CN100445313C - Method for preparing polylactic acid/polyether divalent alcohol copolymers - Google Patents
Method for preparing polylactic acid/polyether divalent alcohol copolymers Download PDFInfo
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- CN100445313C CN100445313C CNB2007100398235A CN200710039823A CN100445313C CN 100445313 C CN100445313 C CN 100445313C CN B2007100398235 A CNB2007100398235 A CN B2007100398235A CN 200710039823 A CN200710039823 A CN 200710039823A CN 100445313 C CN100445313 C CN 100445313C
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Abstract
The invention relates to a producing method for polylactate/polyether diatomic alcohol copolymer belonging to macromolecule material technical field, including: laying the lactate and polyether diatomic alcohol in the vacuum reaction vessel, directly condensating by the effect of catalyst, firstly reacting for 3-5 hours at 100-120 DEG C with the vacuum degree of 1-2 kPa, than pumpdown, controlling the vacuum degree under 100Pa, going on reacting for 3-25 hours at 140-180 DEG C, getting copolymer prepolymer; wherein, the molar ratio of the polyether diatomic alcohol:lactate is 1:10 to 1:1000; placing the copolymer prepolymer in the reaction vessel, polymerizing for 10-300 minutes at the effect of extender with a vacuum degree under 100Pa in the N2 atmosphere, obtaining the target product with a molar ratio of copolymer prepolymer and extender 1:2-1:1. The method is easy and economic and tending to industry production and the produced copolymer resin can be completely degraded and widely used.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of polylactic acid/polyether divalent alcohol copolymers.
Background technology
Poly(lactic acid) (PLA) is a kind of the have good biocompatibility and polymkeric substance of biodegradable; it derives from renewable resources farm crop (as corn); the most outstanding advantage is a biodegradability; it can be degraded fully by the occurring in nature microorganism after using; final carbonic acid gas and the water of generating; free from environmental pollution, highly beneficial to the protection environment.Poly(lactic acid) has favorable mechanical performance and physicals, is applicable to various working methods such as blowing, thermoplastic, and is easy to process.Poly(lactic acid) when many advantageous properties are arranged, the shortcoming that also exists some can not finely satisfy the packing articles needs, its flexibility deficiency usually adopts and adds softening agent or improve its snappiness with degradable polymer blend with soft segment or copolymerization.
The adding softening agent can effectively improve the toughness of poly(lactic acid), but the small molecules softening agent volatilizees easily, oozes out, runs off behind life-time service, thereby causes the goods transparency and flexible decline.Also can improve its toughness to a certain extent with polymer blending with soft segment, but because the problem of consistency, make that site size can increase when flexible polymer added certain proportion to, two alternate bonding forces descend and cause the material monolithic degradation.
Patent CN1563139 discloses and has a kind ofly prepared the method for poly-lactic acid in high molecular weight by direct condensation, and the poly(lactic acid) limiting viscosity that makes reaches 1.0-1.5dl/g.But the toughness deficiency of poly(lactic acid) homopolymer has limited its application at aspects such as wrapping material.
Patent CN1114108 discloses a kind of preparation method of Biodegradable polyester copolymer.This method adopts rac-Lactide and PEG ring opening copolymer to obtain the high-molecular weight multipolymer, and the intensity of multipolymer and toughness all are better than homopolymer.But the purity requirement to the raw material rac-Lactide is higher, need to make with extra care through steps such as distillation, recrystallizations, so productive rate is lower, and cost is higher.
Patent CN1305928 discloses a kind of a kind of Biodegradable material of method copolymerization by lactic acid, polyoxyethylene glycol mass polymerization.This patent belongs to biomedical materials field, and the purpose of invention is in order to prepare biodegradable Antiadhesive film.But because add polyoxyethylene glycol when making esterification the number of hydroxyl increase, destroyed hydroxyl and carboxyl etc. mol ratio, Zhi Bei molecular weight of product is not high like this, can't be used for general-purpose plastics.
