CN102884103A - Method for producing polyalkylene carbonates - Google Patents
Method for producing polyalkylene carbonates Download PDFInfo
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- CN102884103A CN102884103A CN2011800220909A CN201180022090A CN102884103A CN 102884103 A CN102884103 A CN 102884103A CN 2011800220909 A CN2011800220909 A CN 2011800220909A CN 201180022090 A CN201180022090 A CN 201180022090A CN 102884103 A CN102884103 A CN 102884103A
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- 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
- C08G64/02—Aliphatic polycarbonates
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- 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
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
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- 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
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- 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
- C08G64/40—Post-polymerisation treatment
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- 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
- C08G64/40—Post-polymerisation treatment
- C08G64/406—Purifying; Drying
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
Polyalkylene carbonates are produced by polymerizing carbon dioxide with at least one epoxide of the general formula (I), in which the radicals R, independently of one another, can be H, halogen, NO2, CN, COOR' or C1-20 hydrocarbon radical, which can be substituted, wherein one of the radicals R can also mean OH, and wherein two radicals R together can form a C3-5 alkylene radical, 1 R' can be H or C1-20 hydrocarbon radical which can be substituted, in the presence of a zinc salt of C4-8 alkanedicarboxylic acids as catalyst, wherein the reaction mixture obtained after the reaction is admixed with a water-immiscible organic solvent which dissolves the polyalkylene carbonate, and with a carboxylic acid or an acidic ion exchanger, the organic phase is washed with water, and the polyalkylene carbonate is optionally obtained from the organic phase.
Description
The present invention relates to a kind of method for preparing zinc-containing solid catalyst and improve simultaneously the purification of zinc-containing solid catalyst, and relate to method of purification, also relate to carboxylic acid or the purposes of acid ion exchangers in the purification zinc-containing solid catalyst of monomer or polymerization.
Zinc-containing solid catalyst, for example polytrimethylene carbonic ether be by carbonic acid gas and oxyalkylene for example the alternating copolymerization of propylene oxide obtain.For this purpose, use many different homogeneous phases and heterogeneous catalyst.Used heterogeneous catalyst especially comprises pentanedioic acid zinc.
WO03/029325 has described the method for preparing aliphatic polycarbonate.Here operable compound with multi-metal cyanide, can be zinc carboxylate, especially pentanedioic acid zinc or hexanodioic acid zinc.After the preparation aliphatic polycarbonate, the reaction mixture of gained is poured in the methyl alcohol of using the concentrated hydrochloric acid acidifying.Polymer precipitation out, and filtration and dried overnight.
The zinc-containing solid catalyst (PPC) that is purchased with zinc catalysis preparation is the product of not purifying.These materials have the milky turbidity degree, and still contain a large amount of zinc from catalyzer, for example 0.3-1.2gZn/100g polymkeric substance.
When hydrochloric acid is used for the aftertreatment of reaction product, acid catalyzed depolymerization may occur, and this can be unwanted.In addition, the use of hydrochloric acid causes the chlorine of trace to be introduced into the zinc-containing solid catalyst of gained.
The purpose of this invention is to provide a kind of improved at the C as catalyzer
4-8There is the lower method for preparing the polytrimethylene carbonic ether in-alkane dicarboxylic acid zinc salt, wherein in a simple manner aftertreatment of the reaction mixture of gained, and can the Removal of catalyst resistates.Preferred purpose is depolymerization not occur, and can obtain zinc-containing solid catalyst with high purity.
The objective of the invention is to realize by a kind of method for preparing zinc-containing solid catalyst, wherein make carbonic acid gas and at least aly have the epoxide of general formula (I) at the C as catalyzer
4-8Polymerization under the existence of-alkane dicarboxylic acid's zinc salt,
Wherein
R is H, halogen, NO independently of one another
2, CN, COOR ' or C
1-20The hydrocarbon structure part, it can have substituting group, and wherein among the structure division R also can be OH, and wherein two structure division R can form C together
3-5The alkylidene group structure division,
R ' is that H maybe can have substituent C
1-20The hydrocarbon structure part,
Wherein carboxylic acid or acid ion exchangers and the water-immiscible organic solvent that can dissolve zinc-containing solid catalyst and the reaction mixture that after reaction, obtains, and wash organic phase with water, and randomly from organic phase acquisition zinc-containing solid catalyst.
A R in formula (I) can for example be-CH
2-OH or-CH
2-O-C (=C) R ' structure division.C
3-5The alkylidene group structure division is the end alkylidene group structure division of straight chain preferably.
This purpose also contains C by a kind of purification
4-8The method of the zinc-containing solid catalyst of-alkane dicarboxylic acid's zinc salt realizes, wherein carries out above-mentioned purification step.
