CN1616517A - Poly lactic acid microwave radiation synthetic method using silicon carbide as auxiliary reaction medium - Google Patents
Poly lactic acid microwave radiation synthetic method using silicon carbide as auxiliary reaction medium Download PDFInfo
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- CN1616517A CN1616517A CN 200310107681 CN200310107681A CN1616517A CN 1616517 A CN1616517 A CN 1616517A CN 200310107681 CN200310107681 CN 200310107681 CN 200310107681 A CN200310107681 A CN 200310107681A CN 1616517 A CN1616517 A CN 1616517A
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- lactide
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Abstract
The polylactic acid synthesis process includes preparing lactide with industrial lactic acid as material and ZnO and La2O3 as catalyst; the reaction between lactide and toluene solution of stannous caprylate on auxiliary reaction medium SiC inside reactor set in microwave for 15-19 min oven to obtain lactic acid homopolymer; and the reaction between lactide and toluene solution of polyfatty alcohol and stannous caprylate on auxiliary reaction medium SiC inside reactor set in microwave for 35-40 min oven to obtain lactic acid copolymer. The said process of the present invention has short reaction time, high efficiency, simple technological condition, low cost and no exhausted 'three wastes'.
Description
Technical field: the synthetic method that the present invention relates to a kind of poly(lactic acid).
Background technology: poly(lactic acid) is a kind of novel high polymer material, have good biodegradability, biocompatibility and physical strength, be the ideal biodegradable material, it is having broad application prospects aspect sustained release of tissue reparation, wound suture, medicine and agricultural chemicals; In other some fields, poly(lactic acid) replaces the traditional polymer material, also can alleviate pollution and harm to environment.Two kinds of methods of synthetic general employing of PLA: the one, the direct condensing method of employing molecular sieve dehydration, or electric jacket heating or decompression tube sealing, the lactide ring-opening polymerisation method of oil bath heating etc. are reduced pressure in employing in there-necked flask.There is the synthesis device complexity in these synthetic methods, complex operation, and problem such as the reaction times is very long, and energy consumption is bigger is unfavorable for carrying out large-scale production.Recent domestic promotes the research of organic synthesis to carry out many reports to microwave, and microwave technology has also obtained successful application in polymerisation.The microwave radiation synthetic technology has advantages such as speed is fast, even, selective, no lag-effect, and energy-efficient, non-environmental-pollution, receives chemical and environmental science worker's concern, has begun to be used for the preparation of poly-lactic acid material.Domestic scholars has been applied to microwave irradiation technology the synthetic of poly(lactic acid), but because they have adopted measures such as protection of inert gas, system decompression, equipment complexity, inconvenient operation in synthetic; And the reaction times is longer, and energy consumption is bigger, further improves still needing aspect microwave-assisted synthesis technique and the equipment.
Summary of the invention: the present invention adopts microwave to promote the synthetic chemistry reaction technology; take the lactide polymerisation as the basis; select carborundum as microwave assisted reaction medium; under inert free gas protection and condition of normal pressure, react; the method of a kind of microwave synthesizing lactic acid homopolymers and copolymer is provided; the microwave synthetic method of lactic acid homopolymer is: being 80～90% industrial lactic acid and catalyst Z nO with concentration joins in the there-necked flask in the ratio of V: m=140～160: 1; the mixing heating; after reaching 100 ℃, system temperature begins to vacuumize; in 2～2.5 hours, slowly heat up and increase vacuum; when temperature reaches after 120～140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 3～5: 1, kept 30～60 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 170 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 240～255 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2～3 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2～4 times, dry 20～24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of the inferior tin of dry lactide and octoate catalyst of purifying and mix, wherein the mol ratio of stannous octoate and monomer lactide is 0.0005～0.002, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 5～10mm, under the microwave of 400～500W power, reacted 15～19 minutes, and namely got lactic acid homopolymer.The microwave synthetic method of lactic acid copolymer is: being 85% industrial lactic acid and catalyst Z nO with concentration joins in the there-necked flask in the ratio of V: m=140～160: 1, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2～2.5 hours, slowly heat up and increase vacuum, when temperature reaches after 120～140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 3～5: 1, kept 30～60 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 170 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 240～255 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2～3 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2～4 times, dry 20～24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of purify dry lactide and poly-fatty alcohol, the inferior tin of octoate catalyst and mix, wherein the mass content of poly-fatty alcohol accounts for 2.5～3.5% of gross mass, the molar content of stannous octoate accounts for 0.08～0.2% of total content, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 5～10mm, under the microwave of 400～500W power, reacted 35～40 minutes, and namely got lactic acid copolymer.Owing to adopted microwave to promote organic synthesis technology and assisted reaction medium, the present invention has efficiently advantage fast, be the lactic acid homopolymer that obtained higher molecular weight in 19 minutes in the reaction times respectively, in the reaction times is to obtain well behaved lactic acid copolymerization product in 40 minutes, need a few hours and tens of hours relatively with prior synthesizing method, obviously shortened synthesising reacting time, improved working efficiency greatly, and the simple control easily of processing condition, reduced production cost, three-waste free discharge meets the basic demand of process for cleanly preparing.
