CN109265662A - The method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid - Google Patents
The method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid Download PDFInfo
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- CN109265662A CN109265662A CN201811123336.1A CN201811123336A CN109265662A CN 109265662 A CN109265662 A CN 109265662A CN 201811123336 A CN201811123336 A CN 201811123336A CN 109265662 A CN109265662 A CN 109265662A
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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
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- 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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- 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
- C08G63/80—Solid-state polycondensation
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Abstract
The present invention discloses the method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, includes the following steps: that (1) prepares D-ALPHA-Hydroxypropionic acid oligomer using D-ALPHA-Hydroxypropionic acid；(2) D-ALPHA-Hydroxypropionic acid oligomer and melt polycondensation catalyst are added in melt polycondensation reaction kettle, carry out melt polycondensation and prepare the poly- D-ALPHA-Hydroxypropionic acid of low molecular weight, the additional amount of melt polycondensation catalyst is the 0.1-1% of D-ALPHA-Hydroxypropionic acid oligomerization amount of substance；(3) the poly- D-ALPHA-Hydroxypropionic acid of low molecular weight is added in solid state polycondensation kettle, carries out solid phase polycondensation and prepares high-molecular-weight poly D-ALPHA-Hydroxypropionic acid.The present invention has been worth the D-ALPHA-Hydroxypropionic acid oligomer that molecular weight distribution is relatively narrow using D-ALPHA-Hydroxypropionic acid monomer cheap and easy to get in actual industrial production as raw material, and reaction condition is mild and easily controllable, D-ALPHA-Hydroxypropionic acid oligomer high income, is suitable for industrialized production；It recycles D-ALPHA-Hydroxypropionic acid oligomer that poly- D-ALPHA-Hydroxypropionic acid is made through melt polycondensation and solid phase polycondensation, significantly reduces cost, promote product competitiveness.
Description
Technical field
The present invention relates to lactic acid deep process technology fields.It is contracted using D-ALPHA-Hydroxypropionic acid through oligomerization, melting more particularly, to a kind of
The method that poly- and solid phase polycondensation produces poly- D-ALPHA-Hydroxypropionic acid.
Background technique
Polylactic acid is a kind of function admirable, and the polymer with biocompatibility and biodegradability is mainly used for
It is degradable package material and medicine microsphere carrier, antiadhesion barrier, biological duct, orthopaedics fixture, bone surgery device, artificial
In terms of the medical materials such as bone.
By monomer lactic acid prepare polylactic acid during, be that lactic acid oligomer is generated by monomer lactic acid first, then again by
Lactic acid oligomer direct polycondensation prepares polylactic acid；Or by lactic acid oligomer prepare lactide then lactide ring-opening polymerisation generate it is poly-
Lactic acid.In the prior art using the higher cost of former approach preparation polylactic acid, enterprise profit is caused substantially to glide.And it uses
Later approach prepares polylactic acid, and since lactic acid monomer directly obtains the higher cost of the higher lactide of purity, such as China is special
A kind of preparation method of lactic acid oligomer disclosed in sharp document CN1498237A 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 lactic acid oligosaccharide mixture is prepared by lactide；
(2) the tetrahydrofuran equal solvent used is toxic, is not suitable for industrial applications.
Summary of the invention
It is an object of the present invention to provide a kind of produced using D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation to gather
The method of D-ALPHA-Hydroxypropionic acid reduces cost, promotes enterprise profit.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
The method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, includes the following steps:
(1) D-ALPHA-Hydroxypropionic acid oligomer is prepared using D-ALPHA-Hydroxypropionic acid；
(2) D-ALPHA-Hydroxypropionic acid oligomer and melt polycondensation catalyst are added in melt polycondensation reaction kettle, carry out melt polycondensation
The poly- D-ALPHA-Hydroxypropionic acid of low molecular weight is prepared, the additional amount of melt polycondensation catalyst is the 0.1-1% of D-ALPHA-Hydroxypropionic acid oligomerization amount of substance；
(3) the poly- D-ALPHA-Hydroxypropionic acid of low molecular weight is added in solid state polycondensation kettle, carries out solid phase polycondensation and prepares high molecular weight
Poly- D-ALPHA-Hydroxypropionic acid.
