CN103102481A - Synthesis method of aliphatic polycarbonate with regular chain structure - Google Patents
Synthesis method of aliphatic polycarbonate with regular chain structure Download PDFInfo
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Abstract
The invention relates to the field of high-molecular material synthesis, and aims at providing a synthesis method of aliphatic polycarbonate with a regular chain structure. The method comprises the following steps of: adding an end epoxide containing a polar group and a zinc-cobalt bimetal cyanide catalyst into a high-pressure reaction kettle, wherein the mass ratio of the dosage of the catalyst to the dosage of the end epoxide is (0.003-0.01):1; introducing CO2 at a temperature of 20-60 DEG C until the CO2 pressure is 0.5-6MPa; performing a copolymerization reaction for 10-72 hours to obtain a crude product; dissolving the crude product after the reaction in dichloromethane; and precipitating with methanol and repeatedly washing for at least three times to obtain a product of aliphatic polycarbonate with a regular chain structure. The method provided by the invention has the obvious advantages of similar alternate polymerization that copolymerization between multiple polar epoxy monomers and CO2 can be catalyzed, excellent regional selectivity that the obtained polycarbonate has very high regional selectivity, and high catalytic activity that the copolymerization reaction between an end epoxy monomer containing the polar group and CO2 can be catalyzed at relatively low temperature.
Description
Technical field
The invention belongs to the synthesis of polymer material field, be specifically related to adopt end ring oxide compound and the CO of a kind of zinc-cobalt dual-metal cyanide catalyst catalysis polar functionalities
2Copolyreaction is to obtain the synthetic method of the regular polycarbonate of chain structure.
Background technology
Carbonic acid gas (CO
2) aboundresources, cheap, nontoxic, industrial be a kind of very important carbon source, simultaneously it is again a kind of main greenhouse gases, the arch-criminal who is considered to cause global warming, therefore, with CO
2Chemistry is fixed as valuable chemical material, as effective utilization and minimizing CO
2A main path of discharging has caused many research workers' strong interest.Wherein, catalysis CO
2With epoxide copolymerization polycarbonate be an important research direction.The gained polycarbonate can be used as film, medical treatment product and wrapping material, and potential application is widely arranged.
Adopted first zinc ethyl/water catalyst system success catalysis propylene oxide/CO in 1969 since Inoue
2Since the copolymerization polycarbonate, people have developed various homogeneous phase and heterogeneous catalysis system successively.These catalyst system are for propylene oxide and CO
2Copolyreaction all has good catalytic activity and selectivity, the end ring oxide compound and the CO that contain donor residues that simultaneously also can the catalysis other types
2Copolymerization.Yet up to now, these catalyst system of having reported still mainly concentrate on end ring oxide compound such as propylene oxide, cyclohexene oxide and derivative thereof and the CO that contains electron-donating group
2Copolyreaction, and for the end ring oxygen monomer and the CO that contain electron-withdrawing group
2Copolyreaction rarely have report (only having several pieces so far).
In general, for the end ring oxide compound of polar functionalities, because its substituting group has stronger sucting electronic effect, with CO
2During copolyreaction, the easily interior Cheng Huan of its polymer growth chain generates the five-membered ring carbonate ester by product.In addition, in polymerization process, the difference of the activation energy of generation five-membered ring carbonate ester by product and polycarbonate is less.Contrast aliphatics end ring oxygen monomer and CO
2The activation energy of copolymerization is as propylene oxide/CO
2It is 53.5KJ/mol with the complete alternately difference of the activation energy of polycarbonate that reaction generates five-membered ring carbonate ester, and epoxy chloropropane/CO
2In reaction, both differences are 45.4 KJ/mol, Styrene oxide 98min./CO
2In reaction, both differences are 10.3KJ/mol.Therefore for end ring oxygen monomer and the CO of polar functionalities
2Copolyreaction, the polymkeric substance selectivity that the generation that how to suppress the cyclic carbonate ester by product namely improves copolyreaction becomes the crucial and challenge that determines copolymerization.