Find in the present invention to use the carboxylic acid of monomer or polymerization or acid ion exchangers to replace hydrochloric acid can significantly simplify the aftertreatment of zinc-containing solid catalyst, and can basically suppress depolymerization.
The present invention can use any required suitable carboxylic or acid ion exchangers.Carboxylic acid can be monocarboxylic acid or poly carboxylic acid.They can be the carboxylic acids of low-molecular-weight carboxylic acid or polymerization.(gathering) carboxylic acid or acid ion exchangers can use with the form of (part) neutralization.The polyacrylic ester of part neutralization can be for example from BASF SE conduct
Obtain.
Carboxylic acid or acid ion exchangers here use during the purification of zinc-containing solid catalyst, especially in order to remove polymerizing catalyst.Used polymerizing catalyst contains C
4-8-alkane dicarboxylic acid's zinc salt, preferred pentanedioic acid zinc or hexanodioic acid zinc, especially pentanedioic acid zinc.The preparation of described catalyzer and application examples are as referring to WO03/029325.
Carboxyl in the carboxylic acid that uses in the present invention and the sum of hydroxyl preferably at least 2 particularly preferably is at least 3, especially at least 4.For example, this number can be 2-7, preferred 3-6, especially 3-4.
The structure optimization of carboxylic acid contains at least one hydroxyl or at least one nitrogen-atoms.
Carboxylic acid preferably has at least 4 carbon atoms.
So the carboxylic acid that uses in the present invention for example has 2-10 carbon atom, preferred 4-10 carbon atom.
In one embodiment of the invention, carboxylic acid has at least two carboxyls and at least one hydroxyl, or replaces hydroxyl to have at least one nitrogen-atoms.
They are dicarboxylic acid or tricarboxylic acid preferably, and they also have hydroxy functional group.
Operable monocarboxylic acid, except acetic acid and glyconic acid, also especially citric acid, tartrate, toxilic acid, xitix, and Synergist S-421 95, for example ethylenediamine tetraacetic acid (EDTA) (EDTA) and MDGA, for example trisodium salt is (for example
From BASF SE).
Especially, compare with the situation of using acetic acid, use the dicarboxylic acid and the tricarboxylic acid that also have hydroxy functional group also can realize following advantage:
When comparing with acetic acid, can remove with acid still less the catalyzer (the 5-30 % by weight replaces about 40 % by weight, based on the amount meter of catalyzer) of specified quantitative.
Use the polyfunctional carboxylic acids of same amount to obtain better to remove effect.
Can use acid harmless and that really be used as in some cases foodstuff additive, for example citric acid, xitix, tartrate aspect food.
The number of the washing step that the clarification product is required can reduce, and for example reduces to a washing step.
The use of hydroxycarboxylic acid so that potential injury still less, this is because these acid only are irritating, rather than to resemble the acetic acid be corrosive.
The degree of the molecular weight degradation of observing from dicarboxylic acid and the tricarboxylic result of hydroxy-functional is less than acetic acid and hydrochloric acid.
Also can use poly carboxylic acid, polyacrylic acid for example is for example from BASF SE conduct
Those that obtain.
The present invention can also use acid ion exchangers.These can be the ion-exchangers with carboxyl or sulfo group or alkylsulfonyl.The ion-exchanger of deriving from polystyrene substrate usually via with the reaction of the vitriol oil by sour derivatize.
The example of appropriate ions exchanger is conduct
Obtain, for example from the high acidity Dowex50WX8-200 of Dow company.The present invention can also use other similar ion-exchanger.
The most frequently used ion-exchanger is polystyrene resin, and it is crosslinked by Vinylstyrene (DVB), therefore has high-caliber high molecular three-dimensional structure, and great majority are forms of bead.
The sulfonation of crosslinked polystyrene resin is for example carried out with oleum, has produced the cationite of high acidity.As with sulfuric acid reaction outside another scheme, can react with perfluorinated sulfonic acid, referring to Applied Catalysis A:General 221 (2001), 45-62 page or leaf.In order to prepare the cationite of low acidity, replace vinylbenzene, the acrylic acid derivative divinyl benzene crosslinked.The free carboxy of polyacrylic ester can obtain by the alkaline hydrolysis of ester group.In addition, also can use phenol-formaldehyde gel.
The amount of carboxylic acid is the 5-80 % by weight preferably, and particularly preferably 7.5-40 % by weight, especially 10-25 % by weight are based on the zinc-containing solid catalyst meter.
Here, carboxylic acid can use with the form of liquid or solid, or uses with the form of dissolving.
Can dissolve the water-immiscible organic solvent and the reaction mixture that after reaction, obtains of zinc-containing solid catalyst.The example of suitable operable solvent is ester, preferably C
1-12The C of-alkanoic acid
1-12Alkyl ester.Particularly preferably use ethyl acetate as solvent.