The above-mentioned method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, the melting contracting
Poly- catalyst is to be uniformly mixed to be made or by component A, component B and chlorophyll according to mass ratio 1:2-5 by component A and component B
Copper is uniformly mixed according to mass ratio 1:2-5:0.1-0.5 and is made；
Component A's the preparation method is as follows: diacetyl tartaric acid monodiglyceride is added in 50-60 DEG C of water, double second
The mass ratio of acyl tartaric acid list double glyceride and water is 1-5:100, stirs 5-30 minutes, Mn (H is then added2P04)2, Mn
(H2P04)2Be 5-10:100 with the mass ratio of water, 50-60 DEG C stirring 2-3 hours, then heat to 80-100 DEG C and be evaporated, obtain group
Divide A；
Component B's the preparation method is as follows: by N- [N- (3,3- dimethylbutyl)-D- α-aspartoyl]-D- phenylpropyl alcohol ammonia
Acid -1- methyl esters is added in 20-30 DEG C of water, N- [N- (3,3- dimethylbutyl)-D- α-aspartoyl]-D- phenylpropyl alcohol ammonia
The mass ratio of acid -1- methyl esters and water is 5-12:1000, is stirred 5-30 minutes；Then distannous citrate is added, citric acid is sub-
The mass ratio of tin disodium and water is 10-15:1000, is stirred 5-10 minutes；It is warming up to 80-100 DEG C to be evaporated, obtains component B.
The above-mentioned method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, melt polycondensation
Reaction pressure is 500-2000Pa, and reaction time 4-50h, reaction temperature is 150-200 DEG C, speed of agitator 30-100rmp.
The above-mentioned method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, in solid phase polycondensation
Pre-crystallized to the progress of low molecular weight poly- D-ALPHA-Hydroxypropionic acid first, pre-crystallization temperature is 90-120 DEG C, and the pre-crystallized time is 1-5h；It is pre-crystallized
Reaction temperature when the poly- D-ALPHA-Hydroxypropionic acid of low molecular weight afterwards carries out solid phase polycondensation is 140-180 DEG C, reaction time 5-30h.
The above-mentioned method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, in step (1)
In, the method for preparing D-ALPHA-Hydroxypropionic acid oligomer using D-ALPHA-Hydroxypropionic acid is as follows:
(1-1) raw material preparation: the optical purity of the D-ALPHA-Hydroxypropionic acid solution of 35-60wt%, D-ALPHA-Hydroxypropionic acid is greater than or equal to 99.5%；
(1-2) is dehydrated oligomerization, obtains D-ALPHA-Hydroxypropionic acid oligomer.
The above-mentioned method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, in step (1-2)
In, it is added ethyl pyruvate into D-ALPHA-Hydroxypropionic acid solution, the volume ratio of ethyl pyruvate and D-ALPHA-Hydroxypropionic acid solution is 0.5-1:1；Simultaneously
Cobalt oxide and two-acthiol-J vanadyl are added into mixed solution as catalyst, stirring；The usage amount of cobalt oxide is D-
The 0.02%-0.04% of lactic acid quality, two-acthiol-J vanadyl usage amounts are the 0.04%-0.08% of D-ALPHA-Hydroxypropionic acid quality；
Reaction time is 3h-6h, and reaction temperature is 5-30 DEG C.
The above-mentioned method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, in step (1-2)
In:
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 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, in step (1-2)
In, two-acthiol-J vanadyl the preparation method comprises the following steps: acthiol-J and vanadic sulfate in boric acid solution, at room temperature
It is mixed, reacts 3-5h, obtain violet solid；Acthiol-J and vanadic sulfate the mass ratio of the material 5:1, cysteine first
Concentration of the ester in boric acid solution is 0.1-5mol/L.
The above-mentioned method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, in step (1-2)
In, after reaction, filtering, stratification isolates organic phase, washes organic phase；By the organic phase vacuum distillation after washing
Solvent is removed, obtaining white solid is oligomerization D-ALPHA-Hydroxypropionic acid.
Beneficial effects of the present invention are as follows:
Using D-ALPHA-Hydroxypropionic acid monomer cheap and easy to get in actual industrial production as raw material, the D- cream that molecular weight distribution is relatively narrow has been worth it
Sour oligomer, reaction condition is mild and easily controllable, D-ALPHA-Hydroxypropionic acid oligomer high income, is suitable for industrialized production；Recycle D- cream
Poly- D-ALPHA-Hydroxypropionic acid is made through melt polycondensation and solid phase polycondensation in sour oligomer, significantly reduces cost, promotes product competitiveness.
