CN109337052A - Utilize the method for L- lactide ring-opening polymerisation production poly (l-lactic acid) - Google Patents
Utilize the method for L- lactide ring-opening polymerisation production poly (l-lactic acid) Download PDFInfo
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- CN109337052A CN109337052A CN201811157293.9A CN201811157293A CN109337052A CN 109337052 A CN109337052 A CN 109337052A CN 201811157293 A CN201811157293 A CN 201811157293A CN 109337052 A CN109337052 A CN 109337052A
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- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- 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
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- 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
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Abstract
The present invention discloses the method using L- lactide ring-opening polymerisation production poly (l-lactic acid), poly (l-lactic acid) reaction kettle is added in L- lactide, the additional amount of catalyst is the 0.04-0.5% of L- lactide quality, and reaction temperature is 140 DEG C -170 DEG C, reaction time is 10-50h, reaction pressure≤10pa.The present invention provides a kind of methods for preparing poly (l-lactic acid) using L- lactide, and a kind of method that Pfansteihl oligomer is generated by Pfansteihl monomer and L- lactide is prepared with this is additionally provided, to industrially realize the complete process for preparing poly (l-lactic acid) by Pfansteihl monomer.
Description
Technical field
The present invention relates to lactic acid deep process technology field fields.More particularly, to a kind of poly- using the open loop of L- lactide
The method of symphysis production poly (l-lactic acid).
Background technique
Poly (l-lactic acid) is a kind of function admirable, the polymer with biocompatibility and biodegradability, main to use
In degradable package material and medicine microsphere carrier, antiadhesion barrier, biological duct, orthopaedics fixture, bone surgery device, people
In terms of the medical materials such as work bone.
It is that lactic acid oligomer is generated by monomer lactic acid first, then again during preparing poly (l-lactic acid) by monomer lactic acid
Poly (l-lactic acid) is prepared by lactic acid oligomer direct polycondensation, or then L- lactide open loop gathers by lactic acid oligomer preparation L- lactide
Symphysis is at poly (l-lactic acid).
Oligomeric Pfansteihl acts not only as preparing the raw material of poly (l-lactic acid), is also used as medicine intermediate, China is specially
Sharp document CN1498237A discloses a kind of preparation method of lactic acid oligomer, is raw material, the property of can choose using lactide
Ground prepares chain and cyclic lactic acid oligosaccharide mixture.The disadvantages of this method is: (1) must use lactide is raw material, but
It is the most cheap by raw material of lactic acid monomer in industrialized production, the higher cost of lactide is directly prepared by lactic acid monomer, it can only
Use by-product lactide in melt polycondensation as raw material；(2) the tetrahydrofuran equal solvent used is toxic, is not suitable for industrializing
Using.
In the industrial production of scale, it is difficult to directly obtain the higher L- lactide of purity by monomer Pfansteihl；Usually
Lactide in industrialized production is all melt polycondensation technique during melt polycondensation+solid phase polycondensation production poly (l-lactic acid)
The thick L- lactide of the by-product of generation produces high-molecular-weight poly L- to just can be carried out ring-opening polymerisation after these thick L- lactide purifications
Lactic acid.
Summary of the invention
It is an object of the present invention to provide a kind of methods for preparing poly (l-lactic acid) using L- lactide, and also provide
A method of Pfansteihl oligomer is generated by Pfansteihl monomer and L- lactide is prepared with this, to industrially realize by L-
Lactic acid monomer prepares the complete process of poly (l-lactic acid).
In order to achieve the above objectives, the present invention adopts the following technical solutions: producing poly- L- cream using the ring-opening polymerisation of L- lactide
Poly (l-lactic acid) reaction kettle is added in L- lactide by the method for acid, and the additional amount of catalyst is the 0.04- of L- lactide quality
0.5%, reaction temperature is 140 DEG C -170 DEG C, reaction time 10-50h, reaction pressure≤10pa.
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid), catalyst are zirconium oxide and glycine hydroxy acid
The mixture that molybdenum is formed according to 1.5-2.5:1.
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid), the preparation method of glycine hydroxy acid molybdenum is such as
Under: sodium molybdate and glycine hydroxy acid are mixed at room temperature in methanol solution, react 2-3h, obtaining solid is glycine
Hydroxy acid molybdenum；Acthiol-J and sodium molybdate the mass ratio of the material 4:1, concentration of the sodium molybdate in methanol solution are 0.1-2mol/
L。
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid), the additional amount of catalyst are L- lactide matter
The 0.1% of amount, reaction temperature are 160 DEG C, reaction time 20h.
It is above-mentioned using L- lactide ring-opening polymerisation production poly (l-lactic acid) method, L- lactide the preparation method is as follows:
(1) raw material preparation: the optical purity of the Pfansteihl solution of 40-60wt%, Pfansteihl is greater than or equal to 99.5%；
(2) it is dehydrated oligomerization, obtains Pfansteihl oligomer；
(3) depolymerization of Pfansteihl oligomer prepares L- lactide.
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid), in step (2), into Pfansteihl solution
The volume ratio of addition ethyl pyruvate, ethyl pyruvate and Pfansteihl solution is 0.5-1:1；Oxygen is added into mixed solution simultaneously
Change cobalt and two-acthiol-J vanadyl as catalyst, stirring；The usage amount of cobalt oxide is the 0.02%- of Pfansteihl quality
0.04%, two-acthiol-J vanadyl usage amounts are the 0.04%-0.08% of Pfansteihl quality；Reaction time is 3h-6h,
Reaction temperature is 5-30 DEG C.
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid), in step (2):
When initial reaction: the addition mass ratio of cobalt oxide and two-acthiol-J vanadyl is 1:1.5, and cobalt oxide exists
Additional amount when initial reaction is the 1/2 of the total additional amount of cobalt oxide；Reaction temperature goes over two points from initial reaction to the reaction time
One of be always maintained at 5 DEG C -10 DEG C；
When reaction time goes over half: reaction kettle is all added in two-acthiol-J vanadyl of residue；Instead
Past temperature autoreaction time half to the past in reaction time 3/4ths was answered to be always maintained at 15 DEG C -20 DEG C；
When past in reaction time 3/4ths: reaction kettle is all added in remaining cobalt oxide；Reaction temperature autoreaction
Past time 3/4ths terminates to be always maintained at 25-30 DEG C to reaction.
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid), in step (2), two-cysteine first
Ester vanadyl the preparation method comprises the following steps: acthiol-J and vanadic sulfate are mixed at room temperature in boric acid solution, react 3-
5h obtains violet solid；Acthiol-J and vanadic sulfate the mass ratio of the material 5:1, acthiol-J is in boric acid solution
Concentration be 0.1-5mol/L.
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid), in step (2), after reaction, mistake
Filter, stratification isolate organic phase, wash organic phase；Organic phase vacuum distillation after washing is removed into solvent, is obtained white solid
Body.
The above-mentioned method using L- lactide ring-opening polymerisation production poly (l-lactic acid) will obtain in step (3) in step (2)
To Pfansteihl oligomer investment lactide prepare kettle, be warming up to 145-160 DEG C, make Pfansteihl oligomer melt；Synthesize L- third
Catalyst used in lactide is the mixture of nickel oxide and glycine hydroxy acid molybdenum, and nickel oxide usage amount is Pfansteihl oligomerization substance
The 0.01%-0.03% of amount, glycine hydroxy acid molybdenum usage amount is the 0.03%-0.09% of Pfansteihl oligomerization amount of substance, when reaction
Between 3-5h, reaction pressure 0.01 × 105Pa-0.1×105Pa；
When initial reaction: the addition mass ratio of nickel oxide and glycine hydroxy acid molybdenum is 1:2, and nickel oxide is in initial reaction
Additional amount be the total additional amount of nickel oxide 1/3；
When reaction time goes over one third: lactide is all added in remaining nickel oxide and prepares kettle；
When past in reaction time 2/3rds: lactide is all added in remaining glycine hydroxy acid molybdenum and prepares kettle；
Glycine hydroxy acid molybdenum the preparation method comprises the following steps: sodium molybdate and glycine hydroxy acid in methanol solution, at room temperature mixing stir
It mixes, reacts 2-3h, obtaining solid is glycine hydroxy acid molybdenum；Glycine hydroxy acid and sodium molybdate the mass ratio of the material 4:1, sodium molybdate exist
Concentration in methanol solution is 0.1-2mol/L；
Lactide prepares kettle top by heat-insulating pipeline and condensation collecting tank fluid communication, and the L- lactide of generation is condensing
Collecting tank crystallisation by cooling.
Beneficial effects of the present invention are as follows:
(1) using Pfansteihl monomer cheap and easy to get in actual industrial production as raw material, it has been worth molecular weight distribution relatively narrow
Pfansteihl oligomer, reaction condition is mild and easily controllable, Pfansteihl oligomer high income, is suitable for industrialized production.
(2) lactide is prepared by raw material of Pfansteihl oligomer, the yield and purity of L- lactide are all very high, and improve
Reaction pressure, it is energy saving in the industrial production.
(3) complete process flow that poly (l-lactic acid) is prepared by Pfansteihl monomer is industrially realized.
Detailed description of the invention
Fig. 1 catalyst amount is catalyst amount wt% to the influence abscissa of L- lactide ring opening polymerization product, indulges and sits
It is designated as poly- D-ALPHA-Hydroxypropionic acid weight average molecular weight MW×105)；
(abscissa is reaction temperature DEG C, indulges and sits for influence of Fig. 2 reaction temperature to L- lactide ring opening polymerization product molecular weight
It is designated as poly- D-ALPHA-Hydroxypropionic acid weight average molecular weight MW×105)；
Fig. 3 polymerization reaction time to L- lactide ring opening polymerization product molecular weight influence (abscissa be reaction time h,
Ordinate is poly- D-ALPHA-Hydroxypropionic acid weight average molecular weight MW×105)。
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
First part produces the technical study of poly (l-lactic acid) using the ring-opening polymerisation of L- lactide
The production of poly (l-lactic acid) can generate the poly- L- cream of higher molecular weight using melt polycondensation+solid phase polycondensation method
Acid also can use the poly (l-lactic acid) of L- lactide ring-opening polymerisation production higher molecular weight.In melt polycondensation+solid phase polycondensation production
During poly (l-lactic acid), the thick L- lactide of the by-product that melt polycondensation technique can generate, but need to these thick L- lactides
It just can be carried out ring-opening polymerisation production high molecular weight poly (l-lactic acid) after purification.The raw material L- lactide that the present invention uses is by L- cream
The L- lactide (referring specifically to the embodiment 1 of second part) of acid preparation, but be also applied for the by-product of melt polycondensation technique
Poly (l-lactic acid) is produced as raw material after the thick L- lactide purification of object.
1. catalyst (mixture that zirconium oxide and glycine hydroxy acid molybdenum are formed according to 2:1 is as catalyst) dosage is to L- third
The influence for the poly (l-lactic acid) molecular weight that lactide ring-opening polymerisation generates
At reaction pressure≤10pa, the identical situation of the conditions such as reaction time, reaction temperature, test different catalysts are used
Measure the influence to poly (l-lactic acid) molecular weight, the result is shown in Figure 1.
As shown in Figure 1, as catalyst amount (percentage for accounting for L- lactide quality) increases, point of product poly (l-lactic acid)
Son amount first increases to be reduced afterwards, this is because catalyst is excessive, is increased with the coordination activity center that L- lactide is formed, is led to poly- L-
Lactic acid molecules amount reduces.Comprehensively consider formation efficiency, 0.08%, 0.1%, 0.12% 3 index of selecting catalyst dosage combines
Reaction time, reaction temperature carry out orthogonal test.
2. influence of the polymeric reaction temperature to product poly (l-lactic acid) molecular weight
In reaction pressure≤10pa, (zirconium oxide and glycine hydroxy acid molybdenum are mixed according to what 2:1 was formed for reaction time, catalyst
Object is closed as catalyst) in the identical situation of conditions such as dosage, test differential responses temperature is to poly (l-lactic acid) weight average molecular weight
It influences, as a result sees Fig. 2.
As shown in Figure 2, with the increase of reaction temperature, poly (l-lactic acid) molecular mass first increases and then decreases is due to reaction
When the temperature is excessively high, thermal polymer degradation speed is accelerated, and any part fracture occurs for macromolecular chain, and poly (l-lactic acid) molecular weight is caused to drop
It is low.Comprehensively consider, selects 155 DEG C, 160 DEG C, 165 DEG C to do orthogonal test with catalyst dosage, reaction time.
3. influence of the polymerization reaction time to product poly (l-lactic acid) molecular weight
In reaction pressure≤10pa, in the identical situation of other conditions, the differential responses time is tested to poly (l-lactic acid) molecule
The influence of amount, is as a result shown in Fig. 3.
From the figure 3, it may be seen that poly (l-lactic acid) molecular weight first increases and gradually decreases afterwards with the increase of polymerization reaction time.This is
It is the L- third since as time increases, the molecular weight of poly (l-lactic acid) constantly increases, after reaching certain value, in reaction system
Lactide number is reduced, and depolymerization reaction is made to occupy an leading position, part high molecular weight linear poly (l-lactic acid) molecular breakdown, leads to poly- L- cream
Acid molecule amount reduces.To determine optimised process, comprehensive production efficiency selects 15h, 20h, 25h to carry out orthogonal test.
The Combination Design of 4.L- lactide ring-opening polymerisation technic index
Using reaction pressure≤10pa as control constant, with catalyst, (zirconium oxide and glycine hydroxy acid molybdenum are formed according to 2:1
Mixture is as catalyst) dosage, the reaction time, reaction temperature be independent variable, product poly (l-lactic acid) weight average molecular weight MWFor because
Variable is analyzed.
Test result and its significance test
In experiment, we determined that influencing three principal elements of L- lactide ring-opening polymerisation technique, and by a large amount of real
It tests, it is determined that three levels of three factors devise 3 factor, 3 level according to the center combination design principle of Box-Behnken,
Such as table 1, experimental result is shown in Table 2.
1 Three factors-levels table of table
2 Box-Behnken experimental result of table
Regression fit is carried out to test data in table 2 by successive Regression using Design expert statistical software, is gone forward side by side
Row variance analysis and significance test.It has been determined that influence of each influence factor to product poly (l-lactic acid) molecular weight is not simple
Linear relationship.Surface chart and contour plots analysis according to response, it is determined that the Best Point of three factors selects to set out in model scope
Point is optimized according to model using fast-rise approach, and maximum poly- L- is obtained when finally determining A 0.1%, B160 DEG C, C20h
Lactic acid molecules amount.
For the reliability for examining Box-Behnken experimental design result, using the proportioning test of optimization, test result is shown in
Table 3.
3 L- lactide ring-opening polymerisation test result of table
The average value for finally measuring the poly (l-lactic acid) molecular weight of extraction is 1.53 × 105, Box-Behnken experimental design institute
Technological parameter catalyst dosage, reaction time, reaction temperature it is accurate and reliable, there is practical value, be optimal processing parameter.
By testing to obtain the optimization technique of a L- lactide ring-opening polymerisation production poly (l-lactic acid): i.e. reaction pressure≤10Pa above,
Catalyst (mixture that zirconium oxide and glycine hydroxy acid molybdenum are formed according to 2:1 is as catalyst) additive amount accounts for L- lactide quality
0.1wt%, reaction time 20h, 160 DEG C of reaction temperature.
The preparation method of raw materials used L- lactide in the second part present invention
Embodiment 1
A method of L- lactide being produced using Pfansteihl, is included the following steps:
(1) raw material preparation: the Pfansteihl solution of the 45wt% of applicant's production, the optical purity of Pfansteihl are greater than or equal to
99.5%；
(2) it is dehydrated oligomerization, obtains Pfansteihl oligomer；
Mixed solution, ethyl pyruvate and Pfansteihl solution are obtained after ethyl pyruvate stirring is added into Pfansteihl solution
Volume ratio be 1:1；
Cobalt oxide and two-acthiol-J vanadyl are added into mixed solution in accordance with the following steps simultaneously as catalysis
Agent:
When initial reaction (0h): the addition mass ratio of cobalt oxide and two-acthiol-J vanadyl is 1:1.5, oxidation
Additional amount of the cobalt in initial reaction is the 1/2 of the total additional amount of cobalt oxide；Reaction temperature is gone over from initial reaction to the reaction time
Half is always maintained at 5 DEG C；Stirring；
Reaction time goes over when half (2h): reaction is all added in two-acthiol-J vanadyl of residue
Kettle；Past reaction temperature autoreaction time half to the past in reaction time 3/4ths is always maintained at 15 DEG C；Stirring；
When past in reaction time 3/4ths (3h): reaction kettle is all added in remaining cobalt oxide；Reaction temperature is certainly
Past in reaction time 3/4ths terminates to be always maintained at 25 DEG C to reaction；Stirring.
The usage amount of cobalt oxide is the 0.02% of Pfansteihl quality, and two-acthiol-J vanadyl usage amounts are Pfansteihl
The 0.04% of quality；Two-acthiol-J vanadyl the preparation method comprises the following steps: acthiol-J and vanadic sulfate are molten in boric acid
Liquid is mixed at room temperature, reacts 3-5h, obtains violet solid；Acthiol-J and vanadic sulfate the mass ratio of the material 5:
1, concentration of the acthiol-J in boric acid solution is 2mol/L.
After reaction, it filters, stratification, isolates organic phase, wash organic phase；By the organic phase decompression after washing
Solvent is distilled off, obtains white solid, fast atom bombardment mass spectroscopy is carried out to gained white solid and nuclear-magnetism detects, white solid is
For the Pfansteihl oligomer of 6-19 aggressiveness, the yield of Pfansteihl oligomer is 95%.
(3) depolymerization of Pfansteihl oligomer prepares L- lactide；
The investment lactide of Pfansteihl oligomer obtained in step (2) is prepared into kettle, lactide prepare kettle top by every
Heat pipeline and condensation collecting tank fluid communication；Lactide prepares kettle and is warming up to 145 DEG C, melts Pfansteihl oligomer；
The mixture that nickel oxide and glycine hydroxy acid molybdenum are added in kettle is prepared as catalysis to lactide in accordance with the following steps
(nickel oxide usage amount is the 0.01% of Pfansteihl oligomerization amount of substance, and glycine hydroxy acid molybdenum usage amount is Pfansteihl oligomerization substance for agent
The 0.03% of amount, reaction time 3h, reaction pressure 0.01 × 105Pa):
When initial reaction (0h): the addition mass ratio of nickel oxide and glycine hydroxy acid molybdenum is 1:2, and nickel oxide is initial anti-
Seasonable additional amount is the 1/3 of the total additional amount of nickel oxide；
When reaction time goes over one third (1h): lactide is all added in remaining nickel oxide and prepares kettle；
When past in reaction time 2/3rds (2h): lactide preparation is all added in remaining glycine hydroxy acid molybdenum
Kettle.
Glycine hydroxy acid molybdenum the preparation method comprises the following steps: sodium molybdate and glycine hydroxy acid in methanol solution, at room temperature mixing stir
It mixes, reacts 3h, obtaining solid is glycine hydroxy acid molybdenum；Glycine hydroxy acid and sodium molybdate the mass ratio of the material 4:1, sodium molybdate is in first
Concentration in alcoholic solution is 2mol/L.
The L- lactide of generation is 98.5% in condensation collecting tank crystallisation by cooling, L- lactide yield, and optical purity is
99.9%.
Embodiment 2
A method of L- lactide being produced using Pfansteihl, is included the following steps:
(1) raw material preparation: the Pfansteihl solution of the 60wt% of applicant's production, the optical purity of Pfansteihl are greater than or equal to
99.5%；
(2) it is dehydrated oligomerization, obtains Pfansteihl oligomer；
Mixed solution, ethyl pyruvate and Pfansteihl solution are obtained after ethyl pyruvate stirring is added into Pfansteihl solution
Volume ratio be 1:1；Cobalt oxide and two-acthiol-J vanadyl are added into mixed solution as catalyst；Cobalt oxide
Usage amount is the 0.04% of Pfansteihl quality, and two-acthiol-J vanadyl usage amounts are the 0.08% of Pfansteihl quality, room temperature
Under be stirred to react 3h；Two-acthiol-J vanadyl the preparation method comprises the following steps: acthiol-J and vanadic sulfate are molten in boric acid
Liquid is mixed at room temperature, reacts 3-5h, obtains violet solid；Acthiol-J and vanadic sulfate the mass ratio of the material 5:
1, concentration of the acthiol-J in boric acid solution is 0.5mol/L.
After reaction, it filters, stratification, isolates organic phase, wash organic phase；By the organic phase decompression after washing
Solvent is distilled off, obtains white solid, fast atom bombardment mass spectroscopy is carried out to gained white solid and nuclear-magnetism detects, white solid removes
Pfansteihl oligomer containing 6-19 aggressiveness, also the Pfansteihl oligomer containing 30-50 aggressiveness；The yield of Pfansteihl oligomer
It is 82%.
(3) depolymerization of Pfansteihl oligomer prepares L- lactide；
The investment lactide of Pfansteihl oligomer obtained in step (2) is prepared into kettle, lactide prepare kettle top by every
Heat pipeline and condensation collecting tank fluid communication；Lactide prepares kettle and is warming up to 150 DEG C, melts Pfansteihl oligomer；It is handed over to third
Prepared by ester is added the mixture of nickel oxide and glycine hydroxy acid molybdenum as catalyst in kettle:
When initial reaction (0h): the addition mass ratio of nickel oxide and glycine hydroxy acid molybdenum is 1:2, and nickel oxide is initial anti-
Seasonable additional amount is the 1/3 of the total additional amount of nickel oxide；
Reaction time goes over when one third (1h): lactide preparation is all added in remaining glycine hydroxy acid molybdenum
Kettle；
When past in reaction time 3/4ths (2h): lactide is all added in remaining nickel oxide and prepares kettle.
Nickel oxide usage amount is the 0.03% of Pfansteihl oligomerization amount of substance, and glycine hydroxy acid molybdenum usage amount is Pfansteihl oligomerization
The 0.09% of amount of substance, reaction time 3h, reaction pressure 0.1 × 105Pa；Glycine hydroxy acid molybdenum the preparation method comprises the following steps: sodium molybdate
It with glycine hydroxy acid in methanol solution, is mixed at room temperature, reacts 3h, obtaining solid is glycine hydroxy acid molybdenum；Sweet ammonia
Sour hydroxy acid and sodium molybdate the mass ratio of the material 4:1, concentration of the sodium molybdate in methanol solution are 1mol/L.
The L- lactide of generation is 90.2% in condensation collecting tank crystallisation by cooling, L- lactide yield, and optical purity is
99.9%.
Embodiment 3
A method of L- lactide being produced using Pfansteihl, is included the following steps:
(1) raw material preparation: the Pfansteihl solution of the 50wt% of applicant's production, the optical purity of Pfansteihl are greater than or equal to
99.5%；
(2) it is dehydrated oligomerization, obtains Pfansteihl oligomer；
Mixed solution, ethyl pyruvate and Pfansteihl solution are obtained after ethyl pyruvate stirring is added into Pfansteihl solution
Volume ratio be 1:1；
Cobalt oxide and two-acthiol-J vanadyl are added into mixed solution in accordance with the following steps simultaneously as catalysis
Agent:
When initial reaction (0h): the addition mass ratio of cobalt oxide and two-acthiol-J vanadyl is 1:1.5, oxidation
Additional amount of the cobalt in initial reaction is the 1/2 of the total additional amount of cobalt oxide；Reaction temperature is gone over from initial reaction to the reaction time
Half is always maintained at 10 DEG C；Stirring；
Reaction time goes over when half (3h): reaction kettle is all added in remaining cobalt oxide；Reaction temperature is certainly
Past in reaction time half to the past in reaction time 3/4ths is always maintained at 15 DEG C；Stirring；
When past in reaction time 3/4ths (4.5h): two-acthiol-J vanadyl of residue being all added anti-
Answer kettle；Past reaction temperature autoreaction time 3/4ths terminates to be always maintained at 30 DEG C to reaction；Stirring.
The usage amount of cobalt oxide is the 0.03% of Pfansteihl quality, and two-acthiol-J vanadyl usage amounts are Pfansteihl
The 0.06% of quality；Two-acthiol-J vanadyl the preparation method comprises the following steps: acthiol-J and vanadic sulfate are molten in boric acid
Liquid is mixed at room temperature, reacts 3-5h, obtains violet solid；Acthiol-J and vanadic sulfate the mass ratio of the material 5:
1, concentration of the acthiol-J in boric acid solution is 1mol/L.
After reaction, it filters, stratification, isolates organic phase, wash organic phase；By the organic phase decompression after washing
Solvent is distilled off, obtains white solid, fast atom bombardment mass spectroscopy is carried out to gained white solid and nuclear-magnetism detects, white solid is
For the Pfansteihl oligomer of 6-40 aggressiveness, the yield of Pfansteihl oligomer is 90%.
(3) depolymerization of Pfansteihl oligomer prepares L- lactide；
The investment lactide of Pfansteihl oligomer obtained in step (2) is prepared into kettle, lactide prepare kettle top by every
Heat pipeline and condensation collecting tank fluid communication；Lactide prepares kettle and is warming up to 160 DEG C, melts Pfansteihl oligomer；It is handed over to third
Prepared by ester is added the mixture of nickel oxide and glycine hydroxy acid molybdenum as catalyst in kettle；Nickel oxide usage amount is Pfansteihl oligomerization
The 0.02% of amount of substance, glycine hydroxy acid molybdenum usage amount are the 0.06% of Pfansteihl oligomerization amount of substance, reaction time 5h, reaction pressure
Power 0.05 × 105Pa；Glycine hydroxy acid molybdenum the preparation method comprises the following steps: sodium molybdate and glycine hydroxy acid in methanol solution, at room temperature
It is mixed, reacts 3h, obtaining solid is glycine hydroxy acid molybdenum；Glycine hydroxy acid and sodium molybdate the mass ratio of the material 4:1, molybdic acid
Concentration of the sodium in methanol solution is 1mol/L.
The L- lactide of generation is 78.3% in condensation collecting tank crystallisation by cooling, L- lactide yield, and optical purity is
99.9%.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. utilizing the method for L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that poly- L- cream is added in L- lactide
Sour reaction kettle, the additional amount of catalyst are the 0.04-0.5% of L- lactide quality, and reaction temperature is 140 DEG C -170 DEG C, reaction
Time is 10-50h, reaction pressure≤10pa.
2. the method according to claim 1 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that urge
Agent is the mixture that zirconium oxide and glycine hydroxy acid molybdenum are formed according to 1.5-2.5:1.
3. the method according to claim 2 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that sweet
Propylhomoserin hydroxy acid molybdenum the preparation method is as follows: sodium molybdate and glycine hydroxy acid are mixed at room temperature in methanol solution, react 2-
3h, obtaining solid is glycine hydroxy acid molybdenum；Acthiol-J and sodium molybdate the mass ratio of the material 4:1, sodium molybdate are molten in methanol
Concentration in liquid is 0.1-2mol/L.
4. the method according to claim 1 to 3 using L- lactide ring-opening polymerisation production poly (l-lactic acid), feature
It is, the additional amount of catalyst is the 0.1% of L- lactide quality, and reaction temperature is 160 DEG C, reaction time 20h.
5. the method according to claim 4 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that L-
Lactide the preparation method is as follows:
(1) raw material preparation: the optical purity of the Pfansteihl solution of 40-60wt%, Pfansteihl is greater than or equal to 99.5%；
(2) it is dehydrated oligomerization, obtains Pfansteihl oligomer；
(3) depolymerization of Pfansteihl oligomer prepares L- lactide.
6. the method according to claim 5 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that
In step (2), ethyl pyruvate is added into Pfansteihl solution, the volume ratio of ethyl pyruvate and Pfansteihl solution is 0.5-1:
1；Cobalt oxide and two-acthiol-J vanadyl are added into mixed solution simultaneously as catalyst, stirring；The use of cobalt oxide
Amount is the 0.02%-0.04% of Pfansteihl quality, and two-acthiol-J vanadyl usage amounts are the 0.04%- of Pfansteihl quality
0.08%；Reaction time is 3h-6h, and reaction temperature is 5-30 DEG C.
7. the method according to claim 6 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that
In step (2):
When initial reaction: the addition mass ratio of cobalt oxide and two-acthiol-J vanadyl is 1:1.5, and cobalt oxide is initial
Additional amount when reaction is the 1/2 of the total additional amount of cobalt oxide；Reaction temperature goes over half from initial reaction to the reaction time
It is always maintained at 5 DEG C -10 DEG C；
When reaction time goes over half: reaction kettle is all added in two-acthiol-J vanadyl of residue；Reaction temperature
Degree autoreaction time past half to the past in reaction time 3/4ths is always maintained at 15 DEG C -20 DEG C；
When past in reaction time 3/4ths: reaction kettle is all added in remaining cobalt oxide；The reaction temperature autoreaction time
Past 3/4ths terminates to be always maintained at 25-30 DEG C to reaction.
8. the method according to claim 7 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that
In step (2), two-acthiol-J vanadyl the preparation method comprises the following steps: acthiol-J and vanadic sulfate in boric acid solution,
It is mixed at room temperature, reacts 3-5h, obtain violet solid；Acthiol-J and vanadic sulfate the mass ratio of the material 5:1, half Guang
Concentration of the propylhomoserin methyl esters in boric acid solution is 0.1-5mol/L.
9. the method according to claim 8 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that
In step (2), after reaction, filtering, stratification isolates organic phase, washes organic phase；Organic after washing is subtracted each other
Solvent is distilled off in pressure, obtains white solid.
10. the method according to claim 5 using L- lactide ring-opening polymerisation production poly (l-lactic acid), which is characterized in that
In step (3), the investment lactide of Pfansteihl oligomer obtained in step (2) is prepared into kettle, 145-160 DEG C is warming up to, makes
The fusing of Pfansteihl oligomer；Synthesize the mixture that catalyst used in L- lactide is nickel oxide and glycine hydroxy acid molybdenum, oxygen
Change the 0.01%-0.03% that nickel usage amount is Pfansteihl oligomerization amount of substance, glycine hydroxy acid molybdenum usage amount is Pfansteihl oligomer
The 0.03%-0.09% of quality, reaction time 3-5h, reaction pressure 0.01 × 105Pa-0.1×105Pa；
When initial reaction: the addition mass ratio of nickel oxide and glycine hydroxy acid molybdenum is 1:2, nickel oxide adding in initial reaction
Enter 1/3 that amount is the total additional amount of nickel oxide；
When reaction time goes over one third: lactide is all added in remaining nickel oxide and prepares kettle；
When past in reaction time 2/3rds: lactide is all added in remaining glycine hydroxy acid molybdenum and prepares kettle；
Glycine hydroxy acid molybdenum the preparation method comprises the following steps: sodium molybdate and glycine hydroxy acid are mixed, instead at room temperature in methanol solution
2-3h is answered, obtaining solid is glycine hydroxy acid molybdenum；Glycine hydroxy acid and sodium molybdate the mass ratio of the material 4:1, sodium molybdate is in methanol
Concentration in solution is 0.1-2mol/L；
Lactide prepares kettle top by heat-insulating pipeline and condensation collecting tank fluid communication, and the L- lactide of generation is collected in condensation
Tank crystallisation by cooling.
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