CN114516848B - Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition - Google Patents

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

Info

Publication number
CN114516848B
CN114516848B CN202210126906.2A CN202210126906A CN114516848B CN 114516848 B CN114516848 B CN 114516848B CN 202210126906 A CN202210126906 A CN 202210126906A CN 114516848 B CN114516848 B CN 114516848B
Authority
CN
China
Prior art keywords
isothiocyanate
polycarbonate
phenyl isothiocyanate
high temperature
mmol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210126906.2A
Other languages
Chinese (zh)
Other versions
CN114516848A (en
Inventor
孙永旭
徐丹
王磊
耿瑞森
刘彤彤
张宏科
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202210126906.2A priority Critical patent/CN114516848B/en
Publication of CN114516848A publication Critical patent/CN114516848A/en
Application granted granted Critical
Publication of CN114516848B publication Critical patent/CN114516848B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/84—Naphthothiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

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 a molecular chain, has the advantages of outstanding impact resistance, creep resistance, high tensile strength, high heat resistance, cold resistance, excellent dielectric property, good light transmittance and the like, is now the general engineering plastic with the fastest growth speed in five engineering plastics, and has very wide application in the fields of optics, plates, automobile parts, bulletproof glass, electronics, electrics and the like.
However, in the downstream application of polycarbonate, the polycarbonate product prepared by the prior art is often faced with a high-temperature environment in an air atmosphere, and the polycarbonate product prepared by the prior art is limited in degradation resistance in the high-temperature environment and is easy to decompose and lose weight, so that phenomena such as yellowing, reduction of impact strength and the like are caused, and the downstream application quality is affected. Therefore, it is 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 industrialized application is purer, and 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 effect, the prior scholars try to add different antioxidants simultaneously to expect a synergistic effect, for example, the literature 'study on the yellowing resistance of polycarbonate processing' (engineering plastics application, qian Jing, wu Chao, 2015,41 (9): 115-118) reports that phosphite antioxidants 627A are matched with titanium dioxide R-TC30 for use, so that the degradation resistance of polycarbonate under the high-temperature condition is obviously improved, but the dosage is 2000ppm; the literature (influence of phosphite antioxidants on the wet heat aging of polycarbonate) (fine and special chemicals, bi Jingli, zhang Chao, zhang Qin, etc., 2020,28 (8): 44-46) reports the influence of different types and different amounts of phosphite antioxidants on the molecular weight and melt mass flow rate of polycarbonate after the wet heat aging, and can obviously improve the high temperature degradation resistance of the polycarbonate, but the antioxidant usage amount described in the literature is up to 3000ppm. 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 obviously greatly increased, so that the development of a novel high-temperature degradation resistant agent with stronger degradation resistance, especially in a high-temperature extrusion stage, for improving the use efficiency, in order to meet the high requirement of the downstream application on the degradation resistance of polycarbonate under the high-temperature condition, has become the urgent problem to be solved by 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 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, and a high-temperature degradation resistant agent (benzothiazole compound) is prepared under the condition that indium salt is used as a catalyst. Compared with the existing method for synthesizing 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 provided is 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 above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of 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) Heating, stirring and mixing the solution, and reacting to obtain the arylbenzothiazole.
The general structure of the aryl isothiocyanate is as follows:
wherein the substituent R group is an alkyl, alkoxy, aryl, heterocyclic, hydroxy or halogen substituent; can be monosubstituted, disubstituted, trisubstituted or tetrasubstituted; the mutual positioning of the disubstituents in the benzene ring is optionally from ortho, meta and para; the mutual positioning of the trisubstituted groups in the benzene ring is selected from continuous substitution positions or interval substitution positions;
specifically, the aryl isothiocyanate is selected from 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, alpha-naphthalene isothiocyanate, beta-benzothiazolyl isothiocyanate, 5-quinoline isothiocyanate, 6-quinoline isothiocyanate, alpha-benzothiophene, beta-benzothiophene, p-chloro phenyl isothiocyanate, o-chloro phenyl 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-methoxy-2-chloro phenyl isothiocyanate, 1,2, 3-trimethoxyphenyl isothiocyanate, 1, 2-trimethoxyphenyl isothiocyanate, 1, 2-2, 4-dimethoxy phenyl isothiocyanate, 1, 2-dimethoxy phenyl isothiocyanate, 4-methoxy phenyl isothiocyanate; preferably, the aryl isothiocyanate is selected from the group consisting of p-methoxy phenyl isothiocyanate, p-hydroxy phenyl isothiocyanate, piperonyl phenyl isothiocyanate, 1, 3-dimethoxy phenyl isothiocyanate, 1,2,3, 4-tetramethoxy phenyl isothiocyanate.
The indium salt is 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 triflate, 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 1:1-2, preferably 1:1-1.5.
The solvent is used in an amount of 1-2L per mol of aryl isothiocyanate.
The reaction temperature of the system in the step 2) is 80-189 ℃, and the highest temperature is the boiling point of the selected solvent.
