CN106810836A - A kind of biodegradation material and its preparation method and application - Google Patents
A kind of biodegradation material and its preparation method and application Download PDFInfo
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- CN106810836A CN106810836A CN201510846666.3A CN201510846666A CN106810836A CN 106810836 A CN106810836 A CN 106810836A CN 201510846666 A CN201510846666 A CN 201510846666A CN 106810836 A CN106810836 A CN 106810836A
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Abstract
The present invention provides a kind of biodegradation material, is made up of the raw material of following weight percentage：3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 10 ~ 35%；Poly butylene succinate 10 ~ 35%；PLA 0 ~ 50%；Vegetable oil 5 ~ 25%；Plasticizer 1 ~ 10%；Reaction promoter 0.02 ~ 5%.The present invention also provides the preparation method of above-mentioned biodegradation material, and application of this biodegradation material in Biodegradable film is prepared.Biodegradation material of the present invention is degradable biomaterial, with excellent elongation at break and tensile strength, and maintains the preferable transparency, excellent combination property.The preparation method process is simple of biodegradation material of the present invention, it is easy to control, workable, low production cost；And by biodegradation material again through simple processing after, it is possible to obtain Biodegradable film, it is easy to industrialized production and with good economic benefit, have broad application prospects.
Description
Technical field
The present invention relates to the composition of macromolecular compound, and in particular to a kind of biodegradation material, and this biodegradation material preparation method and application.
Background technology
Since being come into operation from the 30's of 20th century plastic material, with excellent properties such as its light weight, bright and clean attractive in appearance, the corrosion-resistant, simple production process of inexpensive, appearance, each department of national economy and each field of people's lives have been widely used in it.Due to the extensive application of plastics, scrapped plastic products are growing day by day, and the most stable performance of plastics, therefore so-called white pollution is occurred in that, bring very big harm to environment.In recent years, improvement of the people to waste plastic takes positive measure, for example, the minimizing of plastic package material, repeatedly uses, and recycling etc..However, being not easily recycled for those, recovery value is little or recycles the product for being economically difficult to run, such as shopping bag, disposable tableware, agricultural mulching, medical plastic ware, made then advantageously using degradative plastics.
But degradative plastics is the later material for growing up, at present also in growth, a perfect stage.Although existing degradative plastics has biodegradability, be conducive to environmental protection, can not keep the good transparency mostly, and/or mechanical property is not good, made product particularly film based article is easily damaged.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of biodegradation material, and the preparation method and application of this biodegradation material, this biodegradation material not only has biological degradability, and with excellent mechanical property, and keep the preferably transparency.The technical scheme of use is as follows：
A kind of biodegradation material, it is characterised in that be made up of the raw material of following weight percentage：
3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer 10 ~ 35%
；
Poly butylene succinate 10 ~ 35%
；
PLA 0 ~ 50%；
Vegetable oil 5 ~ 25%；
Plasticizer 1 ~ 10%；
Reaction promoter 0.02 ~ 5%.
Above-mentioned 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, vegetable oil, plasticizer and reaction promoter are combined, and embody good elongation at break and good tensile strength, and overall mechanical properties are preferable.
It is preferred that above-mentioned biodegradation material is made up of the raw material of following weight percentage：
3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer 15 ~ 22%
；
Poly butylene succinate 15 ~ 22%
；
PLA 25 ~ 50%
；Vegetable oil 14 ~ 25%；
Plasticizer 5 ~ 10%；
Reaction promoter 1 ~ 5%.
The 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, PLA, vegetable oil, plasticizer and reaction promoter of above-mentioned weight proportion are combined, and embody good elongation at break and excellent tensile strength, excellent combination property.
Further preferred above-mentioned biodegradation material is made up of the raw material of following weight percentage：
3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer 15 ~ 19%；
Poly butylene succinate 15 ~ 19%；
PLA 37 ~ 50%；
Vegetable oil 14 ~ 18%；
Plasticizer 5 ~ 7%；
Reaction promoter 1 ~ 2%.
The 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, PLA, vegetable oil, plasticizer and reaction promoter of above-mentioned weight proportion are combined, with good elongation at break and very excellent tensile strength, it is very suitable for making the products such as plastic shopping bag.
Above-mentioned 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate can improve the elongation at break of biodegradation material of the present invention.
Above-mentioned PLA can use L types PLA, D types PLA or LD mixed type PLAs.PLA can improve the intensity of biodegradation material of the present invention.
It is preferred that above-mentioned vegetable oil is one kind or many of combination in rapeseed oil, castor oil, soybean oil, peanut oil, coconut oil, palm oil, linseed oil, cottonseed oil, corn oil, sunflower oil, pine-seed oil and tung oil.Vegetable oil is added, by reaction active groups and matrix resin in vegetable oil（That is 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer and poly butylene succinate）In active function groups interaction, to reach increase-volume purpose.
