CN101260227B - Method for preparing halogen-free flame-proof polylactic acid - Google Patents

Method for preparing halogen-free flame-proof polylactic acid Download PDF

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Publication number
CN101260227B
CN101260227B CN2008100365537A CN200810036553A CN101260227B CN 101260227 B CN101260227 B CN 101260227B CN 2008100365537 A CN2008100365537 A CN 2008100365537A CN 200810036553 A CN200810036553 A CN 200810036553A CN 101260227 B CN101260227 B CN 101260227B
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flame
retardant
fire
halogen
acid
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CN2008100365537A
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CN101260227A (en
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任杰
李树茂
袁华
于涛
任天斌
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Tongji University
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Tongji University
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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
    • 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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention belongs to the high molecular material technical field, and in particular relates to a preparation method of halogen-free fire-retarding poly lactic acid. The preparation method comprises the following steps: firstly, fire retardant, fire-retarding auxiliary agent and antioxidant are stirred according to a certain proportion to obtain fire-retarding mixture; then, poly lactic acid, the fire-retarding mixture, compatibilizer and coupling agent are mixed according to a certain proportion and are fused and mixed; and finally, the materials are made into fire-retarding poly lactic acid after cooling, pelleting and drying. The fire-retarding poly lactic acid, which has excellent fire-retarding performance and less fused dripping and can pass UL94 grade testing, can be used in fields such as airplane, automobile and electronic industry, which have strict requirements on material fire-retarding performance.

Description

A kind of preparation method of halogen-free flame-proof polylactic acid
Technical field
The invention belongs to the polymer modification technical field, be specifically related to a kind of preparation method of halogen-free flame-proof polylactic acid.
Background technology
Energy problem and environmental problem have promoted the development and the application of biomaterial.POLYACTIC ACID is that a kind of raw material sources are in reproducible non-staple food agricultural-food (like cassava) starch and can be degraded into carbonic acid gas fully and water " green polymer " material.POLYACTIC ACID is degradable not only, but also has many favorable mechanical performances and processing characteristics, is called as " green plastic " of optimum prospect.Yet POLYACTIC ACID is the same with other polymer, is easy to burning, has limited the application of POLYACTIC ACID in fields such as aviation, electronics, automobiles, need give the POLYACTIC ACID flame retardant properties through the method for modification.
Additive flame retardant and macromolecular material blend are the domestic methods of the flame-retardant modified ability of material.Halogen containing flame-retardant has higher flame retardant properties, is usually used in the flame-retardant modified of thermoplastic macromolecule material.But development along with flame-retarded technology; It is found that toxic gases such as generating hydrogen halide when utilizing the fire-retardant material reignition of halogen containing flame-retardant; Resultant during halogen containing flame-retardant and burning thereof simultaneously has carcinogenesis, and developed countries such as therefore present America and Europe have issued ban to the part halogen containing flame-retardant.The non-halogen of flame-retarded technology is the flame-retardant modified developing direction of following material.
Halogen-free flame retardants that can flame retardant polyester class material has: phosphorus flame retardant, like red phosphorus, ammonium polyphosphate, melamine phosphate; Inorganic hydroxide is like white lake, Marinco H etc.; Silicon-series five-retardant is like layered silicate etc.(Polym Int such as Galina F; 2000; 49:1095-1100) stir phosphonium flame retardant and mutual-phenenyl two acid bromide two alcohol ester in the machine at height and mix, mixture is 230-240 ℃ of following fusion section, at last hot pressing under the product 230-240 that obtains ℃, 30 tons the pressure.The flame retardant properties of products therefrom can reach UL94 V-0 level.At home, colleges and universities such as Harbin Institute of Technology, Sichuan University are being studied aspect the halogen-free antiflaming polyester class superpolymer, though aspect fire-retardant, obtained some progress, maximum shortcoming is the suitability for industrialized production difficulty.(Polymer Degradation and Stability such as Junfeng Xiao; 2006; 91:2093-2100) fire retardant trimeric cyanamide, triphenylphosphate and mutual-phenenyl two acid bromide two alcohol ester's particle through the two-high rolling mill melt blending (temperature: 235 ℃, revolution: 100).When trimeric cyanamide, the triphenylphosphate content in matrix material is 10wt%, 20%wt%, can be through the test of UL94V-0 level.Sichuan University applied for a patent " phosphor-containing flame-proof polyethylene terephthalate/laminated nm-silicate composite material " in 2002 (CN1396206), and this patent is mentioned and used layered silicate, response type phosphonium flame retardant and the fire-retardant DMT. Dimethyl p-benzenedicarboxylate of other auxiliary agents.Products therefrom has flame retardant properties, mechanical property, but this patent shortcoming is an application response type phosphonium flame retardant, adopts in-situ inserted polymerization, is unfavorable for suitability for industrialized production.The thermoplastic material of halogen-free flameproof is attended by a large amount of melts drippages when burning, when particularly using the phosphoric acid ester fire retardant, along with the increasing of fire retardant consumption, it is quite serious that drip phenomenon becomes, and greatly limited the range of application of material.
