CN108003334A - A kind of method using mixed catalyst synthesizing polylactic acid - Google Patents
A kind of method using mixed catalyst synthesizing polylactic acid Download PDFInfo
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- CN108003334A CN108003334A CN201711314464.XA CN201711314464A CN108003334A CN 108003334 A CN108003334 A CN 108003334A CN 201711314464 A CN201711314464 A CN 201711314464A CN 108003334 A CN108003334 A CN 108003334A
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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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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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- 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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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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
- C08G63/87—Non-metals or inter-compounds thereof
Abstract
The invention discloses a kind of method using mixed catalyst synthesizing polylactic acid：（1）Under conditions of mixed catalyst, 5~20KPa, 70~120 DEG C, inert gas shielding; when the agitated reaction 1~5 of lactic acid is small, the oligomer of lactic acid is obtained, then pressure is down to 0.2~1KPa; temperature rises to 120~180 DEG C, continues to obtain lactic acid oligomers when stirring reaction 1~10 is small；Mixed catalyst is made of rare earth compound, titanium metal compound and molecular sieve, and rare earth compound, titanium metal compound, the mass ratio of molecular sieve are 1:0.07~0.15:1~2；（2）Lactic acid oligomers are when reaction 12~30 is small under the conditions of 0.01~0.8KPa, 180~230 DEG C, inert gas shielding, to obtain the final product.The catalyst stabilization activity higher that the method for the present invention uses, it is more convenient in technique, and obtained polylactic acid is functional, heat endurance is good, narrow molecular weight distribution.
Description
Technical field
The present invention relates to a kind of method using mixed catalyst synthesizing polylactic acid, belongs to synthesis of polymer material technology neck
Domain.
Background technology
Polylactic acid is mainly the macromolecule product obtained using starch as original material after everfermentation, polycondensation reaction.Due to
Polylactic acid has biological degradability, biocompatibility, good mechanical performance, therefore has in medical treatment, environmental protection, agricultural etc.
Wide application prospect.
The synthetic method of polylactic acid is broadly divided into two kinds at present, and one kind is to obtain polylactic acid by direct polycondensation of lactic acid, but
Its molecular weight is general relatively low and distribution is wide.Another kind is by lactic acid Cyclodimerization thing --- poly- breast is made in lactide ring-opening polymerisation
Acid, first prepares polylactic acid with synthesis of lactide from lactic acid, lactide ring-opening polymerisation（Also referred to as polylactide）And copolymer, the method system
The polylactic acid relative molecular weight obtained is higher, and narrowly distributing.
Polylactic acid production process is environmentally safe, and product has biodegradability, and obvious compared with conventional plastic
Degradation time is shortened, realizes the circulation in nature, is a kind of preferable Green Polymer Material.This is to mitigating oil
Crisis, increase agricultural output of preserving the ecological environment have far-reaching and important meaning.
There is the report much on lactide ring-opening polymerisation polylactic acid in recent years, 102643418 A's of Publication No. CN is special
Profit discloses a kind of using titanium class catalyst and the compound complex catalyst of toluenesulfonic acid, the molecule of products therefrom polylactic acid
Amount is 2~200,000；The patent of 105504237 A of Publication No. CN discloses a kind of using rare earth compound, ionic liquid, titanium
Class compound, the quaternary built compound of sulfamic acid compound, obtained polylactic acid molecular weight of product, heat endurance, which have, to be changed
It is kind, but have much room for improvement.
The content of the invention
For the above-mentioned prior art, in order to further improve the stabilization of the molecular weight of polylactic acid, yield and polylactic acid distribution
Property, heat endurance, shorten time of polymerisation, simplify reaction process, closed the present invention provides one kind using mixed catalyst
Into the method for polylactic acid.The catalyst stabilization activity higher that the method for the present invention uses is more convenient in technique and obtained poly-
Lactic acid is functional, and heat endurance is good, narrow molecular weight distribution.The present invention has expanded rare earth catalyst on the basis of existing technology
Application in poly lactic acid polymerized field, there is provided a kind of cost is low, technique simply with rare earth compound, titanium compound, point
Son sieve is the method for composite catalyst synthesizing polylactic acid.