The specific embodiment one: the microwave synthetic method of lactic acid homopolymer is: being 80～90% industrial lactic acid and catalyst Z nO with concentration joins in the there-necked flask in the ratio of V: m=140～160: 1, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2～2.5 hours, slowly heat up and increase vacuum, when temperature reaches after 120～140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 3～5: 1, kept 30～60 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 170 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 240～255 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2～3 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2～4 times, dry 20～24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of the inferior tin of dry lactide and octoate catalyst of purifying and mix, wherein the mol ratio of stannous octoate and monomer lactide is 0.0005～0.002, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 5～10mm, under the microwave of 400～500W power, reacted 15～19 minutes, and namely got lactic acid homopolymer.
The specific embodiment two: optimization control parameter is in the operating process of obtain lactic acid homopolymers: be 85% industrial lactic acid and catalyst Z nO in V: m=150 with concentration: 1 ratio joins in the there-necked flask, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2 hours, slowly heat up and increase vacuum, when temperature reaches after 140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 5: 1, kept 40 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 180 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 250 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2 times, dry 24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of the inferior tin of dry lactide and octoate catalyst of purifying and mix, wherein the mol ratio of stannous octoate and monomer lactide is 0.0005～0.002, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 10mm, reaction is 18 minutes under the microwave of 450W power, namely gets lactic acid homopolymer.
The specific embodiment three: the microwave synthetic method of lactic acid copolymer is: being 85% industrial lactic acid and catalyst Z nO with concentration joins in the there-necked flask in the ratio of V: m=140～160: 1, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2～2.5 hours, slowly heat up and increase vacuum, when temperature reaches after 120～140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 3～5: 1, kept 30～60 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 185 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 240～255 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2～3 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2～4 times, dry 20～24 hours dry lactides of must purifying in vacuum drying chamber; Will be through dry lactide and the poly-fatty alcohol of purifying, the toluene solution of the inferior tin of octoate catalyst joins in the reactor and mixes, wherein the mass content of poly-fatty alcohol accounts for 2.5～3.5% of gross mass, the molar content of stannous octoate accounts for 0.08～0.2% of total content, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 5～10mm, under the microwave of 400～500W power, reacted 35～40 minutes, namely get lactic acid copolymer, poly-fatty alcohol is polyethylene glycol in the present embodiment, and products therefrom is the polylactic acid-polyglycol copolymerization product.
The specific embodiment four: the microwave synthetic method of lactic acid homopolymer is: be 85% industrial lactic acid and catalyst Z nO in V: m=150 with concentration: 1 ratio joins in the there-necked flask, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2 hours, slowly heat up and increase vacuum, when temperature reaches after 140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 5: 1, kept 40 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 180 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 250 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2 times, dry 24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of purify dry lactide and poly-fatty alcohol, the inferior tin of octoate catalyst and mix, wherein the mass content of poly-fatty alcohol accounts for 3.22% of gross mass, the molar content of stannous octoate accounts for 0.118% of total content, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 10mm, reaction is 40 minutes under the microwave of 450W power, namely get lactic acid copolymer, poly-fatty alcohol is polypropylene glycol in the present embodiment, and products therefrom is PLA-polypropylene glycol copolymerization product.
Claims (6)
1, a kind of PLA microwave synthetic method take carborundum as the assisted reaction medium, the microwave synthetic method that it is characterized in that lactic acid homopolymer is: being 80～90% industrial lactic acid and catalyst Z nO with concentration joins in the there-necked flask in the ratio of V: m=140～160: 1, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2～2.5 hours, slowly heat up and increase vacuum, when temperature reaches after 120～140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 3～5: 1, kept 30～60 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 170 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 240～255 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2～3 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2～4 times, dry 20～24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of the inferior tin of dry lactide and octoate catalyst of purifying and mix, wherein the mol ratio of stannous octoate and monomer lactide is 0.0005～0.002, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 5～10mm, under the microwave of 400～500W power, reacted 15～19 minutes, and namely got lactic acid homopolymer.
