WO2019057031A1 - 大分子引发剂暨缩合-开环-固相聚合联用合成超高等规度聚l-/d-乳酸的方法 - Google Patents
大分子引发剂暨缩合-开环-固相聚合联用合成超高等规度聚l-/d-乳酸的方法 Download PDFInfo
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- WO2019057031A1 WO2019057031A1 PCT/CN2018/106198 CN2018106198W WO2019057031A1 WO 2019057031 A1 WO2019057031 A1 WO 2019057031A1 CN 2018106198 W CN2018106198 W CN 2018106198W WO 2019057031 A1 WO2019057031 A1 WO 2019057031A1
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- Prior art keywords
- lactic acid
- molecular weight
- lactide
- plla
- pdla
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 35
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 title claims abstract description 32
- 229940022769 d- lactic acid Drugs 0.000 title claims abstract description 30
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-Lactic acid Natural products C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 title claims abstract description 29
- 229930182843 D-Lactic acid Natural products 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 14
- 239000007790 solid phase Substances 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 239000003999 initiator Substances 0.000 title claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 32
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 28
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 229940109239 creatinine Drugs 0.000 claims description 10
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- 125000002619 bicyclic group Chemical group 0.000 claims description 6
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 231100000252 nontoxic Toxicity 0.000 claims description 5
- 230000003000 nontoxic effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000001785 cerium compounds Chemical class 0.000 claims description 4
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- 229960003624 creatine Drugs 0.000 claims description 3
- 239000006046 creatine Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 claims description 3
- XRVAWUONGLRHRZ-UHFFFAOYSA-N guanidine;2-hydroxypropanoic acid Chemical compound NC(N)=N.CC(O)C(O)=O XRVAWUONGLRHRZ-UHFFFAOYSA-N 0.000 claims description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims 4
- 150000001622 bismuth compounds Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- -1 hydrazine compound Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
-
- 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
Definitions
- the invention belongs to the field of biodegradable and environmentally friendly material synthesis, and particularly relates to a process for synthesizing ultra-high optical purity and isotactic poly L-/D-lactic acid by using a macroinitiator and three polymerization techniques.
- sc-PLA stereocomplex-type PLA
- sc-PLA is prepared by blending pure chiral poly-L-lactic acid (homochiral PLLA, hc-PLLA) with pure chiral poly-D-lactic acid (homochiral PDLA, hc-PDLA) in a certain ratio.
- the melting point T m of sc-PLA is as high as 220-230 ° C, which is 50 ° C or more higher than the T m of a single hc-PLLA/hc-PDLA. Since the T m of the sc-PLA close now widely used as a petroleum-based polyester fiber product produced PET, so as the most likely one of the alternative bio-based high performance polyester PET.
- the object of the present invention is to solve the problem that the conventional products PLLA, PDLA and the like have low regulation and are difficult to be used for synthesizing sc-PLA with T m ⁇ 220 ° C, and provide a synthesis using a macroinitiator and three polymerization techniques. Ultra high optical purity, isotactic PLLA/PDLA process.
- a macroinitiator and condensation-open-loop-solid phase polymerization method for synthesizing ultra-high isotactic PLLA/PDLA is an oligomeric L-/D synthesized by optical pure L-/D-lactic acid polycondensation reaction.
- -Lactic acid ma-OPLLA/ma-OPDLA as a macroinitiator initiated optically pure L-/D-lactide bulk fusion ring-opening polymerization, and then obtained a new high molecular weight, chiral pure PLLA/PDLA by solid phase polymerization technology Process method, the specific steps are as follows:
- Step 1 using optically pure L-/D-lactic acid as raw material, using biomass organic ruthenium compound as catalyst,
- reaction is carried out at 140-160 ° C, 100-30 torr for 2.0-4.0 h.
