Phosphine-containing polycarbonate high-temperature-resistant degradation agent, preparation method and polycarbonate composition

Abstract

The invention provides a phosphine-containing polycarbonate high-temperature-resistant degradation agent, a preparation method and a polycarbonate composition, and the structural general formula of the high-temperature-resistant degradation agent is as follows: # imgabs0. The high-temperature-resistant degradation agent is prepared by mixing and reacting disubstituted phosphine oxide and propylene carbonate, and reacting to obtain the target phosphine-containing polycarbonate high-temperature-resistant degradation agent-diphosphonyl substituted carbonyl compound. The preparation method disclosed by the invention is simple, convenient to operate and high in product yield, and impurities can be prevented from being introduced into the polycarbonate composition; the high-temperature-resistant degradation agent has good oxidation resistance in the air atmosphere and under the high-temperature condition, and the production cost of the polycarbonate composition can be saved.

Description

Technical Field

[0001] The invention relates to a phosphine-containing polycarbonate high temperature degradation resistance agent, in particular to a preparation method of the phosphine-containing polycarbonate high temperature resistance agent and a polycarbonate composition, belonging to the technical field of new chemical materials. Background Art

[0002] Polycarbonate (PC for short) is a high molecular polymer containing carbonate groups in its molecular chain. It has many advantages such as outstanding impact resistance, creep resistance, high tensile strength, strong heat resistance and cold resistance, excellent dielectric properties, good light transmittance, etc. It has become the fastest growing general engineering plastic among the five major engineering plastics, and has very wide applications in optics, panels, automotive parts, bulletproof glass, electronic and electrical fields.

[0003] However, in the downstream applications of polycarbonate, it often faces high temperature environment in air atmosphere, and the polycarbonate products prepared by existing processes have limited antioxidant capacity in high temperature environment, and are prone to oxidation decomposition and weight loss, thus affecting the quality of downstream applications. Therefore, it is particularly important to add a certain amount of antioxidant to polycarbonate to improve the antioxidant capacity of the product.

[0004] At present, the most mature industrial application is to add hindered phenol antioxidants or phosphite antioxidants to polycarbonate. In order to improve the antioxidant effect, some scholars have tried to add different antioxidants at the same time in the expectation of a synergistic effect. For example, the literature "Study on the Anti-yellowing Performance of Polycarbonate Processing" (Engineering Plastics Application, Qian Jing, Wu Chao, 2015, 41 (9): 115-118) reported that the combination of phosphite antioxidant 627A and titanium dioxide R-TC30 significantly improved the antioxidant capacity of polycarbonate under high temperature conditions, but the dosage was 2000ppm; the literature "Effects of Phosphite Antioxidants on Hygrothermal Aging of Polycarbonate" (Fine and Specialty Chemicals, Bi Jingli, Zhang Chao, Zhang Qin, etc., 2020, 28 (8): 44-46) reported The influence of different types and dosages of phosphite antioxidants on the molecular weight and melt mass flow rate of polycarbonate after wet heat aging is reported, which can significantly improve the high temperature degradation resistance of polycarbonate, but the dosage of antioxidant described in the literature is as high as 3000ppm; the document "Preparation and Degradation Performance Research of Antioxidant-Containing Polycarbonate" (Plastic Industry, Zhang Xinlan, Li Bo, Zhang Qin, etc., 2009, 37 (1): 49-52) reports that hindered phenol antioxidants and phosphite antioxidants can be mixed and used by physical stirring to significantly improve the antioxidant capacity of polycarbonate, but the dosage of antioxidant described in the literature is as high as 6000-10000ppm. The diaryl phosphite substituted aromatic amide reported in patent CN201910732426.9 can produce a good antioxidant effect on polycarbonate when the addition amount is 50ppm, based on the test data of molecular weight and molecular weight distribution, but the test data does not specify the changes in transmittance and yellowness. The addition of high dosage of antioxidants indicates that the existing antioxidants have poor resistance to high temperature degradation, which undoubtedly greatly increases the production cost.

[0005] Therefore, in order to meet the high requirements of downstream applications for the anti-degradation ability of polycarbonate under high temperature conditions, the development of new high-temperature anti-degradation agents with stronger anti-degradation ability to improve the use efficiency has become an urgent problem that all polycarbonate manufacturers need to solve. Summary of the invention

[0006] In view of the above problems existing in the prior art, the object of the present invention is to provide a phosphine-containing polycarbonate anti-high temperature degradation agent and a preparation method thereof. The anti-high temperature degradation agent contains a carbonyl compound structure substituted with a bisphosphonyl group. After the phosphine oxygen double bond and the carbonyl carbon oxygen double bond form π-π conjugation, they form a more stable hyperconjugated structure with a more uniform electron cloud density distribution in space with the large π bond of the aromatic ring itself. Therefore, in theory, the anti-high temperature degradation agent has good antioxidant and high temperature degradation resistance.

