CN102329421A - Method for preparing lactide-propylene oxide-CO2 terpolymer by using rare earth three-way catalyst - Google Patents
Method for preparing lactide-propylene oxide-CO2 terpolymer by using rare earth three-way catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing lactide-propylene oxide-CO2 terpolymer by using a rare earth three-way catalyst. The method comprises the following steps of: adding the rare earth three-way catalyst, lactide, propylene oxide and CO2 into a reaction kettle, and performing polymerization on the lactide, the propylene oxide and the CO2 under the action of the rare earth three-way catalyst to obtain the lactide-propylene oxide-CO2 terpolymer, wherein the rare earth three-way catalyst consists of trichloroacetic acid yttrium, diethyl zinc, glycerol and 1,3-dioxolane; a molar ratio of the trichloroacetic acid yttrium to the diethyl zinc to the glycerol is 1:20:10; and the concentration of the diethyl zinc in the 1,3-dioxolane is 0.5*10<-3>mol/ml. Compared with the prior art, the method has the advantages that: the polymerization of the lactide, the propylene oxide and the CO2 is catalyzed by the rare earth three-way catalyst, so the polymerization time is short; and the prepared terpolymer has the ether block content of less than 2 percent, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to technical field of polymer, more particularly, relate to and a kind ofly prepare rac-Lactide-propylene oxide-CO with rare-earth ternary catalyst
2The method of terpolymer.
Background technology
Poly (propylene carbonate) (PPC) is the alternating copolymer of carbonic acid gas and propylene oxide, is environmentally friendly macromolecular material, has good gas barrier property, excellent biological compatibility and biodegradability.But, the lower (T of the second-order transition temperature of poly (propylene carbonate)
g=35～41 ℃), poor heat stability, hot processing window narrower (130～140 ℃), thereby had a strong impact on its processing characteristics and use range.
At present; Adopting the physical blending modification that self local defect of PPC is carried out modification is the domestic method of improving the PPC performance; Publication number be CN1058408 the Chinese patent bibliographical information a kind of method of modifying of aliphatic polycarbonate butadieneacrylonitrirubber rubber; This method is used to improve mechanical property and the thermostability of PPC with PPC and butyl rubber physical blending, and still, the biological degradability of the physical blending thing that this method prepares is relatively poor.In addition; Publication number is that Chinese patent document of CN1371942 etc. has been reported the method that PPC and biodegradable polyester blend is obtained the physical blending thing; Although the biological degradability of the physical blending thing that this method can guarantee to prepare to a certain extent; But the comixing compatibility between PPC and biodegradable polyester is relatively poor, thereby is prone at the two-phase interface place of physical blending thing phenomenon of phase separation (Chinese patent CN1371942 take place; Ma, X.F.et al.J.Polym.Sci.:Polym.Phys.44,94,2006; Pang, M.Z.et al.J.Appl.Polym.Sci.107,2854,2008; Peng, S.W.et al.J.Appl.Polym.Sci.90,4054,2003).
Compare with the physical blending modification, chemical modification is through changing mechanical property and the thermostability of chain structure from improving PPC in essence of PPC, thereby obtained extensive studies.The correlative study personnel find that adding the 3rd monomer rac-Lactide carries out terpolymerization in propylene oxide and carbon dioxide copolymerization close, and can improve the overall performance of PPC.For example; Huang Kelong etc. adopt polymkeric substance supported bimetal catalyst catalysis propylene oxide, carbonic acid gas and DL-rac-Lactide terpolymerization (Polym.Bull.66,327,2011); Polymerization reaction time is 24 hours, and ether section content surpasses 20% in the gained terpolymer molecular structure; Employing pentanedioic acid zinc catalyst catalysis propylene oxide, carbonic acid gas and the rac-Lactide terpolymerization of U.S. Pat 6713593B2 report, polymerization reaction time is 40 hours.But the polymerization reaction time of above-mentioned reported method is long, is unfavorable for suitability for industrialized production.
Summary of the invention
In view of this, the present invention's technical problem that will solve is to provide a kind of and prepares rac-Lactide-propylene oxide-CO with rare-earth ternary catalyst
2The method of terpolymer, the polymerization reaction time of this method is shorter, the rac-Lactide-propylene oxide for preparing-CO
2Ether section content is lower in the terpolymer.
