CN1506391A - 聚(l-乳酸-乙醇酸)的制备方法 - Google Patents
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- 238000000034 method Methods 0.000 title abstract description 6
- XBBVURRQGJPTHH-DKWTVANSSA-N 2-hydroxyacetic acid;(2s)-2-hydroxypropanoic acid Chemical compound OCC(O)=O.C[C@H](O)C(O)=O XBBVURRQGJPTHH-DKWTVANSSA-N 0.000 title 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006068 polycondensation reaction Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
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- GWUDZEJIEQLLHN-CEOVSRFSSA-N (2s)-2-hydroxypropanoic acid;zinc Chemical compound [Zn].C[C@H](O)C(O)=O.C[C@H](O)C(O)=O GWUDZEJIEQLLHN-CEOVSRFSSA-N 0.000 claims description 6
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- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- -1 poly(L-lactic acid-glycolic acid) Polymers 0.000 abstract description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 abstract 2
- ISOONVICQBXLKE-UHFFFAOYSA-N 2-hydroxypropanoic acid;4-methylbenzenesulfonic acid Chemical compound CC(O)C(O)=O.CC1=CC=C(S(O)(=O)=O)C=C1 ISOONVICQBXLKE-UHFFFAOYSA-N 0.000 abstract 1
- 239000003377 acid catalyst Substances 0.000 abstract 1
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- 239000000599 controlled substance Substances 0.000 abstract 1
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- JCEGKJFZOJBPOL-DKWTVANSSA-N C(C)O.C([C@@H](O)C)(=O)O Chemical compound C(C)O.C([C@@H](O)C)(=O)O JCEGKJFZOJBPOL-DKWTVANSSA-N 0.000 description 10
- 229940050168 zinc lactate Drugs 0.000 description 9
- 239000011576 zinc lactate Substances 0.000 description 9
- 238000009434 installation Methods 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229960000448 lactic acid Drugs 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
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- 231100000252 nontoxic Toxicity 0.000 description 2
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- 239000004626 polylactic acid Substances 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- QOOQLKSEGVNYLA-UHFFFAOYSA-N 1-$l^{1}-oxidanylbutane Chemical compound CCCC[O] QOOQLKSEGVNYLA-UHFFFAOYSA-N 0.000 description 1
- LCSKNASZPVZHEG-UHFFFAOYSA-N 3,6-dimethyl-1,4-dioxane-2,5-dione;1,4-dioxane-2,5-dione Chemical group O=C1COC(=O)CO1.CC1OC(=O)C(C)OC1=O LCSKNASZPVZHEG-UHFFFAOYSA-N 0.000 description 1