Detailed description of the invention
(abscissa adds for catalyst for influence of Fig. 1 a different catalysts dosage to the poly- D-ALPHA-Hydroxypropionic acid molecular weight of melt polycondensation process
Amount, ordinate are poly- D-ALPHA-Hydroxypropionic acid molecular weight MW×104)；
(abscissa adds for catalyst for influence of Fig. 1 b different catalysts dosage to the poly- D-ALPHA-Hydroxypropionic acid molecular weight of melt polycondensation process
Amount, ordinate are poly- D-ALPHA-Hydroxypropionic acid molecular weight MW×104)；
Fig. 2 reaction time melt polycondensation process is synthesized poly- D-ALPHA-Hydroxypropionic acid molecular weight influence (abscissa is the reaction time, indulge
Coordinate is poly- D-ALPHA-Hydroxypropionic acid molecular weight MW×104)；
(abscissa is reaction temperature, and ordinate is poly- D-ALPHA-Hydroxypropionic acid for influence of Fig. 3 a reaction temperature to poly- D-ALPHA-Hydroxypropionic acid molecular weight
Molecular weight MW×104)；
(abscissa is reaction temperature, and ordinate is poly- D-ALPHA-Hydroxypropionic acid point for influence of Fig. 3 b reaction temperature to poly- D-ALPHA-Hydroxypropionic acid yield
Son amount MW×104)；
(abscissa is speed of agitator, and ordinate is poly- D-ALPHA-Hydroxypropionic acid molecular weight for influence of Fig. 4 speed of agitator to molecular weight of product
MW×104)；
(abscissa is the pre-crystallized time, and ordinate is poly- for influence of Fig. 5 pre-crystallized time to solid phase polycondensation molecular weight of product
D-ALPHA-Hydroxypropionic acid molecular weight MW×105)；
(abscissa is pre-crystallization temperature, and ordinate is poly- for influence of Fig. 6 pre-crystallization temperature to solid phase polycondensation molecular weight of product
D-ALPHA-Hydroxypropionic acid molecular weight MW×105)；
(abscissa is reaction temperature, and ordinate is poly- D- cream for influence of Fig. 7 reaction temperature to solid phase polycondensation molecular weight of product
Acid molecule amount MW×105)；
(abscissa is the reaction time, and ordinate is poly- D- cream for influence of Fig. 8 reaction time to solid phase polycondensation molecular weight of product
Acid molecule amount 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 is produced the Study of operational conditions of poly- D-ALPHA-Hydroxypropionic acid by D-ALPHA-Hydroxypropionic acid oligomer through melt polycondensation and solid phase polycondensation
1 melt polycondensation-solid phase polycondensation produces high-molecular-weight poly D-ALPHA-Hydroxypropionic acid
1.1 melt polycondensation technology researchs
1.1.1 the influence for the poly- D-ALPHA-Hydroxypropionic acid molecular weight that catalyst amount generates melt polycondensation process
No catalyst, without decompression under conditions of, it is at a slow speed that D-ALPHA-Hydroxypropionic acid oligomer melt polycondensation, which generates poly- D-ALPHA-Hydroxypropionic acid,
Reversible reaction, and catalyst can be such that reaction system carries out to the direction of poly- D-ALPHA-Hydroxypropionic acid, inhibit the generation of lactide.
The catalyst used is uniformly mixed according to mass ratio 1:2 by component A and component B and is made；The preparation method of component A is such as
Under: diacetyl tartaric acid monodiglyceride is added in 60 DEG C of water, the quality of diacetyl tartaric acid monodiglyceride and water
Than for 2:100, stirring 20 minutes, Mn (H is then added2P04)2, Mn (H2P04)2Mass ratio with water is 5:100, and 50-60 DEG C is stirred
It mixes 3 hours, then heats to 80 DEG C and be evaporated, obtain component A；Component B's the preparation method is as follows: by N- [N- (3,3- dimethyl butyrate
Base)-D- α-aspartoyl]-D-phenylalanine -1- methyl esters is added in 20 DEG C of water, N- [N- (3,3- dimethylbutyl) -
D- α-aspartoyl] mass ratio of-D-phenylalanine -1- methyl esters and water is 5:1000, it stirs 10 minutes；Then lemon is added
Acid is Distannous, and the mass ratio of distannous citrate and water is 15:1000, stirs 5 minutes；It is warming up to 90 DEG C to be evaporated, obtains group
Divide B.In the identical situation of other conditions, assay optimization different catalysts dosage synthesizes D-ALPHA-Hydroxypropionic acid oligomer melt polycondensation poly-
The influence of D-ALPHA-Hydroxypropionic acid molecular weight (weight average molecular weight Mw), the result is shown in Figure 1 a.