The addition of solvent is 10-1000% preferably, and particularly preferably 50-500%, especially 70-140% are based on the amount meter of the reaction mixture after polyreaction (polymers soln).This amount can be regulated according to the solid content of polymers soln or the solid content of reaction mixture.The combined amount of ethyl acetate is usually identical with the amount (based on volume) of polymers soln.If the solid content of polymers soln is to be lower than 18 % by weight, then the amount of ethyl acetate can reduce.
And carboxylic acid or and acid ion exchangers between reaction preferably relate to the mobile mixture of being made by reaction mixture and organic solvent.For this purpose, can use suitable mixing device, example is the conventional mixer device.
And carboxylic acid or and acid ion exchangers between reaction preferably carry out time of 5 minutes to 5 days, particularly preferably 15 minutes to 5 hours.
With preferably 10-60 ℃ of the temperature of carboxylic acid reaction.Especially, reaction is carried out under room temperature (22 ℃).
According to used carboxylic acid, usefully zinc-containing solid catalyst and carboxylic acid anhydride reacted before the mixing of carboxylic acid or acid ion exchangers.Used carboxylic acid anhydride can contain any required suitable carboxylic acid anhydride, the acid anhydrides of monocarboxylic acid and the acid anhydrides of dicarboxylic acid.Example is maleic anhydride and diacetyl oxide.Particularly preferably use diacetyl oxide.
The amount of carboxylic acid anhydride is the 0.5-25 % by weight preferably, and particularly preferably 1-15 % by weight, especially 2-10 % by weight are based on the zinc-containing solid catalyst meter.
With the temperature of carboxylic acid anhydride reaction preferably in 10-60 ℃ of scope.Especially, this reaction is carried out under room temperature (22 ℃).It adds preferably and carried out before adding acid.
With carboxylic acid anhydride, especially protected the chain end of zinc-containing solid catalyst with the reaction of diacetyl oxide.This has suppressed any possible because negatively charged ion is attacked the molecular weight degradation that causes, for example from the attack of the acetate moiety of acetic acid.
When using preferred polyfunctional carboxylic acids, when especially using the dicarboxylic acid that yet has hydroxy functional group and tricarboxylic acid, generally there is not zinc-containing solid catalyst molecular weight degradation significantly or apparently.When using them, so can omit by carboxylic acid anhydride, diacetyl oxide protection chain end especially.When citric acid is used as carboxylic acid, for example do not need with carboxylic acid anhydride, for example diacetyl oxide protection chain end.The result is the degree that purifying technique is simplified to single component, and can omit an additional step (for carboxylic acid anhydride).
After reaction mixture reacts with carboxylic acid or with acid ion exchangers, just wash with water., reaction mixture is fully mixed with water for this reason, and after being separated subsequently, remove water.The water yield that when each washing, adds preferably contain the reaction mixture of water-immiscible organic solvent amount (weight) 0.01-5 doubly, particularly preferably 0.5-2 is doubly.Acid solution also can contain water.
One or more washing steps can carry out in the present invention in succession.The washing step that preferably carries out enough numbers is take the final pH that reaches organic phase as about 4 or higher.
The required time of organic phase and water that is separated into can change according to used carboxylic acid.The number of required washing step also can depend on the character of used carboxylic acid, as described in the following examples.
In case wash organic phase with water and remove water, just can obtain zinc-containing solid catalyst from organic phase.For example, this can realize by the evaporation of organic solvent.Degree about zinc-containing solid catalyst is further processed in solution also can be retained in it in organic phase.
The method for preparing zinc-containing solid catalyst by carbonic acid gas and at least a epoxide polymerization with general formula (I) generally can be referring to WO03/029325.That describes in this document passes through the method that the reaction of zinc oxide and pentanedioic acid prepares the pentanedioic acid zinc catalyst and also can carry out in the present invention.The pentanedioic acid zinc catalyst of describing among the WO03/029325 also can be used for the present invention.
In the preparation of catalyzer, the zinc oxide particle preferably with terminal C
4-8-alkane dicarboxylic acid reaction.This reaction is preferably carried out with pentanedioic acid, hexanodioic acid or its mixture.So preferably pentanedioic acid zinc or hexanodioic acid zinc of zinc salt here.
Polyreaction is preferably used the catalyzer of anhydrous form.For the object of the invention, " anhydrous " is illustrated in water-content in the catalyzer preferably less than 1 % by weight, more preferably is at most 10ppm, based on catalyzer total amount meter." anhydrous " particularly preferably represent in this catalyzer not moisture except chemically-bonded water (for example crystal water) or only contain unessential trace water, more particularly do not contain anyly to be attached to the surface or to be wrapped in water in the space with physics mode.