The stirring rotating speed in the step (2) is 100-500 r.min -1 The stirring time is 2.5-5.5h.
Obtaining a target product through separation and purification after the reaction in the step 2); separation and purification methods include, but are not limited to, suction filtration, recrystallization, column chromatography separation, liquid-liquid extraction.
The second aspect of the invention provides the use of a compound in a polycarbonate high temperature degradation resistant agent having the general structural formula:
the R group is alkyl, alkoxy, aryl, heterocyclic group, hydroxyl and halogen substituent; can be monosubstituted, disubstituted, trisubstituted or tetrasubstituted; the mutual positioning of the disubstituents in the benzene ring is optionally from ortho, meta and para; the mutual positioning of the trisubstituted groups in the benzene ring is selected from continuous substitution positions or interval substitution positions.
Preferably, the high temperature resistant degradation agent is
In a third aspect, the invention provides a method for preparing a polycarbonate composition using a polycarbonate resistant to high temperature drop Jie Ji: 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-speed mixer mixing.
In a fourth aspect, the present invention provides a polycarbonate composition comprising a polycarbonate high temperature degradation resistant agent.
The beneficial effects of the invention are as follows:
1) The preparation method of the polycarbonate high-temperature degradation resistant agent uses indium salt as a catalyst. The indium salt has d electron empty orbitals, the sulfur atom of the aryl isothiocyanate has lone pair electrons, the polarity of the sulfur atom is reversed after the two are coordinated, and intramolecular cyclization reaction is easy to occur to generate the benzothiazole compound. Therefore, the preparation method is simple, convenient and easy to operate, and has wide industrial applicability;
2) The polycarbonate prepared by the method has higher yield of the high-temperature degradation resistant agent and convenient post-treatment and purification, 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 benzothiazole structure, wherein nitrogen-carbon double bond and benzene ring form stable conjugated structure in space, thus having good high-temperature degradation resistant capability;
4) Compared with the existing high-temperature degradation resistant agent, the product has more excellent high-temperature degradation resistant capability under the condition of the same high-temperature degradation resistant agent addition amount, and is particularly reflected in that injection molding products have 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 resistance agent is obviously smaller than that of the traditional high-temperature degradation resistance agent, which shows that the high-temperature degradation resistance of the high-temperature degradation resistance agent is stronger and higher in efficiency, and the addition amount of the high-temperature degradation resistance agent can be obviously reduced in practical industrial application, so that the production cost is effectively saved.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The raw materials and sources are shown in Table 1.
TABLE 1
Example 1
Acetonitrile (40 ml) and phenyl isothiocyanate (2.70 g,20 mmol) were successively added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (8.85 g,40 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to the boiling point of acetonitrile and refluxed at 80 ℃, after the indium trichloride was completely dissolved, the reaction was further refluxed for 4 hours, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was filtered off with suction to give Jie Ji A2.62g of polycarbonate with a high temperature resistance and 97% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 condition of the rotating speed of 300r/min and the mixing time of 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent A.
Note that: ppm is used in the present invention to express the content of ingredients in the solid, 1ppm = 1 μg/g.
Example 2
Toluene (40 ml) and p-methyl phenyl isothiocyanate (2.98 g,20 mmol) were successively added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.64 g,30 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 110℃of toluene and refluxed, after the indium trichloride was completely dissolved, the reaction was further refluxed for 4 hours, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give 2.80g of polycarbonate as a high-temperature degradation inhibitor B in 94% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 condition of the rotating speed of 300r/min and the mixing time of 10min, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent B.
Example 3
Chlorobenzene (40 ml) and o-methyl phenyl isothiocyanate (2.98 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (4.43 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 3.5h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give 2.68g of polycarbonate as a high-temperature degradation inhibitor C in 90% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji C are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent C.
Example 4
O-dichlorobenzene (40 ml) and m-methyl phenyl isothiocyanate (2.98 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium triflate (16.86 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 180 ℃ of the boiling point of the o-dichlorobenzene, reflux is carried out, after the indium triflate is completely dissolved, reflux reaction is carried out for 4.5h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give 2.53g of polycarbonate as a high-temperature degradation inhibitor D with a yield of 85%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji D are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent D.
Example 5