The catalyst used is uniformly mixed according to mass ratio 1:2:0.2 by component A, component B and copper chlorophyll and is made, at it
In the identical situation of its condition, assay optimization different catalysts dosage synthesizes poly- D-ALPHA-Hydroxypropionic acid point to D-ALPHA-Hydroxypropionic acid oligomer melt polycondensation
The influence of son amount (weight average molecular weight Mw), the result is shown in Figure 1 b.
As can be seen from figs. 1a and 1b increase of the weight average molecular weight of the poly- D-ALPHA-Hydroxypropionic acid of melt polycondensation process with catalyst amount
First increase and reduce again, catalyst amount excessively causes the degradation rate of poly- D-ALPHA-Hydroxypropionic acid in reaction system to be greater than poly- D-ALPHA-Hydroxypropionic acid generation speed
Rate promotes the reaction of side reaction, when catalyst amount accounts for D-ALPHA-Hydroxypropionic acid oligomer mass fraction greater than 0.35%, poly- D-ALPHA-Hydroxypropionic acid
Molecular weight increases gently, and when catalyst amount accounts for D-ALPHA-Hydroxypropionic acid oligomer mass fraction greater than 0.5%, poly- D-ALPHA-Hydroxypropionic acid molecular weight starts
It reduces.Comprehensively consider productivity effect and poly- D-ALPHA-Hydroxypropionic acid molecular weight, selection is by component A, component B and copper chlorophyll according to mass ratio 1:
2:0.2 is uniformly mixed catalyst obtained, and it is optimum amount that dosage, which accounts for when D-ALPHA-Hydroxypropionic acid oligomer mass fraction is 0.35%,.
1.1.2 influence of the vacuum degree to polymerization reaction
Since the polycondensation reaction of D-ALPHA-Hydroxypropionic acid oligomer is a thermodynamical equilibrium process, need to make using the methods of decompression
React mobile to direction of polymerization.During melt polycondensation, the control of reaction pressure is to influence polymer molecular weight growth and pair
The deciding factor of resulting lactide production quantity, the control of optimum response pressure should make balance mobile to positive reaction direction, and energy
Prevent excessive lactide from generating.Influence of the reaction pressure to the poly- D-ALPHA-Hydroxypropionic acid yield of melt polycondensation process is tested, the results are shown in Table 1.
Influence of 1 reaction pressure of table to poly- D-ALPHA-Hydroxypropionic acid yield
As shown in Table 1, when reaction pressure 1600pa, the poly- D-ALPHA-Hydroxypropionic acid yield of melt polycondensation reaction is maximum, comprehensive benefit highest,
Reaction pressure is selected to be optimal parameter when 1600Pa.
1.1.3 the reaction time generates the influence of poly- D-ALPHA-Hydroxypropionic acid molecular weight to melt polycondensation reaction
In the identical situation of other conditions, the test reaction time generates poly- D-ALPHA-Hydroxypropionic acid molecular weight to melt polycondensation reaction
It influences, as a result sees Fig. 2.
As shown in Figure 2, in 0-20h, with the extension of reaction time, poly- D-ALPHA-Hydroxypropionic acid molecular weight is gradually increased, after 8h,
It increases speed slack-off.And the reaction time is continued growing after 20h, reaction system viscosity increases, and small molecule water discharge is difficult, makes to drop
It solves rate and is greater than poly- D-ALPHA-Hydroxypropionic acid synthesis rate, keep reaction mobile to lactide direction, poly- D-ALPHA-Hydroxypropionic acid molecular weight reduces.Comprehensive examination
Production efficiency selects reaction time 8h, 10h, 12h to carry out orthogonal test.
1.1.4 reaction temperature generates the influence of poly- D-ALPHA-Hydroxypropionic acid molecular weight and yield to melt polycondensation reaction
In the identical situation of other conditions, the test reaction time to melt polycondensation reaction generate poly- D-ALPHA-Hydroxypropionic acid molecular weight and
As a result Fig. 3 a and 3b are shown in the influence of yield.
By Fig. 3 a and 3b it is found that when temperature is lower than 190 DEG C, the molecular weight of the poly- D-ALPHA-Hydroxypropionic acid of product increases as temperature increases
Greatly, when being greater than 190 DEG C, since temperature is excessively high, the rate that poly- D-ALPHA-Hydroxypropionic acid depolymerization generates lactide and hydrolysis is accelerated, is caused
Poly- D-ALPHA-Hydroxypropionic acid molecular weight slowly reduces.When temperature is greater than 180 DEG C, poly- D-ALPHA-Hydroxypropionic acid yield is reduced rapidly.Comprehensive production efficiency is selected
170 DEG C of reaction temperature, 180 DEG C, 190 DEG C of progress orthogonal tests.
1.1.5 speed of agitator generates the influence of poly- D-ALPHA-Hydroxypropionic acid molecular weight to melt polycondensation reaction
In the identical situation of the conditions such as reaction time, pressure, temperature, test speed of agitator generates melt polycondensation reaction
The influence of poly- D-ALPHA-Hydroxypropionic acid molecular weight, is as a result shown in Fig. 4.
