CN109180914A - Method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid) - Google Patents
Method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid) Download PDFInfo
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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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- 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
- C08G63/80—Solid-state polycondensation
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Abstract
The present invention discloses the method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid), includes the following steps: that (1) prepares Pfansteihl oligomer using Pfansteihl；(2) Pfansteihl oligomer and melt polycondensation catalyst are added in melt polycondensation reaction kettle, carry out melt polycondensation and prepare low molecular weight poly (l-lactic acid), the additional amount of melt polycondensation catalyst is the 0.1-1% of Pfansteihl oligomerization amount of substance；(3) low molecular weight poly (l-lactic acid) is added in solid state polycondensation kettle, carries out solid phase polycondensation and prepares high molecular weight poly (l-lactic acid).The present invention has been worth the Pfansteihl oligomer that molecular weight distribution is relatively narrow using Pfansteihl monomer cheap and easy to get in actual industrial production as raw material, and reaction condition is mild and easily controllable, Pfansteihl oligomer high income, is suitable for industrialized production；It recycles Pfansteihl oligomer that poly (l-lactic 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 Pfansteihl through oligomerization, melting more particularly, to a kind of
The method of poly- and solid phase polycondensation production poly (l-lactic 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 Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation to gather
The method of Pfansteihl reduces cost, promotes enterprise profit.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
Method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid), includes the following steps:
(1) Pfansteihl oligomer is prepared using Pfansteihl；
(2) Pfansteihl oligomer and melt polycondensation catalyst are added in melt polycondensation reaction kettle, carry out melt polycondensation
Low molecular weight poly (l-lactic acid) is prepared, the additional amount of melt polycondensation catalyst is the 0.1-1% of Pfansteihl oligomerization amount of substance；
(3) low molecular weight poly (l-lactic acid) is added in solid state polycondensation kettle, carries out solid phase polycondensation and prepares high molecular weight
Poly (l-lactic acid).
The above-mentioned method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid), the melting contracting
Poly- catalyst is to be uniformly mixed to be made according to mass ratio 1:2-5 by component A and component B；
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)-L- α-aspartoyl]-L- phenylpropyl alcohol ammonia
Acid -1- methyl esters is added in 20-30 DEG C of water, N- [N- (3,3- dimethylbutyl)-L- α-aspartoyl]-L- 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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic 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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid), in solid phase polycondensation
Pre-crystallized to the progress of low molecular weight poly (l-lactic 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 low molecular weight poly (l-lactic acid) afterwards carries out solid phase polycondensation is 140-180 DEG C, reaction time 5-30h.
The above-mentioned method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid), in step (1)
In, the method for preparing Pfansteihl oligomer using Pfansteihl is as follows:
(1-1) raw material preparation: the optical purity of the Pfansteihl solution of 40-60wt%, Pfansteihl is greater than or equal to 99.5%；
(1-2) is dehydrated oligomerization, obtains Pfansteihl oligomer.
The above-mentioned method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid), in step (1-2)
In, it is added ethyl pyruvate into Pfansteihl solution, the volume ratio of ethyl pyruvate and Pfansteihl 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 L-
The 0.02%-0.04% of lactic acid quality, two-acthiol-J vanadyl usage amounts are the 0.04%-0.08% of Pfansteihl quality；
Reaction time is 3h-6h, and reaction temperature is 5-30 DEG C.
The above-mentioned method using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic 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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic 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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic 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 Pfansteihl oligomer.
Beneficial effects of the present invention are as follows:
Using Pfansteihl monomer cheap and easy to get in actual industrial production as raw material, the L- cream that molecular weight distribution is relatively narrow has been worth it
Sour oligomer, reaction condition is mild and easily controllable, Pfansteihl oligomer high income, is suitable for industrialized production；Recycle L- cream
Poly (l-lactic acid) is made through melt polycondensation and solid phase polycondensation in sour oligomer, significantly reduces cost, promotes product competitiveness.
Detailed description of the invention
Influence of Fig. 1 different catalysts dosage to melt polycondensation process polylactic acid molecule amount；
Influence of Fig. 2 reaction time to melt polycondensation process synthesizing polylactic acid molecular weight；
Influence of Fig. 3 reaction temperature to polylactic acid molecule amount and yield；
Influence of Fig. 4 speed of agitator to molecular weight of product；
Influence of Fig. 5 pre-crystallized time to solid phase polycondensation molecular weight of product；
Influence of Fig. 6 pre-crystallization temperature to solid phase polycondensation molecular weight of product；
Influence of Fig. 7 reaction temperature to solid phase polycondensation molecular weight of product；
Influence of Fig. 8 reaction time to solid phase polycondensation molecular weight of product.
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.
Study of operational conditions of the first part by Pfansteihl oligomer through melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
1 melt polycondensation-solid phase polycondensation produces high molecular weight poly (l-lactic acid)
1.1 melt polycondensation technology researchs
1.1.1 the influence for the poly (l-lactic acid) molecular weight that catalyst amount generates melt polycondensation process
No catalyst, without decompression under conditions of, Pfansteihl oligomer melt polycondensation generate poly (l-lactic acid) be at a slow speed
Reversible reaction, and catalyst can be such that reaction system carries out to the direction of poly (l-lactic acid), inhibit the generation of lactide.
Catalyst used in the present embodiment is uniformly mixed according to mass ratio 1:2 by component A and component B and is made；Component A's
The preparation method is as follows: diacetyl tartaric acid monodiglyceride is added in 60 DEG C of water, diacetyl tartaric acid monodiglyceride
Mass ratio with water is 2:100, stirs 20 minutes, Mn (H is then added2P04)2, Mn (H2P04)2Mass ratio with water is 5:
100,50-60 DEG C are stirred 3 hours, are then heated to 80 DEG C and are evaporated, obtain component A；Component B's the preparation method is as follows: by N- [N-
(3,3- dimethylbutyl)-L- α-aspartoyl]-L-phenylalanine -1- methyl esters is added in 20 DEG C of water, N- [N- (3,3-
Dimethylbutyl)-L- α-aspartoyl] mass ratio of-L-phenylalanine -1- methyl esters and water is 5:1000, it stirs 10 minutes；
Then it is added distannous citrate, the mass ratio of distannous citrate and water is 15:1000, is stirred 5 minutes；It is warming up to 90
It DEG C is evaporated, obtains component B.
In the identical situation of other conditions, assay optimization different catalysts dosage is to Pfansteihl oligomer melt polycondensation
At the influence of poly (l-lactic acid) molecular weight (weight average molecular weight Mw), the result is shown in Figure 1.
As shown in Figure 1, the weight average molecular weight of melt polycondensation process poly (l-lactic acid) first increases with the increase of catalyst amount
It reduces again, catalyst amount excessively causes the degradation rate of poly (l-lactic acid) in reaction system to be greater than poly (l-lactic acid) generating rate, promotees
Into the reaction of side reaction, when catalyst amount accounts for Pfansteihl oligomer mass fraction greater than 0.35%, the molecule of poly (l-lactic acid)
Amount increases gently, and when catalyst amount accounts for Pfansteihl oligomer mass fraction greater than 0.5%, poly (l-lactic acid) molecular weight starts to subtract
It is few.Comprehensively consider productivity effect, it is optimum amount that selecting catalyst dosage, which accounts for when Pfansteihl oligomer mass fraction is 0.35%,.
1.1.2 influence of the vacuum degree to polymerization reaction
Since the polycondensation reaction of Pfansteihl 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 melt polycondensation process poly (l-lactic acid) yield is tested, the results are shown in Table 1.
Influence of 1 reaction pressure of table to poly (l-lactic acid) yield
As shown in Table 1, when reaction pressure 1600pa, melt polycondensation reaction poly (l-lactic acid) yield 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 (l-lactic acid) molecular weight to melt polycondensation reaction
In the identical situation of other conditions, the test reaction time generates poly (l-lactic 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 (l-lactic 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 (l-lactic acid) synthesis rate, keep reaction mobile to lactide direction, poly (l-lactic 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 (l-lactic acid) molecular weight and yield to melt polycondensation reaction
In the identical situation of other conditions, test the reaction time to melt polycondensation reaction generate poly (l-lactic acid) molecular weight and
The influence of yield, is as a result shown in Fig. 3.
From the figure 3, it may be seen that the molecular weight of product poly (l-lactic acid) increases as temperature increases when temperature is lower than 190 DEG C, it is greater than
At 190 DEG C, since temperature is excessively high, the rate that poly (l-lactic acid) depolymerization generates lactide and hydrolysis is accelerated, causes poly- L- cream
Acid molecule amount slowly reduces.When temperature is greater than 180 DEG C, poly (l-lactic acid) yield is reduced rapidly.Comprehensive production efficiency selects reaction temperature
Spend 170 DEG C, 180 DEG C, 190 DEG C of progress orthogonal tests.
1.1.5 speed of agitator generates the influence of poly (l-lactic 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 (l-lactic 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 (l-lactic 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, causes the reduction of poly (l-lactic acid) molecular weight.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, product poly (l-lactic acid) molecular weight MW 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 product poly (l-lactic acid) molecular weight 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 (l-lactic acid) molecular weight 3.9 ×
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 (l-lactic acid) molecular weight that must be extracted is 3.8 × 104, compared with theoretical expectation values, relative error is less than 2.5%.
Therefore Box-Behnken experimental design resulting technological parameter reaction time, reaction temperature, speed of agitator are accurate and reliable, have
Practical value is optimal processing parameter.
By testing to obtain the optimization technique of a melt polycondensation production poly (l-lactic acid) above: i.e. catalyst loading accounts for cream
The 0.35% of sour 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 (l-lactic acid) molecular weight that melt polycondensation generates is relatively low, on the basis of melt polycondensation, increase
The poly (l-lactic 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 final product poly (l-lactic acid)
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 solid phase polycondensation product poly (l-lactic acid)
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 (l-lactic 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, solid phase polycondensation product poly (l-lactic acid)
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, the increase of poly (l-lactic acid) molecular weight 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 product poly (l-lactic acid) molecular weight
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, product poly (l-lactic acid) 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 (l-lactic acid)
Solution reaction and pellet melting bonding, lead to the reduction of poly (l-lactic acid) molecular weight.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 L- 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 (l-lactic acid) molecular weight is gradually increased, and is greater than in the reaction time
When 15h, the thermal degradation reaction of poly (l-lactic 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 (l-lactic acid)s 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 (l-lactic 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 product poly (l-lactic acid) 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 (l-lactic acid) is poor, isotacticity and crystallinity are low, improve me
State's poly (l-lactic acid) integrated artistic technical level.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 (l-lactic acid) product
| Serial number | Product and material name | Unit consumption | Monovalent (member) | Cost (member) |
| 1 | 90% common Pfansteihl (/T) | 1.53 | 6090 | 9317.70 |
| 2 | Catalyst (/kg) | 5.94 | 91.8 | 545.29 |
| 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 | 11097.99 |
From pilot scale material consumption Cost comparisons analysis as can be seen that 11098 yuan of the direct material consumption cost of project, raw material use common L-
Lactic acid, compared with 7998 yuan/ton of cost of market polymer grade Pfansteihl 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 (l-lactic 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 (l-lactic 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 Pfansteihl oligomer using Pfansteihl monomer
Embodiment 1
A method of poly (l-lactic acid) being produced through oligomerization, melt polycondensation and solid phase polycondensation using Pfansteihl, including is walked as follows
It is rapid:
(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%.
Embodiment 2
A method of poly (l-lactic acid) being produced through oligomerization, melt polycondensation and solid phase polycondensation using Pfansteihl, including is walked as follows
It is rapid:
(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%.
Embodiment 3
A method of poly (l-lactic acid) being produced through oligomerization, melt polycondensation and solid phase polycondensation using Pfansteihl, including is walked as follows
It is rapid:
(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%.
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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid), which is characterized in that including such as
Lower step:
(1) Pfansteihl oligomer is prepared using Pfansteihl；
(2) Pfansteihl oligomer and melt polycondensation catalyst are added in melt polycondensation reaction kettle, carry out melt polycondensation preparation
Low molecular weight poly (l-lactic acid), the additional amount of melt polycondensation catalyst are the 0.1-1% of Pfansteihl oligomerization amount of substance；
(3) low molecular weight poly (l-lactic acid) is added in solid state polycondensation kettle, carries out solid phase polycondensation and prepares high-molecular-weight poly L-
Lactic acid.
2. the side according to claim 1 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
Method, which is characterized in that the melt polycondensation catalyst is to be uniformly mixed to be made according to mass ratio 1:2-5 by component A and component B；
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)-L- α-aspartoyl]-L-phenylalanine -1-
Methyl esters is added in 20-30 DEG C of water, N- [N- (3,3- dimethylbutyl)-L- α-aspartoyl]-L-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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic 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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
Method, which is characterized in that pre-crystallized, pre-crystallization temperature 90-120 is carried out to low molecular weight poly (l-lactic acid) first in solid phase polycondensation
DEG C, the pre-crystallized time is 1-5h；Reaction temperature when low molecular weight poly (l-lactic acid) after pre-crystallized carries out solid phase polycondensation is 140-
180 DEG C, reaction time 5-30h.
5. the side according to claim 1 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
Method, which is characterized in that in step (1), the method for preparing Pfansteihl oligomer using Pfansteihl is as follows:
(1-1) raw material preparation: the optical purity of the Pfansteihl solution of 40-60wt%, Pfansteihl is greater than or equal to 99.5%；
(1-2) is dehydrated oligomerization, obtains Pfansteihl oligomer.
6. the side according to claim 5 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
Method, which is characterized in that in step (1-2), ethyl pyruvate is added into Pfansteihl solution, ethyl pyruvate is molten with Pfansteihl
The volume ratio of liquid is 0.5-1:1；Cobalt oxide and two-acthiol-J vanadyl are added into mixed solution simultaneously as catalysis
Agent, stirring；The usage amount of cobalt oxide is the 0.02%-0.04% of Pfansteihl quality, and two-acthiol-J vanadyl usage amounts are
The 0.04%-0.08% of Pfansteihl quality；Reaction time is 3h-6h, and reaction temperature is 5-30 DEG C.
7. the side according to claim 6 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
Method, which is characterized in that in step (1-2):
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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
Method, which is characterized in that in step (1-2), two-acthiol-J vanadyl the preparation method comprises the following steps: acthiol-J and sulphur
Sour vanadyl is mixed at room temperature in boric acid solution, reacts 3-5h, obtains violet solid；Acthiol-J and sulfuric acid oxygen
Vanadium 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 using Pfansteihl through oligomerization, melt polycondensation and solid phase polycondensation production poly (l-lactic acid)
Method, which is characterized in that in step (1-2), after reaction, filtering, stratification isolates organic phase, washes organic phase；
Organic phase vacuum distillation after washing is removed into solvent, obtaining white solid is Pfansteihl oligomer.
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