CN101538361A - Cyclic esters compound polymerization catalyst, preparation method and application thereof - Google Patents
Cyclic esters compound polymerization catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to a cyclic esters compound polymerization catalyst, a preparation method and the application thereof. The cyclic esters compound polymerization catalyst has the structure of dual (dual trimethyl silica-based amino) zinc (Zn (N (SiMe3)2)2. Hexamethyl bi-silica-based ammonia is taken as substrate, butyl lithium and anhydrous zinc chloride are taken as reactants, and the dual (dual trimethyl silica-based amino) zinc is synthesized by two-step reaction; the dual (dual trimethyl silica-based amino) zinc is uses as catalyst, an alcohols or phenolic compound is taken as initiator, l-lactide, caprolactone and cyclic carbonate are taken as monomers, polyesters homopolymer or copolymer can be prepared by adopting a way of solution polymerization, bulk polymerization or block copolymerization and being stirred for 5min-48h at the reaction temperature of 0-210 DEG C. The method has rapid speed of polymerization reaction and high monomer conversion rate; the obtained polyester has the number average molecular weight of 10-100 thousands and the molecular weight distribution of 1.1-1.7, is higher in three-dimensional regularity and melting point, and is suitable for the production and the application of high performance polyester materials with multiple specifications.
Description
Technical field
The present invention relates to cyclic esters compound polymerization catalyst and method for making and application.
Background technology
Polyester compound (as Poly-L-lactic acid, polycaprolactone, polycarbonate) owing to have excellent biological compatibility, degradability is widely used in medical treatment, pharmacy field, its goods such as operating sutures, nail, medicament slow release capsule etc.; Poly-L-lactic acid has again because of it has the good mechanical performance, is considered to the environment-friend substitution product of traditional polyolefine material and is widely used in the daily necessities.
The preparation of polyester compound is undertaken by the ring-opening polymerization of initiator initiation cyclic monomer mostly, and different initiator systems and different polymerizing conditions all can produce remarkably influenced to structure, the performance of polymkeric substance.Most of initiators cause the monomeric polymerization of cyclic ester class and carry out under hot conditions, this polymerization technique exists the big and high temperature of energy consumption that shortcoming such as racemization easily takes place down, and (Macromolecules 2001,34,3863-3868), resulting melting point polymer is low, poor mechanical property.Simultaneously, many initiators itself have higher bio-toxicity, and initiator remains in after polymerization finishes and is difficult in the polymkeric substance remove fully, and this has just limited the application of this polymkeric substance at medical treatment, pharmaceutical field.Therefore, adopt new initiator system, and the change polymerizing condition is the necessary ways that reduce production energy consumption, improve polymer performance.
Summary of the invention
In order to solve the problem of prior art, the invention provides cyclic esters compound polymerization catalyst and method for making and application.
Cyclic esters compound polymerization catalyst provided by the invention, it is two (two trimethyl silicon based amino) zinc, its chemical formula is (Zn[N (SiMe
3)
2]
2);
The preparation method of two (the two trimethyl silicon based amino) zinc of cyclic esters compound polymerization catalyst provided by the invention is a reaction substrate with hexamethyl two silica-based ammonia, is reactant with butyllithium and Zinc Chloride Anhydrous, and reaction obtains in two steps in the presence of organic solvent; Its reactions steps and condition are as follows:
Step 1) hexamethyl two silica-based ammonia mix in sealed reactor with butyllithium, and reaction generates hexamethyl two silica-based Lithamides; The mol ratio of hexamethyl two silica-based ammonia and butyllithium is 1: 1～1.5, and temperature of reaction is-10～20 ℃, and the reaction times is 10～10 hours;
Step 2) the hexamethyl two silica-based Lithamides that obtain with step 1) with mix in Zinc Chloride Anhydrous is in sealed reactor, and add organic solvent, reaction generates two (two trimethyl silicon based amino) zinc; The mol ratio of hexamethyl two silica-based Lithamides and Zinc Chloride Anhydrous is 2～3: 1, and temperature of reaction is 0～100 ℃, and the reaction times is 10 minutes～10 hours;
A kind of as in ether, toluene and the tetrahydrofuran (THF) of the organic solvent that uses, solvent load is 1～4 times of hexamethyl two silica-based ammonia consumptions;
Cyclic esters compound polymerization catalyst provided by the invention is used for the synthesizing polyester compound.
Provided by the invention is that the step and the condition of the catalyzer method that is used for the synthesizing polyester compound is as follows with two (two trimethyl silicon based amino) zinc:
With two (two trimethyl silicon based amino) zinc is catalyzer, with alcohols or phenolic compound is initiator, with levorotatory lactide, caprolactone or cyclic carbonate is monomer, adopts the method for solution polymerization, mass polymerization or block copolymerization, preparation polyester homopolymer or multipolymer;
The alcohol compound that is adopted is that methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol, butyleneglycol, glycerol and molecular weight are that 750Da～5000Da contains a kind of in the polyethylene oxide of terminal hydroxy group;
The phenolic compound that is adopted is a kind of in phenol, cresylol, pyrocatechol, Resorcinol and the Resorcinol;
The cyclic ester monomer that is adopted is levorotatory lactide, caprolactone or cyclic carbonate; Wherein, the preferred 5-methyl of the cyclic carbonate-5-alkynes third oxygen carbonyl-1,3-dioxane-2-ketone, 5-methyl-5-carbobenzoxy-(Cbz)-1, a kind of in 3-dioxane-2-ketone, 2-benzyloxy amide group trimethylene carbonate and the 2-methyl-2-benzyloxymethyl-trimethylene carbonate;
1) adopt the solution polymerization method as follows: with toluene or tetrahydrofuran (THF) is solvent, add monomer, catalyzer and initiator in sealed reactor successively, solvent and monomeric mass ratio are 5～50: 1, polymeric reaction temperature is in 0～120 ℃ of scope, and the reaction times is 5 minutes～10 hours; The monomer conversion of resulting polyester is 100%, and the number-average molecular weight of polyester is in 5000～40000Da scope, and molecular weight distribution is 1.1～1.4, and wherein the fusing point of poly-levorotatory lactide is in 166 ℃～173 ℃ scopes;
2) adopt the bulk polymerization method as follows: add monomer, catalyzer and initiator in sealed reactor successively, polymeric reaction temperature is 110 ℃～210 ℃, and the reaction times is 24～48 hours; The monomer conversion of resulting polyester is 100%, and the number-average molecular weight of polyester is in 10000～100000Da scope, and molecular weight distribution is 1.5～1.7, and wherein the fusing point of polylactide is in 166 ℃～174 ℃ scopes;
3) adopt the reaction method of block copolymerization as follows: with toluene or tetrahydrofuran (THF) is solvent, with levorotatory lactide or caprolactone is first monomer, the solvent and the first monomeric mass ratio are 5～50: 1, add catalyzer and initiator in sealed reactor successively, polymeric reaction temperature is 0 ℃～120 ℃, reacted 5 minutes～10 hours, adding cyclic carbonate afterwards is second monomer, second monomer and the first monomeric mol ratio are 0～1: 1, continue reaction 1～10 hour in polymeric reaction temperature is 0 ℃～120 ℃ scopes; In the polyester block copolymer of gained, the first monomeric transformation efficiency is that 100%, the second monomeric transformation efficiency is 90～100%, and the number-average molecular weight of polyester is in 5000～40000Da scope, and molecular weight distribution is 1.4～1.6.
Beneficial effect: the invention belongs to cyclic esters compound polymerization catalyst and preparation method and application.With hexamethyl two silica-based ammonia is substrate, is that reactant is by two (the two trimethyl silicon based amino) zinc of the synthetic cyclic esters compound polymerization catalyst of two-step reaction with butyllithium and Zinc Chloride Anhydrous; Reactions steps is few, easy handling, and reaction efficiency height (the reaction overall yield is 76%～90%).
With above-mentioned two (two trimethyl silicon based amino) zinc is catalyzer, with a kind of alcohols or phenolic compound is initiator, polymerization at normal temperatures can prepare the polymkeric substance of molecular weight about 10,000, energy consumption of reaction is low, and polymerization rate height, detect through high performance liquid chromatography (HPLC) and gel permeation chromatography (GPC), after reaction 30 minutes, the polymkeric substance transformation efficiency can reach 100%, resulting polymers narrow molecular weight distribution (molecular weight distribution that solution polymerization obtains is below 1.4), the thermal characteristics of polymkeric substance good (differential scanning analysis (DSC) detects, and the fusing point of polymkeric substance is in 166 ℃～174 ℃ scopes).
Utilize this method can also realize the normal temperature copolymerization of rac-Lactide and cyclic carbonate, polymerization activity height (the transformation efficiency certificate of two kinds of polymer monomers is near 100%), and the distribution of resulting molecular weight of copolymer still can maintain narrower degree, and (the GPC detected result shows that molecular weight of copolymer is distributed in 1.4～1.6 scopes.
Owing to contain a large amount of active groups of biological respinse that have in the prepared polymkeric substance, can with a large amount of micromolecular compound generation bonding reactions, make this polymkeric substance have broad application prospect in the medical treatment in later stage, the application of pharmaceutical field.
This method is equally applicable to the high temperature solution polymerization and the mass polymerization of cyclic monomer, preparation high molecular weight polymers (highest weight can reach 100,000 Da), and prepared polymkeric substance does not produce the meso phenomenon, thermal characteristics good (differential scanning analysis (DSC) detects, and the fusing point of polymkeric substance is in 166 ℃～174 ℃ scopes).
Embodiment
Embodiment 1: two (two trimethyl silicon based amino) zinc synthetic
10.5ml hexamethyl two silica-based ammonia are added in the there-necked flask, bathe under (10 ℃) effect at cryosel and slowly splash into 20ml LiBu (2.5N hexane solution), stirring reaction 10 hours, reaction finishes the back and add the anhydrous ZnCl of 3.46g in there-necked flask
2, and add the 30ml anhydrous diethyl ether, and to react 10 hours down at 0 ℃, reaction after finishing is drained excessive hexamethyl two silica-based ammonia and solvent, in 130 ℃ of following underpressure distillation product is separated again, and the reaction overall yield is 82%.
Embodiment 2: two (two trimethyl silicon based amino) zinc synthetic
12ml hexamethyl two silica-based ammonia are added in the there-necked flask, under 0 ℃, slowly be added dropwise to 20ml LiBu (2.5N hexane solution), stirring reaction 3 hours, reaction finishes the back and add the anhydrous ZnCl of 3.46g in there-necked flask
2, and add the 30ml anhydrous tetrahydro furan, and to react 4 hours down at 70 ℃, reaction after finishing is drained excessive hexamethyl two silica-based ammonia and solvent, in 130 ℃ of following underpressure distillation product is separated again, and the reaction overall yield is 90%.
Embodiment 3: two (two trimethyl silicon based amino) zinc synthetic
15ml hexamethyl two silica-based ammonia are added in the there-necked flask, under 20 ℃, slowly be added dropwise to 20ml LiBu (2.5N hexane solution), stirring reaction 10 minutes, reaction finishes the back and add the anhydrous ZnCl of 3.46g in there-necked flask
2, and add the 60ml dry toluene, and to react 10 minutes down at 100 ℃, reaction after finishing is drained excessive hexamethyl two silica-based ammonia and solvent, in 130 ℃ of following underpressure distillation product is separated again, and the reaction overall yield is 76%.
Embodiment 4: the solution polymerization of rac-Lactide
The levorotatory lactide of 1.0g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 10ml dry tetrahydrofuran with syringe, after the dissolving, add two (two trimethyl silicon based amino) zinc of 10 μ l Virahols and 26.4 μ l, stir down and at room temperature reacted 40 minutes.Reactant with excessive methyl alcohol sedimentation after, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) product in 24 hours, molecular weight is 8800, molecular weight distribution is 1.21.
Embodiment 5: the solution polymerization of rac-Lactide
The levorotatory lactide of 1.78g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 10ml dry tetrahydrofuran with syringe, after the dissolving, add two (two trimethyl silicon based amino) zinc of 10 μ l methyl alcohol and 50 μ l, stir down and reacted 50 minutes down at 0 ℃.Reactant with excessive methyl alcohol sedimentation after, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) product in 24 hours, molecular weight is 9000, molecular weight distribution is 1.18.
Embodiment 6: the solution polymerization of rac-Lactide
The levorotatory lactide of 5.18g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 10ml dry tetrahydrofuran with syringe, after the dissolving, add two (two trimethyl silicon based amino) zinc of 10 μ l ethylene glycol and 72.5 μ l, stir down and at room temperature reacted 45 minutes.Reactant with excessive methyl alcohol sedimentation after, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) product in 24 hours, molecular weight is 9300, molecular weight distribution is 1.24.
Embodiment 7: the solution polymerization of caprolactone
The caprolactone of 3.4g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 10ml dry tetrahydrofuran with syringe, after the dissolving, add two (two trimethyl silicon based amino) zinc of 10 μ l butyleneglycols and 47.9 μ l, stir down and at room temperature reacted 60 minutes.Reactant with excessive methyl alcohol sedimentation after, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the polycaprolactone product in 24 hours, molecular weight is 8900, molecular weight distribution is 1.19.
Embodiment 8: the solution polymerization of rac-Lactide
The levorotatory lactide of 5.9g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 10ml dry tetrahydrofuran with syringe, after the dissolving, add two (two trimethyl silicon based amino) zinc of 10 μ l glycerol and 50 μ l, stir down and at room temperature reacted 5 minutes.Reactant with excessive methyl alcohol sedimentation after, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) product in 24 hours, molecular weight is 9400, molecular weight distribution is 1.25.
Embodiment 9: the solution polymerization of rac-Lactide
The levorotatory lactide of 1.0g is put into the reaction flask of crossing with flame baking,, add the tetrahydrofuran solution (6.53 * 10 of 10ml phenol with nitrogen ventilation three times
-6Mol/ml), the dissolving back adds two (two trimethyl silicon based amino) zinc of 26.4 μ l, and at room temperature stirring reaction is 2 hours.Reactant with excessive methyl alcohol sedimentation after, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) product in 24 hours, molecular weight is 5000, molecular weight distribution is 1.23.
Embodiment 10: the solution polymerization of rac-Lactide
The levorotatory lactide of 6.23g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 60ml dry toluene with syringe, after the dissolving, add two (two trimethyl silicon based amino) zinc of 10 μ l isopropylcarbinols and 30 μ l, stir down and reacted 5 hours down at 90 ℃.Reactant excessive methanol sedimentation, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) product in 24 hours, molecular weight is 40000, molecular weight distribution is 1.4.
Embodiment 11: the high temperature solution polymerization of rac-Lactide
The levorotatory lactide of 6.23g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 60ml dry toluene with syringe, after the dissolving, add two (two trimethyl silicon based amino) zinc of 10 μ l propyl carbinols and 30 μ l, stir down and reacted 10 hours down at 120 ℃.Reactant excessive methanol sedimentation, filter white solid, 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) product in 24 hours, molecular weight is 32000, molecular weight distribution is 1.31.
Embodiment 12: the mass polymerization of rac-Lactide
The levorotatory lactide of 12.0g is put into the reaction flask of crossing with flame baking, and with nitrogen ventilation three times, two (two trimethyl silicon based amino) zinc of adding 14mg Ortho Cresol and 26.4 μ l stir down and reacted 48 hours down at 210 ℃.Reactant dissolves with minimum of chloroform, and the methyl alcohol sedimentation with excessive promptly gets white solid.It is 100000 that 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) molecular weight of product in 24 hours, and molecular weight distribution is 1.72.
Embodiment 13: the mass polymerization of rac-Lactide
The levorotatory lactide of 12.0g is put into the reaction flask of crossing with flame baking, and with nitrogen ventilation three times, two (two trimethyl silicon based amino) zinc of adding 14mg m-cresol and 26.4 μ l stir down and react 51h down at 200 ℃.Reactant dissolves with minimum of chloroform, and the methyl alcohol sedimentation with excessive promptly gets white solid.It is 98000 that 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) molecular weight of product in 24 hours, and molecular weight distribution is 1.74.
Embodiment 14: the mass polymerization of rac-Lactide
The levorotatory lactide of 12.0g is put into the reaction flask of crossing with flame baking, and with nitrogen ventilation three times, two (two trimethyl silicon based amino) zinc of adding 14mg p-cresol and 26.4 μ l stir down and react 50h down at 200 ℃.Reactant dissolves with minimum of chloroform, and the methyl alcohol sedimentation with excessive promptly gets white solid.It is 100000 that 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) molecular weight of product in 24 hours, and molecular weight distribution is 1.66.
Embodiment 15: the mass polymerization of rac-Lactide
The levorotatory lactide of 12.0g is put into the reaction flask of crossing with flame baking, and with nitrogen ventilation three times, two (two trimethyl silicon based amino) zinc of adding 14mg pyrocatechol and 26.4 μ l stir down and reacted 48 hours down at 160 ℃.Reactant dissolves with minimum of chloroform, and the methyl alcohol sedimentation with excessive promptly gets white solid.It is 90000 that 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) molecular weight of product in 24 hours, and molecular weight distribution is 1.5.
Embodiment 16: the mass polymerization of rac-Lactide
The levorotatory lactide of 12.0g is put into the reaction flask of crossing with flame baking, and with nitrogen ventilation three times, two (two trimethyl silicon based amino) zinc of adding 14mg Resorcinol and 26.4 μ l stir down and reacted 48 hours down at 160 ℃.Reactant dissolves with minimum of chloroform, and the methyl alcohol sedimentation with excessive promptly gets white solid.It is 85000 that 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) molecular weight of product in 24 hours, and molecular weight distribution is 1.65.
Embodiment 17: the mass polymerization of rac-Lactide
The levorotatory lactide of 12.0g is put into the reaction flask of crossing with flame baking, and with nitrogen ventilation three times, two (two trimethyl silicon based amino) zinc of adding 14mg Resorcinol and 26.4 μ l stir down and reacted 24 hours down at 110 ℃.Reactant dissolves with minimum of chloroform, and the methyl alcohol sedimentation with excessive promptly gets white solid.It is 10000 that 40 ℃ of vacuum-dryings promptly obtained the poly(lactic acid) molecular weight of product in 24 hours, and molecular weight distribution is 1.67.
Embodiment 18: rac-Lactide and 5-methyl-5-carbobenzoxy-(Cbz)-1, the block copolymerization of 3-dioxane-2-ketone
The levorotatory lactide of 0.5g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 2.5ml dry toluene with syringe, two (the two trimethyl silicon based amino) zinc that add 10 μ l Virahols and 26.4 μ l, 0 ℃ of stirring was reacted 5 minutes down, in reaction flask, add 0.6g 5-methyl-5-carbobenzoxy-(Cbz)-1 again, the 3-dioxane-2-ketone, continuation was stirred 1 hour down at 0 ℃, and reactant promptly gets white solid with methyl alcohol sedimentation and filtration, promptly obtain segmented copolymer 40 ℃ of following vacuum-dryings, lactide conversions is 100%, and the carbonic ether transformation efficiency is 90%, and molecular weight of copolymer is that 10000 molecular weight distribution are 1.4.
Embodiment 19: rac-Lactide and 5-methyl-5-alkynes third oxygen carbonyl-1, the block copolymerization of 3-dioxane-2-ketone
The levorotatory lactide of 0.5g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 25ml dry tetrahydrofuran with syringe, two (the two trimethyl silicon based amino) zinc that add 2.5 μ l Virahols and 6.7 μ l, reaction is 40 minutes under the stirring at room, in reaction flask, add 0.6g 5-methyl-5-alkynes third oxygen carbonyl-1 again, the 3-dioxane-2-ketone, continue at room temperature to stir 10 hours, reactant promptly gets white solid with methyl alcohol sedimentation and filtration, promptly obtain segmented copolymer 40 ℃ of following vacuum-dryings, lactide conversions is 100%, and the carbonic ether transformation efficiency is 100%, and molecular weight of copolymer is that 40000 molecular weight distribution are 1.6.
Embodiment 20: the block copolymerization of rac-Lactide and 2-benzyloxy amide group trimethylene carbonate
The levorotatory lactide of 0.5g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 5ml dry toluene with syringe, two (the two trimethyl silicon based amino) zinc that add 10 μ l Virahols and 26.4 μ l, 120 ℃ of stirrings were reacted 10 hours down, in reaction flask, add 0.6g 2-benzyloxy amide group trimethylene carbonate again, continuation was stirred 1 hour down at 120 ℃, reactant also filters with the methyl alcohol sedimentation, promptly get white solid, promptly obtain segmented copolymer 40 ℃ of following vacuum-dryings, lactide conversions is 100%, the carbonic ether transformation efficiency is 100%, and molecular weight of copolymer is that 12000 molecular weight distribution are 1.4.
Embodiment 21: the block copolymerization of rac-Lactide and 2-methyl-2-benzyloxymethyl-trimethylene carbonate
The levorotatory lactide of 0.5g is put into the reaction flask of crossing with flame baking, with nitrogen ventilation three times, the sealing back adds the 5ml dry toluene with syringe, two (the two trimethyl silicon based amino) zinc that add 10 μ l Virahols and 26.4 μ l, reaction is 40 minutes under the stirring at room, in reaction flask, add 0.6g 2-methyl-2-benzyloxymethyl-trimethylene carbonate again, continue at room temperature to stir 2 hours, reactant also filters with the methyl alcohol sedimentation, promptly get white solid, promptly obtain segmented copolymer 40 ℃ of following vacuum-dryings, lactide conversions is 100%, the carbonic ether transformation efficiency is 94%, and molecular weight of copolymer is that 11000 molecular weight distribution are 1.4.
Claims (5)
1. cyclic esters compound polymerization catalyst is two (two trimethyl silicon based amino) zinc, and its chemical formula is (Zn[N (SiMe
3)
2]
2).
2. the preparation method of a kind of cyclic esters compound polymerization catalyst as claimed in claim 1 is characterized in that, is reaction substrate with hexamethyl two silica-based ammonia, is reactant with butyllithium and Zinc Chloride Anhydrous, and reaction obtains in two steps in the presence of organic solvent; Its reactions steps and condition are as follows:
Step 1) hexamethyl two silica-based ammonia mix in sealed reactor with butyllithium, and reaction generates hexamethyl two silica-based Lithamides; The mol ratio of hexamethyl two silica-based ammonia and butyllithium is 1: 1～1.5, and temperature of reaction is-10～20 ℃, and the reaction times is 10～10 hours;
Step 2) the hexamethyl two silica-based Lithamides that obtain with step 1) with mix in Zinc Chloride Anhydrous is in sealed reactor, and add organic solvent, reaction generates two (two trimethyl silicon based amino) zinc; The mol ratio of hexamethyl two silica-based Lithamides and Zinc Chloride Anhydrous is 2～3: 1, and temperature of reaction is 0～100 ℃, and the reaction times is 10 minutes～10 hours;
A kind of as in ether, toluene and the tetrahydrofuran (THF) of the organic solvent that uses, solvent load is 1～4 times of hexamethyl two silica-based ammonia consumptions.
3. the application of a kind of cyclic esters compound polymerization catalyst as claimed in claim 1 is characterized in that, it is used for the synthesizing polyester compound.
4. a kind of cyclic esters compound polymerization catalyst as claimed in claim 3 is used for the method for synthesizing polyester compound, it is characterized in that step and condition are as follows:
With two (two trimethyl silicon based amino) zinc is catalyzer, with alcohols or phenolic compound is initiator, with levorotatory lactide, caprolactone or cyclic carbonate is monomer, adopts the method for solution polymerization, mass polymerization or block copolymerization, preparation polyester homopolymer or multipolymer;
The alcohol compound that is adopted is that methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylene glycol, butyleneglycol, glycerol and molecular weight are that 750Da～5000Da contains a kind of in the polyethylene oxide of terminal hydroxy group;
The phenolic compound that is adopted is a kind of in phenol, cresylol, pyrocatechol, Resorcinol and the Resorcinol;
The cyclic ester monomer that is adopted is levorotatory lactide, caprolactone or cyclic carbonate;
1) adopt the solution polymerization method as follows: with toluene or tetrahydrofuran (THF) is solvent, add monomer, catalyzer and initiator in sealed reactor successively, solvent and monomeric mass ratio are 5～50: 1, polymeric reaction temperature is in 0～120 ℃ of scope, and the reaction times is 5 minutes～10 hours;
2) adopt the bulk polymerization method as follows: add monomer, catalyzer and initiator in sealed reactor successively, polymeric reaction temperature is 110 ℃～210 ℃, and the reaction times is 24～48 hours;
3) adopt the reaction method of block copolymerization as follows: with toluene or tetrahydrofuran (THF) is solvent, with levorotatory lactide or caprolactone is first monomer, the solvent and the first monomeric mass ratio are 5～50: 1, add catalyzer and initiator in sealed reactor successively, polymeric reaction temperature is 0 ℃～120 ℃, reacted 5 minutes～10 hours, adding cyclic carbonate afterwards is second monomer, second monomer and the first monomeric mol ratio are 0～1: 1, continue reaction 1～10 hour in polymeric reaction temperature is 0 ℃～120 ℃ scopes.
5. a kind of cyclic esters compound polymerization catalyst as claimed in claim 4 is used for the method for synthesizing polyester compound, it is characterized in that, the cyclic carbonate that is adopted is 5-methyl-5-alkynes third oxygen carbonyl-1,3-dioxane-2-ketone, 5-methyl-5-carbobenzoxy-(Cbz)-1, a kind of in 3-dioxane-2-ketone, 2-benzyloxy amide group trimethylene carbonate and the 2-methyl-2-benzyloxymethyl-trimethylene carbonate.
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| CN105985517A (en) * | 2015-02-03 | 2016-10-05 | 深圳光华伟业股份有限公司 | Preparation method for polylactic acid polyol with low acid value |
| CN106496538A (en) * | 2016-10-19 | 2017-03-15 | 安徽红太阳新材料有限公司 | A kind of synthetic method of high molecular polycaprolactone |
| CN109180913A (en) * | 2018-09-25 | 2019-01-11 | 云南民族大学 | A kind of preparation method of polyester trihydroxylic alcohol |
| CN109280157A (en) * | 2018-09-25 | 2019-01-29 | 云南民族大学 | The preparation method of novel aliphatic polyester polyol |
| CN112079999A (en) * | 2020-08-27 | 2020-12-15 | 中国科学院青岛生物能源与过程研究所 | Method for catalyzing ring opening polymerization of cyclic ester by zinc catalyst |
| CN112076790A (en) * | 2020-08-27 | 2020-12-15 | 中国科学院青岛生物能源与过程研究所 | Zinc catalyst for controllable depolymerization by using polyester material and catalysis method thereof |
| CN112079999B (en) * | 2020-08-27 | 2021-11-16 | 中国科学院青岛生物能源与过程研究所 | Method for catalyzing ring opening polymerization of cyclic ester by zinc catalyst |
| WO2022041326A1 (en) * | 2020-08-27 | 2022-03-03 | 中国科学院青岛生物能源与过程研究所 | Zinc catalyst for catalyzing ring-opening polymerization of cyclic esters and controlled depolymerization of polyester materials and catalytic method therefor |
| CN113150375A (en) * | 2021-03-29 | 2021-07-23 | 中国科学院青岛生物能源与过程研究所 | Method for recycling polylactic acid material under catalysis of zinc catalyst |
| CN113234209A (en) * | 2021-05-28 | 2021-08-10 | 大连大学 | Method for initiating lactide ring-opening dispersion polymerization by luteolin in supercritical carbon dioxide |
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