CN101245178B - Method for manufacturing biologically degradable polyester composite material with capacity increasing function - Google Patents
Method for manufacturing biologically degradable polyester composite material with capacity increasing function Download PDFInfo
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- CN101245178B CN101245178B CN2008100343152A CN200810034315A CN101245178B CN 101245178 B CN101245178 B CN 101245178B CN 2008100343152 A CN2008100343152 A CN 2008100343152A CN 200810034315 A CN200810034315 A CN 200810034315A CN 101245178 B CN101245178 B CN 101245178B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of polymer materials, which more particularly relates to a preparation method of a biological decomposable polyester composite material with compatibilization function. The specific steps are that: a method of small molecular diol hydroxyl end capping is adopted for preparing polylactic acid and biological decomposable polyester diol, a diisocyanate series chain extender is used for preparing the block copolymer of the polylactic acid and the decomposable polyester by a method of fusion chain extension, and the block copolymer is used in a blend system of the polylactic acid and the corresponding polyester to play the role of compatibilization function. The preparation method of the biological decomposable polyester composite material is simple in method and technique, easy in industrial production and the prepared block copolymer can increase the compatibility of the polylactic acid and the biological decomposable polyester blend system effectively and play the role of a compatibilizer.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method with biologically degradable polyester composite material of capacity increasing function.
Background technology
(Poly lactic acid PLA) derives from reproducible natural phant to poly(lactic acid), and as Ipomoea batatas, corn and other cereal all can be used as its raw material.Poly(lactic acid) is with its favorable biological degradability and absorbability, and the good mechanical performance, multiple working method such as be applicable to blowing, injection moulding, extrude.Become the emphasis of biomaterial research, can be applicable to industrial and agricultural production fields such as agricultural film, aquatic products material, paper bag articles for use, agriculture chemical slow-release material.Toughness is relatively poor yet PLA matter is hard, and tension set, shock strength are low, lack flexibility and elasticity, very easily flexural deformation; These shortcomings of poly(lactic acid) have greatly limited its purposes and result of use.
Polymer blending is to obtain the polymkeric substance of high comprehensive performance and the easiest, the most effectual way of polymer modification, yet incompatible between the most polymers, directly mixes the blend that can not get excellent property.People have successfully prepared the blend of a series of performance brilliances by introduce segmented copolymer or graft copolymer in co-mixing system.At present, the polyester that is used for not losing again with polylactic acid blend its degradability mainly is some aliphatic polyesters or aliphatic-aromatic copolyester.At first, aliphatic polyester or aliphatic-aromatic copolyester generally all have long-(CH
2)
n-segment, kindliness is relatively good, so sneak into the fragility that can improve poly(lactic acid) in the poly(lactic acid); Secondly, segmental of different nature is introduced, and can destroy the order of molecular chain in the poly(lactic acid), influences its crystal property, the fragility of the reduction poly-lactic acid material that this also can part.But the consistency of aliphatic polyester or aliphatic-aromatic copolyester and polylactic acid blend is bad, causes the mechanical property of poly(lactic acid)/degradable poly ester blend material to improve also not obvious.When add a small amount of corresponding segmented copolymer in the co-mixing system of being made up of two kinds of mutual exclusive homopolymer after, segmented copolymer can play the effect of expanding material, is similar to traditional tensio-active agent.They are dispersed on two kinds of mutual exclusive homopolymer phase interfacies, reduce interfacial tension, strengthen interfacial adhesion, and the phase region size is reduced, and make phase structure become more stable, can obtain the blend of better mechanical property after the blend.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, easy to control, be easy to the preparation method that suitability for industrialized production has the biologically degradable polyester composite material of capacity increasing function.
The preparation method of the biologically degradable polyester composite material that the present invention proposes with capacity increasing function, the method of employing chain extension is prepared the segmented copolymer of poly(lactic acid) and biodegradable polyesters, use the blend of prepared in twin-screw extruder poly(lactic acid) and biodegradable polyesters then, in the blend process, use the segmented copolymer of synthetic poly(lactic acid) and biodegradable polyesters as expanding material.Concrete steps are as follows:
(1) with poly(lactic acid) vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01～2000Pa, and temperature of reaction is 160～180 ℃, react 3～5h, obtain the hydroxy-end capped product poly(lactic acid) dibasic alcohol of poly(lactic acid); Wherein, the mol ratio of small molecules dibasic alcohol and poly(lactic acid) is 1: 1～6: 1;
(2) degradable polyester vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01～2000Pa, and temperature of reaction is 170～270 ℃, react 3～5h, obtain the hydroxy-end capped product degradable polyester dibasic alcohol of biodegradable polyesters; Wherein, the mol ratio of small molecules dibasic alcohol and degradable polyester is 1: 1～6: 1;
(3) the degradable polyester dibasic alcohol that obtains of poly(lactic acid) dibasic alcohol that step (1) is obtained and step (2) proportionally joins in the reactor, and adds catalyzer simultaneously.Inflated with nitrogen vacuumizes, and 3 times repeatedly, under agitation, temperature of reaction kettle is risen to the above 5-25 of fusing point ℃ of melt temperature the higher person in poly(lactic acid) and the degradable polyester, keep reacting 5～30min under this temperature, until the complete fusion of system; Under nitrogen protection, add chainextender and carry out the chain extension reaction then, the pressure in the reactor is 0.01～2000Pa, and temperature of reaction is the above 5-25 of fusing point ℃ of melt temperature the higher person among both, and the reaction times is 20～50min; Reaction under the nitrogen protection condition, is cooled to room temperature after finishing, and obtains the segmented copolymer of poly(lactic acid) and degradable polyester; Wherein, poly(lactic acid) dibasic alcohol and degradable polyester dibasic alcohol mol ratio are 1: 10～10: 1;
(4) segmented copolymer that obtains in the step (3) is made pellet, as expanding material, be mixed together evenly with the pellet of poly(lactic acid) that is used for blend and degradable polyester, and add oxidation inhibitor and mix lubricant and join in the twin screw extruder after evenly and melt extrude, extrusion temperature 150-200 ℃, screw speed 50-300rpm obtains desired product, and wherein the weight percent of each component is:
Poly(lactic acid): 48-97%
Degradable polyester: 1-50%
Expanding material: 1-10%
Oxidation inhibitor: 0.5-1%
Lubricant: 0.5-1%.
Among the present invention, small molecules dibasic alcohol described in the step (1) be in ethylene glycol, butyleneglycol or the hexylene glycol etc. any.
Among the present invention, catalyzer described in the step (1) is the one to multiple kind in stannous octoate, tin protochloride, polyphosphoric acid, toluene-4-semi-annular jade pendant acid, tin acetate or the manganese acetate etc., and the add-on of catalyzer is for adding the 0.1-1% of poly(lactic acid) quality.
Among the present invention, degradable polyester comprises described in the step (2): polycaprolactone (PCL), polyethylene glycol succinate (PES), poly butylene succinate (PBS), poly adipate succinic acid ester (PBA), polyhexamethylene adipate (PHA), poly--3-butyric ester (P3HB) or poly-(mutual-phenenyl two acid bromide two alcohol ester-co-tetramethylene adipate) (PBAT) etc. in any.
Among the present invention, small molecules dibasic alcohol described in the step (2) be in ethylene glycol, butyleneglycol or the hexylene glycol etc. any.
Among the present invention, catalyzer described in the step (2) is stannous octoate, tin protochloride, polyphosphoric acid, toluene-4-semi-annular jade pendant acid, tin acetate, manganese acetate, magnesium acetate, the positive butyl ester of metatitanic acid-4-or one to multiple kind during metatitanic acid-the 4-isopropyl ester is medium, and the add-on of catalyzer is the 0.1-1% of degradable polyester quality.
Among the present invention, in the step (3) catalyzer of chain extending reaction be in stannous octoate, tin protochloride, dibutyltin dilaurate, polyphosphoric acid, toluene-4-semi-annular jade pendant acid, tin acetate, manganese acetate, magnesium acetate, the positive butyl ester of metatitanic acid-4-or the metatitanic acid-4-isopropyl ester etc. one to several, the add-on of catalyzer is the 0.1-1% of poly(lactic acid) dibasic alcohol and degradable polyester dibasic alcohol total mass.
Among the present invention, chainextender is a diisocyanate compound described in the step (3), as MDI, HDI, TDI, IPDI etc.(NCO) (OH) mol ratio of group is calculated ,-NCO :-OH is 3: 1～1: 1 to the contained hydroxyl of group and poly(lactic acid) dibasic alcohol and degradable polyester dibasic alcohol to the chainextender consumption with isocyano contained in the chainextender.
Employed expanding material is the segmented copolymer of preparation in the step (3) in the step of the present invention (4), and is used for preparing the degradable polyester of this multipolymer and the polyester components of poly(lactic acid)/degradable polyester co-mixing system can be different sorts, different molecular weight; The poly(lactic acid) that is used for preparing this multipolymer can be the different trades mark, different molecular weight with the poly(lactic acid) component of poly(lactic acid)/degradable polyester co-mixing system.
Among the present invention, oxidation inhibitor is tricresyl phosphite (2 described in the step (4), the 4-di-tert-butyl-phenyl) one in the dimer of phenyl-phosphite kind antioxidant such as ester, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester, phosphorous acid benzene two isodecyl esters and many alkyl dihydroxyphenyl propane phosphorous acid ester or the trimerical mixture is to multiple.
Among the present invention, lubricant described in the step (4) is one or more in fatty acid acyl aminated compounds, fatty acid metal soap compounds, the long chain fatty acid, as in amine hydroxybenzene, stearic amide, calcium stearate, Magnesium Stearate, the aluminum stearate one or more.
The invention has the advantages that:
(1) adopts the segmented copolymer of the method preparation of chain extension that poly(lactic acid)/degradable polyester co-mixing system is had good compatibilization effect, effectively improve the consistency of poly(lactic acid)/degradable polyester co-mixing system two components, improve the mechanical property of matrix material.
(2) multipolymer of poly(lactic acid) and degradable polyester is still Biodegradable material, adds the biodegradability that can not influence matrix material in the matrix material as expanding material.
(3) proterties of expanding material used in the present invention and poly(lactic acid) and degradable polyester are very close.Work in-process need not to change original equipment and technology.
(4) can be by regulating molecular weight, proportioning and the NCO of poly(lactic acid) and degradable polyester performed polymer in the expanding material preparation process: the mol ratio of OH etc., thus obtain being applicable to the expanding material of different poly(lactic acid)/degradable polyester co-mixing system.
Embodiment
Below by embodiment the present invention further is illustrated.
Embodiment 1:
(1) with 5g poly(lactic acid) vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 165 ℃, react 3h, obtain the hydroxy-end capped product poly(lactic acid) dibasic alcohol of poly(lactic acid); Wherein, the mol ratio of small molecules dibasic alcohol and poly(lactic acid) reaction is 1.5: 1;
(2) with 5g PBAT vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 200 ℃, react 5h, obtain the hydroxy-end capped product degradable polyester dibasic alcohol of biodegradable polyesters; Wherein, the mol ratio of small molecules dibasic alcohol and degradable polyester reaction is 1.5: 1;
(3) will finish in the poly(lactic acid) and PBAT adding vacuum reaction still of termination process, add the inferior tin 0.005g of octoate catalyst, tetrabutyl titanate 0.005g.Inflated with nitrogen vacuumizes, 3 times repeatedly.Under powerful mechanical agitation, temperature of reaction kettle is risen to 165 ℃, keep temperature 5min until the complete fusion of system.Under nitrogen protection, add chainextender hexamethylene diisocyanate (HDI) 0.02g and carry out the chain extension reaction, pressure in the reactor is 0.01Pa, temperature is 175 ℃, reaction 40min, be cooled to room temperature under the nitrogen protection condition, obtain the segmented copolymer of poly(lactic acid) and PBAT: PLA-b-PBAT;
(4) the segmented copolymer PLA-b-PBAT that obtains in the step (3) is made pellet, get 10g as expanding material.Be mixed together with the pellet of PLA 170g that is used for blend and PBAT 30g and 1g lime carbonate, 1g triphenyl phosphite and evenly join twin screw extruder and melt extrude, 170 ℃ of extrusion temperatures, screw speed 100rpm obtains product.Its performance sees Table 1.
Embodiment 2:
(1) with 8g poly(lactic acid) vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 165 ℃, react 3h, obtain the hydroxy-end capped product poly(lactic acid) dibasic alcohol of poly(lactic acid); Wherein, the mol ratio of small molecules dibasic alcohol and poly(lactic acid) reaction is 1.5: 1;
(2) with 2g PBAT vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 200 ℃, react 5h, obtain the hydroxy-end capped product degradable polyester dibasic alcohol of biodegradable polyesters; Wherein, the mol ratio of molecule dibasic alcohol and degradable polyester reaction is 1.5: 1;
(3) will finish in the poly(lactic acid) and PBAT adding vacuum reaction still of termination process, add catalyzer tin protochloride 0.005g, metatitanic acid-4-isopropyl ester 0.005g.Inflated with nitrogen vacuumizes, 3 times repeatedly.Under powerful mechanical agitation, temperature of reaction kettle is risen to 175 ℃, keep temperature 10min until the complete fusion of system.Under nitrogen protection, add chainextender hexamethylene diisocyanate (HDI) 0.02g and carry out the chain extension reaction, pressure in the reactor is 0.01Pa, temperature is 185 ℃, reaction 40min, be cooled to room temperature under the nitrogen protection condition, obtain the segmented copolymer of poly(lactic acid) and PBAT: PLA-b-PBAT;
(4) the segmented copolymer PLA-b-PBAT that obtains in the step (3) is made pellet, get 10g as expanding material.Be mixed together with the pellet of PLA 160g that is used for blend and PBAT 40g and 1g lime carbonate, 1g triphenyl phosphite and evenly join twin screw extruder and melt extrude, 170 ℃ of extrusion temperatures, screw speed 100rpm obtains product.Its performance sees Table 1.
Embodiment 3:
(1) with 8.5g poly(lactic acid) vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 165 ℃, react 3h, obtain the hydroxy-end capped product poly(lactic acid) dibasic alcohol of poly(lactic acid); Wherein, wherein, the mol ratio of small molecules dibasic alcohol and poly(lactic acid) reaction is 1.5: 1;
(2) with 1.5g PBS vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 190 ℃, react 5h, obtain the hydroxy-end capped product degradable polyester dibasic alcohol of biodegradable polyesters; Wherein, the mol ratio of molecule dibasic alcohol and degradable polyester reaction is 1.5: 1;
(3) will finish in the poly(lactic acid) and PBS adding vacuum reaction still of termination process, add catalyzer tin protochloride 0.005g, metatitanic acid-4-isopropyl ester 0.005g.Inflated with nitrogen vacuumizes, 3 times repeatedly.Under powerful mechanical agitation, temperature of reaction kettle is risen to 165 ℃, keep temperature 5～30min until the complete fusion of system.Under nitrogen protection, add chainextender tolylene diisocyanate (MDI) 0.03g and carry out the chain extension reaction, pressure in the reactor is 0.01Pa, and temperature is 185 ℃, reaction 30min, be cooled to room temperature under the nitrogen protection condition, obtain the segmented copolymer of poly(lactic acid) and PBS: PLA-b-PBS;
(4) the segmented copolymer PLA-b-PBS that obtains in the step (3) is made pellet, get 10g as expanding material.Be mixed together with the pellet of PLA 170g that is used for blend and PBS 30g and 1g lime carbonate, 1g triphenyl phosphite and evenly join twin screw extruder and melt extrude, 175 ℃ of extrusion temperatures, screw speed 100rpm obtains product.Its performance sees Table 1.
Embodiment 4:
(1) with 8g poly(lactic acid) vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 165 ℃, react 3h, obtain the hydroxy-end capped product poly(lactic acid) dibasic alcohol of poly(lactic acid); Wherein, wherein, the mol ratio of small molecules dibasic alcohol and poly(lactic acid) reaction is 1.5: 1;
(2) with 2g PBS vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 190 ℃, react 5h, obtain the hydroxy-end capped product degradable polyester dibasic alcohol of biodegradable polyesters; Wherein, the mol ratio of molecule dibasic alcohol and degradable polyester reaction is 1.5: 1;
(3) will finish in the poly(lactic acid) and PBS adding vacuum reaction still of termination process, add catalyzer tin protochloride 0.005g, metatitanic acid-4-isopropyl ester 0.005g.Inflated with nitrogen vacuumizes, 3 times repeatedly.Under powerful mechanical agitation, temperature of reaction kettle is risen to 165 ℃, keep temperature 15min until the complete fusion of system.Under nitrogen protection, add chainextender tolylene diisocyanate (MDI) 0.03g and carry out the chain extension reaction, pressure in the reactor is 0.01Pa, and temperature is 185 ℃, reaction 30min, be cooled to room temperature under the nitrogen protection condition, obtain the segmented copolymer of poly(lactic acid) and PBS: PLA-b-PBS;
(4) the segmented copolymer PLA-b-PBS that obtains in the step (3) is made pellet, get 10g as expanding material.Be mixed together with the pellet of PLA 160g that is used for blend and PBS 40g and 1g lime carbonate, 1g triphenyl phosphite and evenly join twin screw extruder and melt extrude, 165 ℃ of extrusion temperatures, screw speed 100rpm obtains product.Its performance sees Table 1.
Embodiment 5:
(1) with 5g poly(lactic acid) vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 165 ℃, react 3h, obtain the hydroxy-end capped product poly(lactic acid) dibasic alcohol of poly(lactic acid); Wherein, wherein, the mol ratio of small molecules dibasic alcohol and poly(lactic acid) reaction is 1.5: 1;
(2) with 5g PBAT vacuum-drying (moisture content＜50ppm), add in the reactor, add the small molecules dibasic alcohol, vacuumize, react under catalyst action, the pressure in the reactor is 0.01Pa, and temperature of reaction is 190 ℃, react 5h, obtain the hydroxy-end capped product degradable polyester dibasic alcohol of biodegradable polyesters; Wherein, the mol ratio of molecule dibasic alcohol and degradable polyester reaction is 1.5: 1;
(3) will finish in the poly(lactic acid) and PBAT adding vacuum reaction still of termination process, add the inferior tin 0.005g of octoate catalyst, tetrabutyl titanate 0.005g.Inflated with nitrogen vacuumizes, 3 times repeatedly.Under powerful mechanical agitation, temperature of reaction kettle is risen to 185 ℃, keep temperature 30min until the complete fusion of system.Under nitrogen protection, add chainextender hexamethylene diisocyanate (HDI) 0.04g and carry out the chain extension reaction, pressure in the reactor is 0.01Pa, temperature is 185 ℃, reaction 40min, be cooled to room temperature under the nitrogen protection condition, obtain the segmented copolymer of poly(lactic acid) and PBAT: PLA-b-PBAT;
(4) the segmented copolymer PLA-b-PBAT that obtains in the step (3) is made pellet, get 10g as expanding material.Be mixed together with the pellet of PLA 500g that is used for blend and PBAT 100g and evenly join twin screw extruder and melt extrude, 180 ℃ of extrusion temperatures, screw speed 100rpm obtains product.Its performance sees Table 1.
The mechanical property of table 1 poly(lactic acid)/degradable polyester composite material
| Embodiment | Poly(lactic acid) content (g) | The degradable polyester kind | Degradable poly ester content (g) | The expanding material kind | Expanding material content (g) | Tensile strength (MP) | Elongation at break (%) | Young's modulus (MP) | Shock strength (KJ/m 2) |
| 1 | 170 | PBAT | 30 | PLA-b-PBAT | 10 | 47.5 | 92.3 | 1253.1 | 11.3 |
| 170 | PBAT | 30 | Do not have | 0 | 40.2 | 64.2 | 1131.4 | 10.4 | |
| 2 | 160 | PBAT | 40 | PLA-b-PBAT | 10 | 38.6 | 77.1 | 1096.5 | 14.6 |
| 160 | PBAT | 40 | Do not have | 0 | 31.5 | 55.3 | 987.3 | 12.3 | |
| 3 | 170 | PBS | 30 | PLA-b-PBS | 10 | 55.8 | 8.9 | 2035.6 | 9.4 |
| 170 | PBS | 30 | Do not have | 0 | 48.6 | 6.5 | 1856.8 | 8.6 | |
| 4 | 160 | PBS | 40 | PLA-b-PBS | 10 | 52.9 | 9.5 | 1823.6 | 12.5 |
| 160 | PBS | 40 | Do not have | 0 | 46.5 | 7.6 | 1649.4 | 10.3 | |
| 5 | 500 | PBAT | 100 | PLA-b-PBAT | 10 | 41.6 | 85.3 | 1089.6 | 11.2 |
| 500 | PBAT | 100 | Do not have | 0 | 38.6 | 65.6 | 1025.3 | 10.6 |
Claims (3)
1. preparation method with biologically degradable polyester composite material of capacity increasing function, it is characterized in that adopting the method for chain extension to prepare the segmented copolymer of poly(lactic acid) and biodegradable polyesters, use the blend of prepared in twin-screw extruder poly(lactic acid) and biodegradable polyesters then, in the blend process, use the segmented copolymer of synthetic poly(lactic acid) and biodegradable polyesters as expanding material; Concrete steps are as follows:
(1) with poly(lactic acid) vacuum-drying, make its moisture content＜50ppm, add in the reactor, add the small molecules dibasic alcohol, vacuumize, under catalyst action, react, pressure in the reactor is 0.01～2000Pa, temperature of reaction is 160～180 ℃, reacts 3～5h, obtains the hydroxy-end capped product poly(lactic acid) dibasic alcohol of poly(lactic acid); Wherein, the mol ratio of small molecules dibasic alcohol and poly(lactic acid) is 1: 1～6: 1;
(2) degradable polyester vacuum-drying, make its moisture content＜50ppm, add in the reactor, add the small molecules dibasic alcohol, vacuumize, under catalyst action, react, pressure in the reactor is 0.01～2000Pa, temperature of reaction is 170～270 ℃, reacts 3～5h, obtains the hydroxy-end capped product degradable polyester dibasic alcohol of biodegradable polyesters; Wherein, the mol ratio of small molecules dibasic alcohol and degradable polyester is 1: 1～6: 1;
(3) the degradable polyester dibasic alcohol that obtains of poly(lactic acid) dibasic alcohol that step (1) is obtained and step (2) proportionally joins in the reactor, and adds catalyzer simultaneously; Inflated with nitrogen vacuumizes, and 3 times repeatedly, under agitation, temperature of reaction kettle is risen to the above 5-25 of fusing point ℃ of melt temperature the higher person in poly(lactic acid) and the degradable polyester, keep reacting 5～30min under this temperature, until the complete fusion of system; Under nitrogen protection, add chainextender and carry out the chain extension reaction then, the pressure in the reactor is 0.01～2000Pa, and temperature of reaction is the above 5-25 of fusing point ℃ of melt temperature the higher person among both, and the reaction times is 20～50min; Reaction under the nitrogen protection condition, is cooled to room temperature after finishing, and obtains the segmented copolymer of poly(lactic acid) and degradable polyester; Wherein, poly(lactic acid) dibasic alcohol and degradable polyester dibasic alcohol mol ratio are 1: 10～10: 1;
(4) segmented copolymer that obtains in the step (3) is made pellet, as expanding material, be mixed together evenly with the pellet of poly(lactic acid) that is used for blend and degradable polyester, join in the twin screw extruder and melt extrude, extrusion temperature 150-200 ℃, screw speed 50-300rpm obtains desired product, and wherein the weight percent of each component is:
Poly(lactic acid): 48-97%
Degradable polyester: 1-50%
Expanding material: 1-10%
Oxidation inhibitor: 0.5-1%
Lubricant: 0.5-1%;
Wherein: small molecules dibasic alcohol described in the step (1) be in ethylene glycol, butyleneglycol or the hexylene glycol any, described catalyzer is the one to multiple kind in stannous octoate, tin protochloride, polyphosphoric acid, toluene-4-semi-annular jade pendant acid, tin acetate or the manganese acetate, and the add-on of catalyzer is the 0.1-1% of poly(lactic acid) quality;
Degradable polyester is a polycaprolactone described in the step (2), polyethylene glycol succinate, poly butylene succinate, poly adipate succinic acid ester, polyhexamethylene adipate, among poly--3-butyric ester or poly-(mutual-phenenyl two acid bromide two alcohol ester-co-tetramethylene adipate) any, described small molecules dibasic alcohol is an ethylene glycol, in butyleneglycol or the hexylene glycol any, described catalyzer is a stannous octoate, tin protochloride, polyphosphoric acid, toluene-4-semi-annular jade pendant acid, tin acetate, manganese acetate, magnesium acetate, one to multiple kind in positive butyl ester of metatitanic acid-4-or metatitanic acid-4-isopropyl ester, the add-on of catalyzer is the 0.1-1% of degradable polyester quality
The catalyzer of chain extending reaction is a stannous octoate in the step (3), tin protochloride, dibutyltin dilaurate, polyphosphoric acid, toluene-4-semi-annular jade pendant acid, tin acetate, manganese acetate, magnesium acetate, one to several in positive butyl ester of metatitanic acid-4-or metatitanic acid-4-isopropyl ester, the add-on of catalyzer is the 0.1-1% of poly(lactic acid) dibasic alcohol and degradable polyester dibasic alcohol total mass, described chainextender is a diisocyanate compound, the chainextender consumption calculates-NCO with the mol ratio of the contained hydroxyl-OH group of isocyano contained in the chainextender-NCO group and poly(lactic acid) dibasic alcohol and degradable polyester dibasic alcohol :-OH is 3: 1～1: 1.
2. the preparation method with biologically degradable polyester composite material of capacity increasing function according to claim 1 is characterized in that oxidation inhibitor described in the step (4) is that one in the dimer of phenyl-phosphite kind antioxidant, many alkyl dihydroxyphenyl propane phosphorous acid ester or the trimerical mixture is to multiple.
3. the preparation method with biologically degradable polyester composite material of capacity increasing function according to claim 1 is characterized in that lubricant described in the step (4) is one or more in fatty acid acyl aminated compounds, fatty acid metal soap compounds, the long chain fatty acid.
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