CN1995136A - Process for preparing high tenacious biodegradable composite material - Google Patents
Process for preparing high tenacious biodegradable composite material Download PDFInfo
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- CN1995136A CN1995136A CN 200610023114 CN200610023114A CN1995136A CN 1995136 A CN1995136 A CN 1995136A CN 200610023114 CN200610023114 CN 200610023114 CN 200610023114 A CN200610023114 A CN 200610023114A CN 1995136 A CN1995136 A CN 1995136A
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Abstract
The invention discloses a preparing method of biological full-degraded composite material in the macromolecular technical domain, which is characterized by the following: adopting polylactic acid, biological degraded polyester and antioxidant as raw material; utilizing double-screw squeezer to squeeze the grain; obtaining the product.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of high tenacious biodegradable composite material.
Background technology
Poly(lactic acid) (PLA) is a kind of polymkeric substance with good biocompatibility; it derives from renewable resources farm crop (as corn); the most outstanding advantage is a biodegradability; it can be degraded fully by the occurring in nature microorganism after using; final carbonic acid gas and the water of generating; free from environmental pollution, highly beneficial to the protection environment.Poly(lactic acid) has good mechanical character, thermoplasticity, fiberizability, transparency height, is applicable to various working methods such as blowing, thermoplastic, and is easy to process, is decided to be the most rising new packaging material of new millennium by industrial community.Poly(lactic acid) is when having many advantageous properties, and the shortcoming that also exists some can not finely satisfy the packing articles needs is as erosion-resisting characteristics, thermostability etc.Therefore, seek and a kind ofly poly(lactic acid) and other materials are carried out compound, improve its some performance, make poly(lactic acid) can really obtain the goal in research that broader applications are those skilled in the art.
Summary of the invention
But the objective of the invention is to propose a kind of continuous production, easily-controlled operation, the preparation method of the high tenacious biodegradable composite material that quality product and biodegradability are good.
The preparation method of a kind of high tenacious biodegradable composite material that the present invention proposes is poly(lactic acid), biodegradable polyesters, oxidation inhibitor, lubricant to be extruded by the twin screw extruder melt blending promptly get product, and actual conditions is:
With poly(lactic acid), biodegradable polyesters vacuum-drying (after the moisture content＜50ppm), add oxidation inhibitor, mix lubricant is even, melt extrude with twin screw extruder again, extrusion temperature is 155-200 ℃, screw speed is 50-200rpm, the residence time of material is 4-8 minute, obtains product, and wherein each weight percent of forming is:
Poly(lactic acid): 50-95%
Biodegradable polyesters: 5-50%
Oxidation inhibitor: 0.5-1%
Lubricant: 0.5-1%.
Among the present invention, described biodegradable polyesters can adopt one or more in the multicomponent copolyester that contains phenyl ring, polyoxyethylene glycol, polycaprolactone, poly-(Succinic Acid-butyleneglycol) ester, polyoxyethylene or the Polyvinylpyrolidone (PVP) etc.
Among the present invention, described oxidation inhibitor can adopt tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl phenyl) one or more in the dimer of ester, phosphorous acid benzene two isodecyl esters, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl phenyl ester), pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, many alkyl dihydroxyphenyl propane phosphorous acid ester or the trimerical mixture etc.
Among the present invention, described lubricant can adopt one or more in fatty acid acyl aminated compounds, fatty acid metal soap compounds, the long chain fatty acid, as in the two amine hydroxybenzenes of amine hydroxybenzene, stearic amide, ethylene, ethylene bis stearic acid amide, calcium stearate, Magnesium Stearate, the stearic acid etc. one or more.
Among the present invention, described multicomponent copolyester can adopt the terpolymer (PBAT) of terephthalic acid, hexanodioic acid, butyleneglycol.
Among the present invention, extrusion vacuumize and the condition of nitrogen protection under carry out.
Among the present invention, the twin screw extruder that is adopted, its length-to-diameter ratio is 25: 1～45: 1, has special screw combinations, has exhaust and high-shear mixing plasticizing effect.
The invention has the advantages that:
(1) two kinds of component poly(lactic acid) and the biodegradable polyesters that is used to prepare matrix material all has favorable biological degradability, and resulting product can effectively solve " white pollution " problem, is a kind of environment-friendly materials, helps the Sustainable development of human society.
(2) used biodegradable polyesters (as PBAT) has good tensile property and snappiness, density and poly(lactic acid) are approaching, the strength ratio poly(lactic acid) is low slightly, elongation at break is up to 820%, far above 3% of poly(lactic acid), come the mechanical property of improving poly(lactic acid) that plasticizing polylactic acid can be bigger with PBAT.The end-use that makes is extensive, is fit to do wrapping material such as agricultural mulching, refuse bag, shopping bag, food pack.