The present invention is achieved by the following technical solutions：
A kind of method using mixed catalyst synthesizing polylactic acid, comprises the following steps：
（1）In mixed catalyst, 5~20KPa, 70~120 DEG C, inert gas（Such as nitrogen）Under conditions of protection, lactic acid warp
When stirring reaction 1~5 is small, the oligomer of lactic acid is obtained, then pressure is down to 0.2~1KPa, temperature rises to 120~180 DEG C, after
Continuous stirring reaction 1~10 obtains lactic acid oligomers when small；
The mixed catalyst, is made of rare earth compound, titanium metal compound and molecular sieve, rare earth compound, titanium eka-gold
Belong to compound, the mass ratio of molecular sieve three is 1:0.07~0.15:1~2, preferably 1:0.1:1.5；The dosage of rare earth compound
For the 0.4% of material acid quality；
（2）The above-mentioned lactic acid oligomers being prepared, in 0.01~0.8KPa, 180~230 DEG C, inert gas（Such as nitrogen）
When reaction 12~30 is small under protective condition, that is, polylactic acid is obtained, its molecular weight is 20~300,000.
The rare earth compound is selected from rare earth oxide（Ln2O3）, rare earth compound（LnCl3）, rare earth sulfonate（Ln
(RSO3)3）, rare earth carboxylate（Ln(R1COO)3）In one kind or any two or more；It is preferred that rare earth sulfonate.
The Ln represents rare earth element, and rare earth element is selected from lanthanum（La）, praseodymium（Pr）, neodymium（Nd）, yttrium（Y）, samarium（Sm）, europium
（Eu）, more preferably lanthanum（La）, yttrium（Y）, praseodymium（Pr）.
The R is selected from halohydrocarbyl, C6~C12 alkyls, aryl radical or nitrobenzophenone, R1Selected from phenyl or C6~
C12 alkyls.
The rare earth compound, more preferably trifluoromethanesulfonic acid praseodymium, lanthana.
One in the halide of the titanium metal compound selected from titanium, the carboxylate of titanium, the alkoxide of titanium, titanyl compound
Kind is any two or more, preferably titanium tetrachloride, titanium trichloride, titanium chloride, four acetic acid titaniums, two acetic acid titaniums, methanol titanium, ethanol
Titanium, isopropyl titanate, titanium isobutoxide, titanium dioxide, titanium tetrachloride, more preferably titanium chloride, titanium tetrachloride.
The one kind or any two or more of the molecular sieve in Si-Al molecular sieve, phosphate aluminium molecular sieve, silicon phosphorus molecular sieve,
It is preferred that Si-Al molecular sieve, including ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-41, MCM-48, SBA-3, SBA-15 type point
Son sieve, more preferably SBA-3 types molecular sieve.
Preferably, the method using mixed catalyst synthesizing polylactic acid comprises the following steps that：
（1）Under conditions of mixed catalyst, 5~10KPa, 110~120 DEG C, nitrogen protection, the agitated reaction 2~3 of lactic acid is small
When, the oligomer of lactic acid is obtained, then pressure is down to 0.5~0.8KPa, temperature rises to 150~180 DEG C, continues stirring reaction 5
~6 obtain lactic acid oligomers when small；
The mixed catalyst, is made of, rare earth sulfonate, dichloride rare earth sulfonate, titanium chloride and SBA-3 type molecular sieves
Titanium and the mass ratio of SBA-3 type molecular sieve threes are 1:0.1:1.5；The dosage of rare earth sulfonate is material acid quality
0.4%；
（2）The above-mentioned lactic acid oligomers being prepared, react under 0.01~0.8KPa, 210~230 DEG C, nitrogen protective condition
18~24 it is small when, that is, obtain polylactic acid, its molecular weight is 20~300,000.
The synthetic method of the polylactic acid of the present invention, is urged using rare earth compound, titanium metal compound, molecular sieve to be compound
Agent, accelerates the progress of polymerisation, improves the degree of polymerization, and the more traditional tin catalyst of heat endurance, which has, to be obviously improved, and is obtained
The polylactic acid molecule amount narrowly distributing arrived；The addition of molecular sieve shortens the reaction time of lactic acid oligomer, and it is oligomeric to improve lactic acid
The smart yield of thing.Compared with prior art, this production invention mixed catalyst combined activity used is high and easily obtains, nontoxic or low
Poison, does not contain heavy metal, environmentally safe without using organic solvent, shortens the time needed for reaction.Made poly- breast
Acid, molecular weight is high, and narrow molecular weight distribution, heat endurance is good, meets most of required mechanical performance.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Involved instrument, reagent, material etc. in following embodiments, are existing in the prior art unless otherwise noted
Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Involved experimental method in following embodiments, inspection
Survey method etc., is existing normal experiment method, detection method etc. in the prior art unless otherwise noted.