The present invention provides a kind of and prepares rac-Lactide-propylene oxide-CO with rare-earth ternary catalyst
2The method of terpolymer may further comprise the steps:
In reaction kettle, add rare-earth ternary catalyst, rac-Lactide, propylene oxide and CO
2, with said rac-Lactide, propylene oxide and CO
2Under the effect of rare-earth ternary catalyst, carry out polyreaction, obtain rac-Lactide-propylene oxide-CO
2Terpolymer; Said rare-earth ternary catalyst is by trichoroacetic acid(TCA) yttrium, zinc ethyl, USP Kosher and 1, and the 3-dioxolane is formed, and the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10; Said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.
Preferably, the mol ratio of said rac-Lactide and said propylene oxide is (1～10): 100.
Preferably, the mol ratio of said zinc ethyl and said propylene oxide is 1: 143.1.
Preferably, said CO
2Pressure be 3.0～4.5MPa.
Preferably, the temperature of said polyreaction is 60～90 ℃.
Preferably, the temperature of said polyreaction is 65～75 ℃.
Preferably, the time of said polyreaction is 6～15 hours.
Preferably, said rare-earth ternary catalyst prepares by following method:
With trichoroacetic acid(TCA) yttrium, 1,3-dioxolane and USP Kosher mix, and obtain first solution;
In said first solution, drip zinc ethyl, obtain rare-earth ternary catalyst after the ageing, the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10, and said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.
Preferably, also comprise after the polyreaction: the reaction kettle water-bath is cooled to room temperature, gets rid of the residual carbon dioxide in the reaction kettle, and in reaction kettle, add ethanol.
Preferably, also comprise:
With said rac-Lactide-propylene oxide-CO
2Terpolymer adds in the methylene dichloride, obtains mixing solutions, and the mass concentration of this terpolymer in said mixing solutions is 15%;
The hydrochloric acid and alcoholic acid mixing solutions to the multipolymer that in said mixing solutions, added mass ratio and be 1: 100 all settle out, and stir and use washing with alcohol after 1～5 hour, and be washed till neutrality with ethanol, 35～45 ℃ of following vacuum-dryings.
The present invention provides a kind of and prepares rac-Lactide-propylene oxide-CO with rare-earth ternary catalyst
2The method of terpolymer may further comprise the steps: in reaction kettle, add rare-earth ternary catalyst, rac-Lactide, propylene oxide and CO
2, with said rac-Lactide, propylene oxide and CO
2Under the effect of rare-earth ternary catalyst, carry out polyreaction, obtain rac-Lactide-propylene oxide-CO
2Terpolymer; Said rare-earth ternary catalyst is by trichoroacetic acid(TCA) yttrium, zinc ethyl, USP Kosher and 1, and the 3-dioxolane is formed, and the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10; Said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.。Compared with prior art, since the present invention with rare-earth ternary catalyst catalysis rac-Lactide, propylene oxide and CO
2Polymerization, therefore, polymerization reaction time is shorter, and, the rac-Lactide-propylene oxide for preparing-CO
2Ether section content＜2% helps suitability for industrialized production in the terpolymer.Experimental result shows that polyreaction yield of the present invention is 4.77 * 10
3～7.26 * 10
3G polymkeric substance/molZn, the heat decomposition temperature of terpolymer are 229.7 ℃, and elongation at break can reach as high as 40.5% by initial rac-Lactide consumption regulation and control.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the DSC collection of illustrative plates of blend of POLYACTIC ACID (PLA) and poly (propylene carbonate) (PPC) solution of rac-Lactide-propylene oxide-carbonic acid gas terpolymer PPCLA and comparative example 2 preparations of the embodiment of the invention 6 preparation;
Fig. 2 is the rac-Lactide-propylene oxide-CO of the embodiment of the invention 2 preparations
2Terpolymer
1HNMR figure.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses and a kind ofly prepare rac-Lactide-propylene oxide-CO with rare-earth ternary catalyst
2The method of terpolymer may further comprise the steps:
In reaction kettle, add rare-earth ternary catalyst, rac-Lactide, propylene oxide and CO
2, with said rac-Lactide, propylene oxide and CO
2Under the effect of rare-earth ternary catalyst, carry out polyreaction, obtain rac-Lactide-propylene oxide-CO
2Terpolymer; Said rare-earth ternary catalyst is by trichoroacetic acid(TCA) yttrium, zinc ethyl, USP Kosher and 1, and the 3-dioxolane is formed, and the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10; Said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.
