CN102604346A - 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 PDFInfo
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- CN102604346A CN102604346A CN2012100474013A CN201210047401A CN102604346A CN 102604346 A CN102604346 A CN 102604346A CN 2012100474013 A CN2012100474013 A CN 2012100474013A CN 201210047401 A CN201210047401 A CN 201210047401A CN 102604346 A CN102604346 A CN 102604346A
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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
- B29C48/36—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
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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
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
- B29C2948/92885—Screw or gear
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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
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
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 cause great harm also for simultaneously easily human living environment.Common plastics are difficult for degraded, have fabulous chemicalstability, in the occurring in nature long-term existence, make plastic garbage day by day increase, and cause " white pollution ", become one of protection environment and hinder greatly.Plastic garbage not only influences environmental beauty, and has polluted water source and soil, and it is healthy to jeopardize the mankind and plant-animal, has brought heavy burden to ball ecological environment.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 because 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.
POLYACTIC ACID (PLA) is to use maximum environmentally friendly bioabsorbable polymer materials at present.It is to be the biopolymer of raw material with the biomass resource, has broken away from the dependence to petroleum resources, has excellent complete biodegradable property; Carbonic acid gas that degraded produces and water can return to the nature circle; Can not pollute environment, this shows, POLYACTIC ACID can satisfy the requirement of Sustainable development.In recent years, dense day by day to the interest of POLYACTIC 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 POLYACTIC ACID and multipolymer application thereof, it is is further researched and developed and paid close attention to by people.But the price height and the fragility of POLYACTIC ACID are big, mix other raw material at POLYACTIC ACID usually, to improve performance, to reduce cost.
Starch source is abundant, and is cheap, is a kind of reproducible resource.Oil price is raised on the way in recent years, makes with the oil to be the also rise thereupon of polymer series products price of raw material.Starch is as a kind of cheap renewable resources, and its weighting agent as plastics can partly substitute common plastics in some aspects, and excellent biodegradability is arranged, and can solve white pollution problems effectively.With can reducing cost in the starch filled POLYACTIC ACID, and mixture material has completely biodegradable.
POLYACTIC ACID is a kind of inflammable macromolecular material, and limiting oxygen index(LOI) has only 20%, in use runs into high temperature meeting decomposition combustion, initiation fire, and the consideration from aspect safe in utilization has proposed fire-retardant requirement to it.The halogen-free expanded flame-retardant agent has environmental protection as the substitute products of halogenated flame retardant, green and free of contamination characteristics.The expandable flame retardant system generally is made up of acid source (dewatering agent), carbon source (carbon forming agent) and source of the gas (whipping agent) three parts.During with the fire-retardant polymer combustion of expansion type flame retardant; Polymer surfaces forms layer of even carbonaceous foam layer; 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 gas produces, and 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 the flame-proof composite material of this method preparation is low, mechanical property is better, flame retardant effect is better.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is:
A kind of Biodegradable polylactic acids-starch flame-proof composite material, it is composed of the following components by weight:
POLYACTIC 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 POLYACTIC ACID is 50,000～300,000.
The preparation method of described treated starch is following: 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 joined carry out graft reaction in the high-speed mixer, temperature of reaction is 70 ℃, and the time is 30 minutes, obtains graft starch; In graft starch, add coupling agent then and under 60 ℃, carry out surface-treated, modification time is 30 minutes, obtains graft modified starch;
Wherein, described starch be in W-Gum, sweet potato starch, the wheat starch any one or any more than two kinds by the blend of any proportioning; The grafting compatilizer is a maleic anhydride, and coupling agent is a kind of or any two kinds of blends by any proportioning in Triple Pressed Stearic Acid or the silane coupling agent, and initiator is an organic peroxide evocating agent.
Described fire retardant is that any one or this two kinds of fire retardants in ammonium polyphosphate (APP), the melamine phosphate (MP) are pressed the mixture of any proportioning.
Described softening agent is a polyoxyethylene glycol, and weight-average molecular weight is at least a in 2000,6000,10000, is preferably polyethylene glycol 6000 especially.
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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (claiming antioxidant 1010 again), and auxiliary antioxidant is tricresyl phosphite (2, the 4-di-tert-butyl) esters (claiming oxidation inhibitor 168 again).
Described fire retarding synergist be in zinc borate, zinc, 4A molecular sieve, the organo montmorillonite any one or any more than two kinds by the mixture of any proportioning.
The preparation method of above-mentioned described Biodegradable polylactic acids-starch flame-proof composite material is characterized in that
May further comprise the steps:
1) takes by weighing each component successively by above-mentioned described parts by weight, the POLYACTIC ACID that takes by weighing, treated starch, fire retardant, oxidation inhibitor, softening agent, synergist were mixed in high-speed mixer 5～10 minutes;
2) melt extrude through twin screw extruder,, obtain the fire-retardant composite granule of polylactic acid-starch through cooling, pelletizing;
Wherein, the temperature of twin screw extruder is set to step 2): 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min;
3) be in 70～90 ℃ the loft drier dry 2～4 hours with the fire-retardant composite granule of the polylactic acid-starch that makes in temperature;
4) with 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.
POLYACTIC ACID is the more relatively a kind of degradable material of present Application Research, but the POLYACTIC ACID price is comparatively expensive, utilize starch filled POLYACTIC ACID not only can reduce cost, and material has completely biodegradable.Starch is hydrophilic polymer, and POLYACTIC ACID is a 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 can obviously improving after grafting and the surface-treated wetting ability of starch, improve the consistency of starch and POLYACTIC ACID.The present invention is directed to self chemical constitution of Biodegradable polylactic acids-starch composite material; With wherein starch as carbon source; In the process of preparation polylactic acid-starch matrix material, introduce ammonium polyphosphate and melamine phosphate (containing acid source and source of the gas), make the Biodegradable polylactic acids-starch flame-proof composite material of preparation have biodegradable and flame retardant properties simultaneously.
The present invention selects the weighting agent of cheap starch as POLYACTIC ACID, to reduce cost; Simultaneously, starch can be used as carbon source cooperates the formation system with other auxiliary agent fire retardant.Be to solve the compatibility problem of POLYACTIC ACID and starch, at first utilize the method that starch is carried out grafting, surface-treated to prepare treated starch, the consistency of raising starch and POLYACTIC ACID; Then POLYACTIC 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-treated with starch, has improved the consistency of starch and POLYACTIC ACID, has improved material property, and mechanical property is better.
2) to select for use eco-friendly expanding fire retardant and polylactic acid-starch to carry out compound in the present invention, and the gained material satisfies environmental requirement fully.
3) the present invention is according to expandable flame retardant synergistic principle; Self chemical constitution to Biodegradable polylactic acids-starch system; With wherein starch as carbon source; In the process of preparation Biodegradable polylactic acids-starch composite material, introduce ammonium polyphosphate and melamine phosphate (containing acid source and source of the gas), make the polylactic acid-starch matrix material of preparation have biodegradable and flame retardant properties simultaneously, flame retardant effect is better.
Embodiment
Below in conjunction with Comparative Examples and embodiment the present invention is done a detailed elaboration.
Comparative Examples:
By mass parts, with putting into high-speed mixer after 96.5 parts of starch (W-Gum) oven dry, to add 2 parts maleic anhydride and 0.5 part Lucidol and under 70 ℃, carry out graft reaction, the time is 30 minutes, obtains graft starch; In graft starch, add 1 part of Triple Pressed Stearic Acid then and under 60 ℃, carry out surface-treated, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is following: 70.5 parts of POLYACTIC ACIDs, 25 portions of treated starches, 4 parts of polyethylene glycol 6000s, 0.25 part of antioxidant 1010,0.25 part of oxidation inhibitor 168 are put into high-speed mixer, mix under the room temperature and took out in 5 minutes; With above-mentioned mixed uniformly blend composition through twin screw extruder melt extrude, cooling, granulation; And it is in 70 ℃ the loft drier dry 2 hours in temperature with the fire-retardant composite granule of the polylactic acid-starch that obtains; Pellet after the oven dry through the injection moulding machine injection moulding, is obtained Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature of twin screw extruder is set to: 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment one:
With putting into high-speed mixer after 96.5 parts of starch (W-Gum) oven dry, to add 2 parts maleic anhydride and 0.5 part Lucidol and under 70 ℃, carry out graft reaction, the time is 30 minutes, obtains graft starch; In graft starch, add 1 part of Triple Pressed Stearic Acid then and under 60 ℃, carry out surface-treated, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is following: 60 parts of POLYACTIC ACIDs, 25 portions of treated starches, 10 parts of ammonium polyphosphates, 4 parts of polyethylene glycol 6000s, 0.25 part of antioxidant 1010,168,0.5 part of zinc of 0.25 part of oxidation inhibitor are put into high-speed mixer, mix under the room temperature and took out in 5 minutes; With the above-mentioned blend composition that mixes through twin screw extruder melt extrude, cooling, granulation; And it is in 70 ℃ the loft drier dry 2 hours in temperature with the fire-retardant composite granule of the polylactic acid-starch that obtains; Pellet after the oven dry through the injection moulding machine injection moulding, is obtained Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature of twin screw extruder is set to: 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment two:
By mass parts, with putting into high-speed mixer after 95 parts of starch (sweet potato starch) oven dry, to add 2.5 parts maleic anhydride and 0.5 part Lucidol and under 70 ℃, carry out graft reaction, the time is 30 minutes, obtains graft starch; In graft starch, add 2 parts of Triple Pressed Stearic Acid then and under 60 ℃, carry out surface-treated, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is following: 53 parts of POLYACTIC ACIDs, 30 portions of treated starches, 12 parts of melamine phosphates, 4 parts of polyethylene glycol 6000s, 0.25 part of antioxidant 1010,168,0.5 part of 4A molecular sieve of 0.25 part of oxidation inhibitor are put into high-speed mixer, mix under the room temperature and took out in 7 minutes; With the above-mentioned blend composition that mixes through twin screw extruder melt extrude, cooling, granulation; And it is in 75 ℃ the loft drier dry 3 hours in temperature with the fire-retardant composite granule of the polylactic acid-starch that obtains; Pellet after the oven dry through the injection moulding machine injection moulding, is obtained Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature of twin screw extruder is set to: 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment three:
By mass parts, with putting into high-speed mixer after 94 parts of starch (wheat starch) oven dry, to add 2.5 parts maleic anhydride and 0.5 part Lucidol and under 70 ℃, carry out graft reaction, the time is 30 minutes, obtains graft starch; In graft starch, add 3 parts of Triple Pressed Stearic Acid then and under 60 ℃, carry out surface-treated, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is following: 50 parts of POLYACTIC ACIDs, 32.5 portions of treated starches, 11.5 parts of ammonium polyphosphates, 4.5 parts of polyethylene glycol 6000s, 0.5 part of antioxidant 1010,168,0.5 part of zinc borate of 0.5 part of oxidation inhibitor are put into high-speed mixer, mix under the room temperature and took out in 8 minutes; With the above-mentioned blend composition that mixes through twin screw extruder melt extrude, cooling, granulation; And be in 80 ℃ the loft drier dry 3 hours with the fire-retardant composite granule of the polylactic acid-starch that obtains in temperature, the pellet after the oven dry is obtained Biodegradable polylactic acids-starch flame-proof composite material through the injection moulding machine injection moulding.
Wherein, the temperature of twin screw extruder is set to: 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment four:
By mass parts, with putting into high-speed mixer after 93 parts of starch (40 parts of W-Gums, 53 parts of sweet potato starch) oven dry, to add 2.5 parts maleic anhydride and 0.5 part Lucidol and under 70 ℃, carry out graft reaction, the time is 30 minutes, obtains graft starch; In graft starch, add 4 parts of Triple Pressed Stearic Acid then and under 60 ℃, carry out surface-treated, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is following: 47.25 parts of POLYACTIC ACIDs, 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 1010,168,0.75 part of zinc borate of 0.5 part of oxidation inhibitor are put into high-speed mixer, mix under the room temperature and took out in 9 minutes; With the above-mentioned blend composition that mixes through twin screw extruder melt extrude, cooling, granulation; And it is in 85 ℃ the loft drier dry 4 hours in temperature with the fire-retardant composite granule of the polylactic acid-starch that obtains; Pellet after the oven dry through the injection moulding machine injection moulding, is obtained Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature of twin screw extruder is set to: 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
Embodiment five:
By mass parts; With putting into high-speed mixer after 91 starch (20 parts of W-Gums, 21 parts of sweet potato starch, 50 parts of the wheat starches) oven dry; Add 3 parts maleic anhydride and 1 part Lucidol and under 70 ℃, carry out graft reaction, the reaction times is 30 minutes, obtains graft starch; In graft starch, add 5 parts of Triple Pressed Stearic Acid then and under 60 ℃, carry out surface-treated, the time is 30 minutes, obtains graft modified starch.