[0007] The invention also provides a polycarbonate composition prepared by using the anti-high temperature degradation agent, so as to improve the anti-oxidation and anti-high temperature degradation capabilities of the polycarbonate in air atmosphere and high temperature conditions.

[0008] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides a phosphine-containing polycarbonate anti-high temperature degradation agent, which has a general structural formula shown in formula (1):

[0010]

[0011] In the formula, R1, R2, R3, and R4 are each independently selected from a C6-C10 aryl group, a C1-C2 alkoxy group; preferably a phenyl group, a naphthyl group, an alkoxy group, or a phenyl group or a naphthyl group having a single substituent, wherein the alkoxy group is selected from a methoxy group and an ethoxy group; R1, R2, R3, and R4 are the same or different;

[0012] Preferably, R1 and R2 are each independently selected from C6-C10 aryl groups, more preferably phenyl, naphthyl, or phenyl or naphthyl with a single substituent; R3 and R4 are each independently selected from C6-C10 aryl groups, C1-C2 alkoxy groups, more preferably phenyl, alkoxy, or phenyl with a single substituent;

[0013] Preferably, the mono-substituent in R1, R2, R3 and R4 is selected from alkyl, hydroxyl, methoxy and halogen; the position of the mono-substituent in the aromatic group is selected from ortho, meta and para.

[0014] The second aspect of the present invention provides a method for preparing the phosphine-containing polycarbonate anti-high temperature degradation agent represented by the above formula (1), wherein the method comprises dissolving disubstituted phosphine oxide in propylene carbonate and then heating the reaction to obtain the phosphine-containing polycarbonate anti-high temperature degradation agent.

[0015] In the present invention, the disubstituted phosphine oxide is selected from the general structural formula shown in formula (2):

[0016]

[0017] In the formula, R5 and R6 correspond to R1, R2, R3, and R4 in formula (1), and the substituent range is the same, that is, R5 and R6 are independently selected from C6-C10 aryl groups, C1-C2 alkoxy groups, preferably phenyl, naphthyl, alkoxy groups, or phenyl or naphthyl groups with a single substituent, wherein the alkoxy group is selected from methoxy and ethoxy groups; R5 and R6 are the same or different;

[0018] Preferably, the disubstituted phosphine oxide is selected from one or more of diphenylphosphine oxide, dinaphthylphosphine oxide, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, diphenylphosphine oxide with a single substituent on the benzene ring, and diphenyl phosphite compounds with a single substituent on the benzene ring, and the single substituent is selected from alkyl, hydroxyl, methoxy, and halogen;

[0019] More preferably, the disubstituted phosphine oxide is selected from one or more of diphenyl phosphine oxide, dinaphthyl phosphine oxide, di-p-methylphenyl phosphine oxide, di-p-methoxyphenyl phosphine oxide, and diphenyl phosphite.

[0020] In the present invention, the propylene carbonate is used as both a reactant and a solvent;

[0021] The concentration of the disubstituted phosphine oxide in propylene carbonate is 0.5 to 2.0 mol / L, preferably 0.5 to 1.0 mol / L.

[0022] In the present invention, the disubstituted phosphine oxide may be one, two or more disubstituted phosphine oxides;

[0023] When a single type of disubstituted phosphine oxide is used, the disubstituted phosphine oxide raw material is added all at once at the beginning of the reaction;

[0024] When two or more disubstituted phosphine oxides are used, different types of disubstituted phosphine oxides are added in stages during the reaction, and the addition time interval is 3.5 to 6.0 hours, preferably 4.0 to 6.0 hours.

[0025] In the present invention, the reaction temperature is 90 to 220° C., preferably 150 to 220° C., more preferably 175 to 220° C.; the reaction time is 3 to 13.5 h, preferably 6 to 9.5 h.

[0026] In the present invention, after the reaction is completed, the target product is obtained by post-processing methods such as separation and purification; the separation and purification method is a conventional operation in the field and is not particularly limited, for example, including but not limited to suction filtration, recrystallization, column chromatography separation, liquid-liquid extraction, etc.; preferably, in some specific examples of the present invention, the separation and purification method is: after the reaction solution is cooled to room temperature, ethyl acetate is added, and the excess propylene carbonate is removed by rotary evaporation by utilizing the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate to obtain a crude product; the obtained crude product is recrystallized with acetonitrile, and filtered to obtain a white solid, which is the purified phosphine-containing polycarbonate anti-high temperature degradation agent product.

[0027] The third aspect of the present invention provides a polycarbonate composition comprising the above-mentioned phosphine-containing polycarbonate anti-high temperature degradation agent;

[0028] Preferably, in the polycarbonate composition, the mass ratio of polycarbonate to the phosphine-containing polycarbonate anti-high temperature degradation agent is 1000:3.5 to 1000000:1, preferably 100000:9 to 100000:1.