According to the present invention, the mol ratio of said rac-Lactide and said propylene oxide is preferably (1～10): 100, more preferably (2～5): 100, most preferably be (3～5): 100; The mol ratio of said zinc ethyl and said propylene oxide is preferably 1: 143.1.In the preparation process of terpolymer, said CO
2Pressure be preferably 3.0～4.5MPa, 3.5～4.0MPa more preferably; The temperature of said polyreaction is preferably 60～90 ℃, more preferably 65～85 ℃, most preferably is 65～75 ℃; The time of said polyreaction is preferably 6～15 hours, more preferably 8～14 hours, most preferably is 8～10 hours.
Among the present invention with rac-Lactide, propylene oxide and CO
2Polymerization reaction take place is specially under the effect of rare-earth ternary catalyst: reaction kettle is evacuated to 20～40Pa at 80 ℃, charges into CO
2Handle 2 hours, charge into CO altogether
26 times, be cooled to room temperature then; Aged rare-earth ternary catalyst injected respectively with the propylene oxide that is dissolved with rac-Lactide carry out polyreaction in the said reaction kettle, obtain rac-Lactide-propylene oxide-CO
2Terpolymer, the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10, and said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.
In addition, after polyreaction, also preferably include: the reaction kettle water-bath is cooled to room temperature, gets rid of the residual carbon dioxide in the reaction kettle, and in reaction kettle, add ethanol, said alcoholic acid adds and helps settling out of multipolymer.Obtaining rac-Lactide-propylene oxide-CO
2Behind the terpolymer, also preferably include: with said rac-Lactide-propylene oxide-CO
2Terpolymer adds in the methylene dichloride, obtains mixing solutions, and the mass concentration of this terpolymer in said mixing solutions is 15%; The hydrochloric acid and alcoholic acid mixing solutions to the multipolymer that in said mixing solutions, added mass ratio and be 1: 100 all settle out from dichloromethane solution, stir and use washing with alcohol after 1～5 hour, 35～45 ℃ of following vacuum-dryings; Said churning time is preferably 2～3 hours, and said stirring velocity is preferably 150rpm.The multipolymer that settles out is preferably used ethanol (each 100mL) washing in batches under whipped state; Each agitator treating 30 minutes; Be neutral until washings, throw out is inserted the interior vacuum-drying of 35～45 ℃ of vacuum drying ovens to constant weight, obtains white lactide-propylene oxide-carbonic acid gas terpolymer.
The present invention is with rare-earth ternary catalyst catalysis rac-Lactide, propylene oxide and CO
2Polyreaction; Said rare-earth ternary catalyst can be Chinese patent document and the preparation of the method among the U.S. Pat 6815529B2 of CN1257753, CN1257885 and CN1306021 according to publication number, preferably according to following method preparation: with trichoroacetic acid(TCA) yttrium (Y (CCl
3COO)
3), 1,3-dioxolane and USP Kosher mix, and obtain first solution; In said first solution, drip zinc ethyl (ZnEt
2), obtaining rare-earth ternary catalyst after the ageing, the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10, and said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.In the preparation process of rare-earth ternary catalyst, said ageing condition optimization is: the water bath with thermostatic control temperature is 60 ℃; The mechanical oscillation frequency is 150 times/minute; Amplitude is 40mm; Duration of oscillation is 2～2.5 hours.
More specifically; Said rare-earth ternary catalyst can be according to the preparation of following method: the two-mouth bottle that will be used to dispose rare-earth ternary catalyst 80 ℃ down decompression find time (20～40Pa); Whenever with the high-purity argon gas displacement once at a distance from 20 minutes; Replace altogether 5 times, last under the protection of high-purity argon gas, be cooled to room temperature; In the rare-earth ternary catalyst bottle, adding quantitative Y (CCl under the protection of high-purity argon gas
3COO)
3, adding 1 of calculated amount thereafter successively, 3-dioxolane and USP Kosher are treated Y (CCl
3COO)
3All after the dissolving; The zinc ethyl that in bottle, dropwise adds calculated amount, the temperature of reaction in zinc ethyl dropping process in the control bottle is 20～25 ℃, drips zinc ethyl; After reactant gases not had is emitted; To dispose the bottle sealing, and insert and carry out ageing in the water bath with thermostatic control vibrator, the ageing condition is: the water bath with thermostatic control temperature is 60 ℃; The mechanical oscillation frequency is 150 times/minute; Amplitude is 40mm; Mechanical oscillation carried out 2～2.5 hours altogether, and obtaining white suspension liquid is rare-earth ternary catalyst.
