CN100360610C - Degradable plastic composition and preparation method thereof - Google Patents
Degradable plastic composition and preparation method thereof Download PDFInfo
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- CN100360610C CN100360610C CNB2005101003440A CN200510100344A CN100360610C CN 100360610 C CN100360610 C CN 100360610C CN B2005101003440 A CNB2005101003440 A CN B2005101003440A CN 200510100344 A CN200510100344 A CN 200510100344A CN 100360610 C CN100360610 C CN 100360610C
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- Prior art keywords
- vinyl alcohol
- alcohol copolymer
- ethylene
- ethylene vinyl
- composite material
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- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 title claims description 12
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 40
- -1 polymethylethylene carbonate Polymers 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920006237 degradable polymer Polymers 0.000 claims abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract 2
- 239000001569 carbon dioxide Substances 0.000 claims abstract 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract 2
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 20
- 229920003023 plastic Polymers 0.000 abstract description 12
- 239000004033 plastic Substances 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 30
- 239000011159 matrix material Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000003413 degradative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000004308 accommodation Effects 0.000 description 2
- 238000012648 alternating copolymerization Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明涉及了一种可降解塑料复合材料及其制备方法，该可降解塑料复合材料以由二氧化碳和环氧丙烷合成的可降解聚合物聚甲基乙撑碳酸酯为基体，添加乙烯乙烯醇共聚物，通过熔融混合或溶液混合制备，可用于制造一次性塑料制品。聚甲基乙撑碳酸酯中引入乙烯乙烯醇共聚物后，不仅强度得到很大提高，而且由于乙烯乙烯醇共聚物具有吸水性，能促进聚甲基乙撑碳酸酯的生物降解。该可降解塑料复合材料是一种降解性能好，机械强度高，且成本低的降解塑料。The invention relates to a degradable plastic composite material and a preparation method thereof. The degradable plastic composite material is based on a degradable polymer polymethylethylene carbonate synthesized from carbon dioxide and propylene oxide, and ethylene vinyl alcohol is added for copolymerization Compounds, prepared by melt mixing or solution mixing, can be used to make disposable plastic products. After the ethylene vinyl alcohol copolymer is introduced into the polymethylethylene carbonate, not only the strength is greatly improved, but also because the ethylene vinyl alcohol copolymer has water absorption, it can promote the biodegradation of the polymethylethylene carbonate. The degradable plastic composite material is a degradable plastic with good degradation performance, high mechanical strength and low cost.
Description
Technical field
The present invention relates to a kind of degredation plastic matrix material and preparation method thereof, concrete system relates to a kind of prescription and production method thereof of degredation plastic composition.
Background technology
Along with growing with each passing day of quantity of plastics, " white pollution " that waste plastic caused become worldwide public hazards, and the exploitation degradable plastics has become worldwide research focus.Its development has not only enlarged the function of plastics; and alleviated environment contradiction to a certain extent; exhausted day by day petroleum resources are one to be replenished; therefore the research and development of degradative plastics and applying; no matter, still all have great importance from the high molecular academic angle of complex functionality from the actual angle of global environment protection or from inexhaustible renewable resources.
Lined polymethyl ethylene carbonate is a class degradative plastics, and because of its raw material mainly utilizes carbonic acid gas, finished product have degradability again, just more and more come into one's own.But since the drawbacks limit of partial properties own its use, can prepare new material by mixing with other macromolecular material.
Summary of the invention
The objective of the invention is to the mechanical property and the hot workability of lined polymethyl ethylene carbonate are carried out modification, good and lower-cost degradative plastics matrix material of a kind of mechanical property and degradation property and preparation method thereof is provided, this method technology is simple, wide accommodation.
For achieving the above object, degradable plastics of the present invention is the plastics composite of being made by following raw material:
Lined polymethyl ethylene carbonate, ethylene-vinyl alcohol copolymer.
Wherein used raw material fully degradation polymethylethylene carbonic ester ester resin is the product by propylene oxide and carbonic acid gas alternating copolymerization, number-average molecular weight 20,000 to 200,000, and its chemical structure is:
The number-average molecular weight 5,000 to 100,000 of used ethylene-vinyl alcohol copolymer, chemical structure is:
As optimization, the weight proportion of described raw material is:
Lined polymethyl ethylene carbonate 10-95, ethylene-vinyl alcohol copolymer 90-5.
As optimization, the weight proportion of described raw material is:
Lined polymethyl ethylene carbonate 50-95, ethylene-vinyl alcohol copolymer 50-5.
As optimization, the weight proportion of described raw material is:
Lined polymethyl ethylene carbonate 50-80, ethylene-vinyl alcohol copolymer 50-20.
As optimization, the weight proportion of described raw material is:
Lined polymethyl ethylene carbonate 40-80, ethylene-vinyl alcohol copolymer 60-20.
Used raw material fully degradation polymethylethylene carbonic ester ester resin is the product by propylene oxide and carbonic acid gas alternating copolymerization among the present invention, and ethylene-vinyl alcohol copolymer is the multipolymer of ethylene content 5%-95%.In the lined polymethyl ethylene carbonate resin, add ethylene-vinyl alcohol copolymer and can obviously improve thermostability and mechanical property.Ultimate principle is that ethylene-vinyl alcohol copolymer can be partial cross-linked with the by product propylene carbonate reaction formation in the lined polymethyl ethylene carbonate resin, thereby has improved every performance.Degradable plastic product of the present invention is nontoxic, the production process three-waste free pollution.
When the preparation matrix material, also can add oxidation inhibitor, lubricant, dyestuff, filler etc.
The production method of degradable plastics of the present invention comprises following two kinds of methods:
(1) melt-blending process: with the lined polymethyl ethylene carbonate resin, ethylene-vinyl alcohol copolymer adds homogenizer after measuring by prescription, and at room temperature continuously stirring prepares mixed uniformly mixing raw material material; Again with the preparation the mixing raw material material, under 150 ℃-190 ℃ temperature, carry out melt blending, 5-20 minute blend time, make each component thorough mixing after, shred or particle.
The device of implementing the inventive method is a device general in the present technique field, as two roller mills, Banbury mixer, twin screw extruder and homogenizer etc.
(2) solution blended process: with the lined polymethyl ethylene carbonate resin, ethylene-vinyl alcohol copolymer adds in the solvent after measuring by prescription, and the continuously stirring dissolving also mixes, and removes solvent then, is broken into particle.
The device of implementing the inventive method is a device general in the present technique field, as stirring tank, dryer, crusher etc.
The application of degradable plastics of the present invention is that described degradable plastic composition is used to make disposable tableware, industrial pharmaceutical sector non-returnable container,, life and industrial or agricultural disposable product such as Farm mulch.Its manufacture method is as follows:
(1) injecting products comprises: injection moulding, cooling and shaping and arrangement warehouse-in step.
(2) sheet material comprises: sheet material extrusion moulding and packing warehouse-in step; The plastic uptake product also comprises: preheating vacuum forming and cooling and shaping step.
(3) foamed products comprises: hot-pressing and foaming moulding (physical blowing) and arrangement warehouse-in step; The plastic uptake product also comprises: preheating vacuum forming and cooling and shaping step.
The present invention is modified resin to be matrix by carbonic acid gas and propylene oxide synthetic degradable polymer lined polymethyl ethylene carbonate with high-crystallinity, high-intensity ethylene-vinyl alcohol copolymer, prepares matrix material through blend.Technology is simple, wide accommodation.The weight percentage of ethylene-vinyl alcohol copolymer is 5-90% in the product, and the intensity of lined polymethyl ethylene carbonate is improved, and because the water absorption character of ethylene-vinyl alcohol copolymer, has quickened the biodegradability of matrix material.The used lined polymethyl ethylene carbonate of the present invention is a kind of degradable high polymer material with applications well prospect, the blending and modifying patent (as starch, natural plant fibre, natural mineral filler) of itself and various fillers is appeared in the newspapers, but lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer composite study still belongs to blank.Lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer matrix material is a kind of novel green material.
Embodiment
Further describe the present invention with embodiment below.
Embodiment 1-4
The composition and the performance of matrix material are as shown in table 1.After lined polymethyl ethylene carbonate and ethylene-vinyl alcohol copolymer (ethylene content 44%) metering, put into melting mixing equipment, descended 60 rev/mins of rotor speeds mixing 5 minutes in 170 ℃.The compound of gained is 180 ℃ of compressing tablets on vulcanizing press, press the standard sample preparation test force performance of ISO 527-2, can find out from table 1, the intensity of lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer matrix material all has bigger increase than lined polymethyl ethylene carbonate, and ethylene-vinyl alcohol copolymer content is big more, and the intensity of matrix material is high more.
Embodiment 5-8
The composition and the performance of matrix material are as shown in table 2.After lined polymethyl ethylene carbonate and ethylene-vinyl alcohol copolymer (ethylene content 44%) metering, put into the solvent dimethyl sulfoxide (DMSO), be heated to 150 ℃, stirring and dissolving.Fully after the dissolving, remove and desolvate, the compound of gained is 180 ℃ of compressing tablets on vulcanizing press, press the standard sample preparation test force performance of ISO 527-2, can find out from table 2, the intensity of the lined polymethyl ethylene carbonate that solution mixing system is equipped with/ethylene-vinyl alcohol copolymer matrix material all has very big increase than lined polymethyl ethylene carbonate, and ethylene-vinyl alcohol copolymer content is big more, and the intensity of matrix material is high more.And same lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer matrix material of forming, the tensile strength that solution ratio of mixture melting mixing obtains want high.
Table 3 is that matrix material is at 0.2M Na
2HPO
4-KH
2PO
4Degradation data in the buffered soln can find out that from table 3 data the adding of ethylene-vinyl alcohol copolymer has improved the degradation property of lined polymethyl ethylene carbonate.
The composition of table 1 lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer matrix material and performance (melting mixing)
| Embodiment | Lined polymethyl ethylene carbonate weight % | Ethylene-vinyl alcohol copolymer weight % | Hybrid mode | Tensile strength MPa |
| Matrix | ?100 | ?0 | Melting mixing | 15.0 |
| ?1 | ?70 | ?30 | Melting mixing | 16.1 |
| ?2 | ?60 | ?40 | Melting mixing | 22.3 |
| ?3 | ?50 | ?50 | Melting mixing | 28.0 |
| ?4 | ?40 | ?60 | Melting mixing | 36.4 |
The composition of table 2 lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer matrix material and performance (solution mixing)
| Embodiment | Lined polymethyl ethylene carbonate weight % | Ethylene-vinyl alcohol copolymer weight % | Hybrid mode | Tensile strength MPa |
| Matrix | ?100 | ?0 | Solution mixes | 15.1 |
| ?5 | ?70 | ?30 | Solution mixes | 17.0 |
| ?6 | ?60 | ?40 | Solution mixes | 24.2 |
| ?7 | ?50 | ?50 | Solution mixes | 30.0 |
| ?8 | ?40 | ?60 | Solution mixes | 39.4 |
The degradation property of table 3 lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer matrix material
| Time (my god) | Weightless % | ||||
| Pure lined polymethyl ethylene carbonate | The matrix material that contains 30% ethylene-vinyl alcohol copolymer | The matrix material that contains 50% ethylene-vinyl alcohol copolymer | The matrix material that contains 70% ethylene-vinyl alcohol copolymer | The pure ethylene vinyl alcohol copolymer | |
| ?1 | ?0.2 | ?0.1 | ?0.2 | ?0.2 | ?0 |
| ?2 | ?0.3 | ?0.4 | ?0.4 | ?0.5 | ?0 |
| ?5 | ?0.4 | ?0.6 | ?0.7 | ?0.7 | ?0 |
| ?10 | ?0.8 | ?1.4 | ?1.3 | ?1.6 | ?0 |
| ?15 | ?1.0 | ?1.5 | ?1.6 | ?2.2 | ?0 |
| ?25 | ?1.5 | ?2.0 | ?2.2 | ?4.0 | ?0 |
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101003440A CN100360610C (en) | 2005-10-20 | 2005-10-20 | Degradable plastic composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101003440A CN100360610C (en) | 2005-10-20 | 2005-10-20 | Degradable plastic composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1775857A CN1775857A (en) | 2006-05-24 |
| CN100360610C true CN100360610C (en) | 2008-01-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101003440A Expired - Fee Related CN100360610C (en) | 2005-10-20 | 2005-10-20 | Degradable plastic composition and preparation method thereof |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786788B (en) * | 2012-08-10 | 2014-03-26 | 中山大学 | Degradable poly-methyl ethylene carbonate base composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998007782A1 (en) * | 1996-08-20 | 1998-02-26 | Buna Sow Leuna Olefinverbund Gmbh | Biodegradable thermoplastically deformable materials for food packaging |
| CN1422898A (en) * | 2002-12-12 | 2003-06-11 | 中山大学 | Degradable polymer/natural mineal filler composite material and preparation method thereof |
| CN1528811A (en) * | 2003-09-29 | 2004-09-15 | 中山大学 | Completely degradable polymethylethylene carbonate/starch composite material and preparation method thereof |
-
2005
- 2005-10-20 CN CNB2005101003440A patent/CN100360610C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998007782A1 (en) * | 1996-08-20 | 1998-02-26 | Buna Sow Leuna Olefinverbund Gmbh | Biodegradable thermoplastically deformable materials for food packaging |
| CN1422898A (en) * | 2002-12-12 | 2003-06-11 | 中山大学 | Degradable polymer/natural mineal filler composite material and preparation method thereof |
| CN1528811A (en) * | 2003-09-29 | 2004-09-15 | 中山大学 | Completely degradable polymethylethylene carbonate/starch composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 乙烯-乙烯醇共聚物的应用及研究进展. 马沛岚，苑会林.塑料科技，第3期. 2005 * |
| 聚（1,2-亚丙基碳酸酯）的应用研究新进展. 庞浩，廖兵，黄玉惠，丛广民.应用化学，第18卷第5期. 2001 * |
| 聚碳酸亚丙酯/淀粉在城市垃圾中生物降解性能研究. 陆夏莲，葛祥才，孟跃中.中山大学学报（自然科学版），第44卷第4期. 2005 * |
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| CN1775857A (en) | 2006-05-24 |
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