N, N-dimethylformamide (40 ml) and p-methoxy phenyl isothiocyanate (3.30 g,20 mmol) were successively added into a reactor equipped with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 153 ℃ for reflux, after the indium nitrate was completely dissolved, the reaction was refluxed for 4 hours again, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give 3.27g of polycarbonate as a high-temperature degradation inhibitor E in a yield of 99%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent E.
Example 6
Dimethyl sulfoxide (40 ml) and o-methoxy phenyl isothiocyanate (3.30 g,20 mmol) were successively added into a reactor equipped with a thermometer and a reflux condenser, indium sulfate (15.53 g,30 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 189 ℃ of the boiling point of dimethyl sulfoxide, reflux was carried out, after the indium sulfate was completely dissolved, the reaction was carried out for 3.5 hours again, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji F3.20 g of polycarbonate with a 97% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji F are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent F.
Example 7
Chlorobenzene (40 ml) and m-methoxy phenyl isothiocyanate (3.30 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (4.43 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 2.5h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji G3.07G of polycarbonate having a high temperature resistance and a yield of 93%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji G are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent G.
Example 8
Chlorobenzene (40 ml) and p-hydroxy phenyl isothiocyanate (3.02 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 3.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate and the white solid was filtered off with suction to give Jie Ji H2.96 g of polycarbonate with a high temperature resistance and a yield of 98%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji H are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent H.
Example 9
Chlorobenzene (40 ml) and o-hydroxy phenyl isothiocyanate (3.02 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 4.5h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give 2.81g of polycarbonate as a high-temperature degradation inhibitor I in 93% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 stirring and uniformly mixing by using a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent I.
Example 10
Chlorobenzene (40 ml) and m-hydroxyl phenyl isothiocyanate (3.02 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji J2.87 g of polycarbonate with a high temperature resistance and a yield of 95%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji J are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent J.
Example 11
Chlorobenzene (40 ml) and piperonyl phenyl isothiocyanate (3.58 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium triflate (16.86 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of chlorobenzene, reflux is carried out, after the indium triflate is completely dissolved, reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is removed by a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji K3.51 g of polycarbonate with a high temperature resistance and a yield of 98%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced by Jie Ji K are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent K.
Example 12
Chlorobenzene (40 ml) and alpha-naphthalene isothiocyanate (3.70 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium triflate (16.86 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of chlorobenzene, reflux is carried out, after the indium triflate is completely dissolved, reflux reaction is carried out for 5.0h, the filtrate is filtered, and the solvent in the filtrate is removed by a rotary evaporator, thus obtaining a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give 3.40g of polycarbonate as a high temperature degradation inhibitor L in 92% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of the high temperature degradation resistant agent L.
Example 13
Chlorobenzene (40 ml) and beta-naphthalene isothiocyanate (3.70 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium triflate (16.86 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium triflate is completely dissolved, reflux reaction is carried out for 5.5h, the filtrate is filtered, and the solvent in the filtrate is removed by a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate and the white solid was suction filtered off to give Jie Ji M3.29 g of polycarbonate with a high temperature resistance and 89% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji M are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent M.
Example 14
Chlorobenzene (40 ml) and alpha-benzothiazolyl isothiocyanate (3.85 g,20 mmol) were sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 132 ℃ of the boiling point of chlorobenzene, reflux was performed, after the indium nitrate was completely dissolved, the reaction was performed for 4.0h again, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji N3.70 g of polycarbonate with a 96% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ10.22(s,2H),7.72-7.89(m,2H)。
then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji N are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent N.
Example 15
Chlorobenzene (40 ml) and beta-benzothiazolyl isothiocyanate (3.85 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of chlorobenzene, reflux is carried out, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji O3.77 g of polycarbonate with a high temperature resistance and a yield of 98%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ10.32(s,2H),8.23(s,1H),8.12(s,1H).
then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji O are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent O.
Example 16
Chlorobenzene (40 ml) and 5-quinoline isothiocyanate (3.72 g,20 mmol) were sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium sulfate (15.53 g,30 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 132 ℃ of the boiling point of chlorobenzene, reflux was performed, after the indium sulfate was completely dissolved, the reflux reaction was performed for 5.0h, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji P3.46 g of polycarbonate with a high temperature resistance and a yield of 93%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji P are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent P.