Compared with prior art, since the present invention with rare-earth ternary catalyst catalysis rac-Lactide, propylene oxide and CO
2Polymerization, rare-earth ternary catalyst is catalysis rac-Lactide, propylene oxide and CO effectively
2Polymerization, therefore, polymerization reaction time is shorter, and the rac-Lactide-propylene oxide for preparing-CO
2Ether content lower (＜2%) helps suitability for industrialized production in the terpolymer.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The preparation of rare-earth ternary catalyst
Two-mouth bottle decompression under 80 ℃ of 50mL is evacuated to 20～40Pa, whenever at a distance from 20 minutes once, replaces altogether 5 times, under the protection of high-purity argon gas, be cooled to room temperature then with the high-purity argon gas displacement;
In said two-mouth bottle, adding 0.0005mol Y (CCl under the protection of high-purity argon gas
3COO)
3, adding 20mL 1 then successively, 3-dioxolane and 0.005mol USP Kosher are treated the Y (CCl in the two-mouth bottle
3COO)
3All after the dissolving, in bottle, dropwise add the zinc ethyl of 0.01mol, the bottle interior reaction temperature is controlled at 20～25 ℃ in zinc ethyl dropping process; Zinc ethyl dropwises, and after reactant gases to be no longer included is emitted, two-mouth bottle sealing is inserted carry out ageing in the water bath with thermostatic control vibrator; Obtaining white suspension liquid is rare-earth ternary catalyst, and the ageing condition is: the water bath with thermostatic control temperature is 60 ℃, and the mechanical oscillation frequency is 150 times/minute; Amplitude is 40mm, and mechanical oscillation carried out 2.5 hours altogether.
Embodiment 2
Reaction kettle is evacuated to 20～40Pa at 80 ℃, charges into CO
2Handled 2 hours, and charged into CO altogether
26 times, be cooled to room temperature then; Rare-earth ternary catalyst (0.0005mol trichoroacetic acid(TCA) yttrium, 20mL1,3-dioxolane, 0.005mol USP Kosher, 0.01mol ZnEt with embodiment 1 preparation
2) at CO
2Protection adds down in the said reaction kettle, and the propylene oxide that simultaneously 100mL is dissolved with the rac-Lactide of 2.06g recrystallization injects in this reaction kettle, and the mol ratio of rac-Lactide and propylene oxide is 0.01431: 1.431;
Said reaction kettle is inserted during adjustable thermostatically heating bathes, make through the pressurized carbon dioxide draught control mechanism rapidly under stir speed (S.S.) is the condition of 500rpm that pressure carbon dioxide reaches 4.0MPa in the still, polymeric reaction temperature is 70 ℃, and the reaction times is 10 hours;
After polyreaction finishes, reaction kettle is cooled to room temperature with the cooling bath of 12～15 ℃ of temperature, slowly get rid of the residual carbon dioxide in the reaction kettle, and adding 200mL ethanol all settles out polymkeric substance in reaction kettle; The polymkeric substance that settles out dissolves with methylene dichloride; Form the solution of 15wt%, ethanolic soln to the multipolymer that under the stir speed (S.S.) of 150rpm, slowly drips the HCl of 1wt% all settles out from dichloromethane solution, continues to stir 2.5 hours; The multipolymer that settles out is under agitation used washing with alcohol; The agitator treating time is to be neutral to washings in 30 minutes, inserts then that vacuum-drying obtains 47.7g rac-Lactide-propylene oxide-CO to constant weight in 35～45 ℃ of vacuum drying ovens
2Terpolymer.
The yield of polyreaction is 4.77 * 10 in the present embodiment
3G polymkeric substance/mol Zn, the number-average molecular weight of polymkeric substance are 15.4 * 10
4G/mol, second-order transition temperature are 39.3 ℃, and initial decomposition temperature is 216.6 ℃, and tensile strength is 39.9MPa, and elongation at break is 27.6%.Fig. 2 is the rac-Lactide-propylene oxide-CO of present embodiment preparation
2Terpolymer
1HNMR figure is from the integral area calculating of figure, rac-Lactide-propylene oxide-CO
2Ether section content＜2% of terpolymer.