Above-mentioned plasticizer is one kind or many of combination in sorbierite, polyethylene glycol, acetylation citric acid and glycerine.Add plasticizer, it is possible to increase the travelling performance of polymer chain, be improved the plastic effect of biodegradation material, reduce the fragility of biodegradation material, improve the flexibility of biodegradation material.
It is preferred that combination of the above-mentioned reaction promoter for one or both of coupling agent and catalyst.
It is preferred that combination of the above-mentioned coupling agent for one or both of silane compound and isocyanate compound.Preferably, above-mentioned coupling agent is γ-aminopropyl triethoxysilane（KH-550）, methyl diphenylene diisocyanate（MDI）With poly- methyl to phenylisocyanate（Abbreviation PMDI）In a kind of or many of combination.
It is preferred that combination of the above-mentioned catalyst for one or both of organic acid and inorganic proton acid.Preferably, above-mentioned catalyst is a kind of or many of combination in citric acid, adipic acid, succinic acid and hydrochloric acid.
Above-mentioned 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, PLA, vegetable oil, plasticizer, reaction promoter（Including coupling agent, catalyst）Can commercially buy, wherein 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer can choose P (3HB-co-4HB) copolyesters of Tianjin Green Biomaterial Co., Ltd.'s production.
The present invention also provides a kind of preparation method of above-mentioned biodegradation material, it is characterised in that comprise the steps：3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, PLA, vegetable oil, plasticizer and reaction promoter are well mixed, mixed material is obtained；Then mixed material is added to melt blending in double screw extruder, forms material melt；Material melt carries out tie rod, pelletizing from after the die head extrusion of double screw extruder, obtains material particles；After material particles are through dried process, biodegradation material is obtained.It is preferred that the screw slenderness ratio of double screw extruder is 35 ~ 45:1, the temperature of melt blending is 140 ~ 175 DEG C.Above-mentioned tie rod, pelletizing belong to existing conventional granulating technique means.Above-mentioned 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer and poly butylene succinate first carry out dried process using preceding generally requiring.
Application of the above-mentioned biodegradation material in Biodegradable film is prepared, by the biodegradation material through single screw rod inflation film manufacturing machine blown film, obtains Biodegradable film.The screw slenderness ratio of above-mentioned single screw rod inflation film manufacturing machine is 25 ~ 35:1.Because above-mentioned biodegradation material has excellent elongation at break and tensile strength, and the preferable transparency is maintained, thus be particularly suitable for manufacturing Biodegradable film.
The present invention compared with prior art, has the advantages that：
In biodegradation material of the present invention, key component 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, vegetable oil and PLA can all be decomposed by the microorganisms under given conditions, belong to Wholly-degradable biomaterial.In addition, 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, PLA, plasticizer and reaction promoter are combined, can interact, with certain synergy, so that biodegradation material of the invention embodies excellent elongation at break and tensile strength, and maintain the preferable transparency, excellent combination property.
The preparation method process is simple of biodegradation material of the present invention, it is easy to control, workable, low production cost；And by biodegradation material again through simple processing after, it is possible to obtain Biodegradable film, it is easy to industrialized production and with good economic benefit, have broad application prospects.
Biodegradation material of the present invention is highly suitable for preparing Biodegradable film, and the Biodegradable film being made has intensity very high；The shopping bag that this Biodegradable film is made can multiple Reusability, and can still be used as refuse bag after a number of uses, it is discarded after quick absorption is decomposed by the microorganism in soil completely, environmental pollution is small, with good environmental benefit.
Specific embodiment
Embodiment 1
First, the raw material of following weight portion is weighed：3- hydroxybutyric acids and the weight portion of 4- hydroxybutyric acids copolymer 18, the weight portion of poly butylene succinate 17, the weight portion of PLA 42, the weight portion of vegetable oil 16（It is castor oil）, the weight portion of plasticizer 6（It is polyethylene glycol）, the weight portion of reaction promoter 1（It is methyl diphenylene diisocyanate）.Above-mentioned 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer and poly butylene succinate first carry out dried process using preceding.
Then, full-biodegradable material is prepared according to the following steps：Above-mentioned all raw materials are well mixed（All raw materials can be pre-mixed in premixing machine, the initial temperature of mixing is 40 DEG C, the rotating speed of premixing machine is 800 ~ 1200 revs/min, is mixed 30 minutes, and rotating speed can be gradually stepped up in mixed process）, obtain mixed material；Then mixed material is added to melt blending in double screw extruder（Mixed material sequentially passes through temperature and is respectively 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 175 DEG C, 165 DEG C, 160 DEG C, 150 DEG C of each melt blending interval）, form material melt；Material melt from after the die head of double screw extruder extrusion _ _ carry out tie rod, pelletizing, obtain material particles；After material particles are through dried process, biodegradation material is obtained.The screw slenderness ratio of double screw extruder is 40:1.Above-mentioned tie rod, pelletizing belong to existing conventional granulating technique means, are not described in further detail herein.
Above-mentioned biodegradation material can meet U.S. ASTMD6400 and European Union EN13432 degraded standards.
By above-mentioned biodegradation material through single screw rod inflation film manufacturing machine blown film, Biodegradable film is obtained.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Embodiment 2
First, the raw material of following weight portion is weighed：3- hydroxybutyric acids and the weight portion of 4- hydroxybutyric acids copolymer 15, the weight portion of poly butylene succinate 15, the weight portion of PLA 50, the weight portion of vegetable oil 14（It is castor oil）, the weight portion of plasticizer 5（It is polyethylene glycol）, the weight portion of reaction promoter 1（It is γ-aminopropyl triethoxysilane）.Above-mentioned 3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer and poly butylene succinate first carry out dried process using preceding.
Then, full-biodegradable material is prepared according to the following steps：Above-mentioned all raw materials are well mixed（All raw materials can be pre-mixed in premixing machine, the initial temperature of mixing is 40 DEG C, the rotating speed of premixing machine is 800 ~ 1200 revs/min, is mixed 30 minutes, and rotating speed can be gradually stepped up in mixed process）, obtain mixed material；Then mixed material is added to melt blending in double screw extruder（Mixed material sequentially passes through temperature and is respectively 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 175 DEG C, 165 DEG C, 160 DEG C, 150 DEG C of each melt blending interval）, form material melt；Material melt carries out tie rod, pelletizing from after the die head extrusion of double screw extruder, obtains material particles；After material particles are through dried process, biodegradation material is obtained.The screw slenderness ratio of double screw extruder is 40:1.
Above-mentioned biodegradation material can meet U.S. ASTMD6400 and European Union EN13432 degraded standards.
By above-mentioned biodegradation material through single screw rod inflation film manufacturing machine blown film, Biodegradable film is obtained.The screw slenderness ratio of single screw rod inflation film manufacturing machine is 25:1.
Claims (10)
1. a kind of biodegradation material, it is characterised in that be made up of the raw material of following weight percentage：
3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer 10 ~ 35%；
Poly butylene succinate 10 ~ 35%；
PLA 0 ~ 50%；
Vegetable oil 5 ~ 25%；
Plasticizer 1 ~ 10%；
Reaction promoter 0.02 ~ 5%.
2. the biodegradation material according to claim 1, it is characterised in that be made up of the raw material of following weight percentage：3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer 15 ~ 22%
；
Poly butylene succinate 15 ~ 22%；
PLA 25 ~ 50%；
Vegetable oil 14 ~ 25%；
Plasticizer 5 ~ 10%；
Reaction promoter 1 ~ 5%.
3. the biodegradation material according to claim 2, it is characterised in that be made up of the raw material of following weight percentage：3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer 15 ~ 19%
；
Poly butylene succinate 15 ~ 19%；
PLA 37 ~ 50%；
Vegetable oil 14 ~ 18%；
Plasticizer 5 ~ 7%；
Reaction promoter 1 ~ 2%.
4. the biodegradation material according to any one of claim 1-3, it is characterised in that：The vegetable oil is one kind or many of combination in rapeseed oil, castor oil, soybean oil, peanut oil, coconut oil, palm oil, linseed oil, cottonseed oil, corn oil, sunflower oil, pine-seed oil and tung oil.
5. the biodegradation material according to any one of claim 1-3, it is characterised in that：The plasticizer is one kind or many of combination in sorbierite, polyethylene glycol, acetylation citric acid and glycerine.
6. the biodegradation material according to any one of claim 1-3, it is characterised in that：The reaction promoter is the combination of one or both of coupling agent and catalyst.
7. the biodegradation material according to claim 6, it is characterised in that：The coupling agent be γ-aminopropyl triethoxysilane, methyl diphenylene diisocyanate and poly- methyl to phenylisocyanate in a kind of or many of combination.
8. the biodegradation material according to claim 6, it is characterised in that：The catalyst is a kind of or many of combination in citric acid, adipic acid, succinic acid and hydrochloric acid.
9. the preparation method of the biodegradation material described in claim 1, it is characterised in that comprise the steps：3- hydroxybutyric acids and 4- hydroxybutyric acids copolymer, poly butylene succinate, PLA, vegetable oil, plasticizer and reaction promoter are well mixed, mixed material is obtained；Then mixed material is added to melt blending in double screw extruder, forms material melt；Material melt carries out tie rod, pelletizing from after the die head extrusion of double screw extruder, obtains material particles；After material particles are through dried process, biodegradation material is obtained.
10. application of the biodegradation material described in claim 1 in Biodegradable film is prepared, by the biodegradation material through single screw rod inflation film manufacturing machine blown film, obtains Biodegradable film.
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| CN201510846666.3A CN106810836A (en) | 2015-11-30 | 2015-11-30 | A kind of biodegradation material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591311A (en) * | 2019-09-06 | 2019-12-20 | 淮安森辉智能科技有限公司 | Biodegradable plastic film and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591311A (en) * | 2019-09-06 | 2019-12-20 | 淮安森辉智能科技有限公司 | Biodegradable plastic film and preparation method thereof |
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Application publication date: 20170609 |