Summary of the invention
The object of the present invention is to provide a kind of preparation method's simple economy, abundant raw material is easy to get, and is easy to the preparation method of the polylactic acid/polyether divalent alcohol copolymers of suitability for industrialized production.
The preparation method of the polylactic acid/polyether divalent alcohol copolymers that the present invention proposes, concrete steps are as follows:
(1) lactic acid and polyether Glycols are placed the vacuum reaction still, the direct condensation reaction takes place under catalyst action.Be 1-2KPa in vacuum tightness earlier, temperature is 100-120 ℃ reacted 3-5 hour down, vacuumized then, and vacuum degree control below 100Pa, under 140-180 ℃ of temperature, was continued reaction 3-25 hour, obtained the multipolymer performed polymer; Wherein, the mol ratio of polyether Glycols and lactic acid is 1: 10-1: 1000;
(2) the multipolymer performed polymer that obtains in the step (1) being placed reactor, is below the 100Pa in vacuum tightness, at N
2In the atmosphere, polymerization reaction take place under the chainextender effect, polymerization temperature are 150-230 ℃, and polymerization reaction time is 10-300 minute, obtain desired product, multipolymer performed polymer and chainextender are that the hydroxyl of multipolymer performed polymer and the mol ratio of isocyanato are 1: 2-2: 1.
Among the present invention, described lactic acid is L-lactic acid, D-lactic acid or D, one or more in the L-lactic acid etc.
Among the present invention, described polyether Glycols is one or more in polyoxyethylene glycol, polypropylene glycol or poly-(ethylene glycol and 1,2-propylene glycol) multipolymer etc.
Among the present invention, catalyzer described in the step (1) is stannous octoate, tin protochloride, tetrabutyl titanate, antimonous oxide, germanium chloride or is in the huge legendary turtle compound that forms of coordination center etc. one or more with tin, antimony or element Ge that the catalyzer add-on is the 0.04-0.1wt% of lactic acid quality.
Among the present invention, chainextender is an isocyanic ester described in the step (2).Be specially hexamethylene-diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, ditan-4,4 '-vulcabond or tolylene diisocyanate etc.
The invention has the advantages that:
(1) uses lactic acid and polyether Glycols rich and easy to get to prepare multipolymer, simplified the treating process of complexity when using rac-Lactide, be convenient to suitability for industrialized production.
(2) in the molecular chain of poly(lactic acid), introduce the soft segment of polyethers, improved the toughness of poly(lactic acid), enlarged the Application Areas of material.
(3) end group of synthetic multipolymer prepolymer is hydroxyl, uses vulcabond series chainextender chain extension can increase the efficient of chain extension greatly.
The present invention adopts the advantage of the polyether Glycols copolymerization prepolymer with certain polymerization degree to be to have avoided that residual small molecules influences the chain extension effect in the performed polymer.If during employing small molecules dibasic alcohol end-blocking poly(lactic acid), because of melt viscosity is big, remaining small molecules is difficult to remove, small molecules can react with chainextender earlier, has influenced the chain extension effect of chainextender.
Embodiment
Further specify the present invention below by embodiment, helping understanding the present invention, but do not limit content of the present invention.
Embodiment 1:
(1) L-lactic acid 800g and 80g cetomacrogol 1000 are added the vacuum reaction still respectively, add catalyzer 0.5g tin protochloride, vacuumize, control reactor pressure rises to 100 ℃ at 1.0kPa with temperature of reaction kettle, reacts 5 hours; Temperature of reaction kettle rises to 165 ℃ then, and pressure is reduced to below the 100Pa, continues reaction 10 hours, obtains the multipolymer performed polymer;
(2) multipolymer performed polymer and the chainextender ditan-4 that reaction in the step (1) is obtained; 4 '-vulcabond added reactor in 1: 1 in molar ratio, vacuumized inflated with nitrogen; after repeatable operation 3-6 time; system pressure is reduced to below the 100Pa,, reacted 25 minutes then at 170 ℃; the nitrogen protection bottom discharge; promptly obtain desired product, the products obtained therefrom weight-average molecular weight is 104,587.
