CN103483623A - Preparation method for regenerated nanometer flame retardant plastic - Google Patents
Preparation method for regenerated nanometer flame retardant plastic Download PDFInfo
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- CN103483623A CN103483623A CN201310430925.5A CN201310430925A CN103483623A CN 103483623 A CN103483623 A CN 103483623A CN 201310430925 A CN201310430925 A CN 201310430925A CN 103483623 A CN103483623 A CN 103483623A
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Abstract
The invention discloses a preparation method for a regenerated nanometer flame retardant plastic, wherein the regenerated nanometer flame retardant plastic is characterized by comprising the following raw materials in parts by weight: 45-60 parts of plant fiber starch, 4-6 parts of glycerinum, 40 parts of polyethylene, 20-40 parts of polylactic acid, 60-80 parts of synthetic resin, 10-15 parts of an additive, 5-8 parts of pulullan, 2-4 parts of an antioxygen agent, 1-1.5 parts of an ultraviolet light absorber and the like.
Description
Technical field
The present invention relates to a kind of plastics film, particularly a kind of preparation method of the nano flame retardant plastics of regenerating.
Background technology
As everyone knows, the plastics bag of making of plastics film is light, thin, waterproof, intensity is large, cost is low, a kind of good wrapping material, the use of plastics bag brings great convenience to people's life, make the consumption of plastics bag increasing, with waste plastic bag later, be difficult for reclaiming, being difficult for degraded, a large amount of waste plastic bags has become a serious problem of current contaminate environment.In order to alleviate the pollution of plastics film to environment, people have developed some environment-friendly degradable plastic films, as: the patent No.: 200710144500.2, paper-simulating degradable plastic film and manufacture craft thereof; And the patent No.: 201110051187.4, the method for fully biodegradable Plastic Resin and film based article thereof.This class degradable plastic film, its moiety has the film-grade plastics and can cause the component that plastics produce degraded, as starch, calcium carbonate etc., this degradable plastic film is the addition type degradable plastic film, and the addition type degradable plastic film is to improve environment to have brought into play certain active effect.But processing performance plastics film the physical property of product and the outward appearance bad, that make of this degradable plastic film processing are poor.
Biodegradable plastic is one of effective way of administering plastic refuse environmental pollution and buffering petroleum resources contradiction, from the packing bag of food to agricultural film, arrive again the shell of electric equipment products, from non-returnable container, edible products to product durable in use, biodegradable plastic just progressively replaces the conventional plastic material, and market outlook are very wide.It is reported, the biodegradable plastic kind of global development is existing tens kinds at present, principal item has: the microorganism synthetic polyhydroxyalkanoate (PHA, PHB, PHBV etc.) that ferments, the poly(lactic acid) of chemosynthesis (PLA), polycaprolactone, dibasic alcohol dicarboxylic acid aliphatic polyester (PBS), aliphatic/aromatic copolyester, CO2/ epoxy compound composition copolymer (APC), polycaprolactone (PCL), polyvinyl alcohol (PVA) etc., natural polymer starch plastics and biodegradable plastic blend, polyblend etc.The kind that has entered at present pilot scale or batch production has starch plastics, PHA (PHB, PHBV, PHBH-HX etc.), PLA, PBS, APC, modified PVA, starch/PVA, the polyblend such as PLA, PCL and blend etc.
In addition, the degraded of this degradable plastic film needs certain rigid condition, and the environment of plastics film after discarded, done in the refuse disposal system of sealing, be exactly to be exposed in the unfixed physical environment of condition, very difficult guarantor levies the needed rigid condition of this degradation of plastic film, and no matter these degradative plasticss in most of the cases, are because being subject to condition restriction, can not degrade well in refuse disposal system or at physical environment.In prior art, do not have can the environment after discarded in, guarantee the degradable plastic film of degraded.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned deficiency, propose, in a kind of environment after discarded, to guarantee the Degradable environment protection green plastic bag product of degraded.
