CN102898794A - Completely-degradable composite material with high toughness - Google Patents
Completely-degradable composite material with high toughness Download PDFInfo
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- CN102898794A CN102898794A CN2012103962396A CN201210396239A CN102898794A CN 102898794 A CN102898794 A CN 102898794A CN 2012103962396 A CN2012103962396 A CN 2012103962396A CN 201210396239 A CN201210396239 A CN 201210396239A CN 102898794 A CN102898794 A CN 102898794A
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Abstract
The invention discloses a completely-degradable composite material with high toughness, which comprises the following components in percentage by weight: 5 to 94% of PBS or/and PBAT, 5 to 70% of starch, and 0.5 to 60% of plasticize. The use of the starch as a component of the starch reduces production cost and speeds up the degradation of the composite material; and the system of the composite material can increase the melt flow index of the PBAT, so the composite material is easy to process and form. The high toughness of the composite material allows the composite material to be formed into films by casting and blowing or plastic products by blowing, extruding and injecting.
Description
Technical field
The invention belongs to can be degradable the polymer composite processing technique field, the PBS/PBAT/ starch that is specifically related to a kind of high tenacity can degradable matrix material.
Background technology
PBGS (Poly (butylene succinate), PBS) as the thermoplasticity aliphatic polyester with biodegradability, before having good mechanical property, thermally-stabilised and chemical stability, biological degradability, although PBS has fusing point relatively high with respect to the other biological degradation material, resistance toheat is good, the characteristics such as physical strength is comparatively excellent, but for traditional macromolecular material of widespread use, PBS still exists fragility larger, and fusing point is crossed the defectives such as low.
Poly-hexanodioic acid/butylene terephthalate (Poly (butylene adipate-co-butylene terephthalate); PBAT) be tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester's multipolymer; have the characteristic of PBA and PBT concurrently; existing preferably ductility and elongation at break; preferably thermotolerance and impact property are also arranged, and are to enliven with market very much in the present biodegradable plastic research to use one of best degradable material.But because the existence of aromatic series PBT segment has reduced its degradation speed, and its flowability is not good, is unfavorable for processing.
Starch mainly is made of straight chain and amylopectin, and amylose starch is to be formed by connecting by α-Isosorbide-5-Nitrae glycosidic link by glucose unit, and amylopectin is by the highly branched α of α-1,6 glycosidic link connection-Isosorbide-5-Nitrae chain.PBS and PBAT price are higher, and starch have wide material sources, cheap, can be degradable and the advantage such as the regeneration period is short.
This shows the condition such as present PBS and PBAT and matrix material thereof are difficult to satisfy simultaneously the toughness of material height, and degradation rate is fast, and processing characteristics is good, and is with low cost.
Summary of the invention
The object of the present invention is to provide a kind of high tenacity PBS/PBAT/ starch can degradable polymer composite.
The present invention is that the technical scheme that its technical problem of solution adopts is: a kind of high tenacity can degradable matrix material, this matrix material is composed of the following components by weight percentage: PBS is or/and the content of PBAT is 5%-94%, the content of starch is 5%-70%, and the content of softening agent is 0.5%-60%.
Preferably, PBS is or/and PBAT content is the 20%-70% of gross weight, and starch is 10%-50%, and softening agent is 5%-30%.
Preferably, the PBS weight-average molecular weight is at 20000-500000.
In preferred embodiments, the present invention adopts the PBS of weight-average molecular weight more than 200,000 that does not contain the isocyanic ester chainextender.
Preferably, starch is one or more the combination of native starch and treated starch.Concrete, the combination of one or more in native starch employing W-Gum, wheat starch, potato starch and the cereal starch; The combination of one or more in treated starch employing methylol modified starch, hydroxyethyl modified starch, hydroxypropyl modified starch, Sumstar 190, the starch acetate.
Preferably, softening agent is water, glycerine, polyoxyethylene glycol (PEG200, PEG400, PEG600, PEG800, PEG1000), polypropylene glycol, ethylene glycol, propylene glycol (1,2 propylene glycol, 1,3 propylene glycol), butyleneglycol (1,2 butyleneglycols, 1,3 butyleneglycols, Isosorbide-5-Nitrae butyleneglycol), one or more combination of acetic acid sorbitol ester, mannitol monoacetate, mannitol monosubstituted ethoxy compound, carboxymethyl Sorbitol Powder sodium salt, urea, amine.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
1, adopts starch as one of component of matrix material, when reducing production costs, increased the degradation rate of matrix material.
, composite system increased the melt flow index of PBAT, so that the easier machine-shaping of matrix material.
, composite material toughness of the present invention is high, can be widely used in the casting film-forming fabricated product, blown film goods, blow-molded article and extrude, injection-molded item.
Embodiment
The below will come the present invention is further specified by specific embodiment, but described embodiment only is used for explaining the present invention, be not restriction the present invention.
Embodiments of the invention adopt the method that is prepared as follows:
By weight, with PBS/PBAT base material blend 5min in the Haake Banbury mixer, temperature is made as 135 ° of C first, afterwards starch pasting is carried out in starch, softening agent and water blend, and starch that gelatinization is good adds in the Banbury mixer again blend 5min, and temperature is made as 135 ° of C.Material after the blend is 150 ° of C hot pressing 5min in vulcanizer, and the room temperature 5min that colds pressing obtains blended compound material afterwards.
Gained composite material by adopting following methods of the present invention or standard are carried out performance test, all need at 23 ° of C ± 2 ° C of temperature, under the condition of humidity 50% ± 5%, deposit and be not less than 16 hours before all batten tests:
Tensile strength: test clamp distance according to standard A STM D638: 20mm; Rate of extension: 10mm/min; Thickness of sample: 1mm; Sample width: 4mm;
Melting index: test by ASTM D1238,150 ° of C test under 2.160 kilograms of load;
Shore hardness: test by ASTM D2240-05 Shao Shi D type hardness tester.
For the ease of better explanation, the below lists in table 1 for each Example formulations that the present invention provides, and its test result is listed in table 2.
Each Example formulations of table 1
| Numbering | PBS/% | PBAT/% | Starch/% | Softening agent/% | Water/ml/50g |
| Comparative Examples 1 | 100 | 0 | 0 | 0 | 0 |
| Comparative Examples 2 | 0 | 100 | 100 | 0 | 0 |
| Embodiment 1 | 60 | 0 | 25 | 15 | 3 |
| Embodiment 2 | 45.5 | 0 | 45.5 | 9.1 | 8 |
| Embodiment 3 | 0 | 60 | 25 | 15 | 3 |
| Embodiment 4 | 10 | 50 | 25 | 15 | 3 |
Each embodiment resulting materials the performance test results of table 2
| Numbering | Tensile strength/Mpa | Elongation at break/% | Melting index | Shore hardness |
| Comparative Examples 1 | 29.1 | 17.55 | 9.37 | 90 |
| Comparative Examples 2 | 34.78 | 1368.79 | 1.65 | 66 |
| Embodiment 1 | 14.34 | 63.06 | 13.51 | 81 |
| Embodiment 2 | 11.03 | 1.43 | 12.7 | 87 |
| Embodiment 3 | 7.91 | 628.07 | 3.5 | 55 |
| Embodiment 4 | 16.1 | 718 | 9.23 | 62 |
Can be found out by embodiment, the mechanical property of PBS/PBAT/ starch composite material of the present invention obtains larger raising, make its easier processing, reduce production costs, have industrialization value, can be widely used in casting film-forming goods, blown film goods, extruded product and injection-molded item etc.
More than the present invention has been done detailed description, but the present invention is not limited to above embodiment, the equivalence that all essence according to the present invention is done changes or modifies, all within protection scope of the present invention.
Claims (7)
- A high tenacity can degradable matrix material, this matrix material is composed of the following components by weight percentage: PBS is or/and the content of PBAT is 5%-94%, and the content of starch is 5%-70%, and the content of softening agent is 0.5%-60%.
- A kind of high tenacity according to claim 1 can degradable matrix material, PBS wherein is or/and the content of PBAT is 20%-70%, the content of starch is 10%-50%, the content of softening agent is 5%-30%.
- A kind of high tenacity according to claim 1 and 2 can degradable matrix material, the weight-average molecular weight of PBS wherein is at 20000-500000.
- A kind of high tenacity according to claim 1 and 2 can degradable matrix material, starch wherein is one or more combination of native starch and treated starch.
- A kind of high tenacity according to claim 4 can degradable matrix material, wherein native starch is one or more the combination in W-Gum, wheat starch, potato starch and the cereal starch.
- A kind of high tenacity according to claim 4 can degradable matrix material, wherein treated starch is one or more the combination in methylol modified starch, hydroxyethyl modified starch, hydroxypropyl modified starch, Sumstar 190, the starch acetate.
- 7. a kind of high tenacity according to claim 1 and 2 can degradable matrix material, softening agent wherein is water, glycerine, polyoxyethylene glycol (PEG200, PEG400, PEG600, PEG800, PEG1000), polypropylene glycol, ethylene glycol, propylene glycol (1,2 propylene glycol, 1,3 propylene glycol), butyleneglycol (1,2 butyleneglycols, 1,3 butyleneglycols, Isosorbide-5-Nitrae butyleneglycol), one or more combination of acetic acid sorbitol ester, mannitol monoacetate, mannitol monosubstituted ethoxy compound, carboxymethyl Sorbitol Powder sodium salt, urea, amine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2508273A (en) * | 2012-09-26 | 2014-05-28 | Biome Bioplastics Ltd | Starch based polymer blends |
| CN104695135A (en) * | 2013-12-04 | 2015-06-10 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable non-woven fabric and preparation method thereof |
| CN106543486A (en) * | 2016-12-06 | 2017-03-29 | 周潇潇 | A kind of degradable biological plastics |
| CN107974050A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of polymer blend and preparation method thereof |
| CN108948678A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of full biology base PBS biodegradable plastic of starch conversion and preparation method thereof |
| CN112759901A (en) * | 2020-12-29 | 2021-05-07 | 四川坤源杰环保科技有限公司 | Micro-crystallization toughening modified PBS or PBAT biodegradable composite material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2508273A (en) * | 2012-09-26 | 2014-05-28 | Biome Bioplastics Ltd | Starch based polymer blends |
| CN104695135A (en) * | 2013-12-04 | 2015-06-10 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable non-woven fabric and preparation method thereof |
| CN107974050A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of polymer blend and preparation method thereof |
| US10934391B2 (en) | 2016-10-21 | 2021-03-02 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
| CN106543486A (en) * | 2016-12-06 | 2017-03-29 | 周潇潇 | A kind of degradable biological plastics |
| CN108948678A (en) * | 2017-05-18 | 2018-12-07 | 济宁明升新材料有限公司 | A kind of full biology base PBS biodegradable plastic of starch conversion and preparation method thereof |
| CN112759901A (en) * | 2020-12-29 | 2021-05-07 | 四川坤源杰环保科技有限公司 | Micro-crystallization toughening modified PBS or PBAT biodegradable composite material |
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Application publication date: 20130130 |