[0029] The polycarbonate composition of the present invention comprises one or more of the above-mentioned phosphine polycarbonate anti-high temperature degradation agents;

[0030] Preferably, when a plurality of different phosphine polycarbonate anti-high temperature degradation agents are included, they are preferably added in equal amounts.

[0031] The polycarbonate composition of the present invention may optionally include auxiliary agents, such as but not limited to antioxidants, anti-ultraviolet agents, colorants, lubricants, plasticizers, toughening agents, etc., which are not particularly required by the present invention.

[0032] The fourth aspect of the present invention provides a method for preparing a polycarbonate composition using the above-mentioned phosphine-containing polycarbonate anti-high temperature degradation agent: the phosphine-containing polycarbonate anti-high temperature degradation agent, optional auxiliary agents and polycarbonate powder are uniformly mixed to prepare the polycarbonate composition.

[0033] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0034] 1) The phosphine-containing polycarbonate anti-high temperature degradation agent provided by the present invention contains a carbonyl compound structure substituted with a diphosphonyl group. After the phosphine oxygen double bond and the carbonyl carbon oxygen double bond form π-π conjugation, they form a more stable hyperconjugated structure with a more uniform electron cloud density distribution in space with the large π bond of the aromatic ring itself, thereby having good antioxidant and high temperature degradation resistance.

[0035] 2) The phosphine-containing polycarbonate anti-high temperature degradation agent provided by the present invention has a better anti-high temperature degradation ability than the existing anti-high temperature degradation agent when the same amount of anti-high temperature degradation agent is added, which is specifically reflected in that the injection molded products have a higher molecular weight and a narrower molecular weight distribution, lower yellowness and haze, and higher impact strength and tensile strength.

[0036] 3) The phosphine-containing polycarbonate anti-high temperature degradation agent provided by the present invention has an addition amount that is significantly less than that of the traditional anti-high temperature degradation agent under the same anti-high temperature degradation effect, indicating that the anti-high temperature degradation agent of the present invention has a stronger antioxidant capacity and higher efficiency. In actual industrial applications, the addition amount of the anti-high temperature degradation agent can be significantly reduced, thereby effectively saving production costs.

[0037] 4) The preparation method of the phosphine-containing polycarbonate anti-high temperature degradation agent provided by the present invention is simple, easy to operate, and has wide industrial applicability; and the yield is high and the post-processing and purification are convenient, thereby avoiding the introduction of other impurities into the polycarbonate composition. DETAILED DESCRIPTION

[0038] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0039] The main raw materials and their sources used in the examples and comparative examples of the present invention are detailed in Table 1. Other raw materials were obtained from common commercial channels unless otherwise specified.

[0040] Table 1

[0041]

[0042]

[0043] [Example 1]

[0044] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0045] Propylene carbonate (10ml) and diphenylphosphine oxide (2.02g, 10mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 175°C, and the reaction was carried out for 6.0h. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 2.066g of phosphine-containing polycarbonate high temperature degradation resistance agent A, with a yield of 96%. The reaction formula is as follows:

[0046]

[0047] 1 H NMR (CDCl3, 500MHz): δ7.77-7.89(m,8H),7.32-7.45(m,8H),7.05-7.12(m,4H).

[0048] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent A:

[0049] 12 kg of polycarbonate powder and 0.12 g of phosphine-containing polycarbonate anti-high temperature degradation agent A were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent A.

[0050] Note: ppm is used in the present invention to express the content of components in solids, 1ppm=1μg / g.

[0051] [Example 2]

[0052] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0053] Propylene carbonate (10ml) and di-p-methylphenylphosphine oxide (1.15g, 5mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 160°C, and the reaction was carried out for 4.0 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 1.198g of phosphine-containing polycarbonate high temperature degradation resistance agent B, with a yield of 98.5%. The reaction formula is as follows

[0054]

[0055] 1 H NMR (CDCl3, 500MHz): δ7.82-7.95(m,8H),7.17-7.32(m,8H),2.15(s,12H).

[0056] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent B:

[0057] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent B were taken and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent B.

[0058] [Example 3]

[0059] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0060] Propylene carbonate (10ml) and di-p-methoxyphenylphosphine oxide (1.31g, 5mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 150°C, and the reaction was carried out for 3.0 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 1.373g of phosphine-containing polycarbonate anti-high temperature degradation agent C, with a yield of 99.8%. The reaction formula is as follows

[0061]

[0062] 1H NMR (CDCl3, 500MHz): δ7.92-8.05(m,8H),7.42-7.67(m,8H),3.02(s,12H).

[0063] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent C:

[0064] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent C were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent C.