Polylactic acid molecule amount is measured with GPC in following instance and comparative example, and tetrahydrofuran is Flow sample, and polystyrene is mark
Quasi- sample.Using TG Q100 under 190 DEG C of nitrogen atmospheres continue 60min measure polylactic acid thermal weight loss speed, to its hot property into
Row analysis
1 synthesizing polylactic acid of embodiment
The Pfansteihl that 100g purity is 90% is added into there-necked flasks of the 250ml equipped with blender and condenser, is vacuumized, is replaced
Nitrogen 4 times, adds the SBA-3 type molecular sieves after trifluoromethanesulfonic acid praseodymium, titanium chloride, grinding into there-necked flask under nitrogen protection
Mixed catalyst（Three's mass ratio is 1:0.1:1.5, the addition of wherein rare earth compound is the 0.4% of material acid quality）,
System is placed in 100 DEG C of oil bath pans, when stirring dehydration 2 is small under conditions of stagnation pressure is 10KPa, is then gradually dropped to pressure
0.6KPa, while temperature is raised to 170 DEG C, continues to obtain lactic acid oligomers when stirring reaction 6 is small.Temperature is brought rapidly up to 210
DEG C, simultaneity factor pressure is down to 0.05KPa, when reaction 20 is small after obtain the PLLA that weight average molecular weight is 300000, its molecular weight
1.10 are distributed as, degradation rate of the product at 190 DEG C is 0.32（wt%/min）.
2 synthesizing polylactic acid of embodiment
The Pfansteihl that 100g purity is 90% is added into there-necked flasks of the 250ml equipped with blender and condenser, is vacuumized, is replaced
Nitrogen 4 times, the SBA-3 types molecular sieve mixing added under nitrogen protection into there-necked flask after lanthana, titanium chloride, grinding are urged
Agent（Proportions are 1:0.1:1.5, the addition of wherein rare earth compound is the 0.4% of material acid quality）, system is put
In 100 DEG C of oil bath pans, when stirring dehydration 2 is small under conditions of stagnation pressure is 10KPa, pressure is gradually then dropped into 0.6KPa,
Temperature is raised to 170 DEG C at the same time, continues to obtain lactic acid oligomers when stirring reaction 6 is small.Temperature is brought rapidly up to 210 DEG C, at the same time
System pressure is down to 0.05KPa, when reaction 20 is small after obtain the PLLA that weight average molecular weight is 250000, its molecular weight distribution is
1.21, degradation rate of the product at 190 DEG C is 0.47（wt%/min）.
3 synthesizing polylactic acid of embodiment
The Pfansteihl that 100g purity is 90% is added into there-necked flasks of the 250ml equipped with blender and condenser, is vacuumized, is replaced
Nitrogen 4 times, the type ZSM 5 molecular sieve mixing added under nitrogen protection into there-necked flask after lanthana, titanium chloride, grinding are urged
Agent（Proportions are 1:0.1:1.5, the addition of wherein rare earth compound is the 0.4% of material acid quality）, system is put
In 100 DEG C of oil bath pans, when stirring dehydration 2 is small under conditions of stagnation pressure is 10KPa, pressure is gradually then dropped into 0.6KPa,
Temperature is raised to 170 DEG C at the same time, continues to obtain lactic acid oligomers when stirring reaction 6 is small.Temperature is brought rapidly up to 210 DEG C, at the same time
System pressure is down to 0.05KPa, when reaction 20 is small after obtain the PLLA that weight average molecular weight is 200000, its molecular weight distribution is
1.25, degradation rate of the product at 190 DEG C is 0.41（wt%/min）.
4 synthesizing polylactic acid of embodiment
The Pfansteihl that 100g purity is 90% is added into there-necked flasks of the 250ml equipped with blender and condenser, is vacuumized, is replaced
Nitrogen 4 times, adds the type ZSM 5 molecular sieve after trifluoromethanesulfonic acid praseodymium, titanium chloride, grinding into there-necked flask under nitrogen protection
Mixed catalyst（Proportions are 1:0.1:1.5, the addition of wherein rare earth compound is the 0.4% of material acid quality）, will
System is placed in 100 DEG C of oil bath pans, when stirring dehydration 2 is small under conditions of stagnation pressure is 10KPa, is then gradually dropped to pressure
0.6KPa, while temperature is raised to 170 DEG C, continues to obtain lactic acid oligomers when stirring reaction 6 is small.Temperature is brought rapidly up to 210
DEG C, simultaneity factor pressure is down to 0.05KPa, when reaction 20 is small after obtain the PLLA that weight average molecular weight is 230000, its
Molecular weight distribution is 1.17, and degradation rate of the product at 190 DEG C is 0.58（wt%/min）.
