CN102604346B - Biodegradable polylactic acid-starch flame retardant composite material and preparation method thereof - Google Patents

Biodegradable polylactic acid-starch flame retardant composite material and preparation method thereof Download PDF

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CN102604346B
CN102604346B CN201210047401.3A CN201210047401A CN102604346B CN 102604346 B CN102604346 B CN 102604346B CN 201210047401 A CN201210047401 A CN 201210047401A CN 102604346 B CN102604346 B CN 102604346B
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starch
composite
flame
biodegradable polylactic
flame retardant
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CN201210047401.3A
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Chinese (zh)
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CN102604346A (en
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胡珊
张俊
高虎亮
黄裕杰
申应军
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中国地质大学（武汉）
深圳市富恒塑胶新材料有限公司
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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
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • 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
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • 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
    • B29C2948/92885—Screw or gear
    • 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

Abstract

The invention relates to a biodegradable polylactic acid-starch flame retardant composite material and a preparation method of the composite material. The composite material comprises the following components in parts by weight: 40-60 of polylactic acid, 25-40 of modified starch, 10-13 of a flame retardant, 0.5-1 of an antioxidant, 4-5 of a plasticizer, and 0.5-1 of a flame retardant synergist. The preparation method is as follows: mixing the raw materials in a high-speed mixer for 5-10min according to the formula; then extruding and pelleting by a double screw extruder, wherein the extrusion temperature is 135-155 DEG C and the screw rotation speed is 200-300r/min; and performing injection molding on the dried polylactic acid-starch flame retardant aggregates by a injection molding machine to obtain the biodegradable polylactic acid-starch flame retardant composite material. According to the invention, the prepared biodegradable polylactic acid-starch flame retardant composite material is good in biodegradability, and improves the compatibility of polylactic acid and starch, and in addition, by addition of a proper amount of flame retardant according to chemical composition of the material, the prepared composite material has biodegradability and flame retardant property at the same time.

