CN100365064C - Fully degradation polymethylethylene carbonic ester/vinyl-vinyl alcohol copolymer composite foam material and its preparing method - Google Patents
Fully degradation polymethylethylene carbonic ester/vinyl-vinyl alcohol copolymer composite foam material and its preparing method Download PDFInfo
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- CN100365064C CN100365064C CNB2005101003421A CN200510100342A CN100365064C CN 100365064 C CN100365064 C CN 100365064C CN B2005101003421 A CNB2005101003421 A CN B2005101003421A CN 200510100342 A CN200510100342 A CN 200510100342A CN 100365064 C CN100365064 C CN 100365064C
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- vinyl alcohol
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Abstract
The present invention relates to fully degradable plastic composite foaming material and a preparation method thereof. Degradable ploymethyl ethylene carbonate polymers synthesized from carbon dioxide and propylene oxide are used as matrices. The present invention comprises the following steps: firstly, adding ethylene vinyl alcohol copolymers to the matrices; secondly, blending preferable foaming agents, nucleating agents and auxiliary agents; finally, preparing the fully degradable plastic composite foaming material through foaming in the mode of extrusion, moulding and stretching press under a heating condition. The material can be used for manufacturing disposable foaming plastic products, such as disposable table ware, packing supplies, pallets for foodstuff, etc. The present invention has the advantages of simple technology and wide application range. The ethylene vinyl alcohol copolymers are introduced into ploymethyl ethylene carbonate, so that the mechanical properties of the foaming material is improved, and simultaneously, since the ethylene vinyl alcohol copolymers have water absorption, the degradability of the polymethyl ethylene carbonate can be enhanced. The material has the advantages of good mechanical property, light weight, low cost, easy degradation, etc., and belongs to environmental protection material.
Description
Technical field
The present invention relates to a kind of complete degradable plastic composite foam material and preparation method thereof, concrete system relates to a kind of prescription of complete degradable plastic composite foam material, preparation method.
Technical background
Porous plastics is a kind of type material, and it is a base stock with plastics, has light weight, and heat-proof quality is good, can absorb shock load, the specific tenacity advantages of higher.Because these performances all are widely used it in a lot of fields, particularly in packing, daily necessities, building and high-tech sector, porous plastics has occupied the status of not replacing.But the white pollution problems that thereupon brings is also more and more serious, especially disposable food or beverage container and wrapping foam material, as polystyrene, polyvinyl chloride and urethane etc., degradation time is slow and reclaim difficult, environment is caused serious pollution, therefore developed the research focus that its substitute products become this field.Lined polymethyl ethylene carbonate is a class degradation environment protection section bar material, 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.R and D to the lined polymethyl ethylene carbonate foam material not only to a certain degree can alleviated environment contradiction, and exhausted day by day petroleum resources also are one replenish.At present, the research of lined polymethyl ethylene carbonate foam material has obtained certain progress, but has limited its application because of the defective of itself partial properties.Utilizing other macromolecular material that lined polymethyl ethylene carbonate is carried out blending and modifying and prepare composite foam material, is the effective ways that improve the lined polymethyl ethylene carbonate foaming material performance.
Summary of the invention
The object of the present invention is to provide a kind of complete degradable plastic composite foam material and preparation method thereof, this method technology is simple, and resulting material can be degraded fully, wide accommodation.
Composition of raw materials used among the present invention is:
Raw material ratio of components (weight ratio)
100 parts of lined polymethyl ethylene carbonates
5～50 parts of ethylene-vinyl alcohol copolymer
2～8 parts of whipping agents
1～10 part of nucleator
1～2 part of auxiliary agent
The used methyl ethylene carbonate of the present invention is the product by propylene oxide and carbonic acid gas alternating copolymerization, degradable, and its number-average molecular weight is 20,000 to 200,000, chemical structure is:
The used ethylene-vinyl alcohol copolymer of the present invention is that ethylene content is the multipolymer of 5%-95%, and its number-average molecular weight is 5,000 to 100,000, and chemical structure is:
The used whipping agent of the present invention is this area whipping agent commonly used, can be chemical foaming agent, as Cellmic C 121, and dinitrobenzene five methyne tetramines, 4,4 '-the bis oxide benzol sulfohydrazide etc., or these composition; Also can be pneumatogen, as the lower boiling aliphatic hydrocarbon, alcohol, ether, rare gas element etc., or these composition.The kind of whipping agent and consumption are one of important factors of decision expansion ratio and abscess quality.For reaching high expansion ratio, preferred gas forming amount is big, the high organic blowing agent of foaming efficient.The consumption of whipping agent expansion ratio at least is low, and consumption is too much, and expansion ratio and abscess quality also can reduce, preferred 4～6 parts.
The used nucleator of the present invention is one or more the powder mixture in heavy or ground calcium carbonate, talcum powder, silicon dirt, polynite, the kaolin etc.Adding an amount of nucleator can obviously improve expansion ratio, improves foam structure, preferred 8～10 parts of its consumption.