Technical scheme of the present invention is: a kind of biodegradable plastic is characterized in that: its feed composition and parts by weight are respectively:
Plant fiber starch 45-60,
Glycerine 4-6
Polyethylene 40
Poly(lactic acid) 20-40
Synthetic resins 60-80
Auxiliary agent 10-15
Pulullan polysaccharide 5-8
Oxidation inhibitor 2-4
UV light absorber 1-1.5
Nano flame retardant mixture 30-25;
The preparation method of described fire-retardant recombiner is:
(1) silicon hydroxyapatite, red phosphorus, Attapulgite, hydrotalcite, polynite, titanium dioxide, calcite, nano kaoline are mixed according to the mass fraction proportioning of 25-35:15-20:10-15: 10-15:8-10:8-10:7-8:5-7, join in the mixing solutions of 200 parts of methyl-sulphoxides (DMSO) and 50 parts of methyl alcohol, in 65 ℃, stir 60 hours, filter, and wash and remove excessive methyl-sulphoxide (DMSO) for 3 times with the hot ethanol of 60 ℃ of temperature, put into vacuum drying oven, dry 24 hours of 60 ℃ of temperature, grinding is sieved, and obtains the modified flame-retardant mixture one time;
(2), 1 part of modified flame-retardant mixture, 10 parts of Potassium ethanoates and 25 parts of distilled water are mixed, in temperature 50 C, stir more than 10 hours, in 30 ℃ of temperature, first under ultrasonic electric power 350W condition, disperse 2.5 hours, and then disperse 3 hours under ultrasonic electric power 250W condition.Filter, and wash 3 times with distillation, 80 ℃ of vacuum-drying 24 hours, grinding is sieved, and obtains twice-modified fire-retardant mixture;
(3), above-mentioned 1 part of twice-modified fire-retardant mixture is disperseed to 40min at the 600W power ultrasonic, be heated to 90 ℃ with constant temperature heating device, and stir (1200r/min) 60 minutes with mechanical stirrer; Obtain the nano flame retardant mixture.
Polyethylene is that Low Density Polyethylene, medium-density polyethylene, high density polyethylene(HDPE) are according to mass ratio 2:2:1 batch mixing.
Auxiliary agent comprises softening agent, lubricant, thermo-stabilizer, and described softening agent is selected any in tributyl citrate, mineral oil, acetic acid tri-n-butyl, urea, methane amide, and described lubricant is Magnesium Stearate, and described thermo-stabilizer is triphenyl phosphite.
Described oxidation inhibitor is antioxidant 1010 or irgasfos 168.
A kind of method for preparing described biodegradable plastic, is characterized in that: the steps include:
(1) by after plant fiber starch, polyethylene, poly(lactic acid), synthetic resins, nano flame retardant mixture and water pre-mixing, spray in the high-speed stirring mixer that fills auxiliary agent, pulullan polysaccharide, oxidation inhibitor, ultraviolet radiation absorption agent composition and stir, obtain mixture;
(2) mixture obtained in step (1) is put into to Banbury mixer banburying 0.5-1 hour, then with two roll plastic mixing mill open the refining and compressing tablet obtain biodegradable plastic.
Described in step (1), churning time is 3-5 minute.
Described in step (2), the rotating speed of Banbury mixer is set to 60-70r/min.
Described in step (2), the temperature setting of two roll plastic mixing mill is set to 130-140 ℃.
Advantage of the present invention and positively effect are:
1, oxygen barrier provided by the invention and degradable plastic film are selected ripe in the market treated starch degradable plastics masterbatch PBM and Pullulan polysaccharide and film-grade LDPE blending extrusion blown film on the preparation method, utilize the characteristics of LDPE, guarantee the good mechanical property of film; Utilize the degradability of PBM and Pullulan, realize the environment friendly of thin-film material; Utilize the high oxygen barrier of Pullulan, improve the oxygen barrier of thin-film material; Utilize starch and Pullulan as glucide similarity structurally, improve the consistency of plastic film material integral body; By controlling the blend proportioning of LDPE/PBM/Pullulan system, can realize the regulation and control to oxygen barrier and degradability etc.
2, oxygen barrier provided by the invention and degradable plastic film meeting automatic classifying under the effect of oxygen enrichment and microorganism, film after discarded can be by the degradable digestion of occurring in nature microorganism, final carbonic acid gas and the water of generating, can improve 40% than the ldpe film oxygen barrier performance of same thickness.Preparation method's technique of the present invention is simple, production efficiency is high, industrializing implementation is easy, available common plastics inflation film manufacturing machine is produced.Fire retardant prepared by the present invention is not halogen-containing, organism, and asepsis environment-protecting, have a extensive future; The present invention carries out twice-modified, such benefit: increase the reactive behavior point, improve modified effect; In the time of modification, can steam again except the moisture in system, dry and modification is carried out simultaneously, has improved working efficiency; Have a large amount of physics and chemistry planar water in nano silicone hydroxyapatite, Attapulgite, polynite, kaolin etc. self micropore, at high temperature produce water vapor, blocking-up oxygen, absorb heat, reaches multiple fire-retardant effect; Powerful absorption property can effectively improve the synergy of several fire retardants, stops and is raise by the fire retardant matter temperature, has improved flame retarding efficiency; The aboundresources such as silicon hydroxyapatite, Attapulgite, polynite, kaolin, greatly reduce the industrial cost of fire retardant, and also the Application and Development for attapulgite provides a new way; The present invention adopts the solution method ultrasonic wave to disperse and the mechanical high-speed agitator stirs, make fire retardant separately component reached the nano level dispersion in solution, effectively avoided the natural oxidation to matrix material, thereby made matrix material there is better mechanical property.The oxygen index of matrix material is that 41 tensile strength are 5MPa, and elongation at break is 120%, and degradation cycle is 120 days.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the invention is not restricted to these embodiment:
Embodiment 1
A kind of biodegradable plastic is characterized in that: its feed composition and parts by weight are respectively:
Plant fiber starch 45-60,
Glycerine 4-6
Polyethylene 40
Poly(lactic acid) 20-40
Synthetic resins 60-80
Auxiliary agent 10-15
Pulullan polysaccharide 5-8
Oxidation inhibitor 2-4
UV light absorber 1-1.5
Nano flame retardant mixture 30-25;
The preparation method of described fire-retardant recombiner is:
(1) silicon hydroxyapatite, red phosphorus, Attapulgite, hydrotalcite, polynite, titanium dioxide, calcite, kaolin are mixed according to the mass fraction proportioning of 25-35:15-20:10-15: 10-15:8-10:8-10:7-8:5-7, join in the mixing solutions of 200 parts of methyl-sulphoxides (DMSO) and 50 parts of methyl alcohol, in 65 ℃, stir 60 hours, filter, and wash and remove excessive methyl-sulphoxide (DMSO) for 3 times with the hot ethanol of 60 ℃ of temperature, put into vacuum drying oven, dry 24 hours of 60 ℃ of temperature, grinding is sieved, and obtains the modified flame-retardant mixture one time;
(2), 1 part of modified flame-retardant mixture, 10 parts of Potassium ethanoates and 25 parts of distilled water are mixed, in temperature 50 C, stir more than 10 hours, in 30 ℃ of temperature, first under ultrasonic electric power 350W condition, disperse 2.5 hours, and then disperse 3 hours under ultrasonic electric power 250W condition.Filter, and wash 3 times with distillation, 80 ℃ of vacuum-drying 24 hours, grinding is sieved, and obtains twice-modified fire-retardant mixture;
(3), above-mentioned 1 part of twice-modified fire-retardant mixture is disperseed to 40min at the 600W power ultrasonic, be heated to 90 ℃ with constant temperature heating device, and stir (1200r/min) 60 minutes with mechanical stirrer; Obtain the nano flame retardant mixture.
Polyethylene is that Low Density Polyethylene, medium-density polyethylene, high density polyethylene(HDPE) are according to mass ratio 2:2:1 batch mixing.
Auxiliary agent comprises softening agent, lubricant, thermo-stabilizer, and described softening agent is selected any in tributyl citrate, mineral oil, acetic acid tri-n-butyl, urea, methane amide, and described lubricant is Magnesium Stearate, and described thermo-stabilizer is triphenyl phosphite.
Described oxidation inhibitor is antioxidant 1010 or irgasfos 168.
A kind of method for preparing described biodegradable plastic, is characterized in that: the steps include:
(1) by after plant fiber starch, polyethylene, poly(lactic acid), synthetic resins, nano flame retardant mixture and water pre-mixing, spray in the high-speed stirring mixer that fills auxiliary agent, pulullan polysaccharide, oxidation inhibitor, ultraviolet radiation absorption agent composition and stir, obtain mixture;
(2) mixture obtained in step (1) is put into to Banbury mixer banburying 0.5-1 hour, then with two roll plastic mixing mill open the refining and compressing tablet obtain biodegradable plastic.
Described in step (1), churning time is 3-5 minute.
Described in step (2), the rotating speed of Banbury mixer is set to 60-70r/min.
Described in step (2), the temperature setting of two roll plastic mixing mill is set to 130-140 ℃.
Above-described embodiment only, for explanation technical conceive of the present invention and characteristics, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (9)
1. the preparation method of nano flame retardant plastics that regenerates, it is characterized in that: its feed composition and parts by weight are respectively:
Plant fiber starch 45-60,
Glycerine 4-6
Polyethylene 40
Poly(lactic acid) 20-40
PE synthetic resins 60-80
Auxiliary agent 10-15
Glycerine 5-8
Oxidation inhibitor 2-4
UV light absorber 1-1.5
Polyoxyethylene glycol 2-4
Glycerol 2-4
Nano flame retardant mixture 25-30;
The preparation method of described nano flame retardant recombiner is:
(1) silicon hydroxyapatite, red phosphorus, Attapulgite, hydrotalcite, polynite, titanium dioxide, calcite, kaolin are mixed according to the mass fraction proportioning of 25-35:15-20:10-15: 10-15:8-10:8-10:7-8:5-7, join in the mixing solutions of 200 parts of methyl-sulphoxides (DMSO) and 50 parts of methyl alcohol, in 65 ℃, stir 60 hours, filter, and wash and remove excessive methyl-sulphoxide (DMSO) for 3 times with the hot ethanol of 60 ℃ of temperature, put into vacuum drying oven, dry 24 hours of 60 ℃ of temperature, grinding is sieved, and obtains the modified flame-retardant mixture one time;
(2), 1 part of modified flame-retardant mixture, 10 parts of Potassium ethanoates and 25 parts of distilled water are mixed, in temperature 50 C, stir more than 10 hours, in 30 ℃ of temperature, first under ultrasonic electric power 350W condition, disperse 2.5 hours, and then disperse 3 hours under ultrasonic electric power 250W condition.