- Step 2 using the oligomeric L-/D-lactic acid ma-OPLLA/ma-OPDLA synthesized in the step 1 as an initiator, the non-toxic acid salt of the organic ruthenium compound as a catalyst, and optically pure L-/D-lactide
- the monomer is reacted at 100-180 ° C, 1.0-0.1 torr for 2.0-10.0 h, and Mw 6.0 ⁇ 10 4 -8.0 ⁇ 10 4 , PDI 1.5-1.7, Iso.99.0%-99.5% are synthesized.
- Molecular weight, optically pure PLLA/PDLA is hc-MMW-PLLA/hc-MMW-PDLA.
- Step 3 using hc-MMW-PLLA/hc-MMW-PDLA synthesized in step 2 as a raw material
- the crystallization pretreatment is carried out at 70-110 ° C, 1.0-0.1 torr for 0.5-2.0 h,
- optically pure L-/D-lactic acid specifically refers to L-/D-lactic acid having a chiral purity of ⁇ 99.5%
- optically pure L-/D-lactide specifically refers to chirality.
- the biomass organic cerium compound is specifically one of creatinine, thioglycolic acid, and creatine, and the amount thereof is 0.001%-0.005% of the mass of the L-/D-lactic acid monomer;
- the non-toxic acid salt specifically includes one of creatinine acetate, creatinine lactate, bicyclic guanidine acetate, and bicyclic guanidine lactate, and the amount thereof is 0.001% of the mass of the L-/D-lactide monomer- 0.005%.
- the macroinitiator obtained by isotactic condensation polymerization has high isotacticity and can effectively induce the stereospecific open-loop of high optical pure L-/D-lactide due to chiral induction effect.
- Polymerization synthesis gives the medium molecular weight, high isotactic activity, reactive functional group hc-MMW-PLLA/hc-MMW-PDLA.
- the distinguishing feature of this method is that the stereospecificity of the polymerization reaction is much higher than that of conventional high optical.
- Direct ring-opening polymerization of pure L-/D-lactide open-loop polymerization initiated by non-macroinitiators
- a set amount of high optical purity 90% L-/D-lactic acid aqueous solution was added to the reaction kettle, and then a set amount of biomass organic hydrazine compound was added as a catalyst, followed by nitrogen substitution in the reaction vessel, followed by lowering the pressure in the reactor to After P 1-1 , the reaction is t 1-1 h at the reaction temperature T 1-1 ; after the pressure in the autoclave is continuously lowered to P 1-2 , the reaction is continued at the reaction temperature T 1-2 for t 1-2 h; After the pressure in the autoclave was lowered to P 1-3 , the reaction was continued for t 1-3 h at the reaction temperature T 1-3 , and after completion of the reaction, a macroinitiator ma-OPLLA/ma-OPDLA was obtained.
- the inventors need to point out that the macroinitiator ma-OPLLA/ma-OPDLA synthesized in this step can immediately add L-/D-lactide to carry out the reaction in the next step, and can also induce the synthesized macromolecule.
- the agent ma-OPLLA/ma-OPDLA is discharged from the bottom of the bottom of the kettle and stored for later use, and it is preferred to immediately add L-/D-lactide to carry out the reaction in the next step.
- step 1 Taking the ma-OPLLA/ma-OPDLA synthesized in step 1 as an initiator, firstly adding a set amount of high optical pure L-/D-lactide and a set amount of non-toxic acid of the organic cerium compound to the reaction kettle.
- the salt is a catalyst.
- the reactor is subjected to nitrogen replacement, then the reactor pressure is lowered and the reactor is sealed at a constant P 2 , and reacted at a reaction temperature T 2 for t 2 h to synthesize hc-MMW-PLLA/hc-MMW. -PDLA.
- the inventors need to point out the molar ratio of the macroinitiator ma-OPLLA/ma-OPDLA to the monomer L-/D-lactide, as shown in the following formula (taking ma-OPLLA, L-lactide as an example). ):
- [LLA] 0 is the initial molar amount of L-lactide
- [ma-OPLLA] 0 is the initial molar amount of the macroinitiator ma-OPLLA
- M w (hc-MMW-PLLA) is the weight average molecular weight of hc-MMW-PLLA
- M w (ma-OPLLA) is the weight average molecular weight of ma-OPLLA
- M (LLA) is the molecular weight of lactide, and the specific value is 144.