The preparation process of Biodegradable polylactic acids-starch flame-proof composite material is following: 40 parts of POLYACTIC ACIDs, 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 1010,168,1 part of organo montmorillonite of 0.5 part of oxidation inhibitor are put into high-speed mixer, mix under the room temperature and took out in 10 minutes; With the above-mentioned blend composition that mixes through twin screw extruder melt extrude, cooling, granulation; And it is in 90 ℃ the loft drier dry 4 hours in temperature with the fire-retardant composite granule of the polylactic acid-starch that obtains; Pellet after the oven dry through the injection moulding machine injection moulding, is obtained Biodegradable polylactic acids-starch flame-proof composite material.
Wherein, the temperature of twin screw extruder is set to: 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min.
With the injection moulding on injection moulding machine of the Biodegradable polylactic acids that makes among Comparative Examples and the embodiment 1 to 5-starch flame-proof composite material is standard test specimen, and test performance is pressed table 1 and measured:
Table 1
Can find out through table 1; The Biodegradable polylactic acids that the present invention makes-starch flame-proof composite material, mechanical property is better, dimensional stabilizing; Oxygen index content is all 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 invention does not constitute the qualification to protection domain of the present invention.Any modification of within spirit of the present invention and principle, being made, be equal to replacement and improvement etc., all should be included within the claim protection domain of the present invention.
Claims (8)
1. Biodegradable polylactic acids-starch flame-proof composite material is characterized in that, and is composed of the following components by weight:
POLYACTIC 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.
2. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material is characterized in that: the molecular weight of described POLYACTIC ACID is 50,000～300,000.
3. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material; It is characterized in that: the preparation method of described treated starch is following: 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 joined carry out graft reaction in the high-speed mixer, temperature of reaction is 70 ℃, and the time is 30 minutes, obtains graft starch; In graft starch, add coupling agent then and under 60 ℃, carry out surface-treated, modification time is 30 minutes, obtains graft modified starch;
Wherein, described starch be in W-Gum, sweet potato starch, the wheat starch a kind of or any more than two kinds by the blend of any proportioning; Described grafting compatilizer is a maleic anhydride; Described coupling agent is a kind of or any two kinds of blends by any proportioning in Triple Pressed Stearic Acid or the silane coupling agent; Described initiator is an organic peroxide evocating agent.
4. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material is characterized in that: described fire retardant is any one or this two kinds of mixtures by any proportioning of ammonium polyphosphate (APP), melamine phosphate (MP).
5. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material is characterized in that: described oxidation inhibitor is the composite of primary antioxidant and auxiliary antioxidant, and the mass ratio of primary antioxidant and auxiliary antioxidant is 1: 1; Primary antioxidant is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and auxiliary antioxidant is tricresyl phosphite (2, a 4-di-tert-butyl) ester.
6. a kind of biodegradable polylactic acid according to claim 1-starch flame-proof composite material is characterized in that: described softening agent is a polyoxyethylene glycol, and weight-average molecular weight is 2000,6000 or 10000.
7. a kind of Biodegradable polylactic acids according to claim 1-starch flame-proof composite material is characterized in that: described fire retarding synergist be in zinc borate, zinc, 4A molecular sieve, the organo montmorillonite a kind of or any more than two kinds by the mixture of any proportioning.
8. 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, take by weighing each component successively, the POLYACTIC ACID that takes by weighing, treated starch, fire retardant, oxidation inhibitor, softening agent, synergist were mixed in high-speed mixer 5～10 minutes by above-mentioned described parts by weight;
Step 2, melt extrude,, obtain the fire-retardant composite granule of polylactic acid-starch through cooling, pelletizing through twin screw extruder;
Wherein, the temperature of twin screw extruder is set in this step: 135～140 ℃ in a district; 140～145 ℃ in two districts; 140～145 ℃ in three districts; 145～150 ℃ in four districts; 150～155 ℃ in five districts, 150～155 ℃ of head temperatures, the extruder screw rotating speed is controlled at 200～300r/min;
Step 3, it is in 70～90 ℃ the loft drier dry 2～4 hours in temperature with the fire-retardant composite granule of the polylactic acid-starch that makes;
Step 4, with 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.
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