5 synthesizing polylactic acid of embodiment
The Pfansteihl that 100g purity is 90% is added into there-necked flasks of the 250ml equipped with blender and condenser, is vacuumized, is replaced
Nitrogen 4 times, adds the SBA-3 type molecular sieves after trifluoromethanesulfonic acid praseodymium, titanium chloride, grinding into there-necked flask under nitrogen protection
Mixed catalyst（Proportions are 1:0.1:1, the addition of wherein rare earth compound is the 0.4% of material acid quality）, by body
System is placed in 100 DEG C of oil bath pans, when stirring dehydration 2 is small under conditions of stagnation pressure is 10KPa, is then gradually dropped to pressure
0.6KPa, while temperature is raised to 170 DEG C, continues to obtain lactic acid oligomers when stirring reaction 6 is small.Temperature is brought rapidly up to 210
DEG C, simultaneity factor pressure is down to 0.05KPa, when reaction 20 is small after obtain the PLLA that weight average molecular weight is 260000, its
Molecular weight distribution is 1.17, and degradation rate of the product at 190 DEG C is 0.39（wt%/min）.
Comparative example 1
The Pfansteihl that 100g purity is 90% is added into there-necked flasks of the 250ml equipped with blender and condenser, is vacuumized, is replaced
Nitrogen 4 times, adds the SBA-3 types molecular sieve mixing after stannous octoate, titanium chloride, grinding into there-necked flask under nitrogen protection
Catalyst（Proportions are 1:0.1:1, the addition of wherein stannous octoate is the 0.4% of material acid quality）, system is placed in
In 100 DEG C of oil bath pans, when stirring dehydration 2 is small under conditions of stagnation pressure is 10KPa, pressure is gradually then dropped into 0.6KPa, together
Shi Wendu is raised to 170 DEG C, continues to obtain lactic acid oligomers when stirring reaction 6 is small.Temperature is brought rapidly up to 210 DEG C, is at the same time
System pressure is down to 0.05KPa, when reaction 20 is small after obtain the PLLA that weight average molecular weight is 290000, its molecular weight distribution
For 2.12, degradation rate of the product at 190 DEG C is 0.88（wt%/min）.
Comparative example 2
The Pfansteihl that 100g purity is 90% is added into there-necked flasks of the 250ml equipped with blender and condenser, is vacuumized, is replaced
Nitrogen 4 times, adds stannous octoate and zinc oxide into there-necked flask under nitrogen protection（The mass ratio of stannous octoate and zinc oxide is
1:0.2, the addition of wherein stannous octoate is the 0.4% of material acid quality）, system is placed in 100 DEG C of oil bath pans, total
Press as when stirring dehydration 2 is small under conditions of 10KPa, pressure gradually then is dropped to 0.6KPa, while temperature is raised to 170 DEG C, after
Continuous stirring reaction 6 obtains lactic acid oligomers when small.Temperature is brought rapidly up to 210 DEG C, simultaneity factor pressure is down to 0.05KPa,
React 20 it is small when after obtain weight average molecular weight be 200000 PLLA, its molecular weight distribution be 2.45, product is at 190 DEG C
Under degradation rate be 0.97（wt%/min）.
Found by contrast experiment, compared with traditional tin compound, rare earth compound has urges with what it compared favourably
Change activity and heavy metal free, heat endurance is also good compared with the former, and the progress for accelerating reaction of molecular sieve, and of the invention is dilute
Earth compounds, titanium compound, molecular sieve mixed catalyst are a kind of efficient catalysts.