The used auxiliary agent of the present invention has: blowing promotor, as zinc oxide, urea etc.; Oxidation inhibitor is as antioxidant 1010, oxidation inhibitor 168 etc.; Lubricant is as paraffin, polyethylene wax etc.; Pigment is as titanium dioxide etc.
The used synthetic resins of the present invention, whipping agent, nucleator and various auxiliary agent all are nontoxic materials, meet the food sanitation requirement, the production process three-waste free pollution.
The preparation method of complete degradable plastic composite foam material of the present invention, its step comprises:
A. after lined polymethyl ethylene carbonate and ethylene-vinyl alcohol copolymer are pressed ratio of components pre-mixing at room temperature, under 150 ℃～190 ℃ temperature, carry out melt blending, 5～20 minutes blend time, after mixing, granulation.
B. whipping agent, nucleator and auxiliary agent are pressed ratio of components and mixed, under 160 ℃～180 ℃, extrude, mold pressing or calendering, preparation foam material with above-mentioned pellet.
Implement the producing apparatus that the inventive method relates to, mainly contain two roller mill, Banbury mixer or twin screw extruder, homogenizers, extrude pulling-on piece flattener and heat baking foaming drying tunnel etc., equipment used is plastics and produces general-purpose equipment.
The prepared complete degradable plastic composite foam material of the present invention is mainly used in and makes disposable food or beverage container, package packing supplies, food with pallet or correlated product.For some the product of particular requirement is arranged, can prolong in the pressure process extruding pulling-on piece, adopt the multiple membrane process in surface, make the film of the compound one deck 0.1～0.2mm of material surface.The degradable performance of products obtained therefrom is good, if take recycling, can be used as weighting material and prepares other plastics.
Used degradable poly methyl ethylene carbonate resin is the product by propylene oxide and carbonic acid gas alternating copolymerization among the present invention, is a kind of degradable high polymer material with applications well prospect.In the lined polymethyl ethylene carbonate resin, add ethylene-vinyl alcohol copolymer and not only improved the thermostability and the mechanical property of foam material, and because the water absorption character of ethylene-vinyl alcohol copolymer, quickened the biodegradability of composite foam material.Lined polymethyl ethylene carbonate/vinyl-vinyl alcohol copolymer composite foam material is a kind of novel green material.Compare with traditional polystyrol foam material, composite foam material of the present invention has good mechanical property, light weight, low cost and other advantages, and easily degraded, belongs to ep-type material, can be used as the substitute of existing foam material.
Embodiment
Further describe the present invention with embodiment below.
Embodiment 1-4
The composition and the expansion ratio of composite foam 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, 60 rev/mins of rotor speeds in 170 ℃ of dischargings in following mixing 5 minutes, promptly get lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer masterbatch.Masterbatch, whipping agent Cellmic C 121 and blowing promotor zinc oxide and pigmentary titanium dioxide are put into melting mixing equipment by proportioning, 60 rev/mins of rotor speeds, descended mixing 10 minutes in 140 ℃, after mixing, extrude pulling-on piece in 160～180 ℃ extruding the pulling-on piece flattener, promptly get composite foamed sheet material, hot-forming on moulding press again, can get various foaming products.
Embodiment 5-8
The composition and the expansion ratio of composite foam material are as shown in table 2.After lined polymethyl ethylene carbonate and ethylene-vinyl alcohol copolymer (ethylene content 44%) metering, put into melting mixing equipment, 60 rev/mins of rotor speeds in 170 ℃ of dischargings in following mixing 5 minutes, promptly get lined polymethyl ethylene carbonate/ethylene-vinyl alcohol copolymer masterbatch.Masterbatch, nucleator lime carbonate, whipping agent Cellmic C 121 and blowing promotor zinc oxide and pigmentary titanium dioxide are put into melting mixing equipment by proportioning, 60 rev/mins of rotor speeds, descended mixing 10 minutes in 140 ℃, after mixing, extrude pulling-on piece in 160～180 ℃ extruding the pulling-on piece flattener, promptly get composite foamed sheet material.Hot-forming on moulding press at last, can get various foaming products.
The composition of table 1 lined polymethyl ethylene carbonate/vinyl-vinyl alcohol copolymer composite foam material and expansion ratio
| Embodiment | 1 | ?2 | ?3 | ?4 |
| Lined polymethyl ethylene carbonate quality/part | 100 | ?100 | ?100 | ?100 |
| Ethylene-vinyl alcohol copolymer quality/part | 10 | ?20 | ?30 | ?40 |
| Cellmic C 121 quality/part | 4 | ?5 | ?6 | ?8 |
| Zinc oxide quality/part | 0.4 | ?0.5 | ?0.6 | ?0.8 |
| Titanium dioxide quality/part | 2 | ?2 | ?2 | ?2 |
| Expansion ratio | 8 | ?13 | ?12 | ?9 |
The composition of table 2 lined polymethyl ethylene carbonate/vinyl-vinyl alcohol copolymer composite foam material and expansion ratio
| Embodiment | 5 | ?6 | ?7 | ?8 |
| Lined polymethyl ethylene carbonate quality/part | 100 | ?100 | ?100 | ?100 |
| Ethylene-vinyl alcohol copolymer quality/part | 10 | ?20 | ?30 | ?40 |
| Lime carbonate quality/part | 10 | ?10 | ?10 | ?10 |
| Cellmic C 121 quality/part | 4 | ?5 | ?6 | ?8 |
| Zinc oxide quality/part | 0.4 | ?0.5 | ?0.6 | ?0.8 |
| Titanium dioxide quality/part | 2 | ?2 | ?2 | ?2 |
| Expansion ratio | 11 | ?17 | ?14 | ?10 |
Claims (7)
1. a complete degradable plastic composite foam material is characterized in that the weight ratio of its each component is: 100 parts of lined polymethyl ethylene carbonates, 5～50 parts of ethylene-vinyl alcohol copolymer, 2～8 parts of whipping agents, 1～10 part of nucleator, 1～2 part of auxiliary agent.
2. complete degradable plastic composite foam material as claimed in claim 1 is characterized in that described lined polymethyl ethylene carbonate by propylene oxide and carbonic acid gas alternating copolymerization, degradable product, and its number-average molecular weight is 20,000 to 200,000, and chemical structure is:
Wherein n is 100-1000;
3. complete degradable plastic composite foam material as claimed in claim 1 is characterized in that described ethylene-vinyl alcohol copolymer is that ethylene content is the multipolymer of 5%-95%, and its number-average molecular weight is 5,000 to 100,000, and chemical structure is:
4. complete degradable plastic composite foam material as claimed in claim 1, it is characterized in that described whipping agent be chemical foaming agent Cellmic C 121, dinitrobenzene five methyne tetramines or 4,4 '-one or more composition in the bis oxide benzol sulfohydrazide; Or one or more the composition in pneumatogen lower boiling aliphatic hydrocarbon, alcohol, ether or the rare gas element.
5. complete degradable plastic composite foam material as claimed in claim 1 is characterized in that described nucleator is one or more the powder mixture in heavy or ground calcium carbonate, talcum powder, silicon dirt, polynite, the kaolin.
6. complete degradable plastic composite foam material as claimed in claim 1 is characterized in that described auxiliary agent comprises: blowing promotor zinc oxide, urea; Oxidation inhibitor antioxidant 1010, oxidation inhibitor 168; Lubricant paraffin, polyethylene wax; TiO 2 pigment.
7. the preparation method of complete degradable plastic composite foam material as claimed in claim 1 is characterized in that steps of the method are:
A. after lined polymethyl ethylene carbonate and ethylene-vinyl alcohol copolymer are pressed ratio of components pre-mixing at room temperature, under 150 ℃～190 ℃ temperature, carry out melt blending, 5～20 minutes blend time, after mixing, granulation;
B. whipping agent, nucleator and auxiliary agent are pressed ratio of components and mixed, under 160 ℃～180 ℃, extrude, mold pressing or calendering, preparation foam material with the pellet of step a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101003421A CN100365064C (en) | 2005-10-20 | 2005-10-20 | Fully degradation polymethylethylene carbonic ester/vinyl-vinyl alcohol copolymer composite foam material and its preparing method |
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|---|---|---|---|
| CNB2005101003421A CN100365064C (en) | 2005-10-20 | 2005-10-20 | Fully degradation polymethylethylene carbonic ester/vinyl-vinyl alcohol copolymer composite foam material and its preparing method |
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| CN1749320A CN1749320A (en) | 2006-03-22 |
| CN100365064C true CN100365064C (en) | 2008-01-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BR112015023773A2 (en) * | 2013-03-15 | 2017-07-18 | Owens Corning Intellectual Capital Llc | processing support for use in the manufacture of extruded polystyrene foam using potential global warming blowing agents |
| CN106752007B (en) * | 2016-12-25 | 2022-12-30 | 深圳市金凌软件有限公司 | Poly (propylene carbonate)/agriculture and forestry biomass composite material, preparation method and application |
| CN114525025B (en) * | 2021-09-23 | 2023-08-15 | 山东联欣环保科技有限公司 | Copolymer foam material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19613484A1 (en) * | 1996-04-04 | 1997-10-09 | Buna Sow Leuna Olefinverb Gmbh | Biodegradable gas separation membrane with high selectivity for carbon di:oxide permeation |
| WO1998007782A1 (en) * | 1996-08-20 | 1998-02-26 | Buna Sow Leuna Olefinverbund Gmbh | Biodegradable thermoplastically deformable materials for food packaging |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19613484A1 (en) * | 1996-04-04 | 1997-10-09 | Buna Sow Leuna Olefinverb Gmbh | Biodegradable gas separation membrane with high selectivity for carbon di:oxide permeation |
| WO1998007782A1 (en) * | 1996-08-20 | 1998-02-26 | Buna Sow Leuna Olefinverbund Gmbh | Biodegradable thermoplastically deformable materials for food packaging |
Non-Patent Citations (1)
| Title |
|---|
| 聚（1，2-亚丙基碳酸酯）的应用研究新进展. 庞浩.应用化学，第18卷第3期. 2001 * |
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