- the hc-MMW-PLLA/hc-MMW-PDLA synthesized in the step 2 is fed into the granulation apparatus through a melt pump through a jacketed material line, and after granulation and sieving, particles having a particle diameter of 30-60 mesh are obtained.
- the pellets of acceptable particle size are then fed to the pre-crystallization apparatus through a vacuum transfer line, the pressure of the apparatus is maintained at P 3-0 , and the temperature is maintained at T 3-0 for t 3-0 h for crystallization pretreatment.
- the pellet obtained in the crystallization pretreatment step is directly dropped into the vacuum drum through the hopper, firstly reducing the vacuum drum pressure to P 3-1 , and then reacting t 3-1 h at the reaction temperature T 3-1 ; 3-2 under the reaction the reaction temperature T t 3-2 h; t 3-3 h last reactor at the reaction temperature T 3-3.
- hc-HMW-PLLA/hc-HMW-PDLA can be obtained.
- step 1
- the raw material is 90% L-lactic acid, the L-lactic acid chiral body purity is 99.5%, and the feeding amount is 100.0 Kg;
- the catalyst is creatinine and the dosage is 0.9g;
- the raw material is L-lactide, the L-lactide chiral purity is 99.5%, and the dosage is 1641.6Kg;
- the catalyst is creatinine acetate, and the dosage is 16.4g;
- the raw material is hc-MMW-PLLA particles with a particle size of 30 mesh;
- step 1
- the raw material is 90% L-lactic acid, the L-lactic acid chiral body purity is 99.8%, and the feeding amount is 50.0 Kg;
- the catalyst is thioglycolic acid, and the amount of the feed is 2.3 g;
- the product ma-OPLLA M w 5.0 ⁇ 10 3 , PDI 1.5, Iso.99.5%.
- the raw material is L-lactide, the L-lactide chiral purity is 99.8%, and the dosage is 810.0Kg;
- the catalyst is creatinine lactate, and the amount of the feed is 40.5 g;
- the raw material is hc-MMW-PLLA particles with a particle size of 60 mesh;
- t 3-1 8.0h
- step 1
- the raw material is 90% D-lactic acid, the D-lactic acid chiral body purity is 99.5%, and the feeding amount is 100.0 Kg;
- the catalyst is creatine, and the amount of the feed is 1.8 g;
- the raw material is D-lactide, the purity of D-lactide chiral body is 99.5%, and the dosage is 1644.7Kg;
- the catalyst is bicyclic guanidine acetate, and the dosage is 32.9 g;
- the raw material is hc-MMW-PDLA particles with a particle size of 40 mesh;
- step 1
- the raw material is 90% D-lactic acid, the purity of D-lactic acid chiral body is 99.8%, and the feeding amount is 50.0 Kg;
- the catalyst is creatinine and the dosage is 1.8g;
- the raw material is D-lactide, the purity of D-lactide chiral body is 99.8%, and the dosage is 789.6Kg;
- the catalyst is bicyclic guanidine lactate, and the dosage is 31.6 g;
- the raw material is hc-MMW-PDLA particles with a particle size of 50 mesh;
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种大分子引发剂暨缩合-开环-固相聚合联用合成超高等规度聚L-/D-乳酸的工艺方法，该方法采用高光学纯L-/D-乳酸缩聚反应合成的大分子引发剂，引发高光学纯L-/D-丙交酯本体熔融开环聚合，继而通过固相聚合技术获得高分子量、手性纯聚L-/D-乳酸的全新工艺方法。采用该全新工艺可合成得到重均分子量Mw为1.8×105-6.0×105、分子量分布PDI为 1.5-1.7、等规度Iso.为99.0-99.5％、熔点Tm为185.0-188.0℃、结晶度Xc为85.0-90.0％的高分子量、高光学纯聚L-/D-乳酸。
Description
本发明属于生物可降解暨环境友好材料合成领域，具体涉及一种利用大分子引发剂和三种聚合反应技术联用合成超高光学纯度、等规度聚L-/D-乳酸的工艺方法。
近年来，关于立构复合聚乳酸(stereocomplex-type PLA，sc-PLA)的研发受到国际高分子科学及材料学界的极大重视。sc-PLA是由纯手性聚L-乳酸(homochiral PLLA，hc-PLLA)与纯手性聚D-乳酸(homochiral PDLA，hc-PDLA)以一定的比例共混复合制备而得。sc-PLA的熔点T
m高达220-230℃，比单一hc-PLLA/hc-PDLA的T
m高50℃以上。由于sc-PLA的T
m已接近目前广泛用作生产纤维制品的石油基聚酯PET，因此被誉为最有可能替代PET的生物基高性能聚酯之一。
目前，商品生产的聚L-乳酸(PLLA)、聚D-乳酸(PDLA)其T
m在168-170℃，远低于hc-PLLA/hc-PDLA的T
m(174-175℃)，难以作为制备sc-PLA的原料。因此，至今尚不能生产得到T
m＞220℃的sc-PLA纤维商品。
发明人及其团队于2012年首次采用生物质有机胍系催化剂实现了L-/D-乳酸的受控、立构专一性缩合聚合，合成得到了具有高等规度的PLLA/PDLA(Jiang W.et al.，Polymer，2012，53，5476)。采用单一缩合聚合技术难以合成高质量(重均分子量M
w≥6.0×10
4，等规度Iso.≥99.5％，分子量分布指数PDI≤1.85)的hc-PLLA/hc-PDLA。
发明内容
本发明的目的是针对现有商品PLLA、PDLA等规度低，难以用于合成T
m≥220℃的sc-PLA的问题，提供一种利用大分子引发剂和三种聚合反应技术联用合成超高光学纯度、等规度PLLA/PDLA的工艺方法。
一种大分子引发剂暨缩合-开环-固相聚合联用合成超高等规度PLLA/PDLA的工艺方法，是采用光学纯L-/D-乳酸缩聚反应合成得到的寡聚L-/D-乳酸ma-OPLLA/ma-OPDLA作为大分子引发剂，引发光学纯L-/D-丙交酯本体熔融开环聚合，继而通过固相聚合技术获得高分子量、手性纯PLLA/PDLA的全新工艺方法，具体步骤如下：
步骤1：以光学纯L-/D-乳酸为原料，采用生物质有机胍化合物为催化剂，
首先在100-120℃、700-500torr条件下反应1.0-2.0h，
然后在120-140℃、500-100torr条件下反应1.0-2.0h，
最后在140-160℃、100-30torr条件下反应2.0-4.0h，
合成得到重均分子量M
w 3.0×10
3-5.0×10
3、分子量分布指数PDI 1.2-1.5、等规度Iso.99.0％-99.5％的寡聚L-/D-乳酸ma-OPLLA/ma-OPDLA。
步骤2：采用步骤1合成得到的寡聚L-/D-乳酸ma-OPLLA/ma-OPDLA为引发剂，有机胍化合物的无毒酸盐为催化剂，以光学纯L-/D-丙交酯为单体在100-180℃、1.0～0.1torr的条件下反应2.0-10.0h，合成得到M
w 6.0×10
4-8.0×10
4、PDI 1.5-1.7、Iso.99.0％-99.5％的中分子量、光学纯PLLA/PDLA即hc-MMW-PLLA/hc-MMW-PDLA。
步骤3：采用步骤2合成得到的hc-MMW-PLLA/hc-MMW-PDLA为原料，
首先在70-110℃、1.0-0.1torr的条件下进行结晶预处理0.5-2.0h，
然后维持压力为1.0-0.1torr，在130-140℃反应4.0-8.0h；在140-150℃反应4.0-8.0h；在150-170℃反应4.0-8.0h，
合成得到M
w 1.8×10
5-6.0×10
5、PDI 1.5-1.7、Iso.99.0％-99.5％、T
m185-188℃、结晶度X
c85％-90％的高分子量、光学纯PLLA/PDLA即hc-HMW-PLLA/hc-HMW-PDLA。
本发明所述的工艺方法中，光学纯L-/D-乳酸具体是指手性体纯度≥99.5％的L-/D-乳酸；光学纯L-/D-丙交酯具体是指手性体纯度≥99.5％的L-/D-丙交酯。
本发明所述的工艺方法中，生物质有机胍化合物具体为肌酐、胍基乙酸、肌酸之一，其添加量为L-/D-乳酸单体质量的0.001％-0.005％；有机胍化合物的无毒酸盐具体包括肌酐醋酸盐、肌酐乳酸盐、双环胍醋酸盐、双环胍乳酸盐之一，其添加量为L-/D-丙交酯单体质量的0.001％-0.005％。
本发明的优点和有益效果：
1.采用等规缩聚合成得到的大分子引发剂由于本身具有高等规度，且由于手性诱导效应故可有效的引发高光学纯L-/D-丙交酯的立构专一性开环聚合合成得到中分子量、高等规度带活性、反应性功能基hc-MMW-PLLA/hc-MMW-PDLA，这种方法的鲜明特点是聚合反应的立构专一性大大高于常规的高光学纯L-/D-丙交酯直接开环聚合反应(非大分子引发剂引发的开环聚合)；
2.采用所合成的hc-MMW-PLLA/hc-MMW-PDLA，继而通过固相聚合技术合成得到高分子量、超高等规度聚L-/D-乳酸hc-HMW-PLLA/hc-HMW-PDLA，由于固相聚合反应温度低于本体熔融开环聚合反应温度，因此避免了已合成的纯手性、中分子量聚合物在 高温下发生消旋化的可能性，并大大降低了hc-HMW-PLLA/hc-HMW-PDLA合成的能耗。
下面发明人通过具体实施方式对本发明所述工艺方法加以说明，但并不用来限定本发明的范围。
本发明所述的工艺方法在具体实施过程中的一般操作步骤如下：
步骤1
将设定量的高光学纯90％L-/D-乳酸水溶液加入反应釜，然后加入设定量的生物质有机胍化合物为催化剂，随后对反应釜内进行氮气置换，继而降低釜内压力至P
1-1后，在反应温度T
1-1下反应t
1-1h；继续降低釜内压力至P
1-2后，在反应温度T
1-2下继续反应t
1-2h；继续降低釜内压力至P
1-3后，在反应温度T
1-3下继续反应t
1-3h，反应结束后得到大分子引发剂ma-OPLLA/ma-OPDLA。
发明人需要指出的是，本步骤所合成的大分子引发剂ma-OPLLA/ma-OPDLA可即刻加入L-/D-丙交酯进行下一步骤的反应，也可将所合成的大分子引发剂ma-OPLLA/ma-OPDLA由釜底排出、储存备用，优选即刻加入L-/D-丙交酯进行下一步骤的反应。
步骤2
以步骤1合成得到的ma-OPLLA/ma-OPDLA为引发剂，首先向反应釜中加入设定量的高光学纯L-/D-丙交酯和设定量的有机胍化合物的无毒酸盐为催化剂。投加完毕之后，对反应釜内进行氮气置换，然后降低反应釜压力并恒定在P
2后密封反应釜，在反应温度T
2下反应t
2h，合成得到hc-MMW-PLLA/hc-MMW-PDLA。
发明人需要指出的是大分子引发剂ma-OPLLA/ma-OPDLA与单体L-/D-丙交酯的摩尔比例关系，如下式所示(以ma-OPLLA、L-丙交酯为例)：
式中：
[LLA]
0为L-丙交酯的起始摩尔量；
[ma-OPLLA]
0为大分子引发剂ma-OPLLA的起始摩尔量；
M
w(hc-MMW-PLLA)为hc-MMW-PLLA的重均分子量；
M
w(ma-OPLLA)为ma-OPLLA的重均分子量；
M(LLA)为丙交酯的分子量，具体数值为144。
步骤3
将步骤2合成得到的hc-MMW-PLLA/hc-MMW-PDLA通过带夹套的物料管线经熔体泵加入造粒设备，经造粒、筛分后得到粒径在30-60目的粒子。
随后将合格粒径的粒料通过真空输送管线加入预结晶装置，维持装置的压力在P
3-0，温度在T
3-0下停留t
3-0h，进行结晶预处理。
结晶预处理工序所获得的粒料，经过料斗直接落入真空转鼓中，首先降低真空转鼓压力至P
3-1，然后在反应温度T
3-1下反应t
3-1h；继续在反应温度T
3-2下反应t
3-2h；最后在反应温度T
3-3下反应t
3-3h。
反应结束后可得到hc-HMW-PLLA/hc-HMW-PDLA。
下面发明人进一步通过具体实施例来说明本发明所述工艺方法，但并不用来限定本发明的范围。
实施例1
本实施例的操作过程如上所述，具体过程参数如下：
步骤1：
原料为90％L-乳酸，L-乳酸手性体纯度99.5％，投料量为100.0Kg；
催化剂为肌酐，投料量为0.9g；
反应条件参数P
1-1＝700torr，T
1-1＝100℃，t
1-1＝1.0h；P
1-2＝500torr，T
1-2＝120℃，
t
1-2＝1.0h；P
1-3＝100torr，T
1-3＝140℃，t
1-3＝2.0h；
产品ma-OPLLA M
w 3.0×10
3，PDI 1.2，Iso.99.0％。
步骤2：
原料为L-丙交酯，L-丙交酯手性体纯度99.5％，投料量为1641.6Kg；
催化剂为肌酐醋酸盐，投料量为16.4g；
反应条件参数P
2＝1.0torr，T
2＝100℃，t
2＝2.0h；
产品hc-MMW-PLLA M
w 6.0×10
4，PDI 1.5，Iso.99.0％。
步骤3：
原料为hc-MMW-PLLA粒子，粒径30目；
反应条件参数P
3-0＝1.0torr，T
3-0＝70℃，t
3-0＝0.5h；P
3-1＝1.0torr，T
3-1＝130℃，
t
3-1＝4.0h；P
3-2＝1.0torr，T
3-2＝140℃，t
3-2＝4.0h；P
3-3＝1.0torr，T
3-3＝150℃，t
3-3＝4.0h；
产品hc-HMW-PLLA M
w 1.8×10
5，PDI 1.5，Iso.99.0％，T
m185.0℃，X
c85.0％。
实施例2
本实施例的操作过程如上所述，具体过程参数如下：
步骤1：
原料为90％L-乳酸，L-乳酸手性体纯度99.8％，投料量为50.0Kg；
催化剂为胍基乙酸，投料量为2.3g；
反应条件参数P
1-1＝500torr，T
1-1＝120℃，t
1-1＝2.0h；P
1-2＝100torr，T
1-2＝140℃，
t
1-2＝2.0h；P
1-3＝30torr，T
1-3＝160℃，t
1-3＝4.0h；
产品ma-OPLLA M
w 5.0×10
3，PDI 1.5，Iso.99.5％。
步骤2：
原料为L-丙交酯，L-丙交酯手性体纯度99.8％，投料量为810.0Kg；
催化剂为肌酐乳酸盐，投料量为40.5g；
反应条件参数P
2＝0.1torr，T
2＝180℃，t
2＝10.0h；
产品hc-MMW-PLLA M
w 8.0×10
4，PDI 1.7，Iso.99.5％。
步骤3：
原料为hc-MMW-PLLA粒子，粒径60目；
反应条件参数P
3-0＝0.1torr，T
3-0＝110℃，t
3-0＝2.0h；P
3-1＝0.1torr，T
3-1＝140℃，
t
3-1＝8.0h；P
3-2＝0.1torr，T
3-2＝150℃，t
3-2＝8.0h；P
3-3＝0.1torr，T
3-3＝170℃，t
3-3＝8.0h；
产品hc-HMW-PLLA M
w 6.0×10
5，PDI 1.7，Iso.99.5％，T
m188.0℃，X
c90.0％。
实施例3
本实施例的操作过程如上所述，具体过程参数如下：
步骤1：
原料为90％D-乳酸，D-乳酸手性体纯度99.5％，投料量为100.0Kg；
催化剂为肌酸，投料量为1.8g；
反应条件参数P
1-1＝550torr，T
1-1＝108℃，t
1-1＝1.0h；P
1-2＝350torr，T
1-2＝120℃，
t
1-2＝1.0h；P
1-3＝80torr，T
1-3＝140℃，t
1-3＝2.0h；
产品ma-OPDLA M
w 3.5×10
3，PDI 1.5，Iso.99.2％。
步骤2：
原料为D-丙交酯，D-丙交酯手性体纯度99.5％，投料量为1644.7Kg；
催化剂为双环胍醋酸盐，投料量为32.9g；
反应条件参数P
2＝0.7torr，T
2＝120℃，t
2＝4.0h；
产品hc-MMW-PDLA M
w 6.5×10
4，PDI 1.5，Iso.99.2％。
步骤3：
原料为hc-MMW-PDLA粒子，粒径40目；
反应条件参数P
3-0＝0.7torr，T
3-0＝80℃，t
3-0＝1.0h；P
3-1＝0.7torr，T
3-1＝130℃，
t
3-1＝4.5h；P
3-2＝0.7torr，T
3-2＝140℃，t
3-2＝4.5h；P
3-3＝0.7torr，T
3-3＝150℃，t
3-3＝4.5h；
产品hc-HMW-PDLA M
w 2.5×10
5，PDI 1.5，Iso.99.0％，T
m186.0℃，X
c87.0％。
实施例4
本实施例的操作过程如上所述，具体过程参数如下：
步骤1：
原料为90％D-乳酸，D-乳酸手性体纯度99.8％，投料量为50.0Kg；
催化剂为肌酐，投料量为1.8g；
反应条件参数P
1-1＝600torr，T
1-1＝112℃，t
1-1＝2.0h；P
1-2＝250torr，T
1-2＝140℃，
t
1-2＝2.0h；P
1-3＝50torr，T
1-3＝160℃，t
1-3＝4.0h；
产品ma-OPDLA M
w 4.5×10
3，PDI 1.4，Iso.99.3％。
步骤2：
原料为D-丙交酯，D-丙交酯手性体纯度99.8％，投料量为789.6Kg；
催化剂为双环胍乳酸盐，投料量为31.6g；
反应条件参数P
2＝0.4torr，T
2＝160℃，t
2＝8.0h；
产品hc-MMW-PDLA M
w 7.5×10
4，PDI 1.7，Iso.99.3％。
步骤3：
原料为hc-MMW-PDLA粒子，粒径50目；
反应条件参数P
3-0＝0.4torr，T
3-0＝100℃，t
3-0＝1.5h；P
3-1＝0.4torr，T
3-1＝140℃，
t
3-1＝6.0h；P
3-2＝0.4torr，T
3-2＝150℃，t
3-2＝6.0h；P
3-3＝0.4torr，T
3-3＝170℃，t
3-3＝6.0h；
产品hc-HMW-PDLA M
w 4.0×10
5，PDI 1.7，Iso.99.5％，T
m187.0℃，X
c88.0％。
Claims (5)
- 一种大分子引发剂暨缩合-开环-固相聚合联用合成超高等规度聚L-乳酸/聚D-乳酸(PLLA/PDLA)的工艺方法，采用光学纯L-/D-乳酸缩聚反应合成得到的寡聚L-/D-乳酸ma-OPLLA/ma-OPDLA作为大分子引发剂，引发光学纯L-/D-丙交酯本体熔融开环聚合，继而通过固相聚合技术获得高分子量、手性纯PLLA/PDLA的全新工艺方法，具体步骤如下：步骤1)：以光学纯L-/D-乳酸为原料，采用生物质有机胍化合物为催化剂，首先在100-120℃、700-500torr条件下反应1.0-2.0h，然后在120-140℃、500-100torr条件下反应1.0-2.0h，最后在140-160℃、100-30torr条件下反应2.0-4.0h，合成得到重均分子量M w3.0×10 3-5.0×10 3、分子量分布指数PDI 1.2-1.5、等规度Iso.99.0％-99.5％的寡聚L-/D-乳酸ma-OPLLA/ma-OPDLA；步骤2)：采用步骤1合成得到的ma-OPLLA/ma-OPDLA为引发剂，有机胍化合物的无毒酸盐为催化剂，以光学纯L-/D-丙交酯为单体在100-180℃、1.0～0.1torr的条件下反应2.0-10.0h，合成得到M w6.0×10 4-8.0×10 4、PDI 1.5-1.7、Iso.99.0％-99.5％的中分子量、光学纯PLLA/PDLA即hc-MMW-PLLA/hc-MMW-PDLA；步骤3)：采用步骤2)合成得到的hc-MMW-PLLA/hc-MMW-PDLA为原料，首先在70-110℃、1.0-0.1torr的条件下进行结晶预处理0.5-2.0h，然后维持压力为1.0-0.1torr，在130-140℃反应4.0-8.0h；在140-150℃反应4.0-8.0h；在150-170℃反应4.0-8.0h，合成得到M w1.8×10 5-6.0×10 5、PDI 1.5-1.7、Iso.99.0％-99.5％、T m185.0-188.0℃、结晶度X c85.0％-90.0％的高分子量、光学纯PLLA/PDLA hc-HMW-PLLA/hc-HMW-PDLA。
- 根据权利要求1所述的工艺方法，其特征在于，所述的光学纯L-/D-乳酸具体是指手性体纯度≥99.5％的L-/D-乳酸；光学纯L-/D-丙交酯具体是指手性体纯度≥99.5％的L-/D-丙交酯。
- 根据权利要求1所述的工艺方法，其特征在于，所述的生物质有机胍化合物具体为肌酐、胍基乙酸或肌酸之一，其添加量为L-/D-乳酸单体质量的0.001％-0.005％；有机胍化合物的无毒酸盐具体包括肌酐醋酸盐、肌酐乳酸盐、双环胍醋酸盐或双环胍乳酸盐之 一，其添加量为L-/D-丙交酯单体质量的0.001％-0.005％。
- 根据权利要求1所述的工艺方法，其特征在于，步骤2)中大分子引发剂ma-OPLLA与单体L-丙交酯的摩尔比例关系，如下式所示：
式中：[LLA] 0为L-丙交酯的起始摩尔量；[ma-OPLLA] 0为大分子引发剂ma-OPLLA的起始摩尔量；M w(hc-MMW-PLLA)为hc-MMW-PLLA的重均分子量；M w(ma-OPLLA)为ma-OPLLA的重均分子量；M(LLA)为丙交酯的分子量。 - 根据权利要求1所述的工艺方法，其特征在于，步骤2)中大分子引发剂ma-OPDLA与单体D-丙交酯的摩尔比例关系，如下式所示：
式中：[DLA] 0为D-丙交酯的起始摩尔量；[ma-OPDLA] 0为大分子引发剂ma-OPDLA的起始摩尔量；M w(hc-MMW-PDLA)为hc-MMW-PDLA的重均分子量；M w(ma-OPDLA)为ma-OPDLA的重均分子量；M(DLA)为丙交酯的分子量。
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| CN106831700A (zh) * | 2017-03-28 | 2017-06-13 | 南京大学 | 一种全绿色封闭循环工艺生产光学纯l‑/d‑丙交酯的方法 |
| CN107540824A (zh) * | 2017-09-21 | 2018-01-05 | 南京大学 | 大分子引发剂暨缩合‑开环‑固相聚合联用合成超高等规度聚l‑/d‑乳酸的方法 |
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