Example 17
Chlorobenzene (40 ml) and 6-quinoline isothiocyanate (3.72 g,20 mmol) were sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium sulfate (15.53 g,30 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 132 ℃ of the boiling point of chlorobenzene, reflux was performed, after the indium sulfate was completely dissolved, the reflux reaction was performed for 5.0h, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji Q3.39 g of polycarbonate having a high temperature resistance and a yield of 91%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji Q are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent Q.
Example 18
Chlorobenzene (40 ml) and alpha-benzothiophene isothiocyanate (3.83 g,20 mmol) were sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 132 ℃ of the boiling point of chlorobenzene and refluxed, after the indium trichloride was completely dissolved, the reaction was refluxed for 4.0 hours again, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate and the white solid was filtered off with suction to give Jie Ji R3.39 g of polycarbonate with a high temperature resistance and a yield of 88.5%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji R are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300R/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent R.
Example 19
Chlorobenzene (40 ml) and beta-thiobenzothiophene isothiocyanate (3.83 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off by a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give 3.42g of polycarbonate as a high-temperature degradation inhibitor S, with a yield of 89.3%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji S are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent S.
Example 20
Chlorobenzene (40 ml) and p-chloro-phenyl isothiocyanate (3.39 g,20 mmol) were sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) was added into the reactor at one time, the temperature of the reaction system was raised to 132 ℃ of the boiling point of chlorobenzene, reflux was performed, after the indium trichloride was completely dissolved, the reaction was performed for 5.5 hours again, the filtrate was filtered, and the solvent in the filtrate was distilled off by a rotary evaporator to obtain a crude product. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji T2.78 g of polycarbonate with a high temperature resistance and a yield of 82.0%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji T are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent T.
Example 21
Chlorobenzene (40 ml) and o-chloro phenyl isothiocyanate (3.39 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji U2.72 g of polycarbonate having a high temperature resistance and a yield of 81.0%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji U were stirred and mixed uniformly by a high-speed mixer under the working condition of the rotation speed of 300r/min and the mixing time of 10min, so as to prepare a polycarbonate composition containing 10ppm of high temperature degradation agent U.
Example 22
Chlorobenzene (40 ml) and m-chloro phenyl isothiocyanate (3.39 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji V2.88 g of polycarbonate with a high temperature resistance of 85.0% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced by Jie Ji V are stirred and mixed uniformly by a high-speed mixer under the working condition of the rotating speed of 300r/min and the mixing time of 10min, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation agent V.
Example 23
Chlorobenzene (40 ml) and 1, 4-dimethoxy phenyl isothiocyanate (3.90 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of chlorobenzene for reflux, after the indium trichloride is completely dissolved, the reflux reaction is carried out for 3.5h, the filtrate is filtered, and the solvent in the filtrate is distilled off by a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered to obtain Jie Ji W3.86 g of polycarbonate having a high temperature resistance and a yield of 99.0%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji W were stirred and mixed uniformly by a high-speed mixer under the working condition of the rotation speed of 300r/min and the mixing time of 10min, so as to prepare a polycarbonate composition containing 10ppm of high temperature degradation agent W.
Example 24
Chlorobenzene (40 ml) and 1, 3-dimethoxy phenyl isothiocyanate (3.90 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of chlorobenzene for reflux, after the indium trichloride is completely dissolved, the reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off by a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji X3.86 g of polycarbonate with a high temperature resistance and a yield of 99.0%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 with high temperature resistance reduced Jie Ji X are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent X.
Example 25
Chlorobenzene (40 ml) and 1, 2-dimethoxy phenyl isothiocyanate (3.90 g,20 mmol) are sequentially added into a reactor equipped with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of chlorobenzene for reflux, after the indium trichloride is completely dissolved, the reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is distilled off by a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered to give Jie Ji Y3.86 g of polycarbonate having a high temperature resistance and a yield of 99.0%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 resistant drop Jie Ji Y are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature resistant degradation agent Y.
Example 26
Chlorobenzene (40 ml) and 1, 4-dichloro phenyl isothiocyanate (4.08 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.5h, the filtrate is filtered, and the solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate and the white solid was suction filtered off to give Jie Ji Z3.22 g of polycarbonate with a high temperature resistance and a yield of 79.0%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ10.89(s,1H),7.34-7.50(m,2H)。