To this situation, this patent provides the preparation method of a kind of suitable suitability for industrialized production environmental friendliness, biodegradable POLYACTIC ACID fire retardant material, and when adding flame retardants such as polynite, Zinic stearas and reduce material combustion the drippage of melts.This method has characteristics such as technology is simple, throughput height, has important application value.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of halogen-free flame-proof polylactic acid of suitable suitability for industrialized production.
The preparation method of the halogen-free flame-proof polylactic acid that the present invention proposes is earlier fire retardant to be carried out surface-treated, again the fire retardant after the modification, POLYACTIC ACID, other auxiliary agent blend is extruded and is obtained product.
The preparation method of the halogen-free flame-proof polylactic acid that the present invention proposes, concrete steps are following:
(1) with POLYACTIC ACID, fire retardant respectively 30～120 ℃ of following vacuum-dryings 1～24 hour, to remove moisture;
(2) fire retardant and flame retardant, oxidation inhibitor after the processing that step (1) is obtained stir in the exsiccant container according to weight ratio, and it is mixed, and obtain flame-retardant mixture; The weight percent of its each component is:
Fire retardant 69～98.5wt%
Flame retardant 0.5～30wt%
Oxidation inhibitor 1～10wt%
Its gross weight satisfies 100%;
(3) POLYACTIC ACID after the processing that step (1) is obtained, the flame-retardant mixture that step (2) obtains, coupling agent, expanding material mix, then melt blending by weight joining in the exsiccant container; Adopt forcing machine or two roller mill to obtain desired product; Wherein each weight percent of forming is:
POLYACTIC ACID 59.4～95wt%
Flame-retardant mixture 2～40wt%
Coupling agent 0.5～8wt%
All the other are expanding material, and its gross weight satisfies 100%;
Among the present invention, step adopts forcing machine described in (3), and its screw speed is 15～280rpm, and extrusion temperature is 100～190 ℃, and material extrudes after cooling, pelletizing, dry getting final product.
Among the present invention, adopt two roller mills described in the step (3), the preceding roll temperature of two roller mills is 80～180 ℃, and back roll temperature is 60～170 ℃.
Among the present invention, the weight-average molecular weight of said POLYACTIC ACID is 1 * 10 5～3 * 10 5
Among the present invention; Said fire retardant is not halogen-containing halogen-free flame retardants; Being specially in polynite, white lake, phosphoric acid, phosphorous acid, ammonium polyphosphate, triphenylphosphate, trioctyl phosphate, tributyl phosphate, tricresyl phosphate (2,3 one two chloropropyl), triphenyl phosphite, phosphoric acid salt, melamine cyanurate, expanded polystyrene veneer graphite or the red phosphorus etc. one or several mixes and uses.
Among the present invention, said flame retardant is one or more in tetramethylolmethane, trimeric cyanamide, starch, titanium oxide, calcium stearate, Zinic stearas, lime carbonate, zinc borate, weisspiessglanz, zeolite, silicon-dioxide, Marinco H, anti-dripping agent or the linking agent etc.
Among the present invention, said coupling agent is one or more in metatitanic acid fat or the silane coupling agent etc.
Among the present invention, said expanding material is an one to multiple kind in polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyoxyethylene glycol (PEG) or the epoxy resin etc.
Among the present invention; Said oxidation inhibitor is tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, phosphorous acid ester three (2; 4-di-tert-butyl phenyl) one to multiple kind in the dimer of ester, phosphorous acid benzene two isodecyl esters, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl phenyl ester), pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, many alkyl dihydroxyphenyl propane phosphorous acid ester or the trimerical mixture etc.
The invention has the advantages that:
(1) it is compound to select for use eco-friendly halogen-free flame retardants and POLYACTIC ACID to carry out, and the goods of gained satisfy environmental protection requirement fully.
(2) it is compound to select for use halogen-free flame retardants and POLYACTIC ACID to carry out, and the goods of gained have good flame retardancy, and goods satisfy UL 94V0 or UL 94V1 grade standard, can be applicable to aviation, automobile, electronics etc. flame retardant properties is required harsh field.
(3) preparation method is simple effectively, processing condition are gentle, is applicable to suitability for industrialized production.
(4) can regulate consumption, the prescription of fire retardant according to requirement of products, the control production cost;
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
With POLYACTIC ACID, ammonium polyphosphate respectively 30 ℃ of following vacuum-dryings 24 hours, to remove moisture.
2. dried ammonium polyphosphate flame retardant and flame retardant tetramethylolmethane, trimeric cyanamide, Zinic stearas, oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester are mixed by weight high-speed stirring in the exsiccant container, obtain flame-retardant mixture.Wherein ammonium polyphosphate is that 3 parts, tetramethylolmethane are that 2 parts, trimeric cyanamide are 1 part, and 1 part of Zinic stearas, oxidation inhibitor are 0.5 part.
3. the flame-retardant mixture that exsiccant POLYACTIC ACID and step (2) is obtained, expanding material polycaprolactone, coupling agent metatitanic acid fat LD-101 mix in the exsiccant container according to certain weight ratio; In forcing machine, carrying out blend then extrudes; Wherein the screw rod revolution is 250rpm, and extrusion temperature is 180 ℃.Wherein POLYACTIC ACID is 90 parts, and flame-retardant mixture is 8.5 parts, and coupling agent is 0.5 part, 1 part of expanding material.Material extrudes after cooling, pelletizing, drying obtain fire-retardant POLYACTIC ACID.
Flame retardant resistance UL-94V test:
UL-94V specification: will grow 127 millimeters, wide 12.7 millimeters, thick 1.6 millimeters test film and vertically place, and, remove flame afterwards, the self-extinguishing time that the determination test sheet catches fire through test furnace igniting 10 seconds.Secondly, 10 seconds of regnition immediately in the time of fray-out of flame, same test flame self-extinguishing time.Investigate the kindling material that falls simultaneously and can light absorbent cotton.Through for the first time having or not to come the evaluating material grade of burning with secondary time of catching fire and absorbent cotton catch fire.Burning grade V-0 level is the highest, and next is respectively V-1, V-2.
The limiting oxygen index(LOI) of product can pass through V-1 level combustion testing greater than 29.
Embodiment 2
With POLYACTIC ACID, polynite, ammonium polyphosphate respectively 80 ℃ of following vacuum-dryings 3 hours, to remove moisture.
2. dried fire retardant polynite, ammonium polyphosphate and flame retardant tetramethylolmethane, trimeric cyanamide, oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester are mixed by weight high-speed stirring in the exsiccant container, obtain flame-retardant mixture.Wherein polynite is that 15 parts, ammonium polyphosphate are that 8 parts, tetramethylolmethane are that 4 parts, trimeric cyanamide are 3 parts, and oxidation inhibitor is 1 part.
3. the flame-retardant mixture that exsiccant POLYACTIC ACID and step (2) is obtained, expanding material polycaprolactone, coupling agent silane coupling agent KH550 mix in the exsiccant container according to certain weight ratio; In forcing machine, carrying out blend then extrudes; Wherein the screw rod revolution is 30rpm, and extrusion temperature is 150 ℃.Wherein POLYACTIC ACID is 64 parts, and flame-retardant mixture is 31 parts, and coupling agent is 4 parts, 1 part of expanding material.Material extrudes after cooling, pelletizing, drying obtain fire-retardant POLYACTIC ACID.
Flame retardant resistance UL-94V test is with embodiment 1.
The limiting oxygen index(LOI) of product can pass through V-1 level combustion testing greater than 30.
Embodiment 3
With POLYACTIC ACID, calcium stearate 80 ℃ of following vacuum-dryings 3 hours, to remove moisture.
2. this ester of fire retardant tricresyl phosphate and flame retardant calcium stearate, oxidation inhibitor phosphorous acid benzene two isodecyl esters are mixed by weight high-speed stirring in the exsiccant container, obtain flame-retardant mixture.Wherein this ester of tricresyl phosphate is that 15 parts, calcium stearate are 3 parts, and oxidation inhibitor is 1 part.
3. the flame-retardant mixture that exsiccant POLYACTIC ACID and step (2) is obtained, expanding material polyoxyethylene glycol, coupling agent silane coupling agent KH550 mix in the exsiccant container according to certain weight ratio; In forcing machine, carrying out blend then extrudes; Wherein the screw rod revolution is 130rpm, and extrusion temperature is 190 ℃.Wherein POLYACTIC ACID is 77.9 parts, and flame-retardant mixture is 19 parts, and coupling agent is 3 parts, 0.1 part of expanding material.Material extrudes after cooling, pelletizing, drying obtain fire-retardant POLYACTIC ACID.
Flame retardant resistance UL-94V test is with instance 1.
The limiting oxygen index(LOI) of product can pass through V-2 level combustion testing greater than 29.
Embodiment 4
With POLYACTIC ACID, ammonium polyphosphate respectively 70 ℃ of following vacuum-dryings 10 hours, to remove moisture.
2. with exsiccant ammonium polyphosphate flame retardant and flame retardant Marinco H, tetramethylolmethane, oxidation inhibitor phosphorous acid benzene two isodecyl esters, mix, obtain flame-retardant mixture by weight high-speed stirring in the exsiccant container.Wherein Marinco H is that 5 parts, ammonium polyphosphate are that 12 parts, tetramethylolmethane are 6 parts, and oxidation inhibitor is 1 part.
3. the flame-retardant mixture that exsiccant POLYACTIC ACID and step (2) is obtained, expanding material polyoxyethylene glycol, coupling agent silane coupling agent KH560 mix in the exsiccant container according to certain weight ratio; In forcing machine, carrying out blend then extrudes; Wherein the screw rod revolution is 150rpm, and extrusion temperature is 170 ℃.Wherein POLYACTIC ACID is 75.5 parts, and flame-retardant mixture is 24 parts, and coupling agent is 2 parts, 0.5 part of expanding material.Material extrudes after cooling, pelletizing, drying obtain fire-retardant POLYACTIC ACID.
Flame retardant resistance UL-94V test is with embodiment 1.
The limiting oxygen index(LOI) of sample can pass through V-0 level combustion testing greater than 31.
Embodiment 5
With POLYACTIC ACID, expanded polystyrene veneer graphite respectively 60 ℃ of following vacuum-dryings 20 hours, to remove moisture.
2. with exsiccant fire retardant expanded polystyrene veneer graphite and fire retardant red phosphorus, flame retardant tetramethylolmethane, oxidation inhibitor penta tetrol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, mix, obtain flame-retardant mixture by weight high-speed stirring in the exsiccant container.Wherein expanded polystyrene veneer graphite is that 5 parts, red phosphorus are that 3 parts, tetramethylolmethane are 1 part, and oxidation inhibitor is 1 part.
3. the flame-retardant mixture that exsiccant POLYACTIC ACID and step (2) is obtained, expanding material polyoxyethylene glycol, coupling agent silane coupling agent KH560 mix in the exsiccant container according to certain weight ratio; In forcing machine, carrying out blend then extrudes; Wherein the screw rod revolution is 70rpm, and extrusion temperature is 180 ℃.Wherein POLYACTIC ACID is 88.9 parts, and flame-retardant mixture is 10 parts, coupling agent be 1 for part, 0.1 part of expanding material.Material extrudes after cooling, pelletizing, drying obtain fire-retardant POLYACTIC ACID.
Flame retardant resistance UL-94V test is with embodiment 1.
The limiting oxygen index(LOI) of product can pass through V-2 level combustion testing greater than 27.
Embodiment 6
With POLYACTIC ACID, ammonium polyphosphate, polynite 50 ℃ of following vacuum-dryings 10 hours, to remove moisture.
2. dried ammonium polyphosphate, polynite and tetramethylolmethane, trimeric cyanamide, expanding material polycaprolactone, oxidation inhibitor phosphorous acid benzene two isodecyl esters are mixed by weight high-speed stirring in the exsiccant container, obtain flame-retardant mixture.Wherein polynite is 25 parts, ammonium polyphosphate be 45 parts, tetramethylolmethane be 18 parts, trimeric cyanamide be 8 parts, polycaprolactone 3 for part, oxidation inhibitor phosphorous acid benzene two isodecyl esters are 1 part.
3. the flame-retardant mixture, expanding material polyoxyethylene glycol, the coupling agent silane coupling agent KH560 that exsiccant POLYACTIC ACID and step (2) are obtained carry out blend according to certain weight ratio in two roller mills, obtain flame-proof polylactic acid.Wherein preceding roll temperature is 140 ℃, and 100 ℃ of back roll temperatures, POLYACTIC ACID are 60.2 parts, and flame-retardant mixture is 38 parts, and expanding material is 0.8 part, and coupling agent is 1 part.
Flame retardant resistance UL-94V test is with embodiment 1.
The limiting oxygen index(LOI) of product is greater than 27, and sample can pass through V-0 level combustion testing.
Embodiment 7
With POLYACTIC ACID, ammonium polyphosphate, polynite 100 ℃ of following vacuum-dryings 5 hours, to remove moisture.
2. dried ammonium polyphosphate, polynite and tetramethylolmethane, expanding material polyhydroxyalkanoate (PHA), oxidation inhibitor phosphorous acid benzene two isodecyl esters are mixed by weight high-speed stirring in the exsiccant container, obtain fire-retardant Preblend.Wherein polynite is 15 parts, and ammonium polyphosphate is that 55 parts, tetramethylolmethane are that 23 parts, polyhydroxyalkanoate are that 5 parts, oxidation inhibitor phosphorous acid benzene two isodecyl esters are 2 parts.
3. the fire-retardant premix flame-retardant mixture, expanding material polyoxyethylene glycol, the coupling agent silane coupling agent KH550 that exsiccant POLYACTIC ACID and step (2) are obtained carry out blend according to certain weight ratio in two roller mills, obtain flame-proof polylactic acid.Wherein preceding roll temperature is 130 ℃, and 120 ℃ of back roll temperatures, POLYACTIC ACID are 65 parts, and flame-retardant mixture is 33.2 parts, and expanding material is 1 part, and coupling agent is 0.8 part.
Flame retardant resistance UL-94V test is with embodiment 1.
The limiting oxygen index(LOI) of sample is greater than 28, and sample can pass through V-0 level combustion testing.
Embodiment 8
With POLYACTIC ACID, melamine cyanurate, polynite 120 ℃ of following vacuum-dryings 1 hour, to remove moisture.
2. dried melamine cyanurate, polynite and tetramethylolmethane, expanding material polyhydroxyalkanoate (PHA), oxidation inhibitor phosphorous acid benzene two isodecyl esters are mixed by weight high-speed stirring in the exsiccant container, obtain fire-retardant Preblend.Wherein polynite is 20 parts, and melamine cyanurate is that 46 parts, tetramethylolmethane are that 24 parts, polyhydroxyalkanoate are that 8 parts, oxidation inhibitor phosphorous acid benzene two isodecyl esters are 2 parts.
3. the flame-retardant mixture, expanding material polyoxyethylene glycol, the coupling agent silane coupling agent KH570 that exsiccant POLYACTIC ACID and step (2) are obtained carry out blend according to certain weight ratio in two roller mills, obtain flame-proof polylactic acid.Wherein preceding roll temperature is 135 ℃, and 125 ℃ of back roll temperatures, POLYACTIC ACID are 85 parts, and flame-retardant mixture is 15 parts, and expanding material is 0.9 part, and coupling agent is 0.9 part.
Flame retardant resistance UL-94V test is with embodiment 1.
The limiting oxygen index(LOI) of product is greater than 28, and sample can pass through V-1 level combustion testing, and the melts drippage is few during burning.
In addition, and only compare with the fire-retardant POLYACTIC ACID of halogen-free flame retardants (like ammonium polyphosphate, triphenylphosphate etc.), the sample for preparing with the present invention has less fusion dropping in combustion processes.

Claims (7)

1. the preparation method of a halogen-free flame-proof polylactic acid is characterized in that concrete steps are following:
(1) with POLYACTIC ACID, fire retardant respectively 30～120 ℃ of following vacuum-dryings 1～24 hour, to remove moisture;
(2) fire retardant and flame retardant, oxidation inhibitor after the processing that step (1) is obtained stir in the exsiccant container according to weight ratio, and it is mixed, and obtain flame-retardant mixture; The weight percent of its each component is:
Fire retardant 69～98.5wt%
Flame retardant 0.5～30wt%
Oxidation inhibitor 1～10wt%
Its gross weight satisfies 100%;
(3) POLYACTIC ACID after the processing that step (1) is obtained, the flame-retardant mixture that step (2) obtains, coupling agent, expanding material mix, then melt blending by weight joining in the exsiccant container; Adopt forcing machine or two roller mill to obtain desired product; Wherein each weight percent of forming is:
POLYACTIC ACID 59.4～95wt%
Flame-retardant mixture 2～40wt%
Coupling agent 0.5～8wt%
All the other are expanding material, and its gross weight satisfies 100%;
Said fire retardant is that in polynite, white lake, phosphoric acid, phosphorous acid, ammonium polyphosphate, triphenylphosphate, trioctyl phosphate, tributyl phosphate, tricresyl phosphate (2,3 one two chloropropyl), triphenyl phosphite, phosphoric acid salt, melamine cyanurate, expanded polystyrene veneer graphite or the red phosphorus one or several mix and use; Said flame retardant is one or more in tetramethylolmethane, trimeric cyanamide, starch, titanium oxide, calcium stearate, Zinic stearas, lime carbonate, zinc borate, weisspiessglanz, zeolite, silicon-dioxide, Marinco H, anti-dripping agent or the linking agent.
2. the preparation method of halogen-free flame-proof polylactic acid according to claim 1 is characterized in that adopting forcing machine described in the step (3), and its screw speed is 15～280rpm, and extrusion temperature is 100～190 ℃, and material extrudes after cooling, pelletizing, dry getting final product.
3. the preparation method of halogen-free flame-proof polylactic acid according to claim 1 is characterized in that adopting the preceding roll temperature of two roller mills described in the step (3) is 80～180 ℃, and back roll temperature is 60～170 ℃.
4. the preparation method of halogen-free flame-proof polylactic acid according to claim 1, the weight-average molecular weight that it is characterized in that said POLYACTIC ACID is 1 * 10 5～3 * 10 5
5. the preparation method of halogen-free flame-proof polylactic acid according to claim 1 is characterized in that said coupling agent is one or more in metatitanic acid fat or the silane coupling agent.
6. the preparation method of halogen-free flame-proof polylactic acid according to claim 1 is characterized in that said expanding material is an one to multiple kind in polycaprolactone, polyhydroxyalkanoate, polyoxyethylene glycol or the epoxy resin.
7. the preparation method of halogen-free flame-proof polylactic acid according to claim 1; It is characterized in that said oxidation inhibitor is tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, phosphorous acid ester three (2; 4-di-tert-butyl phenyl) one to multiple kind in ester, phosphorous acid benzene two isodecyl esters, three (nonyl is for phenyl) phosphorous acid esters or tricresyl phosphite (nonyl phenyl ester) or pentaerythritol bis-phosphite two (2, the 4-di-tert-butyl phenyl) ester.
CN2008100365537A 2008-04-24 2008-04-24 Method for preparing halogen-free flame-proof polylactic acid Expired - Fee Related CN101260227B (en)

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