CN102964580B - Linear comb polylactic acid and preparation method thereof - Google Patents
Linear comb polylactic acid and preparation method thereof Download PDFInfo
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Abstract
The invention provides a linear comb polylactic acid and a preparation method thereof. The linear comb polylactic acid is characterized by having the following structure: the linear comb polylactic acid has number-average molecular weight of 1*10<4>-100*10<4>, and single-arm number-average molecular weight of 0.1*10<4>-3*10<4>; and a linear macromolecular initiator is a hydroxylated linear liquid polymer, and has hydroxy number of 8-60 and number-average molecular weight of 0.1*10<4>- 1*10<4>. The method employs the linear macromolecular initiator hydroxylated linear liquid polymer to prepare a biodegradable material polylactic acid, and has simple efficient process and low cost; the initiator contains no metal, and the polymer has no metallic impurity residue; large molecular weight effectively improves the physical and mechanical properties of the polylactic acid; and a high branched structure effectively improves the processing property of the polylactic acid.
Description
Technical field
The invention belongs to synthesis of polymer material and preparing technical field, be related specifically to the biodegradable poly-lactic acid material of a class, it is characterized in that high molecular, high cladodification Linear comb polylactic acid and preparation method thereof, the poly(lactic acid) prepared by the present invention has excellent physical and mechanical properties and excellent processing characteristics.
Background technology
Poly(lactic acid) is a kind of biodegradable macromolecular material with good biocompatibility, and in numerous biodegradable polymers, poly(lactic acid) is with the performance of its excellence, and wide application field, achieves suitability for industrialized production at home and abroad.But the application of poly-lactic acid material is still subject to the restriction of two broad aspect: one is that the heat-resisting of poly(lactic acid) and erosion-resisting characteristics are poor, and due to its melt strength low, be difficult to carry out the processing such as blown film, foaming, hollow blow molding; Two is poly-lactic acid in high molecular weight complicated process of preparation, and condition is harsh, and generally need to react at high temperature under high pressure, molecular weight is difficult to effective control, remains simultaneously, greatly limit its range of application with metal catalyst.Further raising physical and mechanical properties, improve processing characteristics, optimal preparation technology, will greatly improve the market competitiveness of poly(lactic acid), promote the development of poly(lactic acid) industry.
Current poly(lactic acid) adopts rac-Lactide ring-opening polymerization legal system standby mostly, and the method can obtain the polymkeric substance that molecular weight is high, dispersion coefficient is little.Adopt both at home and abroad mostly pink salt class initiator, as adopted stannous octoate as the initiator of rac-Lactide ring-opening polymerization, but the residue of this initiator metallic tin has been proved to be and has been harmful to organism, significantly limit its application in biomaterial for medical purpose.In recent years, the Novel non-metal initiator with higher biological safety has become the study hotspot of ring-opening polymerization initiator.Chinese patent CN101429276A discloses a kind of poly(lactic acid) preparation method controlled without metal residual, molecular weight, in rac-Lactide solvent, add small molecular alcohol as initiator, add 1 again, 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), completes the ring-opening polymerization of rac-Lactide in the short period of time at normal temperatures and pressures; The molecular weight of product poly(lactic acid) is 0.1 × 10
4-5 × 10
4; Although above-mentioned preparation method can prepare the poly(lactic acid) without metal residual, comparatively inferior on molecular weight.
Polylactic acid melt intensity is low, is difficult to carry out the processing such as blown film, foaming, hollow blow molding and limits its application in the goods such as film and foam.Generally, by improving molecular weight, widening molecular weight distribution, introducing processing characteristics, particularly melt strength that the means such as long-chain branch can improve polymkeric substance.Chinese patent CN101597374A a kind of poly(lactic acid) of openly knowing clearly reacts with polyfunctional monomer the method preparing long chain branch polylactic acid in the molten state, and poly(lactic acid) is after branching, and its melt strength is significantly improved; Because reaction is carried out under the high temperature of 190-210 DEG C, need a large amount of oxidation inhibitor that adds to suppress high temperature degradation, thus increase production cost; Adopt poly(lactic acid) and multifunction group epoxy monomer at high temperature to react simultaneously, very easily crosslinking reaction occurs.
In sum, develop a kind of simple metal-free initiators efficiently and can be used in preparing the poly(lactic acid) of high molecular height branched structure, be have technical problem to be solved, and the solution of this problem greatly will expand the range of application of poly(lactic acid), the market competitiveness of strengthening poly(lactic acid).
Summary of the invention
The object of the present invention is to provide a class Linear comb polylactic acid, this kind of Linear comb polylactic acid has the feature of high cladodification Linear comb structure, high molecular narrow ditribution, have excellent physical and mechanical properties and splendid processing characteristics, be that a class is nontoxic, degradable, high biological safe medical biomaterial simultaneously.Another object of the present invention is to provide a kind of method preparing the simple and effective of above-mentioned Linear comb polylactic acid.Technical characteristic of the present invention is that prepared Linear comb polylactic acid is without metal residual with the linear liquid polymers of hydroxylation for linear molecule initiator.
One class Linear comb polylactic acid, is characterized in that this polymkeric substance has following structure: the number-average molecular weight of Linear comb polylactic acid is 1 × 10
4-100 × 10
4, be preferably 5 × 10
4-70 × 10
4; The single armed number-average molecular weight of poly(lactic acid) is 0.1 × 10
4-3 × 10
4, be preferably 0.5 × 10
4-2.5 × 10
4; ; Linear molecule initiator is the linear liquid polymers of hydroxylation, and the hydroxyl quantity in linear molecule initiator is 8-60, is preferably 12-40; The number-average molecular weight of linear molecule initiator is 0.1 × 10
4-1 × 10
4, be preferably 0.2 × 10
4-0.8 × 10
4.
The preparation method of one class Linear comb polylactic acid, it is characterized in that: at normal temperature, under normal pressure and protection of inert gas, rare gas element is selected from nitrogen, argon gas, by the solvent chloroparaffin of aequum, monomers lactide joins with in the reactor stirred successively, be mixed with the Lactide solution that volumetric molar concentration is 0.5-1.5M, open stirring, according to the size of designed molecular weight of product, add the linear liquid polymers of linear molecule initiator hydroxylation more successively, organic non-metal alkali 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), the mol ratio of monomers lactide and hydroxyl is 8-200, the mol ratio of DBU and hydroxyl is 0.06-1.0, is preferably 0.06-0.35, polymerization reactor control is at 60-90min, and then termination reaction, the mol ratio of terminator and hydroxyl is 3-5, and terminator is phenylformic acid, adopts classical way to carry out aftertreatment, product drying to polymers soln, finally obtains Linear comb polylactic acid.Monomers lactide involved in the present invention is selected from the mixture of one or more rac-Lactides in L-rac-Lactide, D-rac-Lactide, DL-rac-Lactide, and Linear comb polylactic acid can be homopolymer or the multipolymer of above-mentioned monomer.
Linear molecule initiator involved in the present invention is selected from the linear liquid polymers of any poly-hydroxy disclosed in prior art, comprising: the linear liquid polybutadiene of hydroxylation, the linear liquid polyisoprene of hydroxylation, linear liquid butadiene/the isoprene copolymer of hydroxylation, preferably from the linear liquid polybutadiene of hydroxylation, the linear liquid polyisoprene of hydroxylation.The preparation method of the linear liquid polymers of linear molecule initiator hydroxylation, is characterized in that comprising following three parts: the preparation of the preparation of linear liquid polymers, the linear liquid polymers of epoxidation, the preparation of the linear liquid polymers of hydroxylation; Wherein the preparation method of liquid polymers and epoxidized liquid polymer is see Chinese invention patent ZL200710157403.7(butadiene/isoprene/diolefin star comb-shaped polymer and preparation method thereof) and ZL200810190932.1(star-shaped comb type butadiene/phenylethylene block copolymers and preparation method thereof) in disclosed preparation method, compared with the preparation method of star liquid polymers, preparation method's difference of linear liquid polymers no longer needs to add coupling agent (as: SiCl after monomer total overall reaction completes
4) carry out linked reaction, and the preparation method of the linear liquid polymers of epoxidation is identical with the preparation method of epoxidation star liquid polymers; The preparation method of the linear liquid polymers of hydroxylation, it is characterized in that: solvents tetrahydrofurane, the linear liquid polymers of epoxidation are joined in reactor, stir at room temperature or 25 DEG C-30 DEG C, drip the trifluoromethanesulfonic acid aqueous solution, react 3-4 hour again after being added dropwise to complete, add trichloromethane termination reaction; After glue being washed till neutrality with deionized water, the most of solvent of distillation removing, then remove residual solvent further with cold-trap vacuum deep cooling and THF azeotropic, obtain transparent glue.
The preparation method of linear molecule initiator of the present invention is now described for the linear liquid polybutadiene of hydroxylation, but is not limited to the linear liquid polybutadiene of hydroxylation, the preparation method of other linear molecule initiator is identical with following method.The preparation method of the linear liquid polybutadiene of hydroxylation, is characterized in that comprising following three parts: the preparation of the preparation of linear liquid polybutadiene, the linear liquid polybutadiene of epoxidation, the preparation of the linear liquid polybutadiene of hydroxylation; Wherein the preparation method of liquid polybutadiene and epoxidized liquid polyhutadiene is see Chinese invention patent ZL200710157403.7(butadiene/isoprene/diolefin star comb-shaped polymer and preparation method thereof) and ZL200810190932.1(star-shaped comb type butadiene/phenylethylene block copolymers and preparation method thereof) in disclosed preparation method, compared with the preparation method of star liquid polybutadiene, preparation method's difference of linear liquid polybutadiene no longer needs to add coupling agent (as: SiCl after divinyl total overall reaction completes
4) carry out linked reaction, and the preparation method of the linear liquid polybutadiene of epoxidation is identical with the preparation method of epoxidation star liquid polybutadiene; The preparation method of the linear liquid polybutadiene of hydroxylation, it is characterized in that: 40g solvents tetrahydrofurane (THF), the linear liquid polybutadiene of 5g epoxidation (oxirane value is 19.73%) are joined in reactor, stir at room temperature or 25 DEG C-30 DEG C, drip the trifluoromethanesulfonic acid aqueous solution (TfOH:2.8mL; H
2o:10.26g), react 3.5 hours again after being added dropwise to complete, add 150mL trichloromethane termination reaction; After glue being washed till neutrality with deionized water, the most of solvent of distillation removing, then remove residual solvent further with cold-trap vacuum deep cooling and THF azeotropic, obtain transparent glue.
Effect of the present invention and benefit are just: adopt the linear liquid polymers of linear molecule initiator hydroxylation to prepare Biodegradable material poly(lactic acid), and technical process is simply efficient, and cost is lower; Initiator is containing metal not, and polymkeric substance remains without metallic impurity; High molecular, narrow ditribution improve the physical and mechanical properties of poly(lactic acid) effectively; Meanwhile, high branched structure effectively improves the processing characteristics of high molecular, narrow ditribution poly(lactic acid).
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but and the scope of unrestricted the claims in the present invention protection.The mensuration of hydroxylated polybutadiene hydroxylation degree (E): hydroxylated polymer hydroxylation degree adopts
1h-NMR method is tested, and calculates publicity as follows:
Wherein: hydroxyl peak position is 3.4ppm and 3.6ppm; Polyhutadiene different structure peak position: 1,2 structures are 4.9ppm, suitable anti-Isosorbide-5-Nitrae structure is 5.4ppm.
Embodiment 1
The preparation of the linear liquid polybutadiene of hydroxylation liquid: adopt classical anionic polymerisation process, take hexanaphthene as solvent, n-Butyl Lithium is initiator, divinyl is monomer, prepare linear liquid polybutadiene, the number-average molecular weight of polyhutadiene is 3900(GPC test), molecular weight distributing index PDI is 1.38.In 250mL reactor, add the toluene solution 150mL being dissolved with aforesaid liquid polyhutadiene 7.2g, open stirring, add 88% formic acid of 2.2g when temperature rises to 45 DEG C, in 30min, drip off 30% hydrogen peroxide of 6.6g, react 2 hours; After glue being washed till neutrality with deionized water, the most of solvent of distillation removing, obtains transparent glue, and epoxy content is the test of 18.64%(nuclear-magnetism method).Get the linear liquid polybutadiene of 11g epoxidation, 82.1g tetrahydrofuran (THF) stirs in reactor, is dissolved in by 2.8mL trifluoromethanesulfonic acid in the deionized water of 10.26g and is added drop-wise in reactor, reacts 3.5 hours, adds 150mL trichloromethane termination reaction.After glue being washed till neutrality with deionized water, distill away most of solvent, then after using cold-trap vacuum deep cooling and THF azeotropic to constant weight, obtain transparent glue; Product hydroxy degree is 14.73%, and hydroxyl value is 21.27, and number-average molecular weight is 4200(GPC test), PDI is 1.16.
Embodiment 2
The preparation of Linear comb polylactic acid: normal temperature and pressure; under inert nitrogen gas protection; the DL-lactide monomer of 11.4g is dissolved in 160mL dichloromethane solvent and is made into Lactide solution; add the linear liquid polybutadiene initiator of hydroxylation of synthesis in 0.1g embodiment 1; the mol ratio 150 of monomers lactide and hydroxyl; single armed number-average molecular weight is 21700; add 1; 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU; be 0.15 metering by the mol ratio of DBU and hydroxyl), reaction 75min.Add terminator phenylformic acid (be 3 meterings by the mol ratio of terminator and hydroxyl), carry out aftertreatment to polymkeric substance glue after reaction terminating, monomer conversion is greater than 99%, carries out analytical test after drying, obtains the finished product Linear comb polylactic acid.Product is through gpc analysis weight-average molecular weight 53.71 × 10
4, number-average molecular weight 46.61 × 10
4, PDI is 1.15.
Embodiment 3
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 19, single armed number-average molecular weight is the mol ratio of 2800, DBU and hydroxyl is 0.55, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 7.60 × 10
4, number-average molecular weight 6.49 × 10
4, PDI is 1.17.
Embodiment 4
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 35, single armed number-average molecular weight is 5000, the mol ratio of DBU and hydroxyl is 0.35, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 12.10 × 10
4, number-average molecular weight 11.10 × 10
4, PDI is 1.09.
Embodiment 5
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 16, monomer is L-rac-Lactide, single armed number-average molecular weight is 2400, the mol ratio of DBU and hydroxyl is 0.75, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 6.46 × 10
4, number-average molecular weight 5.43 × 10
4, PDI is 1.19.
Embodiment 6
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 33, monomer is D-rac-Lactide, single armed number-average molecular weight is 4800, the mol ratio of DBU and hydroxyl is 0.90, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 12.50 × 10
4, number-average molecular weight 10.63 × 10
4, PDI is 1.17.
Embodiment 7
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 141, monomer is D-rac-Lactide, single armed number-average molecular weight is 20500, the mol ratio of DBU and hydroxyl is 0.15, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 50.18 × 10
4, number-average molecular weight 44.12 × 10
4, PDI is 1.14.
Embodiment 8
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 75, monomer is L-rac-Lactide, single armed number-average molecular weight is 11060, the mol ratio of DBU and hydroxyl is 0.15, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 27.75 × 10
4, number-average molecular weight 23.52 × 10
4, PDI is 1.18.
Embodiment 9
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 105, monomer is L-rac-Lactide, single armed number-average molecular weight is 15400, the mol ratio of DBU and hydroxyl is 0.15, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 38.21 × 10
4, number-average molecular weight 32.11 × 10
4, PDI is 1.19.
Embodiment 10
The preparation of Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 185, monomer is L-rac-Lactide, single armed number-average molecular weight is 28500, the mol ratio of DBU and hydroxyl is 0.15, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 71.05 × 10
4, number-average molecular weight 59.71 × 10
4, PDI is 1.19.
Embodiment 11
The preparation of the linear liquid polyisoprene of hydroxylation liquid: preparation method is with embodiment 1, and product hydroxy degree is 13.16%, and hydroxyl value is 28.59, number-average molecular weight is 6300(GPC test), PDI is 1.21.The linear liquid polyisoprene of hydroxylation liquid prepared with the present embodiment is initiator, the preparation of preparation Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 105, monomer is D-rac-Lactide, single armed number-average molecular weight is 14800, the mol ratio of DBU and hydroxyl is 0.15, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 49.92 × 10
4, number-average molecular weight 42.31 × 10
4, PDI is 1.18.
Embodiment 12
The preparation of the linear liquid polybutadiene of hydroxylation liquid: preparation method is with embodiment 1, and hydroxyl value is 12.31.The linear liquid polybutadiene of hydroxylation liquid prepared with the present embodiment is initiator, prepare the preparation of star-shaped comb type poly(lactic acid): test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 105, monomer is DL-rac-Lactide, single armed number-average molecular weight is 16800, the mol ratio of DBU and hydroxyl is 0.15, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 24.21 × 10
4, number-average molecular weight 20.69 × 10
4, PDI is 1.17.
Embodiment 13
The preparation of the linear liquid polybutadiene of hydroxylation liquid: preparation method is with embodiment 1, and hydroxyl value is 39.25.The hydroxylation liquid star liquid polybutadiene prepared with the present embodiment is initiator, the preparation of preparation Linear comb polylactic acid: test recipe and preparation method are with embodiment 2, difference is the mol ratio of monomers lactide and hydroxyl is 110, monomer is DL-rac-Lactide, single armed number-average molecular weight is 15160, the mol ratio of DBU and hydroxyl is 0.15, and product Linear comb polylactic acid is through gpc analysis weight-average molecular weight 70.81 × 10
4, number-average molecular weight 59.50 × 10
4, PDI is 1.19.
Claims (7)
1. a class Linear comb polylactic acid, is characterized in that this polymkeric substance has following structure: the number-average molecular weight of Linear comb polylactic acid is 1 × 10
4-100 × 10
4, the single armed number-average molecular weight of poly(lactic acid) is 0.1 × 10
4-3 × 10
4; Linear molecule initiator is the linear liquid polymers of hydroxylation, and the hydroxyl quantity in linear molecule initiator is 8-60, and the number-average molecular weight of linear molecule initiator is 0.1 × 10
4-1 × 10
4;
The preparation method of a described class Linear comb polylactic acid, comprises the steps:
Under normal temperature, normal pressure and protection of inert gas; solvent chloroparaffin, monomers lactide are joined successively with in the reactor stirred; be mixed with the Lactide solution that volumetric molar concentration is 0.5-1.5M; open stirring; according to the size of molecular weight of product; add the linear liquid polymers of linear molecule initiator hydroxylation, organic non-metal alkali 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene more successively, the number-average molecular weight of linear molecule initiator is 0.1 × 10
4-1 × 10
4the mol ratio of monomers lactide and hydroxyl is 8-200, organic non-metal alkali 1, the mol ratio of 8-diazabicylo [5.4.0] 11 carbon-7-alkene and hydroxyl is 0.06-1.0, polymerization reactor control at 60-90min, then termination reaction, the mol ratio of terminator and hydroxyl is 3-5, terminator is phenylformic acid, carries out aftertreatment, product drying, finally obtain Linear comb polylactic acid to polymers soln;
Wherein hydroxylation linear molecule initiator is selected from the mixture of one or more the hydroxylation liquid polymerses in the linear liquid polybutadiene of hydroxylation, the linear liquid polyisoprene of hydroxylation, the linear liquid butadiene/isoprene copolymer of hydroxylation.
2. Linear comb polylactic acid according to claim 1, is characterized in that the number-average molecular weight of wherein Linear comb polylactic acid is 5 × 10
4-70 × 10
4, the single armed number-average molecular weight of poly(lactic acid) is 0.5 × 10
4-2.5 × 10
4.
3. Linear comb polylactic acid according to claim 1, is characterized in that the hydroxyl quantity in wherein linear molecule initiator is 12-40.
4. the Linear comb polylactic acid according to claim 1 or 2 or 3, is characterized in that wherein monomers lactide is selected from the mixture of one or more rac-Lactides in L-rac-Lactide, D-rac-Lactide, DL-rac-Lactide.
5. the Linear comb polylactic acid according to claim 1 or 2 or 3, is characterized in that wherein solvent is selected from the mixture of one or more in dichloro-alkane, three chloroparaffins.
6. the Linear comb polylactic acid according to claim 1 or 3, is characterized in that the number-average molecular weight of wherein linear molecule initiator is 0.2 × 10
4-0.8 × 10
4.
7. the Linear comb polylactic acid according to claim 1 or 2 or 3, is characterized in that the mol ratio of wherein organic non-metal alkali 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and hydroxyl is 0.06-0.35.
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