As epoxide, preferably use ethylene oxide, propylene oxide, oxybutylene, cyclopentene oxide, cyclohexene oxide, oxidation iso-butylene, acryl oxide compound or their mixture.Particularly preferably use propylene oxide, cyclohexene oxide, ethylene oxide or their mixture.Especially use propylene oxide.
For other possible epoxide, can be referring to the 6th and 7 page of WO03/029325.Using CO
2In the situation of two or more epoxide, obtain polycarbonate terpolymer.The mixture of operable two kinds of epoxide for example is: ethylene oxide and propylene oxide, ethylene oxide and cyclohexene oxide, propylene oxide and cyclohexene oxide, oxidation iso-butylene and ethylene oxide or propylene oxide, oxybutylene and ethylene oxide or propylene oxide.
Quantitative ratio between carbonic acid gas and the epoxide can change in wide region.Usually, use excessive carbonic acid gas, namely more than 1 mole of carbon dioxide/1 mole epoxide.
The inventive method preferably includes basically following steps:
1. dry catalyst or make catalyzer anhydrous,
2. in polymerization reactor, use anhydrous catalyzer as initial charging,
3. randomly add the inert reaction medium,
4. adding carbonic acid gas,
5. adding epoxide,
6. reactor is heated to temperature of reaction,
7. randomly add other carbonic acid gas, and
8. after polyreaction finishes, the reactor content processing is obtained polycarbonate, wherein can exchange step 5 and 6.
This reaction can be carried out in the inert reaction medium that can dissolve or disperse described catalyzer.
The material that is suitable as the inert reaction medium is all substances, the especially aromatic hydrocarbons that catalyst activity is not had disadvantageous effect, for example toluene, dimethylbenzene, benzene, and aliphatic hydrocrbon, for example hexane, hexanaphthene, and halohydrocarbon, for example methylene dichloride, chloroform and chlorination isobutyl-.Suitable also is ether, for example ether, and tetrahydrofuran (THF), diglyme (diglyme), two
Alkane, and nitro-compound Nitromethane 99Min. for example.The preferred toluene that uses.
Inert media can for example inject polymerization reactor in undiluted situation, or can preferably inject with gas streams, and used gas can comprise for example nitrogen of rare gas element in this case, or reactant CO
2
When preferably beginning with catalyzer as the initial charging in the reactor, and it is anhydrous by heating in inert gas flow and optional cooling catalyzer to be become, and uses gas with inert reaction medium injecting reactor, stirs simultaneously.
Based on catalyst solution or catalyst dispersion (summation of catalyzer and reaction medium) meter, catalyst concn is the 0.01-20 % by weight preferably, especially the 0.1-10 % by weight.
Based on the summation meter of epoxide and inert reaction medium, catalyst concn is the 0.01-10 % by weight preferably, particularly preferably is the 0.1-1 % by weight.
Also in the preferred embodiment, operation is to carry out in the situation of not using the inert reaction medium at another.
When the present invention begins with the CO of catalyzer and at least a portion
2Before adding epoxide, contact.
In this respect, " with at least a portion " is illustrated in and adds before the epoxide, adds used CO
2Part in the total amount, or in this stage, add all CO of amount
2
Preferably, only add a part of CO
2, and particularly preferably this part is CO
2The 20-80 % by weight of total amount, especially 55-65 % by weight.
CO
2Usually add as gas, and via CO
2Gaseous tension is regulated CO according to the variation of temperature
2Amount.In reactor under room temperature (23 ℃), the CO before adding epoxide
2Pressure (CO hereinafter referred to as
2Authorised pressure), this is corresponding to the CO of preferred proportion
2, be that 5-70 bar, especially 10-30 cling in the situation of using zinc polycarboxylate catalyst; That 5-70 bar, especially 10-50 cling in the situation of using the multi-metal cyanide catalyzer.Be used for CO
2The representative value of authorised pressure is 15 bar for zinc polycarboxylate catalyst, is 50 bar for the multi-metal cyanide catalyzer, under each comfortable 23 ℃.
All pressure datas are absolute pressures.CO
2Authorised pressure can maybe can be divided into discontinuously a plurality of steps and reach in single step, perhaps can be continuously, reach between given period according to linear mode, and perhaps the gradient mode according to linear, index or segmentation reaches.
At CO
2In the selection of authorised pressure, owing to subsequently reactor is heated to temperature of reactor, should be noted that the pressure in reactor raises.Should select CO
2Authorised pressure (for example under 23 ℃) is so that be no more than required final CO under temperature of reaction (for example 80 ℃)
2Pressure.
Catalyzer and CO
2Between contact be generally under 20-80 ℃ temperature, to carry out, preferred 20-40 ℃.Particularly preferably in the lower operation of room temperature (23 ℃).Catalyzer and CO
2Between duration of contact depend on reactor volume, and normally 30 seconds to 120 minutes.