Description

A kind of Biodegradable polylactic acids-starch flame-proof composite material and preparation method thereof
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of biodegradable flame-proof composite material and preparation method thereof.
Background technology
Plastics bring people, and the while is also caused great harm to the mankind's living environment easily.Common plastics are difficult for degraded, have fabulous chemical stability, in the occurring in nature long-term existence, make plastic garbage day by day increase, and cause " white pollution ", become one of protection of the environment and hinder greatly.Plastic garbage not only affects environmental beauty, and has polluted water source and soil, jeopardizes the mankind and animals and plants health, to ball ecological environment, has brought heavy burden.Therefore, the pollution problem of plastic garbage has obtained the generally attention of countries in the world, launches respectively laws and regulations and limits using and reclaiming of plastics, and obtained certain active effect.But, due to the excellent properties of plastics, the usage quantity of plastics will increase at a high speed in long-term scope, fundamentally solve the plastic garbage problem and just be to develop superior performance, degradable environmentally friendly plastics.
Poly(lactic acid) (PLA) is to apply at present maximum environmentally friendly bioabsorbable polymer materials.It is to take the biopolymer that biomass resource is raw material, has broken away from the dependence to petroleum resources, has excellent complete biodegradable, the carbonic acid gas that degraded produces and water can return to the nature circle, can be to environment, as can be seen here, poly(lactic acid) can meet the requirement of Sustainable development.In recent years, day by day dense to the interest of poly(lactic acid) research both at home and abroad, relate to all respects such as industrial and agricultural production field, medical field.Along with the continuous expansion to the polylactide and its copolymer application, it is is further researched and developed and paid close attention to by people.But the price of poly(lactic acid) is high and fragility is large, usually in poly(lactic acid), mix other raw material, to improve performance, to reduce costs.
Starch source is abundant, cheap, is a kind of reproducible resource.Oil price is raised on the way in recent years, makes to take the polymer series products price that oil is raw material and also go up thereupon.Starch is as a kind of cheap renewable resources, and its weighting agent as plastics can partly substitute common plastics in some aspects, and good biological degradability is arranged, and can effectively solve white pollution problems.To in starch filled poly(lactic acid), can reduce costs, and mixture material has completely biodegradable.
Poly(lactic acid) is a kind of inflammable macromolecular material, and limiting oxygen index(LOI) only has 20%, in use runs into high temperature meeting decomposition combustion, initiation fire, and the consideration for using secure context, proposed fire-retardant requirement to it.The halogen-free expanded flame-retardant agent, as the substitute products of halogenated flame retardant, has environmental protection, green and free of contamination characteristics.Intumescent Retardant System generally is comprised of acid source (dewatering agent), carbon source (carbon forming agent) and source of the gas (whipping agent) three parts.With expansion type flame retardant during fire-retardant polymer combustion, polymer surfaces forms the uniform carbonaceous foam layer of one deck, that this layer plays in condensed phase is heat insulation, oxygen barrier, press down cigarette and prevent the effect of molten drop, and low cigarette, low toxicity, non-corrosiveness γ-ray emission, is a kind of fire retardant of high-efficiency environment friendly.
Summary of the invention
The object of the present invention is to provide a kind of Biodegradable polylactic acids-starch flame-proof composite material and preparation method thereof, the cost of flame-proof composite material prepared by the method is low, mechanical property is better, flame retardant effect is better.
For achieving the above object, the technical solution used in the present invention is:
A kind of Biodegradable polylactic acids-starch flame-proof composite material, it is composed of the following components by weight:
Poly(lactic acid) 40～60,
Treated starch 25～40,
Fire retardant 10～13,
Oxidation inhibitor 0.5～1,
Softening agent 4～5,
Fire retarding synergist 0.5～1.
The molecular weight of described poly(lactic acid) is 50,000～300,000.
The preparation method of described treated starch is as follows: starch, grafting compatilizer, initiator, coupling agent are 91～96.5,2～3,0.5～1,1～5 to choose by mass fraction; Starch, grafting compatilizer and initiator are joined in high-speed mixer and carry out graft reaction, and temperature of reaction is 70 ℃, and the time is 30 minutes, obtains graft starch; Then add coupling agent and carry out surface modification in graft starch under 60 ℃, modification time is 30 minutes, obtains graft modified starch;
Wherein, described starch is any one or any two or more in W-Gum, sweet potato starch, the wheat starch blend by any proportioning; The grafting compatilizer is maleic anhydride, and coupling agent is a kind of or any two blend by any proportioning in stearic acid or silane coupling agent, and initiator is organic peroxide evocating agent.
Described fire retardant is that any one or this two kinds of fire retardants in ammonium polyphosphate (APP), melamine phosphate (MP) are pressed the mixture of any proportioning.
Described softening agent is polyoxyethylene glycol, and weight-average molecular weight is at least one in 2000,6000,10000, is particularly preferably polyethylene glycol 6000.
Described oxidation inhibitor is the composite of primary antioxidant and auxiliary antioxidant, and the weight ratio of primary antioxidant and auxiliary antioxidant is 1: 1; Primary antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (claiming again antioxidant 1010), and auxiliary antioxidant is tricresyl phosphite (2,4-di-tert-butyl) ester (claiming again irgasfos 168).
Described fire retarding synergist is any one or any two or more in zinc borate, zinc, 4A molecular sieve, the organo montmorillonite mixture by any proportioning.
The preparation method of Biodegradable polylactic acids described above-starch flame-proof composite material, is characterized in that
Comprise the following steps:
1) take successively each component by parts by weight described above, the poly(lactic acid), treated starch, fire retardant, oxidation inhibitor, softening agent, the synergist that take are mixed 5～10 minutes in high-speed mixer;
2) melt extrude by twin screw extruder, through cooling, pelletizing, obtain the fire-retardant composite granule of polylactic acid-starch;
Wherein, step 2), the temperature setting of twin screw extruder is set to: 135～140 ℃, a district; Two 140～145 ℃, districts; Three 140～145 ℃, districts; Four 145～150 ℃, districts; Five 150～155 ℃, districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min;
3) in the loft drier that is 70～90 ℃ by the fire-retardant composite granule of the polylactic acid-starch made in temperature, drying is 2～4 hours;
4) by the injection moulding in injection moulding machine of the fire-retardant composite granule of the polylactic acid-starch of above-mentioned oven dry, make Biodegradable polylactic acids-starch flame-proof composite material.
Poly(lactic acid) is the relatively many a kind of degradable materials of research application at present, but the poly(lactic acid) price is comparatively expensive, utilize starch filled poly(lactic acid) not only can reduce costs, and material has completely biodegradable.Starch is hydrophilic polymer, and poly(lactic acid) is hydrophobic polymer, when these two kinds of different polymkeric substance of character are combined with each other, the interface binding power between two kinds of high molecular polymers too a little less than, cause the two consistency too poor, processing difficulties, insufficient formability.Starch is carried out after grafting and surface modification obviously improving to the wetting ability of starch, improve the consistency of starch and poly(lactic acid).The present invention is directed to self chemical constitution of Biodegradable polylactic acids-starch composite material, the starch of usining wherein is as carbon source, introduce ammonium polyphosphate and melamine phosphate (containing acid source and source of the gas) in the process for preparing the polylactic acid-starch matrix material, make the Biodegradable polylactic acids of preparation-starch flame-proof composite material there is biodegradable and flame retardant properties simultaneously.
The present invention selects the weighting agent of cheap starch as poly(lactic acid), to reduce costs; Simultaneously, starch can be used as carbon source and coordinates the fire retardant of formation system with other auxiliary agent.For solving the compatibility problem of poly(lactic acid) and starch, at first utilize the method that starch is carried out to grafting, surface modification to prepare treated starch, the consistency of raising starch and poly(lactic acid); Then poly(lactic acid), treated starch, fire retardant and other auxiliary agent are processed together, obtained the biodegradable flame-proof composite material.
The invention has the beneficial effects as follows:
1) the present invention carries out grafting and surface modification by starch, has improved the consistency of starch and poly(lactic acid), has improved material property, and mechanical property is better.
2) to select eco-friendly expanding fire retardant and polylactic acid-starch to carry out compound in the present invention, and resulting materials meets environmental requirement fully.
3) the present invention is according to expandable flame retardant synergistic principle, self chemical constitution for Biodegradable polylactic acids-starch system, the starch of usining wherein is as carbon source, introduce ammonium polyphosphate and melamine phosphate (containing acid source and source of the gas) in preparing the process of Biodegradable polylactic acids-starch composite material, make the polylactic acid-starch matrix material of preparation have biodegradable and flame retardant properties, flame retardant effect is better simultaneously.
Embodiment
Below in conjunction with Comparative Examples and embodiment, the present invention is done to a detailed elaboration.
Comparative Examples:
By mass parts, after being dried, 96.5 parts of starch (W-Gum) put into high-speed mixer, and to add the maleic anhydride of 2 parts and the benzoyl peroxide of 0.5 part and carry out graft reaction under 70 ℃, the time is 30 minutes, obtains graft starch; Then add 1 part of stearic acid and carry out surface modification in graft starch under 60 ℃, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is as follows: 70.5 parts of poly(lactic acid), 25 portions of treated starches, 4 parts of polyethylene glycol 6000s, 0.25 part of antioxidant 1010,0.25 part of irgasfos 168 are put into to high-speed mixer, mix under room temperature and take out in 5 minutes; By above-mentioned mixed uniformly blend composition by twin screw extruder melt extrude, cooling, granulation, and in the loft drier that is 70 ℃ in temperature by the fire-retardant composite granule of the polylactic acid-starch obtained dry 2 hours, pellet after drying, by the injection moulding machine injection moulding, is obtained to Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature setting of twin screw extruder is set to: 135～140 ℃, a district; Two 140～145 ℃, districts; Three 140～145 ℃, districts; Four 145～150 ℃, districts; Five 150～155 ℃, districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment mono-:
Put into high-speed mixer after 96.5 parts of starch (W-Gum) are dried, add the maleic anhydride of 2 parts and the benzoyl peroxide of 0.5 part and carry out graft reaction under 70 ℃, the time is 30 minutes, obtains graft starch; Then add 1 part of stearic acid and carry out surface modification in graft starch under 60 ℃, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is as follows: 60 parts of poly(lactic acid), 25 portions of treated starches, 10 parts of ammonium polyphosphates, 4 parts of polyethylene glycol 6000s, 0.25 part of antioxidant 1010,0.25 part of irgasfos 168,0.5 part of zinc are put into to high-speed mixer, mix under room temperature and take out in 5 minutes; By the above-mentioned blend composition mixed by twin screw extruder melt extrude, cooling, granulation, and in the loft drier that is 70 ℃ in temperature by the fire-retardant composite granule of the polylactic acid-starch obtained dry 2 hours, pellet after drying, by the injection moulding machine injection moulding, is obtained to Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature setting of twin screw extruder is set to: 135～140 ℃, a district; Two 140～145 ℃, districts; Three 140～145 ℃, districts; Four 145～150 ℃, districts; Five 150～155 ℃, districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment bis-:
By mass parts, after being dried, 95 parts of starch (sweet potato starch) put into high-speed mixer, and to add the maleic anhydride of 2.5 parts and the benzoyl peroxide of 0.5 part and carry out graft reaction under 70 ℃, the time is 30 minutes, obtains graft starch; Then add 2 parts of stearic acid and carry out surface modification in graft starch under 60 ℃, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is as follows: 53 parts of poly(lactic acid), 30 portions of treated starches, 12 parts of melamine phosphates, 4 parts of polyethylene glycol 6000s, 0.25 part of antioxidant 1010,0.25 part of irgasfos 168,0.5 part of 4A molecular sieve are put into to high-speed mixer, mix under room temperature and take out in 7 minutes; By the above-mentioned blend composition mixed by twin screw extruder melt extrude, cooling, granulation, and in the loft drier that is 75 ℃ in temperature by the fire-retardant composite granule of the polylactic acid-starch obtained dry 3 hours, pellet after drying, by the injection moulding machine injection moulding, is obtained to Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature setting of twin screw extruder is set to: 135～140 ℃, a district; Two 140～145 ℃, districts; Three 140～145 ℃, districts; Four 145～150 ℃, districts; Five 150～155 ℃, districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment tri-:
By mass parts, after being dried, 94 parts of starch (wheat starch) put into high-speed mixer, and to add the maleic anhydride of 2.5 parts and the benzoyl peroxide of 0.5 part and carry out graft reaction under 70 ℃, the time is 30 minutes, obtains graft starch; Then add 3 parts of stearic acid and carry out surface modification in graft starch under 60 ℃, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is as follows: 50 parts of poly(lactic acid), 32.5 portions of treated starches, 11.5 parts of ammonium polyphosphates, 4.5 parts of polyethylene glycol 6000s, 0.5 part of antioxidant 1010,0.5 part of irgasfos 168,0.5 part of zinc borate are put into to high-speed mixer, mix under room temperature and take out in 8 minutes; By the above-mentioned blend composition mixed by twin screw extruder melt extrude, cooling, granulation, and in the loft drier that is 80 ℃ in temperature by the fire-retardant composite granule of the polylactic acid-starch obtained dry 3 hours, the pellet after drying is obtained to Biodegradable polylactic acids-starch flame-proof composite material by the injection moulding machine injection moulding.
Wherein, the temperature setting of twin screw extruder is set to: 135～140 ℃, a district; Two 140～145 ℃, districts; Three 140～145 ℃, districts; Four 145～150 ℃, districts; Five 150～155 ℃, districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment tetra-:
By mass parts, put into high-speed mixer after 93 parts of starch (40 parts of W-Gums, 53 parts of sweet potato starch) are dried, add the maleic anhydride of 2.5 parts and the benzoyl peroxide of 0.5 part and carry out graft reaction under 70 ℃, time is 30 minutes, obtains graft starch; Then add 4 parts of stearic acid and carry out surface modification in graft starch under 60 ℃, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is as follows: 47.25 parts of poly(lactic acid), 35 portions of treated starches, 5.5 parts of ammonium polyphosphates, 5.5 parts of melamine phosphates, 5 parts of polyethylene glycol 6000s, 0.5 part of antioxidant 1010,0.5 part of irgasfos 168,0.75 part of zinc borate are put into to high-speed mixer, mix under room temperature and take out in 9 minutes; By the above-mentioned blend composition mixed by twin screw extruder melt extrude, cooling, granulation, and in the loft drier that is 85 ℃ in temperature by the fire-retardant composite granule of the polylactic acid-starch obtained dry 4 hours, pellet after drying, by the injection moulding machine injection moulding, is obtained to Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature setting of twin screw extruder is set to: 135～140 ℃, a district; Two 140～145 ℃, districts; Three 140～145 ℃, districts; Four 145～150 ℃, districts; Five 150～155 ℃, districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment five:
By mass parts, after being dried, 91 starch (20 parts of W-Gums, 21 parts of sweet potato starch, 50 parts of wheat starches) put into high-speed mixer, add the maleic anhydride of 3 parts and the benzoyl peroxide of 1 part and carry out graft reaction under 70 ℃, the reaction times is 30 minutes, obtains graft starch; Then add 5 parts of stearic acid and carry out surface modification in graft starch under 60 ℃, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is as follows: 40 parts of poly(lactic acid), 40 portions of treated starches, 6.5 parts of ammonium polyphosphates, 6.5 parts of melamine phosphates, 5 parts of polyethylene glycol 6000s, 0.5 part of antioxidant 1010,0.5 part of irgasfos 168,1 part of organo montmorillonite are put into to high-speed mixer, mix under room temperature and take out in 10 minutes; By the above-mentioned blend composition mixed by twin screw extruder melt extrude, cooling, granulation, and in the loft drier that is 90 ℃ in temperature by the fire-retardant composite granule of the polylactic acid-starch obtained dry 4 hours, pellet after drying, by the injection moulding machine injection moulding, is obtained to Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature setting of twin screw extruder is set to: 135～140 ℃, a district; Two 140～145 ℃, districts; Three 140～145 ℃, districts; Four 145～150 ℃, districts; Five 150～155 ℃, districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
By in Comparative Examples and embodiment 1 to 5, make Biodegradable polylactic acids-injection moulding on injection moulding machine of starch flame-proof composite material is standard test specimen, test performance is pressed table 1 and is measured:
Table 1
By table 1, can find out, the Biodegradable polylactic acids that the present invention makes-starch flame-proof composite material, mechanical property is better, dimensional stabilizing, oxygen index content all is greater than 30, belong to nonflammable material, the vertical combustion performance all reaches V0, and visible Biodegradable polylactic acids of the present invention-starch flame-proof composite material effect is better.
The above-described embodiment of the present invention, do not form limiting the scope of the present invention.Any modification of making within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in claim protection domain of the present invention.

