CN1060188C - Bio-degradatable resin azeotropic mixture - Google Patents
Bio-degradatable resin azeotropic mixture Download PDFInfo
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- CN1060188C CN1060188C CN96106752A CN96106752A CN1060188C CN 1060188 C CN1060188 C CN 1060188C CN 96106752 A CN96106752 A CN 96106752A CN 96106752 A CN96106752 A CN 96106752A CN 1060188 C CN1060188 C CN 1060188C
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- polycaprolactone
- blending
- pce
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- polyester
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Abstract
The present invention relates to a biodegradable resin blending of a polyester-polyether copolymer. Because the biodegradable polymer blending of the present invention is prepared by blending a biodegradable polycaprolactone-polyether block copolymer and polyolefin or polyester or polyacrylic ester substituted or not substituted by alkyl according to the weight ratio of (5:95) to (80:20), the polymer blending has the advantages of capability of being spun into fine denier fiber, good air tightness and convenient machine shaping. At the same time, the use quantity of the polycaprolactone-polyether copolymer is reduced, and the biodegradation rate can be controlled by adjusting the proportion of the two components.
Description
The present invention relates to a kind of resin blend with polyester-copolyether of biological degradability.
Polyolefins polymer and polyester polymer be owing to have good mechanical property and a hot mouldable good workability, and because cheap and be easy to scale operation, therefore all obtained the development that is exceedingly fast in the application of every field.Yet because these polymers do not possess biodegradability, also can be changed hardly even bury in underground 200 years, the accumulation of therefore increasing high molecular waste material develops into the substantial pollution to environment gradually.In addition, since be poured in the ocean waste plastic caused to fishing class resource and boats and ships Navigational hazards, and being embedded in rainwater underground leakage that subterranean waste plastic causes and serious day by day to the harm of farmland soil conservation, the modification of macromolecular material biodegrade is handled has become the important topic that presses for solution in the polymer industrial development.
Because starch is natural macromolecular compound, will becomes water and carbonic acid gas after its degraded and can not cause pollution environment.In addition, because starch yield height, cheap, therefore with starch polymer being carried out blending and modifying is the current research aspect of gazing at the most.Yet Japanese patent application document flat 4-57953, point out among the Te Kaiping 5-179110: be not the blending and modifying that general starch can both be used for plastics, even also can not fusion after the starch specialized heating, therefore, they can only be distributed in other macromolecular material with graininess.So when using starch as plastic modifier, the intermingling material after the modification can't be spun into fine-titred fiber.In addition and since the addition of starch after a little while blend can not present biodegradability, and for a long time, because the non-plastic and the opacity of starch, therefore can have influence on the transparency, mechanical property of intermingling material and further processing characteristics at the starch addition.In addition, because starch granules is stronger to the perviousness of organic compound, the result can make the resistance to air loss of this class blending and modifying Tetramune descend, and is restricted thereby use.Also reported in the above-mentioned document with polycaprolactone and for example, polyethylene to have been made the polyethylene polycaprolactone blend, thereby to become thermoplastic resin, can be processed into fine-titred fibre product with it with microorganism slaking with polymer blend such as polyolefine.But because all the crystallinity of polycaprolactone is very strong, structure tight, wetting ability is very poor again, so the biodegradation rate of self is just very slow.Therefore, the resin biodegradation rate of carrying out behind the blending and modifying with equal polycaprolactone is also very slow.Just require to increase the addition of polycaprolactone for improving degradation speed, thereby cost is improved.
The invention reside in and solve being difficult to that more current degradative resins exist and be spun into fine denier fiber, poor air-tightness, be difficult to machine-shaping and biodegradation rate defective slowly, provide that a kind of collection resistance to air loss is good, processing characteristics is good, biodegradation rate is very fast, and the controlled biodegradation high molecular blend of degradation speed.
1992, we reported that a class has the modification polycaprolactone-polycaprolactone-polyether block copolymer better than polycaprolactone biological degradability (be called for short PCE) (Chinese patent application number 92113100.3, notification number CN1087098A).This class polycaprolactone-polyether block copolymer not only has the biodegradability of polycaprolactone: can quicken the degraded of polycaprolactone owing to the promoter action of (in the animal body) enzyme and (in the soil) microorganism, and owing to have than higher wetting ability of pure polycaprolactone and lower crystallinity, therefore not only biodegradation rate has increased significantly than pure polycaprolactone, and biodegradation rate can be controlled by the ratio of regulating two components.The present invention carries out blending and modifying with polycaprolactone-polyether block copolymer to polymers such as polyolefine, polyester.Can realize by the method for thermoplastic blend macromolecule modified with PCE.Wherein PCE is meant the polycaprolactone-polyether block copolymer with following structural formula.
R=H or C in the formula
1-C
4Alkyl, m=2-10, n=4-440, P=1-500, wherein the polycaprolactone chain segment molecular weight is 450～50000, the polyether segment molecular weight is 44-22000.
The macromolecular material that is modified is meant polyolefine polymers such as polyethylene, polypropylene, polystyrene, polyvinyl chloride; Polyester such as polyethylene terephthalate, polybutylene terephthalate polymer and polymethylmethacrylate, poly-n-butyl methacrylate, polymethyl acrylate, the polyacrylic ester family macromolecule that alkyl such as butyl polyacrylate replace or do not replace.
In order to reach PCE and to be modified the mixing of macromolecular material, can realize with various mixing machineries such as screw extrusion press, double roll mill or mixing tanks under 10-20 ℃ of temperature condition more than the melt polymer material temperature being heated to be modified.
The blending ratio (weight ratio) of macromolecular material and PCE of being modified is 95: 5 to 20: 80, is 90: 10～30: 70 preferably.
In order to improve the macromolecular material that is modified mixed performance, the macromolecular material that is modified can be handled through modified by maleic acid anhydride graft earlier, to improve their consistencies with PCE with PCE.
Macromolecular material by the technology of the present invention modification not only can make the resistance to air loss of goods be improved, biodegradation rate is controlled, and can still have the favorable biological degradability energy under the situation that the equal polycaprolactone consumption of PCE amount ratio reduces.Because the price of PCE is cheaper than equal polycaprolactone, therefore by the biodegradation high molecular blend of the technology of the present invention modification also have cheap, physical strength good, processing characteristics is good, can be processed as the advantage of film, sheet material, tubing, fine denier fiber and different shape the part with complicated structure.
The data of following specific embodiment further illustrate the degradation property by the macromolecular material of modification of the present invention.The dumbbell shaped film sample is adopted in strength test, with Instron 1122 material-testing machine, at room temperature, is that the condition that 10cm/ divides is carried out strength test to sample with the draw speed.
Embodiment 1,
Melting index be/10 minutes 100 parts of new LDPE (film grade)s of 35.0 grams with weight-average molecular weight be 64000, caprolactone and polyethers link units ratio are 25 parts of the polycaprolactone-copolyethers of 60: 40 (CL/EG=60/40), again at 140 ℃ use 10kg/cm at 140 ℃ after mixing 20 minutes with mixing tank
2Pressure is pressed into 0.2mm thick film sheet.The tensile rupture intensity of film is 7.07PMa; This film is immersed in containing in the sugar and the standard plant tissue culture media MS substratum of each metal ion species after one month of pH4.7, and tensile rupture intensity drops to 6.30PMa, has descended 10.9%.And the pure polyethylene film that does not contain PCE is after the same terms and time soak, and intensity does not change, and still is 8.02PMa.
Embodiment 2,
The melting index that to handle with modified by maleic acid anhydride graft is 100 parts of the new LDPE (film grade)s that divide of 18.0g/10, and with example 1 same ratio and condition, with identical PCE resin alloy be hot pressed into the thick film of 0.2mm that is, the tensile rupture intensity of film is 8.0PMa.In the tensile rupture strength degradation of soaking caudacoria through the Ms of pH4.7 substratum in month is 5.04PMa, has descended 37.0%, and has not added the polyethylene film with modified by maleic acid anhydride graft of PCE, and intensity still is 8.07PMa, does not change.
Embodiment 3,
With melting index is/10 minutes 100 parts of new LDPE (film grade)s of 35.0 grams with 25 parts of polycaprolactone blend, with condition press mold, immersion treatment and the test identical with example 1, the result shows that film toughness drops to 6.65PMa from 7.27PMa, has descended 8.5%.
Embodiment 4,
Melting index is that 100 parts of/10 minutes new LDPE (film grade)s of 35.0 grams are respectively 65000 PCL with weight-average molecular weight; Weight-average molecular weight is 57000, ratio of components is the PCE of CL/EG=60/40.With weight ratio is that 80: 20 ratios are pressed into about 0.5mm thick film sheet after mixing, bury in the muddy water that the people plants the lotus lotus root, and 15-33 ℃ of environment are placed after two months down and taken out out of doors, washing, and the Strength Changes of sample is measured in the dry back of the decompression universe.List in table 1.Table 1, the variation of sample intensity after embedding two months in the muddy water of lotus lotus root is arranged in sanction
| Sample | Intensity MPa |
| Green strength is strength decline % after embedding two months |
Pure LDPE 7.59 7.59 0
Pure PCL 21.60 20.00 7.41
Pure PCE 15.20 12.80 15.79
LDPE／PCL(80／20) 7．92 7．48 5．56
LDPE／PCE(80／20) 7．79 6．81 12．58
Embodiment 5,
It is mixing with weight ratio 84: 16 and 80: 20 ratios respectively with embodiment 4 identical PCL and PCE that melting index is the LDPE that divides of 20g/10, is pressed into 0.5mm thick film sheet, is dipped in temperature and is in 50 ℃ the 1%NaOH solution.Take out after one month, washing, dry back test intensity, the results are shown in Table 2.
Table 2 blend sample soaks the result in 50 ℃ of 1%NaOH solution
| Sample | Intensity MPa | ||
| Green strength | Soak intensity after one month | Strength degradation % | |
| LDPE PCL PCE LDE/PCL(84/16) LDE/PCL(80/20) LDE/PCE(84/16) LDPE/PCE(80/20) | 11.20 21.60 15.20 11.41 14.29 7.83 10.69 | 11.19 pulverize 8.84 10.44 5.84 7.27 | 0.08 100 100 22.52 26.94 25.42 31.99 |
Claims (2)
1, a kind of biodegradable resin blend, it is characterized in that handling or changing without grafting by polycaprolactone-polyether block copolymer with modified by maleic acid anhydride graft giving birth to the new LDPE (film grade) of handling and forming, its polycaprolactone polyether block polymer and new LDPE (film grade) blending ratio are (weight ratio) 5: 95-80: 20.
2, biodegradable resin blend according to claim 1 is characterized in that described blending ratio (weight ratio), is 10: 90-70: 30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106752A CN1060188C (en) | 1996-07-03 | 1996-07-03 | Bio-degradatable resin azeotropic mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106752A CN1060188C (en) | 1996-07-03 | 1996-07-03 | Bio-degradatable resin azeotropic mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149065A CN1149065A (en) | 1997-05-07 |
| CN1060188C true CN1060188C (en) | 2001-01-03 |
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ID=5119358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106752A Expired - Fee Related CN1060188C (en) | 1996-07-03 | 1996-07-03 | Bio-degradatable resin azeotropic mixture |
Country Status (1)
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080744C (en) * | 1997-09-25 | 2002-03-13 | 中国科学院化学研究所 | Biodegradation high molecular composition and its preparing method and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5179110A (en) * | 1974-12-28 | 1976-07-09 | Daido Steel Co Ltd | |
| CN1087098A (en) * | 1992-11-19 | 1994-05-25 | 中国科学院化学研究所 | Biodegradable polycaprolactone polyether block polymer and preparation method thereof |
| JP4057953B2 (en) * | 2003-05-27 | 2008-03-05 | 三井住友建設株式会社 | Bridge and its construction method |
-
1996
- 1996-07-03 CN CN96106752A patent/CN1060188C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5179110A (en) * | 1974-12-28 | 1976-07-09 | Daido Steel Co Ltd | |
| CN1087098A (en) * | 1992-11-19 | 1994-05-25 | 中国科学院化学研究所 | Biodegradable polycaprolactone polyether block polymer and preparation method thereof |
| JP4057953B2 (en) * | 2003-05-27 | 2008-03-05 | 三井住友建設株式会社 | Bridge and its construction method |
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| Publication number | Publication date |
|---|---|
| CN1149065A (en) | 1997-05-07 |
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