As shown in Figure 4, when mixing speed is less than 60rpm, within the same reaction time, the molecular weight of poly- D-ALPHA-Hydroxypropionic acid with
The increase of revolving speed increases, this is because stirring makes in kettle, each portion's temperature is uniform, accelerates the progress of reaction.And when mixing speed is big
When 60rpm, mixing speed is too fast, and poly- D-ALPHA-Hydroxypropionic acid molecular weight is caused to reduce.Comprehensive production efficiency, selection 50rpm, 60rpm,
Tri- speed of 70rpm do orthogonal test.
1.1.6 the Combination Design of melt polycondensation technic index
Using catalyst dosage, reaction pressure as melt polycondensation control constant, with reaction time, reaction temperature, speed of agitator
For independent variable, the poly- D-ALPHA-Hydroxypropionic acid molecular weight MW of product is that dependent variable is analyzed.
Test result and its significance test:
In experiment, we determined that influencing three principal elements of melt polycondensation technique, and pass through many experiments, it is determined that
Three levels of three factors devise 3 factor, 3 level according to the center combination design principle of Box-Behnken, real such as table 2
It tests and the results are shown in Table 3.
2 Three factors-levels table of table
3 Box-Behnken experimental result of table
Regression fit and mould are carried out to 3 test data of table by successive Regression using Design expert statistical software
Type carries out variance analysis, and influence of each influence factor to the poly- D-ALPHA-Hydroxypropionic acid molecular weight of product is not simple linear relationship.According to sound
Answer surface chart and contour plots analysis, it is determined that the Best Point of three factors selects starting point in model scope, uses according to model
Fast-rise approach optimizes, obtained when finally determining A10h, B180 DEG C, C60rpm maximum poly- D-ALPHA-Hydroxypropionic acid molecular weight 4.0 ×
104。
It is final to survey using proportioning test 10 times of optimization for the reliability for examining Box-Behnken experimental design result
The average value for the poly- D-ALPHA-Hydroxypropionic acid molecular weight that must be extracted is 3.9 × 104.Therefore the resulting technique ginseng of Box-Behnken experimental design
Number reaction time, reaction temperature, speed of agitator are accurate and reliable, have practical value, are optimal processing parameter.
The optimization technique for producing poly- D-ALPHA-Hydroxypropionic acid by testing to obtain a melt polycondensation above: i.e. catalyst loading accounts for D-
The 0.35% of lactic acid oligomer quality, reaction pressure 1600Pa, reaction time 10h, 180 DEG C of reaction temperature, speed of agitator
60rpm。
1.2 solid phase polycondensation process technical research
Since the poly- D-ALPHA-Hydroxypropionic acid molecular weight that melt polycondensation generates is relatively low, on the basis of melt polycondensation, increase
The poly- D-ALPHA-Hydroxypropionic acid of higher molecular weight can be made in solid phase polycondensation process.Since conventional solid polycondensation reaction time is longer, the present invention is adopted
With pre-crystallized method, shorten the distribution of melt polycondensation molecular weight of product, to improve production efficiency.
1.2.1 influence of the pre-crystallized time to solid phase polycondensation molecular weight of product
Under solid phase polycondensation and the identical situation of other conditions, the test different pre-crystallized times are to the poly- D-ALPHA-Hydroxypropionic acid of final product
The influence of molecular weight, is as a result shown in Fig. 5.
As shown in Figure 5, with the increase of pre-crystallized time, under the same terms, the molecule of the poly- D-ALPHA-Hydroxypropionic acid of solid phase polycondensation product
Amount gradually increases, and when the pre-crystallized time being greater than 2h, molecule increase is slower, illustrates that the crystallization degree of melt polycondensation product has become
To perfect, formation efficiency is considered, selecting pre-crystallized time 2h is optimal parameter.
1.2.2 influence of the pre-crystallization temperature to prepolymer molecular weight
In the identical situation of other conditions, test pre-crystallization temperature generates poly- D-ALPHA-Hydroxypropionic acid molecular weight to solid state polycondensation
Influence, as a result see Fig. 6.
