CN110724255B - Compound catalyst and application thereof in preparation of bio-based polycarbonate - Google Patents
Compound catalyst and application thereof in preparation of bio-based polycarbonate Download PDFInfo
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- CN110724255B CN110724255B CN201911112682.4A CN201911112682A CN110724255B CN 110724255 B CN110724255 B CN 110724255B CN 201911112682 A CN201911112682 A CN 201911112682A CN 110724255 B CN110724255 B CN 110724255B
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Abstract
The invention provides a compound catalyst and application thereof in preparation of bio-based polycarbonate, wherein the compound catalyst comprises halide and an organic salt catalyst, and the halide comprises any one or combination of at least two of alkali metal halide, metal halide and alkaline earth metal halide. The organic salt catalyst comprises any one or the combination of at least two of organic alkali metal catalysts or organic alkaline earth metal catalysts, the halide and the organic salt catalyst in the compound catalyst are mutually cooperated to play a catalytic role, so that the compound catalyst has better catalytic activity and high stability, the catalytic selectivity of the catalytic reaction is improved, the product yield is improved, the compound catalyst is used for preparing the bio-based polycarbonate, the activity and the selectivity of the catalyst are improved, the reaction time is shortened, the product yield is improved, and the bio-based polycarbonate with higher molecular weight can be prepared.
Description
Technical Field
The invention belongs to the technical field of green and clean catalysis, and particularly relates to a compound catalyst and application thereof in preparation of bio-based polycarbonate.
Background
Polycarbonate (PC) is a colorless and transparent amorphous and thermoplastic material, has the characteristics of heat resistance, impact resistance, chemical corrosion resistance and the like, and is widely applied to various fields. With the concern of green chemistry and sustainable development, the development of bio-based polymer materials has become a new trend. The production process of PC is gradually developing towards green and environmental protection, and gradually gets rid of the existing traditional phosgene method and diphenyl carbonate/bisphenol A molten ester exchange method route, so that the preparation of PC by using isosorbide which is a renewable resource becomes a hot point of recent research.
The isosorbide is derived from plant starch, is a cyclic aliphatic diol with relatively stable chemical property and thermal property, and has the characteristics of rigidity, chiral structure, no toxicity and the like, so that the isosorbide is hopeful to become a bio-based monomer for preparing PC. Therefore, we investigated a process for preparing isosorbide-type Polycarbonate (PIC) by transesterification of dimethyl carbonate (DMC) with isosorbide. The method has the following three advantages: firstly, diphenyl carbonate and bisphenol A used in the traditional process are avoided, isosorbide replaces bisphenol A, and DMC replaces diphenyl carbonate; secondly, the reaction process is simple, and the one-step synthesis method directly synthesizes the polycarbon by the reaction of DMC and isosorbide, thereby avoiding the defects of multi-step reaction, complex steps, overhigh reaction temperature, large equipment investment and the like in the traditional process; and thirdly, the byproduct methanol is simple and easy to recycle compared with the byproduct phenol in the traditional process (as shown in a synthetic route 1).
Scheme 1: one-step synthetic route of bio-based polycarbonate
The patents and articles for synthesizing polycarbonates reported so far have focused on the conventional phosgene process or the melt transesterification process using diphenyl carbonate and bisphenol A as raw materials, and many catalysts have been developed, but relatively few studies have been made on the synthesis of isosorbide-type polycarbonates, and partly only on the modification of isosorbide, and various copolycarbonates synthesized by copolymerizing dihydroxy compounds and isosorbide have been sought (for example, JP56055425, WO2004111106, JP06145336 and JP 63012896).
In the methods for synthesizing bio-based polycarbonate by using carbonic acid diester and isosorbide as raw materials, basic inorganic/organic salt catalysts, quaternary ammonium and imidazole ionic liquid catalysts and the like are mainly used, wherein the basic metal oxide comprises alkali metal oxide (CN107674190), and the basic metal salt catalyst comprises sodium hydroxide, lithium acetylacetonate, lithium carbonate, zinc acetate, phenylphosphate and the like (CN101889040, Polymer Chemistry,2013,51, 1387-; imidazole based catalysts include methyl imidazole lactate (CN 107573497); quaternary ammonium catalysts include tetrabutylammonium hydroxides (CN 101883808). Although a plurality of types of reported catalysts are provided, specific research is not deep, the problems of low reaction catalytic activity, low selectivity, poor catalyst stability, high cost and the like of the existing developed catalysts exist, and finally, a trace amount of isosorbide is not sufficiently reacted in a prepolymerization stage to cause yellowing of products in a polycondensation stage, so that the development of a high-activity, high-selectivity and stable-structure catalytic system is particularly important for industrialization.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a compound catalyst and an application thereof in preparation of bio-based polycarbonate, wherein the compound catalyst contains ingredients which have synergistic effect and high stability, and promotes the forward reaction of catalysis through the nucleophilicity of anions and cations and the action of hydrogen bonds, so that the activity and selectivity of the catalyst are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a compound catalyst, which comprises a halide and an organic salt catalyst, wherein the halide comprises any one or at least two of alkali metal halide, metal halide and alkaline earth metal halide, and the organic salt catalyst comprises any one or at least two of organic alkali metal catalyst or organic alkaline earth metal catalyst.