2, the PLA microwave synthetic method take carborundum as the assisted reaction medium according to claim 1, the microwave synthetic method that it is characterized in that lactic acid homopolymer is: be 85% industrial lactic acid and catalyst Z nO in V: m=150 with concentration: 1 ratio joins in the there-necked flask, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2 hours, slowly heat up and increase vacuum, when temperature reaches after 140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 5: 1, kept 40 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 180 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 250 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2 times, dry 24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of the inferior tin of dry lactide and octoate catalyst of purifying and mix, wherein the mol ratio of stannous octoate and monomer lactide is 0.0005～0.002, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 10mm, reaction is 18 minutes under the microwave of 450W power, namely gets lactic acid homopolymer.
3, a kind of PLA microwave synthetic method take carborundum as the assisted reaction medium, the microwave synthetic method that it is characterized in that lactic acid copolymer is: being 85% industrial lactic acid and catalyst Z nO with concentration joins in the there-necked flask in the ratio of V: m=140～160: 1, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2～2.5 hours, slowly heat up and increase vacuum, when temperature reaches after 120～140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 3～5: 1, kept 30～60 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 170 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 240～255 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2～3 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2～4 times, dry 20～24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of purify dry lactide and poly-fatty alcohol, the inferior tin of octoate catalyst and mix, wherein the mass content of poly-fatty alcohol accounts for 2.5～3.5% of gross mass, the molar content of stannous octoate accounts for 0.08～0.2% of total content, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 5～10mm, under the microwave of 400～500W power, reacted 35～40 minutes, and namely got lactic acid copolymer.
4, the PLA microwave synthetic method take carborundum as the assisted reaction medium according to claim 3, the microwave synthetic method that it is characterized in that lactic acid homopolymer is: be 85% industrial lactic acid and catalyst Z nO in V: m=150 with concentration: 1 ratio joins in the there-necked flask, the mixing heating, after reaching 100 ℃, system temperature begins to vacuumize, in 2 hours, slowly heat up and increase vacuum, when temperature reaches after 140 ℃, add mixed catalyst ZnO and La
2O
3Totally 0.5 restrain, wherein ZnO and La
2O
3Mass ratio be 5: 1, kept 40 minutes during for 0.035MPa in vacuum, after not having water to distill, change receiving bottle, be warmed up to more than 180 ℃, increase vacuum to 0.098MPa, receive pale yellow or yellow organic liquid, reaction finishes when temperature reaches 250 ℃; The liquid spontaneous nucleation gets lactide after taking off receiving bottle, washs lactide 2 times with distilled water, and suction filtration adopts re-crystallizing in ethyl acetate to purify 2 times, dry 24 hours dry lactides of must purifying in vacuum drying chamber; To join in the reactor through the toluene solution of purify dry lactide and poly-fatty alcohol, the inferior tin of octoate catalyst and mix, wherein the mass content of poly-fatty alcohol accounts for 3.22% of gross mass, the molar content of stannous octoate accounts for 0.118% of total content, this reactor is put into microwave oven cavity, placing thickness is on the SiC assisted reaction medium of 10mm, reaction is 40 minutes under the microwave of 450W power, namely gets lactic acid copolymer.
5, according to claim 3 or 4 described be the poly(lactic acid) microwave radiation synthetic method of assisted reaction medium with silicon carbide, it is characterized in that described poly-Fatty Alcohol(C12-C14 and C12-C18) is a polyoxyethylene glycol, products therefrom is the polylactic acid-polyglycol copolymerization product.
6, according to claim 3 or 4 described be the poly(lactic acid) microwave radiation synthetic method of assisted reaction medium with silicon carbide, it is characterized in that described poly-Fatty Alcohol(C12-C14 and C12-C18) is a polypropylene glycol, products therefrom is poly(lactic acid)-polypropylene glycol copolymerization product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150094096A (en) * | 2014-02-10 | 2015-08-19 | 삼성전자주식회사 | Preparation method of polylactic acid, polylactic acid resin prepared therefrom, resin composition comprising the resin, and catalyst system for preparing polylactic acid |
| CN108358690A (en) * | 2018-02-06 | 2018-08-03 | 兰溪市沉默生物科技有限公司 | A kind of preparation method of selenium-enriched plant source synergy biology complex capsule fertilizer |
-
2003
- 2003-11-11 CN CN 200310107681 patent/CN1616517A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150094096A (en) * | 2014-02-10 | 2015-08-19 | 삼성전자주식회사 | Preparation method of polylactic acid, polylactic acid resin prepared therefrom, resin composition comprising the resin, and catalyst system for preparing polylactic acid |
| CN108358690A (en) * | 2018-02-06 | 2018-08-03 | 兰溪市沉默生物科技有限公司 | A kind of preparation method of selenium-enriched plant source synergy biology complex capsule fertilizer |
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