[0065] [Example 4]

[0066] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0067] Propylene carbonate (10ml) and dinaphthylphosphine oxide (4.53g, 15mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 220°C, and the reaction was carried out for 8.0 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 4.034g of phosphine-containing polycarbonate high temperature degradation resistance agent D, with a yield of 85.3%. The reaction formula is as follows

[0068]

[0069] 1 H NMR (CDCl3, 500MHz): δ8.01-8.35(m,12H),7.35-7.69(m,16H).

[0070] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent D:

[0071] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent D were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of the anti-high temperature degradation agent D.

[0072] [Example 5]

[0073] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0074] Propylene carbonate (10 ml) and dimethylphenylphosphine oxide (1.15 g, 5 mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 185°C, and the reaction was carried out for 6.5 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good solubility with propylene carbonate, the excess propylene carbonate was evaporated by rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 1.147 g of phosphine-containing polycarbonate high temperature degradation agent E, with a yield of 94.3%. The reaction formula is as follows

[0075]

[0076] 1 H NMR (CDCl3, 500MHz): δ7.60-7.88(m,8H),7.34-7.53(m,8H),2.32(s,12H).

[0077] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent E:

[0078] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent E were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent E.

[0079] [Example 6]

[0080] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0081] Propylene carbonate (10ml) and di-o-methylphenylphosphine oxide (1.15g, 5mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 195°C, and the reaction was carried out for 7.5 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 1.097g of phosphine-containing polycarbonate high temperature degradation agent F, with a yield of 90.2%. The reaction formula is as follows

[0082]

[0083] 1 H NMR (CDCl3, 500MHz): δ7.49-7.62(m,4H),7.27-7.41(m,12H),2.46(s,12H).

[0084] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent F:

[0085] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent F were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent F.

[0086] [Example 7]

[0087] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0088] Propylene carbonate (10ml) and di-p-hydroxyphenylphosphine oxide (1.17g, 5mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 155°C, and the reaction was carried out for 3.5 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 1.195g of phosphine-containing polycarbonate high temperature degradation resistance agent G, with a yield of 96.7%. The reaction formula is as follows

[0089]

[0090] 1 H NMR (CDCl3, 500MHz): δ8.34-8.65(m,8H),7.98-8.28(m,8H),9.87(s,4H).

[0091] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent G:

[0092] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent G were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent G.

[0093] [Example 8]

[0094] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0095] Propylene carbonate (10ml) and di-p-chlorophenylphosphine oxide (5.42g, 20mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 220°C, and the reaction was carried out for 9.5 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 4.688g of phosphine-containing polycarbonate high temperature degradation resistance agent H, with a yield of 82.5%. The reaction formula is as follows

[0096]

[0097] 1 H NMR (CDCl3, 500MHz): δ7.69-7.81(m,8H),7.43-7.61(m,8H).

[0098] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent H:

[0099] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent H were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of the anti-high temperature degradation agent H.

[0100] [Example 9]

[0101] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0102] Propylene carbonate (10ml) and di-p-bromophenylphosphine oxide (7.20g, 20mmol) were added to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, and the thick-walled pressure-resistant tube was tightened. The temperature of the reaction system was controlled to be 220°C, and the reaction was carried out for 11.3 hours. After cooling to room temperature, ethyl acetate was added to the system. Using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 5.841g of phosphine-containing polycarbonate high temperature degradation resistance agent I, with a yield of 78.3%. The reaction formula is as follows

[0103]

[0104] 1 H NMR (CDCl3, 500MHz): δ8.09-8.33(m,8H),7.69-7.93(m,8H).

[0105] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent I:

[0106] Take 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent I, use a high-speed mixer to stir and mix them evenly under the working conditions of a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent I.

[0107] [Example 10]

[0108] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0109] Propylene carbonate (10 ml) and diphenyl phosphite (1.17 g, 5 mmol) were added to a thick-walled pressure tube equipped with a clean magnet in advance, the thick-walled pressure tube was tightened, the temperature of the reaction system was controlled to 90°C, and the reaction was carried out for 5.5 hours. After cooling to room temperature, the stopper of the thick-walled pressure tube was opened, diphenylphosphine oxide (1.01 g, 5 mmol) was added to the system, and then the thick-walled pressure tube was tightened again, the temperature of the reaction system was controlled to 220°C, and the reaction was carried out for 6.0 hours. After cooling to room temperature, ethyl acetate was added to the system. Taking advantage of the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate, the excess propylene carbonate was evaporated by rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 1.672 g of phosphine-containing polycarbonate anti-high temperature degradation agent J with a yield of 72.3%. The reaction formula is as follows

[0110]

[0111] 1 H NMR (CDCl3, 500MHz): δ7.91-8.13(m,4H),7.71-7.89(m,6H),7.31-7.65(m,8H),7.15-7.23(m,2H).

[0112] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent J:

[0113] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent J were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent J.

