CN101665588B - Biodegradable flame resistance material and preparation method thereof - Google Patents
Biodegradable flame resistance material and preparation method thereof Download PDFInfo
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- CN101665588B CN101665588B CN2009101174851A CN200910117485A CN101665588B CN 101665588 B CN101665588 B CN 101665588B CN 2009101174851 A CN2009101174851 A CN 2009101174851A CN 200910117485 A CN200910117485 A CN 200910117485A CN 101665588 B CN101665588 B CN 101665588B
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Abstract
The invention provides a biodegradable flame resistance material. The flame resistance material is characterized in that starch and chitosan are used as main components, red phosphorus is used as flame resistance additive, starch/chitosan can provides a great deal of carbon, chitosan contains nitrogen element, when acid source is added in red phosphorus, the flame resistance of the biodegradable material is effectively improved and the usable range of the biodegradable composite material is expanded so that the biodegradable composite material has wider application area; the preparation method adopts solution method, ultrasonic dispersion and mechanical high-speed agitation so that red phosphorus used as fire retardant can be dispersed in solution on nano-scale and the autoxidation of the composite material can be effectively avoided, thus the composite material can have better mechanical performance.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of biodegradable fire retardant material, being specifically related to a kind of is the biodegradable fire retardant material of fire retardant preparation with red phosphorus.
Background technology
Plastics have become a kind of indispensable material in industrial production and the people's lives.Meanwhile, along with the extensive application of petrochemical complex plastics, the waste plastic goods also grow with each passing day.Because the current most stable performance of general-purpose plastics is difficult for degrading rapidly for the effect of various environmental factorss at occurring in nature, has therefore occurred so-called " white pollution ".The method that is used for handling " white garbage " at present is a lot, such as burnings, landfill etc., but during the waste plastic burning, will cause serious secondary pollution to environment.Therefore green, environmental friendliness degradation material is that we press for.
Degradable plastics, particularly biodegradable plastic are focuses of studying now.Biodegradable plastic is mainly used in the fields such as military material at industrial packaging material, disposable product, laminating material, sanitary product and some tips.Though biodegradable plastic has environment friendly, the same with conventional plastic, the inflammableness of biodegradable plastic will limit it to a great extent and use safely and effectively.Therefore, Biodegradable material is carried out fire-retardant finish, can make it be widely used in industrial packaging material, sports goods such as golf course and fields such as ball seat, nursery stock immobilization material and explosion wrapping material.
The used fire retardant of plastics nearly 80% is a halogen containing flame-retardant at home, and the Halogen flame-retardant system all can increase the growing amount (as halogen-sb system) of toxic gas and cigarette usually.Consider from the angle of eco-friendly angle and HUMAN HEALTH, reduce use or do not use halogen containing flame-retardant will become the development trend of flame retardant plastics industry.Therefore, green fire-retardant product also will be the flame retardant products of tool advantage on the market.
Starch is that a kind of source is abundant, low-cost natural high molecular substance, is a kind of inexhaustible renewable resources, can be by biological degradation under multiple environment, and eventual degradation product C O
2And H
2O can carry out recirculation by photosynthesis, can not produce any pollution to environment.Chitosan also is a kind of inexhaustible renewable resources, extensively is present in cell walls of the shell of microorganism, lower plant mushroom, alga cells, yeast, arthropods shrimp, crab and insect and cartilage, molluscan inner casing and cartilage, higher plant etc.Can degrade fully because of its biology, be the recent research focus of preparation degradation material.
Summary of the invention
The purpose of this invention is to provide a kind of is the biodegradable flame-proof composite material of fire retardant with red phosphorus.
Biodegradable fire retardant material of the present invention is that the raw material by following mass percent is composited:
Wherein starch can adopt yam starch, W-Gum, wheat starch, tapioca (flour), pea starch, sorghum starch etc.; Chitosan employing deacetylation is the chitosan product more than 80%.
Degradable anti-flaming preparation methods of the present invention is chitosan to be dissolved in to be configured to concentration in the acetate of 1～2% (w/v) be 1～2% chitosan solution; Add 1～5 times starch of chitosan mass, stir; The red phosphorus that adds chitosan starch total amount 6%～10% again, the water that adds 20～40 times of the softening agent of chitosan starch total amount 30%～50% and chitosan starch total amounts simultaneously, mix, place the ultra-sonic dispersion instrument, ultrasonic dispersing 20～30min under the power of 600W; Be heated to 80～90 ℃ constant temperature, machinery is mixed 40～50min; Be poured into then in the mould, put into thermostatic drying chamber, film forming behind 50～60 ℃ of down dry 24～48h is taken off film, room temperature preservation 24～48h under the humidity of relative humidity 40～50%; Vulcanize in 100～130 ℃ with thermocompressor and chilling press, film-making is at last with the injection moulding on injection moulding machine of conventional Shooting Technique.
The fire retardant mechanism of red phosphorus among the present invention: this material is under 400 ℃～450 ℃, the red phosphorus depolymerization forms white phosphorus, the latter is oxidized to the phosphorus oxyacid of viscosity in the presence of aqueous vapor, then phosphoric acid again further dehydration generate metaphosphoric acid and poly-metaphosphoric acid, thereby form the non-flame properties liquid protective film of one deck at polymer surfaces; Simultaneously, the strong dehydration of metaphosphoric acid and poly-metaphosphoric acid, impel the surface of polymer material dehydration carbonization, form the charring layer of one deck densification, liquid membrane and charring layer be heat insulation resistance oxygen on the one hand, also stop the diffusion of the inflammable gas of polymkeric substance pyrolytic decomposition generation simultaneously effectively, thereby suppressed the burning of material, reached fire-retardant purpose.
The mechanical property of Biodegradable flame resistance material of the present invention, flame retardant properties and degradation property analysis:
1, the Different Red phosphorus content is seen Fig. 1 to the influence of composite materials property.As can be seen from Figure 1, in not adding the starch of red phosphorus/chitosan pure sample, its tensile strength is 11.7MPa, and elongation at break is 122%; When adding 7% red phosphorus in starch/chitosan, the tensile strength of matrix material is 6.2MPa, and elongation at break is 132%, and the tensile strength of matrix material descends, but elongation at break has but increased by 10%.The adding of red phosphorus is described, makes the toughness of matrix material that good raising be arranged.
2, different red phosphorus content is seen Fig. 2 to the influence of the oxygen index of matrix material.As can be seen from Figure 2, in not adding the starch of red phosphorus/chitosan pure sample, the oxygen index of matrix material is below 18.0, adding along with red phosphorus, the oxygen index of matrix material significantly improves, when the add-on of red phosphorus 7～10% the time, the oxygen index of matrix material remains on more than 35.5, illustrates that the adding of red phosphorus improves the flame retardant properties of matrix material.
3, the test of degradation property.From the degradable composite material of above-mentioned preparation, get 5 samples, test its degradation property with the soil method of burying according to standard GB/T20197-2006:
| Degradation time (my god) | 10 | 20 | 30 | 40 | 50 | 60 | 80 | 100～150 |
| Degradation rate (%) | 12 | 26 | 35 | 48 | 59 | 72 | 85 | 100 |
Data from last table as can be known, nanometer degradable plastics of the present invention within 6 months substantially fully the degraded, show that this matrix material is the environment friendly composite material that can degrade fully.
The present invention compared with prior art has the following advantages:
1, the present invention is a main component with starch and chitosan, is flame retardant with red phosphorus, and starch/chitosan provides a large amount of carbon sources, and self contains nitrogen in the chitosan, adds acid source red phosphorus, has effectively improved the flame retardant properties of Biodegradable material.
2, the present invention adopts solution method, ultrasonic dispersing and mechanical high-speed agitator to stir, and makes fire retardant red phosphorus reach the nano level dispersion in solution, has effectively avoided the natural oxidation to matrix material, thereby has made matrix material have better mechanical property.
3, the present invention makes biodegradable plastic have flame retardant resistance, has expanded the degradable composite material use range, makes it that more wide application prospect be arranged.
Description of drawings
Fig. 1 is the influence of red phosphorus content to the mechanical property of matrix material;
Fig. 2 is the influence of red phosphorus content to the oxygen index of matrix material.
Embodiment
Embodiment 1, in three mouthfuls of round-bottomed flasks, chitosan is dissolved in the chitosan solution of configuration 2% in 2% acetate (w/v), add the starch of chitosan mass 1.5, stir; The red phosphorus that adds starch/chitosan total amount 6%, the deionized water that adds 25 times of 35% glycerine of the total matter of starch/chitosan and chitosan starch total amounts simultaneously, mix, disperse 20min with the 600W power ultrasonic, be heated to 90 ℃ with constant temperature heating device, and stirred (1200r/min) 50 minutes with mechanical stirrer.Water in cut-and-dried mould, put into thermostatic drying chamber, film forming behind dry 24h under 50 ℃ is taken off film, and room temperature preservation is 24 hours in the humidity cabinet of relative humidity 50%.Vulcanize in about 120 ℃ with thermocompressor and chilling press, film-making with the injection moulding on injection moulding machine of conventional Shooting Technique, obtains the degradable composite flame-proof material then.
The oxygen index of matrix material is 36.0, and tensile strength is 4.7MPa, and elongation at break is 110%, and degradation cycle is 98 days.
Embodiment 2, in three mouthfuls of round-bottomed flasks, chitosan be dissolved in 1.5% acetate (w/v) be configured to 2% chitosan solution, add the starch of 2.0 times of chitosan masses, stir; The red phosphorus that adds starch/chitosan total amount 7%, the deionized water that adds 30 times of 40% softening agent glycerine of starch/chitosan total amount and chitosans/starch total amount simultaneously, mix, disperse 20min with the 600W power ultrasonic, be heated to 90 ℃ with constant temperature heating device, and stirred (1200r/min) 50 minutes with mechanical stirrer.Watering in cut-and-dried mould, put into thermostatic drying chamber, 50 ℃ of following film forming behind the dry 24h, take off film, is room temperature preservation 24 hours in 50% the humidity cabinet in relative humidity (RH).Vulcanize in about 120 ℃ with thermocompressor and chilling press, film-making with the injection moulding on injection moulding machine of conventional Shooting Technique, obtains the degradable composite flame-proof material then.
The oxygen index of matrix material is 38.5, and tensile strength is 5.9MPa, and elongation at break is 125%, and degradation cycle is 105 days.
Embodiment 3, in three mouthfuls of round-bottomed flasks, chitosan be dissolved in 1.5% acetate (w/v) be configured to 2% chitosan solution, add the starch of 4.0 times of chitosan masses, stir; The red phosphorus that adds starch/chitosan total amount 8% adds the deionized water of 40 times of the glycerine of chitosan starch total amount 50% and chitosan starch total amounts simultaneously, mixes; Disperse 20min with the 600W power ultrasonic, be heated to 90 ℃, and stirred (1200r/min) 50 minutes with mechanical stirrer with constant temperature heating device.Watering in cut-and-dried mould, put into thermostatic drying chamber, 50 ℃ of following film forming behind the dry 24h, take off film, is room temperature preservation in 50% the humidity cabinet in relative humidity (RH).Vulcanize in about 120 ℃ with thermocompressor and chilling press, film-making with the injection moulding on injection moulding machine of conventional Shooting Technique, obtains the degradable composite flame-proof material then.
The oxygen index of matrix material is 39.6, and tensile strength is 5.7MPa, and elongation at break is 130%, and degradation cycle is 110 days.
Embodiment 4, in three mouthfuls of round-bottomed flasks, chitosan is dissolved in the chitosan solution of configuration 2% in 2% acetate (w/v), add the starch of 3.5 times of chitosan masses, stir; The red phosphorus that adds starch/chitosan total amount 10% adds the deionized water of 35 times of the glycerine of chitosan starch total amount 45% and chitosan starch total amounts simultaneously, mixes; Disperse 20min with the 600W power ultrasonic, be heated to 90 ℃, and stirred (1200r/min) 50 minutes with mechanical stirrer with constant temperature heating device.Watering in cut-and-dried mould, put into thermostatic drying chamber, 50 ℃ of following film forming behind the dry 24h, take off film, is room temperature preservation in 50% the humidity cabinet in relative humidity (RH).Vulcanize in about 120 ℃ with thermocompressor and chilling press, film-making with the injection moulding on injection moulding machine of conventional Shooting Technique, obtains the degradable composite flame-proof material then.
The oxygen index of matrix material is 40.2, and tensile strength is 4.9MPa, and elongation at break is 122%, and degradation cycle is 130 days.
Claims (1)
1. the preparation method of a biodegradable fire retardant material is in three mouthfuls of round-bottomed flasks, and it is to be configured to 2% chitosan solution in 1.5% acetate that chitosan is dissolved in mass volume ratio, adds the starch of 2.0 times of chitosan masses, stirs; The red phosphorus that adds starch/chitosan total amount 7%, the deionized water that adds 30 times of the softening agent glycerine of starch/chitosan total amount 40% and chitosans/starch total amount simultaneously, mix, disperse 20min with the 600W power ultrasonic, be heated to 90 ℃ with constant temperature heating device, and stirred 50 minutes with the rotating speed of mechanical stirrer with 1200r/min; Watering in cut-and-dried mould, put into thermostatic drying chamber, 50 ℃ of following film forming behind the dry 24h, take off film, is room temperature preservation 24 hours in 50% the humidity cabinet in relative humidity; In 120 ℃ of sulfurations, film-making with the injection moulding on injection moulding machine of conventional Shooting Technique, obtains the degradable composite flame-proof material then with thermocompressor and chilling press.
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| CN2009101174851A CN101665588B (en) | 2009-09-25 | 2009-09-25 | Biodegradable flame resistance material and preparation method thereof |
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| CN2009101174851A CN101665588B (en) | 2009-09-25 | 2009-09-25 | Biodegradable flame resistance material and preparation method thereof |
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| CN101665588B true CN101665588B (en) | 2011-11-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102558617B (en) * | 2011-12-23 | 2014-11-05 | 中国科学技术大学 | Intumescent flame retardant and preparation method thereof |
| CN102794806B (en) * | 2012-08-23 | 2015-03-11 | 德华兔宝宝装饰新材股份有限公司 | Manufacturing method for anti-flaming wooden louver blade |
| CN103351483B (en) * | 2013-07-24 | 2016-05-11 | 济南大学 | Microspheric high hydrophobicity starch and preparation method thereof and application |
| CN103483623B (en) * | 2013-09-22 | 2015-09-09 | 苏州市湘园特种精细化工有限公司 | A kind of biodegradable plastic and production method thereof |
| CN103627037B (en) * | 2013-11-07 | 2016-03-02 | 青岛文创科技有限公司 | A kind of sea grass polyphenol-inulin based coextruded film and preparation method thereof |
| CN103627036B (en) * | 2013-11-07 | 2016-06-01 | 青岛文创科技有限公司 | A kind of sea grass polyphenol-inulin base degradable laminated film and its preparation method |
| WO2023129062A2 (en) * | 2021-12-29 | 2023-07-06 | A.Ü.Strateji̇ Geli̇şti̇rme Dai̇resi̇ Başkanliği | Flame retardant antimicrobial additive material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066077A (en) * | 1991-03-19 | 1992-11-11 | 帕克戴维斯公司 | Biodegradable amyloid composition |
| CN1587306A (en) * | 2004-07-30 | 2005-03-02 | 胡靖� | Foam and curtain coating forming method for environmental protection anti-fake safety biological degradation plastics |
| CN101195694A (en) * | 2007-12-22 | 2008-06-11 | 西北师范大学 | Degradable composite plastics and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066077A (en) * | 1991-03-19 | 1992-11-11 | 帕克戴维斯公司 | Biodegradable amyloid composition |
| CN1587306A (en) * | 2004-07-30 | 2005-03-02 | 胡靖� | Foam and curtain coating forming method for environmental protection anti-fake safety biological degradation plastics |
| CN101195694A (en) * | 2007-12-22 | 2008-06-11 | 西北师范大学 | Degradable composite plastics and method for producing the same |
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Effective date of registration: 20180428 Address after: 315400 37 weir head, two high village, Yangming street, Yuyao, Ningbo, Zhejiang Patentee after: Yuyao Huan Hua Electric Appliance Co., Ltd. Address before: 730070 No. 967 Ning Ning Road, Anning District, Lanzhou, Gansu Patentee before: Northwest Normal University |
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