So far, the end ring oxide compound and the CO that only have the relevant polar functionalities of only a few
2The report of copolyreaction.Can be used for catalyzed oxidation vinylbenzene and CO such as some based on the heterogeneous catalyst of metallic zinc such as zinc ethyl/aqueous systems, pentanedioic acid zinc and hybrid collosol-catalyst system such as gel bimetallic cyaniding complex
2Copolyreaction, but these catalyst system activity are low, selectivity of product is poor, and generally contains a large amount of ether chain links and cyclic carbonate ester (Makromol. Chem. 1969,130,210 – 220 in reaction product; J. Korean Int. Eng. Chem. 2008,19,133 – 136; Polym. Mater. Sci. Eng. 2010,26,1 – 4; Green Chem. 2012,14,1168-1177).In addition, although some highly active homogeneous catalysts such as beta-diimine zinc also are used to catalyzed oxidation vinylbenzene/CO
2Copolyreaction, yet its polymkeric substance selectivity is very low, only has 35%, most of product be five-membered ring carbonate ester (ACS Symposium 2006,921,116-128).Recently, the people such as Lv Xiaobing adopts homogeneous phase salen catalyzer at 25 ℃ of lower catalyzed oxidation vinylbenzene/CO
2Copolyreaction, success synthesized the polycarbonate that entirely replaces, and the polymkeric substance selectivity can reach 100%, namely there is no the generation (Macromolecules 2010,43,9202 – 9204) of cyclic carbonate ester by product.For end ring oxygen monomer such as the epoxy chloropropane of the typical polar functionalities of another kind, due to the stronger electrophilic character of chlorine atom, therefore the synthetic single polycarbonate that entirely replaces seems more difficult.At present, use difunctional salen catalyzer 0 except people such as Lv Xiaobing
oUnder C success synthesized 100% polymkeric substance selectivity and 100% carbonic ether optionally outside polycarbonate, also do not have so far other relevant reports to deliver (J. Am. Chem. Soc. 2011,133,15191 – 15199).Although under low reaction temperatures, the salen homogeneous catalyst is end ring oxygen monomer such as the Styrene oxide 98min. of some polar functionalities of catalysis successfully, epoxy chloropropane and CO
2Copolyreaction, the synthetic single polycarbonate that entirely replaces of preparation, yet, catalytic activity and selectivity that the salen system needs the cooperation of promotor just can embody.What is interesting is, with salen catalyst racemation epoxy propane/CO
2Copolyreaction have high regioselectivity different be, salen catalyst Styrene oxide 98min./CO
2Copolyreaction does not have regioselectivity, as racemize Styrene oxide 98min.-CO
2Head-to-tail structure in multipolymer only has 51%, when the salen catalyzer that adopts chiral catalyst as (1R, 2R) comes catalysis (S)-Styrene oxide 98min., also can only obtain head-to-tail structure and be 82% multipolymer.In fact end ring oxide compound and the CO of the racemic polar functionalities of catalysis
2Copolymerization does not also have disclosed bibliographical information so far.
In sum, for end ring oxide compound and the CO of polar functionalities
2The reaction of copolymerization, because the difference of the activation energy that generates cyclic carbonate ester and polycarbonate is less, the general requirement temperature of reaction is lower, to suppress the generation of five-membered ring carbonate ester.So just require catalyst system still will have higher catalytic activity under lower temperature of reaction.On the other hand, the salen catalyzer can successful catalysis polar functionalities end ring oxygen monomer and CO
2The complete alternately polycarbonate of copolymerization preparation, but the regioselectivity of present uncontrollable copolyreaction namely can't obtain the polycarbonate product of compound with regular structure.The structure of this explanation catalyst system may have on the regioselectivity of polyreaction important impact.Analyze theoretically, in the homogeneous system of report, only under the condition of using the promotors such as large steric hindrance organic bases, could realize better active alternating copolymerization, therefore we think under organic bases exists, the nucleophilic that the methylene radical of epoxy monomer inevitably is subject to strong organic bases attracts (dipole-dipole interaction), thereby strengthened the carbon positivity of mesomethylene carbon, make it more be conducive to the attack in active centre, in this case, electric charge on epoxide group on mesomethylene carbon and methine carbon " is evened up ", is unfavorable for thus regioselective reaction.If find without the need for the catalyst system of machine alkali with regard to the energy catalyzed copolymerization, so just may evade above-mentioned " evening up " effect, the feasible region selective polymerisation.Namely develop end ring oxide compound and CO that a kind of new simple catalyst system comes the catalysis polar functionalities
2High reactivity, high polymers selectivity and regioselectivity copolymerization need to be satisfied following requirement: can affect the factor of the charge distribution of carbon in epoxide group without other in system except the growing chain active centre.Based on this understanding, the contriver has obtained the present invention's technology after serial experiment.
Summary of the invention
The problem to be solved in the present invention is, overcomes deficiency of the prior art, and the synthetic method of the regular aliphatic polycarbonate of a kind of chain structure is provided.Be the technical solution problem, solution of the present invention is:
The synthetic method of the regular aliphatic polycarbonate of a kind of chain structure is provided, comprises the following steps:
Add end ring oxide compound and the zinc-cobalt dual-metal cyanide catalyst of polar functionalities in autoclave, the mass ratio of catalyst levels and end ring oxide compound consumption is 0.003 ~ 0.01: 1; 20 ~ 60
oAt the temperature of C, pass into CO
2To CO
2Pressure is 0.5 ~ 6MPa, obtains crude product after copolyreaction 10 ~ 72h, and reacted crude product is dissolved in methylene dichloride, then uses methanol extraction, repetitive scrubbing at least three times, obtains the regular aliphatic polycarbonate product of chain structure;
Described zinc-cobalt dual-metal cyanide catalyst prepares in the steps below:
At first prepare zinc hydroxide sol: take acetate, halide salt, nitrate or the vitriol of zinc as raw material, triammonium citrate is properties-correcting agent, and the mass ratio of zinc salt and properties-correcting agent is 1:0.5 ~ 10, and compound concentration is 10 ~ 30% zinc solution; After stirring, be placed in 40
oIn the C Water Tank with Temp.-controlled, add the ethanol of cumulative volume 15 ~ 60%, zinc salt complete hydrolysis after 3 ~ 8 hours obtains the zinc hydroxide precipitation; Add again appropriate peptizing agent ammoniacal liquor to zinc hydroxide precipitation to disappear, obtain zinc hydroxide sol after standing 2 ~ 5h; Then potassium hexacyanocobaltate salt is dissolved in the deionized water that volume ratio is 1:1/trimethyl carbinol mixing solutions, concentration is 10-20%, adds a small amount of hydrochloric acid conditioning solution pH value extremely less than 3, and is added to aforesaid zinc hydroxide sol.The mol ratio of potassium hexacyanocobaltate and zinc hydroxide is 1:3, and namely zinc hydroxide need be excessive.Then 40 ~ 80
oStirred under C 5 ~ 72 hours, and obtained required zinc-cobalt dual-metal cyanide catalyst by separation, drying.
In the present invention, in described copolyreaction, the catalytic activity of zinc-cobalt dual-metal cyanide catalyst is greater than 0.25kg polymkeric substance/g catalyzer.
In the present invention, the end ring oxide compound of described polar functionalities is: the Styrene oxide 98min. that fluorine on phenyl ring, chlorine, bromine, alkyl, alkoxyl group and aryl replace, or at least a in epoxy chloropropane, epoxy bromopropane, glycidyl allyl ether, Styrene oxide 98min., (methyl) glycidyl acrylate or oxidation limonene.
In the present invention, when the end ring oxide compound that adds polar functionalities and zinc-cobalt dual-metal cyanide catalyst, also comprise the step that adds organic solvent; The volume ratio of organic solvent and end ring oxide compound is 0.1 ~ 1:1.
In the present invention, described organic solvent is non-proton polar organic solvent.Use solution polymerization process in the present invention, with respect to bulk polymerization, can further improve the content of polymerisate carbonic ether chain link.
In the present invention, the non-proton polar organic solvent that uses is: any one in methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, DMF, methyl-sulphoxide, propylene carbonate or NSC 11801.
In the present invention, the aliphatic polycarbonate that the chain structure for preparing is regular, modular construction content is more than or equal to 80% end to end for it, and molecular weight is greater than 3000g/mol, molecular weight distribution is 1.5 ~ 4, the alternate degree of multipolymer〉70%.
Temperature of reaction in above-mentioned synthetic method is preferably 25 ~ 50
oC, too low temperature of reaction can cause the reduction of catalytic activity and the prolongation of decomposition induction time, too high temperature of reaction can significantly reduce polymkeric substance selectivity and carbonic ether selectivity, causes the significantly increase of ether chain link in polymkeric substance and the generation of five-membered ring carbonate ester by product.
Reaction pressure in above-mentioned synthetic method is CO
2Dividing potential drop is preferably 3 ~ 5MPa.This polyreaction is carried out in airtight reactor, is passing into CO
2Vacuum-treat closed reactor before.Experimental result shows: under too low reaction pressure, though polyreaction can be carried out smoothly, in polymkeric substance, to contain quantitative change large for the ether chain link, and catalytic activity descends; Although and too high reaction pressure is favourable to polyreaction, all not obvious to catalytic activity and polymkeric substance selectivity and carbonic ether selectivity, but also can significantly increase facility investment.
Therefore, the temperature and pressure in the present invention is based on considering of efficient, cost and quality and carries out preferred result.
In above-mentioned polymerisation process, if adopt solution polymerization, the volume ratio of organic solvent and end ring oxide compound is preferably 0.1 ~ 0.5:1.Introduce polar aprotic solvent in polymerization system, can reduce the viscosity of reaction system, be conducive to the rapid dispersion of catalyzer, the more important thing is the generation that can effectively suppress polyethers chain link in polyreaction, thereby improve the selectivity of carbonic ether chain link.Yet, often contain Trace water in organic solvent and divide, be difficult to remove totally, therefore, the introducing of organic solvent sometimes can cause catalytic activity, decrease in molecular weight and molecular weight distribution to broaden.After dewatering through links such as super-dry and distillations, can improve polymerization activity and polymericular weight.
The zinc that adopts in the present invention-cobalt dual-metal cyanide catalyst contains zinc-hydroxyl structure, be sheet structure, ball-like structure or nano-pore structure, sheet thickness is 15 ~ 200 nanometers, the mean diameter of ball-like structure catalyzer is 50 ~ 300 nanometers, nanoporous is 2 ~ 100 nanometers, by the means such as end group sign of infrared spectra, Electronic Speculum, ultimate analysis, nitrogen adsorption-desorption and polymkeric substance are proved.Significantly be different from the synthetic catalyzer of traditional method, this catalyzer is epoxide and the CO of catalysis polar functionalities at a lower temperature
2Copolyreaction, and significantly suppress the generation of five-membered ring carbonate ester, catalytic activity is greater than 0.25kg polymkeric substance/g catalyzer.The consumption of zinc in the present invention-cobalt dual-metal cyanide catalyst be polar functionalities end ring oxygen monomer weight 0.003 ~ 0.01, be preferably 0.003 ~ 0.006.
Significantly different from prior synthesizing method is that in the present invention, the employing zinc hydroxide sol both can produce more zinc-hydroxyl structure, also easily obtained the catalyzer of nanostructure.
In the present invention, adopt zinc as above-cobalt dual-metal prussiate, end ring oxygen monomer and the CO of catalysis polar functionalities
2Copolyreaction, can obtain significant reaction effect.With catalyzed oxidation vinylbenzene/CO
2Copolyreaction is example, and in polyreaction, catalytic activity can reach 0.25kg polymkeric substance/g catalyzer, the content of five-membered ring carbonate ester by product can be controlled in below 1%, in polymkeric substance, the carbonic ether selectivity can reach more than 99%, and the multipolymer number-average molecular weight can reach 20,000, and molecular weight distribution is between 2.0 ~ 3.3.The multipolymer that this catalyzer prepares also has good thermomechanical property, and its second-order transition temperature reaches as high as 82
oC, the complete alternately high-molecular-weight poly (Styrene oxide 98min.-CO that even prepares than homogeneous phase salen catalyzer
2) (Mn=25000) second-order transition temperature (80
oC) taller 2
oC。In general, after zinc-cobalt dual-metal cyanide catalysis polymerization, the content of modular construction end to end of resulting polymers is more than or equal to 80%, and molecular weight is greater than 3000g/mol, be preferably more than 10000g/mol, molecular weight distribution is 1.5 ~ 4, the alternate degree of multipolymer〉70%, be preferably more than 90.High molecular weight and high alternate degree determine that polymkeric substance has better mechanics and thermal property.
Especially surprisingly, zinc provided by the invention-cobalt dual-metal cyanide catalysis polar functionalities end ring oxide compound and CO
2During copolymerization, the gained polycarbonate has high chain structure regularity, and this is at present relevant racemize Styrene oxide 98min./CO
2Unique report of regioselectivity copolyreaction.The carbonic ether chain link greater than 99% polycarbonate in, head-to-tail structure content is the tallest and the biggest in 96%, generally greater than 90%.This meets the reaction principle that we propose previously.Be that phenyl is as an electron-withdrawing group, the methine carbon cloud density that is connected with phenyl is lower, present certain carbon positivity, easily by catalyst active center's nucleophilic attack optionally, thereby form distinctive regioselectivity, owing to not containing other organic bases in this reaction system, so this regioselectivity is not disturbed, thereby has obtained high regioselectivity.And the salen catalyst system of contrast homogeneous phase, because containing large steric hindrance Lewis alkali in system, and the existence meeting of Lewis alkali produces certain nucleophilicity to the less methylene radical of the steric hindrance of epoxide group in the end ring oxide compound of polar functionalities, thereby weakened the cloud density difference of methine carbon and mesomethylene carbon in the epoxide group, be unfavorable for the selectivity nucleophilic attack of catalytic active center.Therefore, the end ring oxide compound/CO of the zinc of single component-cobalt dual-metal cyanide catalyst to polar functionalities
2Copolyreaction has good regioselectivity.In addition, in polycarbonate product end to end configuration content be subjected to the content influence of ether chain link in polymkeric substance, and with catalyst preparation process in the coordination agent that uses, metal-salt kinds etc. are irrelevant.In general, in polymkeric substance, carbonate content is higher, and chain link content is more end to end.This explanation is with zinc-cobalt dual-metal cyanide catalyst catalyzed oxidation vinylbenzene/CO
2The polycarbonate that preparation is synthetic, its microstructure regularity and reaction conditions such as temperature, pressure and reaction times etc. has certain relation, because the variation of these reaction conditionss can affect the relative content of carbonic ether in polymkeric substance.
With respect to prior art, remarkable advantage of the present invention is:
1, polymerization is replaced in inbreeding, but and the epoxy monomer of catalysis various polarity and CO
2Copolymerization.The zinc that uses in the present invention-cobalt dual-metal cyanide catalyst is compared with existing homogeneous catalyst, can suppress the generation of five-membered ring carbonate ester by product under higher temperature of reaction.For example: catalyzed oxidation vinylbenzene/CO
2In 35 ~ 50
oThe C copolyreaction, the selectivity of polymkeric substance can reach more than 98%, and the homogeneous phase salen catalyst system of the effect optimum of reporting now will obtain same polymkeric substance selectivity, temperature of reaction must be controlled at 25
oBelow C.For another example, for epoxy chloropropane/CO
2The catalyzer in the present invention is used in copolyreaction, under relatively high temperature of reaction (20 ~ 50
oC), its polymkeric substance selectivity can reach 95%, and homogeneous phase salen catalyzer will obtain same polymkeric substance selectivity, and its temperature of reaction will be lower than 0
oC。React under comparatively high temps and don't generation cyclic side products and polyethers chain link, thereby be conducive to increase the activity of polyreaction.Have no at present similar heterogeneous catalyst, homogeneous catalyst also must react at a lower temperature.
2, excellent regioselectivity.Catalyzer in the present invention is at catalysis racemize Styrene oxide 98min. and CO
2Copolyreaction the time, the polycarbonate that obtains has very high regioselectivity, in polymkeric substance end to end configuration content reach as high as 96%.And the same polyreaction of other catalyst system catalysis does not have regioselectivity.And the polymkeric substance of regioselectivity polymerization gained often has good thermal characteristics.
3, high catalytic activity.Catalyzer in the present invention can be at a lower temperature (＜50
oC) catalysis polar functionalities end ring oxygen monomer/CO
2Copolyreaction, and other heterogeneous catalyst of having reported all can not react at low temperatures.
Description of drawings
Fig. 1 is for implementing catalyzed oxidation vinylbenzene/CO in 7
2Copolyreaction
1H NMR result, polymkeric substance selectivity and carbonic ether selectivity are that 99%(curve 1 is the polymkeric substance after purifying
1H NMR spectrogram, curve 2 is reacting coarse products
1H NMR spectrogram);
Fig. 2 is catalyzed oxidation vinylbenzene/CO in embodiment 9
2Copolyreaction
13C NMR result, configuration content 96% end to end;
Fig. 3 is Epichlorohydrin/CO in embodiment 12
2Copolyreaction
1H NMR result, polymkeric substance selectivity are 95%, and the carbonic ether selectivity is 70%;
Fig. 4 is catalysis glycidyl methacrylate/CO in embodiment 13
2Copolyreaction
1H NMR result, polymkeric substance selectivity are 90%, and the carbonic ether selectivity is 70%;
Fig. 5 is Styrene oxide 98min.-CO in embodiment 6
2The second-order transition temperature of multipolymer;
Fig. 6 is epoxy chloropropane/CO in embodiment 11
2The second-order transition temperature of multipolymer.
(second-order transition temperature is recorded by the DSC method, test condition: under condition of nitrogen gas 10
oC/min rises to 100 from room temperature
oThen C is down to-20
oC, then with 10
oC/min rises to 100
oC, getting the thermal transition temperature that heating curve for the second time obtains is second-order transition temperature.）
Embodiment
Describe the present invention in detail below in conjunction with drawings and Examples, but the present invention is not limited to this.
The present invention's zinc used-cobalt dual-metal cyanide catalyst prepares in the steps below:
The preparation of embodiment 1 zinc-cobalt dual-metal cyanide catalyst
At first with the 5.0g zinc acetate, the 2.5g triammonium citrate joins in the single port flask of 100ml, pours the 17ml deionized water into, and vigorous stirring is dissolved zinc acetate and triammonium citrate fully, is mixed with concentration and is 30% zinc acetate aqueous solution.Then the zinc acetate solution that configures is placed in 40
oIn the Water Tank with Temp.-controlled of C, after solution temperature is stable, add the 3ml dehydrated alcohol in flask, slowly stir 6h, make the zinc acetate hydrolysis fully, generate the zinc hydroxide precipitation.Under agitation condition, add appropriate peptizing agent ammoniacal liquor in system at last, the add-on of ammoniacal liquor then with solution left standstill 2h, generates zinc hydroxide sol to the zinc hydroxide precipitation is disappeared, and wherein the content of zinc hydroxide is 2.7g.The 3.0g potassium hexacyanocobaltate is dissolved in the mixing solutions that 15ml deionized water and the 15ml trimethyl carbinol form, drips a small amount of concentrated hydrochloric acid after dissolve complete in potassium salt soln, use PH detection paper to the solution pH value lower than 3.Then be added drop-wise in aforesaid zinc hydroxide sol, both mol ratios are 1:3 just.40
oVigorous stirring 15h under C, then pressure filtration, drying obtains required zinc-cobalt dual-metal cyanide catalyst.
The preparation of embodiment 2 zinc-cobalt dual-metal cyanide catalyst
At first with the 3.8g zinc chloride, the 20g triammonium citrate joins in the single port flask of 200ml, pours the 27ml deionized water into, and vigorous stirring is dissolved zinc acetate and triammonium citrate fully, is mixed with concentration and is 14% zinc acetate aqueous solution.Then the zinc acetate solution that configures is placed in 40
oIn the Water Tank with Temp.-controlled of C, after solution temperature is stable, add the 40ml dehydrated alcohol in flask, slowly stir 3h, make the zinc acetate hydrolysis fully, generate the zinc hydroxide precipitation.Under agitation condition, add appropriate peptizing agent ammoniacal liquor in system at last, the add-on of ammoniacal liquor then with solution left standstill 5h, generates zinc hydroxide sol to the zinc hydroxide precipitation is disappeared, and wherein the content of zinc hydroxide is 2.7g.The 3.0g potassium hexacyanocobaltate is dissolved in the mixing solutions that 7.5ml deionized water and the 7.5ml trimethyl carbinol form, drips a small amount of concentrated hydrochloric acid after dissolve complete in potassium salt soln, use PH detection paper to the solution pH value lower than 3.Then be added drop-wise in aforesaid zinc hydroxide sol, both mol ratios are 1:3 just.80
oVigorous stirring 5h under C, then pressure filtration, drying obtains required zinc-cobalt dual-metal cyanide catalyst.
The preparation of embodiment 3 zinc-cobalt dual-metal cyanide catalyst
At first with 4.4 g zinc sulfate, the 44g triammonium citrate joins in the single port flask of 250ml, pours the 44ml deionized water into, and vigorous stirring is dissolved zinc acetate and triammonium citrate fully, is mixed with concentration and is 10% zinc acetate aqueous solution.Then the zinc acetate solution that configures is placed in 40
oIn the Water Tank with Temp.-controlled of C, after solution temperature is stable, add the 50ml dehydrated alcohol in flask, slowly stir 8h, make the zinc acetate hydrolysis fully, generate the zinc hydroxide precipitation.Under agitation condition, add appropriate peptizing agent ammoniacal liquor in system at last, the add-on of ammoniacal liquor then with solution left standstill 4h, generates zinc hydroxide sol to the zinc hydroxide precipitation is disappeared, and wherein the content of zinc hydroxide is 2.7g.The 3.0g potassium hexacyanocobaltate is dissolved in the mixing solutions that 10ml deionized water and the 10ml trimethyl carbinol form, drips a small amount of concentrated hydrochloric acid after dissolve complete in potassium salt soln, use PH detection paper to the solution pH value lower than 3.Then be added drop-wise in aforesaid zinc hydroxide sol, both mol ratios are 1:3 just.65
oVigorous stirring 72h under C, then pressure filtration, drying obtains required zinc-cobalt dual-metal cyanide catalyst.
Before reaction beginning, with the 10ml autoclave 120
oToast 4h under C, then be cooled to room temperature in dry vessel.Then add the Styrene oxide 98min. 3ml of the zinc described in embodiment 1-cobalt dual-metal cyaniding coordination catalyst 9 mg and purifying in the still, be filled with CO
2Pressure is to 4.0MPa, 40
oUnder C, reaction 10h.Reaction is placed in ice-water bath with reactor after finishing, and then fast cooling emits unnecessary CO
2, take out a small amount of crude product and be used for carrying out
1H NMR and GPC test to measure polymkeric substance selectivity in product, the molecular weight and molecualr weight distribution of carbonic ether selectivity and polymkeric substance in polymkeric substance.Remaining crude product dissolves with a small amount of methylene dichloride, and use methanol extraction, repetitive scrubbing at least three times are with final vacuum 60
oDry under C, the calculating catalytic activity of weighing.The polymer samples of a small amount of purifying is used for carrying out
13C NMR test is to characterize head-to-tail structure content in polycarbonate.Test result sees Table 1.
Adopt the method for embodiment 1, just temperature of reaction is increased to 60
oC, CO
2Pressure rises to 6.0MPa, and other reaction conditionss remain unchanged, and test result sees Table 1.
Adopt the method for embodiment 1, just temperature of reaction is reduced to 35
oC, CO
2Pressure rises to 5.0MPa, and other reaction conditionss remain unchanged, and test result sees Table 1.
Before reaction beginning, with the 10ml autoclave 120
oToast 4h under C, then be cooled to room temperature in dry vessel.Then add the zinc described in embodiment 1-cobalt dual-metal cyaniding coordination catalyst 15 mg in still, the Styrene oxide 98min. 3ml of purifying and the dichloromethane solution 0.3ml of purifying are filled with CO
2Pressure is to 3.0MPa, 35
oUnder C, reaction 15h.Reaction is placed in ice-water bath with reactor after finishing, and then fast cooling emits unnecessary CO
2The crude product that will contain dichloromethane solvent takes out, and inserts in the single port flask of 50ml, and the room temperature backspin steams removes dichloromethane solvent, and the product that then takes out after a small amount of desolventizing goes to carry out
1H NMR and GPC test to measure polymkeric substance selectivity in product, the molecular weight and molecualr weight distribution of carbonic ether selectivity and polymkeric substance in polymkeric substance.Remaining product dissolves with a small amount of methylene dichloride, and use methanol extraction, repetitive scrubbing at least three times are with final vacuum 60
oDry under C, the calculating catalytic activity of weighing.The polymer samples of a small amount of purifying is used for carrying out
13C NMR test is to characterize head-to-tail structure content in polycarbonate.Test result sees Table 1.
Embodiment 8 Styrene oxide 98min.s and CO
2Solution polymerization
Adopt the method for embodiment 3, just organic solvent is changed to the 0.4ml tetrahydrofuran (THF) by the 0.3ml methylene dichloride, catalyzer becomes the zinc described in embodiment 2-cobalt dual-metal cyanide catalyst, and the add-on of catalyzer is 18mg, other reaction conditionss remain unchanged, and test result sees Table 1.
Embodiment 9 Styrene oxide 98min.s and CO
2Solution polymerization
Adopt the method for embodiment 3, just the add-on of methylene dichloride is brought up to 1.5ml by 0.3ml, other reaction conditionss remain unchanged, and test result sees Table 1.
Embodiment 10 Styrene oxide 98min.s and CO
2Solution polymerization
Adopt the method for embodiment 3, just organic solvent is changed to the 3ml dioxane by the 0.3ml methylene dichloride, the add-on of catalyzer is 18mg, CO
2Pressure is 0.5MPa, and other reaction conditionss remain unchanged, and test result sees Table 1.
Embodiment 11 epoxy chloropropane and CO
2Bulk polymerization
Before reaction beginning, with the 10ml autoclave 120
oToast 4h under C, then be cooled to room temperature in dry vessel.Then add zinc in embodiment 3-cobalt dual-metal cyaniding coordination catalyst 31mg in the still, the epoxy chloropropane 3ml of purifying is filled with CO
2Pressure is to 4.0MPa, 25
oUnder C, reaction 48h.Reaction is placed in ice-water bath with reactor after finishing, and then fast cooling emits unnecessary CO
2A small amount of crude product is taken out, carry out
1H NMR and GPC test to measure polymkeric substance selectivity in product, the molecular weight and molecualr weight distribution of carbonic ether selectivity and polymkeric substance in polymkeric substance.Remaining crude product dissolves with a small amount of methylene dichloride, and use methanol extraction, repetitive scrubbing at least three times are with final vacuum 60
oDry under C, the calculating catalytic activity of weighing.The polymer samples of a small amount of purifying is used for carrying out
13C NMR test is to characterize head-to-tail structure content in polycarbonate.Test result sees Table 1.
Embodiment 12 epoxy chloropropane and CO
2Bulk polymerization
Adopt the method for embodiment 6, just temperature of reaction is reduced to 20
oC, the reaction times extends to 72h, and other reaction conditionss are constant, and test result sees Table 1.
Embodiment 13 glycidyl methacrylate and CO
2Bulk polymerization
Before reaction beginning, with the 10ml autoclave 120
oToast 4h under C, then be cooled to room temperature in dry vessel.Then add the zinc described in embodiment 3-cobalt dual-metal cyaniding coordination catalyst 15mg in still, the glycidyl methacrylate 3ml of purifying is filled with CO
2Pressure is to 3.0MPa, 50
oUnder C, reaction 20h.Reaction is placed in ice-water bath with reactor after finishing, and then fast cooling emits unnecessary CO
2A small amount of crude product is taken out, carry out
1H NMR and GPC test to measure polymkeric substance selectivity in product, the molecular weight and molecualr weight distribution of carbonic ether selectivity and polymkeric substance in polymkeric substance.Remaining crude product dissolves with a small amount of methylene dichloride, and use methanol extraction, repetitive scrubbing at least three times are with final vacuum 60
oDry under C, the calculating catalytic activity of weighing.The polymer samples of a small amount of purifying is used for carrying out
13C NMR test is to characterize head-to-tail structure content in polycarbonate.Test result sees Table 1.
The test result of the polymerisate of table 1 embodiment 4-13
1Fco
2Refer to the molar fraction of carbonic ether chain link in main chain in the reactive polymeric thing, by
1H NMR method is measured;
2Polymer (%) refers to that polymkeric substance in reacting coarse product accounts for the massfraction of reacting coarse product, by
1H NMR method is measured;
3Mn refers to the number-average molecular weight of polymkeric substance, by gel permeation chromatography;
4PDI refers to the molecular weight distribution of polymkeric substance, by gel permeation chromatography;
5H-Tcontent refers to the content of head-to-tail structure unit in polycarbonate product, by
13C NMR method is measured;
6Productivity refer to finally the to purify consumption of catalyzer on dried polymer weight ratio, namely every gram catalyzer institute can catalysis generate polymer weight, is measured by weighting method.
We can learn as a result by above:
Adopt the zinc described in the present invention-cobalt dual-metal cyanide catalyst, effectively end ring oxide compound and CO of catalysis polar functionalities
2Copolyreaction, the polycarbonate molecular weight of gained are greater than 3000g/mol, and molecular weight distribution is 1.5 ~ 4, the alternate degree of multipolymer〉70%, head-to-tail structure content reaches more than 80%, cyclic carbonate ester by product＜5wt%.
Claims (8)
1. the synthetic method of the regular aliphatic polycarbonate of a chain structure, is characterized in that, comprises the following steps:
Add end ring oxide compound and the zinc-cobalt dual-metal cyanide catalyst of polar functionalities in autoclave, the mass ratio of catalyst levels and end ring oxide compound consumption is 0.003 ~ 0.01: 1; 20 ~ 60
oAt the temperature of C, pass into CO
2To CO
2Pressure is 0.5 ~ 6MPa, obtains crude product after copolyreaction 10 ~ 72h, and after reacting, crude product is dissolved in methylene dichloride, then uses methanol extraction, repetitive scrubbing at least three times, obtains the regular aliphatic polycarbonate product of chain structure;
Described zinc-cobalt dual-metal cyanide catalyst prepares in the steps below:
At first prepare zinc hydroxide sol: take acetate, halide salt, nitrate or the vitriol of zinc as raw material, triammonium citrate is properties-correcting agent, and the mass ratio of zinc salt and properties-correcting agent is 1: 0.5 ~ 10, and compound concentration is 10 ~ 30% zinc solution; After stirring, be placed in 40
oIn the C Water Tank with Temp.-controlled, add the ethanol of cumulative volume 15 ~ 60%, zinc salt complete hydrolysis after 3 ~ 8 hours obtains the zinc hydroxide precipitation; Add again appropriate peptizing agent ammoniacal liquor to zinc hydroxide precipitation to disappear, obtain zinc hydroxide sol after standing 2 ~ 5h; Then potassium hexacyanocobaltate salt is dissolved in the deionized water that volume ratio is 1:1/trimethyl carbinol mixing solutions, concentration is 10-20%, adds a small amount of hydrochloric acid conditioning solution pH value extremely less than 3, and is added to aforesaid zinc hydroxide sol; The mol ratio of potassium hexacyanocobaltate and zinc hydroxide is 1: 3, and namely zinc hydroxide need be excessive; Then 40 ~ 80
oStirred under C 5 ~ 72 hours, and obtained required zinc-cobalt dual-metal cyanide catalyst by separation, drying.
2. method according to claim 1, is characterized in that, described zinc-cobalt dual-metal cyanide catalyst contains zinc-hydroxyl structure, and its surface topography is sheet, spherical or nano-pore structure, and sheet thickness is 15 ~ 200 nanometers; Wherein, the mean diameter of ball-like structure catalyzer is 50 ~ 300 nanometers, and nanoporous is 2 ~ 100 nanometers.
3. method according to claim 1, is characterized in that, in described copolyreaction, the catalytic activity of zinc-cobalt dual-metal cyanide catalyst is greater than 0.25kg polymkeric substance/g catalyzer.
4. method according to claim 1, it is characterized in that, the end ring oxide compound of described polar functionalities is: the Styrene oxide 98min. that fluorine on phenyl ring, chlorine, bromine, alkyl, alkoxyl group and aryl replace, or at least a in epoxy chloropropane, epoxy bromopropane, glycidyl allyl ether, Styrene oxide 98min., (methyl) glycidyl acrylate or oxidation limonene.
5. method according to claim 1, is characterized in that, when the end ring oxide compound that adds polar functionalities and zinc-cobalt dual-metal cyanide catalyst, also comprises the step that adds organic solvent; The volume ratio of organic solvent and end ring oxide compound is 0.1 ~ 1:1.
6. method according to claim 1, is characterized in that, described organic solvent is non-proton polar organic solvent.
7. method according to claim 6, it is characterized in that, the non-proton polar organic solvent that uses is: any one in methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, DMF, methyl-sulphoxide, propylene carbonate or NSC 11801.
8. the method described according to claim 1 ~ 7 any one, is characterized in that, the aliphatic polycarbonate that the chain structure for preparing is regular, its end to end modular construction content more than or equal to 80%, molecular weight is greater than 3000g/mol, and molecular weight distribution is 1.5 ~ 4, the alternate degree of multipolymer〉70%.
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| CN103275313A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Polythiocarbonate and preparation method thereof |
| CN105542044A (en) * | 2016-01-22 | 2016-05-04 | 浙江大学 | Method for preparing transparent polyacrylate for selectively absorbing ultraviolet light |
| CN106795278A (en) * | 2014-08-11 | 2017-05-31 | 科思创德国股份有限公司 | The method for preparing polyether carbonate polyol |
| CN110809590A (en) * | 2017-07-07 | 2020-02-18 | 科思创德国股份有限公司 | Process for preparing functionalized polyoxyalkylene polyols |
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| CN112358607A (en) * | 2020-11-16 | 2021-02-12 | 中国科学院长春应用化学研究所 | Preparation method of carbon dioxide-propylene oxide copolymer |
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| CN103275313A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Polythiocarbonate and preparation method thereof |
| CN103275313B (en) * | 2013-05-27 | 2015-05-20 | 浙江大学 | Polythiocarbonate and preparation method thereof |
| CN106795278A (en) * | 2014-08-11 | 2017-05-31 | 科思创德国股份有限公司 | The method for preparing polyether carbonate polyol |
| CN106795278B (en) * | 2014-08-11 | 2021-02-19 | 科思创德国股份有限公司 | Method for producing polyether carbonate polyols |
| US10577462B2 (en) | 2014-11-04 | 2020-03-03 | Lg Chem, Ltd. | Production method of poly(alkylene carbonate) particles |
| CN105542044A (en) * | 2016-01-22 | 2016-05-04 | 浙江大学 | Method for preparing transparent polyacrylate for selectively absorbing ultraviolet light |
| CN105542044B (en) * | 2016-01-22 | 2017-09-12 | 浙江大学 | A kind of preparation method of polyacrylate that is transparent and absorbing ultraviolet light |
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| US20210213431A1 (en) * | 2018-09-29 | 2021-07-15 | Hangzhou Poly Material Science & Technology Co., Ltd. | Mixed-acid modified zinc-cobalt double metal cyanide catalyst and preparation method thereof |
| CN112358607A (en) * | 2020-11-16 | 2021-02-12 | 中国科学院长春应用化学研究所 | Preparation method of carbon dioxide-propylene oxide copolymer |
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