Embodiment 3
Reaction kettle is evacuated to 20～40Pa at 80 ℃, charges into CO
2Handled 2 hours, and charged into CO altogether
26 times, be cooled to room temperature then; Rare-earth ternary catalyst (0.0005mol trichoroacetic acid(TCA) yttrium, 20mL 1,3-dioxolane, 0.005mol USP Kosher, 0.01mol ZnEt with embodiment 1 preparation
2) at CO
2Protection adds down in the said reaction kettle, and the propylene oxide that simultaneously 100mL is dissolved with the rac-Lactide of 4.12g recrystallization injects in this reaction kettle, and the mol ratio of rac-Lactide and propylene oxide is 0.02862: 1.431;
Said reaction kettle is inserted during adjustable thermostatically heating bathes, make through the pressurized carbon dioxide draught control mechanism rapidly under stir speed (S.S.) is the condition of 500rpm that pressure carbon dioxide reaches 4.0MPa in the still, polymeric reaction temperature is 70 ℃, and the reaction times is 10 hours;
After polyreaction finishes, reaction kettle is cooled to room temperature with the cooling bath of 12～15 ℃ of temperature, slowly get rid of the residual carbon dioxide in the reaction kettle, and adding 200mL ethanol all settles out polymkeric substance in reaction kettle; The polymkeric substance that settles out dissolves with methylene dichloride; Form the solution of 15wt%, ethanolic soln to the multipolymer that under the stir speed (S.S.) of 150rpm, slowly drips the HCl of 1wt% all settles out from dichloromethane solution, continues to stir 2.5 hours; The multipolymer that settles out is under agitation used washing with alcohol; The agitator treating time is to be neutral to washings in 30 minutes, inserts then that vacuum-drying obtains 50.7g rac-Lactide-propylene oxide-CO to constant weight in 35～45 ℃ of vacuum drying ovens
2Terpolymer.
The polyreaction yield is 5.07 * 10 in the present embodiment
3G polymkeric substance/mol Zn, polymkeric substance number-average molecular weight are 11.0 * 10
4G/mol, second-order transition temperature are 38.9 ℃, and initial decomposition temperature is 229.7 ℃, and tensile strength is 40.6MPa, and elongation at break is 40.5%, and the ether section content of multipolymer is with embodiment 2.
Embodiment 4
Reaction kettle is evacuated to 20～40Pa at 80 ℃, charges into CO
2Handled 2 hours, and charged into CO altogether
26 times, be cooled to room temperature then; Rare-earth ternary catalyst (0.0005mol trichoroacetic acid(TCA) yttrium, 20mL1,3-dioxolane, 0.005mol USP Kosher, 0.01mol ZnEt with embodiment 1 preparation
2) at CO
2Protection adds down in the said reaction kettle, and the propylene oxide that simultaneously 100mL is dissolved with the rac-Lactide of 6.87g recrystallization injects in this reaction kettle, and the mol ratio of rac-Lactide and propylene oxide is 0.0477: 1.431;
Said reaction kettle is inserted during adjustable thermostatically heating bathes, make through the pressurized carbon dioxide draught control mechanism rapidly under stir speed (S.S.) is the condition of 500rpm that pressure carbon dioxide reaches 4.0MPa in the still, polymeric reaction temperature is 70 ℃, and the reaction times is 10 hours;
After polyreaction finishes, reaction kettle is cooled to room temperature with the cooling bath of 12～15 ℃ of temperature, slowly get rid of the residual carbon dioxide in the reaction kettle, and adding 200mL ethanol all settles out polymkeric substance in reaction kettle; The polymkeric substance that settles out dissolves with methylene dichloride; Form the solution of 15wt%, ethanolic soln to the multipolymer that under the stir speed (S.S.) of 150rpm, slowly drips the HCl of 1wt% all settles out from dichloromethane solution, continues to stir 2.5 hours; The multipolymer that settles out is under agitation used washing with alcohol; The agitator treating time is to be neutral to washings in 30 minutes, inserts then that vacuum-drying obtains 59.3g rac-Lactide-propylene oxide-CO to constant weight in 35～45 ℃ of vacuum drying ovens
2Terpolymer.