In the invention, the halide and the organic salt catalyst jointly enhance the catalytic activity through the nucleophilicity of anions and cations and the action of hydrogen bonds, and the halide and the organic salt catalyst exert the catalytic effect synergistically, so that the halide and the organic salt catalyst have better catalytic activity and high stability, the catalytic selectivity of the catalytic reaction is improved, and the product yield is improved.
Preferably, the molar ratio of the halide to the organic salt-based catalyst is 50:1 to 1:50, such as 50:1, 48:1, 45:1, 40:1, 38:1, 35:1, 33:1, 30:1, 25:1, 23:1, 20:1, 18:1, 15:1, 13:1, 10:1, 8:1, 5:1, 3:1, 1:5, 1:10, 1:13, 1:15, 1:18, 1:20, 1:23, 1:25, 1:28, 1:30, 1:33, 1:35, 1:38, 1:40, 1:43, 1:45, 1:48, or 1:50, and the like. When the molar ratio of the halide to the organic salt catalyst is 50:1-1:50, the synergistic effect of the halide and the organic salt catalyst can be better exerted, and the catalytic effect is improved.
Preferably, the alkali metal halide is any one of or a combination of at least two of chlorides, bromides or iodides of Li, Na, K, Rb or Cs.
Preferably, the metal halide is any one of or a combination of at least two of chlorides, bromides or iodides of Ba, Co, Zn, Ni, Cu, Pb, Rh, Ag or W.
Preferably, the alkaline earth metal halide is any one of or a combination of at least two of chloride, bromide or iodide of Mg or Ca.
Preferably, the structure of the organic alkali metal catalyst is represented by MY, wherein M is an alkali metal cation, the alkali metal is selected from Li, Na, K or Cs, and Y is any one of the following organic anions:
wherein R is C1-C16Alkyl of (C)4-C20Cycloalkyl and C4-C20Any one of the aryl groups of (1).
Preferably, there areThe structure of the organic alkaline earth metal catalyst is represented as XY2Wherein X is divalent alkaline earth metal ion, Y is any one of the following organic anions:
wherein R is C1-C16Alkyl of (C)4-C20Cycloalkyl and C4-C20Any one of the aryl groups of (1).
Preferably, X is magnesium ion or calcium ion.
Preferably, R is C1-C4Alkyl of (C)4-C10Cycloalkyl of, C2-C8The aromatic group of (1).
In the present invention, said C1-C16The alkyl group of (b) may be an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 carbon atoms, preferably a methyl, ethyl or tert-butyl group.
In the present invention, said C4-C20The cycloalkyl group of (b) may be a cycloalkyl group having 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, and is preferably cyclohexane.
In the present invention, said C4-C20The aryl group of (a) may be an aryl group having 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, preferably a phenyl group.
In the invention, the halide contained in the compound catalyst is mixed with the organic salt catalyst to obtain the compound catalyst.
In another aspect, the invention provides the application of the compound catalyst in the preparation of the bio-based polycarbonate.
Preferably, the application is specifically: dihydroxy compounds and carbonic acid diester are used as raw materials, and are catalyzed by the compound catalyst to obtain a prepolymer through ester exchange reaction, and then the prepolymer is subjected to polycondensation reaction to synthesize the bio-based polycarbonate.
The reaction formula is as follows:
R1is a benzene ring or a methyl group; r2Is alkylene, cycloalkylene or aromatic group, and y/x is 0/100-60/40.
Preferably, the molar ratio of dihydroxy compound to carbonic acid diester is 1:0.5 to 30, such as 1:0.5, 1:0.8, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:13, 1:15, 1:18, 1:20, 1:22, 1:24, 1:25, 1:27, 1:29, or 1:30, and the like.