- 101100379079 Emericella variicolor andA gene Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- JCEGKJFZOJBPOL-UHFFFAOYSA-N ethanol;2-hydroxypropanoic acid Chemical compound CCO.CC(O)C(O)=O JCEGKJFZOJBPOL-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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Abstract
一种聚(L－乳酸－乙醇酸)的制备方法。在L－乳酸、乙醇酸中加入L－乳酸锌－对甲苯磺酸复合催化剂，于160～200℃、0.32～2.56Kpa条件下缩聚反应8～40小时。反应结束放料冷却后即得粗品，外观呈无色透明树脂状。粗品经精制处理，干燥后可得特性粘度为15～85ml/g的共聚物产品，其性能完全满足医用辅料，特别是缓、控释药物制剂辅料的要求。本工艺收率≥90％，过程简单。
Description
一、技术领域
本发明涉及一种医用高分子材料的制备方法，具体地说是一种聚(L-乳酸-乙醇酸)的制备方法。
二、背景技术
早期合成聚(乳酸-乙醇酸)，多以氧化锌、氯化锌、锡、氧化锡、二氯化锡、四氯化锡、三氧化二砷等作催化剂，采用DL-乳酸、乙醇酸直接缩聚，所得共聚物分子量较低，一般为2,000～4,000，机械强度差，无实际使用价值(USP4960866)。为了提高聚(乳酸-乙醇酸)的分子量，近年来主要以丙交酯、乙交酯为原料，采用开环聚合方法。采用此项技术，美国于1975年开发出一种聚(乳酸-乙醇酸)共聚物Vicryl缝线(90/10摩尔比)(Pearce E M.et aleditor，“Comtemperary Topic in PolymerScience”，1977，2，251)。目前美国Medisorb公司、Birmingham-Polymers公司、德国Boehriger Ingelheim公司等已有不同组分比和不同分子量的聚(乳酸-乙醇酸)共聚物产品供科研和医药生产使用(Middleton J C，Tipton A J，Medical Plastics andBiomaterials，1998，5(2)，30)。催化剂多采用辛酸亚锡(D.K.Gilding andA.M.Reed.Polymer，1979，20：1459；Spinu M，Jackson C.J.，macromol Sci Pure ApplChem，1996，A33(10)：1497；Kricheldorf H.R.，Kreiser S.I.，Polymer，1993，36(6)：1253；D.W.Grijpma，A.J.Nijenhuis.，Polymer，1990，31：2201)、异丙醇铝(Kricheldrof H.R.，Beerl M.，Macromolecules，1988，21：286；Dubois P.，JacobsC.. Macromolecules，1991，24：2266)、双金属氧桥烷氧化合物[(n-C4H9O)2AlO]2Zn(FengX.D.，Polymer，1985，17(1)：189)、含金属锌的引发体系(FP，7829978，1978)、稀土类引发体系(Hajime Yasuda，Eiji Ihara，Macromol.Chem.Phys.1995，196(8)：2417)等。该制备方法工艺路线长、设备要求高、以单体乳酸、乙醇酸为基准的转化率低、溶剂消耗量大、能耗高、成本高。
目前还未见到用L-乳酸与乙醇酸直接熔融缩聚生产高分子量的聚(L-乳酸-乙醇酸)的报道，但它已引起科技界的兴趣。日本三井公司在专利USP5310865、USP5428126、USP5440008和USP5444143中报道了采用溶液聚合，直接法制备高分子量的聚乳酸、聚乙醇酸和其它的含羟基羧酸及其共聚物的工艺。该工艺以乳酸、乙醇酸和其它羟基羧酸为原料，以芳香烷烃和芳醚作溶剂，以I、II、III、IV和V簇的金属及其氧化物、氢氧化物、卤化物、无机盐、羧酸盐和金属有机化合物为催化剂，在聚合温度130℃、高真空度和分子筛共沸回流条件下反应，得到高分子量的聚乳酸、聚乙醇酸、乳酸/乙醇酸和其它的含羟基羧酸的聚和物。高勤卫等人在专利CN1385452A中采用SnCl2·2H2O与对甲苯磺酸复合制备聚(L-乳酸-乙醇酸)。但其中所用的催化剂都存在一定程度的毒性。
三、发明内容
本发明对现有的工艺进行改进，用L-乳酸与乙醇酸直接进行缩聚反应，并选择无毒、无害的L-乳酸锌与很易脱除的对甲苯磺酸复合催化剂和相应的工艺条件，制得特性粘度为15～85ml/g的共聚物。
具体地说本制备方法包括缩聚和缩聚后的冷却、精制和干燥各单元过程，所述的缩聚是单体L-乳酸和乙醇酸直接在由L-乳酸锌和对甲苯磺酸构成的复合催化剂存在条件下的缩聚。
乳酸锌对人体无毒、无害，为常规使用的人体补锌剂。L-乳酸锌(I)和对甲苯磺酸(II)都溶于水，可以用水、无水乙醇分步萃取除去粗品中的催化剂、残留单体与低聚物，大大降低了聚(L-乳酸-乙醇酸)的生产成本，减少了有机溶剂对环境的污染。复合时I和II的摩尔比为0.2～4∶1；复合催化剂的用量以单体计，其摩尔比为1∶100～5000，单体摩尔数为两单体摩尔数之和。
缩聚的工艺条件为160～200℃、0.32～2.56Kpa条件下反应8～40小时，反应结束后冷却、精制，除去粗品中的催化剂、残留单体和低聚物，经干燥后得到特性粘度为15～85ml/g的聚(L-乳酸-乙醇酸)。
本工艺将现有的两步反应简化为一步反应，可得到特性粘度为15～85ml/g的聚(L-乳酸-乙醇酸)，收率≥90％。反应结束后冷却即得粗品，外观呈无色透明树脂状。采用分步萃取法精制处理除去未反应的单体、催化剂及低聚物，干燥后呈白色粉末状，其性能完全满足医用辅料，特别是缓、控释药物制剂辅料的要求。
四、具体实施方式
以下通过实施例，对本发明作进一步地描述。
实施例1：
在配备有搅拌器、蒸馏柱、冷凝器、温度计和减压蒸馏装置的500ml三口烧瓶中投入318gL-乳酸(浓度85.0％)、76g乙醇酸、1.9838gL-乳酸锌、6.3407g对甲苯磺酸，在均匀搅拌下，缓慢升温，减压脱水。当温度升到160℃时，减压到0.67KPa。保持此状态8小时，将物料倒出冷却后，可得到近乎无色透明树脂状的聚(L-乳酸-乙醇酸)，用水、无水乙醇分步萃取除去粗品中的催化剂、残留单体与低聚物，经干燥后得成品聚(L-乳酸-乙醇酸)249.2g，为理论收率的90.8％，经测试特性粘度为15.23ml/g。
实施例2：
实验装置和实验条件与实施例1相同，用0.7935gL-乳酸锌、1.0145g对甲苯磺酸。温度升到165℃后的反应时间为16小时，得聚(L-乳酸-乙醇酸)251.6g，为理论收率的91.7％，经测试特性粘度为27.54ml/g。
实施例3：
实验装置和实验条件与实施例1相同，用0.5592gL-乳酸锌、0.3804g对甲苯磺酸。温度升到170℃后的反应时间为24小时，得聚(L-乳酸-乙醇酸)252.1g，为理论收率的91.9％，经测试特性粘度为33.75ml/g。
实施例4：
实验装置和实验条件与实施例1相同，用0.4761gL-乳酸锌、0.2029g对甲苯磺酸。温度升到175℃后的反应时间为32小时，得聚(L-乳酸-乙醇酸)252.5g，为理论收率的92.1％，经测试特性粘度为38.37ml/g。
实施例5：
实验装置和实验条件与实施例1相同，用0.3968gL-乳酸锌、0.1268g对甲苯磺酸。温度升到180℃后的反应时间为40小时，得聚(L-乳酸-乙醇酸)250.4g，为理论收率的91.3％，经测试特性粘度为45.82ml/g。
实施例6：
实验装置和实验条件与实施例1相同，用0.2976gL-乳酸锌、0.0634g对甲苯磺酸。温度升到185℃后的反应时间为40小时，得聚(L-乳酸-乙醇酸)249.8g，为理论收率的91.1％，经测试特性粘度为48.27ml/g。
实施例7：
实验装置和实验条件与实施例1相同，用0.1904gL-乳酸锌、0.0304g对甲苯磺酸。温度升到190℃后的反应时间为40小时，得聚(L-乳酸-乙醇酸)248.2g，为理论收率的90.5％，经测试特性粘度为38.65ml/g。
实施例8：
实验装置与实施例1相同，投料时乙醇酸改为40.5g，用1.5768gL-乳酸锌、0.6720g对甲苯磺酸。温度升到195℃后的反应时间为36小时，反应温度为183℃，减压到0.52Kpa，得聚(L-乳酸-乙醇酸)228.6g，为理论收率的92.5％，经测试特性粘度为84.62ml/g。
实施例9：
实验装置与实施例1相同，投料时L-乳酸212g、乙醇酸152g、L-乳酸锌0.9921g、对甲苯磺酸0.6341g。，反应温度为200℃，反应时间为36小时，减压到1.05Kpa得聚(L-乳酸-乙醇酸)239.6g，为理论收率的92.1％，经测试特性粘度为54.82ml/g。
Claims (3)
1.一种聚(L-乳酸-乙醇酸)的制备方法，包括缩聚和缩聚后的冷却、精制和干燥各单元过程，其特征在于：所述的缩聚是单体L-乳酸和乙醇酸直接在由L-乳酸锌和对甲苯磺酸构成的复合催化剂存在条件下的缩聚。
2.根据权利要求1所述的制备方法，其特征在于：复合催化剂中L-乳酸锌与对甲苯磺酸的摩尔比为0.2～4∶1，所述的复合催化剂的用量以两单体总量计，其摩尔比为1∶100～5000。
3.根据权利要求1或2所述的制备方法，其特征在于：缩聚在160～200℃、0.32～2.56Kpa条件下反应8～40小时。
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| CN 03158335 CN1203107C (zh) | 2002-12-10 | 2003-09-23 | 聚(l－乳酸－乙醇酸)的制备方法 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532501A (zh) * | 2010-12-29 | 2012-07-04 | 安徽生建可降解聚乳酸新材料有限公司 | 一种聚（l-乳酸）及聚（l-乳酸-乙醇酸）的精制方法 |
| CN103342800A (zh) * | 2013-07-15 | 2013-10-09 | 湖南尔康制药股份有限公司 | 一种负载型催化剂催化合成药用聚（乳酸 乙醇酸）的方法 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532501A (zh) * | 2010-12-29 | 2012-07-04 | 安徽生建可降解聚乳酸新材料有限公司 | 一种聚（l-乳酸）及聚（l-乳酸-乙醇酸）的精制方法 |
| CN102532501B (zh) * | 2010-12-29 | 2014-07-09 | 安徽生建可降解聚乳酸新材料有限公司 | 一种聚（l-乳酸）及聚（l-乳酸-乙醇酸）的精制方法 |
| CN103342800A (zh) * | 2013-07-15 | 2013-10-09 | 湖南尔康制药股份有限公司 | 一种负载型催化剂催化合成药用聚（乳酸 乙醇酸）的方法 |
| CN103342800B (zh) * | 2013-07-15 | 2015-03-18 | 湖南尔康制药股份有限公司 | 一种负载型催化剂催化合成药用聚(乳酸 乙醇酸)的方法 |
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| CN1203107C (zh) | 2005-05-25 |
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