CN1757659A - Method for preparing high molecular wt. polylactic-acid - Google Patents
Method for preparing high molecular wt. polylactic-acid Download PDFInfo
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- CN1757659A CN1757659A CN 200510029963 CN200510029963A CN1757659A CN 1757659 A CN1757659 A CN 1757659A CN 200510029963 CN200510029963 CN 200510029963 CN 200510029963 A CN200510029963 A CN 200510029963A CN 1757659 A CN1757659 A CN 1757659A
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Abstract
A process for preparing the high-molecular polylactic acid from the carboxy terminated polylactic acid prepolymer prepared by direct fusion-polycondensation method features the reaction between said raw material and epoxy resin in vacuum condition. Its advantages are high viscosity average molecular weight (130000-220000) and low cost.
Description
Technical field
The invention belongs to the organic polymer material field, specifically a kind of preparation method of poly-lactic acid in high molecular weight can be used for preparing the high-performance poly lactate material.
Background technology
Poly(lactic acid) is a kind of reproducible biodegradable material, has excellent biological compatibility.Because it is nontoxic, degradable, characteristics such as can regenerate, and meets the requirement of environmental protection and Sustainable development, thereby more and more receives investigation of materials person and business people's concern.The second-order transition temperature of poly-lactic acid in high molecular weight is about 60 ℃, fusing point is about 180 ℃, be and polystyrene (PS), the polyester close thermal plasticity high polymers of physical and mechanical properties such as (PET), its processing characteristics is good, can utilize that general device of plastic processing is extruded, injection, blow molding, also can with general-purpose plastics blend or copolymerization, in addition, poly(lactic acid) also can be spun into fiber by melt spinning method, and its fabric crease resistance is strong, good permeability, comfortable and easy to wear.Therefore, as a kind of new bio degradable material, poly(lactic acid) has very wide application prospect.
Because poly(lactic acid) application in many aspects all requires high molecular, in recent years, the technology of preparing of low-cost poly-lactic acid in high molecular weight has become the focus of research.Use the more method for preparing poly-lactic acid in high molecular weight at present and comprise direct polycondensation method, ring-opening polymerization method, copolymerization method and chain extension method.Industrial main employing ring-opening polymerization method is made rac-Lactide with lactic acid earlier, again by the rac-Lactide ring-opening polymerization.U.S. Cargill-Dow company utilizes this method to build up 140,000 tons/year industrial production line, and has applied for numerous patents.The disadvantage of this method is the rac-Lactide that needs preparation polymerization-grade purity, complex process, and cost is higher relatively.The melt direct polycondensation method is the most economic method, but at present lower with this method synthetic polylactic acid molecule amount, does not still have commercial scale production.In order to improve the molecular weight of poly(lactic acid), improve performances such as its shock resistance, degradation resistant, numerous investigators have carried out the research work of copolymerization method.Patents such as US5631344, US5916998, US5952913 have been described and added comonomer in the ring-opening polymerization processes, thereby make the high-molecular weight multipolymer.But it is raw material that these methods all adopt rac-Lactide, and cost is higher, is difficult to apply.Patents such as US5922832 are used high-molecular weight PLA and other polymer blending, and to improve shock resistance, it uses the preparation that prerequisite remains high molecular PLA.
Recently we are at Journal of Polymer Science:Part A:Polymer Chemistry, 2004,42,5045-5053 has reported that the lower molecular weight PLA that makes with direct polycondensation method and two ends are material copolymerization synthetic macromolecule amount PLA-PCL segmented copolymer for the polycaprolactone (PCL) of-NCO group, but, be used for the still comparatively waste of production of engineering plastics because the PCL price is higher.For obtaining the sufficiently high poly(lactic acid) of molecular weight, can also adopt the method for chain extension.Jukka Tuominen etc. are at Macromolecules, 2000,33 (10): 3530-3535. has reported that adopting bisoxazoline is that the low molecular weight of carboxyl carries out the method that chain extension prepares poly-lactic acid in high molecular weight to two ends, but the synthetic difficulty of used chainextender bisoxazoline, and resulting polymers contains-NH-behind the chain extension, make that processing stability is relatively poor thereafter, be difficult to realize suitability for industrialized production.The report that is equipped with poly-lactic acid in high molecular weight with the general monomer chain extension of lower molecular weight legal system is less, and the present invention aims to provide the method that the general monomer chain extension of a kind of low cost legal system is equipped with poly-lactic acid in high molecular weight.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the high performance poly(lactic acid) of high molecular.