The polyreaction yield is 5.93 * 10 in the present embodiment
3G polymkeric substance/mol Zn, polymkeric substance number-average molecular weight are 11.5 * 10
4G/mol, second-order transition temperature are 39.6 ℃, and initial decomposition temperature is 231.9 ℃, and tensile strength is 39.9MPa, and elongation at break is 13.4%, and the ether section content of multipolymer is with embodiment 2.
Embodiment 5
Reaction kettle is evacuated to 20～40Pa at 80 ℃, charges into CO
2Handled 2 hours, and charged into CO altogether
26 times, be cooled to room temperature then; Rare-earth ternary catalyst (0.0005mol trichoroacetic acid(TCA) yttrium, 20mL1,3-dioxolane, 0.005mol USP Kosher, 0.01mol ZnEt with embodiment 1 preparation
2) at CO
2Protection adds down in the said reaction kettle, and the propylene oxide that simultaneously 100mL is dissolved with the rac-Lactide of 10.3g recrystallization injects in this reaction kettle, and the mol ratio of rac-Lactide and propylene oxide is 0.07155: 1.431;
Said reaction kettle is inserted during adjustable thermostatically heating bathes, make through the pressurized carbon dioxide draught control mechanism rapidly under stir speed (S.S.) is the condition of 500rpm that pressure carbon dioxide reaches 4.0MPa in the still, polymeric reaction temperature is 70 ℃, and the reaction times is 10 hours;
After polyreaction finishes, reaction kettle is cooled to room temperature with the cooling bath of 12～15 ℃ of temperature, slowly get rid of the residual carbon dioxide in the reaction kettle, and adding 200mL ethanol all settles out polymkeric substance in reaction kettle; The polymkeric substance that settles out dissolves with methylene dichloride; Form the solution of 15wt%, ethanolic soln to the multipolymer that under the stir speed (S.S.) of 150rpm, slowly drips the HCl of 1wt% all settles out from dichloromethane solution, continues to stir 2.5 hours; The multipolymer that settles out is under agitation used washing with alcohol; The agitator treating time is to be neutral to washings in 30 minutes, inserts then that vacuum-drying obtains 65.5g rac-Lactide-propylene oxide-CO to constant weight in 35～45 ℃ of vacuum drying ovens
2Terpolymer.
The polyreaction yield is 6.55 * 10 in the present embodiment
3G polymkeric substance/mol Zn, polymkeric substance number-average molecular weight are 5.5 * 10
4G/mol, second-order transition temperature are 39.5 ℃, and initial decomposition temperature is 242.9 ℃, and tensile strength is 45.0MPa, and elongation at break is 5.97%, and the ether section content of multipolymer is with embodiment 2.
Embodiment 6
Reaction kettle is evacuated to 20～40Pa at 80 ℃, charges into CO
2Handled 2 hours, and charged into CO altogether
26 times, be cooled to room temperature then; Rare-earth ternary catalyst (0.0005mol trichoroacetic acid(TCA) yttrium, 20mL1,3-dioxolane, 0.005mol USP Kosher, 0.01mol ZnEt with embodiment 1 preparation
2) at CO
2Protection adds down in the said reaction kettle, and the propylene oxide that simultaneously 100mL is dissolved with the rac-Lactide of 20.6g recrystallization injects in this reaction kettle, and the mol ratio of rac-Lactide and propylene oxide is 0.1431: 1.431;
Said reaction kettle is inserted during adjustable thermostatically heating bathes, make through the pressurized carbon dioxide draught control mechanism rapidly under stir speed (S.S.) is the condition of 500rpm that pressure carbon dioxide reaches 3.5MPa in the still, polymeric reaction temperature is 75 ℃, and the reaction times is 8 hours;
After polyreaction finishes, reaction kettle is cooled to room temperature with the cooling bath of 12～15 ℃ of temperature, slowly get rid of the residual carbon dioxide in the reaction kettle, and adding 200mL ethanol all settles out polymkeric substance in reaction kettle; The polymkeric substance that settles out dissolves with methylene dichloride; Form the solution of 15wt%, ethanolic soln to the multipolymer that under the stir speed (S.S.) of 150rpm, slowly drips the HCl of 1wt% all settles out from dichloromethane solution, continues to stir 2.5 hours; The multipolymer that settles out is under agitation used washing with alcohol; The agitator treating time is to be neutral to washings in 30 minutes, inserts then that vacuum-drying obtains 72.6g rac-Lactide-propylene oxide-CO to constant weight in 35～45 ℃ of vacuum drying ovens
2Terpolymer.