then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji Z are taken, and stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent Z.
Example 27
Chlorobenzene (40 ml) and 1, 3-dichloro phenyl isothiocyanate (4.08 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.5h, the filtrate is filtered, and the solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji. Alpha.3.14 g of polycarbonate having a high temperature resistance and a yield of 77.0%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ10.81(s,1H),8.01(s,1H),7.57(s,1H)。
then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji alpha are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent alpha.
Example 28
Chlorobenzene (40 ml) and 1, 2-dichloro phenyl isothiocyanate (4.08 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium trichloride (6.65 g,30 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium trichloride is completely dissolved, reflux reaction is carried out for 5.5h, the filtrate is filtered, and the solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered to give Jie Ji.06 g of polycarbonate having a high temperature resistance of 75.0% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 high temperature resistant and Jie Ji beta are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of the rotating speed of 300r/min and the mixing time of 10min, so as to prepare the polycarbonate composition containing 10ppm of high temperature resistant degradation agent beta.
Example 29
Chlorobenzene (40 ml) and 1-methoxy-2-chloro phenyl isothiocyanate (4.00 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji. Gamma.3.70 g of polycarbonate having a high temperature resistance and a yield of 92.5%. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ9.25(s,1H),7.45-7.76(m,2H),4.02(s,3H)。
then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji gamma are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent gamma.
Example 30
Chlorobenzene (40 ml) and 1,2, 3-trimethoxyphenyl isothiocyanate (4.50 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji 4.41.41 g of polycarbonate having a high temperature resistance of 98.0% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ9.01(s,1H),6.78(s,1H),3.78(s,9H)。
then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji delta are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation resistant agent delta.
Example 31
Chlorobenzene (40 ml) and 1,2, 4-trimethoxyphenyl isothiocyanate (4.50 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji 4.41.41 g of polycarbonate having a high temperature resistance of 98.0% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ9.07(s,1H),6.82(s,1H),3.88(s,9H)。
Then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji epsilon were stirred and mixed uniformly by a high-speed mixer under the working condition of the rotation speed of 300r/min and the mixing time of 10min, so as to prepare a polycarbonate composition containing 10ppm of high temperature degradation resistant epsilon.
Example 32
Chlorobenzene (40 ml) and 1, 2-dimethoxy-4-chlorophenyl isothiocyanate (4.60 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux reaction is carried out for 4.0h after the indium nitrate is completely dissolved, the filtrate is filtered, and the solvent in the filtrate is distilled off by a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate and the white solid was suction filtered off to give Jie Ji 4.40.40 g of polycarbonate with a high temperature resistance drop of 95.5% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,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 resistant drop Jie Ji zeta were taken, and stirred and mixed uniformly under the working condition of a rotation speed of 300r/min and a mixing time of 10min by using a high-speed mixer, so as to prepare a polycarbonate composition containing 10ppm of high temperature resistant degradation agent zeta.
Example 33
Chlorobenzene (40 ml) and 1,2,3, 4-tetramethoxyl phenyl isothiocyanate (5.11 g,20 mmol) are sequentially added into a reactor provided with a thermometer and a reflux condenser, indium nitrate (4.10 g,20 mmol) is added into the reactor at one time, the temperature of the reaction system is raised to 132 ℃ of the boiling point of the chlorobenzene, reflux is carried out, after the indium nitrate is completely dissolved, reflux reaction is carried out for 4.0h, the filtrate is filtered, and the solvent in the filtrate is removed by evaporation through a rotary evaporator, so that a crude product is obtained. The crude product obtained was recrystallized from ethyl acetate, and the white solid was suction-filtered off to give Jie Ji 5.06.06 g of polycarbonate having a high temperature resistance of 99.0% yield. The reaction formula is as follows:
1 H NMR(CDCl 3 ,500MHz):δ8.78(s,1H),3.52(s,12H)。
then, 12kg of polycarbonate powder and 0.12g of polycarbonate with high temperature resistance reduced Jie Ji eta are taken, and are stirred and mixed uniformly by a high-speed mixer under the working condition of 300r/min of rotating speed and 10min of mixing time, so as to prepare the polycarbonate composition containing 10ppm of high temperature degradation 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 Jie Ji H, and stirring and mixing uniformly by using a high-speed mixer under the working condition of 300r/min and 10min of mixing time to prepare the polycarbonate composition containing 5ppm of high-temperature degradation resistant agent E and 5ppm of 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 Jie Ji X, and stirring and mixing uniformly by using a high-speed mixer under the working condition of 300r/min and 10min of mixing time to prepare the polycarbonate composition containing 5ppm of high-temperature degradation resistant agent K and 5ppm of 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 Jie Ji eta, and stirring and mixing uniformly by using a high-speed mixer under the working condition of 300r/min and 10min of mixing time to prepare the polycarbonate composition containing 10ppm of high-temperature degradation resistant agent X and 10ppm of 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 is 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 stirring and uniformly mixing under the working condition of the rotating speed of 300r/min and the mixing time of 10min by using a high-speed mixer 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 stirring and uniformly mixing under the working condition of the rotating speed of 300r/min and the mixing time of 10min by using a high-speed mixer 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-methylbenzothiazolin, and stirring and uniformly mixing under the working condition of 300r/min of rotating speed and 10min of mixing time by using a high-speed mixer to prepare the polycarbonate composition added with 10ppm of antioxidant 2-methylbenzothiazolin.