Embodiment 2:
(1) D-lactic acid 800g and 8g cetomacrogol 1000 0 are added the vacuum reaction still, add catalyzer 0.8g stannous octoate, vacuumize, control reactor pressure rises to 110 ℃ at 1.2kPa with temperature of reaction kettle, reacts 4 hours; Temperature of reaction kettle rises to 170 ℃ then, and pressure is reduced to below the 100Pa, continues reaction 7 hours, obtains the multipolymer performed polymer;
(2) performed polymer that reaction in the step (1) is obtained and chainextender hexamethylene-diisocyanate added reactor in 1: 1.3 in molar ratio; vacuumize; behind the inflated with nitrogen, repeatable operation 4-5 time, system pressure is reduced to below the 100Pa; then at 170 ℃; reacted 200 minutes, the nitrogen protection bottom discharge promptly obtains desired product; the products obtained therefrom weight-average molecular weight is 189,791.
Embodiment 3:
(1) with D-lactic acid 300g, L-lactic acid 500g and catalyzer 40g Macrogol 4000 add the vacuum reaction still, add the 0.6g tetrabutyl titanate, vacuumize, and control reactor pressure rises to 120 ℃ at 2kPa with temperature of reaction kettle, reacts 3 hours; Temperature of reaction kettle rises to 180 ℃ then, and pressure is reduced to below the 100Pa, continues reaction 5 hours, obtains the multipolymer performed polymer;
(2) performed polymer that reaction in the step (1) is obtained and chainextender isophorone diisocyanate added reactor in 1: 1.5 in molar ratio; vacuumize; inflated with nitrogen, repeatable operation several times after, system pressure is reduced to below the 100Pa; then at 180 ℃; reacted 85 minutes, the nitrogen protection bottom discharge promptly obtains desired product; the products obtained therefrom weight-average molecular weight is 210,121.
Embodiment 4:
(1) L-lactic acid 800g and 20g Macrogol 2000 0 are added the vacuum reaction still, add catalyzer 0.6g antimonous oxide, vacuumize, control reactor pressure rises to 120 ℃ at 2kPa with temperature of reaction kettle, reacts 3 hours; Temperature of reaction kettle rises to 165 ℃ then, and pressure is reduced to below the 100Pa, continues reaction 5 hours, obtains the multipolymer performed polymer;
(2) performed polymer that reaction in the step (1) is obtained and chainextender dicyclohexyl methane diisocyanate added reactor in 1: 1.5 in molar ratio; vacuumize; behind the inflated with nitrogen, repeatable operation 4-6 time, system pressure is reduced to below the 100Pa; then at 200 ℃; reacted 45 minutes, the nitrogen protection bottom discharge promptly obtains desired product; the products obtained therefrom weight-average molecular weight is 163,286.
Embodiment 5:
(1) L-lactic acid 800g and 20g polypropylene glycol 1000 are added the vacuum reaction still, add catalyzer 0.4g germanium chloride, vacuumize, control reactor pressure rises to 120 ℃ at 2kPa with temperature of reaction kettle, reacts 3 hours; Temperature of reaction kettle rises to 165 ℃ then, and pressure is reduced to below the 100Pa, continues reaction 5 hours, obtains the multipolymer performed polymer;
(2) performed polymer that reaction in the step (1) is obtained and chainextender tolylene diisocyanate added reactor in 1: 1.5 in molar ratio; vacuumize; behind the inflated with nitrogen, repeatable operation 4-5 time, system pressure is reduced to below the 100Pa; then at 220 ℃; reacted 60 minutes, the nitrogen protection bottom discharge promptly obtains desired product; the products obtained therefrom weight-average molecular weight is 158,077.
Claims (6)
1, a kind of preparation method of polylactic acid/polyether divalent alcohol copolymers is characterized in that concrete steps are as follows:
(1) lactic acid and polyether Glycols are placed the vacuum reaction still, the direct condensation reaction takes place under catalyst action, be 1-2KPa in vacuum tightness earlier, temperature is 100-120 ℃ and reacted 3-5 hour down, vacuumize then, with vacuum degree control below 100Pa, under 140-180 ℃ of temperature, continue reaction 3-25 hour, and obtained the multipolymer performed polymer; Wherein, the mol ratio of polyether Glycols and lactic acid is 1: 10-1: 1000;
(2) the multipolymer performed polymer that obtains in the step (1) being placed reactor, is below the 100Pa in vacuum tightness, at N
2In the atmosphere, polymerization reaction take place under the chainextender effect, polymerization temperature are 150-230 ℃, and polymerization reaction time is 10-300 minute, obtain desired product, multipolymer performed polymer and chainextender add-on are that the hydroxyl in the multipolymer performed polymer and the mol ratio of chainextender are 1: 2-2: 1.
2, the preparation method of polylactic acid/polyether divalent alcohol copolymers according to claim 1 is characterized in that described lactic acid is L-lactic acid, D-lactic acid or D, one or more in the L-lactic acid.
3, the preparation method of polylactic acid/polyether divalent alcohol copolymers according to claim 1 is characterized in that described polyether Glycols is one or more in polyoxyethylene glycol, polypropylene glycol or poly-(ethylene glycol and 1,2-propylene glycol) multipolymer.
4, the preparation method of polylactic acid/polyether divalent alcohol copolymers according to claim 1, it is characterized in that catalyzer described in the step (1) is stannous octoate, tin protochloride, tetrabutyl titanate, antimonous oxide, germanium chloride or is in the huge legendary turtle compound that forms of coordination center one or more with tin, antimony or element Ge that the catalyzer add-on is the 0.04-0.1wt% of lactic acid quality.
5, the preparation method of polylactic acid/polyether divalent alcohol copolymers according to claim 1 is characterized in that described chainextender is an isocyanic ester.
6, the preparation method of polylactic acid/polyether divalent alcohol copolymers according to claim 5, it is characterized in that isocyanic ester is hexamethylene-diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, ditan-4,4 '-vulcabond or tolylene diisocyanate.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199279B (en) * | 2010-03-26 | 2014-01-22 | 东丽纤维研究所（中国）有限公司 | Method for preparing poly lactic acid-polyethylene glycol copolymer by using composite catalyst |
| CN104277209B (en) * | 2013-07-08 | 2016-08-10 | 江南大学 | A kind of polyelectrolyte terpolymer and the preparation of nano-micelle thereof |
| CN103495211B (en) * | 2013-10-15 | 2016-03-23 | 山东赛克赛斯药业科技有限公司 | For the absorbent antiseize film and preparation method thereof of heart operation |
| KR102149304B1 (en) * | 2014-09-17 | 2020-08-28 | 에스케이케미칼 주식회사 | Polylactic acid resin composition for 3d printing |
| CN104558504B (en) * | 2015-01-12 | 2017-10-20 | 杨凌瑞丰环保科技有限公司 | A kind of preparation method of polylactic acid poly glycol copolymer |
| CN106633016A (en) * | 2016-09-14 | 2017-05-10 | 东华大学 | Method for preparing polylactic acid-polypropylene glycol copolymer |
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Effective date of registration: 20200420 Address after: No. 2196, South Hongqi Road, Ma'anshan economic and Technological Development Zone, Anhui Province 243000 Patentee after: MAANSHAN TONGJIELIANG BIOLOGICAL MATERIAL Co.,Ltd. Address before: 313 room 65, 200092 Chifeng Road, Shanghai Patentee before: Shanghai Tong-Jie-Liang Biomaterials Co.,Ltd. |
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Application publication date: 20071017 Assignee: Hangzhou Dehong Technology Co.,Ltd. Assignor: MAANSHAN TONGJIELIANG BIOLOGICAL MATERIAL CO.,LTD. Contract record no.: X2022330000058 Denomination of invention: A preparation method of polylactic acid / polyether diol copolymer Granted publication date: 20081224 License type: Common License Record date: 20220318 |