The polyreaction yield is 7.26 * 10 in the present embodiment
3G polymkeric substance/mol Zn, polymkeric substance number-average molecular weight are 7.2 * 10
4G/mol, second-order transition temperature are 39.6 ℃, and initial decomposition temperature is 227.8 ℃, and elongation at break is 5.25%, and the ether section content of multipolymer is with embodiment 2.
Comparative example 1
Reaction kettle is evacuated to 20～40Pa at 80 ℃, charges into CO
2Handled 2 hours, and charged into CO altogether
26 times, be cooled to room temperature then; Rare-earth ternary catalyst (0.0005mol trichoroacetic acid(TCA) yttrium, 20mL1,3-dioxolane, 0.005mol USP Kosher, 0.01mol ZnEt with embodiment 1 preparation
2) at CO
2Protection adds in the said reaction kettle down, and 100mL propylene oxide (1.431mol) is injected in this autoclave;
Said reaction kettle is inserted during adjustable thermostatically heating bathes, make through the pressurized carbon dioxide draught control mechanism rapidly under stir speed (S.S.) is the condition of 500rpm that pressure carbon dioxide reaches 4.0MPa in the still, polymeric reaction temperature is 70 ℃, and the reaction times is 10 hours;
After polyreaction finishes, reaction kettle is cooled to room temperature with the cooling bath of 12～15 ℃ of temperature, slowly get rid of the residual carbon dioxide in the reaction kettle, and adding 200mL ethanol all settles out polymkeric substance in reaction kettle; The polymkeric substance that settles out dissolves with methylene dichloride; Form the solution of 15wt%, ethanolic soln to the multipolymer that under the stir speed (S.S.) of 150rpm, slowly drips the HCl of 1wt% all settles out from dichloromethane solution, continues to stir 2.5 hours; The multipolymer that settles out is under agitation used washing with alcohol; The agitator treating time is to be neutral to washings in 30 minutes, inserts then that vacuum-drying obtains 45.3g propylene oxide-CO to constant weight in 35～45 ℃ of vacuum drying ovens
2Multipolymer.
In this comparative example, the yield of polyreaction is 4.53 * 10
3G polymkeric substance/mol Zn, polymkeric substance number-average molecular weight are 11.9 * 10
4G/mol, second-order transition temperature are 38.5 ℃, and initial decomposition temperature is 197 ℃, and tensile strength is 50.4MPa, and elongation at break is 12.9%, and the ether section content of multipolymer is 3.5%.
Comparative example 2
With mass ratio is 70: 30 POLYACTIC ACID (PLA) and poly (propylene carbonate) (PPC) solution blending, obtains blend.Utilize the rac-Lactide-propylene oxide-CO of dsc to embodiment 6 preparations
2Terpolymer PPCLA analyzes with the blend of this comparative example preparation; As shown in Figure 1; Rac-Lactide-propylene oxide-carbonic acid gas terpolymer PPCLA and the DSC collection of illustrative plates of this comparative example POLYACTIC ACID (PLA) for embodiment 6 preparations with the blend of poly (propylene carbonate) (PPC) solution blending; Wherein, curve a is rac-Lactide-propylene oxide-carbonic acid gas terpolymer, and wherein rac-Lactide unit content is 25.8%; B is poly (propylene carbonate) (PPC) and POLYACTIC ACID (PLA) blend, and wherein the mass ratio of PPC and PLA is 70: 30.Can find out from the DSC spectrogram, obtain rac-Lactide-propylene oxide-CO under the rare-earth ternary catalyst
2Terpolymer has only a Tg, and two Tg appear in the blend of POLYACTIC ACID and PPC, it is generally acknowledged that only there is a Tg in random copolymers, and there are two Tg (IX and absorption, 23,1,2007) in blend incompatible or that part is compatible.
Can find out that from the foregoing description and comparative example under the effect of rare-earth ternary catalyst, the present invention has realized rac-Lactide-propylene oxide-carbonic acid gas terpolymerization, the polyreaction yield is 4.77 * 10
3～7.26 * 10
3G polymkeric substance/mol Zn, the heat decomposition temperature of terpolymer are 229.7 ℃, compare with pure PPC heat decomposition temperature to be greatly improved; And elongation at break reaches as high as 40.5%.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. one kind prepares rac-Lactide-propylene oxide-CO with rare-earth ternary catalyst
2The method of terpolymer may further comprise the steps:
In reaction kettle, add rare-earth ternary catalyst, rac-Lactide, propylene oxide and CO
2, with said rac-Lactide, propylene oxide and CO
2Under the effect of rare-earth ternary catalyst, carry out polyreaction, obtain rac-Lactide-propylene oxide-CO
2Terpolymer; Said rare-earth ternary catalyst is by trichoroacetic acid(TCA) yttrium, zinc ethyl, USP Kosher and 1, and the 3-dioxolane is formed, and the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10; Said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.
2. according to the said preparation method of claim 1, it is characterized in that the mol ratio of said rac-Lactide and said propylene oxide is (1～10): 100.
3. according to the said preparation method of claim 1, it is characterized in that the mol ratio of said zinc ethyl and said propylene oxide is 1: 143.1.
4. according to the said preparation method of claim 1, it is characterized in that said CO
2Pressure be 3.0～4.5MPa.
5. according to the said preparation method of claim 1, it is characterized in that the temperature of said polyreaction is 60～90 ℃.
6. according to the said preparation method of claim 5, it is characterized in that the temperature of said polyreaction is 65～75 ℃.
7. according to the said preparation method of claim 1, it is characterized in that the time of said polyreaction is 6～15 hours.
8. according to the said preparation method of claim 1, it is characterized in that said rare-earth ternary catalyst prepares by following method:
With trichoroacetic acid(TCA) yttrium, 1,3-dioxolane and USP Kosher mix, and obtain first solution;
In said first solution, drip zinc ethyl, obtain rare-earth ternary catalyst after the ageing, the mol ratio of said trichoroacetic acid(TCA) yttrium, zinc ethyl and USP Kosher is 1: 20: 10, and said zinc ethyl is said 1, and the concentration in the 3-dioxolane is 0.5 * 10
-3Mol/mL.
9. according to the said preparation method of claim 1, it is characterized in that, also comprise after the polyreaction: the reaction kettle water-bath is cooled to room temperature, gets rid of the residual carbon dioxide in the reaction kettle, and in reaction kettle, add ethanol.
10. according to the said preparation method of claim 1, it is characterized in that, also comprise:
With said rac-Lactide-propylene oxide-CO
2Terpolymer adds in the methylene dichloride, obtains mixing solutions, and the mass concentration of this terpolymer in said mixing solutions is 15%;
The hydrochloric acid and alcoholic acid mixing solutions to the multipolymer that in said mixing solutions, added mass ratio and be 1: 100 all settle out, and stir and use washing with alcohol after 1～5 hour, and be washed till neutrality with ethanol, 35～45 ℃ of following vacuum-dryings.
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| CN103865047A (en) * | 2014-02-28 | 2014-06-18 | 浙江大学 | Synthetic method of fully-degradable multi-block copolymer and product thereof |
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|---|---|---|---|---|
| CN1257885A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Process for preparing high-molecular aliphatic polycarbonate |
| US20030013840A1 (en) * | 2000-10-11 | 2003-01-16 | Moon-Hor Ree | Copolymer comprising alkylene carbonate and method of preparing same |
| CN101440158A (en) * | 2008-12-25 | 2009-05-27 | 中国科学院长春应用化学研究所 | Furan glycidyl ether or ester-epoxypropane-CO2 copolymer and preparation thereof |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257885A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Process for preparing high-molecular aliphatic polycarbonate |
| US20030013840A1 (en) * | 2000-10-11 | 2003-01-16 | Moon-Hor Ree | Copolymer comprising alkylene carbonate and method of preparing same |
| CN101440158A (en) * | 2008-12-25 | 2009-05-27 | 中国科学院长春应用化学研究所 | Furan glycidyl ether or ester-epoxypropane-CO2 copolymer and preparation thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865047A (en) * | 2014-02-28 | 2014-06-18 | 浙江大学 | Synthetic method of fully-degradable multi-block copolymer and product thereof |
| CN103865047B (en) * | 2014-02-28 | 2016-04-13 | 浙江大学 | Synthetic method of a kind of segmented copolymer of degradable and products thereof |
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