2. filter, and wash 3 times with distillation, 80 ℃ of vacuum-drying 24 hours, grinding is sieved, and obtains twice-modified fire-retardant mixture;
(3), above-mentioned 1 part of twice-modified fire-retardant mixture is disperseed to 40min at the 600W power ultrasonic, be heated to 90 ℃ with constant temperature heating device, and stir (1200r/min) 60 minutes with mechanical stirrer; Obtain the nano flame retardant mixture.
3. biodegradable plastic according to claim 1, it is characterized in that: polyethylene is that Low Density Polyethylene, medium-density polyethylene, high density polyethylene(HDPE) are according to mass ratio 2:2:1 batch mixing.
4. biodegradable plastic according to claim 1, it is characterized in that: auxiliary agent comprises softening agent, lubricant, thermo-stabilizer, described softening agent is selected any in tributyl citrate, mineral oil, acetic acid tri-n-butyl, urea, methane amide, described lubricant is Magnesium Stearate, and described thermo-stabilizer is triphenyl phosphite.
5. biodegradable plastic according to claim 1, it is characterized in that: described oxidation inhibitor is antioxidant 1010 or irgasfos 168.
6. a method for preparing biodegradable plastic as claimed in claim 1, is characterized in that: the steps include:
(1) by after plant fiber starch, polyethylene, poly(lactic acid), synthetic resins, nano flame retardant mixture and water pre-mixing, spray in the high-speed stirring mixer that fills auxiliary agent, pulullan polysaccharide, oxidation inhibitor, ultraviolet radiation absorption agent composition and stir, obtain mixture;
(2) mixture obtained in step (1) is put into to Banbury mixer banburying 0.5-1 hour, then with two roll plastic mixing mill open the refining and compressing tablet obtain biodegradable plastic.
7. the production method of biodegradable plastic according to claim 5, is characterized in that, described in step (1), churning time is 3-5 minute.
8. the production method of biodegradable plastic according to claim 5, is characterized in that, described in step (2), the rotating speed of Banbury mixer is set to 60-70r/min.
9. the production method of biodegradable plastic according to claim 5, is characterized in that, described in step (2), the temperature setting of two roll plastic mixing mill is set to 130-140 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104877181A (en) * | 2015-06-09 | 2015-09-02 | 苏州市湘园特种精细化工有限公司 | Biological nano-plastics |
| CN106945195A (en) * | 2017-02-24 | 2017-07-14 | 蚌埠市振华包装机械有限责任公司 | A kind of recoverying and utilizing method of packing plastics filler |
| CN109181047A (en) * | 2018-06-21 | 2019-01-11 | 四川塑金科技有限公司 | A kind of preparation method regenerating nanometer flame retardant plastic |
| WO2024047688A1 (en) * | 2022-08-29 | 2024-03-07 | 孝 大野 | Polymer composite material and method for producing same |
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| US4552918A (en) * | 1983-06-18 | 1985-11-12 | Cpc International Inc. | Flame resistant starch-sulfamate products |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104877181A (en) * | 2015-06-09 | 2015-09-02 | 苏州市湘园特种精细化工有限公司 | Biological nano-plastics |
| CN106945195A (en) * | 2017-02-24 | 2017-07-14 | 蚌埠市振华包装机械有限责任公司 | A kind of recoverying and utilizing method of packing plastics filler |
| CN109181047A (en) * | 2018-06-21 | 2019-01-11 | 四川塑金科技有限公司 | A kind of preparation method regenerating nanometer flame retardant plastic |
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| JP7562199B2 (en) | 2022-08-29 | 2024-10-07 | 孝 大野 | Polymer composite material and its manufacturing method |
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Address after: 215138 No. 1 Zhangtangbangxiang, Yangchenghu Town, Xiangcheng District, Suzhou City, Jiangsu Province Patentee after: Suzhou Xiangyuan New Materials Co., Ltd. Address before: 215100 Jiangsu, Xiangcheng District Yang Cheng lake town (Hunan City) figure ten Village Patentee before: Suzhou Xiangyuan Speical Fine Chemical Co., Ltd. |