It will be appreciated from fig. 6 that within the scope of 90-120 DEG C, with the raising of pre-crystallization temperature, the poly- D-ALPHA-Hydroxypropionic acid of solid phase polycondensation product
Molecular weight be in increase trend, be the raising due to temperature, promote the growth of crystal, be conducive to the progress of polycondensation reaction.When
When temperature is greater than 105 DEG C, poly- D-ALPHA-Hydroxypropionic acid molecular weight increase is less, is since in this temperature range, reactant bonding is agglomerating, unfavorable
In the raising of molecular weight, this is also to lead to conventional solid polycondensation time long reason.Therefore, comprehensively consider production efficiency, select 105
DEG C be best pre-crystallization temperature.
1.2.3 influence of the reaction temperature to solid phase polycondensation molecular weight of product
Prepolymer after pre-crystallized improves rapidly suitable temperature, can keep the growth of the poly- D-ALPHA-Hydroxypropionic acid molecular weight of product
Trend, to reduce the solid phase polycondensation time.Influence of the differential responses temperature to solid phase polycondensation molecular weight of product is tested, as a result sees figure
7。
As shown in Figure 7, the poly- D-ALPHA-Hydroxypropionic acid of product is reduced afterwards as the increase of reaction temperature first increases, and is due to reaction temperature
The increase of degree, terminal groups segment activity increase, and are conducive to solid phase reaction progress, but excessively high temperature, drop poly- D-ALPHA-Hydroxypropionic acid
Solution reaction and pellet melting bonding, cause poly- D-ALPHA-Hydroxypropionic acid molecular weight to reduce.Comprehensively consider, select 155 DEG C it is best for solid phase polycondensation
Reaction temperature.
1.2.4 influence of the reaction time to solid phase polycondensation molecular weight of product
155 DEG C of reaction temperature, in the case that other conditions are all the same, test reaction temperature D- cream poly- to solid phase polycondensation product
The influence of acid molecule amount, is as a result shown in Fig. 8.
As shown in Figure 8, with the increase in reaction time, poly- D-ALPHA-Hydroxypropionic acid molecular weight is gradually increased, and is greater than in the reaction time
When 15h, the thermal degradation reaction of poly- D-ALPHA-Hydroxypropionic acid is begun to ramp up, and molecular weight increases slow.When considering reaction time 15h, products therefrom
Molecular weight can meet application requirement, and in conjunction with production efficiency, selecting solid state polycondensation time 15h is optimal processing parameter.
2 poly- D-ALPHA-Hydroxypropionic acids synthesize main control parameters
By the selection Optimum Experiment of each technic index of pilot scale it is found that the main control parameters such as table 4 that poly- D-ALPHA-Hydroxypropionic acid synthesizes.
4 main technique control parameter list of table
3 pilot product results
The test result of continuous 10 batch of pilot plant test is shown in Table 5.
5 pilot plant test continuous operation result of table
It can be seen that the molecular weight, fusing point, heat point of the poly- D-ALPHA-Hydroxypropionic acid of product from the pilot plant test result of 10 batch of continuous operation
The items important indicator such as solution point, crystallinity is stablized, reliable in quality.Trial production it was verified that this technology has raw high income, matter
The features such as measuring, is at low cost has the condition of type approval test completely.
4 pilot plant test results and the both at home and abroad comparison of similar advanced technology
The technical bottlenecks such as the thermal stability that the project breaches poly- D-ALPHA-Hydroxypropionic acid is poor, isotacticity and crystallinity are low, improve me
The poly- D-ALPHA-Hydroxypropionic acid integrated artistic technical level of state.Its key technical indexes and the comparison of domestic and international advanced technology index are shown in Table 6.
6 Project Technical product of table and domestic and international advanced technology compare
Note: foreign countries are U.S. Nature Works product technology, and the country is certain Products technology.
5. cost analysis
According to completed pilot plant test, we carry out Biodegradable high-molecular new material key technology production cost
Analysis, is shown in Table 7:
The direct material consumption cost accounting < of table 7 calculates > by 1 ton of poly- D-ALPHA-Hydroxypropionic acid product
| Serial number | Product and material name | Unit consumption | Monovalent (member) | Cost (member) |
| 1 | 90% common D-ALPHA-Hydroxypropionic acid (/T) | 1.53 | 6090 | 9317.70 |
| 2 | Catalyst (/kg) | 5.94 | 91.8 | 547.08 |
| 3 | Steam (/T) | 3.2 | 130 | 416.00 |
| 4 | Water (/T) | 6 | 4 | 24.00 |
| 5 | Electric (/Kwh) | 650 | 0.5 | 325.00 |
| 6 | Packaging | 470.00 | ||
| It is total | 11099.78 |
From pilot scale material consumption Cost comparisons analysis as can be seen that 11100 yuan of the direct material consumption cost of project, raw material use common D-
Lactic acid, compared with 7998 yuan/ton of cost of market polymer grade D-ALPHA-Hydroxypropionic acid material consumption, only material consumption cost can reduce by 3100 yuan to raw material per ton.
Project industrialization is expected to produce 10000 tons of poly- D-ALPHA-Hydroxypropionic acid production scales per year, can increase newly in year 175000000 yuan of income from sales (when
19000 yuan -25000 yuan/ton of preceding similar product market price), increase 41,480,000 yuan of profits tax newly.The poly- D-ALPHA-Hydroxypropionic acid product of production is meeting
While domestic market demand, multiple countries and regions in the world can be also exported to, it is contemplated that product can occupy 40% or more the country
The market share, occupy the market share in 8% or more the world.
Second part prepares the technical study of D-ALPHA-Hydroxypropionic acid oligomer using D-ALPHA-Hydroxypropionic acid monomer
Embodiment 1
A method of D-ALPHA-Hydroxypropionic acid oligomer being prepared using D-ALPHA-Hydroxypropionic acid monomer, is included the following steps:
(1) raw material preparation: the D-ALPHA-Hydroxypropionic acid solution of the 40wt% of applicant's production, the optical purity of D-ALPHA-Hydroxypropionic acid are greater than or equal to
99.5%；
(2) it is dehydrated oligomerization, obtains D-ALPHA-Hydroxypropionic acid oligomer；
Mixed solution, ethyl pyruvate and D-ALPHA-Hydroxypropionic acid solution are obtained after ethyl pyruvate stirring is added into D-ALPHA-Hydroxypropionic acid 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 D-ALPHA-Hydroxypropionic acid quality, and two-acthiol-J vanadyl usage amounts are D-ALPHA-Hydroxypropionic acid
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 D-ALPHA-Hydroxypropionic acid oligomer of 6-21 aggressiveness, the yield of D-ALPHA-Hydroxypropionic acid oligomer is 96%.
Embodiment 2
A method of D-ALPHA-Hydroxypropionic acid oligomer being prepared using D-ALPHA-Hydroxypropionic acid monomer, is included the following steps:
(1) raw material preparation: the D-ALPHA-Hydroxypropionic acid solution of the 60wt% of applicant's production, the optical purity of D-ALPHA-Hydroxypropionic acid are greater than or equal to
99.5%；
(2) it is dehydrated oligomerization, obtains D-ALPHA-Hydroxypropionic acid oligomer；
Mixed solution, ethyl pyruvate and D-ALPHA-Hydroxypropionic acid solution are obtained after ethyl pyruvate stirring is added into D-ALPHA-Hydroxypropionic acid 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 D-ALPHA-Hydroxypropionic acid quality, and two-acthiol-J vanadyl usage amounts are the 0.08% of D-ALPHA-Hydroxypropionic acid 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
D-ALPHA-Hydroxypropionic acid oligomer containing 6-19 aggressiveness, also the D-ALPHA-Hydroxypropionic acid oligomer containing 25-46 aggressiveness；The yield of D-ALPHA-Hydroxypropionic acid oligomer
It is 78%.
Embodiment 3
A method of D-ALPHA-Hydroxypropionic acid oligomer being prepared using D-ALPHA-Hydroxypropionic acid monomer, is included the following steps:
(1) raw material preparation: the D-ALPHA-Hydroxypropionic acid solution of the 50wt% of applicant's production, the optical purity of D-ALPHA-Hydroxypropionic acid are greater than or equal to
99.5%；
(2) it is dehydrated oligomerization, obtains D-ALPHA-Hydroxypropionic acid oligomer；
Mixed solution, ethyl pyruvate and D-ALPHA-Hydroxypropionic acid solution are obtained after ethyl pyruvate stirring is added into D-ALPHA-Hydroxypropionic acid 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 D-ALPHA-Hydroxypropionic acid quality, and two-acthiol-J vanadyl usage amounts are D-ALPHA-Hydroxypropionic acid
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 D-ALPHA-Hydroxypropionic acid oligomer of 6-38 aggressiveness, the yield of D-ALPHA-Hydroxypropionic acid oligomer is 85%.
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 (9)
1. the method for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid, which is characterized in that including such as
Lower step:
(1) D-ALPHA-Hydroxypropionic acid oligomer is prepared using D-ALPHA-Hydroxypropionic acid；
(2) D-ALPHA-Hydroxypropionic acid oligomer and melt polycondensation catalyst are added in melt polycondensation reaction kettle, carry out melt polycondensation preparation
The poly- D-ALPHA-Hydroxypropionic acid of low molecular weight, the additional amount of melt polycondensation catalyst are the 0.1-1% of D-ALPHA-Hydroxypropionic acid oligomerization amount of substance；
(3) the poly- D-ALPHA-Hydroxypropionic acid of low molecular weight is added in solid state polycondensation kettle, carries out solid phase polycondensation and prepares high-molecular-weight poly D-
Lactic acid.
2. the side according to claim 1 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, which is characterized in that the melt polycondensation catalyst be by component A and component B according to mass ratio 1:2-5 be uniformly mixed be made or
Person is uniformly mixed according to mass ratio 1:2-5:0.1-0.5 by component A, component B and copper chlorophyll and is made；
Component A's the preparation method is as follows: diacetyl tartaric acid monodiglyceride is added in 50-60 DEG C of water, biacetyl wine
The mass ratio of the single double glyceride of stone acid and water is 1-5:100, stirs 5-30 minutes, Mn (H is then added2P04)2, Mn (H2P04)2
Be 5-10:100 with the mass ratio of water, 50-60 DEG C stirring 2-3 hours, then heat to 80-100 DEG C and be evaporated, obtain component A；
Component B's the preparation method is as follows: by N- [N- (3,3- dimethylbutyl)-D- α-aspartoyl]-D-phenylalanine -1-
Methyl esters is added in 20-30 DEG C of water, N- [N- (3,3- dimethylbutyl)-D- α-aspartoyl]-D-phenylalanine -1- first
The mass ratio of ester and water is 5-12:1000, is stirred 5-30 minutes；Then distannous citrate, distannous citrate is added
Mass ratio with water is 10-15:1000, is stirred 5-10 minutes；It is warming up to 80-100 DEG C to be evaporated, obtains component B.
3. the side according to claim 1 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, which is characterized in that the reaction pressure of melt polycondensation is 500-2000Pa, reaction time 4-50h, reaction temperature 150-
200 DEG C, speed of agitator 30-100rmp.
4. the side according to claim 1 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, which is characterized in that pre-crystallized, pre-crystallization temperature 90-120 is carried out to the poly- D-ALPHA-Hydroxypropionic acid of low molecular weight first in solid phase polycondensation
DEG C, the pre-crystallized time is 1-5h；Reaction temperature when the poly- D-ALPHA-Hydroxypropionic acid of low molecular weight after pre-crystallized carries out solid phase polycondensation is 140-
180 DEG C, reaction time 5-30h.
5. the side according to claim 1 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, which is characterized in that in step (1), the method for preparing D-ALPHA-Hydroxypropionic acid oligomer using D-ALPHA-Hydroxypropionic acid is as follows:
(1) raw material preparation: the optical purity of the D-ALPHA-Hydroxypropionic acid solution of 35-60wt%, D-ALPHA-Hydroxypropionic acid is greater than or equal to 99.5%；
(2) it is dehydrated oligomerization, obtains D-ALPHA-Hydroxypropionic acid oligomer.
6. the side according to claim 5 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, which is characterized in that in step (2), ethyl pyruvate, ethyl pyruvate and D-ALPHA-Hydroxypropionic acid solution are added into D-ALPHA-Hydroxypropionic acid solution
Volume ratio be 0.5-1:1；Cobalt oxide and two-acthiol-J vanadyl are added into mixed solution simultaneously as catalyst,
Stirring；The usage amount of cobalt oxide is the 0.02%-0.04% of D-ALPHA-Hydroxypropionic acid quality, and two-acthiol-J vanadyl usage amounts are D-
The 0.04%-0.08% of lactic acid quality；Reaction time is 3h-6h, and reaction temperature is 5-30 DEG C.
7. the side according to claim 6 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, 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 side according to claim 7 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, which is characterized in that in step (2), two-acthiol-J vanadyl the preparation method comprises the following steps: acthiol-J and sulfuric acid
Vanadyl is mixed at room temperature in boric acid solution, 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 are 0.1-5mol/L.
9. the side according to claim 8 for producing poly- D-ALPHA-Hydroxypropionic acid through oligomerization, melt polycondensation and solid phase polycondensation using D-ALPHA-Hydroxypropionic acid
Method, which is characterized in that in step (2), after reaction, filtering, stratification isolates organic phase, washes organic phase；It will
Organic phase vacuum distillation after washing removes solvent, and obtaining white solid is oligomerization D-ALPHA-Hydroxypropionic acid.
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