[0114] [Example 11]

[0115] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0116] Add propylene carbonate (10 ml) and dinaphthyl phosphite (1.67 g, 5 mmol) in sequence to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, tighten the thick-walled pressure-resistant tube, control the temperature of the reaction system to 100°C, and react for 6.0 hours. After cooling to room temperature, open the stopper of the thick-walled pressure-resistant tube, add diphenylphosphine oxide (1.01 g, 5 mmol) to the system, and then tighten the thick-walled pressure-resistant tube again, control the temperature of the reaction system to 220°C, and react for 7.5 hours. After cooling to room temperature, add ethyl acetate to the system, and use ethyl acetate's lower boiling point and its good solubility with propylene carbonate to evaporate excess propylene carbonate using a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized with acetonitrile, and the white solid is filtered out to obtain 1.972 g of phosphine-containing polycarbonate high-temperature degradation agent K with a yield of 70.1%. The reaction formula is as follows

[0117]

[0118] 1 H NMR (CDCl3, 500MHz): δ8.09-8.22(m,4H),7.56-7.72(m,10H),7.28-7.45(m,8H),6.56-6.79(m,2H).

[0119] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent K:

[0120] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent K were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent K.

[0121] [Example 12]

[0122] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0123] Propylene carbonate (10ml) and di-p-methylphenyl phosphite (1.31g, 5mmol) were added to a thick-walled pressure tube equipped with a clean magnet in advance, the thick-walled pressure tube was tightened, the temperature of the reaction system was controlled to 95°C, and the reaction was carried out for 4.5h. After cooling to room temperature, the stopper of the thick-walled pressure tube was opened, diphenylphosphine oxide (1.01g, 5mmol) was added to the system, and then the thick-walled pressure tube was tightened again, the temperature of the reaction system was controlled to 220°C, and the reaction was carried out for 6.0h. After cooling to room temperature, ethyl acetate was added to the system, and the excess propylene carbonate was evaporated by rotary evaporator using the lower boiling point of ethyl acetate and its good mutual solubility with propylene carbonate to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 2.042g of phosphine-containing polycarbonate anti-high temperature degradation agent L with a yield of 83.3%. The reaction formula is as follows

[0124]

[0125] 1 H NMR (CDCl3, 500MHz): δ7.52-7.77(m,4H),7.26-7.46(m,6H),6.97-7.11(m,4H),6.65-6.83(m,4H), 3.05(s,6H).

[0126] Then, 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent L were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent L.

[0127] [Example 13]

[0128] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0129] Add propylene carbonate (10 ml) and dimethyl phosphite (0.55 g, 5 mmol) in sequence to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, tighten the thick-walled pressure-resistant tube, control the temperature of the reaction system to 95°C, and react for 3.5 hours. After cooling to room temperature, open the stopper of the thick-walled pressure-resistant tube, add diphenylphosphine oxide (1.01 g, 5 mmol) to the system, and then tighten the thick-walled pressure-resistant tube again, control the temperature of the reaction system to 220°C, and react for 6.0 hours. After cooling to room temperature, add ethyl acetate to the system, and use ethyl acetate's lower boiling point and its good solubility with propylene carbonate to evaporate excess propylene carbonate using a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized with acetonitrile, and the white solid is filtered out to obtain 1.447 g of phosphine-containing polycarbonate anti-high temperature degradation agent M with a yield of 85.6%. The reaction formula is as follows

[0130]

[0131] 1 H NMR (CDCl3, 500MHz): δ7.47-7.65 (m, 4H), 7.21-7.39 (m, 6H), 4.03 (s, 6H).

[0132] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent M:

[0133] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent M were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of the anti-high temperature degradation agent M.

[0134] [Example 14]

[0135] Preparation of phosphine-containing polycarbonate anti-high temperature degradation agent:

[0136] Add propylene carbonate (10 ml) and diethyl phosphite (0.69 g, 5 mmol) in sequence to a thick-walled pressure-resistant tube equipped with a clean magnet in advance, tighten the thick-walled pressure-resistant tube, control the temperature of the reaction system to 95°C, and react for 4.0 hours. After cooling to room temperature, open the stopper of the thick-walled pressure-resistant tube, add diphenylphosphine oxide (1.01 g, 5 mmol) to the system, and then tighten the thick-walled pressure-resistant tube again, control the temperature of the reaction system to 220°C, and react for 5.5 hours. After cooling to room temperature, add ethyl acetate to the system, and use ethyl acetate's lower boiling point and its good solubility with propylene carbonate to evaporate excess propylene carbonate using a rotary evaporator to obtain a crude product. The obtained crude product is recrystallized with acetonitrile, and the white solid is filtered out to obtain 1.608 g of phosphine-containing polycarbonate high-temperature degradation resistance agent with a yield of 87.8%. The reaction formula is as follows

[0137]

[0138] 1 H NMR (CDCl3, 500MHz): δ7.43-7.66 (m, 4H), 7.18-7.36 (m, 6H), 4.78 (q, J = 7.12Hz, 4H), 1.98 (t, J = 6.89Hz, 6H).

[0139] The polycarbonate composition is prepared by using the above-mentioned phosphine-containing polycarbonate high temperature degradation resistance agent N:

[0140] 12 kg of polycarbonate powder and 0.12 g of polycarbonate anti-high temperature degradation agent N were taken, and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of anti-high temperature degradation agent N.

[0141] [Example 15]

[0142] The polycarbonate composition was prepared by using the phosphine-containing polycarbonate high temperature degradation resistance agents A and D prepared in Examples 1 and 4:

[0143] Take 12 kg of polycarbonate powder, 0.06 g of polycarbonate anti-high temperature degradation agent A, and 0.06 g of polycarbonate anti-high temperature degradation agent D, and use a high-speed mixer to stir and mix them evenly under the working conditions of a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 5 ppm of anti-high temperature degradation agent A and 5 ppm of anti-high temperature degradation agent D.

[0144] [Example 16]

[0145] The polycarbonate composition was prepared by using the phosphine-containing polycarbonate high temperature degradation resistance agents B and E prepared in Examples 2 and 5:

[0146] Take 12 kg of polycarbonate powder, 0.06 g of polycarbonate anti-high temperature degradation agent B, and 0.06 g of polycarbonate anti-high temperature degradation agent E, and use a high-speed mixer to stir and mix them evenly under the working conditions of a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 5 ppm of anti-high temperature degradation agent B and 5 ppm of anti-high temperature degradation agent E.

[0147] [Example 17]

[0148] The polycarbonate composition was prepared using the phosphine-containing polycarbonate high temperature degradation resistant agents C, F and G prepared in Examples 3, 6 and 7:

[0149] Take 12kg of polycarbonate powder, 0.036g of polycarbonate anti-high temperature degradation agent C, 0.036g of polycarbonate anti-high temperature degradation agent F, and 0.036g of polycarbonate anti-high temperature degradation agent G, and use a high-speed mixer to stir and mix them evenly under the working conditions of a speed of 300r / min and a mixing time of 10min to prepare a polycarbonate composition containing 3ppm of anti-high temperature degradation agent C, 3ppm of anti-high temperature degradation agent F, and 3ppm of anti-high temperature degradation agent G.

[0150] In order to verify the technical effect of the present invention, the following comparative examples are set for comparative analysis:

[0151] [Comparative Example 1]

[0152] Take 12 kg of polycarbonate powder without adding any antioxidant.

[0153] [Comparative Example 2]

[0154] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced by antioxidant 1010, and other operations and conditions remained unchanged, to prepare a polycarbonate composition with 10 ppm of antioxidant 1010 added thereto.

[0155] [Comparative Example 3]

[0156] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced by antioxidant 330, and other operations and conditions remained unchanged, thereby preparing a polycarbonate composition to which 10 ppm of antioxidant 330 was added.

[0157] [Comparative Example 4]

[0158] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced by antioxidant 1035, and other operations and conditions remained unchanged, thereby preparing a polycarbonate composition with 10 ppm of antioxidant 1035 added thereto.

[0159] [Comparative Example 5]

[0160] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced by antioxidant 1076, and other operations and conditions remained unchanged, thereby preparing a polycarbonate composition to which 10 ppm of antioxidant 1076 was added.

[0161] [Comparative Example 6]

[0162] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced by antioxidant 168, and other operations and conditions remained unchanged, thereby preparing a polycarbonate composition to which 10 ppm of antioxidant 168 was added.

[0163] [Comparative Example 7]

[0164] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced with 0.06 g of antioxidant 168 and 0.06 g of antioxidant 1076, and other operations and conditions remained unchanged, to prepare a polycarbonate composition with 5 ppm of antioxidant 168 and 5 ppm of antioxidant 1076 added thereto.

[0165] [Comparative Example 8]

[0166] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced by 0.036 g of antioxidant 168, 0.036 g of antioxidant 1076, and 0.036 g of antioxidant 1010, and other operations and conditions remained unchanged, to prepare a polycarbonate composition to which 3 ppm of antioxidant 168, 3 ppm of antioxidant 1076, and 3 ppm of antioxidant 1010 were added.

[0167] [Comparative Example 9]

[0168] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced with 12.00 g of antioxidant 168, and other operations and conditions remained unchanged, to prepare a polycarbonate composition to which 1000 ppm of antioxidant 168 was added.

[0169] [Comparative Example 10]

[0170] A polycarbonate composition was prepared by referring to the method of Example 1, except that the phosphine-containing polycarbonate anti-high temperature degradation agent A was replaced by 42.00 g of antioxidant 168, and other operations and conditions remained unchanged, to prepare a polycarbonate composition to which 3500 ppm of antioxidant 168 was added.

