycarbonate composition (with the addition of 4000ppm of the existing high-temperature degradation resistant agent) prepared in a comparative example, and the result shows that under the same high-temperature degradation resistance, the addition of the high-temperature degradation resistant agent in the technical scheme of the invention is obviously reduced, which indicates that the high-temperature degradation resistance efficiency of the polycarbonate high-temperature degradation resistant agent prepared by the invention is higher, the high-temperature degradation resistance is stronger, and the addition of the high-temperature degradation resistant agent can be obviously reduced when the polycarbonate high-temperature degradation resistant agent is applied to industrial production, so that the production cost is saved, and the economic benefit of enterprises is ensured.

In conclusion, the preparation method of the polycarbonate high-temperature degradation resistant agent provided by the invention is simple and convenient to operate, high in yield, convenient to purify after treatment and low in cost, and can be used for preparing the polycarbonate additive with good high-temperature degradation resistance, so that the polycarbonate still has high molecular weight, narrow molecular weight distribution, high light transmittance, low yellowness and good mechanical property after long-time high-temperature processing, and the degradation resistance of the polycarbonate under the air atmosphere and high-temperature conditions is practically improved.

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a polycarbonate high-temperature degradation resistant agent comprises the following steps:

1) dissolving aryl isothiocyanate and an indium salt in a solvent;

2. The method of claim 1, wherein the aryl isothiocyanate has the general structure:

wherein, the substituent R group is alkyl, alkoxy, aryl, heterocyclic radical, hydroxyl, halogen substituent; can be mono-substituent, di-substituent, tri-substituent and tetra-substituent; the mutual positioning of the disubstituent in the benzene ring is selected from ortho-position, meta-position and para-position; the mutual positioning of the trisubstituents in the benzene ring is selected from continuous substitution positions or interval substitution positions.

3. The process according to claim 1 or 2, wherein the aryl isothiocyanate is selected from the group consisting of p-methyl phenyl isothiocyanate, o-methyl phenyl isothiocyanate, m-methyl phenyl isothiocyanate, p-methoxy phenyl isothiocyanate, o-methoxy phenyl isothiocyanate, m-methoxy phenyl isothiocyanate, p-hydroxy phenyl isothiocyanate, o-hydroxy phenyl isothiocyanate, m-hydroxy phenyl isothiocyanate, piperonyl phenyl isothiocyanate, α -naphthyl isothiocyanate, β -naphthyl isothiocyanate, α -benzothiazolyl isothiocyanate, β -benzothiazolyl isothiocyanate, 5-quinolinyl isothiocyanate, 6-quinolinyl isothiocyanate, α -benzothienyl isothiocyanate, β -benzothienyl isothiocyanate, p-chloroshiophenyl isothiocyanate, o-chloroshiophenyl isothiocyanate, p-chloroshiophenyl isothiocyanate, M-chloro phenyl isothiocyanate, 1, 4-dimethoxy phenyl isothiocyanate, 1, 3-dimethoxy phenyl isothiocyanate, 1, 2-dimethoxy phenyl isothiocyanate, 1, 4-dichloro phenyl isothiocyanate, 1, 3-dichloro phenyl isothiocyanate, 1, 2-dichloro phenyl isothiocyanate, 1-methoxy-2-chloro phenyl isothiocyanate, 1,2, 3-trimethoxy phenyl isothiocyanate, 1,2, 4-trimethoxy phenyl isothiocyanate, 1, 2-dimethoxy-4-chloro phenyl isothiocyanate, 1,2,3, 4-tetramethoxy phenyl isothiocyanate; preferably, the aryl isothiocyanate is selected from the group consisting of p-methoxyphenyl isothiocyanate, p-hydroxyphenyl isothiocyanate, piperonyl phenyl isothiocyanate, 1, 3-dimethoxyphenyl isothiocyanate, 1,2,3, 4-tetramethoxyphenyl isothiocyanate.

4. The method of any one of claims 1 to 3 wherein the indium salt is selected from one or more of indium salts corresponding to inorganic acids, indium salts corresponding to organic acids; preferably, the indium salt is selected from one of indium trichloride, indium trifluoromethanesulfonate, indium nitrate and indium sulfate.

5. The process according to any one of claims 1 to 4, wherein the solvent is selected from one or more of acetonitrile, toluene, chlorobenzene, o-dichlorobenzene, N-dimethylformamide and dimethylsulfoxide; preferably, the solvent is chlorobenzene.

6. The process of any of claims 1-5, wherein the molar ratio of aryl isothiocyanate to indium salt is 1:1 to 2, preferably 1:1 to 1.5.

7. The method as claimed in any one of claims 1 to 6, wherein the system reaction temperature in step 2) is 80-189 ℃, and the stirring speed in step 2 is 100-500 r-min^-1Stirring for 2.5-5.5 h; and/or, after the reaction in the step 2) is finished, obtaining a target product through separation and purification, wherein the separation and purification method comprises but is not limited to suction filtration, recrystallization, column chromatography separation and liquid-liquid extraction.

8. Use of a compound obtainable by the process according to any one of claims 1 to 7 in polycarbonate anti-pyrolysis agents having the general structural formula:

the R group is alkyl, alkoxy, aryl, heterocyclic group, hydroxyl and halogen substituent; can be mono-substituent, di-substituent, tri-substituent and tetra-substituent; the mutual positioning of the disubstituent in the benzene ring is selected from ortho-position, meta-position and para-position; the mutual positioning of the trisubstituents in the benzene ring is selected from continuous substitution positions or interval substitution positions.

9. A method of making a polycarbonate composition, comprising the steps of: adding one or more high-temperature degradation resistant agents into polycarbonate powder, and uniformly mixing to obtain the polycarbonate composition, wherein the high-temperature degradation resistant agents have the following structural general formula:

10. A polycarbonate composition obtained by the production method according to claim 9.