CN102757432A - Synthesis of glycollic bicyclic guanidine and technique for catalyzing ring-opening polymerization synthesis of degradable polymers by using glycollic bicyclic guanidine - Google Patents
Synthesis of glycollic bicyclic guanidine and technique for catalyzing ring-opening polymerization synthesis of degradable polymers by using glycollic bicyclic guanidine Download PDFInfo
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Abstract
The invention relates to a glycollic bicyclic guanidine and a synthesis technique thereof, and a technique for catalyzing ring-opening polymerization synthesis of polylactic acid, poly-morpholine-dione and polyesteramide. The glycollic bicyclic guanidine has the following structure, and is synthesized by directly reacting bicyclic guanidine and glycollic acid in a water system. The glycollic bicyclic guanidine can be used as a catalyst to catalyze the ring-opening polymerization synthesis of polylactic acid from lactide, the ring-opening polymerization synthesis of poly-morpholine-dione from morpholine-dione with functional side groups, and the ring-opening co-polymerization synthesis of polyesteramide from morpholine-dione with functional side groups. The polymerization reaction adopts a mass polymerization or solution polymerization method; and the number-average molecular weight of the polymers is Mn:2800-30000, the molecular weight distribution is narrow (PDI: 1.10-1.60), and the amino acid content is 1-5%. The catalyst glycollic bicyclic guanidine is a metal-free non-toxic organic compound, and has the advantages of low production cost, simple technological operation, high catalyst yield (at least 90%) and high purity (at least 98%). The polymerization reaction is quick and simple to operate; and the obtained polymers are degradable and have high biosafety.
Description
Technical field
The present invention relates to a kind of medical biodegradable material, particularly a kind of process for catalytic synthesis of medical use biological degradable polymkeric substance belongs to technical field of polymer chemistry.
Background technology
In recent years, along with the fast development of medicine and bioengineered tissue field technology, both at home and abroad to the demand sharp increase of degradation material with good biocompatibility and biological safety.The synthetic catalyst system therefor of biological degradation polyalcohol is generally transition metal organometallic compound or metal organic complex.In recent years; Scientist's research both at home and abroad proves that fully heavy metal ion is harmful; Adopting transition metal organometallic compound or golden transition to belong to organic complex is that heavy metal in the catalyst synthetic Biodegradable polymer can't thoroughly be removed, thereby hides some dangers for for the practical application of said material.For this reason, nontoxic, nonmetal, the organic catalyst of research and development has become the key subjects in the synthetic field of Biodegradable material.Inst. of High-Molecular Chemistry, Nankai Univ. and " functional high molecule material key lab of the Board of Education " Li Hong professor and research department thereof develop the catalyzer that can be used for catalysis cyclic ester class monomer, serine morpheline-2,5-dione ring-opening polymerization---acetate bicyclo guanidine TBDA (Li Hong etc. under state natural sciences fund (No.20474030) and state natural sciences fund (No.21074057) subsidy; Chinese invention patent CN101318960B); And catalyzer TBDA is used for the synthesising process research (Li Hong etc., Chinese invention patent CN102443166A) of ring-opening copolymerization synthesizing lactic acid-Serine multipolymer.And Li Hong professor and research department thereof are under state natural sciences fund (No.21074057) is subsidized; Synthesize 3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2 first in both at home and abroad; 5-diketone BCEMD (Li Hong etc., Chinese invention patent CN102408389A), and under catalyst acetic acid bicyclo guanidine TBDA catalysis; Carry out the equal polymerization of open loop reaction or be that second monomer carries out ring-opening copolymerization repercussion study (Li Hong etc., Chinese invention patent CN102408553A) with rac-Lactide.
Recently, Inst. of High-Molecular Chemistry, Nankai Univ. and " functional high molecule material key lab of the Board of Education " Li Hong professor and research department thereof subsidize in state natural sciences fund (No.21074057) and develop nontoxic, nonmetal, organic catalyst---the oxyacetic acid bicyclo guanidine TBDG that cyclic esters such as can be used for catalysis rac-Lactide, morpholine diketone, cyclic amide class monomer ring-opening polymerization or ring-opening copolymerization react down in both at home and abroad first.
Summary of the invention
The synthetic process that the purpose of this invention is to provide a kind of nontoxic, nonmetal, organic catalyst oxyacetic acid bicyclo guanidine, and to adopt the oxyacetic acid bicyclo guanidine be catalyst ring-opening polymerization synthesizing polylactic acid, the process method of gathering morpholine diketone, polyesteramide.
Oxyacetic acid bicyclo guanidine TBDG provided by the invention has following structure:
Oxyacetic acid bicyclo guanidine of the present invention is synthetic by bicyclo guanidine (systematic naming method: 1,5,7-three nitrogen dicyclos [4,4,0]-5-decene, english abbreviation TBD) and oxyacetic acid (english abbreviation GA) direct reaction in aqueous systems.
Catalyzer oxyacetic acid bicyclo guanidine (TBDG) synthetic practical implementation route is:
The preparation process of TBDG is: the oxyacetic acid (GA) of a certain amount of bicyclo guanidine (TBD) and 1.1 times of amount of substances of about corresponding bicyclo guanidine is joined in the reactor drum, after bottle air is removed in strictness, under argon atmospher, add the zero(ppm) water that has outgased and handled; In 110 ℃ of oil baths backflow 24-48 hour; Be cooled to room temperature again, rotary evaporation is removed moisture, and 50 ℃ of following vacuum-drying 1-3 weeks of products therefrom are promptly obtained catalyzer oxyacetic acid bicyclo guanidine; Productive rate 91-95%, purity >=98%.
It is catalyzer that the present invention adopts the oxyacetic acid bicyclo guanidine, catalysis ring-opening polymerization synthesizing polylactic acid, gathers morpholine diketone, polyesteramide.Division is following:
One, the concrete building-up process of POLYACTIC ACID comprises:
Adopting the oxyacetic acid bicyclo guanidine is catalyzer, carries out cyclic ester class monomer L-rac-Lactide (LLA) or DL-rac-Lactide (DLLA) ring-opening polymerization, the POLYACTIC ACID of composite number average molecular weight Mn:2820-29000, MWD PDI:1.15-1.58.
N=20-200 in the formula; Concrete polymerization process comprises:
Method one, bulk polymerization: LLA or DLLA and TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 20/1-200/1, after the degassing; 100-140 ℃ was reacted 36-72 hour under vacuum state; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:2860-28800, MWD PDI:1.15-1.55;
Method two, solution polymerization process: LLA or DLLA and TBDG are joined in the reactor drum; The mol ratio of monomer rac-Lactide and catalyzer is 20/1-200/1; Degassing operation back adds the toluene 2mL through the degassing, in 110 ℃ of reactions 72-144 hour, behind the naturally cooling; With solid matter in the acetone solution reactor drum; Solution is splashed in the zero(ppm) water again and precipitate, throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:2820-29000, MWD PDI:1.20-1.58.
The concrete building-up process of two, gathering morpholine diketone comprises:
Adopting the oxyacetic acid bicyclo guanidine is catalyzer, carry out the morpholine diketone monomer (3S, 6SR)-3-benzyloxymethyl-6-methyl-morpholine-2,5-diketone [(3S; 6SR)-BMMD], (3S, 6S)-3-benzyloxymethyl-6-methyl-morpholine-2,5-diketone [(3S; 6S)-BMMD], (3S, 6SR)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2,5-diketone [(3S; 6SR)-BCEMD], (3S, 6S)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2,5-diketone [(3S; 6S)-and BCEMD] ring-opening polymerization, composite number average molecular weight Mn:12000-29500, MWD PDI:1.28-1.60 gather morpholine diketone (PMD)
＊R＝CH
2OCH
2Ph，CH
2CH
2COOCH
2Ph
N=50-100 in the formula; R=CH
2OCH
2During Ph, MD indication compound is BMMD; R=CH
2CH
2COOCH
2During Ph, MD indication compound is BCEMD.Concrete polymerization process comprises:
Method one, bulk polymerization: will (3S, 6SR)-BMMD or (3S, 6S)-BMMD or (3S; 6SR)-BCEMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1-100/1; After the degassing, 100-140 ℃ was reacted 48-96 hour under vacuum state, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12500-29000, MWD PDI:1.30-1.59;
Method two, solution polymerization process: will (3S, 6SR)-BMMD or (3S, 6S)-BMMD or (3S; 6SR)-BCEMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1-100/1; Degassing operation back adds the toluene 2mL through the degassing, in 110 ℃ of reactions 72-144 hour, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12000-29500, MWD PDI:1.28-1.60;
Three, the concrete building-up process of polyesteramide comprises:
Adopting the oxyacetic acid bicyclo guanidine is catalyzer, carry out DL-rac-Lactide (DLLA) with (3S, 6SR)-3-benzyloxymethyl-6-methyl-morpholine-2,5-diketone [(3S; 6SR)-BMMD] or (3S, 6SR)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2, the 5-diketone [(3S, 6SR)-BCEMD] ring-opening copolymerization; Perhaps carry out L-rac-Lactide (LLA) with (3S, 6S)-3-benzyloxymethyl-6-methyl-morpholine-2,5-diketone [(3S; 6S)-BMMD] or (3S, 6S)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2,5-diketone [(3S; 6S)-and BCEMD] the ring-opening copolymerization reaction, the polyesteramide of composite number average molecular weight Mn:13500-16000, MWD PDI:1.12-1.51
＊R＝CH
2OCH
2Ph，CH
2CH
2COOCH
2Ph
X=90-98 in the formula, y=2-10, x+y=100; R=CH
2OCH
2During Ph, MD indication compound is BMMD; R=CH
2CH
2COOCH
2During Ph, MD indication compound is BCEMD.Concrete polymerization process comprises:
Method one, bulk polymerization: with DLLA with (3S, 6SR)-BMMD or (3S, 6SR)-BCEMD and TBDG join in the reactor drum; Perhaps with LLA with (3S, 6S)-BMMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum; The mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1-90/10/1, and after the degassing, 100-140 ℃ was reacted 48-96 hour under vacuum state; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:14600-15700, MWD PDI:1.12-1.40;
Method two, solution polymerization process: with DLLA with (3S, 6SR)-BMMD or (3S, 6SR)-BCEMD and TBDG join in the reactor drum; Perhaps with LLA with (3S, 6S)-BMMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum; The mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1-90/10/1; Degassing operation back adds the toluene 2mL through the degassing, in 110 ℃ of reactions 96-120 hour, behind the naturally cooling; With solid matter in the acetone solution reactor drum; Solution is splashed in the zero(ppm) water again and precipitate, throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:13500-16000, MWD PDI:1.18-1.51.
Advantage of the present invention and beneficial effect:
1. synthesizing in aqueous systems of oxyacetic acid bicyclo guanidine directly carries out, and technological operation is easy, pollution-free, production cost is low, productive rate high (>=90%), purity good (>=98%); 2. institute's synthetic oxyacetic acid bicyclo guanidine can be used for catalysis open loop (being total to) polyreaction, has high catalytic activity, and has advantages such as applied range, environmental resistance be good; Institute's synthetic POLYACTIC ACID, gather morpholine diketone, polyesteramide etc. and have excellent biological compatibility and biological safety, comparatively wide application prospect is arranged in fields such as biological medicine and organizational projects; Institute's synthetic POLYACTIC ACID, gather morpholine diketone, the polyesteramide equimolecular quantity is controlled, narrow molecular weight distribution (PDI:1.10-1.60); 5. polyreaction can be chosen mass polymerization or solution polymerization process, and is swift to operate easy.This method is laid a good foundation for further such new medical degradability biopolymer being carried out action oriented research.
Embodiment
One, the preparation of oxyacetic acid bicyclo guanidine TBDG
Embodiment 1
0.200g (1.437mmol) bicyclo guanidine and 0.120g (1.578mmol) oxyacetic acid are joined in the reactor drum, after bottle air is removed in strictness, under argon atmospher, add the 10mL zero(ppm) water that has outgased and handled; In 110 ℃ of oil baths, refluxed 24 hours; Be cooled to room temperature again, rotary evaporation is removed moisture, and 50 ℃ of following 3 weeks of vacuum-drying of products therefrom are promptly obtained catalyzer oxyacetic acid bicyclo guanidine; Productive rate 91%, purity 98%.
Embodiment 2
0.140g (1.006mmol) bicyclo guanidine and 0.084g (1.105mmol) oxyacetic acid are joined in the reactor drum, after bottle air is removed in strictness, under argon atmospher, add the 5mL zero(ppm) water that has outgased and handled; In 110 ℃ of oil baths, refluxed 36 hours; Be cooled to room temperature again, rotary evaporation is removed moisture, and 50 ℃ of following 2 weeks of vacuum-drying of products therefrom are promptly obtained catalyzer oxyacetic acid bicyclo guanidine; Productive rate 94%, purity 99%.
Embodiment 3
1.001g (7.191mmol) bicyclo guanidine and 0.602g (7.916mmol) oxyacetic acid are joined in the reactor drum, after bottle air is removed in strictness, under argon atmospher, add the 20mL zero(ppm) water that has outgased and handled; In 110 ℃ of oil baths, refluxed 48 hours; Be cooled to room temperature again, rotary evaporation is removed moisture, and 50 ℃ of following 1 weeks of vacuum-drying of products therefrom are promptly obtained catalyzer oxyacetic acid bicyclo guanidine; Productive rate 95%, purity 98%.
Two, TBDG catalysis synthetic macromolecule POLYACTIC ACID
Embodiment 4, TBDG catalysis LLA ring-opening polymerization (mass polymerization-method one)
0.134g (0.930mmol) LLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 20/1, after the degassing; In the following 100 ℃ of reactions of vacuum state 72 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:2860, MWD PDI:1.15.
Embodiment 5TBDG catalysis LLA ring-opening polymerization (mass polymerization-method one)
0.335g (2.326mmol) LLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 50/1, after the degassing; In the following 120 ℃ of reactions of vacuum state 48 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:7400, MWD PDI:1.25.
Embodiment 6TBDG catalysis LLA ring-opening polymerization (mass polymerization-method one)
0.669g (4.644mmol) LLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 100/1, after the degassing; In the following 110 ℃ of reactions of vacuum state 72 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:13000, MWD PDI:1.31.
Embodiment 7TBDG catalysis LLA ring-opening polymerization (mass polymerization-method one)
1.338g (9.289mmol) LLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 200/1, after the degassing; In the following 140 ℃ of reactions of vacuum state 36 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:28800, MWD PDI:1.55.
Embodiment 8TBDG catalysis LLA ring-opening polymerization (solution polymerization process-method two)
0.134g (0.930mmol) LLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 20/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 72 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:2820, MWD PDI:1.20.
Embodiment 9TBDG catalysis LLA ring-opening polymerization (solution polymerization process-method two)
0.669g (4.644mmol) LLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 96 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:16500, MWD PDI:1.46.
Embodiment 10TBDG catalysis LLA ring-opening polymerization (solution polymerization process-method two)
1.338g (9.289mmol) LLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 200/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 144 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:29000, MWD PDI:1.58.
Embodiment 11TBDG catalysis DLLA ring-opening polymerization (mass polymerization)
0.134g (0.930mmol) DLLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 20/1, after the degassing; In the following 110 ℃ of reactions of vacuum state 36 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:2990, MWD PDI:1.23.
Embodiment 12TBDG catalysis DLLA ring-opening polymerization (mass polymerization)
0.335g (2.326mmol) DLLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 50/1, after the degassing; In the following 100 ℃ of reactions of vacuum state 72 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:6500, MWD PDI:1.33.
Embodiment 13TBDG catalysis DLLA ring-opening polymerization (mass polymerization)
1.338g (9.289mmol) DLLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 200/1, after the degassing; In the following 140 ℃ of reactions of vacuum state 48 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:27400, MWD PDI:1.49.
Embodiment 14TBDG catalysis DLLA ring-opening polymerization (solution polymerization process)
0.134g (0.930mmol) DLLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 20/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 72 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:3200, MWD PDI:1.26.
Embodiment 15TBDG catalysis DLLA ring-opening polymerization (solution polymerization process)
0.669g (4.644mmol) DLLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 108 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:14800, MWD PDI:1.42.
Embodiment 16TBDG catalysis DLLA ring-opening polymerization (solution polymerization process)
1.338g (9.289mmol) DLLA and 0.010g (46.46 μ mol) TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 200/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 144 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:27900, MWD PDI:1.56.
Three, oxyacetic acid bicyclo guanidine catalysis synthetic macromolecule gathers morpholine diketone
Embodiment 17TBDG catalysis (3S, 6SR)-BMMD ring-opening polymerization (mass polymerization)
With 0.579g (2.323mmol) (3S, 6SR)-BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1; After the degassing, in the following 100 ℃ of reactions of vacuum state 72 hours, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12500, MWD PDI:1.46.
Embodiment 18TBDG catalysis (3S, 6SR)-BMMD ring-opening polymerization (mass polymerization)
With 0.579g (2.323mmol) (3S, 6SR)-BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1; After the degassing, in the following 110 ℃ of reactions of vacuum state 48 hours, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:13600, MWD PDI:1.30.
Embodiment 19TBDG catalysis (3S, 6SR)-BMMD ring-opening polymerization (mass polymerization)
With 1.158g (4.646mmol) (3S; 6SR)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, after the degassing; In the following 140 ℃ of reactions of vacuum state 96 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:22200, MWD PDI:1.59.
Embodiment 20TBDG catalysis (3S, 6SR)-BMMD ring-opening polymerization (solution polymerization process)
With 0.579g (2.323mmol) (3S; 6SR)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 72 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12000, MWD PDI:1.28.
Embodiment 21TBDG catalysis (3S, 6SR)-BMMD ring-opening polymerization (solution polymerization process)
With 1.158g (4.646mmol) (3S; 6SR)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 120 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:20700, MWD PDI:1.60.
Embodiment 22TBDG catalysis (3S, 6SR)-BMMD ring-opening polymerization (solution polymerization process)
With 1.158g (4.646mmol) (3S; 6SR)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 144 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:25600, MWD PDI:1.46.
Embodiment 23TBDG catalysis (3S, 6S)-BMMD ring-opening polymerization (mass polymerization)
With 0.579g (2.323mmol) (3S, 6S)-BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1; After the degassing, in the following 130 ℃ of reactions of vacuum state 48 hours, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:14000, MWD PDI:1.35.
Embodiment 24TBDG catalysis (3S, 6S)-BMMD ring-opening polymerization (mass polymerization)
With 1.158g (4.646mmol) (3S, 6S)-BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 100/1; After the degassing, in the following 140 ℃ of reactions of vacuum state 84 hours, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:25300, MWD PDI:1.44.
Embodiment 25TBDG catalysis (3S, 6S)-BMMD ring-opening polymerization (mass polymerization)
With 1.158g (4.646mmol) (3S, 6S)-BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 100/1; After the degassing, in the following 130 ℃ of reactions of vacuum state 96 hours, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:21500, MWD PDI:1.50.
Embodiment 26TBDG catalysis (3S, 6S)-BMMD ring-opening polymerization (solution polymerization process)
With 0.579g (2.323mmol) (3S; 6S)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 72 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12100, MWD PDI:1.35.
Embodiment 27TBDG catalysis (3S, 6S)-BMMD ring-opening polymerization (solution polymerization process)
With 0.579g (2.323mmol) (3S; 6S)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 96 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:13200, MWD PDI:1.32.
Embodiment 28TBDG catalysis (3S, 6S)-BMMD ring-opening polymerization (solution polymerization process)
With 1.158g (4.646mmol) (3S; 6S)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 144 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:24100, MWD PDI:1.55.
Embodiment 29TBDG catalysis (3S, 6SR)-BCEMD ring-opening polymerization (mass polymerization)
With 0.677g (2.324mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, after the degassing; In the following 110 ℃ of reactions of vacuum state 72 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:13600, MWD PDI:1.36.
Embodiment 30TBDG catalysis (3S, 6SR)-BCEMD ring-opening polymerization (mass polymerization)
With 0.677g (2.324mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, after the degassing; In the following 130 ℃ of reactions of vacuum state 48 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:15200, MWD PDI:1.43.
Embodiment 31TBDG catalysis (3S, 6SR)-BCEMD ring-opening polymerization (mass polymerization)
With 1.353g (4.645mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, after the degassing; In the following 130 ℃ of reactions of vacuum state 96 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:29000, MWD PDI:1.37.
Embodiment 32TBDG catalysis (3S, 6SR)-BCEMD ring-opening polymerization (solution polymerization process)
With 0.677g (2.324mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 96 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12900, MWD PDI:1.29.
Embodiment 33TBDG catalysis (3S, 6SR)-BCEMD ring-opening polymerization (solution polymerization process)
With 1.353g (4.645mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 120 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:26700, MWD PDI:1.32.
Embodiment 34TBDG catalysis (3S, 6SR)-BCEMD ring-opening polymerization (solution polymerization process)
With 1.353g (4.645mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 144 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:27800, MWD PDI:1.41.
Embodiment 35TBDG catalysis (3S, 6S)-BCEMD ring-opening polymerization (mass polymerization)
With 0.677g (2.324mmol) (3S, 6S)-BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1; After the degassing, in the following 130 ℃ of reactions of vacuum state 48 hours, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:15600, MWD PDI:1.45.
Embodiment 36TBDG catalysis (3S, 6S)-BCEMD ring-opening polymerization (mass polymerization)
With 1.353g (4.645mmol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, after the degassing; In the following 130 ℃ of reactions of vacuum state 96 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:28600, MWD PDI:1.40.
Embodiment 37TBDG catalysis (3S, 6S)-BCEMD ring-opening polymerization (mass polymerization)
With 1.353g (4.645mmol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, after the degassing; In the following 140 ℃ of reactions of vacuum state 72 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:28300, MWD PDI:1.51.
Embodiment 38TBDG catalysis (3S, 6S)-BCEMD ring-opening polymerization (solution polymerization process)
With 0.677g (2.324mmol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 96 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:13600, MWD PDI:1.38.
Embodiment 39TBDG catalysis (3S, 6S)-BCEMD ring-opening polymerization (solution polymerization process)
With 0.677g (2.324mmol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 50/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 120 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:14700, MWD PDI:1.40.
Embodiment 40TBDG catalysis (3S, 6S)-BCEMD ring-opening polymerization (solution polymerization process)
With 1.353g (4.645mmol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer morpholine diketone and catalyzer is 100/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 144 hours; Behind the naturally cooling,, solution is splashed in the ether precipitate again with solid matter in the methylene dichloride dissolution reactor; Throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:29100, MWD PDI:1.45.
Four, oxyacetic acid bicyclo guanidine catalysis synthesis of polyester amide
Embodiment 41TBDG catalysis DLLA with (3S, 6SR)-BMMD ring-opening copolymerization (mass polymerization)
With 0.656g (4.554mmol) DLLA and 0.023g (92.27 μ mol) (3S; 6SR)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1, after the degassing; In the following 100 ℃ of reactions of vacuum state 48 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:14600, MWD PDI:1.12.
Embodiment 42TBDG catalysis DLLA with (3S, 6SR)-BMMD ring-opening copolymerization (mass polymerization)
With 0.629g (4.367mmol) DLLA and 0.069g (0.2768mmol) (3S; 6SR)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 94/6/1, after the degassing; In the following 110 ℃ of reactions of vacuum state 48 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:15100, MWD PDI:1.29.
Embodiment 43TBDG catalysis DLLA with (3S, 6SR)-BMMD ring-opening copolymerization (mass polymerization)
With 0.602g (4.179mmol) DLLA and 0.116g (0.4654mmol) (3S; 6SR)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 90/10/1, after the degassing; In the following 120 ℃ of reactions of vacuum state 72 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:15500, MWD PDI:1.40.
Embodiment 44TBDG catalysis LLA with (3S, 6S)-BMMD ring-opening copolymerization (solution polymerization process)
With 0.656g (4.554mmol) LLA and 0.023g (92.27 μ mol) (3S; 6S)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 96 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:13500, MWD PDI:1.20.
Embodiment 45TBDG catalysis LLA with (3S, 6S)-BMMD ring-opening copolymerization (solution polymerization process)
With 0.629g (4.367mmol) LLA and 0.069g (0.2768mmol) (3S; 6S)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 94/6/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 108 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:15200, MWD PDI:1.36.
Embodiment 46TBDG catalysis LLA with (3S, 6S)-BMMD ring-opening copolymerization (solution polymerization process)
With 0.602g (4.179mmol) LLA and 0.116g (0.4654mmol) (3S; 6S)-and BMMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 90/10/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 120 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:15700, MWD PDI:1.51.
Embodiment 47TBDG catalysis DLLA with (3S, 6SR)-BCEMD ring-opening copolymerization (solution polymerization process)
With 0.656g (4.554mmol) DLLA and 0.027g (92.69 μ mol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 96 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:14900, MWD PDI:1.18.
Embodiment 48TBDG catalysis DLLA with (3S, 6SR)-BCEMD ring-opening copolymerization (solution polymerization process)
With 0.629g (4.367mmol) DLLA and 0.081g (0.278mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 94/6/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 108 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:15400, MWD PDI:1.40.
Embodiment 49TBDG catalysis DLLA with (3S, 6SR)-BCEMD ring-opening copolymerization (solution polymerization process)
With 0.602g (4.179mmol) DLLA and 0.135g (0.4634mmol) (3S; 6SR)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 90/10/1, and degassing operation back adds the toluene 2mL through the degassing; In 110 ℃ of reactions 120 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:16000, MWD PDI:1.49.
Embodiment 50TBDG catalysis LLA with (3S, 6S)-BCEMD ring-opening copolymerization (mass polymerization)
With 0.656g (4.554mmol) LLA and 0.027g (92.69 μ mol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1, after the degassing; In the following 120 ℃ of reactions of vacuum state 48 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:14900, MWD PDI:1.16.
Embodiment 51TBDG catalysis LLA with (3S, 6S)-BCEMD ring-opening copolymerization (mass polymerization)
With 0.629g (4.367mmol) LLA and 0.081g (0.278mmol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 94/6/1, after the degassing; In the following 130 ℃ of reactions of vacuum state 72 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:15400, MWD PDI:1.26.
Embodiment 52TBDG catalysis LLA with (3S, 6S)-BCEMD ring-opening copolymerization (mass polymerization)
With 0.602g (4.179mmol) LLA and 0.135g (0.4634mmol) (3S; 6S)-and BCEMD and 0.010g (46.46 μ mol) TBDG join in the reactor drum, and the mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 90/10/1, after the degassing; In the following 140 ℃ of reactions of vacuum state 96 hours; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:15700, MWD PDI:1.37.
Claims (5)
1. oxyacetic acid bicyclo guanidine TBDG has following structure:
2. the synthetic process of the described oxyacetic acid bicyclo guanidine of claim 1 is characterized in that: described oxyacetic acid bicyclo guanidine is synthetic by bicyclo guanidine and oxyacetic acid direct reaction in aqueous systems,
The building-up reactions of oxyacetic acid bicyclo guanidine is that the oxyacetic acid with bicyclo guanidine and 1.1 times of amount of substances of bicyclo guanidine joins in the reactor drum, after bottle air is removed in strictness, under argon atmospher, adds the zero(ppm) water that has outgased and handled; In 110 ℃ of oil baths backflow 24-48 hour; Be cooled to room temperature again, rotary evaporation is removed moisture, and 50 ℃ of following vacuum-drying 1-3 weeks of products therefrom are promptly obtained catalyzer oxyacetic acid bicyclo guanidine; Productive rate 91-95%, purity >=98%.
3. the application of the described oxyacetic acid bicyclo guanidine of claim 1 TBDG in catalysis synthesized degradable biomedical polymer POLYACTIC ACID; It is characterized in that: with the oxyacetic acid bicyclo guanidine is catalyzer; Carry out cyclic ester class monomer L-rac-Lactide (LLA) or DL-rac-Lactide (DLLA) ring-opening polymerization; The POLYACTIC ACID of composite number average molecular weight Mn:2820-29000, MWD PDI:1.15-1.58
N=20-200 in the formula; Concrete polymerization process comprises:
Method one, bulk polymerization: LLA or DLLA and TBDG are joined in the reactor drum, and the mol ratio of monomer rac-Lactide and catalyzer is 20/1-200/1, after the degassing; 100-140 ℃ was reacted 36-72 hour under vacuum state; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:2860-28800, MWD PDI:1.15-1.55;
Method two, solution polymerization process: LLA or DLLA and TBDG are joined in the reactor drum; The mol ratio of monomer rac-Lactide and catalyzer is 20/1-200/1; Degassing operation back adds the toluene 2mL through the degassing, in 110 ℃ of reactions 72-144 hour, behind the naturally cooling; With solid matter in the acetone solution reactor drum; Solution is splashed in the zero(ppm) water again and precipitate, throw out descended dry 24 hours at 50 ℃, obtained the POLYACTIC ACID of number-average molecular weight Mn:2820-29000, MWD PDI:1.20-1.58.
4. the described oxyacetic acid bicyclo guanidine of claim 1 TBDG gathers the application in the morpholine diketone at catalysis synthesized degradable biomedical polymer, and it is characterized in that: with the oxyacetic acid bicyclo guanidine is catalyzer, carries out morpholine diketone monomer (3S; 6SR)-3-benzyloxymethyl-6-methyl-morpholine-2, the 5-diketone [(3S, 6SR)-BMMD], (3S; 6S)-3-benzyloxymethyl-6-methyl-morpholine-2, the 5-diketone [(3S, 6S)-BMMD], (3S; 6SR)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2, the 5-diketone [(3S, 6SR)-BCEMD], (3S; 6S)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2, the 5-diketone [(3S, 6S)-BCEMD] ring-opening polymerization; Composite number average molecular weight Mn:12000-29500, MWD PDI:1.28-1.60 gather morpholine diketone (PMD)
＊R＝CH
2OCH
2Ph，CH
2CH
2COOCH
2Ph
N=50-100 in the formula; R=CH
2OCH
2During Ph, MD indication compound is BMMD; R=CH
2CH
2COOCH
2During Ph, MD indication compound is BCEMD; Concrete polymerization process comprises:
Method one, bulk polymerization: will (3S, 6SR)-BMMD or (3S, 6S)-BMMD or (3S; 6SR)-BCEMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1-100/1; After the degassing, 100-140 ℃ was reacted 48-96 hour under vacuum state, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12500-29000, MWD PDI:1.30-1.59;
Method two, solution polymerization process: will (3S, 6SR)-BMMD or (3S, 6S)-BMMD or (3S; 6SR)-BCEMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum, the mol ratio of monomer morpholine diketone and catalyzer is 50/1-100/1; Degassing operation back adds the toluene 2mL through the degassing, in 110 ℃ of reactions 72-144 hour, behind the naturally cooling; With solid matter in the methylene dichloride dissolution reactor; Solution is splashed in the ether again and precipitate, throw out descended dry 24 hours at 30 ℃, obtained the morpholine diketone that gathers of number-average molecular weight Mn:12000-29500, MWD PDI:1.28-1.60.
5. the application of the described oxyacetic acid bicyclo guanidine of claim 1 TBDG in catalysis synthesized degradable biomedical polymer polyesteramide, it is characterized in that: with the oxyacetic acid bicyclo guanidine is catalyzer, carries out DL-rac-Lactide (DLLA) and (3S; 6SR)-3-benzyloxymethyl-6-methyl-morpholine-2, the 5-diketone [(3S, 6SR)-BMMD] or (3S; 6SR)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2, the 5-diketone [(3S, 6SR)-BCEMD] ring-opening copolymerization; Perhaps carry out L-rac-Lactide (LLA) with (3S, 6S)-3-benzyloxymethyl-6-methyl-morpholine-2,5-diketone [(3S; 6S)-BMMD] or (3S, 6S)-3-carbobenzoxy-(Cbz) ethylidene-6-methyl-morpholine-2,5-diketone [(3S; 6S)-and BCEMD] the ring-opening copolymerization reaction, the polyesteramide of composite number average molecular weight Mn:13500-16000, MWD PDI:1.12-1.51
＊R＝CH
2OCH
2Ph，CH
2CH
2COOCH
2Ph
X=90-98 in the formula, y=2-10, x+y=100; R=CH
2OCH
2During Ph, MD indication compound is BMMD; R=CH
2CH
2COOCH
2During Ph, MD indication compound is BCEMD; Concrete polymerization process comprises:
Method one, bulk polymerization: with DLLA with (3S, 6SR)-BMMD or (3S, 6SR)-BCEMD and TBDG join in the reactor drum; Perhaps with LLA with (3S, 6S)-BMMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum; The mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1-90/10/1, and after the degassing, 100-140 ℃ was reacted 48-96 hour under vacuum state; Behind the naturally cooling,, solution is splashed in the zero(ppm) water precipitate again with solid matter in the acetone solution reactor drum; Throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:14600-15700, MWD PDI:1.12-1.40;
Method two, solution polymerization process: with DLLA with (3S, 6SR)-BMMD or (3S, 6SR)-BCEMD and TBDG join in the reactor drum; Perhaps with LLA with (3S, 6S)-BMMD or (3S, 6S)-BCEMD and TBDG join in the reactor drum; The mol ratio of monomer rac-Lactide, monomer morpholine diketone and catalyzer is 98/2/1-90/10/1; Degassing operation back adds the toluene 2mL through the degassing, in 110 ℃ of reactions 96-120 hour, behind the naturally cooling; With solid matter in the acetone solution reactor drum; Solution is splashed in the zero(ppm) water again and precipitate, throw out descended dry 24 hours at 50 ℃, obtained the polyesteramide of number-average molecular weight Mn:13500-16000, MWD PDI:1.18-1.51.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102324241A CN102757432A (en) | 2012-07-06 | 2012-07-06 | Synthesis of glycollic bicyclic guanidine and technique for catalyzing ring-opening polymerization synthesis of degradable polymers by using glycollic bicyclic guanidine |
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|---|---|---|---|
| CN2012102324241A CN102757432A (en) | 2012-07-06 | 2012-07-06 | Synthesis of glycollic bicyclic guanidine and technique for catalyzing ring-opening polymerization synthesis of degradable polymers by using glycollic bicyclic guanidine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105131259A (en) * | 2015-09-14 | 2015-12-09 | 南京大学 | High molecular weight poly(alpha-hydroxyl acid) synthesized by biological guanidine compound system catalytic melting-solid-phase polymerization |
| CN105273175A (en) * | 2015-10-21 | 2016-01-27 | 南京工业大学 | Polylactide preparation method regulated and controlled by organic small molecule catalysts |
| CN105367763A (en) * | 2015-12-14 | 2016-03-02 | 南京工业大学 | Method for preparing polyester by ring opening polymerization |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131259A (en) * | 2015-09-14 | 2015-12-09 | 南京大学 | High molecular weight poly(alpha-hydroxyl acid) synthesized by biological guanidine compound system catalytic melting-solid-phase polymerization |
| CN105273175A (en) * | 2015-10-21 | 2016-01-27 | 南京工业大学 | Polylactide preparation method regulated and controlled by organic small molecule catalysts |
| CN105273175B (en) * | 2015-10-21 | 2017-06-13 | 南京工业大学 | The polylactide preparation method of organic micromolecule catalyst regulation and control |
| CN105367763A (en) * | 2015-12-14 | 2016-03-02 | 南京工业大学 | Method for preparing polyester by ring opening polymerization |
| CN105367763B (en) * | 2015-12-14 | 2018-07-06 | 南京工业大学 | A kind of method that ring-opening polymerisation prepares polyester |
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