(3) adopted big L/D ratio, have the twin screw extruder of exhaust and high-shear mixing plasticizing effect, and vacuumize and the condition of nitrogen protection under extrude, guaranteed the quality of resin.
(4) preparation method is simply effective, and the matrix material that obtains has good comprehensive performances.Shock strength has improved more than 100%, and elongation at break has improved more than 250%, and Vicat softening point also has raising in various degree.Its performance sees Table 1.
Embodiment
Embodiment 1
After 190g poly(lactic acid) and 10gPBAT vacuum-drying, with 2g oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, 2g calcium stearate mix, extrude with twin screw extruder, extrusion temperature is 155-200 ℃, screw speed is 50-200rpm, and the residence time of material is 4-8 minute, gets product.Its performance sees Table 1.
Embodiment 2
180g poly(lactic acid), 20gPBAT, 2g oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, 2g amine hydroxybenzene are mixed, extrude with twin screw extruder, extrusion temperature is 155-200 ℃, screw speed is 50-200rpm, and the residence time of material is 4-8 minute, gets product.Its performance sees Table 1.
Embodiment 3
After 170g poly(lactic acid), the vacuum-drying of 30g polycaprolactone, with 2g oxidation inhibitor tricresyl phosphite (2,4-di-tert-butyl phenyl) ester, 2g stearic acid mix, extrude with twin screw extruder, extrusion temperature is 155-200 ℃, screw speed is 50-200rpm, and the residence time of material is 4-8 minute, gets product.Its performance sees Table 1.
Embodiment 4
After 140g poly(lactic acid), the vacuum-drying of 60g polycaprolactone, with 2g oxidation inhibitor tricresyl phosphite (2,4-di-tert-butyl phenyl) ester, the two amine hydroxybenzenes of 2g ethylene mix, extrude with twin screw extruder, extrusion temperature is 155-200 ℃, screw speed is 50-200rpm, and the residence time of material is 4-8 minute, gets product.Its performance sees Table 1.
Embodiment 5
After 100g poly(lactic acid), the vacuum-drying of 100g (poly-succinic-butyleneglycol) ester, mix with 2g oxidation inhibitor tricresyl phosphite (nonyl phenyl ester), 2g Magnesium Stearate, extrude with twin screw extruder, extrusion temperature is 155-200 ℃, screw speed is 50-200rpm, the residence time of material is 4-8 minute, gets product.Its performance sees Table 1.
The performance of table 1 poly(lactic acid)/biologically degradable polyester composite material
| Embodiment | Poly(lactic acid) content (g) | Biodegradable polyesters content (g) | Tensile strength (MPa) | Elongation at break (%) | Young's modulus (MPa) | Flexural strength (MPa) | Modulus in flexure (MPa) | Shock strength (KJ/m 2) | Vicat softening point (℃) |
| 1 | 190 | 10 | 49.6 | 3.5 | 1315.6 | 96.7 | 2938.7 | 6.7 | 58.9 |
| 2 | 180 | 20 | 44.6 | 5.2 | 1205.3 | 75.9 | 3324.1 | 8.0 | 59.6 |
| 3 | 170 | 30 | 38.2 | 6.4 | 1131.4 | 67.2 | 2355.4 | 10.4 | 61.2 |
| 4 | 140 | 60 | 24.2 | 9.1 | 734.6 | 44.1 | 1665.8 | 12.1 | 60.6 |
| 5 | 100 | 100 | 12.2 | 12.9 | 394.1 | 30.9 | 903.5 | 20.6 | 62.3 |
Claims (6)
1, a kind of preparation method of high tenacious biodegradable composite material is characterized in that poly(lactic acid), biodegradable polyesters, oxidation inhibitor, lubricant extruded by the twin screw extruder melt blending and promptly gets product, and actual conditions is:
After poly(lactic acid), biodegradable polyesters vacuum-drying, add oxidation inhibitor, mix lubricant is even, melt extrude with twin screw extruder again, extrusion temperature is 155-200 ℃, screw speed is 50-200rpm, the residence time of material is 4-8 minute, obtains product, and wherein each weight percent of forming is:
Poly(lactic acid): 50-95%
Biodegradable polyesters: 5-50%
Oxidation inhibitor: 0.5-1%
Lubricant: 0.5-1%.
2, the preparation method of high tenacious biodegradable composite material according to claim 1 is characterized in that biodegradable polyesters is one or more in the multicomponent copolyester that contains phenyl ring, polyalcohols, polycaprolactone, poly-(Succinic Acid-butyleneglycol) ester, polyoxyethylene or the Polyvinylpyrolidone (PVP).
3, the preparation method of high tenacious biodegradable composite material according to claim 1, it is characterized in that oxidation inhibitor is tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, phosphorous acid ester three (2,4-di-tert-butyl phenyl) dimer of ester, phosphorous acid benzene two isodecyl esters, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl phenyl ester), pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, many alkyl dihydroxyphenyl propane phosphorous acid ester or in the trimerical mixture one or more.
4, the preparation method of high tenacious biodegradable composite material according to claim 1 is characterized in that lubricant is one or more in fatty acid acyl aminated compounds, fatty acid metal soap compounds or the long chain fatty acid.
5, the preparation method of high tenacious biodegradable composite material according to claim 2, the multicomponent copolyester that it is characterized in that containing phenyl ring is the terpolymer of terephthalic acid, hexanodioic acid, butyleneglycol.
6, the preparation method of high tenacious biodegradable composite material according to claim 1, it is characterized in that extrusion vacuumize and the condition of nitrogen protection under carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610023114 CN1995136A (en) | 2006-01-05 | 2006-01-05 | Process for preparing high tenacious biodegradable composite material |
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|---|---|---|---|
| CN 200610023114 CN1995136A (en) | 2006-01-05 | 2006-01-05 | Process for preparing high tenacious biodegradable composite material |
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| CN1995136A true CN1995136A (en) | 2007-07-11 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914272A (en) * | 2010-08-02 | 2010-12-15 | 深港产学研基地产业发展中心 | Biodegradable modified polylactic acid material and preparation method thereof and method for preparing non-woven fabric by same |
| CN107083032A (en) * | 2017-04-10 | 2017-08-22 | 同济大学 | Cross-linking reaction prepares high intensity and the method for high tenacious biodegradable polylactic acid-base composite material in a kind of processing extrusion |
| CN107501616A (en) * | 2017-09-30 | 2017-12-22 | 四会市启德信息咨询服务有限公司 | A kind of preparation method of the biodegradable plastic material of high tenacity |
| CN108017888A (en) * | 2017-12-02 | 2018-05-11 | 无锡福尔顺科技有限公司 | One kind sealing polycaprolactone pack case and its application |
| CN109456581A (en) * | 2018-09-30 | 2019-03-12 | 嘉兴凡高电子商务有限公司 | A kind of PLA Biocomposite material and preparation method thereof of toy for children degradation |
| CN112813530A (en) * | 2021-01-26 | 2021-05-18 | 苏州塑发生物材料有限公司 | Hydrophilic soft polylactic acid spinning composite material and preparation method thereof |
| CN114230987A (en) * | 2022-01-11 | 2022-03-25 | 南通富士美帽业有限公司 | Environment-friendly high-transparency composite material capable of being sewn and preparation method thereof |
| CN114269862A (en) * | 2019-06-13 | 2022-04-01 | 斯瓦蒙卢森堡公司 | Degradable extruded webs made from polymer blend compositions |
| CN115322527A (en) * | 2022-06-27 | 2022-11-11 | 广东春夏新材料科技股份有限公司 | Biodegradable polyester composite material and preparation method thereof |
-
2006
- 2006-01-05 CN CN 200610023114 patent/CN1995136A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914272A (en) * | 2010-08-02 | 2010-12-15 | 深港产学研基地产业发展中心 | Biodegradable modified polylactic acid material and preparation method thereof and method for preparing non-woven fabric by same |
| CN101914272B (en) * | 2010-08-02 | 2012-07-04 | 深港产学研基地产业发展中心 | Biodegradable modified polylactic acid material and preparation method thereof and method for preparing non-woven fabric by same |
| CN107083032A (en) * | 2017-04-10 | 2017-08-22 | 同济大学 | Cross-linking reaction prepares high intensity and the method for high tenacious biodegradable polylactic acid-base composite material in a kind of processing extrusion |
| CN107501616A (en) * | 2017-09-30 | 2017-12-22 | 四会市启德信息咨询服务有限公司 | A kind of preparation method of the biodegradable plastic material of high tenacity |
| CN108017888A (en) * | 2017-12-02 | 2018-05-11 | 无锡福尔顺科技有限公司 | One kind sealing polycaprolactone pack case and its application |
| CN109456581A (en) * | 2018-09-30 | 2019-03-12 | 嘉兴凡高电子商务有限公司 | A kind of PLA Biocomposite material and preparation method thereof of toy for children degradation |
| CN114269862A (en) * | 2019-06-13 | 2022-04-01 | 斯瓦蒙卢森堡公司 | Degradable extruded webs made from polymer blend compositions |
| CN112813530A (en) * | 2021-01-26 | 2021-05-18 | 苏州塑发生物材料有限公司 | Hydrophilic soft polylactic acid spinning composite material and preparation method thereof |
| CN114230987A (en) * | 2022-01-11 | 2022-03-25 | 南通富士美帽业有限公司 | Environment-friendly high-transparency composite material capable of being sewn and preparation method thereof |
| CN115322527A (en) * | 2022-06-27 | 2022-11-11 | 广东春夏新材料科技股份有限公司 | Biodegradable polyester composite material and preparation method thereof |
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