CN110078634A - A kind of preparation method and application of amino acid stannous complex - Google Patents
A kind of preparation method and application of amino acid stannous complex Download PDFInfo
- Publication number
- CN110078634A CN110078634A CN201910435710.XA CN201910435710A CN110078634A CN 110078634 A CN110078634 A CN 110078634A CN 201910435710 A CN201910435710 A CN 201910435710A CN 110078634 A CN110078634 A CN 110078634A
- Authority
- CN
- China
- Prior art keywords
- amino acid
- stannous
- lactide
- homopolymerization
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/76—Metal complexes of amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a kind of preparation method and applications of amino acid stannous complex.The preparation step of amino acid stannous complex: triethylamine and amino acid react in organic media first obtains amino-acid salt, metathesis reaction then occurs with neutral tin salt ligand, using the amino acid stannous complex compound for filtering, being dried to obtain target.This amino acid stannous complex compound of the present invention is a kind of efficient lactone ring opening polymerization catalyst, can be used for being catalyzed the ring-opening polymerization of the lactones such as lactide；The polylactic acid of high molecular weight can be obtained especially for levorotatory lactide polymerization.The novel synthesis of amino acid stannous of the invention and as the lactone ring opening polymerizations catalyst such as lactide the advantages of are fairly obvious: raw material is cheap, synthetic route is simple, product yield high, with very high catalytic activity and compared with highly-solid selectively, the polyester material that higher molecular weight, relatively low cell toxicant can be obtained can satisfy the needs of large-scale industrial production.
Description
Technical field
Make the present invention relates to a kind of novel synthesis of organo-metallic compound and its in lactide and lactone ring opening polymerization
The novel synthesis and amino acid stannous of the purposes of catalyst more particularly to a kind of amino acid stannous are in catalysis lactide and interior
The purposes of ester ring-opening polymerisation.
Background technique
The method that early stage prepares amino acid stannous is in the case of DMF makees catalyst, with tin or alkyl-tin oxide and amino
Acid mode of azeotropic water removing in benzole soln obtains the complex of amino acid stannous, and this method is organic using what is be largely more toxic
Solvent, method is complicated, and yield is lower, and can only obtain the amino acid stannous complex of part, can not be applied to large-scale production
[B.Y.K.HO and J.J.ZUCKERMAN*, Inorganic Chemistry, 1973, (7): 1552-1561].
From exhaustion resources economy to during renewable resource economic transition, countries in the world are all paid much attention to degradable
The development and application of high molecular material, and from the perspective of environmental protection, it is also desirable to polymer is biodegradable to subtract
The discarding and pollution of few waste.Polylactic acid, polycaprolactone etc. are all that belong to biocompatibility good and can be with biodegradable height
Molecular material, compared with polyolefin, they have unrivaled excellent characteristics.In medical domain, the application of these polyester
It is more and more extensive, such as: they can be used as suture, bone bracket, drug controlled release carrier etc..
The catalyst that lactone and lactide ring-opening polymerisation generally use has aluminium isopropoxide, stannous octoate and organic RE chemical combination
Object etc., wherein using being most stannous octoate extensively, its toxicity is smaller and can synthesize high molecular weight and the good polyester of optical purity.
But its catalytic reaction activity is not high, it is desirable that longer polymerization reaction time and higher reaction temperature, it is therefore desirable to develop
A kind of activity is higher, the smaller ring-opening polymerization catalyst of toxicity.
Summary of the invention
The present invention for the existing synthetic method of amino acid stannous is directly reacted in a solvent with tin salt with amino acid
It obtains, prepares using this method using the organic solvent being largely more toxic during amino acid stannous, method is complicated, yield
It is lower, and can only obtain the amino acid and tin complex of part, it is only suitable for sub- as a small amount of amino acid is prepared in the lab
The research of tin is used, and can not be carried out large-scale industrial production, for disadvantages mentioned above, be provided a kind of new synthesis of amino acid stannous
Method.Novel synthesis technical process according to the present invention is simple, production cost is low, and it is raw to can be applied to large-scale industrialization
It produces.
Technical solution of the present invention:
A kind of preparation method of amino acid stannous complex, steps are as follows:
The first step, dehydrogenation salt-forming reaction:
Amino acid is dissolved in methanol, 50~70 DEG C is heated to, triethylamine is added dropwise under agitation, keeps amino acid raw
It is dissolved in methanol at amino-acid salt, as amino acid salt solution；Wherein, the time for adding of triethylamine was controlled at 20~30 minutes
In range, the molar ratio of triethylamine and amino acid is 1.2:1；
Second step, metathesis reaction:
Amino-acid salt and divalent stannous reactant salt generate amino acid stannous complex；Divalent is added dropwise in amino acid salt solution
The methanol solution of tin salt reacts under the conditions of being full of nitrogen or atmosphere of inert gases and 50~70 DEG C of temperature, reacts 5 hours,
Up to amino acid stannous complex；The methanol solution time for adding of the divalent tin salt of control is 30~40 minutes.
Further, the amino acid is phenylalanine, proline or valine.
Further, the divalent tin salt is stannous chloride or stannous sulfate, uses stannous chloride and stannous sulfate master
If stannous ion is not oxidizable because the price of chloride ion and sulfate ion is lower, thus the amino acid stannous generated
Yield is higher, and the molar ratio for controlling amino acid and divalent tin salt is 2:1.
Further, in second step, reaction temperature is 60 DEG C.
Purposes of the above-mentioned amino acid stannous complex as lactide or lactone ring opening polymerization catalyst, described is polymerized to
Polymerization or combined polymerization, wherein when homopolymerization described in polymerized monomer be lactide, caprolactone, valerolactone, trimethylene carbonate
One kind, after the lactide homopolymerization product be polylactic acid, after the caprolactone homopolymerization product be polycaprolactone, institute
Product is poly- valerolactone after the valerolactone homopolymerization stated；Wherein when combined polymerization described in polymerized monomer be lactide, caprolactone, penta
Two or three in lactone, trimethylene carbonate.
Further, the lactide is L- lactide, D- lactide, D, and one or more of L- lactide is mixed
It closes.
Further, the homopolymerization and copolymerization are combined into bulk polymerization, specific steps are as follows: under the conditions of anhydrous and oxygen-free, point
Not Jia Ru monomer and amino acid stannous composition catalyst, reaction temperature be 120~200 DEG C, preferably 140 DEG C, the reaction time 5
~24 hours, preferably 16 hours.
Further, the homopolymerization and copolymerization process add alcohols initiator.
Since stannous chloride exposure is easily oxidized in air, stannous chloride solution has to ready-to-use, chlorine
The concentration for changing stannous methanol or aqueous solution is set as 0.2~1mmol/ml, preferably 0.03mmol/ml, reaction of the invention
Journey should carry out in the environment of inert gas.
It is not high also directed to the ring-opening polymerization activity of existing catalyst lactide and cyclic ester, it is desirable that longer polymerization is anti-
Between seasonable and higher reaction temperature, therefore provide purposes of the amino acid stannous as high activity ring-opening polymerization catalyst.
Beneficial effects of the present invention:
(1) amino acid stannous simple production process is prepared using novel synthesis of the invention, production cost is low, can be used for
Large-scale industrial production.
(2) it using the novel synthesis of amino acid stannous of the invention during preparing amino acid stannous, is not used
The yield of a large amount of toxic solvent, amino acid stannous is higher, show that product is purer through elemental analysis.
(3) catalyst the present invention relates to amino acid stannous as lactide and lactone ring opening polymerization has catalyst amount
Low (only the 0.0001~0.01% of monomer mole ratio), high income (75~95%), molecular weight product is very high.
(4) the present invention relates to amino acid stannous as glycolide, lactide, caprolactone, valerolactone, trimethylene carbonate
The characteristics of catalyst of ring-opening polymerisation has polymerization rate fast, and molecular weight of product is high, is suitable for bulk polymerization.
(5) amino acid stannous of the present invention is catalyzed as the stereoselective polymerization of rac-lactide ring-opening polymerisation
Agent has polymerization rate mild, and molecular weight of product is high, and syndiotaxy selectivity is high, can reach Pr=0.68, is suitable for this
The characteristics of body polymerize.
Detailed description of the invention
Fig. 1 is the nuclear magnetic spectrogram characterization effect picture of complex.
Fig. 2 is the infrared spectrum characterization effect picture of complex.
Fig. 3 is impact effect figure of the temperature to the complex-catalyzed lactide ring-opening polymerisation of the series.
Fig. 4 is the kinetics figure of Different Complex catalyzing ring-opening polymerization of lactide.
Fig. 5 is the polylactic acid homonuclear decoupling nuclear magnetic spectrogram that complex-catalyzed rac-lactide polymerize.
Specific embodiment
The present invention is further illustrated below by the specific descriptions to the embodiment of the present invention, but embodiment is not to this hair
Bright limitation.
The synthesis of 1 catalyst L-phenylalanine stannous of embodiment
L-phenylalanine (9.9g, 0.06mol) and methanol (40ml) are added in 100ml there-necked flask, in 60 DEG C of thermostatted waters
It is stirred to react 20min in bath, is added dropwise triethylamine solution (6.07g, 0.06mol), is added dropwise within 30 minutes, L-phenylalanine is complete
Portion's dissolution, is then passed through nitrogen 10min into solution, removes the oxygen in solution neutralization reaction bottle, and in the ring for being full of nitrogen
Stannous chloride (SnCl is added in border2·2H2O, 6.78g, 0.03mol) 10ml methanol solution, after 30 minutes are added dropwise,
60 DEG C are reacted 5 hours, and L-phenylalanine stannous is in granular form and is settled, and are filtered, vacuum drying oven desciccate 24 hours, are obtained
To 12.4g, yield 12.4/13.38 × 100%=92.68%.Elemental analysis value (composition C18H20N2O4Sn) (%) C:48.43
(47.23), (4.42) H:4.48, Sn:26.46 (26.53), (measuring under air).
The synthesis of 2 catalyst L-Leu stannous of embodiment
Experimental procedure is changed to 0.06molL- leucine with embodiment 1, by L-phenylalanine, obtains 10.82gL- leucine
Stannous, yield 95.33%.Elemental analysis value (composition C12H24N2O4Sn) (%) C:38.05 (37.93), H:6.34 (6.21),
Sn:31.22 (30.83), (measuring under air).
The synthesis of 3 catalyst l-Isoleucine stannous of embodiment
Experimental procedure is changed to 0.06molL- isoleucine with embodiment 1, by L-phenylalanine, obtains the different bright ammonia of 9.93gL-
Sour stannous, yield 87.49%.Elemental analysis value (composition C12H24N2O4Sn) (%) C:38.05 (37.81), H:6.34 (6.26),
Sn:31.22 (29.87), (measuring under air).
The synthesis of 4 catalyst Valine stannous of embodiment
Experimental procedure is changed to 0.06molL- valine with embodiment 1, by L-phenylalanine, and it is sub- to obtain 9.10gL- valine
Tin, yield 86.67%.Elemental analysis value (composition C10H20N2O4Sn) (%) C:34.29 (33.91), H:5.71 (5.62), Sn:
33.71 (32.62), (measuring under air).
The synthesis of 5 catalyst L-PROLINE stannous of embodiment
Experimental procedure is changed to 0.06molL- proline with embodiment 1, by L-phenylalanine, and it is sub- to obtain 5.43gL- proline
Tin, yield 52.31%.Elemental analysis value (composition C10H16N2O4Sn) (%) C:34.68 (34.12), H:4.62 (4.23), Sn:
34.10 (33.82), (measuring under air).
The synthesis of 6 catalyst l-tyrosine stannous of embodiment
Experimental procedure is changed to 0.06molL- tyrosine with embodiment 1, by L-phenylalanine, obtains 12.64gL- tyrosine
Stannous, yield 88.16%.Elemental analysis value (composition C18H20N2O6Sn) (%) C:45.18 (44.23), H:4.18 (4.23),
Sn:24.69 (24.33), (measuring under air).
The synthesis of 7 catalyst L-Trp stannous of embodiment
Experimental procedure is changed to 0.06molL- tryptophan with embodiment 1, by L-phenylalanine, obtains 11.83gL- tryptophan
Stannous, yield 75.25%.Elemental analysis value (composition C22H22N4O4Sn) (%) C:50.38 (49.56), H:4.20 (4.12),
Sn:22.52 (25.36), (measuring under air).
The synthesis of 8 catalyst Pidolidone stannous of embodiment
Experimental procedure is changed to 0.06molL- glutamic acid with embodiment 1, by L-phenylalanine, and it is sub- to obtain 8.6gL- glutamic acid
Tin, yield 82.61%.Elemental analysis value (composition C10H18N2O8Sn) (%) C:29.13 (28.93), H:4.37 (4.34), Sn:
28.64 (27.83), (measuring under air).
The synthesis of 9 catalyst L-lysine stannous of embodiment
Experimental procedure is changed to 0.06molL- lysine with embodiment 1, by L-phenylalanine, obtains 10.68gL- glutamic acid
Stannous, yield 87.25%.Elemental analysis value (composition C12H26N4O4Sn) (%) C:35.29 (34.93), H:6.37 (6.28),
Sn:28.92 (28.24), (measuring under air).
The synthesis of 10 catalyst L-Histidine stannous of embodiment
Experimental procedure is changed to 0.06molL- histidine with embodiment 1, by L-phenylalanine, obtains 10.86gL- histidine
Stannous, yield 84.98%.Elemental analysis value (composition C12H16N6O4Sn) (%) C:33.80 (33.64), H:3.76 (3.40),
Sn:27.7 (27.83), (measuring under air).
Embodiment 11
The stannous sulfate of any of embodiment 1 to 10 embodiment is replaced with into stannous chloride, is equally able to achieve the present invention
Identical effect.
Embodiment 12
L-configuration in embodiment 1 to 10 is changed into the amino acid of D, DL configuration, is able to achieve the identical effect of the present invention.
Embodiment 13
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add L- lactide (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L- phenylpropyl alcohol ammonia
Sour stannous (0.013g, 0.219mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform is added after reaction by product
Dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Obtain l-lactic acid 4.68g, product yield 87%,
Number-average molecular weight is 64.38KDa, weight average molecular weight 86.48KDa, molecular weight distribution index 1.32.
Embodiment 14
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add L- lactide (5.40g, 37.4mmol), benzyl alcohol (0.001mL, 0.01mmol) and L- phenylpropyl alcohol
Propylhomoserin stannous (0.013g, 0.219mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform will be added after reaction to be produced
Object dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Obtain l-lactic acid 4.79g, product yield
89%, number-average molecular weight 122.82KDa, weight average molecular weight 140.78KDa, molecular weight distribution index 1.15
Embodiment 15
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add D- lactide (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and D, L- phenylpropyl alcohol
Propylhomoserin stannous (0.013g, 0.219mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform will be added after reaction to be produced
Object dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Obtain dextrorotation polylactic acid 4.65g, product yield
86%, number-average molecular weight 44.13KDa, weight average molecular weight 60.91KDa, molecular weight distribution index 1.38.
Embodiment 16
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add Rac- lactide (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and D, L- benzene
Alanine stannous (0.013g, 0.219mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform is added after reaction will
Product dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Racemic rotation polylactic acid 4.45g is obtained, product is received
Rate 82%, number-average molecular weight 64.53KDa, weight average molecular weight 80.65KDa, molecular weight distribution index 1.25.
Embodiment 17
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add L- lactide (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L-PROLINE
Stannous (0.013g, 0.0374mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform is added after reaction product is molten
Solution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Obtain l-lactic acid 4.79g, product yield 89%, number
Average molecular weight is 44.13KDa, weight average molecular weight 60.91KDa, molecular weight distribution index 1.38.
Embodiment 18
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add L- lactide (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L-Histidine
Stannous (0.013g, 0.0305mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform is added after reaction product is molten
Solution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.L-lactic acid 4.29g, product yield 79-% are obtained, number
Average molecular weight is 27.68KDa, weight average molecular weight 49.85KDa, molecular weight distribution index 1.80.
Embodiment 19
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add L- lactide (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L-Trp
Stannous (0.013g, 0.0248mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform is added after reaction product is molten
Solution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.L-lactic acid 4.59g, product yield 85-% are obtained, number
Average molecular weight is 25.69KDa, weight average molecular weight 46.46KDa, molecular weight distribution index 1.81.
Embodiment 20
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add L- lactide (5.4g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L-lysine
Stannous (0.0153g, 0.0374mmol) is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform is added after reaction by product
Dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.L-lactic acid 4.70g, product yield 87-% are obtained,
Number-average molecular weight is 26.70KDa, weight average molecular weight 51.01KDa, molecular weight distribution index 1.91.
Embodiment 21
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add L- lactide (2.88g, 20mmol) and L-phenylalanine stannous (0.0045g,
0.001mmol), it is placed in 140 DEG C of oil baths and whisks reaction 16h.Chloroform is added after reaction to dissolve product, uses methanol extraction
And it is repeatedly washcoated, vacuum drying oven is done to constant weight.L-lactic acid 2.60g, product yield 90-% are obtained, number-average molecular weight is
192.83KDa, weight average molecular weight 223.42KDa, molecular weight distribution index 1.16.
Embodiment 22
The L- lactide of any of embodiment 13 to 20 embodiment is replaced with into D- lactide or Rac- lactide, together
Sample is able to achieve the identical effect of the present invention.
Embodiment 23
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add caprolactone (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L-phenylalanine
Stannous (0.098g, 0.0219mmol) is placed in 130 DEG C of oil baths and whisks reaction 16h.Methylene chloride will be added after reaction to be produced
Object dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Polycaprolactone 4.18g, product yield 77-% are obtained,
Number-average molecular weight is 48.47KDa, weight average molecular weight 56.02KDa, molecular weight distribution index 1.16.
Embodiment 24
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add caprolactone (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and Valine sub-
Tin (0.0098g, 0.028mmol) is placed in 130 DEG C of oil baths and whisks reaction 16h.Methylene chloride is added after reaction by product
Dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Polycaprolactone 3.52g, product yield 65-% are obtained, number
Average molecular weight is 49.96KDa, weight average molecular weight 57.99KDa, molecular weight distribution index 1.16.
Embodiment 25
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add caprolactone (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L-PROLINE sub-
Tin (0.0098g, 0.028mmol) is placed in 130 DEG C of oil baths and whisks reaction 16h.Methylene chloride is added after reaction by product
Dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Polycaprolactone 4.12g, product yield 76-% are obtained, number
Average molecular weight is 39.06KDa, weight average molecular weight 55.58KDa, molecular weight distribution index 1.42.
Embodiment 26
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add δ-valerolactone (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L-PROLINE
Stannous (0.098g, 0.0219mmol) is placed in 130 DEG C of oil baths and whisks reaction 16h.Methylene chloride will be added after reaction to be produced
Object dissolution, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Poly- valerolactone 3.62g, product yield 67-% are obtained,
Number-average molecular weight is 25.03KDa, weight average molecular weight 33.43KDa, molecular weight distribution index 1.34.
Embodiment 27
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add δ-valerolactone (5.40g, 37.4mmol), benzyl alcohol (0.01mL, 0.1mmol) and L- phenylpropyl alcohol ammonia
Sour stannous (0.0098g, 0.0219mmol) is placed in 130 DEG C of oil baths and whisks reaction 16h.Methylene chloride is added after reaction
Product is dissolved, with methanol extraction and repeatedly washcoated, vacuum drying oven is done to constant weight.Obtain polycaprolactone 4.67g, product yield
86-%, number-average molecular weight 24.92KDa, weight average molecular weight 33.88KDa, molecular weight distribution index 1.36.[00050]
Embodiment 28
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add trimethylene carbonate (9.8g, 96mmol), benzyl alcohol (0.05mL, 0.48mmol) and D, L-
Phenylalanine stannous (0.043g, 0.096mmol) is placed in 130 DEG C of oil baths and whisks reaction for 24 hours.Dichloro is added after reaction
Methane dissolves product, with methanol extraction and repeatedly washcoated, and vacuum drying oven is done to constant weight.Obtain polytrimethylene carbonate
7.62g, product yield 78%, number-average molecular weight 24.49KDa, weight average molecular weight 33.59KDa, molecular weight distribution index are
1.37。
Embodiment 29
Under nitrogen protection to the 100mL after high pure nitrogen evacuates-toast-nitrogen charging operation 3 times with air extraction connector
Round-bottomed flask in sequentially add trimethylene carbonate (1.02g, 10mmol), L- lactide (1.44g, 10mmol), ε-oneself
Lactone (1.14,10mmol), benzyl alcohol (0.05mL, 0.48mmol) and L-phenylalanine stannous (0.026g, 0.048mmol),
It is placed in 130 DEG C of oil baths and whisks reaction 16h.Methylene chloride is added after reaction to dissolve product, with methanol extraction and repeatedly
Washcoated, vacuum drying oven is done to constant weight.Polymer 3.41g, product yield 86-%, number-average molecular weight 34.40KDa are obtained, weight is equal
Molecular weight is 53.69KDa, molecular weight distribution index 1.56.
The result of Different Complex catalysis monomer ring-opening polymerisation
It is described in the present invention that specific embodiments are merely illustrative of the spirit of the present invention.Technology belonging to the present invention
The technical staff in field can make various modifications or additions to the described embodiments or by a similar method
Substitution, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Although some specific examples have been made a detailed description and have been cited to the present invention, to the skilled skill in this field
For art personnel, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of preparation method of amino acid stannous complex, which is characterized in that steps are as follows:
The first step, dehydrogenation salt-forming reaction:
Amino acid is dissolved in methanol, 50~70 DEG C is heated to, triethylamine is added dropwise under agitation, amino acid is made to generate ammonia
Base hydrochlorate and be dissolved in methanol, as amino acid salt solution；Wherein, the time for adding of triethylamine is controlled in 20~30 minutes ranges
Interior, the molar ratio of triethylamine and amino acid is 1.2:1；
Second step, metathesis reaction:
Amino-acid salt and divalent stannous reactant salt generate amino acid stannous complex；Divalent stannous is added dropwise in amino acid salt solution
The methanol solution of salt is reacted full of nitrogen or atmosphere of inert gases and 50~70 DEG C of temperature under the conditions ofs, react 5 hours to get
Amino acid stannous complex；The molar ratio for controlling amino acid and divalent tin salt is 2:1, and the methanol of the divalent tin salt of control is molten
Liquid time for adding is 30~40 minutes.
2. preparation method according to claim 1, which is characterized in that the amino acid be phenylalanine, proline or
Valine.
3. preparation method according to claim 1 or 2, which is characterized in that the divalent tin salt be stannous chloride or
Stannous sulfate.
4. preparation method according to claim 1 or 2, which is characterized in that in second step, reaction temperature is 60 DEG C.
5. preparation method according to claim 3, which is characterized in that in second step, reaction temperature is 60 DEG C.
6. purposes of the amino acid stannous complex as lactide or lactone ring opening polymerization catalyst, which is characterized in that described is poly-
Be combined into homopolymerization or combined polymerization, wherein when homopolymerization described in polymerized monomer be lactide, caprolactone, valerolactone, trimethylene
One kind of carbonic ester, product is polylactic acid after the lactide homopolymerization, and product is to gather oneself after the caprolactone homopolymerization
Lactone, product is poly- valerolactone after the valerolactone homopolymerization；Wherein when combined polymerization described in polymerized monomer be lactide, oneself
Lactone, valerolactone, two or more mixing in trimethylene carbonate.
7. purposes according to claim 6, which is characterized in that the lactide include L- lactide, D- lactide and
D, L- lactide.
8. purposes according to claim 6 or 7, which is characterized in that the homopolymerization and copolymerization is combined into bulk polymerization, tool
Body step are as follows: under the conditions of anhydrous and oxygen-free, be separately added into monomer and amino acid stannous composition catalyst, reaction temperature 120
~200 DEG C, the reaction time is 5~24 hours.
9. purposes according to claim 6 or 7, which is characterized in that the homopolymerization and copolymerization process add alcohols
Initiator.
10. purposes according to claim 8, which is characterized in that the homopolymerization and copolymerization process addition alcohols draw
Send out agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910435710.XA CN110078634B (en) | 2019-05-23 | 2019-05-23 | Preparation method and application of stannous amino acid complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910435710.XA CN110078634B (en) | 2019-05-23 | 2019-05-23 | Preparation method and application of stannous amino acid complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110078634A true CN110078634A (en) | 2019-08-02 |
| CN110078634B CN110078634B (en) | 2022-05-17 |
Family
ID=67421588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910435710.XA Active CN110078634B (en) | 2019-05-23 | 2019-05-23 | Preparation method and application of stannous amino acid complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078634B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393174A (en) * | 2023-04-04 | 2023-07-07 | 大连理工大学 | Catalyst for preparing glycolide and polyglycolide simultaneously and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806919A (en) * | 2006-01-27 | 2006-07-26 | 浙江海正生物材料股份有限公司 | Use of stannous benzoate as catalyst |
| CN101367921A (en) * | 2008-10-06 | 2009-02-18 | 中国人民解放军第二军医大学 | Method for synthesis of polylactic acid with lactide opened loop |
-
2019
- 2019-05-23 CN CN201910435710.XA patent/CN110078634B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806919A (en) * | 2006-01-27 | 2006-07-26 | 浙江海正生物材料股份有限公司 | Use of stannous benzoate as catalyst |
| CN101367921A (en) * | 2008-10-06 | 2009-02-18 | 中国人民解放军第二军医大学 | Method for synthesis of polylactic acid with lactide opened loop |
Non-Patent Citations (4)
| Title |
|---|
| MOAMEN S. REFAT等: "Preparation, structural characterization and biological evaluation of L-tyrosinate metal ion complexes", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| PAUL A.CUSACK等: "Synthesis and Spectroscopic Studies of Inorganic Tin Derivatives of Amino-acids and their Esters", 《J.C.S.DALTON》 * |
| YUAN LIANG等: "A Strategy of In Situ Catalysis and Nucleation of Biocompatible Zinc Salts of Amino Acids towards Poly(l-lactide) with Enhanced Crystallization Rate", 《POLYMERS》 * |
| 刘继延，刘学淸: "天然氨基酸作用下丙交酯的开环聚合反应", 《中国塑料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393174A (en) * | 2023-04-04 | 2023-07-07 | 大连理工大学 | Catalyst for preparing glycolide and polyglycolide simultaneously and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110078634B (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112079999B (en) | Method for catalyzing ring opening polymerization of cyclic ester by zinc catalyst | |
| WO2022041326A1 (en) | Zinc catalyst for catalyzing ring-opening polymerization of cyclic esters and controlled depolymerization of polyester materials and catalytic method therefor | |
| JP3392411B1 (en) | Copolymer containing alkylene carbonate and method for producing the same | |
| CN107022069A (en) | A kind of method that utilization bionic catalyst is catalyzed γ valerolactone ring-opening polymerisations | |
| CN110092892B (en) | Preparation method of polyester | |
| CN106947067A (en) | A kind of preparation method of polyester | |
| CN109880073A (en) | A kind of preparation method of polylactone | |
| CN107022068B (en) | 6-caprolactone and L- lactide catalyst for copolymerization and copolymerization process | |
| CN110078634A (en) | A kind of preparation method and application of amino acid stannous complex | |
| CN105367762A (en) | Method for preparing aliphatic polyesters | |
| CN110183639A (en) | A kind of preparation method and applications of the catalyst for polyester synthesis | |
| CN101318960A (en) | Process for synthesizing acetate bicyclo guanidine and catalysis synthesis for poly-lactide and poly-serine morpholine diketone | |
| CN108503803B (en) | A method of poly- γ-fourth lactones is prepared using urea/alkoxide | |
| CN110256657A (en) | A kind of aliphatic-aromatic copolyester and preparation method thereof | |
| CN1304457C (en) | Diamine modified poly-latic acid, method for preparing same and use thereof | |
| CN109705159A (en) | A kind of preparation method and application of phosphorous nitrogen ligand alkyl aluminum compound | |
| CN104592501B (en) | A kind of preparation method of polycaprolactone | |
| CN109749065A (en) | A kind of macrolide copolymer high-efficiency preparation method of binary catalyst catalysis | |
| CN108570066A (en) | Aluminium compound and its preparation method and application containing chiral cyclohexanediamine base | |
| CN104497280B (en) | A kind of preparation method of PGA | |
| CN101591349B (en) | Nitrogen-bridged bis(phenolate) yttrium dibenzyl oxygen compound and preparation and application thereof | |
| CN101550126B (en) | Epsilon-caprolactone derivative and polymer thereof | |
| KR101456758B1 (en) | Carbon dioxide based terpolymer with ester and ether group and method for preparing same | |
| CN105294745B (en) | Nitrogenous aryloxy rare earth metal Lanthanide complex and its preparation method and its application in ester ring-opening polymerization | |
| CN114891035B (en) | Difunctional tetranuclear metal lithium complex and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230627 Address after: 116024 No. 2 Ling Road, Ganjingzi District, Liaoning, Dalian Patentee after: DALIAN University OF TECHNOLOGY Address before: 116601 No.9, 6th floor, NO.201 Guoshang building, Huanghai West 4th Road, Dalian Free Trade Zone, Liaoning Province Patentee before: Dalian Huipengda Chemical Co.,Ltd. Patentee before: DALIAN University OF TECHNOLOGY |