CN101302309A - Microcapsule expansion flame-proof starch-based degradable material and preparation thereof - Google Patents
Microcapsule expansion flame-proof starch-based degradable material and preparation thereof Download PDFInfo
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- CN101302309A CN101302309A CNA2008101231239A CN200810123123A CN101302309A CN 101302309 A CN101302309 A CN 101302309A CN A2008101231239 A CNA2008101231239 A CN A2008101231239A CN 200810123123 A CN200810123123 A CN 200810123123A CN 101302309 A CN101302309 A CN 101302309A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a microcapsule intumescent flame-retarding starch-based degradable material and a method for preparing the same. The method is characterized in that: starch is mixed with plasticizer and compatibilizer, heated to between 70 and 100 DEG C, added with biodegradable high molecular compound, microcapsule intumescent flame retardant and flame-retarding catalyst, and the intumescent flame-retarding starch-based degradable material which is formed by the starch, the plasticizer, the compatibilizer, the biodegradable high molecular compound, the microcapsule intumescent flame retardant and the flame-retarding catalyst is obtained by extruding obtained powder lot for granulation. The method utilizes the flame-retarding synergistic effect of C, N and P, introduces the microcapsule intumescent flame retardant to inhibit untoward reaction of the flame retardant and the starch, and improves the flammability of the material; and the product obtained has excellent flexibility and mechanical property, good water resistance and oil resistance and good flame retardant property, is nontoxic and harmless, can be completely biodegraded, and can be used in the fields such as packages, laminated materials, sport and sanitary articles and so on.
Description
Technical field
The invention belongs to the expansion type flame retardant technical field, be specifically related to a kind of synthetic method of microcapsule intumescent flame retardant and utilize this fire retardant to prepare the method for expansion flame-proof starch-based degradable material.
Background technology
The birth of plastics brought very big convenience for human life, yet along with the development of plastics industry, some hidden danger that itself exist also come out gradually.Common plastics has fabulous chemical stability, and this makes plastics be difficult to degraded at occurring in nature, and plastic garbage is more and more; Not only influence environmental beauty, and polluted water source and soil, jeopardize fowl poultry and wildlife, brought heavy burden to ball ecological environment.
Therefore, degradative plastics---particularly the research and development of biodegradable plastic have become one of research focus of attracting attention, and wherein starch-based degradable plastics is a class biodegradable plastic of developing at most now." plastics " (2005, mention in " preparation of starch-based bio degradable plastics and sign " literary composition 34:51-55), because the decomposition temperature of starch is lower than melt temperature, can not on processing units, directly be processed into goods.Therefore, starch must be carried out modification, make it have thermoplasticity.Starch under the effect of high temperature, shear-stress and fluidizer, is formed amorphous state behind glass transition and melting transition, degree of crystallinity reduces greatly, and Intermolecular Forces reduces, thus the thermoplasticity of showing and flowability.Starch-based degradable material can be water and carbonic acid gas by the last katabolism of microbial process under physical environment, and raw materials used is inexhaustible renewable resources, so starch-based degradable plastics demonstrates huge development prospect in its Application Areas.At present, thermoplastic starch is obtaining positive exploitation, is mainly used in fields such as packing, laminating material and sports hygiene articles for use.The development of this " green material " with good environment consistency with use the inexorable trend that has become 21 century.
" polymer degradation is with stable " magazine (PolymerDegradation and Stablity of Holland's Ai Ersi scientific company (Elsevier science), 2005,88:138-145) mention in " fire-retardant biodegradable polymer and mixture thereof " literary composition, though than conventional plastic, starch-based degradable plastics has good environment friendly; But the same with conventional plastic, the inflammableness of starch-based degradable plastics will limit it greatly and use safely and effectively.
Consider from the angle of environment protection and health of human body, substituted by the flame-retardant system of " green " just gradually based on traditional flame-retardant system of halogen.In these " green " fire retardants, the expandable flame retardant system has been catered to the requirement of preserving the ecological environment now because of characteristics such as the fire-retardant mechanism of its uniqueness and Halogen, low cigarette, low toxicities, has also caused numerous investigators' concern." plastics industry " (2006,34:69-72) point out in " Progress in Research of Halogen-free Flame Retardant " literary composition, expansion type flame retardant (Intumescent Flame Retardant, be called for short IFR) is to be a based flame retardant of core composition with carbon (C), nitrogen (N) and phosphorus (P).IFR mainly is made up of three parts: acid source is generally mineral acid or can generates sour compound in position when heating, as ammonium polyphosphate (APP), melamine phosphate (MP) etc.; The charcoal source is generally the polyol that contains carbon rich, as starch, tetramethylolmethane (PER) and derivative thereof etc.; Source of the gas generally mostly is nitrogenous compound, as urea, trimeric cyanamide (MEL) etc.Expansion type flame retardant mainly is to play fire retardation by forming porous foam charcoal layer at condensed phase, the effect that this charcoal layer is on good terms and is played heat insulation, oxygen barrier, presses down cigarette and anti-molten drop in cohesion.Though IFR has unique fire retardant mechanism and characteristic, overcome the shortcoming that many conventional flame retardant exist.But, as " polyurethane industrial " (2002,17:17-19) pointed in " flame retardant microcapsule Study on Technology " literary composition: that IFR exists in actual applications is poor with the polymer phase capacitive, poor water resistance and the problem of easily reuniting, and in the course of processing, acid source in the system and charcoal source are easy to reaction and produce micromolecular compound; These defectives are brought disadvantageous effect to the physical and mechanical properties of matrix material, have limited the use range of matrix material.In order to overcome the above-mentioned shortcoming of fire retardant, in recent years, developed the micro-capsule package technology of fire retardant in the world, promptly with natural or synthesized polymer material solid or liquid composition being rolled into diameter is micron-sized capsule, thereby improve the water tolerance and the consistency of fire retardant, suppress the untoward reaction that fire retardant takes place in the course of processing.
Though a lot of document and patents about starch-based degradable material and preparation method thereof are arranged at present both at home and abroad, rarely have patent or document about improving its flame retardant properties, safety in utilization.
Summary of the invention
The objective of the invention is to propose a kind of microcapsule expansion flame-proof starch-based degradable material and preparation method thereof,, improve its safety in utilization to improve the starch-based degradable material inflammableness.
Microcapsule expansion type flame-proof starch-based degradable material of the present invention is characterized in that being made up of following composition and weight proportion thereof:
Starch 60.0-80.0%;
Softening agent 1.0-1.5%;
Expanding material 1.0-1.5%;
Biodegradable macromolecular compound 15.0-35.0%;
Microcapsule intumescent flame retardant 1.5-10.0%;
Fire-retardant catalyzer 0.05%-3.0%.
The preparation method of microcapsule expansion flame-proof starch-based degradable material of the present invention is characterized in that: by mass ratio the starch of 60.0-80.0% and the softening agent of 1.0-1.5% and the expanding material of 1.0-1.5% are mixed; Be heated to 70-100 ℃, add biodegradable macromolecular compound of 15.0-35.0% and 0.5-10.0% microcapsule intumescent flame retardant and the fire-retardant catalyzer of 0.05%-3.0% again; Cooling discharge; The powder that obtains at 160-220 ℃ of extruding pelletization, is promptly obtained microcapsule expansion flame-proof starch-based degradable material.
Described starch is selected from tapioca (flour), sweet potato starch, early rice starch, yam starch, W-Gum, konjak starch and/or wheat-flour;
Described softening agent is selected from aliphatic carboxylic acid, aliphatic amide and/or aliphatics metal-salt; Described aliphatic carboxylic acid comprises linolenic acid, stearic acid, lauric acid, oleic acid, oxysuccinic acid and/or succsinic acid; Described aliphatic amide comprises hexanolactam, oleylamide, inferior oleylamide and/or stearylamide; Described aliphatics metal-salt comprises Magnesium Stearate, calcium stearate, manganese stearate and/or Zinic stearas;
Described expanding material is selected from maleic anhydride, diacetyl oxide and/or Succinic anhydried;
Described degradable biological macromolecular compound is selected from poly(lactic acid), polylactide, poly-second propyl ester, polyvinyl alcohol and/or aliphatic polyester-polyamide copolymer;
Described fire-retardant catalyzer is selected from chromium sesquioxide, titanium dioxide, Manganse Dioxide, lanthanum oxide, zirconium dioxide, nickelous phosphate, zirconium phosphate, molybdenum oxide, antimonous oxide, zinc borate, boric acid, magnesium hydroxide, aluminium hydroxide, hydrotalcite, layered double-hydroxide and/or polynite.
Microcapsule intumescent flame retardant in microcapsule expansion flame-proof starch-based degradable material of the present invention and preparation method thereof, one of can be in the following ways synthetic:
1. with trimeric cyanamide and formaldehyde in molar ratio 1: 2.2-3.3 adds in the reaction vessel, is 10% Na with mass percent concentration
2CO
3The pH that solution is adjusted system is 9-10, is heated to 60-100 ℃ then, to solution becomes clear after, be incubated 20-60 minute, make the carbamide prepolymer; Mass ratio by phosphoric acid salt or poly-phosphate and prepolymer resin is 1: 0.1-0.3 blend, stirring, the stiffening agent that when the temperature of reaction system is 60-100 ℃, adds prepolymer resin quality 1-5%, reflux, 100-200 minute postcooling of reaction, discharging, after filtration, promptly get the expansion type flame retardant that microcapsule wrap up after the drying; Described stiffening agent is ammonium hydrogen phosphate, ammonium chloride, primary ammonium phosphate, potassium primary phosphate and/or SODIUM PHOSPHATE, MONOBASIC.
Or, the mol ratio 1 of 2. pressing epoxide group and quadrol: 0.2-1: 0.3, bisphenol A type epoxy resin and quadrol are added in the reaction vessel, be heated to 60-90 ℃ then, be incubated 20-40 minute, make epoxy prepolymer; Mass ratio by phosphoric acid salt or poly-phosphate and prepolymer resin is 1: 0.1-0.3 blend, stirring, when the temperature of reaction system is 60-90 ℃, reflux, 200-400 minute postcooling of reaction, discharging, after filtration, promptly get the expansion type flame retardant that microcapsule wrap up after the drying.
Microcapsule intumescent flame retardant by the aforesaid way preparation of the present invention, be characterised in that it is is capsule-core with ammonium polyphosphate (APP) or melamine phosphate (MP), thermosetting resin melamine formaldehyde resin or Resins, epoxy are the microcapsule intumescent flame retardant of capsule material.
Starch-based degradable material is to be main component with starch; Obviously, fire-retardant at starch-based degradable material, expandable flame retardant will be efficient, convenient, an eco-friendly approach.According to the fire-retardant synergistic principle of carbon (C), nitrogen (N) and phosphorus (P), as the charcoal source,, can reach effective flammable purpose of starch-based degradable material of improving by in the course of processing, adding acid source, source of the gas with the starch in the material.But if add traditional acid source, source of the gas, under the high temperature in the course of processing, the effect of high shear force, acid source, source of the gas can be easy to same starch reaction, impel starch charing degraded, can't obtain having the starch-based degradable material of higher comprehensive performance.Therefore; need carry out the modification of microcapsule parcel to traditional expansion type flame retardant; the protection fire retardant with stop its in the course of processing with the untoward reaction of starch; and in combustion processes; microcapsule then can break and discharge acid source or source of the gas; thereby form porous foam charcoal layer and play fire retardation, improve the security that starch-based degradable material uses.
Maximum characteristics of the present invention are the expandable flame retardant synergistic principles according to C, N and P, self chemical constitution at starch-based degradable material, with wherein starch as the charcoal source, in the process of preparation starch-based degradable material, introduce microcapsule intumescent flame retardant (containing acid source and source of the gas), the untoward reaction that stops fire retardant and starch to take place in the course of processing, preparation have starch-based degradable material better fire-retardant and mechanical property.
The microcapsule expansion flame-proof starch-based degradable material of the present invention that adopts the inventive method to prepare, has excellent mechanical property, having water-fast preferably and oil-proofness, is nontoxic, the microcapsule expansion flame-proof starch-based degradable material of energy complete biodegradable; Have preferable flame retardant properties, can be by the V0 level in the UL-94 test.This kind expansion flame-proof starch-based degradable material contains abundant P, N and C, and its goods can be used as fertilizer or soilless culture substrate and use with reclaiming later, have realized benign cycle fully, are truly " green ecological materials ".
Embodiment
Further specify the present invention with embodiment below.
Embodiment 1:
With 40 gram trimeric cyanamides, 80 gram weight percentage concentrations are that 37% formaldehyde solution joins in 1000 milliliters of there-necked flasks, add 200 ml deionized water, with weight percent concentration is that the PH that 20% sodium hydroxide solution is adjusted solution is 9.0, be heated to 80 ℃, be incubated 40 minutes, make the carbamide prepolymer.Add 240 gram ammonium polyphosphates (APP) and 300 milliliters of ethanol then, drop into the ammonium hydrogen phosphate of prepolymer resin weight 2%, stir, react after 120 minutes, through suction filtration, washing, oven dry obtains white microcapsule intumescent flame retardant 270 grams.
Take by weighing 4.8 kilograms of W-Gums, 0.05 kilogram of stearic acid, 0.05 kilogram of Magnesium Stearate, 0.1 kilogram of maleic anhydride, add preheating successively and be in 70 ℃ the high-speed mixer, start is stirred, and is warming up to 100 ℃ after 5 minutes, add 1.5 kilograms of polyvinyl alcohol, 0.2 kilogram of microcapsule intumescent flame retardant, fire-retardant catalyzer lanthanum oxide 1g, zirconium dioxide 1.5g, zinc borate 1.5g stirs discharging after 15 minutes.
Above-mentioned powder is joined twin screw extruder, 180-185 ℃ of unit temperature, 165 ℃ of die head temperatures, screw speed 300rpm, extruding pelletization obtains expandable flame retardant thermoplastic starch based degradable material.
This its oxygen index of expandable flame retardant thermoplastic starch based degradable material can reach the V0 level in the UL-94 test up to 31.0.The tensile strength of this material can reach 8.0MPa, and elongation at break is 90%.Illustrate that it has good flame retardant property and mechanical property.
Embodiment 2:
With 25 gram trimeric cyanamides, 50 gram weight percentage concentrations are that 37% formaldehyde solution joins in 1000 milliliters of there-necked flasks, add 125 ml deionized water, with weight percent concentration is that the PH that 20% sodium hydroxide solution is adjusted solution is 9.0, be heated to 70 ℃, be incubated 40 minutes, make the carbamide prepolymer.Add 250 gram melamine phosphates (MP) and 500 milliliters of ethanol then, drop into the ammonium chloride of prepolymer resin weight 2%, stir, reaction 180 minutes, after suction filtration, washing, oven dry obtains white microcapsule intumescent flame retardant 276.0 grams.
Take by weighing 4.8 kilograms of W-Gums, 0.05 kilogram of stearic acid, 0.05 kilogram of Magnesium Stearate, 0.1 kilogram of maleic anhydride, add preheating successively and be in 70 ℃ the high-speed mixer, start is stirred, and is warming up to 100 ℃ after 5 minutes, adds 2 kilograms of polyvinyl alcohol and 0.4 kilogram of microcapsule intumescent flame retardant, fire-retardant catalyzer nickelous phosphate 30g, molybdenum sesquioxide 20g, polynite 35g stirs discharging after 15 minutes.
Above-mentioned powder is joined twin screw extruder, 180-185 ℃ of unit temperature, 165 ℃ of die head temperatures, screw speed 300rpm, extruding pelletization obtains expandable flame retardant thermoplastic starch based degradable material.
This expandable flame retardant thermoplastic starch based degradable material, its oxygen index can reach the V0 level in the UL-94 test up to 29.5.The tensile strength of this material can reach 7.5MPa, and elongation at break is 70%.
Embodiment 3:
With 50 gram trimeric cyanamides, 70 gram weight percentage concentrations are that 37% formaldehyde solution joins in 1000 milliliters of there-necked flasks, add 250 ml deionized water, with weight percent concentration is that the PH that 20% sodium hydroxide solution is adjusted solution is 9.0, be heated to 75 ℃, be incubated 20 minutes, make the carbamide prepolymer.Add 300 gram ammonium polyphosphates (APP) and 400 milliliters of ethanol then, drop into the ammonium hydrogen phosphate of prepolymer resin weight 2%, stir, reaction 120 minutes, after suction filtration, washing, oven dry obtains white microcapsule intumescent flame retardant 345.0 grams.
Take by weighing 4.6 kilograms of sweet potato starch, 0.042 kilogram of oleic acid, 0.058 kilogram of Magnesium Stearate and stearic acid mixture add preheating successively and are in 70 ℃ the high-speed mixer, and start is stirred, be warming up to 100 ℃ after 15 minutes, add 1.8 kilograms of polyvinyl alcohol and 0.3 kilogram of microcapsule intumescent flame retardant, fire-retardant catalyst oxidation zirconium 10g, Manganse Dioxide 10g, boric acid 15g stirs discharging after 10 minutes.
Above-mentioned powder is joined twin screw extruder, 180-185 ℃ of unit temperature, 165 ℃ of die head temperatures, screw speed 300rpm, extruding pelletization obtains expandable flame retardant thermoplastic starch based degradable material.
This expandable flame retardant thermoplastic starch based degradable material have good flame retardant property and a mechanical property.Its oxygen index can reach the V0 level in the UL-94 test up to 31.5.The tensile strength of this material can reach 8.2MPa, and elongation at break is 75%.
Embodiment 4:
With 5 gram Resins, epoxy (E44, oxirane value 0.44), 33.1 gram quadrols join in 1000 milliliters of there-necked flasks, add 200 milliliters of ethanol, are heated to 75 ℃, are incubated 25 minutes, make epoxy prepolymer.Add 250 gram ammonium polyphosphates (APP) then, stir, reaction 240 minutes, after suction filtration, ethanol are washed, washed, oven dry obtains little yellow microcapsule intumescent flame retardant 280 grams.
Take by weighing 4.8 kilograms of W-Gums, 0.05 kilogram of stearic acid, 0.05 kilogram of Magnesium Stearate, 0.1 kilogram of maleic anhydride, add preheating successively and be in 70 ℃ the high-speed mixer, start is stirred, and is warming up to 100 ℃ after 5 minutes, add 1.5 kilograms of polyvinyl alcohol, 0.2 kilogram of microcapsule intumescent flame retardant, fire-retardant catalyzer titanium dioxide 1g, hydrotalcite 1.5g, zinc borate 1.5g stirs discharging after 15 minutes.
Above-mentioned powder is joined twin screw extruder, 180-185 ℃ of unit temperature, 165 ℃ of die head temperatures, screw speed 300rpm, extruding pelletization obtains expandable flame retardant thermoplastic starch based degradable material.
This its oxygen index of expandable flame retardant thermoplastic starch based degradable material can reach the V0 level in the UL-94 test up to 29.5.The tensile strength of this material can reach 8.0MPa, and elongation at break is 90%.
Claims (10)
1, a kind of microcapsule expansion type flame-proof starch-based degradable material is characterized in that being made up of following composition and weight proportion thereof:
Starch 60.0-80.0%;
Softening agent 1.0-1.5%;
Expanding material 1.0-1.5%;
Biodegradable macromolecular compound 15.0-35.0%;
Microcapsule intumescent flame retardant 1.5-10.0%;
Fire-retardant catalyzer 0.05%-3.0%.
2, the preparation method of the described microcapsule expansion flame-proof starch-based degradable material of claim 1 is characterized in that: by mass ratio the starch of 60.0-80.0% and the softening agent of 1.0-1.5% and the expanding material of 1.0-1.5% are mixed; Be heated to 70-100 ℃, add biodegradable macromolecular compound of 15.0-35.0% and 0.5-10.0% microcapsule intumescent flame retardant and the fire-retardant catalyzer of 0.05%-3.0% again; Cooling discharge; The powder that obtains at 160-220 ℃ of extruding pelletization, is promptly obtained microcapsule expansion flame-proof starch-based degradable material.
3, the described preparation method of microcapsule expansion flame-proof starch-based degradable material or claim 2 according to claim 1 is characterised in that described starch is selected from tapioca (flour), sweet potato starch, early rice starch, yam starch, W-Gum, konjak starch and/or wheat-flour.