The objective of the invention is to implement like this: with lactic acid, aliphatic dibasic acid is starting raw material, and dehydration is stirred in decompression at a certain temperature, the dehydration adding catalyzer that finishes, and the decompression reaction that further heats up makes the poly(lactic acid) prepolymer that two ends are carboxyl; Poly(lactic acid) prepolymer fusion with the known molecular amount adds Resins, epoxy by a certain percentage, under certain temperature, pressure condition, aggregates into poly-lactic acid in high molecular weight.
Reaction process is as follows:
Wherein, m+n=40～250
Method of the present invention can be divided into for two steps:
The first step prepares the poly(lactic acid) prepolymer that two ends are carboxyl; The second step two ends are the poly(lactic acid) prepolymer and the Resins, epoxy reaction synthetic macromolecule amount poly(lactic acid) of carboxyl.
Now details are as follows respectively:
1, two ends are the preparation of carboxyl poly(lactic acid) prepolymer
With lactic acid, aliphatic dibasic acid is starting raw material.Earlier lactic acid is joined in the reaction vessel, the molecular weight of estimation synthetic prepolymer calculates the mole number that should add diprotic acid by containing an aliphatic dicarboxylic acid unit in each macromole, joins in the above-mentioned reaction vessel by the amount of calculating good diprotic acid, after heating makes its dissolving, decompression dehydration.Dehydration temperaturre is 100～130 ℃, and pressure is 300～100Pa, and dewatering time is 1～15 hour.Dehydration finishes, and adds the Bivalent Tin compound as catalyst account for lactic acid production 0.1～10%, is that 130～200 ℃, pressure are under 20～300Pa in temperature, reacts 5～25 hours.The viscosity-average molecular weight of described poly(lactic acid) prepolymer is 0.6～30,000.The mol ratio of lactic acid and aliphatic dibasic acid is (400: 1)～(40: 1).
2, the preparation of poly-lactic acid in high molecular weight
Behind the poly(lactic acid) prepolymer determining molecular weight that obtains, get in a certain amount of adding reaction vessel, heating and melting, be 1: 1.0～1: 2.0 ratio adding Resins, epoxy then in poly(lactic acid) prepolymer and Resins, epoxy mol ratio, in temperature is that 130～200 ℃, pressure are under 20～300Pa, stirring reaction 10～180 minutes takes out polymkeric substance and naturally cools to room temperature, obtains poly-lactic acid in high molecular weight.The poly(lactic acid) prepolymer is different with the mol ratio of Resins, epoxy, and the molecular weight that obtains poly(lactic acid) is also different.Described poly-lactic acid in high molecular weight viscosity-average molecular weight is 13-22 ten thousand.
The preparation method's of poly-lactic acid in high molecular weight provided by the invention characteristics are:
1. adopt the direct melt polycondensation method, production technique, equipment are simple, and cost is low, is easy to realize the industrialization continuous production.
2. Zhi Bei poly(lactic acid) better heat stability is difficult for oxidation, degraded, variable color in the post-treatment process.
3. reaction relatively relaxes in the production process, than more easy to control, safer with the isocyanates chain extension.
Description of drawings
Fig. 1. the nmr spectrum of poly(lactic acid), lactic acid oligomer and bis phenol-a epoxy resins
Fig. 2. the blend of bis phenol-a epoxy resins, lactic acid oligomer, bis phenol-a epoxy resins and lactic acid oligomer and the infrared spectrum of poly-lactic acid in high molecular weight
In the accompanying drawing 1, Fig. 1-the 1st, the nmr spectrum of lactic acid oligomer, Fig. 1-2 are the nmr spectrums of bis phenol-a epoxy resins, and Fig. 1-the 3rd makes the nmr spectrum of poly-lactic acid in high molecular weight;
In the accompanying drawing 2, (a) be the infrared spectrum of bis phenol-a epoxy resins (E-44); (b) be lactic acid oligomer
Infrared spectrum; (c) be the infrared spectrum of lactic acid oligomer and E-44 blend; (d) be the infrared spectrum of poly-lactic acid in high molecular weight;
Embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
Embodiment 1:
With 6000g concentration is that 90% L-lactic acid joins in the 5000ml two neck flasks that have whipping appts, adds hexanodioic acid 64.2g (mol ratio of lactic acid and hexanodioic acid is 136: 1) then, slowly is heated to 130 ℃ and makes its dissolving.This solution under 130 ℃, is decompressed to 150～130Pa, stirs dehydration 8hr, add 27g tin protochloride (account for pure lactic acid weight 0.5%) then and make catalyzer, stir, remain under 130 ℃, 150～130Pa, reaction 2hr, be warming up to 170 ℃ again, be decompressed to 70～20Pa, continue reaction 22hr, product is poured out, the room temperature cooling, getting water white molecule two ends is the solid lactic acid oligopolymer of carboxyl, recording its viscosity-average molecular weight by viscosimetry is 2.7 ten thousand.Get this oligopolymer 400g, put into the three-necked flask of 500ml band whipping appts, add bis phenol-a epoxy resins (E-44) in lactic acid oligomer and 1: 1.2 ratio of Resins, epoxy mol ratio, in 180 ℃, react under 70～20Pa to increase to and be difficult to stir (50～60min) to viscosity, melt is taken out, naturally cool to room temperature, obtain poly-lactic acid in high molecular weight.Fig. 1 is the poly(lactic acid) of present embodiment preparation and the nmr spectrum of lactic acid oligomer and used E-44 Resins, epoxy.This spectrogram has proved the structure of synthesizing polylactic acid.Fig. 2 is its infrared spectrum, and the epoxy bond in the final product disappears as can be seen, shows that reaction has taken place for E-44 Resins, epoxy and lactic acid oligomer.Further proof has been synthesized poly-lactic acid in high molecular weight.Recording the viscosity-average molecular weight that makes poly(lactic acid) by viscosimetry is 21.6 ten thousand.
Embodiment 2:
Prepare the lactic acid oligomer that the molecule two ends are carboxyl by embodiment 1 described method.Get this oligopolymer 400g, put into the three-necked flask of 500ml band whipping appts, add E-44 Resins, epoxy in lactic acid oligomer and 1: 1.3 ratio of Resins, epoxy mol ratio, in 180 ℃, react under 70～20Pa to increase to and be difficult to stir (50～60min) to viscosity, melt is taken out, naturally cool to room temperature, obtain poly-lactic acid in high molecular weight.Recording the viscosity-average molecular weight that makes poly(lactic acid) by viscosimetry is 14.5 ten thousand.
Embodiment 3:
Prepare the lactic acid oligomer that the molecule two ends are carboxyl by embodiment 1 described method.Get this oligopolymer 400g, put into the three-necked flask of 500ml band whipping appts, add E-44 Resins, epoxy in lactic acid oligomer and 1: 1.1 ratio of Resins, epoxy mol ratio, in 180 ℃, react under 70～20Pa to increase to and be difficult to stir (50～60min) to viscosity, melt is taken out, naturally cool to room temperature, obtain poly-lactic acid in high molecular weight.Recording the viscosity-average molecular weight that makes poly(lactic acid) by viscosimetry is 13.5 ten thousand.
Embodiment 4:
Prepare the lactic acid oligomer that the molecule two ends are carboxyl by embodiment 1 described method.Get this oligopolymer 400g, put into the three-necked flask of 500ml band whipping appts, add E-44 Resins, epoxy in lactic acid oligomer and 1: 1.2 ratio of Resins, epoxy mol ratio, in 170 ℃, react under 70～20Pa to increase to and be difficult to stir (50～60min) to viscosity, melt is taken out, naturally cool to room temperature, obtain poly-lactic acid in high molecular weight.Recording the viscosity-average molecular weight that makes poly(lactic acid) by viscosimetry is 14.3 ten thousand.
Embodiment 5:
Prepare the lactic acid oligomer that the molecule two ends are carboxyl by embodiment 1 described method.Get this oligopolymer 400g, put into the three-necked flask of 500ml band whipping appts, add 711 Resins, epoxy in lactic acid oligomer and 1: 1.2 ratio of Resins, epoxy mol ratio, in 180 ℃, react under 70～20Pa to increase to and be difficult to stir (50～60min) to viscosity, melt is taken out, naturally cool to room temperature, obtain poly-lactic acid in high molecular weight.Recording the viscosity-average molecular weight that makes poly(lactic acid) by viscosimetry is 18.2 ten thousand.
Claims (6)
1. the preparation method of a poly-lactic acid in high molecular weight is characterized in that adopting following two one step process to obtain:
(1), under 100～130 ℃ and 100～300Pa pressure, lactic acid and aliphatic chain length are the aliphatic dibasic acid heating for dissolving of 2～18 carbon atoms, decompression dehydration 1～15 hour; Add the Bivalent Tin compound as catalyst account for lactic acid weight 0.1～10% again, under temperature was 130～200 ℃ and 20～300Pa pressure, reacting 5～25 hours acquisition molecule two ends was the poly(lactic acid) prepolymer of carboxyl; Wherein, the mol ratio of lactic acid and aliphatic dibasic acid is (400: 1)～(40: 1);
(2), be the poly(lactic acid) prepolymer heating and melting of carboxyl by above-mentioned molecule two ends, add Resins, epoxy, under 20～300Pa pressure and 130-200 ℃ of temperature, polymerization obtained poly-lactic acid in high molecular weight in 10～180 minutes; The mol ratio of described poly(lactic acid) prepolymer and Resins, epoxy is (1: 1.0)～(1: 2.0).
2. preparation method as claimed in claim 1 is characterized in that the add-on of the described catalyzer Bivalent Tin compound in the described method (1) is 0.5～5% of a lactic acid weight.
3. preparation method as claimed in claim 1 is characterized in that the viscosity-average molecular weight of the poly(lactic acid) prepolymer that described method (1) obtains is 0.6～30,000.
4. preparation method as claimed in claim 1 is characterized in that the Bivalent Tin compound is tin protochloride or stannous octoate in the described method (1).
5. preparation method as claimed in claim 1 is characterized in that the poly-lactic acid in high molecular weight viscosity-average molecular weight that described method (2) obtains is 13-22 ten thousand.
6. preparation method as claimed in claim 1 is characterized in that the used Resins, epoxy of described method (2) is the Resins, epoxy of the molecule two ends band oxygen groups of glycidyl ester, glycidyl ether or Racemic glycidol amine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100558795C (en) * | 2006-09-07 | 2009-11-11 | 同济大学 | The preparation method of biodegradation polylactic acid based multicomponent block polymer |
| CN102010583A (en) * | 2010-10-15 | 2011-04-13 | 浙江大学 | High-molecular weight long-chain branched crystalline polylactic acid material and preparation method thereof |
| CN101240465B (en) * | 2007-02-05 | 2011-05-04 | 东丽纤维研究所（中国）有限公司 | Polylactic acid hydrolysis-resisting fibre and preparation method thereof |
| CN105315416A (en) * | 2015-12-02 | 2016-02-10 | 河北麦格尼菲复合材料股份有限公司 | Renewable bio-based vinyl ester resin and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3349755B2 (en) * | 1993-04-15 | 2002-11-25 | 三井化学株式会社 | Macromonomer |
| EP1721935B1 (en) * | 2004-03-04 | 2010-09-08 | Unitika Ltd. | Biodegradable polyester resin composition, process for producing the same, and foam and molding obtained therefrom |
| CN100424111C (en) * | 2004-03-25 | 2008-10-08 | 上海同杰良生物材料有限公司 | Method for preparing high-branched poly lactic acid through bulk polymerization |
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2005
- 2005-12-16 CN CNB2005100299635A patent/CN1328299C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100558795C (en) * | 2006-09-07 | 2009-11-11 | 同济大学 | The preparation method of biodegradation polylactic acid based multicomponent block polymer |
| CN101240465B (en) * | 2007-02-05 | 2011-05-04 | 东丽纤维研究所（中国）有限公司 | Polylactic acid hydrolysis-resisting fibre and preparation method thereof |
| CN102010583A (en) * | 2010-10-15 | 2011-04-13 | 浙江大学 | High-molecular weight long-chain branched crystalline polylactic acid material and preparation method thereof |
| CN102010583B (en) * | 2010-10-15 | 2012-12-19 | 浙江大学 | High-molecular weight long-chain branched crystalline polylactic acid material and preparation method thereof |
| CN105315416A (en) * | 2015-12-02 | 2016-02-10 | 河北麦格尼菲复合材料股份有限公司 | Renewable bio-based vinyl ester resin and preparation method thereof |
| CN105315416B (en) * | 2015-12-02 | 2018-02-23 | 河北麦格尼菲复合材料股份有限公司 | Recyclable organism-based vinyl ester resin and preparation method thereof |
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