Generally, catalyzer or catalyzer in the inert reaction medium solution or dispersion with CO
2Period of contact stirs.
Only catalyzer with CO
2After the contact, epoxide is introduced in the reactor.Usually with undiluted ground of epoxide injecting reactor, or preferred and on a small quantity rare gas element or CO
2Inject together.
Epoxide adds when stirring usually, and in a lump (in the situation that especially reactor volume is little) or within general 1-100 minute, preferred 10-40 minute time, add continuously, and adding speed can be along with time-invariant, or can be according to graded, this for example can be to rise or descend, or the mode of linearity, index or segmentation.
Temperature when adding epoxide generally is 20-100 ℃, preferred 20-70 ℃.More particularly, can a) epoxide be added (for example room temperature is 23 ℃) and then reactor is adjusted to temperature of reaction T at low temperature
R(for example 80 ℃), or b on the contrary) first reactor is adjusted to temperature of reaction T
RThen add epoxide.Scheme is preferred a).
Therefore, reactor reaches temperature of reaction T after adding epoxide before adding epoxide or preferably
RGenerally temperature of reaction is adjusted to 30-180 ℃, especially 50-130 ℃.This is usually by under agitation heating reactor to realize.Temperature of reaction generally is 40-120 ℃, preferred 60-90 ℃.
After reaching temperature of reaction, at catalyzer and CO
2Not yet introduce whole amount CO during contact
2Situation under (referring to above), with the CO of residual content
2Add reactor, preferably under agitation add.Usually, CO
2Amount so that via CO
2Gaseous tension is regulated.
The preferred CO that adds
2Until CO
2Pressure is (hereinafter referred to as final CO
2Pressure) be the 1-200 bar in the situation of using zinc polycarboxylate catalyst, preferred 10-100 bar, and be the 20-200 bar in the situation of using the multi-metal cyanide catalyzer, preferred 80-100 bar.Be used for final CO
2The representative value of pressure is the 20-100 bar for zinc carboxylate, is 100 bar for the multi-metal cyanide catalyzer.
All force value are absolute pressures.The CO that in this step, adds
2Amount (final CO
2Pressure) also depend on the CO that has added in advance
2Ratio.
From described CO
2Pressure and temperature of reaction obviously as seen, the CO in reactor
2Can there be with above-critical state (being liquid form).Especially be higher than the final CO of 74 bar
2Pressure and be higher than 31 ℃ temperature of reaction T
RLower, CO
2To exist with above-critical state.But, and at supercritical CO
2In the difference of conventional chemical reacting phase ratio be: CO in the methods of the invention
2Be not only reaction medium, and be raw material simultaneously (reactant) and reaction medium.
Final CO
2Pressure can be discontinuously in a step or regulate continuously, for example for CO
2Authorised pressure is described like that.
Reaching final CO
2During pressure, if necessary, this pressure can add and the CO that has consumed by continuous measurement
2Corresponding additional quantity keeps.If no longer be metered into CO
2, CO then
2Pressure is usually during reaction because CO
2Consumption and reduce.This operation is possible too.
Usually, being used for finishing the required time of polyreaction is 60-500 minute, preferred 120-300 minute.The representative value that is used for the rear time of this reaction is 3-4 hour.
Usually, temperature of reaction keeps constant here; But temperature of reaction also can raise or reduces according to reaction process.
The CO that uses in the methods of the invention
2: the epoxide ratio is to instruct by required polymer performance according to known manner.Usually, CO
2Total amount: the ratio (weight ratio) of epoxide total amount is 1:1 to 2:1.
In a preferred embodiment, all above-mentioned processing steps are to carry out in the situation of getting rid of water: not only catalyzer, and inert reaction medium, CO
2With epoxide be anhydrous, or become in a conventional manner anhydrous.
After polyreaction finishes, the reactor content processing is obtained polycarbonate.General operation is to make reactor cooling and simultaneously stirring, makes pressure be equal to environment (inflation of reactor), and discharges the reaction mixture that contains carbonate polymer.Here, if necessary, can add suitable precipitation agent to reactor content.
Usually used precipitation agent contains alcohol, for example methyl alcohol, ethanol, propyl alcohol, perhaps ketone, for example acetone.Methyl alcohol is preferred.Advantageously precipitation agent is acidified to the pH of 0-5.5.
The polymkeric substance of precipitation can separate in a conventional manner, for example by filtration, and dry in a vacuum.
In some cases, the polycarbonate reaction product of a part also exists as the form of dissolving or be dispersed in the precipitation agent, for example in the methyl alcohol of acidifying.This polycarbonate can separate by removing precipitation agent in a conventional manner.For example, methyl alcohol can under reduced pressure distill to be removed, for example on rotatory evaporator.
But, preferably, water-immiscible organic solvent and carboxylic acid or ion-exchanger directly and reaction mixture, and without in advance precipitation.The polymkeric substance of precipitation also can be dissolved in the water-immiscible organic solvent subsequently again in advance.
The zinc-containing solid catalyst that obtains in the present invention can further process to obtain moulded work, paper tinsel, film, coating and sheet material according to many different modes, in this regard can be referring to the 21st and 22 page of for example WO03/029325.
Describe the present invention in detail below by embodiment.
Embodiment
By preparing the polytrimethylene carbonic ether with the similar method of WO03/029325.
1. the preparation of catalyzer
In the 1L four neck flasks that are equipped with by stirring rod, heating bath and water trap, in the 250ml dry toluene, use the zinc oxide of the grinding of 35g as initial charging.After adding the 53g pentanedioic acid, mixture stirred down at the same time in 2 hours, be heated to 55 ℃.Then, be heated to boiling point, under refluxing, remove reaction water by the component distillation mode during this period, until no longer can distill water outlet.Remove toluene by distillation, and with resistates under high vacuum in 80 ℃ of dryings.
2. polymerization
In reactor, add 12g pentanedioic acid zinc as initial charging.Use the 3.5L autoclave that is equipped with mechanical stirrer.After reactor is closed, repeatedly use nitrogen purging.Then add 620g toluene, and with the CO of 6 bar
2In the lower injecting reactor of room temperature (23 ℃).Inject the 310g propylene oxide and be heated to 80 ℃ to reactor.Then, inject CO at 80 ℃ of downhill reaction devices
2, until reach the CO of 40 bar
2Pressure.This reactor 80 ℃ of lower maintenances 4 hours, no longer is metered into other CO during this period
2Subsequently, with the mixture cool to room temperature.
3.1 carry out aftertreatment (contrast) with HCl
Carry out aftertreatment with HCl: aftertreatment is carried out according to WO03/029325A1.Reactor is inflated, and reactor content is poured in the 1L methyl alcohol of using 5ml concentrated hydrochloric acid (37 % by weight) acidifying.Polymer precipitation also filters out, and in 60 ℃ of dried overnight under vacuum.
3.2 carry out aftertreatment (HAc) with acetic acid
The ethyl acetate of same amount is mixed with polymers soln from 2.If the solid content of polymers soln should be lower than 18%, then the amount correction of ethyl acetate is reduced to a certain degree.After stirring subsequently, add 4% diacetyl oxide (based on the amount of second acidimeter), and mixture is stirred again.After 40% acetic acid and stirring that add based on the solid content meter, water is used for dilution (amount of water is corresponding to the amount of organic phase) and is used for washing.Be separated and should carry out 1-48 hour, this depends on mixture.Described washing step carries out 4-5 time.Initial pH, namely the pH after adding described acid is that about 1. pH after 4-5 time is washed are 4.
4. carry out aftertreatment with polyfunctional carboxylic acids/hydroxycarboxylic acid
4.1 citric acid C
6H
8O7
The ethyl acetate of same amount is mixed with polymers soln.If the solid content of polymers soln should be lower than 18%, then the amount correction of ethyl acetate is reduced to a certain degree.After stirring subsequently, add 4% diacetyl oxide (based on the amount of lemon acidimeter), and mixture is stirred again.The amount of the citric acid that must add based on solid content (the 500g citric acid is for 1L water), is only 20% in the saturated solution form.Here, polymers soln is rear with regard to bleach in only once washing.
So required washing times is less than the washing times in acetic acid washing situation.In addition, another the obvious advantage when using citric acid is: here its initial pH itself is 2.5-3, is that the number of times of 4 required washing steps is less so reach final pH.2-3 washing step here arranged, and be 4-5 washing step by contrast in the acetic acid scheme.
When using citric acid, for separating of the remarkable situation (15-30 minute) when using HAc of time (maximum 5 minutes) of organic phase and water.In addition, when using citric acid, just become transparent after organic phase is only once washed.When using HAc, only after repeated washing, just reach this effect.
Compare with acetic acid, another advantage of citric acid is aspect chemical property: acetic acid is categorized as corrosive (C) (R10-35, S (1/2)-23-26-45), and citric acid only is irritating (R36, S26).This is also so that the processing of acid is obviously more satisfactory.These acid are excessive uses, based on the amount meter of the catalyzer that will destroy.So possible is not attack the chain end of polymkeric substance with the deprotonation acid of catalyst particle reaction sometimes.This also observes in the situation of hydrochloric acid and (rare) acetic acid.Do not have this phenomenon in dicarboxylic acid and tricarboxylic situation, wherein dicarboxylic acid and tricarboxylic acid also have hydroxy functional group.This may be the geometry because of acid, and namely the negative charge of carboxylate salt passes through the hydrogen bond conductively-closed via the proton of contiguous hydroxyl unit.So carboxylate salt becomes less for the aggressiveness of polymer chain end, so reduced molecular weight degradation.
Optional reason of adding about 4% diacetyl oxide (AA) is as described below: purpose is the chain end with diacetyl oxide protection PPC, and therefore suppresses to attack the molecular weight degradation that causes by negatively charged ion, for example from the attack of the acetate moiety of acetic acid.If wherein add 20% citric acids and 4% diacetyl oxide and carry out the experiment of washing for three times and the similar experiment of not using diacetyl oxide under 40 ℃, then not existing of diacetyl oxide do not bring shortcoming when using citric acid replacement acetic acid.So, when using citric acid, do not need to protect the end of the chain with diacetyl oxide, so aftertreatment technology is simplified to the degree of single component and an additional step.The quality of washing process is maintained, and the zinc value is about 20ppm.Molar mass is that Mn is 100000g/mol, and Mw is 800000g/mol.
When the amount of citric acid be reduced to based on the polymer solids level meter 10% the time, also in the situation of not adding diacetyl oxide, keep very well in the scourability under 40 ℃ (40ppm zinc) and molar mass (Mn=99700g/mol, Mw=773000g/mol).If the amount of citric acid only is reduced to 5%, molecular weight remains unaffected, but the content of remaining zinc can not be reduced in three washings and is lower than 200ppm.If these reactions are at room temperature carried out with 5% and 10%, remarkable longer time (10-30 minute) when then organic phase and water separating each other need to be than 40 ℃, but the property retention of polymkeric substance does not change (Mn=124000g/mol), and zinc content also is (150ppm) like this.
4.2 tartrate C
4H
6O
6(2,3-dihydroxysuccinic acid or 2,3 dihydroxybutanedioic acid)
The experiment of carrying out with tartrate is by similarly carrying out with those experiments of using acetic acid and citric acid.Tartrate is showing slightly poorlyer than citric acid aspect the quality of washing process, but also is better than conventional acetic acid.At room temperature, as in the situation of acetic acid, here must add based on 40% of solid content meter, but only need three washing steps to replace 4-5 washing step.In tartaric situation, also the number of required washing step can be minimized to 1-2, if the temperature of the temperature of polymers soln and washing soln is elevated to 40 ℃.Under 40 ℃ service temperature, this amount can be reduced to 20% from 40%.But remaining zinc concentration is elevated to 0.06g/100g polymkeric substance and 20% acid under 40 ℃ from room temperature 0.023g/100g polymkeric substance and 40% acid.
4.3 glyconic acid C
6H
12O
7
In the situation of glyconic acid, the amount similar to the situation of acetic acid (about 40%) that must use.Separation performance also is similar.Zinc content after three washings is 2-40mg zinc/100g polymkeric substance.But only also similarly vitrify is transparent after three separating technologies for polymkeric substance.Even essential consumption and the acetic acid as much of acid, but required washing times only is 3 times, replaces 4-5 time.The transparent advantage of use glyconic acid shows the molar mass aspect of polytrimethylene carbonic ether.Molar mass is 40000-50000g/mol (Mn) always, so be significantly higher than the typical molar mass (Mn=25000-40000g/mol) that obtains with the acetic acid aftertreatment time.
4.4 ethylenediamine tetraacetic acid (EDTA) (EDTA) C
10H
16N
2O
8
When 40 % by mole of Na EDTA at room temperature being added the polymers soln (based on the solid content meter) of needs washing, it is medium reaching the degree of removing pentanedioic acid zinc by three washings.The amount of zinc resistates is about 1g/100g polymkeric substance.Polymers soln neither be transparent.But, finding the high molecular weight for PPC here, Mn is higher than 50000g/mol.PH also is about 7, so even only just be in the ideal range after three washings.This is to be beyond one's reach in common process or the situation with above-mentioned acid.
4.5 toxilic acid C
4H
6O
5
If will (use with aqueous solution form: 500g/L) mix with PPC solution and wash mixture with water three times, then obtain transparent polymers soln based on 40 % by weight toxilic acids of solid content meter.Separation performance is suitable with tartaric situation with citric acid.Under 40 ℃, as expected, compare with the technique when the room temperature, aspect washing process, slight improvement is arranged.
5. acid ion exchangers (high acidity Dowex50WX8-200)
Ion-exchanger is added in the post that the glass filter material is housed (hole width is 1), and wetting with ethyl acetate.Then filter very rare PPC solution (5% solid content) with ion-exchanger.
Although polymers soln must be very rare, the filtration of ion-exchanger has obtained transparent polymers soln.Ion-exchanger can destroy and remove pentanedioic acid zinc from PPC solution.In addition, can realize continuous processing here.
Following table has gathered the result.
Abbreviation:
The EA ethyl acetate
The SC solid content
The AA diacetyl oxide
The GPC gel permeation chromatography
Claims (12)
1. method for preparing zinc-containing solid catalyst wherein makes carbonic acid gas and at least aly has the epoxide of general formula (I) at the C as catalyzer
4-8Polymerization under the existence of-alkane dicarboxylic acid's zinc salt,
Wherein
R is H, halogen, NO independently of one another
2, CN, COOR ' or C
1-20The hydrocarbon structure part, it can have substituting group, and wherein among the structure division R also can be OH, and wherein two structure division R can form C together
3-5The alkylidene group structure division,
R ' is that H maybe can have substituent C
1-20The hydrocarbon structure part,
Comprising with following material and the reaction mixture that after reaction, obtains: carboxylic acid or acid ion exchangers and can dissolve the water-immiscible organic solvent of zinc-containing solid catalyst, and wash organic phase with water, and randomly obtain zinc-containing solid catalyst from organic phase.
2. the process of claim 1 wherein C
4-8-alkane dicarboxylic acid's zinc salt is pentanedioic acid zinc or hexanodioic acid zinc.
3. claim 1 or 2 method, wherein the sum of the carboxyl in the carboxylic acid and hydroxyl is at least 2.
4. each method among the claim 1-3, wherein the structure of carboxylic acid contains at least one hydroxyl or at least one nitrogen-atoms.
5. each method among the claim 1-4, wherein carboxylic acid has at least 4 carbon atoms.
6. each method among the claim 1-5, wherein carboxylic acid is to be selected from: acetic acid, citric acid, tartrate, glyconic acid, toxilic acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), MDGA (MGDA), xitix, poly carboxylic acid, or their mixture.
7. each method among the claim 1-6, wherein the amount of carboxylic acid is the 5-80 % by weight, based on the zinc-containing solid catalyst meter.
8. each method among the claim 1-7, wherein organic solvent is ester.
9. each method among the claim 1-8, wherein zinc-containing solid catalyst and carboxylic acid anhydride reacted before the mixing of carboxylic acid or acid ion exchangers.
10. the method for claim 9, wherein the amount of carboxylic acid anhydride is the 0.5-25 % by weight, based on the zinc-containing solid catalyst meter.
11. carboxylic acid or the acid ion exchangers purposes in the purification zinc-containing solid catalyst.
12. a purification contains C
4-8The method of the zinc-containing solid catalyst of-alkane dicarboxylic acid's zinc salt comprises and carrying out according to each described purification step among the claim 1-8.
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| EP2557104A1 (en) * | 2011-08-12 | 2013-02-13 | Basf Se | Method for producing low molecular weight polyalkylene carbonate |
| US9458285B2 (en) | 2013-05-27 | 2016-10-04 | Lg Chem, Ltd. | Method for preparing polyalkylenecarbonate |
| CN112126054B (en) | 2013-09-09 | 2022-11-18 | Lg化学株式会社 | Method for preparing polyalkylene carbonate resin |
| WO2015034328A1 (en) * | 2013-09-09 | 2015-03-12 | 주식회사 엘지화학 | Polyalkylene carbonate resin and method for producing same |
| KR101640244B1 (en) | 2013-10-30 | 2016-07-15 | 주식회사 엘지화학 | Preparation method of organic zinc catalyst and poly(alkylene carbonate) resin |
| KR101639364B1 (en) * | 2013-11-04 | 2016-07-13 | 주식회사 엘지화학 | Organic zinc catalyst |
| JP6272473B2 (en) | 2013-11-18 | 2018-01-31 | エルジー・ケム・リミテッド | Method for producing polyalkylene carbonate resin |
| KR101799093B1 (en) | 2014-11-04 | 2017-11-17 | 주식회사 엘지화학 | Production method of poly(alkylene carbonate) particles |
| WO2016072741A1 (en) * | 2014-11-04 | 2016-05-12 | 주식회사 엘지화학 | Polyalkylene carbonate particle preparation method |
| KR101659681B1 (en) * | 2015-01-30 | 2016-09-23 | 국민대학교산학협력단 | Method for synthesizing copolymer of compound containing epoxide and CO2 cross-linked by vulcanization |
| KR102332741B1 (en) * | 2017-05-10 | 2021-11-30 | 주식회사 엘지화학 | Purification method of polyalkylenecarbonate |
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| WO2010033705A1 (en) * | 2008-09-17 | 2010-03-25 | Novomer, Inc. | Aliphatic polycarbonate quench method |
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| CN104662065A (en) * | 2013-05-27 | 2015-05-27 | Lg化学株式会社 | Method of manufacturing polyalkylene carbonate |
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| US9447236B2 (en) | 2013-05-27 | 2016-09-20 | Lg Chem, Ltd. | Method of manufacturing polyalkylene carbonate |
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