Preferably, the dihydroxy compound is selected from at least one of isosorbide, an aromatic dihydroxy compound, or an aliphatic dihydroxy compound.
Preferably, the aromatic dihydroxy compound is selected from the group consisting of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9-bis (4- (3-hydroxy-2, 2-dimethylpropoxy) phenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, and mixtures thereof, 9, 9-bis (4- (2-hydroxyethoxy) -3, 5-dimethylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, 4' - (1-phenylethyl) bisphenol, 2-bis (4-hydroxyphenyl) butane, 4' -ethylenebiphenol, 4' -dihydroxydiphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, 4' -dihydroxytetraphenylmethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2, 9-bis (4- (2-hydroxyethoxy) -3, 5-dimethylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 4' - (1-, 2, 2-di (4-hydroxyphenyl) propane and hydroquinone.
Preferably, the aliphatic dihydroxy compound is selected from the group consisting of dihydroxy compounds of the chain type such as diethylene glycol, triethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, etc.; any one of alicyclic dihydroxy compounds such as 1, 3-cyclopentanediol, 1, 4-cyclohexanediol, and 1, 4-cyclohexanedimethanol.
Preferably, the carbonic acid diester is selected from dimethyl carbonate, diethyl carbonate or diphenyl carbonate.
Preferably, in such applications, the built catalyst of the present invention is used in an amount of 1 to 30% by mole of the dihydroxy compound, e.g., 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 24%, 26%, 28%, or 30%.
Preferably, the transesterification stage temperature is controlled at 60-180 deg.C, such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C or 180 deg.C.
Preferably, the transesterification reaction is carried out under the protection of a protective gas, preferably nitrogen.
Preferably, the transesterification reaction is carried out at atmospheric pressure.
Preferably, the transesterification reaction time is 0.5 to 8h, such as 0.5h, 0.8h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8 h.
Preferably, the polycondensation reaction is carried out at a temperature of 180 ℃ to 260 ℃, such as 180 ℃, 185 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃ or 260 ℃.
Preferably, the degree of vacuum in the polycondensation reaction is controlled to be 4.0X 10-3MPa-1.0×10-5MPa, e.g. 4.0X 10-3MPa、1.0×10-3MPa、8.0×10-4MPa、4.0×10-4MPa、1.0×10-4MPa、9.0×10-5MPa、5.0×10- 5MPa、3.0×10-5MPa、2.0×10-5MPa or 1.0X 10-5MPa。
Preferably, the time of the polycondensation reaction is 0.1 to 6h, such as 0.1h, 0.3h, 0.5h, 0.8h, 1h, 1.5h, 2h, 2.5h, 2.8h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6 h.
Compared with the existing catalyst, the compound catalyst inhibits Fries rearrangement, reduces branching of polycarbonate, greatly improves activity and selectivity of the catalyst, shortens reaction time by 40-60% in a prepolymerization stage and 60-80% in a polycondensation stage compared with the developed catalyst, improves product yield, and can prepare the bio-based polycarbonate with higher molecular weight.
Compared with the prior art, the invention has the following beneficial effects:
the halide and the organic salt catalyst in the compound catalyst of the invention mutually cooperate to play a catalytic role, so that the compound catalyst has better catalytic activity and high stability, improves the catalytic selectivity of catalytic reaction and improves the product yield, compared with the existing catalyst, the compound catalyst is used for preparing the bio-based polycarbonate, the invention inhibits Fries rearrangement, reduces the branching of the polycarbonate, greatly improves the activity and the selectivity of the catalyst, shortens the reaction time by 40 to 60 percent in a prepolymerization stage and 60 to 80 percent in a polycondensation stage, improves the product yield, and can prepare the bio-based polycarbonate with higher molecular weight.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The polycarbonate synthesis method comprises the following steps:
the implementation method comprises the following steps: in the ester exchange stage, under normal pressure, 14.6g (0.10mol) of isosorbide and 63g (0.70mol) of dimethyl carbonate are added into a compound catalyst under nitrogen atmosphere, and the compound catalyst comprises a main catalyst of 30 multiplied by 10 sodium iodide-3g (2X 10 of the amount of isosorbide material)-2%) and a cocatalyst of 20X 10 sodium triazole-3g (2X 10 of the amount of isosorbide material)-2%) is heated to make itMelting, refluxing under normal pressure, raising the reaction temperature to 160 ℃, and reacting for 1h in a nitrogen atmosphere to synthesize a prepolymer; the temperature is raised to 180 ℃ and the removal of excess dimethyl carbonate and the formation of methanol is maintained. The polycondensation stage is that the prepolymer is processed under the vacuum degree of 1.0X 10-5And (5) reacting for 15min at the reaction temperature of 210 ℃ under MPa to obtain the bio-based polycarbonate. After the reaction, the reaction mixture was cooled to room temperature under vacuum, dissolved in chloroform and precipitated in anhydrous methanol. The yield of the obtained polycarbonate was 87%, and the number average molecular weight was 2.4X 104. (Agilent PL-GPC 50, the number average molecular weights of the following examples and comparative examples were measured by using the apparatus)
Comparative example 1
This comparative example 1 differs from example 1 only in that the formulated catalyst described in example 1 was replaced with 42.4X 10-3g of lithium acetylacetonate (0.4% of the amount of isosorbide material). The same conditions were applied to the other preparations, and the yield of the obtained polycarbonate was 85%, and the number average molecular weight was 1.7X 104。
Comparative example 2
This comparative example 1 differs from example 1 only in that the formulated catalyst described in example 1 was replaced with 42.4X 10-3g of lithium acetylacetonate (0.4% of the amount of isosorbide material). When the yield of the obtained polycarbonate was 87%, the number average molecular weight was 2.4X 104The required pre-polymerization transesterification reaction time is 2.5h, the polycondensation time is 1h, and the polycondensation temperature is 250 ℃.
Comparative example 3
This comparative example differs from example 1 only in that the formulated catalyst described in example 1 was replaced with sodium iodide alone, 60X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 45% and a number average molecular weight of 0.9X 10, without changing other conditions4。
Comparative example 4
The comparative example differs from example 1 only in that the formulated catalyst described in example 1 was replaced with sodium triazole 40 × 10 alone-3g (4X 10 of the amount of isosorbide material)-2%) and other conditions were not changed, and the obtained polycarbon was obtainedThe yield of the acid ester was 35%, and the number average molecular weight was 0.7X 104。
Example 2
The difference from comparative example 1 is that the catalyst used was changed to 30X 10 sodium iodide as the main catalyst-3g (2X 10 of the amount of isosorbide material)-1%) cocatalyst imidazole sodium 18X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 95% and the number average molecular weight was 2.5X 104。
Example 3
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the starting materials used were 14.6g (0.10mol) of isosorbide and 270g (3mol) of dimethyl carbonate, and the cocatalyst was sodium phenolate 23.5X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 99% and the number average molecular weight was 3X 104。
Example 4
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the starting materials used were 14.6g (0.10mol) of isosorbide and 4.5g (0.05mol) of dimethyl carbonate, and the cocatalyst was sodium phenolate 23.5X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in a yield of 40% and a number average molecular weight of 1X 10, under otherwise unchanged conditions4。
Example 5
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2Percent) and the cocatalyst is sodium triazole 20 multiplied by 10-3g (2X 10 of the amount of isosorbide material)-1% of the total amount of polycarbonate, the reaction temperature in the prepolymerization stage was raised to 180 ℃ under otherwise unchanged conditions, the yield of the obtained polycarbonate was 93%, and the number-average molecular weight was 2.7X 104。
Example 6
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2Percent) and the cocatalyst is sodium triazole 20 multiplied by 10-3g (2X 10 of the amount of isosorbide material)-1% of the total amount of polycarbonate, the reaction temperature in the prepolymerization stage is raised to 60 ℃, other conditions are unchanged, the yield of the obtained polycarbonate is 25%, and the number average molecular weight is 0.4 multiplied by 104。
Example 7
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2Percent) and the cocatalyst is sodium triazole 20 multiplied by 10-3g (2X 10 of the amount of isosorbide material)-1% of the total amount of polycarbonate, the reaction time of the prepolymerization stage is 0.5h, other conditions are not changed, the yield of the obtained polycarbonate is 45%, and the number average molecular weight is 0.9 multiplied by 104。
Example 8
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2Percent) and the cocatalyst is sodium triazole 20 multiplied by 10-3g (2X 10 of the amount of isosorbide material)-1% of the total amount of polycarbonate, reaction time of the prepolymerization stage is 8h, other conditions are not changed, the yield of the obtained polycarbonate is 97%, and the number average molecular weight is 2.9 multiplied by 104。
Example 9
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2Percent) and the cocatalyst is sodium triazole 20 multiplied by 10-3g (2X 10 of the amount of isosorbide material)-1% of the total amount of polycarbonate in the polycondensation stage for 0.1h, the yield of the polycarbonate obtained is 95%, and the number-average molecular weight is 2X 104。
Example 10
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2%) and the cocatalyst is sodium methoxide 11X 10-3g (2X 10 of the amount of isosorbide material)-1%) for 6h in the polycondensation stage, the yield of the obtained polycarbonate is 96%, and the number average molecular weight is 2.2X 10 without changing other conditions4。
Example 11
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2%) and the cocatalyst is sodium methoxide 11X 10-3g (2X 10 of the amount of isosorbide material)-1%) at 260 ℃ in the polycondensation stage, the yield of the polycarbonate obtained was 93% and the number-average molecular weight was 1.7X 10 without changing the other conditions4。
Example 12
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst sodium iodide used is 30X 10-4g (2X 10 of the amount of isosorbide material)-2Percent) and the cocatalyst is sodium triazole 20 multiplied by 10-3g (2X 10 of the amount of isosorbide material)-1% of the total amount of polycarbonate in the polycondensation stage, the reaction temperature in the polycondensation stage is 180 ℃, the other conditions are not changed, the yield of the obtained polycarbonate is 90%, and the number average molecular weight is 1.8 multiplied by 104。
Example 13
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is sodium phenate 23.5X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 86% and the number average molecular weight was 1.8X 104。
Example 14
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the main catalyst used is sodium iodide 15X 10-4g (1X 10 of the amount of isosorbide material)-2%) and the cocatalyst is sodium phenolate 23.5X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in a yield of 66% and a number average molecular weight of 1X 10 under otherwise unchanged conditions4。
Example 15
The polycarbonate synthesis method comprises the following steps:
the difference from example 1 is only that 0.3g of sodium iodide (2% of the amount of isosorbide) as a main catalyst is used and 11.7X 10% of sodium phenate as a cocatalyst is used-3g (1X 10 of the amount of isosorbide material)-1%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 86% and the number average molecular weight was 1.8X 104。
Example 16
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the catalyst used was changed to the main catalyst sodium iodide 15X 10-3g (1X 10 of the amount of isosorbide material)-1%) cocatalyst imidazole sodium 36X 10-2g (4% of the isosorbide substance), and the polycarbonate obtained in the same conditions as those described above was obtained in a yield of 97% and a number average molecular weight of 2.6X 104。
Example 17
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the catalyst used was changed to 6X 10 sodium iodide as the main catalyst-1g (4% of the amount of isosorbide material) cocatalyst sodium imidazole 9X 10-3g (1X 10 of the amount of isosorbide material)-1%) was prepared in a yield of 98% and a number average molecular weight of 2.7X 10 under otherwise unchanged conditions4。
Example 18
The polycarbonate synthesis method comprises the following steps:
the difference from example 1 is only that the catalyst used is changed to the main catalyst potassium iodide 33.2X 10-3g (2X 10 of the amount of isosorbide material)-1%) cocatalyst imidazole sodium 18X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 88% and the number average molecular weight was 1.7X 104。
Example 19
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the catalyst used was changed to the main catalyst lithium iodide 26.6X 10-3g (2X 10 of the amount of isosorbide material)-1%) cocatalyst imidazole sodium 18X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in a yield of 82% and a number average molecular weight of 1.6X 10 under otherwise unchanged conditions4。
Example 20
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the catalyst used was changed to the main catalyst lithium iodide 26.6X 10-3g (2X 10 of the amount of isosorbide material)-1%) cocatalyst imidazole sodium 18X 10-3g (2X 10 of the amount of isosorbide material)-1%) was prepared in a yield of 82% and a number average molecular weight of 1.6X 10 under otherwise unchanged conditions4。
Example 21
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is sodium benzoate 29X 10-3g (2X 10 of the amount of isosorbide material)-2%) was added, the yield of the obtained polycarbonate was 10% and the number average molecular weight was 3000, without changing other conditions.
Example 22
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is benzenePotassium phenolate 26.5X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 95% and the number average molecular weight was 2.2X 104。
Example 23
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that sodium methoxide 11X 10 is used as co-catalyst-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 65% and the number average molecular weight was 1.4X 104。
Example 24
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is sodium ethoxide 14X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in a manner not changing the other conditions, and the yield of the obtained polycarbonate was 85.01%, and the number average molecular weight was 1.9X 104。
Example 25
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is sodium acetate 16.5X 10-3g (2X 10 of the amount of isosorbide material)-2%) was added, the yield of the obtained polycarbonate was 25% and the number average molecular weight was 3000, without changing other conditions.
Example 26
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is sodium tert-butoxide, 24X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 95% and the number average molecular weight was 2.4X 104。
Example 27
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is potassium methoxide 14X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 75% and a number average molecular weight of 1X 10 under otherwise unchanged conditions4。
Example 28
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is potassium ethoxide 17X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the polycarbonate obtained was 80% and the number average molecular weight was 1.5X 104。
Example 29
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is potassium tert-butoxide 22.5X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 99% and the number average molecular weight was 2X 104。
Example 30
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is lithium tert-butoxide, 16X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 87% and a number average molecular weight of 1.8X 10, without changing other conditions4。
Example 31
The polycarbonate synthesis method comprises the following steps:
the only difference from example 1 is that the cocatalyst used is magnesium tert-butoxide 29X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 88% and the number average molecular weight was 1.9X 104。
Example 32
The polycarbonate synthesis method comprises the following steps:
the implementation method comprises the following steps: the ester exchange stage is to add 14.6g (0.1mol) of isosorbide, 1.18g (0.1mol) of 1, 6-hexanediol and 27g (0.3mol) of dimethyl carbonate into a built catalyst under the condition of normal pressure in a nitrogen atmosphere, wherein the built catalyst comprises 30 x 10 times of sodium iodide serving as a main catalyst-3g (2X 10 of the amount of isosorbide material)-2%) cocatalyst imidazole sodium 18X 10-3g (2X 10 of the amount of isosorbide material)-2Percent), heating to melt the mixture, refluxing, raising the reaction temperature to 150 ℃, and reacting for 2 hours in a nitrogen atmosphere to synthesize a prepolymer; the methanol and other by-products formed are then removed at elevated temperature and maintained. The polycondensation stage is that the prepolymer is processed under the vacuum degree of 1.0X 10-5And (5) reacting for 1h at the reaction temperature of 240 ℃ under MPa to obtain the polycarbonate. After the reaction, the reaction mixture was cooled to room temperature under vacuum, dissolved in chloroform and precipitated in anhydrous methanol. The yield of the obtained polycarbonate was 85%, and the number average molecular weight was 5.4X 104。
Comparative example 5
This comparative example differs from example 32 only in that the formulated catalyst described in example 32 was replaced with sodium iodide alone, 60X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 50% and a number average molecular weight of 1.2X 10, without changing other conditions4。
Comparative example 6
This comparative example differs from example 32 only in that the formulated catalyst described in example 32 was replaced with sodium imidazolium alone, 36X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 40% and a number average molecular weight of 1.0X 10, without changing other conditions4。
Example 33
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 32, 14.6g (0.1mol) of isosorbide were used as the comonomer, 3.54g (0.3mol) of 1, 6-hexanediol and 9g (0.1mol) of dimethyl carbonate were used as the catalyst instead of potassium iodide 33X 10 as the procatalyst-3g (2X 10 of the amount of isosorbide material)-2%) cocatalyst potassium tert-butoxide 22.5X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 70% and a number average molecular weight of 4.5X 10 under otherwise unchanged conditions4。
Example 34
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 32, the comonomers used were 14.6g (0.1mol) of isosorbide, 0.354g (0.03mol) of 1, 6-hexanediol and 54g (0.6mol) of dimethyl carbonate, the catalyst being potassium iodide 33X 10 as the procatalyst-3g (2X 10 of the amount of isosorbide material)-2%) cocatalyst potassium tert-butoxide 22.5X 10-3g (2X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 98% and a number average molecular weight of 4.2X 10 under otherwise unchanged conditions4。
Comparative example 7
This comparative example differs from example 32 only in that the formulated catalyst described in example 32 was replaced with 66X 10 potassium iodide alone-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 49% and a number average molecular weight of 1.1X 10 under otherwise unchanged conditions4。
Comparative example 8
This comparative example differs from example 32 only in that the compounded catalyst described in example 32 was replaced with potassium tert-butoxide alone, 45X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 45% and a number average molecular weight of 1.0X 10, without changing other conditions4。
Example 35
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 32, 14.6g (0.1mol) of isosorbide, 10.4g (0.1mol) of 1, 5-pentanediol and 27g (0.3mol) of dimethyl carbonate were added to conduct a reaction under a nitrogen atmosphere, and the yield of the obtained polycarbonate was 88.4% and the number-average molecular weight was 4.0X 104。
Example 36
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 32, 14.6g (0.1mol) of isosorbide, 14.4g (0.1mol) of 1, 4-cyclohexanedimethanol and 64.3g (0.3mol) of diphenyl carbonate were added under nitrogen atmosphere to conduct reaction, and the yield of the obtained polycarbonate was 83.2% and the number-average molecular weight was 9.5X 104。
Example 37
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 32, 14.6g (0.1mol) of isosorbide, 10.6g (0.1mol) of diethylene glycol and 64.3g (0.3mol) of dimethyl carbonate were charged under nitrogen atmosphere, and the yield of the obtained polycarbonate was 91% and the number average molecular weight was 7.2X 104。
Example 38
The polycarbonate synthesis method comprises the following steps:
the implementation method comprises the following steps: the ester exchange stage is carried out under normal pressure by adding 14.6g (0.10mol) of isosorbide and 63g (0.70mol) of dimethyl carbonate into 15X 10 times of sodium iodide as a main catalyst under nitrogen atmosphere-3g (1X 10 of the amount of isosorbide material)-2%) cocatalyst imidazole sodium 27X 10-3g (3X 10 of the amount of isosorbide material)-2Percent), heating to melt the mixture, refluxing under normal pressure, raising the reaction temperature to 160 ℃, and reacting for 1 hour in a nitrogen atmosphere to synthesize a prepolymer; the temperature is raised to 180 ℃, and the removal of the excessive dimethyl carbonate and the generated methanol is maintained. The polycondensation stage is that the prepolymer is processed under the vacuum degree of 1.0X 10-5And (5) reacting for 15min at the reaction temperature of 230 ℃ under MPa to obtain the bio-based polycarbonate. After the reaction, the reaction mixture was cooled to room temperature under vacuum, dissolved in chloroform and precipitated in anhydrous methanol. The yield of the obtained polycarbonate was 92%, and the number average molecular weight was 3.3X 104And PDI is 1.65.
Example 39
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 38, the catalyst used was changed to 36X 10 of sodium imidazolide as a cocatalyst-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 95% and the number average molecular weight was 3.6X 104And PDI is 1.60.
Example 40
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 38, the catalyst used was changed to 30X 10 sodium iodide as the main catalyst-3g (2X 10 of the amount of isosorbide material)-2%) cocatalyst imidazole sodium 27X 10-3g (3X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 95% and the number average molecular weight was 4.0X 104And PDI is 1.50.
EXAMPLE 41
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 38, the cocatalyst used was changed to sodium triazole 39X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in a manner not changing the other conditions, and the yield of the obtained polycarbonate was 85%, and the number average molecular weight was 2.5X 104And PDI is 1.55.
Example 42
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 38, the cocatalyst used was changed to sodium tert-butoxide 48X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in a yield of 98% and a number average molecular weight of 3.8X 10 under otherwise unchanged conditions4And PDI is 1.50.
Example 43
The polycarbonate synthesis method comprises the following steps:
in the same manner as in example 38, potassium tert-butoxide 45X 10 was used as cocatalyst-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 99% and the number average molecular weight was 3.3X 104And PDI is 1.55.
Example 44
The polycarbonate synthesis method comprises the following steps:
the only difference from example 38 is that the cocatalyst used is lithium tert-butoxide 32X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 95% and the number average molecular weight was 3.4X 104And PDI is 1.45.
Example 45
The polycarbonate synthesis method comprises the following steps:
the only difference from example 38 is that the cocatalyst used is magnesium tert-butoxide 58X 10-3g (4X 10 of the amount of isosorbide material)-2%) was prepared in the same manner as above, and the yield of the obtained polycarbonate was 88% and the number average molecular weight was 2.9X 104And PDI is 1.6.
The compound catalyst disclosed by the invention can improve the yield when being applied to the preparation of polycarbonate, and can obtain a product with a narrow number average molecular weight distribution, and the number average molecular weight of the product can be higher. The comparison of the comparative examples shows that the compound catalyst has synergistic effect in improving the catalytic performance and the product conversion rate and improving the number average molecular weight of the product.
It should be noted that although only the comparative examples of the compounded catalyst in some examples are provided to demonstrate the synergistic effect of the compounded catalyst, the same verification is carried out in other examples, and the synergistic effect is found in all the catalysts used.
The invention is illustrated by the above examples, but the invention is not limited to the above examples, i.e. it is not meant to be dependent on the above examples to practice the invention. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (18)
1. A compound catalyst, which plays a catalytic role in the process of synthesizing bio-based polycarbonate by taking a dihydroxy compound and a carbonic diester as raw materials;
the bio-based polycarbonate is prepared by the following method:
taking a dihydroxy compound and a carbonic diester as raw materials, obtaining a prepolymer through ester exchange reaction under the catalysis of the compound catalyst, and then synthesizing the bio-based polycarbonate through polycondensation;
the compound catalyst comprises halide and an organic salt catalyst, wherein the halide is alkali metal halide, and the organic salt catalyst is an organic alkali metal catalyst or an organic alkaline earth metal catalyst;
the alkali metal halide is any one or combination of at least two of chlorides, bromides or iodides of Li, Na, K, Rb or Cs;
the structure of the organic alkali metal catalyst is represented as MY, wherein M is an alkali metal cation, the alkali metal is selected from Li, Na, K or Cs, and Y is any one of the following organic anions:
wherein R is C1-C16Alkyl of (C)4-C20Cycloalkyl and C6-C20Any one of the aryl groups of (a);
the structure of the organic alkaline earth metal catalyst is represented as XY2Wherein X is divalent alkaline earth metal ion, Y is any one of the following organic anions:
wherein R is C1-C16Alkyl of (C)4-C20Cycloalkyl and C6-C20Any of the aryl groups ofOne kind of the medicine.
2. The compound catalyst according to claim 1, wherein the molar ratio of the halide to the organic salt catalyst is 50:1-1: 50.
3. The built catalyst of claim 1, wherein X is magnesium ion or calcium ion.
4. The built catalyst of claim 1, wherein R is C1-C4Alkyl of (C)4-C10Cycloalkyl and C6Any one of the aromatic groups of (1).
5. The use of the built catalyst according to any one of claims 1-4 in the preparation of bio-based polycarbonate;
the application specifically comprises the following steps: taking a dihydroxy compound and a carbonic diester as raw materials, obtaining a prepolymer through ester exchange reaction under the catalysis of the compound catalyst of any one of claims 1-4, and then synthesizing the bio-based polycarbonate through polycondensation reaction.
6. Use according to claim 5, wherein the molar ratio of dihydroxy compound and carbonic acid diester is 1: 0.5-30.
7. The use according to claim 5, wherein the dihydroxy compound is selected from at least one of isosorbide, an aromatic dihydroxy compound, or an aliphatic dihydroxy compound.
8. Use according to claim 7, wherein the aromatic dihydroxy compound is selected from the group consisting of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9-bis (4- (3-hydroxy-2, 2-dimethylpropoxy) phenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene 9, 9-bis (4- (2-hydroxyethoxy) -3, 5-dimethylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 1, 3-bis [2- (4-hydroxyphenyl) -2-propyl ] benzene, 4' - (1-phenylethyl) bisphenol, 2-bis (4-hydroxyphenyl) butane, 4' -ethylenebiphenol, 4' -dihydroxydiphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, 4' -dihydroxytetraphenylmethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2, 9-bis (4- (2-hydroxyethoxy) -3, 5-dimethylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 4' - (1-phenylethyl, 2, 2-bis (4-hydroxyphenyl) propane or hydroquinone.
9. The use according to claim 7, wherein the aliphatic dihydroxy compound is selected from any of diethylene glycol, triethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 3-cyclopentanediol, 1, 4-cyclohexanediol, or 1, 4-cyclohexanedimethanol.
10. The use according to claim 5, wherein the carbonic acid diester is selected from any one of dimethyl carbonate, diethyl carbonate or diphenyl carbonate.
11. The use according to claim 5, wherein the built catalyst is used in an amount of 1 to 30% by mole based on the dihydroxy compound.
12. Use according to claim 5, wherein the temperature of the transesterification reaction stage is controlled between 60 ℃ and 180 ℃.
13. Use according to claim 5, wherein the transesterification reaction is carried out under the protection of a protective gas, the protective gas being nitrogen.
14. Use according to claim 5, wherein the transesterification reaction is carried out at atmospheric pressure.
15. Use according to claim 5, wherein the transesterification reaction time is between 0.5 and 8 hours.
16. The use according to claim 5, wherein the temperature of the polycondensation reaction is 180-260 ℃.
17. The use according to claim 5, wherein the degree of vacuum is controlled to 4.0X 10 during the polycondensation reaction- 3MPa-1.0×10-5MPa。
18. Use according to claim 5, wherein the polycondensation is carried out for a period of time of 0.1 to 6 hours.
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