CN102850741A - Polyhydroxyalkanoate full-degradation composite material, preparation method and applications thereof - Google Patents
Polyhydroxyalkanoate full-degradation composite material, preparation method and applications thereof Download PDFInfo
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- CN102850741A CN102850741A CN201210326759XA CN201210326759A CN102850741A CN 102850741 A CN102850741 A CN 102850741A CN 201210326759X A CN201210326759X A CN 201210326759XA CN 201210326759 A CN201210326759 A CN 201210326759A CN 102850741 A CN102850741 A CN 102850741A
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Abstract
The present invention discloses a polyhydroxyalkanoate full-degradation composite material, a preparation method and applications thereof. The composite material comprises the following components, by weight, 30-80 parts of homopolymerization polyhydroxyalkanoate, 20-70 parts of copolymerization polyhydroxyalkanoate, 15-40 parts of plant fibers, 1.5-6 parts of a coupling agent, 0.5-10 parts of an antioxidant, and 1-6 parts of a processing additive. The polyhydroxyalkanoate full-degradation composite material of the present invention can completely replace the traditional modified polypropylene and other general purpose plastics, and has a characteristic of full biodegradation, wherein 100% recovery of the polyhydroxyalkanoate full-degradation composite material can be achieved.
Description
Technical field
The invention belongs to technical field of polymer materials, specifically a kind of polyhydroxyalkanoate biodegradable composites preparation method and application thereof.
Background technology
Polyhydroxyalkanoatefrom (PHA) PHA has physicochemical characteristic and the biodegradability of similar chemical plastic, is used as Environmental lysis film and is applied, to alleviate at present more and more serious white pollution problems.Polyhydroxyalkanoatefrom (PHA) homopolymer or multipolymer are the bio-based degradable high polymer materials that a class has good mechanical property, biocompatibility and biological degradability.PHA homopolymer or multipolymer are of a great variety, mainly comprise tens kinds of homopolymer such as poly-3-butyric ester (P-3HB), poly-4-butyric ester (P-4HB), poly-3-hydroxyl valerate (P-3HV), poly-3-hydroxybutyric acid-4-hydroxybutyric acid copolyesters (P-3HB-4HB), polyhydroxybutyrate valeric acid copolyesters (PHBV) and multipolymer.PHA homopolymer or multipolymer mainly are prepared from by biofermentation method with biomass materials such as starch, can be decomposed into carbonic acid gas, water and biomass under soil or composting conditions.Be conducive to provide a kind of matrix material kind that meets environmental protection and Sustainable development requirement take PHA homopolymer or multipolymer as raw material prepares Biobased degradable composite material, expand simultaneously its Application Areas, thereby have very important marketable value.PHA also has many excellent in performance such as biocompatibility, optical activity, piezoelectricity, being separated by property of gas simultaneously, can be promoted application in plastics industry.
Summary of the invention
The purpose of this invention is to provide a kind of intensity higher, can substitute the general-purpose plastics such as traditional modified polypropene fully, having biodegradation character can 100% matrix material that reclaims.
In order to achieve the above object, the invention provides a kind of polyhydroxyalkanoate biodegradable composites, this matrix material comprises following component by weight ratio: homopolymerization polyhydroxyalkanoate 30-80 part, copolymerization polyhydroxyalkanoate 20-70 part, vegetable fibre 15-40 part, coupling agent 1.5-6 part, oxidation inhibitor 0.5-10 part, processing aid 1-6 part.
Wherein, vegetable fibre is one or more mixtures in flax fiber, ramee, sisal fibers, the bamboo-carbon fibre.
Coupling agent is titanate coupling agent, and coupling agent function functional group is any one or several mixture in carboxyl, alkoxyl group, sulfonic group, the phosphorus base.
Oxidation inhibitor is one or more the mixture in the phosphorous acid esters.
Processing aid is one or more mixture of stearic acid, stearate, polyethylene wax, oxidized polyethlene wax or polyglycerol fatty acid ester.
The present invention also provides the preparation method of above-mentioned polyhydroxyalkanoate biodegradable composites, may further comprise the steps:
(1) with homopolymerization polyhydroxyalkanoate and copolymerization polyhydroxyalkanoate crushed after being dried, mix with oxidation inhibitor, processing aid, place high-speed mixer high speed blend 3-10 minute, the mixture that makes adds in the twin screw extruder for subsequent use;
(2) get vegetable fibre with coupling agent treatment after, place the side spout of above-mentioned twin screw extruder, mixing by the mixture of preparation in twin screw extruder and the step (1) again, namely get described matrix material at 150-200 ℃ of lower process melt blending extruding pelletization at last.
The present invention also provides application, especially the application household electrical appliance or automotive industry on of above-mentioned polyhydroxyalkanoate biodegradable composites aspect alternative general-purpose plastics.As: domestic air conditioning indoor unit casing, automotive trim column etc.
The present invention has the following advantages compared to existing technology: the present invention adopts polyhydroxyalkanoate and vegetable fibre melt blending, has improved the performance of polyhydroxyalkanoate material; Take into full account simultaneously the fully bio-degradable characteristic, selected matrix resin (polyhydroxyalkanoate), enhancing weighting material (vegetable fibre) are renewable, degradable resource, under the prerequisite that keeps the material biodegradation character, have expanded use range.And regulate toughness of material by the content of adjusting the copolymerization polyhydroxyalkanoate, avoided the use of nondegradable petroleum base toughner.The prepared polyhydroxyalkanoate biodegradable composites of the present invention had both had the characteristics such as the performance, erosion resistance, weathering resistance of the resins for universal use such as polyethylene, polypropylene, has again the fully bio-degradable characteristic, 100% is recyclable, can be widely used in the fields such as household electrical appliance and automotive industry.General Promotion of the present invention polyhydroxyalkanoate biodegradable composites production technology level, be conducive to promote the development of China's Biodegradable material technology.
Embodiment
Below in conjunction with example, the present invention is further elaborated.
Embodiment 1
With homopolymerization, copolymerization polyhydroxyalkanoate crushed after being dried, mix in following ratio weighing with raw materials such as oxidation inhibitor, processing aids, place high-speed mixer high speed blend 3 minutes (rotating speed 1300-1500 turns/min), add in the forcing machine and prepare extruding pelletization; Again with the vegetable fibre coupling agent treatment, and weighing places the side spout in proportion, and the raw material of preparing by twin screw extruder and above-mentioned steps again is mixing, at 150 ℃ by twin screw extruder melting mixing, extruding pelletization.
Component and the parts by weight of raw material are respectively:
40 parts of homopolymerization polyhydroxyalkanoates
60 parts of copolymerization polyhydroxyalkanoates
30 parts on vegetable fibre (flax fiber)
4 parts of coupling agents (CT114 is available from the sharp evolution worker in newly developed area, Changzhou company limited)
3 parts in oxidation inhibitor (phosphorous acid ester, AT168 is available from Yixing angel's synthetic chemistry company limited)
3 parts of processing aids (Zinic stearas)
Embodiment 2
With homopolymerization, copolymerization polyhydroxyalkanoate crushed after being dried, mix in following ratio weighing with raw materials such as oxidation inhibitor, processing aids, place high-speed mixer high speed blend 10 minutes, add in the forcing machine and prepare extruding pelletization; Again with the vegetable fibre coupling agent treatment, and weighing places the side spout in proportion, and the raw material of preparing by twin screw extruder and above-mentioned steps again is mixing, at 200 ℃ by twin screw extruder melting mixing, extruding pelletization.
Component and the parts by weight of raw material are respectively:
50 parts of homopolymerization polyhydroxyalkanoates
50 parts of copolymerization polyhydroxyalkanoates
30 parts on vegetable fibre (ramee)
5 parts of coupling agents (CT114)
Oxidation inhibitor (phosphorous acid ester, AT168) 4 parts
5 parts of processing aids (stearic acid)
Embodiment 3
With homopolymerization, copolymerization polyhydroxyalkanoate crushed after being dried, mix in following ratio weighing with raw materials such as oxidation inhibitor, processing aids, place high-speed mixer high speed blend 10 minutes, add in the forcing machine and prepare extruding pelletization; Again with the vegetable fibre coupling agent treatment, and weighing places the side spout in proportion, and the raw material of preparing by twin screw extruder and above-mentioned steps again is mixing, at 200 ℃ by twin screw extruder melting mixing, extruding pelletization.
Component and the parts by weight of raw material are respectively:
60 parts of homopolymerization polyhydroxyalkanoates
40 parts of copolymerization polyhydroxyalkanoates
30 parts on vegetable fibre (bamboo-carbon fibre)
5 parts of coupling agents (CT114)
Oxidation inhibitor (phosphorous acid ester, AT168) 6 parts
5 parts of processing aids (calcium stearate)
Product to the embodiment preparation carries out performance test, and the modified polypropene of test result and contrast (MODIFIED PP 1) test result is as shown in the table.
Table 1 embodiment material property and contrast
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | MODIFIED PP 1 |
| Tensile strength (MPa) | 29 | 30 | 33 | 28 |
| Flexural strength (MPa) | 35 | 33 | 37 | 35 |
| Shock strength (Kj/m 2) | 5.0 | 4.6 | 3.5 | 2.5 |
Detected result shows, compares with traditional modified polypropene, and performance of the present invention is comparatively approaching, can substitute related products fully.And the prepared polyhydroxyalkanoate biodegradable composites of the present invention has the fully bio-degradable characteristic, and 100% is recyclable, can be widely used in the fields such as household electrical appliance and automotive industry.General Promotion polyhydroxyalkanoate biodegradable composites production technology level of the present invention is conducive to promote the development of China's Biodegradable material technology.
Claims (8)
1. polyhydroxyalkanoate biodegradable composites, it is characterized in that, comprise following component by weight ratio: homopolymerization polyhydroxyalkanoate 30-80 part, copolymerization polyhydroxyalkanoate 20-70 part, vegetable fibre 15-40 part, coupling agent 1.5-6 part, oxidation inhibitor 0.5-10 part, processing aid 1-6 part.
2. polyhydroxyalkanoate biodegradable composites according to claim 1 is characterized in that, described vegetable fibre is one or more in flax fiber, ramee, sisal fibers, the bamboo-carbon fibre.
3. polyhydroxyalkanoate biodegradable composites according to claim 1 is characterized in that, described coupling agent is titanate coupling agent.
4. polyhydroxyalkanoate biodegradable composites according to claim 1 is characterized in that, described oxidation inhibitor is phosphite ester kind antioxidant.
5. according to claim 1, it is characterized in that described processing aid is one or more in stearic acid, stearate, polyethylene wax, oxidized polyethlene wax, the polyglycerol fatty acid ester.
One kind arbitrary such as claim 1 to 5 as described in the preparation method of polyhydroxyalkanoate biodegradable composites, it is characterized in that, may further comprise the steps:
(1) with homopolymerization polyhydroxyalkanoate and copolymerization polyhydroxyalkanoate crushed after being dried, mix with oxidation inhibitor, processing aid, place high-speed mixer high speed blend 3-10 minute, the mixture that makes adds in the twin screw extruder for subsequent use;
(2) get vegetable fibre with coupling agent treatment after, place the side spout of described twin screw extruder, mixing by the mixture of preparation in twin screw extruder and the described step (1) again, namely get described matrix material at 150-200 ℃ of lower process melt blending extruding pelletization at last.
7. the application of the arbitrary described polyhydroxyalkanoate biodegradable composites of claim 1 to 5 aspect alternative general-purpose plastics.
8. the application of polyhydroxyalkanoate biodegradable composites according to claim 7 aspect alternative general-purpose plastics is characterized in that the application of described polyhydroxyalkanoate biodegradable composites on household electrical appliance or automotive industry.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177797A (en) * | 2014-09-12 | 2014-12-03 | 江苏旭华圣洛迪建材有限公司 | Degradable reinforced wood-plastic and preparation method thereof |
| CN104788920A (en) * | 2015-05-04 | 2015-07-22 | 苏州汉丰新材料股份有限公司 | Full-biodegradable composite material having high strength and high modulus as well as formula and preparation method of full-biodegradable composite material |
| CN103602047B (en) * | 2013-11-25 | 2015-09-23 | 大连路阳科技开发有限公司 | Polyhydroxyalkanoate matrix material and its production and use |
| CN105199391A (en) * | 2015-08-17 | 2015-12-30 | 李星锋 | Sole material of sneakers |
| CN107383818A (en) * | 2017-09-02 | 2017-11-24 | 天津科技大学 | A kind of string enhancing polyhydroxyalkanoate composite and preparation method thereof |
| CN108034107A (en) * | 2017-12-05 | 2018-05-15 | 徐州耐克盾机械制造有限公司 | A kind of environmentally-friendly plastic raw particles and its production technology |
| CN110128804A (en) * | 2019-06-03 | 2019-08-16 | 北京化工大学 | A method of improving polyhydroxyalkanoate melt-processable and mechanical property |
| CN111205604A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Ultrathin high-strength high-toughness biodegradable mulching film material and film, and preparation method and application thereof |
| CN112358712A (en) * | 2020-12-07 | 2021-02-12 | 深圳市裕同包装科技股份有限公司 | Bagasse fiber/PHA (polyhydroxyalkanoate) completely-degradable composite material and preparation method thereof |
| CN115537966A (en) * | 2022-11-09 | 2022-12-30 | 广东必得福医卫科技股份有限公司 | PHA (polyhydroxyalkanoate) bio-based degradable fiber and melt spinning method thereof |
| EP4276142A1 (en) | 2022-05-09 | 2023-11-15 | Politechnika Rzeszowska im. Ignacego Lukasiewicza | Method for multiple processing of biodegradable thermoplastic composite products |
| EP4393998A1 (en) | 2023-01-02 | 2024-07-03 | Politechnika Rzeszowska im. Ignacego Lukasiewicza | A biodegradable thermoplastic composite and a method for producing the biodegradable thermoplastic composite |
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| CN1521213A (en) * | 2003-01-31 | 2004-08-18 | 汕头保税区联亿生物工程有限公司 | Biodegradable material comprising polyhydroxy fotty acid ester blending polymer |
| CN101469111A (en) * | 2008-06-12 | 2009-07-01 | 深圳市意可曼生物科技有限公司 | Wholly-degradable biological plastic poly(3-hydroxybutyrate 4-hydroxybutyrate copolymer) and plant fibre blending alloy |
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Patent Citations (2)
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| CN1521213A (en) * | 2003-01-31 | 2004-08-18 | 汕头保税区联亿生物工程有限公司 | Biodegradable material comprising polyhydroxy fotty acid ester blending polymer |
| CN101469111A (en) * | 2008-06-12 | 2009-07-01 | 深圳市意可曼生物科技有限公司 | Wholly-degradable biological plastic poly(3-hydroxybutyrate 4-hydroxybutyrate copolymer) and plant fibre blending alloy |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602047B (en) * | 2013-11-25 | 2015-09-23 | 大连路阳科技开发有限公司 | Polyhydroxyalkanoate matrix material and its production and use |
| CN104177797A (en) * | 2014-09-12 | 2014-12-03 | 江苏旭华圣洛迪建材有限公司 | Degradable reinforced wood-plastic and preparation method thereof |
| CN104788920A (en) * | 2015-05-04 | 2015-07-22 | 苏州汉丰新材料股份有限公司 | Full-biodegradable composite material having high strength and high modulus as well as formula and preparation method of full-biodegradable composite material |
| CN105199391A (en) * | 2015-08-17 | 2015-12-30 | 李星锋 | Sole material of sneakers |
| CN107383818A (en) * | 2017-09-02 | 2017-11-24 | 天津科技大学 | A kind of string enhancing polyhydroxyalkanoate composite and preparation method thereof |
| CN108034107A (en) * | 2017-12-05 | 2018-05-15 | 徐州耐克盾机械制造有限公司 | A kind of environmentally-friendly plastic raw particles and its production technology |
| CN111205604A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Ultrathin high-strength high-toughness biodegradable mulching film material and film, and preparation method and application thereof |
| CN110128804A (en) * | 2019-06-03 | 2019-08-16 | 北京化工大学 | A method of improving polyhydroxyalkanoate melt-processable and mechanical property |
| CN112358712A (en) * | 2020-12-07 | 2021-02-12 | 深圳市裕同包装科技股份有限公司 | Bagasse fiber/PHA (polyhydroxyalkanoate) completely-degradable composite material and preparation method thereof |
| EP4276142A1 (en) | 2022-05-09 | 2023-11-15 | Politechnika Rzeszowska im. Ignacego Lukasiewicza | Method for multiple processing of biodegradable thermoplastic composite products |
| CN115537966A (en) * | 2022-11-09 | 2022-12-30 | 广东必得福医卫科技股份有限公司 | PHA (polyhydroxyalkanoate) bio-based degradable fiber and melt spinning method thereof |
| EP4393998A1 (en) | 2023-01-02 | 2024-07-03 | Politechnika Rzeszowska im. Ignacego Lukasiewicza | A biodegradable thermoplastic composite and a method for producing the biodegradable thermoplastic composite |
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Application publication date: 20130102 |