[0171] [Comparative Example 11]

[0172] Preparation of diphenylphosphite-N-phenylamide:

[0173] Acetonitrile (10ml) and diphenyl phosphite (4.68g, 20mmol) were added to a reactor equipped with a thermometer, a reflux condenser and a constant pressure funnel. Sodium hydride (0.576g, 24mmol) was added to the reactor several times. The reaction system temperature was controlled to be 60°C. After sodium hydride was completely dissolved, the temperature was raised to 80°C, the boiling point of acetonitrile, and then a 25ml constant pressure funnel was installed. A 10ml acetonitrile solution containing phenyl isocyanate (4.28g, 36mmol) was dripped from the constant pressure funnel. The reaction was refluxed for 2h. The filtrate was filtered and the solvent in the filtrate was removed by a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized with acetonitrile, and the white solid was filtered out to obtain 6.78g of diphenyl phosphite-N-phenylamide with a yield of 96%. The reaction formula is as follows:

[0174]

[0175] 1H NMR (CDCl3, 500MHz): δ9.08-9.22(m,1H),7.58-7.62(m,2H),7.40-7.45(m,2H),7.25-7.32(m,4H),7.15-7.22(m,7H).

[0176] Preparation of polycarbonate composition using diphenyl phosphite-N-phenylamide:

[0177] 12 kg of polycarbonate powder and 0.12 g of diphenyl phosphite-N-phenylamide were taken and stirred and mixed evenly using a high-speed mixer at a speed of 300 r / min and a mixing time of 10 min to prepare a polycarbonate composition containing 10 ppm of diphenyl phosphite-N-phenylamide.

[0178] The polycarbonate compositions prepared in the above Examples 1-17 and Comparative Examples 1-11 were tested for performance after injection molding, wherein the injection molding temperature was 300° C., the residence time in the barrel was 30 min, and the parameters and processing equipment used in each Example and Comparative Example were consistent.

[0179] In addition, a group of blank polycarbonate powders that have not been injection molded are set as blank controls to more intuitively demonstrate the test results of each embodiment and comparative example. It should be noted that when the blank polycarbonate powders that have not been injection molded are tested for yellowness, light transmittance, notched impact strength, and tensile strength of the test piece, the powder is first dissolved in dichloromethane, and then the dichloromethane is dried in a 40-degree oven, and then tested in accordance with the relevant provisions of each standard. The test results of various properties of the injection molded products prepared in each embodiment and comparative example are shown in Table 2, where:

[0180] Molecular weight and molecular weight distribution: The molecular weight and molecular weight distribution were tested according to ASTM D3593-80 standard, and the testing instrument was 2695 gel chromatograph from Waters Company.

[0181] Yellowness of test piece: The yellowness YI of 3mm test piece was tested according to ASTM E313 standard, and the testing instrument was VIS colorimeter of HUNTER LAB.

[0182] Light transmittance: tested according to ASTM D1003 standard, the test piece thickness is 3mm, and the testing instrument is BYK's HAZE-GARP PLUS haze meter.

[0183] The notched impact strength was measured according to ASTM D256 standard, the test condition was 23°C, and the test instrument was CEAST9050 pendulum impact tester.

[0184] The tensile strength was measured according to ASTM D638 standard, the test condition was a tensile speed of 50 mm / min, and the test instrument was a CMT4104-BZ microcomputer-controlled electronic universal testing machine from MTS.

[0185] Table 2 Performance test table

[0186]

[0187]

[0188] It is well known to those skilled in the art that the high temperature degradation resistance of polycarbonate can be reflected in molecular weight, molecular weight distribution, light transmittance, yellowness, impact strength and tensile strength, which can be further explained as follows: after being degraded by high temperature, polycarbonate has a smaller molecular weight, a wider molecular weight distribution, a lower light transmittance and a higher yellowness, and both the impact strength and the tensile strength are reduced.

[0189] It can be seen from the above test results that, under the same addition amount of anti-high temperature degradation agent (10ppm), the embodiments of the present invention have higher molecular weight, narrower molecular weight distribution, higher light transmittance and lower yellowness compared with the comparative example, and both impact strength and tensile strength are higher, indicating that under the same addition amount, the technical solution of the present invention has better resistance to high temperature degradation than the prior art;

[0190] Furthermore, the high temperature degradation resistance of the polycarbonate composition prepared in each embodiment of the present invention (the amount of anti-high temperature degradation agent added is 10 ppm) is compared with that of the polycarbonate composition prepared in Comparative Example 10 (the existing amount of anti-high temperature degradation agent added is 3500 ppm). The results show that under the same high temperature degradation resistance, the technical scheme of the present invention significantly reduces the amount of polycarbonate anti-high temperature degradation agent added, indicating that the polycarbonate anti-high temperature degradation agent prepared by the present invention has higher anti-high temperature degradation efficiency and stronger anti-high temperature degradation ability. When applied to industrial production, the amount of anti-high temperature degradation agent added can be significantly reduced, thereby saving production costs and ensuring the economic benefits of the enterprise.