4, the described preparation method of microcapsule expansion flame-proof starch-based degradable material or claim 2 according to claim 1 is characterised in that described softening agent is selected from aliphatic carboxylic acid, aliphatic amide and/or aliphatics metal-salt; Described aliphatic carboxylic acid comprises linolenic acid, stearic acid, lauric acid, oleic acid, oxysuccinic acid and/or succsinic acid; Described aliphatic amide comprises hexanolactam, oleylamide, inferior oleylamide and/or stearylamide; Described aliphatics metal-salt comprises Magnesium Stearate, calcium stearate, manganese stearate and/or Zinic stearas.
5, the described preparation method of microcapsule expansion flame-proof starch-based degradable material or claim 2 according to claim 1 is characterised in that described expanding material is selected from maleic anhydride, diacetyl oxide and/or Succinic anhydried.
6, the described preparation method of microcapsule expansion flame-proof starch-based degradable material or claim 2 according to claim 1 is characterised in that described degradable biological macromolecular compound is selected from poly(lactic acid), polylactide, poly-second propyl ester, polyvinyl alcohol and/or aliphatic polyester-polyamide copolymer.
7, the described preparation method of microcapsule expansion flame-proof starch-based degradable material or claim 2 according to claim 1 is characterised in that described fire-retardant catalyzer is selected from chromium sesquioxide, titanium dioxide, Manganse Dioxide, lanthanum oxide, zirconium dioxide, nickelous phosphate, zirconium phosphate, molybdenum oxide, antimonous oxide, zinc borate, boric acid, magnesium hydroxide, aluminium hydroxide, hydrotalcite, layered double-hydroxide and/or polynite.
8, the synthetic method of used microcapsule intumescent flame retardant among described microcapsule expansion flame-proof starch-based degradable material of claim 1 or the described preparation method of claim 2, it is characterized in that: with trimeric cyanamide and formaldehyde in molar ratio 1: 2.2-3.3 adds in the reaction vessel, is 10% Na with mass percent concentration
2CO
3The pH that solution is adjusted system is 9-10, is heated to 60-100 ℃ then, to solution becomes clear after, be incubated 20-60 minute, make the carbamide prepolymer; Mass ratio by phosphoric acid salt or poly-phosphate and prepolymer resin is 1: 0.1-0.3 blend, stirring, the stiffening agent that when the temperature of reaction system is 60-100 ℃, adds prepolymer resin quality 1-5%, reflux, 100-200 minute postcooling of reaction, discharging, after filtration, promptly get the expansion type flame retardant that microcapsule wrap up after the drying; Described stiffening agent is ammonium hydrogen phosphate, ammonium chloride, primary ammonium phosphate, potassium primary phosphate and/or SODIUM PHOSPHATE, MONOBASIC.
9, the synthetic method of used microcapsule intumescent flame retardant among described microcapsule expansion flame-proof starch-based degradable material of claim 1 or the described preparation method of claim 2, it is characterized in that: the mol ratio 1 of pressing epoxide group and quadrol: 0.2-1: 0.3, bisphenol A type epoxy resin and quadrol are added in the reaction vessel, be heated to 60-90 ℃ then, be incubated 20-40 minute, make epoxy prepolymer; Mass ratio by phosphoric acid salt or poly-phosphate and prepolymer resin is 1: 0.1-0.3 blend, stirring, when the temperature of reaction system is 60-90 ℃, reflux, 200-400 minute postcooling of reaction, discharging, after filtration, promptly get the expansion type flame retardant that microcapsule wrap up after the drying.
10, claim 8,9 described method synthetic microcapsule intumescent flame retardants, be characterised in that it is is capsule-core with ammonium polyphosphate or melamine phosphate, thermosetting resin melamine formaldehyde resin or Resins, epoxy are the microcapsule intumescent flame retardant of capsule material.
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| CN101812305A (en) * | 2010-03-11 | 2010-08-25 | 中科院广州化学有限公司 | Three-source integrated microcapsule intumescent flame retardant and preparation method thereof |
| CN101812186A (en) * | 2010-03-11 | 2010-08-25 | 中科院广州化学有限公司 | Microencapsulation expansion type flame retardant and application in epoxy resin composite material thereof |
| CN101608060B (en) * | 2009-07-09 | 2011-06-29 | 中国科学技术大学 | Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and preparation method thereof |
| CN102229712A (en) * | 2011-04-25 | 2011-11-02 | 同济大学 | Preparation method of melamine/formaldehyde resin cladded melamine phosphatic microcapsules for fire retardant |
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