Claims (7)

1. Biodegradable polylactic acids-starch flame-proof composite material, is characterized in that, composed of the following components by weight:
Poly(lactic acid) 40 ~ 60,
treated starch 25 ~ 40,
Fire retardant 10 ~ 13,
Oxidation inhibitor 0.5 ~ 1,
Softening agent 4 ~ 5,
Fire retarding synergist 0.5 ~ 1;
The preparation method of described treated starch is as follows: starch, grafting compatilizer, initiator, coupling agent are 91 ~ 96.5,2 ~ 3,0.5 ~ 1,1 ~ 5 by mass fraction, choose; Starch, grafting compatilizer and initiator are joined in high-speed mixer and carry out graft reaction, and temperature of reaction is 70 ℃, and the time is 30 minutes, obtains graft starch; Then add coupling agent and carry out surface modification in graft starch under 60 ℃, modification time is 30 minutes, obtains graft modified starch;
Wherein, described starch is a kind of or any two the above blend by any proportioning in W-Gum, sweet potato starch, wheat starch; Described grafting compatilizer is maleic anhydride; Described coupling agent is a kind of or any two blend by any proportioning in stearic acid or silane coupling agent; Described initiator is organic peroxide evocating agent.
2. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material, it is characterized in that: the molecular weight of described poly(lactic acid) is 50,000 ~ 300,000.
3. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material is characterized in that: any one or this two kinds of mixtures by any proportioning that described fire retardant is ammonium polyphosphate, melamine phosphate.
4. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material, it is characterized in that: described oxidation inhibitor is the composite of primary antioxidant and auxiliary antioxidant, the mass ratio of primary antioxidant and auxiliary antioxidant is 1:1; Primary antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and auxiliary antioxidant is tricresyl phosphite (2,4-di-tert-butyl) ester.
5. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material, it is characterized in that: described softening agent is polyoxyethylene glycol, weight-average molecular weight is 2000,6000 or 10000.
6. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material is characterized in that: described fire retarding synergist is a kind of or any two the above mixture by any proportioning in zinc borate, zinc, 4A molecular sieve, organo montmorillonite.
7. the preparation method of Biodegradable polylactic acids as claimed in claim 1-starch flame-proof composite material, is characterized in that it comprises the steps:
Step 1, by parts by weight described above, take successively each component, the poly(lactic acid), treated starch, fire retardant, oxidation inhibitor, softening agent, the synergist that take are mixed 5 ~ 10 minutes in high-speed mixer;
Step 2, by twin screw extruder, melt extrude, through cooling, pelletizing, obtain the fire-retardant composite granule of polylactic acid-starch;
Wherein, in this step, the temperature setting of twin screw extruder is set to: 135 ~ 140 ℃, a district; Two 140 ~ 145 ℃, districts; Three 140 ~ 145 ℃, districts; Four 145 ~ 150 ℃, districts; Five 150 ~ 155 ℃, districts, 150 ~ 155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200 ~ 300r/min;
In step 3, the loft drier that is 70 ~ 90 ℃ by the fire-retardant composite granule of the polylactic acid-starch made in temperature dry 2 ~ 4 hours;
step 4, by the injection moulding in injection moulding machine of the fire-retardant composite granule of the polylactic acid-starch of above-mentioned oven dry, make Biodegradable polylactic acids-starch flame-proof composite material.
CN201210047401.3A 2012-02-28 2012-02-28 Biodegradable polylactic acid-starch flame retardant composite material and preparation method thereof CN102604346B (en)

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