[0191] In summary, the preparation method of the phosphine-containing polycarbonate anti-high temperature degradation agent provided by the present invention is simple to operate, has a high yield, is convenient for post-processing and purification, and has low cost. A polycarbonate additive with good resistance to high temperature degradation can be prepared, so that the polycarbonate still has a high molecular weight, a narrow molecular weight distribution, a high light transmittance, a low yellowness and good mechanical properties after long-term high-temperature processing, and effectively improves the anti-degradation ability of polycarbonate in air atmosphere and high temperature conditions.

[0192] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A phosphine-containing polycarbonate anti-high temperature degradation agent, characterized in that: It has the general structural formula shown in formula (1): In the formula, R1, R2, R3, and R4 are each independently selected from a C6-C10 aryl group, a C1-C2 alkoxy group; preferably a phenyl group, a naphthyl group, an alkoxy group, or a phenyl group or a naphthyl group having a single substituent, wherein the alkoxy group is selected from a methoxy group and an ethoxy group; R1, R2, R3, and R4 are the same or different.

2. The phosphine-containing polycarbonate anti-high temperature degradation agent according to claim 1, characterized in that: R1 and R2 are each independently selected from C6-C10 aryl groups, preferably phenyl, naphthyl, or phenyl or naphthyl groups having a single substituent; R3 and R4 are each independently selected from C6-C10 aryl groups, C1-C2 alkoxy groups, preferably phenyl, alkoxy, or phenyl groups having a single substituent; Preferably, the mono-substituent in R1, R2, R3 and R4 is selected from alkyl, hydroxyl, methoxy and halogen; the position of the mono-substituent in the aromatic group is selected from ortho, meta and para.

3. A method for preparing the phosphine-containing polycarbonate high temperature degradation resistance agent according to claim 1 or 2, characterized in that: The phosphine-containing polycarbonate high temperature degradation resistance agent is prepared by dissolving disubstituted phosphine oxide in propylene carbonate and then heating the reaction.

4. The preparation method according to claim 3, characterized in that: The disubstituted phosphine oxide is selected from the general structural formula shown in formula (2): In the formula, R5 and R6 correspond to R1, R2, R3, and R4 in formula (1), and the substituent range is the same, that is, R5 and R6 are independently selected from C6-C10 aryl groups, C1-C2 alkoxy groups, preferably phenyl, naphthyl, alkoxy groups, or phenyl or naphthyl groups with a single substituent, wherein the alkoxy group is selected from methoxy and ethoxy groups; R5 and R6 are the same or different; Preferably, the disubstituted phosphine oxide is selected from one or more of diphenylphosphine oxide, dinaphthylphosphine oxide, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, diphenylphosphine oxide with a single substituent on the benzene ring, and diphenyl phosphite compounds with a single substituent on the benzene ring, and the single substituent is selected from alkyl, hydroxyl, methoxy, and halogen; More preferably, the disubstituted phosphine oxide is selected from one or more of diphenyl phosphine oxide, dinaphthyl phosphine oxide, di-p-methylphenyl phosphine oxide, di-p-methoxyphenyl phosphine oxide, and diphenyl phosphite.

5. The preparation method according to claim 3 or 4, characterized in that: The concentration of the disubstituted phosphine oxide in propylene carbonate is 0.5 to 2.0 mol / L, preferably 0.5 to 1.0 mol / L.

6. The preparation method according to any one of claims 3 to 5, characterized in that: The disubstituted phosphine oxide may be one, two or more disubstituted phosphine oxides; When a single type of disubstituted phosphine oxide is used, the disubstituted phosphine oxide raw material is added all at once at the beginning of the reaction; When two or more disubstituted phosphine oxides are used, different types of disubstituted phosphine oxides are added sequentially in stages during the reaction, and the addition time interval is 3.5 to 6.0 hours, preferably 4.0 to 6.0 hours.

7. The preparation method according to any one of claims 3 to 6, characterized in that: The reaction temperature is 90 to 220°C, preferably 150 to 220°C, more preferably 175 to 220°C; the reaction time is 3 to 13.5 hours, preferably 6 to 9.5 hours.

8. A polycarbonate composition comprising the phosphine-containing polycarbonate anti-high temperature degradation agent according to claim 1 or 2.

9. The polycarbonate composition according to claim 8, characterized in that The mass ratio of the polycarbonate to the phosphine-containing polycarbonate anti-high temperature degradation agent is 1000:3.5 to 1000000:1, preferably 100000:9 to 100000:

1.

10. The polycarbonate composition according to claim 8 or 9, characterized in that: Containing one or more of the above-mentioned phosphine polycarbonate anti-high temperature degradation agents; Preferably, when a plurality of different phosphine polycarbonate anti-high temperature degradation agents are included, they are preferably added in equal amounts.

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