Comparative example 5
Polyphosphoric acid (40 ml) and 2-aminophenylthiophenol (2.50 g,20 mmol) were successively charged into a reactor equipped with a thermometer and a reflux condenser, the temperature of the reaction system was raised to 150℃and formic acid (1.01 g,22 mmol) was added dropwise to the reactor with a constant pressure dropping funnel over about 2 minutes, and the reaction was continued for 24 hours. And after the reaction is finished, filtering the system to obtain filtrate, and evaporating the solvent in the filtrate by a rotary evaporator to obtain a crude product. Ethyl acetate was used: petroleum ether=4:1 (volume ratio) mixed solution is used as an eluent, the obtained crude product is subjected to silica gel column chromatography purification, target components are collected, and rotary evaporation treatment is carried out, so that 1.485g of white solid (polycarbonate high temperature degradation resistant agent A) is obtained, and the yield is 55%. The reaction formula is as follows:
Comparative example 6
Toluene (20 ml), 2-aminophenylthiophenol (2.50 g,20 mmol) and phosphorus trichloride (27.47 mg,0.2 mmol) 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 (1.01 g,22 mmol) was added dropwise to the reactor with a constant pressure dropping funnel over about 1 minute, 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 a rotary evaporator to obtain a crude product. Ethyl acetate was used: petroleum ether=4:1 (volume ratio) mixed solution is used as an eluent, the obtained crude product is subjected to silica gel column chromatography purification, target components are collected, and rotary evaporation treatment is carried out, so that 2.106g of white solid (polycarbonate high temperature degradation resistant agent A) is obtained, and the yield is 78%. The reaction formula is as follows:
the polycarbonate compositions prepared in the above examples and comparative examples were tested for properties after injection molding. Wherein the injection molding 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 each example and comparative example 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, the test instrument being a 1515 gel chromatograph from waters Corp.
Test piece yellowness: the yellowness YI of a 3mm test piece was measured according to ASTM E313, and the measuring instrument was a VIS color difference meter manufactured by HUNTER LAB company.
Transmittance: the test piece was 3mm thick according to ASTM D1003, and the test instrument was a BYK company HAZE-GARP PLUS HAZE meter.
Notched impact strength was measured according to ASTM D256 under test conditions of 23℃and CEAST9050 type pendulum impact machine.
The tensile strength was measured according to ASTM D638, the test conditions were a tensile speed of 50mm/min, and the test instrument was a MTS company's CMT4104-BZ microcomputer controlled electronic universal tester.
Table 2 performance test table
/>
It is well known to those skilled in the art that the high temperature degradation resistance of polycarbonates can be expressed in terms of molecular weight, molecular weight distribution, light transmittance, yellowness, impact strength, tensile strength, further explained by: polycarbonates have smaller molecular weights, broader molecular weight distributions, lower light transmittance and higher yellowness after being degraded at high temperatures, and reduced impact and tensile strength.
As shown by the test results, compared with the comparative example, each example of the invention has higher molecular weight, narrower molecular weight distribution, higher light transmittance and lower yellowness and has higher impact strength and tensile strength under the condition of the same high-temperature degradation resistance agent addition amount (10 ppm), which indicates that the technical scheme of the invention has more excellent high-temperature degradation resistance capability than the prior art under the condition of the same addition amount;
Further, when the polycarbonate composition (the addition amount of the high-temperature degradation resistant agent is 10 ppm) prepared in each embodiment of the invention is compared with the polycarbonate composition (the addition amount of the existing high-temperature degradation resistant agent is 4000 ppm) prepared in the comparative example, the result shows that the addition amount of the high-temperature degradation resistant agent to the polycarbonate is obviously reduced under the same high-temperature degradation resistant capability, and the high-temperature degradation resistant efficiency of the high-temperature degradation resistant agent prepared in the invention is higher, the high-temperature degradation resistant capability is stronger, and the addition amount of the high-temperature degradation resistant agent can be obviously reduced when the 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 post-treat and purify, and low in cost, and the polycarbonate additive with good high-temperature degradation resistance can be prepared, so that the polycarbonate still has high molecular weight, narrow molecular weight distribution, high light transmittance, low yellowness and good mechanical properties 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 foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (6)

