CN101130599A - Heat-resistance polylactic acid copolymer and ring opening polymerization method for preparing the same - Google Patents
Heat-resistance polylactic acid copolymer and ring opening polymerization method for preparing the same Download PDFInfo
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- CN101130599A CN101130599A CNA2006100862121A CN200610086212A CN101130599A CN 101130599 A CN101130599 A CN 101130599A CN A2006100862121 A CNA2006100862121 A CN A2006100862121A CN 200610086212 A CN200610086212 A CN 200610086212A CN 101130599 A CN101130599 A CN 101130599A
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Abstract
The invention discloses a heat resistant polylactic acid copolymer and ring-opening polymerizing making method, which is made of D-lactide and L-lactide acted by chiral catalyst to do ring-opening polymerization, wherein the fusing point is 180-225 deg. c with the molar rate of the quantity of D-lactic acid and L-lactic acid at 20: 80-80: 20 in the polylactic acid copolymer. The invention has good heat resistance, which is convenient to manufacture.
Description
Technical field:
The present invention relates to a kind of heat-proof polylactic acid copolymer and preparation method.
Background technology:
Poly(lactic acid) (PLA) does not exist at nature, makes by synthetic.Monomer-lactic acid as synthesis material then is by biological fermentation.Poly(lactic acid) belongs to synthetic straight chain aliphatic polyester, obtains by the ring-opening polymerization of lactic acid cyclisation dimer-rac-Lactide or the direct polymerization of lactic acid.Poly(lactic acid) has good biodegradability, and degraded product is carbonic acid gas and water, environment is not produced any problem.Poly(lactic acid) also has good biological blending and bioresorbable, has been considered to the most promising degradable high polymer material in medical field, and is very active to its research and development.But because the too high restriction of poly(lactic acid) production cost, starting late as uses such as general degradative plastics, fibers, in recent years, because environmental requirement, people are extraordinarily paid attention to poly(lactic acid), begun it is replaced as general-purpose plastics, fiber etc. the exploration exploitation of product.Though the price of PLA resin along with the input of great amount of manpower and financial resources, will produce breakthrough still than higher at present.
The poly(lactic acid) that attracts people's attention is in the Biodegradable polymkeric substance, and from mechanical characteristic, the balance of thermotolerance and cost several respects considers that poly(lactic acid) also is optimum.Yet even if most promising like this poly(lactic acid), the polymer phase ratio with traditional still has some shortcomings.Wherein bigger scarce be that thermostability is bad, in the course of processing, often cause comparatively serious thermal destruction, cause the decline significantly of molecular weight.Poor heat resistance makes the expansion of poly(lactic acid) polymer aspect purposes be very limited.Therefore, people wish to obtain a kind of poly(lactic acid) superpolymer of excellent heat resistance.
Summary of the invention:
The object of the present invention is to provide a kind of good heat resistance, heat-proof polylactic acid copolymer convenient for production and ring-opening polymerization preparation method.
Technical solution of the present invention is:
A kind of heat-proof polylactic acid copolymer, it is characterized in that: the copolymer of poly lactic acid of ring-opening polymerization preparation under the catalyst action of chirality by D-rac-Lactide and L-rac-Lactide mixture, its fusing point is 180 ℃～225 ℃, and the mol ratio of poly-D-lactic acid production and poly (l-lactic acid) amount is 20: 80～80: 20 in the copolymer of poly lactic acid.
A kind of ring-opening polymerization prepares the method for heat-proof polylactic acid copolymer, carries out ring-opening polymerization by polymerization single polymerization monomer under catalyst action, it is characterized in that:
A. the catalyzer that uses in the ring-opening polymerization is the chiral selectivity compound with following structural formula:
(formula 1)
Wherein M is a metallic element; R is the ring-type hydrocarbons; R
1=H or methyl or sec.-propyl or phenyl or t-butyl; R
2=H or methyl or t-butyl; R
3=methyl oxygen base or sec.-propyl oxygen base;
B. polymerization single polymerization monomer is D-rac-Lactide and L-rac-Lactide mixture.
M is metallic element aluminium or zinc.The chiral catalyst of aluminum metal correspondence is better to the space multistory selectivity under identical coordination.
The ring-type hydrocarbons of R is
(formula 2) or
(formula 3).
Polymerization single polymerization monomer is the mixture of D-rac-Lactide and L-rac-Lactide, and the mol ratio between D-rac-Lactide and the L-rac-Lactide is 20: 80～80: 20.The mol ratio of catalyzer addition and polymerization single polymerization monomer amount is 1: 100～1: 1000.The method of ring-opening polymerization is solution polymerization or melt polymerization; The methylene chloride of solution polymerization or toluene; Melt polymerization is that decompression was reacted 3～16 hours under 130～200 ℃ of temperature.
The Preparation of catalysts method is a lot, here used Preparation of catalysts feature is that Schiff's base chiral ligand and metal alkoxide react in toluene or dichloromethane solvent, temperature of reaction is controlled between 30～110 ℃, and the mol ratio between the metallic element in chiral ligand and the metal alkoxide is 1: 1.The catalyzer that makes exists left-handed and two kinds of optically active forms of dextrorotation, and the racemic modification of catalyzer is that levo form and dextrorotatory form obtain according to 1: 1 mixed in molar ratio.In the ring-opening polymerization process of the D-of certain mol proportion rac-Lactide and L-rac-Lactide mixture, generally adopt the racemize catalyzer, the poly(lactic acid) that makes of condition is the multipolymer of D-rac-Lactide and L-rac-Lactide like this.
The method of ring-opening polymerization generally has two kinds, and a kind of is solution polymerization, and another kind is a melt polymerization.The solution ring-opening polymerization is that catalyzer and polymerization single polymerization monomer are dissolved in methylene dichloride or the toluene, and under churned mechanically condition, 30～110 ℃ of temperature ranges were reacted 5～60 hours.Be settled out polymkeric substance with excessive methanol.In this method, catalyzer is stronger to the space multistory selectivity.The melt polymerization ring-opening polymerization is that catalyzer and polymerization single polymerization monomer are sealed in the three-necked flask and reduce pressure, and reacts 3～16 hours under 130～200 ℃ of temperature.This method requires catalyzer certain thermotolerance to be arranged and have stronger space multistory selectivity.
Under above-mentioned chirality selecting catalyst effect, be optically pure poly-D-lactic acid or optically pure poly (l-lactic acid) or poly-D-lactic acid and poly (l-lactic acid) segmented copolymer co-polymer according to the polymkeric substance of the different gained of reaction monomers.Wherein poly (l-lactic acid) or poly-D-lactic acid and poly (l-lactic acid) segmented copolymer have better crystallization, and its fusing point can be higher than 180 ℃ (fusing point of optically pure poly(lactic acid) generally is lower than 180 ℃), and corresponding thermotolerance is higher.By mol ratio is that D-rac-Lactide and L-rac-Lactide mixture prepared its fusing point of copolymer of poly lactic acid under racemic above-mentioned catalyst action of 20: 80～80: 20 can reach more than 180 ℃.The product good heat resistance that the present invention produces, convenient for production.
Embodiment:
Embodiment 1:
Preparation of catalysts
Under stirring and protection of nitrogen gas condition, the R of 4ml, the R-Schiff's base (formula 1 structural formula, wherein
R
1=t-butyl, R
2=t-butyl) ALO of toluene solution and 4ml
iPr toluene solution (1mol/L) mixes, and 70 ℃ of temperature controls stirred 48 hours, and cooling vacuumizes and removes volatile matter then, obtains catalyzer 2.2g, ultimate analysis observed value: C:73.94, H:9.53, N:4.52.
Embodiment 2～6 is as follows, and other experiment conditions are identical with embodiment 1.
| Embodiment | The Schiff's base substituting group | Metal alcoholate | The ultimate analysis test value | ||||
| R | R 1 | R 2 | Classification | C | H | N | |
| 2 | S, S-Schiff's base substituting group is with embodiment 1 | AL-O iPr | 74.28 | 9.42 | 4.50 | ||
| 3 | Formula 3 | The hydrogen base | The hydrogen base | AL-O iPr | 76.37 | 5.34 | 4.50 |
| 4 | S, S-Schiff's base substituting group is with embodiment 5 | AL-O iPr | 77.01 | 5.02 | 4.47 | ||
R, the R-Schiff's base is meant: the Schiff's base dextrorotatory form; S, the S-Schiff's base is meant: the Schiff's base levo form.
AL-O
iPr is meant: aluminum isopropylate; Al-OEt is meant: aluminum ethylate
Embodiment 5
The poly(lactic acid) preparation
Under nitrogen protection; earlier toward adding each 0.1mmol of catalyzer and the 40ml toluene that rac-lactide 20mmol, embodiment 1,2 make through order in the ampere bottle of anhydrous and oxygen-free processing; again the ampere bottle is placed 70 ℃ of oil baths; react after 12 hours; with methylene dichloride (or toluene) 60ml dissolve polymer, go out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 2.5g polymkeric substance at last, is standard substance with the polystyrene, and the weight-average molecular weight that GPC records product is 2.4 ten thousand, and polymkeric substance has crystallinity, and fusing point is 190 ℃.
Embodiment 6
The poly(lactic acid) preparation
Under nitrogen protection; earlier toward adding each 0.1mmol of catalyzer and the 40ml toluene that rac-lactide 20mmol, embodiment 3,4 make through order in the ampere bottle of anhydrous and oxygen-free processing; again the ampere bottle is placed 70 ℃ of oil baths; react after 12 hours; with methylene dichloride (or toluene) 60ml dissolve polymer, go out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 2.5g polymkeric substance at last, is standard substance with the polystyrene, and the weight-average molecular weight that GPC records product is 11.3 ten thousand, and polymkeric substance has crystallinity, and fusing point is 205 ℃.
Embodiment 7～11 is as follows, and other experiment conditions are identical with embodiment 8.
| Embodiment | Catalyzer | Reaction times (h) | The reactant composition | Mw 10 3 | Fusing point (℃) |
| 7 | With embodiment 5 | 12 | L-rac-Lactide/D-rac-Lactide=70/30 | 22 | 195 |
| 8 | With embodiment 5 | 48 | Rac-lactide | 101 | 201 |
| 9 | With embodiment 6 | 48 | L-rac-Lactide/D-rac-Lactide=70/30 | 114 | 199 |
| 10 | With embodiment 6 | 60 | Rac-lactide | 154 | 225 |
Rac-lactide: L-rac-Lactide/D-rac-Lactide=50%/50%
Embodiment 11
Under the nitrogen protection, the catalyzer 0.2mmol that rac-lactide 20mmol and embodiment 1,2 make adds 130 ℃ of fusions in the ampere bottle of handling through anhydrous and oxygen-free, and reaction is 16 hours under agitation condition.Obtaining the 2.5g polymkeric substance, is standard substance with the polystyrene, and the weight-average molecular weight that GPC records product is 5.7 ten thousand, and polymkeric substance has crystallinity, and fusing point is 196 ℃.
Embodiment 13:
Catalyzer adopts the material of following structural formula:
Wherein M is metallic element zinc (or aluminium); R is the ring-type hydrocarbons; R
1=methyl (or sec.-propyl or phenyl); R
2=methyl; R
3=sec.-propyl oxygen base (or methyl oxygen base); Polymerization single polymerization monomer adopts D-rac-Lactide and L-rac-Lactide mixture, and mol ratio D-rac-Lactide: the L-rac-Lactide is 20: 80～80: 20 (example 20: 80,40: 60,60: 40,80: 20).Melt temperature is 130 ℃～200 ℃ (130 ℃, 160 ℃, 200 ℃ of examples), in 3～16 hours reaction times (example 3,10,16 hours), the mol ratio of catalyzer addition and polymerization single polymerization monomer is 1: 100～1: 1000 (example 1: 100,1: 500,1: 1000).The remaining reaction step obtains heat-proof polylactic acid copolymer with embodiment 11.
Testing method
(1) weight-average molecular weight (Mw)
The gel permeation chromatograph (GPC) of Tianjin, island company, test condition: probe temperature is 30 ℃, and moving phase is tetrahydrofuran (THF), and standard model is a polystyrene.
(2) differential scanning tester (DSC)
Instrument is TA-Q100, under nitrogen atmosphere, with the variation in 0～250 ℃ of scope of 10 ℃/min temperature rise rate observation.
Claims (7)
1. heat-proof polylactic acid copolymer, it is characterized in that: the copolymer of poly lactic acid of ring-opening polymerization preparation under the chiral catalyst effect by D-rac-Lactide and L-rac-Lactide mixture, its fusing point is 180 ℃～225 ℃, and the mol ratio of poly-D-lactic acid production and poly (l-lactic acid) amount is 20: 80～80: 20 in the copolymer of poly lactic acid.
2. a ring-opening polymerization prepares the method for heat-proof polylactic acid copolymer, carries out ring-opening polymerization by polymerization single polymerization monomer under catalyst action, it is characterized in that:
A. the catalyzer that uses in the ring-opening polymerization is the chiral selectivity compound with following structural formula:
Wherein M is a metallic element; R is the ring-type hydrocarbons; R
1=H or methyl or sec.-propyl or phenyl or t-butyl; R
2=H or methyl or t-butyl; R
3=methyl oxygen base or sec.-propyl oxygen base;
B. polymerization single polymerization monomer is D-rac-Lactide and L-rac-Lactide mixture.
3. ring-opening polymerization according to claim 2 prepares the method for heat-proof polylactic acid copolymer, it is characterized in that: M is metallic element aluminium or metallic element zinc.
4. ring-opening polymerization according to claim 2 prepares the method for heat-proof polylactic acid copolymer, it is characterized in that: the ring-type hydrocarbons of R is
Or
5. ring-opening polymerization according to claim 2 prepares the method for heat-proof polylactic acid copolymer, it is characterized in that: polymerization single polymerization monomer is the mixture of D-rac-Lactide and L-rac-Lactide, and the mol ratio between D-rac-Lactide and the L-rac-Lactide is 20: 80～80: 20.
6. ring-opening polymerization according to claim 2 prepares the method for heat-proof polylactic acid copolymer, it is characterized in that: the mol ratio of catalyzer addition and polymerization single polymerization monomer amount is 1: 100～1: 1000.
7. described ring-opening polymerization prepares the method for heat-proof polylactic acid copolymer according to claim 2, and it is characterized in that: the method for ring-opening polymerization is solution polymerization or melt polymerization; The methylene chloride of solution polymerization or toluene; Melt polymerization is that decompression was reacted 3～16 hours under 130～200 ℃ of temperature.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266593A (en) * | 2011-07-27 | 2011-12-07 | 长春圣博玛生物材料有限公司 | Absorbable internal fracture fixing piece |
| CN102838637A (en) * | 2012-09-18 | 2012-12-26 | 华东理工大学 | Imine phenol oxymagnesium compound, and preparation method and application thereof |
| CN107236118A (en) * | 2017-06-23 | 2017-10-10 | 四川大学 | A kind of new many block PLA and its synthetic method |
| CN113549202A (en) * | 2021-08-24 | 2021-10-26 | 濮阳市盛源石油化工（集团）有限公司 | Copolymerized polylactic acid and preparation method thereof |
| CN115612071A (en) * | 2022-08-30 | 2023-01-17 | 山东理工大学 | Preparation method of antibacterial colored polylactic acid |
-
2006
- 2006-08-22 CN CNA2006100862121A patent/CN101130599A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266593A (en) * | 2011-07-27 | 2011-12-07 | 长春圣博玛生物材料有限公司 | Absorbable internal fracture fixing piece |
| CN102838637A (en) * | 2012-09-18 | 2012-12-26 | 华东理工大学 | Imine phenol oxymagnesium compound, and preparation method and application thereof |
| CN102838637B (en) * | 2012-09-18 | 2015-08-19 | 华东理工大学 | Imine phenol oxygen base magnesium compound and its preparation method and application |
| CN107236118A (en) * | 2017-06-23 | 2017-10-10 | 四川大学 | A kind of new many block PLA and its synthetic method |
| CN113549202A (en) * | 2021-08-24 | 2021-10-26 | 濮阳市盛源石油化工（集团）有限公司 | Copolymerized polylactic acid and preparation method thereof |
| CN115612071A (en) * | 2022-08-30 | 2023-01-17 | 山东理工大学 | Preparation method of antibacterial colored polylactic acid |
| CN115612071B (en) * | 2022-08-30 | 2023-08-01 | 山东理工大学 | Preparation method of antibacterial colored polylactic acid |
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Application publication date: 20080227 |