Claims (10)
- A kind of 1. method using mixed catalyst synthesizing polylactic acid, it is characterised in that：Comprise the following steps：（1）Under conditions of mixed catalyst, 5~20KPa, 70~120 DEG C, inert gas shielding, the agitated reaction 1 of lactic acid~ 5 it is small when, obtain the oligomer of lactic acid, then pressure is down to 0.2~1KPa, temperature rises to 120~180 DEG C, continues stirring reaction 1 ~10 obtain lactic acid oligomers when small；The mixed catalyst, is made of rare earth compound, titanium metal compound and molecular sieve, rare earth compound, titanium eka-gold Belong to compound, the mass ratio of molecular sieve three is 1:0.07~0.15:1~2；The rare earth compound is selected from Ln2O3、LnCl3、Ln(RSO3)3、Ln(R1COO)3In one kind or any two or more；The Ln represents rare earth element, and rare earth element is selected from lanthanum（La）, praseodymium（Pr）, neodymium（Nd）, yttrium（Y）, samarium（Sm）, europium（Eu）；The R is selected from halohydrocarbyl, C6~C12 alkyls, aryl radical or nitrobenzophenone；The R1Selected from phenyl or C6~C12 Alkyl；（2）The above-mentioned lactic acid oligomers being prepared, under the conditions of 0.01~0.8KPa, 180~230 DEG C, inert gas shielding When reaction 12~30 is small, that is, obtain polylactic acid.
- 2. the method according to claim 1 using mixed catalyst synthesizing polylactic acid, it is characterised in that：The rare earth Compound is selected from trifluoromethanesulfonic acid praseodymium, lanthana.
- 3. the method according to claim 1 using mixed catalyst synthesizing polylactic acid, it is characterised in that：The titanium eka-gold Belong to halide of the compound selected from titanium, the carboxylate of titanium, the alkoxide of titanium, one kind in titanyl compound or any two or more.
- 4. the method using mixed catalyst synthesizing polylactic acid according to claim 1 or 3, it is characterised in that：The titanium Metal compound is selected from titanium tetrachloride, titanium trichloride, titanium chloride, four acetic acid titaniums, two acetic acid titaniums, methanol titanium, titanium ethanolate, different Titanium propanolate, titanium isobutoxide, titanium dioxide, titanium tetrachloride.
- 5. the method according to claim 1 using mixed catalyst synthesizing polylactic acid, it is characterised in that：The molecular sieve One kind or any two or more in Si-Al molecular sieve, phosphate aluminium molecular sieve, silicon phosphorus molecular sieve.
- 6. the method for mixed catalyst synthesizing polylactic acid is utilized according to claim 1 or 5, it is characterised in that：Described point Son is screened from ZSM-5, ZSM-11, ZSM-23, MCM-22, MCM-41, MCM-48, SBA-3, SBA-15 type Si-Al molecular sieve.
- 7. the method according to claim 1 using mixed catalyst synthesizing polylactic acid, it is characterised in that：The rare earth Compound, titanium metal compound, the mass ratio of molecular sieve three are 1:0.1:1.5.
- 8. the method according to claim 1 using mixed catalyst synthesizing polylactic acid, it is characterised in that：The rare earth The dosage of compound is the 0.4% of lactic acid quality.
- 9. according to the method according to any one of claims 1 to 8 using mixed catalyst synthesizing polylactic acid, its feature exists In：The method using mixed catalyst synthesizing polylactic acid comprises the following steps that：（1）Under conditions of mixed catalyst, 5~10KPa, 110~120 DEG C, nitrogen protection, the agitated reaction 2~3 of lactic acid is small When, the oligomer of lactic acid is obtained, then pressure is down to 0.5~0.8KPa, temperature rises to 150~180 DEG C, continues stirring reaction 5 ~6 obtain lactic acid oligomers when small；The mixed catalyst, is made of, rare earth sulfonate, dichloride rare earth sulfonate, titanium chloride and SBA-3 type molecular sieves Titanium and the mass ratio of SBA-3 type molecular sieve threes are 1:0.1:1.5；The dosage of rare earth sulfonate is material acid quality 0.4%；（2）The above-mentioned lactic acid oligomers being prepared, react under 0.01~0.8KPa, 210~230 DEG C, nitrogen protective condition 18~24 it is small when, that is, obtain polylactic acid.
- 10. synthesized using the method using mixed catalyst synthesizing polylactic acid any one of claim 1~9 Polylactic acid.
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| CN110563932A (en) * | 2019-08-21 | 2019-12-13 | 金发科技股份有限公司 | Polylactic resin and preparation method and application thereof |
| CN113174036A (en) * | 2021-04-28 | 2021-07-27 | 浙江联盛化学股份有限公司 | Rare earth doped molecular sieve catalyst, preparation method and application thereof |
| CN114752048A (en) * | 2022-04-11 | 2022-07-15 | 深圳光华伟业股份有限公司 | Catalyst and application of preparation method thereof in preparation of biomedical polylactic acid |
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