1. A preparation method of a polycarbonate high-temperature degradation resistant agent comprises the following steps:
1) Dissolving aryl isothiocyanate and indium salt in a solvent;
2) Heating, stirring and mixing the solution, and reacting to obtain aryl benzothiazole, wherein the indium salt is one or more of indium salt corresponding to inorganic acid and indium salt corresponding to organic acid.
2. The method of claim 1, wherein the aryl isothiocyanate has the general structure:
wherein the substituent R group is an alkyl, alkoxy, aryl, heterocyclic, hydroxy or halogen substituent; can be monosubstituted, disubstituted, trisubstituted or tetrasubstituted; the mutual positioning of the disubstituents in the benzene ring is optionally from ortho, meta and para; the mutual positioning of the trisubstituted groups in the benzene ring is selected from continuous substitution positions or interval substitution positions.
3. The method of claim 1, 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, a-naphthalene isothiocyanate, β -naphthalene isothiocyanate, a-benzothiazolyl isothiocyanate, β -benzothiazolyl isothiocyanate, 5-quinoline isothiocyanate, 6-quinoline isothiocyanate, a-benzothiophene, β -benzothiophene isothiocyanate, p-chloro phenyl isothiocyanate, o-chloro phenyl 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-methoxy-2-chloro phenyl isothiocyanate, 1, 2-trimethoxyphenyl isothiocyanate, 1, 2-trimethoxyphenyl isothiocyanate, 1, 4-2-dichloro phenyl isothiocyanate, 4-methoxy phenyl isothiocyanate.
4. A process according to any one of claims 1 to 3, wherein the solvent is selected from one or more of acetonitrile, toluene, chlorobenzene, o-dichlorobenzene, N-dimethylformamide and dimethylsulfoxide.
5. A method according to any one of claims 1 to 3, wherein the molar ratio of aryl isothiocyanate to indium salt is 1:1 to 2.
6. A process according to any one of claims 1 to 3, wherein the reaction temperature of the system in step 2) is 80 to 189 ℃, and the stirring speed in step (2) is 100 to 500 r.min -1 Stirring for 2.5-5.5h; and/or, after the reaction in the step 2), obtaining a target product through separation and purification, wherein the separation and purification method comprises suction filtration, recrystallization, column chromatography separation and liquid-liquid extraction.
CN202210126906.2A 2022-02-11 2022-02-11 Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition Active CN114516848B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210126906.2A CN114516848B (en) 2022-02-11 2022-02-11 Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210126906.2A CN114516848B (en) 2022-02-11 2022-02-11 Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition

Publications (2)

Publication Number Publication Date
CN114516848A CN114516848A (en) 2022-05-20
CN114516848B true CN114516848B (en) 2024-02-02

Family

ID=81597325

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210126906.2A Active CN114516848B (en) 2022-02-11 2022-02-11 Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition

Country Status (1)

Country Link
CN (1) CN114516848B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3262907A (en) * 1962-09-20 1966-07-26 Monsanto Co Stabilization of polyaldehydes with benzothiazole and derivatives thereof
US4803236A (en) * 1986-02-25 1989-02-07 Celanese Corporation Stabilization of aromatic polyesters with mercaptobenzothiazole
JPH02218744A (en) * 1989-02-18 1990-08-31 Idemitsu Petrochem Co Ltd Polycarbonate resin composition
US5055505A (en) * 1990-04-25 1991-10-08 Industrial Technology Research Institute Heat stabilized ABS-polycarbonate polymer blend compositions
DE4030511A1 (en) * 1990-09-27 1992-04-02 Basf Ag HIGH-TEMPERATURE-RESISTANT, POLYARYL ETHERS CONTAINING BENZTHIAZOLE
DE19509511A1 (en) * 1995-03-16 1996-09-19 Bayer Ag (Co) polycarbonates stabilized against gamma radiation
CN102030964A (en) * 2009-09-28 2011-04-27 杭州巨星科技股份有限公司 Blending modified acrylonitrile butadiene styrene (ABS) alloy material
CN104557768A (en) * 2014-12-09 2015-04-29 温州大学 Synthesis method of benzothiazole derivatives
CN107090168A (en) * 2017-06-26 2017-08-25 宁波市特尔佳塑料科技有限公司 A kind of anlistatig PC/ABS compositions
CN110483569A (en) * 2019-08-09 2019-11-22 万华化学集团股份有限公司 A kind of polycarbonate antioxidant, preparation method and a kind of polycarbonate compositions
CN112795160A (en) * 2020-12-30 2021-05-14 宁波能之光新材料科技股份有限公司 Antibacterial masterbatch for transparent polycarbonate and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3262907A (en) * 1962-09-20 1966-07-26 Monsanto Co Stabilization of polyaldehydes with benzothiazole and derivatives thereof
US4803236A (en) * 1986-02-25 1989-02-07 Celanese Corporation Stabilization of aromatic polyesters with mercaptobenzothiazole
JPH02218744A (en) * 1989-02-18 1990-08-31 Idemitsu Petrochem Co Ltd Polycarbonate resin composition
US5055505A (en) * 1990-04-25 1991-10-08 Industrial Technology Research Institute Heat stabilized ABS-polycarbonate polymer blend compositions
DE4030511A1 (en) * 1990-09-27 1992-04-02 Basf Ag HIGH-TEMPERATURE-RESISTANT, POLYARYL ETHERS CONTAINING BENZTHIAZOLE
DE19509511A1 (en) * 1995-03-16 1996-09-19 Bayer Ag (Co) polycarbonates stabilized against gamma radiation
CN102030964A (en) * 2009-09-28 2011-04-27 杭州巨星科技股份有限公司 Blending modified acrylonitrile butadiene styrene (ABS) alloy material
CN104557768A (en) * 2014-12-09 2015-04-29 温州大学 Synthesis method of benzothiazole derivatives
CN107090168A (en) * 2017-06-26 2017-08-25 宁波市特尔佳塑料科技有限公司 A kind of anlistatig PC/ABS compositions
CN110483569A (en) * 2019-08-09 2019-11-22 万华化学集团股份有限公司 A kind of polycarbonate antioxidant, preparation method and a kind of polycarbonate compositions
CN112795160A (en) * 2020-12-30 2021-05-14 宁波能之光新材料科技股份有限公司 Antibacterial masterbatch for transparent polycarbonate and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ABS树脂的共混改性;曾威;《合成树脂及塑料》;第16卷(第6期);第53-56页 *
Acidic Co-Catalysts in Cationic Gold Catalysis;Pablo Barrio et al.;《Gold Catalysis》;第22卷;第16410-16414页 *
InCl3 -assisted, synthesis and cytotoxic studies of some novel heteroaryl thiazoles;Kallimeledoddi Boregowda. Puttaraju et al.,;《International Journal of Chemical and Pharmaceutical Sciences》;第4卷(第3期);第33-41页 *

Also Published As

Publication number Publication date
CN114516848A (en) 2022-05-20

Similar Documents

Publication Publication Date Title
US3678044A (en) Substituted flavanones
US4111899A (en) Heat stabilized thermoplastic resins containing compounds with phosphorus to phosphorus bonds
CN110183727B (en) Benzothiazole nitrogen phosphorus sulfur ternary synergistic flame retardant containing double DOPO units, and preparation method and application thereof
CN114516848B (en) Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition
US4834909A (en) Thermochromic double-complex salts
CN110981912A (en) Phosphoric acid triester DOPO derivative flame retardant and preparation method thereof
CN110483569B (en) Polycarbonate antioxidant, preparation method and polycarbonate composition
US4274998A (en) Diester of 3,5,3',5'-tetrabromo-bisphenol A with halogenated aromatic carboxylic acid
JP5476992B2 (en) Process for producing triphenylenes and crystals obtained by the process
JP5090107B2 (en) Method for producing tetrakis (allyloxyphenyl) hydrocarbon compound
CA1119608A (en) Aryl phosphonites and thiophosphonites
JP4211121B2 (en) Silicon-containing organophosphate compound, method for producing the same, flame retardant containing the same, and flame retardant resin composition
EP0763540A1 (en) New crystalline form of tetrakis-(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite
CN113429629A (en) Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin
US4946991A (en) Transhexahydroterephthalic acid ester derivatives
CH470410A (en) Process for the preparation of benzoxazole derivatives and the use thereof
US4365055A (en) Process for producing substantially linear carbonate polymer
JPS63238055A (en) Fluorinated alkylamidosulfonates, synthesis thereof, use as flame retardant and polycarbonate forming composition
KR20150055895A (en) Xanthene dye compounds and method for producing thereof
JPS61112059A (en) 2-anilino-1,6-dihydro-6-oxo-5-pyrimidinecarbonitrile derivative
JPH06116191A (en) Production of 1,3-dihydroxy-4,6-bis(alpha-methyl-alpha-@(3754/24)4'-hydroxyphenyl)ethyl)benzene
JP7303076B2 (en) Method for producing compound having binaphthalene skeleton
US4442293A (en) Di-acetylenyl-substituted 2-phenylbenzothiazoles
JPS5913514B2 (en) Oxazolyl ethylene powder
US4971725A (en) Thermochromic double-complex salts

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant