CN105949451A - Method for preparing polycarbonate through basic ionic liquid catalysis - Google Patents

Method for preparing polycarbonate through basic ionic liquid catalysis Download PDF

Info

Publication number
CN105949451A
CN105949451A CN201610555312.8A CN201610555312A CN105949451A CN 105949451 A CN105949451 A CN 105949451A CN 201610555312 A CN201610555312 A CN 201610555312A CN 105949451 A CN105949451 A CN 105949451A
Authority
CN
China
Prior art keywords
anion
double
hydroxyl
phenyl
fluorenes
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.)
Granted
Application number
CN201610555312.8A
Other languages
Chinese (zh)
Other versions
CN105949451B (en
Inventor
张锁江
徐菲
成卫国
孙剑
张延强
孙玮
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.)
Institute of Process Engineering of CAS
Original Assignee
Institute of Process Engineering of CAS
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 Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201610555312.8A priority Critical patent/CN105949451B/en
Publication of CN105949451A publication Critical patent/CN105949451A/en
Application granted granted Critical
Publication of CN105949451B publication Critical patent/CN105949451B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a method for preparing polycarbonate through basic ionic liquid catalysis. The method is characterized in that quaternary ammonium and quaternary phosphonium basic ionic liquid serves as a catalyst, the dosage of the catalyst is 5*10<-3>%-5% that of a dihydroxy compound, the dihydroxy compound and dialkyl carbonate serve as the raw materials, the feeding molar ratio of the dihydroxy compound to dialkyl carbonate is 1:0.8 to 1:10, and polycarbonate is synthesized through melting ester exchange. The synthetic processes of polycarbonate comprise the two stages of ester exchange and polycondensation, wherein for the ester exchange stage, on the condition that the reaction temperature ranges from 98 DEG C to 150 DEG C, the pressure is atmospheric pressure, and the reaction time ranges from 3 h to 6 h, prepolymer is obtained, and for the polycondensation stage, polycarbonate is obtained by synthesizing the prepolymer on the condition that the temperature ranges from 210 DEG C to 260 DEG C, the vacuum degree ranges from 4.0*10<-3> MPa to 1.0*10<-5> MPa, and the reaction time ranges from 1 h to 7 h. The synthetic method has the following advantages that the catalyst is simple in component and high in activity, a by-product phenol can be recycled, and the cost is reduced; toxic phosgene is cleared off, and the method is environmentally friendly; zero emission is almost achieved, and the method completely conforms to the concept of cleaning production.

Description

A kind of method of alkali ionic liquid catalyzed preparation of poly carbonic ester
Technical field:
The present invention relates to green, clean catalysis technical field, refer specifically to a kind of with dihydroxy compounds and carbonic acid two Ester is raw material, synthesizes poly-carbonic acid by melting state transesterification reaction under quaternary ammonium, the catalysis of quaternary phosphonium class alkali ionic liquid The method of ester.
Background technology:
Merlon is the thermoplastic engineering plastic of a kind of high comprehensive performance, be in global five large-engineering plastics only One product having good light permeability, is widely used in electronic/electrical device product, building and auto manufacturing etc. Field.Merlon is typically got by petroleum resources derived feed manufacture, in recent years, owing to worrying oil The problems such as the exhaustion of resource, earth environment, substitute conventional petroleum derived feed with biomass resources such as plants and prepare The research of Merlon also receives increasing attention.Isosorbide is a kind of highly stable chiral compound Thing, can by glucose hydrogenation dehydration prepare, have been reported for recently synthesizing polyester (Macromolecules, 2006, 39,9064-9070；Journal of Applied Polymer Science, 2011,121,1450-1463) etc. polycondensation Macromolecule.Particularly ring-shaped structure--two adjacent furan nucleuss make this base polymer present molecular structure rigidity big, Heat stability high.Although isosorbide type Merlon has higher glass transition temperature with preferable Heat resistance, but its strand rigidity is very big, causes this base polymer to be difficult to processing, poor mechanical property, It is difficult to the requirement to material property in satisfied reality application, accordingly, it would be desirable to isosorbide type Merlon is carried out Modified.The research of aspect polycarbonate modified for isosorbide type at present focuses mostly at synthetic copolymer, therefore Also explore different dihydroxy compounds and isosorbide copolymerization copolymerization polycarbonate (JP56055425, WO2004111106, JP06145336, JP63012896).
The method producing Merlon reported at present is to use basic mineral salt catalyst, Heterocyclic nitrogen mostly Class catalyst, quaternary ammonium, season phosphor catalyst etc..Wherein alkalinous metal salt catalyst includes sodium hydroxide, acetyl (Polymer, the 1970,11,415-420 such as acetone lanthanum, tetrahydro boron lithium；Macromolecular Chemistry and Physics,2001,202,1941-1949)；Heterocyclic nitrogen class catalyst include 2-phenylimidazole, benzimidazole, Three (dodecyl) ammonium etc. (US5319066, US5373083, US5362840, CN96104293, CN98806925)；Quaternary ammonium, season phosphor catalyst include triethylamine, tetraphenyl phosphine phenates, tetraalkyl ammonium acetate Deng (US5097002, CN03825367, CN200480036316).Although the catalyst type of report is a lot, But the problems such as it is low to still suffer from reactivity, and selectivity is the highest, poor catalyst stability, therefore develop a class height and live Property, high selectivity and constitutionally stable catalyst system and catalyzing seem particularly significant.
Summary of the invention
The present invention studies use quaternary ammonium, quaternary phosphonium class alkaline ionic liquid catalyst, is not using severe toxicity phosgene and molten Under conditions of agent, with dihydroxy compounds and carbonic diester as raw material, melt transesterification prepares the side of Merlon Method.Utilize the structure designability of ionic liquid, quaternary ammonium, quaternary phosphonium compounds introduce the spies such as nitrogen heterocyclic ring Different group is just promoting reaction as ionic liquid anion, the nucleophilicity that on the one hand improve ionic liquid anion To carrying out, compared with existing quaternary ammonium, season phosphor catalyst, it is suppressed that the generation that Fries resets, reduce The collateralization of Merlon, is greatly improved the activity and selectivity of catalyst；On the other hand catalyst has been regulated and controled Heat stability, make catalyst both can guarantee that from ester exchange to the catalysis of polycondensation later stage activity, again can be Reaction final stage thermal decomposition, will not affect polymer quality.
The reaction expression of the present invention is:
R is phenyl ring or methyl；R' is alkylidene, cycloalkylidene or aromatic group；M, n are different mountain Pears alcohol and the mol ratio of another kind of dihydroxy compounds, n/m=0/100～60/40.
Concrete carbonic diester one in dimethyl carbonate and diphenyl carbonate；Dihydroxy compounds is selected from different One in sorbitol, aliphatic dihydroxy compounds and aromatic dihydroxy compound.Wherein aliphatic dihydroxy Based compound includes chain type dihydroxy compounds and ester ring type dihydroxy compounds, is not particularly limited, specifically may be used To enumerate: diethylene glycol, triethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-oneself two The chain type dihydroxy compounds such as alcohol, 1,7-heptandiol；1,3-ring pentanediol, 1,4-cyclohexanediol, 1,4-hexamethylene two The ester ring type dihydroxy compounds such as methanol；Aromatic dihydroxy compound can be enumerated: double (4-(the 2-hydroxyl second of 9,9- Epoxide) phenyl) fluorenes, double (4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes of 9,9-, double (4-(the 2-'-hydroxyethoxy of 9,9- Base)-3-first isopropyl phenyl) fluorenes, double (4-(2-the hydroxyl-oxethyl)-3-isobutyl phenenyl) fluorenes of 9,9-, the double (4-(2-of 9,9- Hydroxyl-oxethyl)-3-tert-butyl-phenyl) fluorenes, 9,9-double (4-(2-hydroxyl-oxethyl)-3-cyclohexyl phenyl) fluorenes, 9,9- Double (4-(2-the hydroxyl-oxethyl)-3,5-3,5-dimethylphenyl) fluorenes of double (4-(2-hydroxyl-oxethyl)-3-phenyl) fluorenes, 9,9-, Double (4-(2-the hydroxyl-oxethyl)-3-tert-butyl group-6-aminomethyl phenyl) fluorenes of 9,9-, the double (4-(3-hydroxyl-2,2-dimethyl propylene of 9,9- Epoxide) phenyl) fluorenes, 4,4'-(1-phenethyl) bis-phenol, 2,2-bis-(4-hydroxyphenyl) butane, 4,4'-ethylenebis phenol, 4,4'-dioxydiphenyl methane, 1,3-double [2-(4-hydroxyphenyl)-2-propyl group] benzene, 4,4'-dihydroxy Tetrabenzene methane, 2,2- Double (4-hydroxyl-3,5-3,5-dimethylphenyl) propane, 2,2-double (4-hydroxyl-3-tolyl) propane, 2,2-bis-(4-hydroxy benzenes Base) structure such as propane, hydroquinone, terephthalyl alcohol has the glycols of aromatic group.
A kind of method that the present invention relates to alkali ionic liquid catalyzed preparation of poly carbonic ester, is characterized in that being to use Quaternary ammonium, quaternary phosphonium class alkali ionic liquid are as catalyst, with dihydroxy compounds and carbonic diester as raw material, molten Melt ester exchange and synthesize corresponding Merlon.Merlon building-up process is divided into ester exchange and two stages of polycondensation, The ester exchange stage is 98-150 DEG C in reaction temperature, normal pressure, under conditions of response time 3-6h, obtains pre- Polymers；Polycondensation phase be described prepolymer at 210-260 DEG C, vacuum is 4.0 × 10-3MPa-1.0×10-5 MPa, under conditions of response time 1-7h, final synthesis obtains Merlon.
Catalyst amount used in the present invention is the 5 × 10 of the amount of dihydroxy compounds material-3-5%, raw material two Hydroxy compounds and carbonic diester molar ratio are 1:0.8-1:10.
According to synthetic method described above, quaternary ammonium, quaternary phosphonium class alkali ionic liquid structure as follows:
Quaternary ammonium, the quaternary phosphonium class alkali ionic liquid one in (1)-(4).(1) R in-(4)1, R2, R3And R4For C1-C20Alkyl, C4-C20Cycloalkyl and C4-C20Aryl in any one, Can be identical, it is also possible to different.Wherein anion X in alkali ionic liquid (1) and (3) can be two Any one in cyanamide root anion, lactic acid anion, imidazole anion and 1,2,4-triazole anion； Anion X in alkali ionic liquid (2) and (4) can be cdicynanmide root anion, lactic acid anion, Imidazole anion, 1,2,4-triazole anion, benzoate anion, dihydrogen phosphate anion, hydrogen-oxygen Any one in root anion, acetate anion, bicarbonate anion, preferably imidazole anion and 1,2,4-triazole anion.
Alkali ionic liquid synthesis example used by the present invention is as follows:
(1) synthesis(etamon dicyan amine salt)
By the deionized water dissolving of 0.98g (0.011mol) cdicynanmide sodium 10mL, it is added drop-wise to use 10mL In 1.87g (0.011mol) silver nitrate solution of deionized water dissolving, there is white solid to produce, be stirred at room temperature 1h, filters, washing.Gained white solid is joined 2.10g (0.010mol) tetraethylammonium bromide (10 ML deionized water dissolving) in, there is faint yellow material to occur after stirring, be heated to 40 DEG C, react 1h, mistake Filter, the rotation of gained filtrate is steamed, then the liquid obtained with the rotation steaming of dichloromethane lotion, is then vacuum dried 24h, Colourless transparent liquid 1.90g, productivity 96.8%.
(2) synthesis(etamon imidazole salts)
0.68g (0.010mol) imidazoles and 0.40g (0.010mol) sodium hydroxide are joined 20mL's In isopropanol, it is heated to reflux 30min, is cooled to room temperature, add 2.10g (0.010mol) tetraethyl bromination Ammonium, adds 10mL isopropanol, is heated to reflux 12h, solution turned yellow, solids removed by filtration, filter Liquid rotary evaporation, steams the sticky mass of gained, is then vacuum dried 24h, obtains Fructus Citri tangerinae with anhydrous propanone washing rotation Yellow, viscous liquid 1.87g, productivity 95.0%.
(3) synthesis(tetraethyl DL-Lactic acid ammonium salt .)
0.90g (0.010mol) lactic acid and 1.47g (0.010mol) tetraethyl ammonium hydroxide are mixed and adds In 20mL deionized water, stirring 5h under room temperature, rotary evaporation removes water, is then vacuum dried 24h, obtains shallow Yellow, viscous liquid 2.10g, productivity 95.8%.
(4) synthesis(double quaternary ammonium-1,2,4-triazole salt)
12.14g (0.120mol) triethylamine and 7.52g (0.040mol) glycol dibromide are added 250mL In there-necked flask, add 50mL acetone, be heated to reflux 24h, to not having white solid to occur, fall Filtration under diminished pressure after temperature, washs the solid obtained with absolute ether, is vacuum dried 24h, obtains double quaternary ammonium bromine white Solid product 14.50g, productivity 93.4%.
1.36g (0.020mol) imidazoles and 0.80g (0.020mol) sodium hydroxide are joined 40mL different In propanol, it is heated to reflux 30min, is cooled to room temperature, add 3.88g (0.010mol) double quaternary ammonium bromine, then Adding 10mL isopropanol, be heated to reflux 12h, solution turned yellow, solids removed by filtration, filtrate rotates Evaporation, steams the sticky mass of gained, is then vacuum dried 24h, obtain crocus and glue with anhydrous propanone washing rotation Thick liquid 3.46g, productivity 94.5%.
Detailed description of the invention
Present invention following example illustrate, but the present invention is not limited to following embodiment, without departing from institute of front and back Stating under the scope of objective, change is included in the technical scope of the present invention.
Comparative example 1
Implementation: the ester exchange stage is in atmospheric conditions, by 4.38g (0.030mol) isosorbide and 6.43g (0.030mol) diphenyl carbonate is heated to 98 DEG C in a nitrogen atmosphere makes it melt, and adds 1.52 × 10-3 G (the 5 × 10 of the amount of isosorbide material-2Triethylamine %), reacts 5h synthetic prepolymer under nitrogen atmosphere； Polycondensation phase is that above-mentioned prepolymer is in vacuum 1.0 × 10-5MPa, at reaction temperature 230 DEG C, reaction 5h obtains Merlon.After reaction terminates, it is cooled to room temperature under vacuum conditions, without water beetle after dissolving with chloroform Alcohol separates out.The yield of gained Merlon is 71.41%, and molecular weight is 0.9 × 104。
Comparative example 2
With comparative example 1, used catalyst is tetraethyl ammonium hydroxide 2.21 × 10-3G (the amount of isosorbide material 5 × 10-2%), other conditions are constant, and the yield of gained Merlon is 85.01%, and molecular weight is 1.4 × 104。
Embodiment 1
Implementation: the ester exchange stage is in atmospheric conditions, by 4.38g (0.030mol) isosorbide and 6.43g (0.030mol) diphenyl carbonate is heated to 98 DEG C in a nitrogen atmosphere makes it melt, and adds 2.96 × 10-3 G (the 5 × 10 of the amount of isosorbide material-2Etamon imidazole salts %), reacts 5h synthesis pre-under nitrogen atmosphere Polymers；Polycondensation phase is that above-mentioned prepolymer is in vacuum 1.0 × 10-5MPa, at reaction temperature 230 DEG C, reacts 5 H obtains Merlon.Reaction terminate after, be cooled to room temperature under vacuum conditions, with chloroform dissolve after Absolute methanol separates out.The yield of gained Merlon is 93.08%, and molecular weight is 2.4 × 104。
Embodiment 2
With embodiment 1, used catalyst is etamon dicyan amine salt 2.89 × 10-3G (the amount of isosorbide material 5 × 10-2%), its structural formula isOther conditions are constant, the poly-carbonic acid of gained The yield of ester is 74.7%, and molecular weight is 1.8 × 104。
Embodiment 3
With embodiment 1, used catalyst is etamon-1,2,4-triazole salt 2.97 × 10-3G (isosorbide thing The 5 × 10 of the amount of matter-2%), its structural formula isOther conditions are constant, the poly-carbon of gained The yield of acid esters is 92.3%, and molecular weight is 1.9 × 104。
Embodiment 4
With embodiment 1, used catalyst is tetraethyl DL-Lactic acid ammonium salt. 3.29 × 10-3G be (amount of isosorbide material 5×10-2%), its structural formula isOther conditions are constant, gained Merlon Yield be 77.4%, molecular weight is 1.6 × 104。
Embodiment 5
With embodiment 1, the amount of used catalyst is 1.48 × 10-3G (the 2.5 × 10 of the amount of isosorbide material-2%), Other conditions are constant, and the yield of gained Merlon is 90.9%, and molecular weight is 2.1 × 104。
Embodiment 6
With embodiment 1, the amount of used catalyst is 4.44 × 10-3G (the 7.5 × 10 of the amount of isosorbide material-2%), Other conditions are constant, and the yield of gained Merlon is 91.6%, and molecular weight is 2.4 × 104。
Embodiment 7
With embodiment 1, the amount of used catalyst is 5.92 × 10-3G (the 0.1% of the amount of isosorbide material), Other conditions are constant, and the yield of gained Merlon is 90.9%, and molecular weight is 2.2 × 104。
Embodiment 8
With embodiment 1, adding the diphenyl carbonate of 6.23g (0.029mol), other conditions are constant, the poly-carbon of gained The yield of acid esters is 91.2%, and molecular weight is 1.9 × 104。
Embodiment 9
With embodiment 1, adding the diphenyl carbonate of 6.62g (0.031mol), other conditions are constant, gained The yield of Merlon is 92.6%, and molecular weight is 2.2 × 104。
Embodiment 10
With embodiment 1, adding the diphenyl carbonate of 6.81g (0.032mol), other conditions are constant, gained The yield of Merlon is 90.8%, and molecular weight is 2.2 × 104。
Embodiment 11
With embodiment 1, the polycondensation time is 3h, and other conditions are constant, and the yield of gained Merlon is 91.1%, Molecular weight is 1.7 × 104。
Embodiment 12
With embodiment 1, the polycondensation time is 4h, and other conditions are constant, and the yield of gained Merlon is 90.7%, Molecular weight is 1.9 × 104。
Embodiment 13
With embodiment 1, the polycondensation time is 6h, and other conditions are constant, and the yield of gained Merlon is 90.9%, Molecular weight is 2.2 × 104。
Embodiment 14
With embodiment 1, condensation temperature is 240 DEG C, and other conditions are constant, and the yield of gained Merlon is 91.8%, molecular weight is 2.7 × 104。
Embodiment 15
With embodiment 1, condensation temperature is 250 DEG C, and other conditions are constant, and the yield of gained Merlon is 90.7%, molecular weight is 2.4 × 104。
Embodiment 16
With embodiment 1, condensation temperature is 220 DEG C, and other conditions are constant, and the yield of gained Merlon is 92.1%, molecular weight is 1.9 × 104。
Embodiment 17
With embodiment 1, by 4.38g (0.030mol) isosorbide and 6.43g (0.030mol) carbonic acid two Phenyl ester is heated to 150 DEG C in a nitrogen atmosphere makes it melt, and other conditions are constant, the receipts of gained Merlon Rate is 87.7%, and molecular weight is 1.8 × 104。
Embodiment 18
With embodiment 1, by 4.38g (0.030mol) isosorbide and 6.43g (0.030mol) carbonic acid two Phenyl ester is heated to 120 DEG C in a nitrogen atmosphere makes it melt, and other conditions are constant, the receipts of gained Merlon Rate is 89.4%, and molecular weight is 1.7 × 104。
Embodiment 19
Implementation: the ester exchange stage is in atmospheric conditions, by 2.19g (0.015mol) isosorbide, 1.77g (0.015mol) 1,6-HD and 6.43g (0.030mol) diphenyl carbonate are heated in a nitrogen atmosphere 98 DEG C make it melt, add 2.96 × 10-3G (the 5 × 10 of the amount of isosorbide material-2Etamon imidazoles %) Salt, reacts 5h synthetic prepolymer under nitrogen atmosphere；Polycondensation phase is that above-mentioned prepolymer is in vacuum 1.0 × 10-5 MPa, at reaction temperature 240 DEG C, reaction 5h obtains Merlon.After reaction terminates, under vacuum conditions It is cooled to room temperature, separates out in absolute methanol after dissolving with chloroform.The yield of gained Merlon is 82.2%, molecular weight is 4.4 × 104。
Embodiment 20
With embodiment 19, by 2.19g (0.015mol) isosorbide, 1.56g (0.015mol) 1,5-penta 2 Alcohol and 6.43g (0.030mol) diphenyl carbonate are heated to 98 DEG C in a nitrogen atmosphere, and other conditions are constant, The yield of gained Merlon is 88.4%, and molecular weight is 4.0 × 104。
Embodiment 21
With embodiment 19, by 2.19g (0.015mol) isosorbide, 2.16g (0.015mol) Isosorbide-5-Nitrae-hexamethylene Alkane dimethanol and 6.43g (0.030mol) diphenyl carbonate are heated to 98 DEG C in a nitrogen atmosphere, other Part is constant, and the yield of gained Merlon is 83.2%, and molecular weight is 9.5 × 104。
Embodiment 22
With embodiment 19, by 2.19g (0.015mol) isosorbide, 1.59g (0.015mol) diethyl two Alcohol and 6.43g (0.030mol) diphenyl carbonate are heated to 98 DEG C in a nitrogen atmosphere, and other conditions are constant, The yield of gained Merlon is 89.4%, and molecular weight is 1.12 × 105。

Claims (10)

1. a method for alkali ionic liquid catalyzed preparation of poly carbonic ester, is characterized in that being to use quaternary ammonium, quaternary phosphonium Class alkali ionic liquid is as catalyst, with dihydroxy compounds and carbonic diester for the poly-carbonic acid of Material synthesis Ester；Described catalyst amount is the 5 × 10 of the amount of raw material dihydroxy compounds material-3-5%；Merlon closes One-tenth process is divided into ester exchange and two stages of polycondensation, and the ester exchange stage is 98-150 DEG C in reaction temperature, often Pressure, under conditions of response time 3-6h, obtains prepolymer；Polycondensation phase is that described prepolymer exists 210-260 DEG C, vacuum is 4.0 × 10-3MPa-1.0×10-5MPa, the condition of response time 1-7h Under, it is thus achieved that described Merlon.
Method the most according to claim 1, it is characterised in that described quaternary ammonium, quaternary phosphonium class alkali ionic liquid Structure as follows:
Method the most according to claim 2, it is characterised in that described alkali ionic liquid (1) and (3) In anion X be cdicynanmide root anion, lactic acid anion, imidazole anion and 1,2,4-tri-nitrogen Any one in azoles anion；Anion X in alkali ionic liquid (2) and (4) is cdicynanmide Root anion, lactic acid anion, imidazole anion, 1,2,4-triazole anion, benzoate anion cloudy from In son, dihydrogen phosphate anion, hydroxide radical anion, acetate anion, bicarbonate anion Any one.
Method the most according to claim 2, it is characterised in that in described alkali ionic liquid (1)-(4) R1, R2, R3And R4For C1-C20Alkyl, C4-C20Cycloalkyl and C4-C20Aryl in Any one.
Method the most according to claim 1, it is characterised in that described raw material dihydroxy compounds and carbonic acid two Ester molar ratio is 1:0.8-1:10.
Method the most according to claim 1, it is characterised in that the equation of described melt polymerization is:
R is phenyl ring or methyl；R' is alkylidene, cycloalkylidene or aromatic group；M, n are different mountain Pears alcohol and the mol ratio of another kind of dihydroxy compounds, n/m=0/100～60/40.
7. according to the method described in patent requirements 1, it is characterised in that described carbonic diester selected from dimethyl carbonate and Any one in diphenyl carbonate.
Method the most according to claim 1, it is characterised in that described dihydroxy compounds selected from isosorbide, At least one in aliphatic dihydroxy compounds and aromatic dihydroxy compound.
Method the most according to claim 8, it is characterised in that described aliphatic dihydroxy compounds is selected from chain At least one in formula dihydroxy compounds and ester ring type dihydroxy compounds.
Method the most according to claim 8, it is characterised in that described aromatic dihydroxy compound is: 9,9- Double (4-(2-hydroxyl-oxethyl) phenyl) fluorenes, 9,9-double (4-(2-hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes, 9,9- Double (4-(2-the hydroxyl-oxethyl)-3-isobutyl group of double (4-(2-hydroxyl-oxethyl)-3-first isopropyl phenyl) fluorenes, 9,9- Phenyl) fluorenes, double (4-(2-the hydroxyl-oxethyl)-3-tert-butyl-phenyl) fluorenes of 9,9-, double (4-(the 2-'-hydroxyethoxy of 9,9- Base)-3-cyclohexyl phenyl) fluorenes, double (4-(2-the hydroxyl-oxethyl)-3-phenyl) fluorenes of 9,9-, the double (4-(2-of 9,9- Hydroxyl-oxethyl)-3,5-3,5-dimethylphenyl) fluorenes, double (4-(2-the hydroxyl-oxethyl)-3-tert-butyl group-6-methylbenzene of 9,9- Base) fluorenes, 9,9-double (4-(3-hydroxyl-2,2-dimethyl propylene epoxide) phenyl) fluorenes, 4,4'-(1-phenethyl) bis-phenol, 2,2- Double [2-(the 4-hydroxyl of two (4-hydroxyphenyl) butane, 4,4'-ethylenebis phenol, 4,4'-dioxydiphenyl methane, 1,3- Phenyl)-2-propyl group] benzene, 4,4'-dihydroxy Tetrabenzene methane, double (4-hydroxyl-3,5-3,5-dimethylphenyl) propane of 2,2-, 2,2-double (4-hydroxyl-3-tolyl) propane, 2,2-bis-(4-hydroxy phenyl) propane, hydroquinone, terephthaldehyde Alcohol structure has the glycols of aromatic group.
CN201610555312.8A 2016-07-14 2016-07-14 A kind of method of alkali ionic liquid catalyzed preparation of poly carbonic ester Active CN105949451B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610555312.8A CN105949451B (en) 2016-07-14 2016-07-14 A kind of method of alkali ionic liquid catalyzed preparation of poly carbonic ester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610555312.8A CN105949451B (en) 2016-07-14 2016-07-14 A kind of method of alkali ionic liquid catalyzed preparation of poly carbonic ester

Publications (2)

Publication Number Publication Date
CN105949451A true CN105949451A (en) 2016-09-21
CN105949451B CN105949451B (en) 2017-10-20

Family

ID=56900795

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610555312.8A Active CN105949451B (en) 2016-07-14 2016-07-14 A kind of method of alkali ionic liquid catalyzed preparation of poly carbonic ester

Country Status (1)

Country Link
CN (1) CN105949451B (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573497A (en) * 2017-09-30 2018-01-12 中国科学院过程工程研究所 A kind of method that makrolon is prepared based on ionic liquid efficient catalytic
KR101815945B1 (en) * 2017-05-25 2018-02-22 주식회사 삼양사 Polyester resin prepared by using carbonate diol derived from anhydrosugar alcohol and method for preparing the same, and powder coating composition comprising the resin
CN108727192A (en) * 2017-04-24 2018-11-02 中国石油化工股份有限公司 The preparation method of dipheryl carbonate esters compound
CN109280160A (en) * 2017-07-21 2019-01-29 中国科学院过程工程研究所 A kind of ionic liquid-catalyzed method for preparing polycarbonate
CN110538481A (en) * 2019-10-11 2019-12-06 中国科学院过程工程研究所 Phenol continuous extraction system, polycarbonate resin production system comprising phenol continuous extraction system and production method
CN110982054A (en) * 2019-12-28 2020-04-10 中国科学院过程工程研究所 Composite catalyst for catalytically synthesizing polycarbonate and method for catalytically synthesizing polycarbonate
CN111019111A (en) * 2019-12-28 2020-04-17 中国科学院过程工程研究所 Ionic liquid catalyst for synthesizing bio-based polycarbonate and method for synthesizing bio-based polycarbonate
CN111138650A (en) * 2020-01-16 2020-05-12 中国科学院过程工程研究所 High-molecular-weight high-flexibility bio-based polycarbonate copolymer and preparation method thereof
CN111205448A (en) * 2020-01-14 2020-05-29 中国科学院过程工程研究所 Method for preparing polycarbonate by catalysis
CN111825836A (en) * 2019-04-23 2020-10-27 中国科学院过程工程研究所 Preparation method of polycarbonate
CN113801313A (en) * 2021-09-22 2021-12-17 宁波浙铁大风化工有限公司 Preparation method of high molecular weight polycarbonate and polycarbonate
CN115057778A (en) * 2022-07-28 2022-09-16 西安思科赛实业有限公司 Novel method for synthesizing di-tert-butyl dicarbonate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101249456A (en) * 2008-03-14 2008-08-27 中国科学院过程工程研究所 Catalyst for alcoholysis polyethylene glycol terephthalate
CN101327449A (en) * 2008-07-10 2008-12-24 浙江大学 Ion liquid carried Salen metallic catalyst and preparation method
CN101328264A (en) * 2008-07-10 2008-12-24 浙江大学 Process for producing polycarbonate using ion liquid supported catalysts
WO2010035190A3 (en) * 2008-09-29 2011-01-13 Sabic Innovative Plastics Ip B.V. Method for producing phenolphthalein compound using ionic liquid catalyst composition
CN103936976A (en) * 2014-04-25 2014-07-23 新疆康润洁环保科技有限公司 Method for preparing polycarbonate by utilizing ionic liquid as catalyst
CN105085895A (en) * 2015-08-28 2015-11-25 华东理工大学 Melting ester exchange method of preparing catalysts for polycarbonate and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101249456A (en) * 2008-03-14 2008-08-27 中国科学院过程工程研究所 Catalyst for alcoholysis polyethylene glycol terephthalate
CN101327449A (en) * 2008-07-10 2008-12-24 浙江大学 Ion liquid carried Salen metallic catalyst and preparation method
CN101328264A (en) * 2008-07-10 2008-12-24 浙江大学 Process for producing polycarbonate using ion liquid supported catalysts
WO2010035190A3 (en) * 2008-09-29 2011-01-13 Sabic Innovative Plastics Ip B.V. Method for producing phenolphthalein compound using ionic liquid catalyst composition
CN103936976A (en) * 2014-04-25 2014-07-23 新疆康润洁环保科技有限公司 Method for preparing polycarbonate by utilizing ionic liquid as catalyst
CN105085895A (en) * 2015-08-28 2015-11-25 华东理工大学 Melting ester exchange method of preparing catalysts for polycarbonate and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
夏征农等: "《辞海 数学•物理学•化学分册》", 31 December 1987, 上海辞书出版社 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108727192A (en) * 2017-04-24 2018-11-02 中国石油化工股份有限公司 The preparation method of dipheryl carbonate esters compound
CN108727192B (en) * 2017-04-24 2021-02-05 中国石油化工股份有限公司 Preparation method of diphenyl carbonate compound
KR101815945B1 (en) * 2017-05-25 2018-02-22 주식회사 삼양사 Polyester resin prepared by using carbonate diol derived from anhydrosugar alcohol and method for preparing the same, and powder coating composition comprising the resin
CN109280160A (en) * 2017-07-21 2019-01-29 中国科学院过程工程研究所 A kind of ionic liquid-catalyzed method for preparing polycarbonate
CN109280160B (en) * 2017-07-21 2020-10-27 中国科学院过程工程研究所 Method for preparing polycarbonate by ionic liquid catalysis
CN107573497A (en) * 2017-09-30 2018-01-12 中国科学院过程工程研究所 A kind of method that makrolon is prepared based on ionic liquid efficient catalytic
CN111825836A (en) * 2019-04-23 2020-10-27 中国科学院过程工程研究所 Preparation method of polycarbonate
CN111825836B (en) * 2019-04-23 2021-09-17 中国科学院过程工程研究所 Preparation method of polycarbonate
CN110538481A (en) * 2019-10-11 2019-12-06 中国科学院过程工程研究所 Phenol continuous extraction system, polycarbonate resin production system comprising phenol continuous extraction system and production method
CN110982054B (en) * 2019-12-28 2021-03-12 中国科学院过程工程研究所 Composite catalyst for catalytically synthesizing polycarbonate and method for catalytically synthesizing polycarbonate
CN111019111A (en) * 2019-12-28 2020-04-17 中国科学院过程工程研究所 Ionic liquid catalyst for synthesizing bio-based polycarbonate and method for synthesizing bio-based polycarbonate
CN111019111B (en) * 2019-12-28 2021-03-30 中国科学院过程工程研究所 Ionic liquid catalyst for synthesizing bio-based polycarbonate and method for synthesizing bio-based polycarbonate
CN110982054A (en) * 2019-12-28 2020-04-10 中国科学院过程工程研究所 Composite catalyst for catalytically synthesizing polycarbonate and method for catalytically synthesizing polycarbonate
CN111205448A (en) * 2020-01-14 2020-05-29 中国科学院过程工程研究所 Method for preparing polycarbonate by catalysis
CN111205448B (en) * 2020-01-14 2021-07-02 中国科学院过程工程研究所 Method for preparing polycarbonate by catalysis
CN111138650A (en) * 2020-01-16 2020-05-12 中国科学院过程工程研究所 High-molecular-weight high-flexibility bio-based polycarbonate copolymer and preparation method thereof
CN111138650B (en) * 2020-01-16 2021-07-16 中国科学院过程工程研究所 High-molecular-weight high-flexibility bio-based polycarbonate copolymer and preparation method thereof
CN113801313A (en) * 2021-09-22 2021-12-17 宁波浙铁大风化工有限公司 Preparation method of high molecular weight polycarbonate and polycarbonate
CN115057778A (en) * 2022-07-28 2022-09-16 西安思科赛实业有限公司 Novel method for synthesizing di-tert-butyl dicarbonate

Also Published As

Publication number Publication date
CN105949451B (en) 2017-10-20

Similar Documents

Publication Publication Date Title
CN105949451A (en) Method for preparing polycarbonate through basic ionic liquid catalysis
CN107573497B (en) Method for preparing polycarbonate based on ionic liquid high-efficiency catalysis
CN109280160B (en) Method for preparing polycarbonate by ionic liquid catalysis
US20130171397A1 (en) 2,5-furan dicarboxylic acid-based polyesters prepared from biomass
KR101881022B1 (en) Method for preparing a dialkyl carbonate of dianhydrohexitol
US20140024853A1 (en) Synthesis of Lactic Acid and Alkyl Lactate from Carbohydrate-Containing Materials
JP5264483B2 (en) Organic acid catalysts for polylactic acid synthesis
CN109206606B (en) Method for preparing polycarbonate by using ionic liquid catalytic melting transesterification method
CN101724159A (en) Method for producing thermoplastic resin, polyester resin and polycarbonate resin, and their applications
CN102633996B (en) Method for catalytically synthesizing polylactic acid by utilizing ionic liquid
EP3119750B1 (en) Pendant furyl containing bisphenols, polymers therefrom and a process for the preparation thereof
KR20130112462A (en) A method for lactide synthesis from lactic acid salt
CN102229745B (en) Crystallizable polycarbonate material based on carbon dioxide and preparation method thereof
CN111825836B (en) Preparation method of polycarbonate
EP3805208A1 (en) Method for preparing alkylene carbonate from epoxyalkane and carbon dioxide
CN103249736A (en) Bisphenol polymer structural units and method of making the same
CN112812287B (en) Method for preparing polycarbonate by ionic liquid catalysis
US10689488B2 (en) Method for preparing polycarbonate polyol and composition comprising the polycarbonate polyol
CN108250074A (en) Biology base carbonate-containing structure glycol polymerisable monomer and its preparation method and application
CN110935435B (en) Catalyst for preparing cyclic polyol and application thereof
CN102442911A (en) Preparation method of intermediate dimethoxy carbonic acid bisphenol A diester
Wang et al. Efficient synthesis of high-molecular-weight biobased polycarbonates by lithium lactate
CN104193599A (en) 2-(2-chloroethoxy ethyl) acetal synthesis method
US20120123136A1 (en) Process for the preparation of 2-oxo-[1,3] dioxolane-4-carboxylic acid esters
CN110003458A (en) A kind of load type solid body base catalyst and its application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant