CN101798448A - Method for preparing glass fiber-reinforced flame-retardant heat-resistant polylactic acid composite material - Google Patents
Method for preparing glass fiber-reinforced flame-retardant heat-resistant polylactic acid composite material Download PDFInfo
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- CN101798448A CN101798448A CN 201010138717 CN201010138717A CN101798448A CN 101798448 A CN101798448 A CN 101798448A CN 201010138717 CN201010138717 CN 201010138717 CN 201010138717 A CN201010138717 A CN 201010138717A CN 101798448 A CN101798448 A CN 101798448A
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- polylactic acid
- glass fibre
- composite material
- flame retardant
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 80
- 239000003063 flame retardant Substances 0.000 title claims abstract description 53
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 52
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title abstract description 3
- 239000011521 glass Substances 0.000 title abstract 2
- 239000003365 glass fiber Substances 0.000 claims abstract description 52
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- -1 poly(lactic acid) Polymers 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000004902 Softening Agent Substances 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000003754 machining Methods 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- 229940059574 pentaerithrityl Drugs 0.000 claims description 5
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- MAMMVUWCKMOLSG-UHFFFAOYSA-N Cyclohexyl propionate Chemical compound CCC(=O)OC1CCCCC1 MAMMVUWCKMOLSG-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- YTXCAJNHPVBVDJ-UHFFFAOYSA-N octadecyl propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC YTXCAJNHPVBVDJ-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a method for preparing a glass fiber-reinforced flame-retardant heat-resistant polylactic acid composite material, which can effectively realize the reinforcement and heat-resistant modification of polylactic acid with glass fibers. The technical scheme comprises the following steps of: modifying the glass fibers with a silane coupling agent; drying the polylactic acid and a flame retardant under a vacuum condition; uniformly mixing the dried polylactic acid, the dried flame retardant, a plasticizer, a compatibilizer and an antioxidant and then performing reaction on the mixture in a double-screw extruder so as to produce the flame-retardant polylactic acid; and adding the flame-retardant polylactic acid and the modified glass fibers into the double-screw extruder for combined processing.
Description
Technical field
The present invention relates to a kind of preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material.
Background technology
Along with the exhausted day by day of fossil resource (as oil, coal) and because the white pollution that a large amount of use caused of petroleum base goods is serious day by day, it is found that and have only the environmentfriendly products of utilizing renewable resources production can satisfy people's needs, the realization nature resources circulation is utilized, and human society could be realized Sustainable development.For the consideration to energy problem and environmental problem, biodegradable renewable polyester material becomes the focus that people pay close attention to gradually just.
Poly(lactic acid) is as a kind of aliphatic polyester, it is that non-oil resource is a raw material synthetic bio-based polymer with reproducible biomass resource (starch etc.), it has not only broken away from the dependence to petroleum resources, and its manufacturing process is little to the load that environment brings, it has certain mechanical property and good thermoplastic, compostability in addition, especially have degradation property and raw material sources recyclability fully, it is got more and more people's extensive concerning, be successfully applied to fields such as automotive trim, weaving, mechanical fitting, medical science at present.
But because the crystallization velocity of poly(lactic acid) is slow, degree of crystallinity is low, almost is amorphous polymer after the processing, causes poly-lactic acid products very easily to be out of shape when temperature is higher than its second-order transition temperature (60 ℃), and dimensional stability is very poor; Because the poly(lactic acid) macromolecular chain is made up of C, H, three kinds of elements of O, and its limiting oxygen index(LOI) has only 21, make be easy to the same of poly(lactic acid) burn simultaneously with other polymers.These factors have all limited the application of poly-lactic acid material in fields such as automobile, electronics and aviations greatly.
Therefore, exploitation has the lactic acid composite material of good heat resistance energy, flame retardant properties, mechanical property and degradation property, is that it can be applicable to field problem demanding prompt solutions such as aviation, automobile and electronics heat-resisting, fire-retardant and that mechanical property requirements is harsh.
In the prior art, as denomination of invention is " a kind of natural fibre reinforced polylactic acid composite material and preparation method thereof " patent (patent No.: 200710171660.6) disclosed technical scheme, be a kind of natural fiber that utilizes to poly(lactic acid) is strengthened method for modifying flame, but utilize glass fibre carry out the enhancing of poly(lactic acid) flame-retardant modified still belong to blank.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material, and it is flame-retardant modified effectively to realize utilizing glass fibre to carry out the enhancing of poly(lactic acid).
Realize the object of the invention technical scheme:
A kind of preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material is characterized in that:
Step 1: glass fibre is carried out modification with silane coupling agent handle;
Step 2: poly(lactic acid) and fire retardant are carried out vacuum-drying;
Step 3: after dried poly(lactic acid) and fire retardant and softening agent, expanding material, oxidation inhibitor mixed, in twin screw extruder, react, obtain flame-proof polylactic acid;
Step 4: aforementioned flame-proof polylactic acid and aforementioned modified glass-fiber joined carry out Compound Machining in the twin screw extruder.
The concentration of silane coupling agent is 0.1%-1%.
The shared parts by weight of each composition of poly(lactic acid), fire retardant, softening agent, expanding material and oxidation inhibitor are poly(lactic acid) 60-95, fire retardant 3-18, softening agent 1-10, expanding material 1-10, oxidation inhibitor 0.1-2.
The weight ratio of flame-proof polylactic acid and modified glass-fiber is 9 in the step 4: 1-1: 1.
The operating parameter of twin screw extruder is in the step 3, and screw speed is 15rpm-180rpm, and extrusion temperature is 150 ℃-190 ℃.
The operating parameter of twin screw extruder is in the step 4, and screw speed is 35rpm-200rpm, and extrusion temperature is 160 ℃-200 ℃.
The length-to-diameter ratio of glass fibre is 5-30.
The poly(lactic acid) weight-average molecular weight is 3-30 ten thousand.
Silane coupling agent can be γ-r-chloropropyl trimethoxyl silane, vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy Trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(beta-aminoethyl)-γ TSL 8330, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane or γ-methyl mercapto propyl trimethoxy silicane.
Fire retardant can be wherein a kind of of triphenyl phosphite, ammonium polyphosphate, melamine, triphenylphosphate, phosphoric acid salt, melamine cyanurate, magnesium hydroxide, aluminium hydroxide, trioctyl phosphate, tributyl phosphate, zinc borate, tetramethylolmethane, polynite, or aforementioned several combination.
Softening agent can be dioctyl phthalate (DOP), polyoxyethylene glycol, diethyl phthalate, tributyl citrate, acetylize triethyl citrate or methane amide acetylize tributyl citrate.
Expanding material can be polycaprolactone, polyhydroxyalkanoate or Resins, epoxy.
Oxidation inhibitor can be four (β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate or Tyox B.
The beneficial effect that the present invention has:
The present invention utilize glass fibre compound carry out polylactic acid modified, both can play the effect of strongthener mechanical property, simultaneously because glass fibre is not flammable, thereby can effectively improve the flame retardant properties of matrix material again, widened the range of application of poly(lactic acid) greatly, and material modifiedly can degrade no toxic substance discharging, environmental protection more fully at occurring in nature.
Embodiment
Embodiment one:
(1) be that 5 glass fibre soaks in concentration to be in the aqueous solution of 0.1% silane coupling agent (selecting γ-An Bingjisanyiyangjiguiwan for use) after 5 hours, to carry out drying treatment, obtain the consistency glass fibre of surface modification with length-to-diameter ratio.
(2) poly(lactic acid) (the poly(lactic acid) weight-average molecular weight is 100,000), fire retardant (selecting triphenyl phosphite for use) were removed moisture down in dry 24 hours at 30 ℃ respectively.
(3) poly(lactic acid) after the processing that step (2) is obtained and fire retardant and softening agent (selecting dioctyl phthalate (DOP) for use), expanding material (selecting polyhydroxyalkanoate for use), oxidation inhibitor (are selected four (β-(3 for use, 5 di-tert-butyl-hydroxy phenyls) pentaerythritol ester propionic acid)) be respectively 95,3,1,1,0.1 ratio according to parts by weight, even in the high speed blender and mixing, in twin screw extruder, react then, product is through cooling, pelletizing, oven dry obtains the flame-proof polylactic acid master batch, wherein screw speed is 180rpm, 150 ℃ of extrusion temperatures.
(4) glass fibre after the processing that obtains of flame-proof polylactic acid that step (3) is obtained and step (1) successively joins and carries out Compound Machining in the twin screw extruder, heat-stable flame-proof polylactic acid/glass fiber compound material is enhanced, wherein the weight ratio of flame-proof polylactic acid and glass fibre is 9: 1, screw speed is 200rpm, and extrusion temperature is 160 ℃.
Flame retardant resistance UL94V experiment:
The UL94V specification: will grow 127 millimeters, wide 12.7 millimeters, thick 1.6 millimeters experiment slice and vertically place, furnace igniting is 10 seconds after tested, removes flame afterwards, the self-extinguishing time that the determination experiment sheet catches fire.Secondly, lighted a fire for 10 seconds same test flame self-extinguishing time in the time of fray-out of flame immediately.Investigate the kindling material that falls simultaneously and can light absorbent cotton.By for the first time and secondary time of catching fire and absorbent cotton catch fire have or not to come the evaluating material grade of burning.Burning grade V0 level is the highest, and next is respectively V-1, V-2.
Embodiment two:
(1) be that 10 glass fibre soaks in concentration to be in the aqueous solution of 0.3% silane coupling agent (selecting γ-An Bingjisanyiyangjiguiwan for use) after 5 hours, to carry out drying treatment, obtain the consistency glass fibre of surface modification with length-to-diameter ratio.
(2) poly(lactic acid) (the poly(lactic acid) weight-average molecular weight is 100,000), fire retardant (selecting magnesium hydroxide for use) were removed moisture down in dry 18 hours at 45 ℃ respectively.
(3) poly(lactic acid) after the processing that step (2) is obtained and fire retardant, softening agent (selecting polyoxyethylene glycol for use), expanding material (selecting polycaprolactone for use), oxidation inhibitor (select (3 for use, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester) is respectively 85,8.5,3,3,0.5 ratio according to parts by weight, even in the high speed blender and mixing, in twin screw extruder, react then, product is through cooling, pelletizing, oven dry obtains the flame-proof polylactic acid master batch.Wherein screw speed is 120rpm, 165 ℃ of extrusion temperatures.
(4) glass fibre after the processing that obtains of flame-proof polylactic acid that step (3) is obtained and step (1) successively joins and carries out Compound Machining in the twin screw extruder, heat-stable flame-proof polylactic acid/glass fiber compound material is enhanced, wherein the weight ratio of flame-proof polylactic acid and glass fibre is 3: 1, screw speed is 135rpm, and extrusion temperature is 175 ℃.
Flame retardant resistance UL94V experiment is identical with embodiment one.
Embodiment three:
(1) be that to soak in concentration be in the aqueous solution of 0.7% silane coupling agent (selecting [N-(beta-aminoethyl)-γ TSL 8330] for use) after 5 hours for 20 glass fibre with length-to-diameter ratio, carry out drying treatment, obtain the consistency glass fibre of surface modification.
(2) poly(lactic acid) (the poly(lactic acid) weight-average molecular weight is 100,000), fire retardant (selecting trioctyl phosphate for use) were removed moisture down in dry 10 hours at 60 ℃ respectively.
(3) poly(lactic acid) after the processing that step (2) is obtained and fire retardant and softening agent (selecting diethyl phthalate for use), expanding material (selecting Resins, epoxy for use), oxidation inhibitor (are selected β-(3 for use, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate) is respectively 75,12,6,6,1 ratio according to parts by weight, even in the high speed blender and mixing, in twin screw extruder, react then, product is through cooling, pelletizing, oven dry obtains the flame-proof polylactic acid master batch, wherein screw speed is 60rpm, 175 ℃ of extrusion temperatures.
(4) glass fibre after the processing that obtains of flame-proof polylactic acid that step (3) is obtained and step (1) successively joins and carries out Compound Machining in the twin screw extruder, heat-stable flame-proof polylactic acid/glass fiber compound material is enhanced, wherein the weight ratio of flame-proof polylactic acid and glass fibre is 3: 2, screw speed is 75rpm, and extrusion temperature is 185 ℃.
Flame retardant resistance UL94V experiment is identical with embodiment one.
Embodiment four:
(1) be that to soak in concentration be in the aqueous solution of 1% silane coupling agent (selecting [N-(beta-aminoethyl)-γ TSL 8330] for use) after 5 hours for 30 glass fibre with length-to-diameter ratio, carry out drying treatment, obtain the consistency glass fibre of surface modification.
(2) poly(lactic acid) (the poly(lactic acid) weight-average molecular weight is 100,000), fire retardant (selecting trioctyl phosphate for use) were removed moisture down in dry 3 hours at 80 ℃ respectively.
(3) poly(lactic acid) after the processing that step (2) is obtained and fire retardant and softening agent (selecting the acetylize tributyl citrate for use), expanding material (selecting Resins, epoxy for use), oxidation inhibitor (selecting Tyox B for use) are respectively 60,18,10,10,2 ratio according to parts by weight; even in the high speed blender and mixing; in twin screw extruder, react then; product is through cooling; pelletizing; oven dry obtains the flame-proof polylactic acid master batch, and wherein screw speed is 15rpm, 190 ℃ of extrusion temperatures.
(4) glass fibre after the processing that obtains of flame-proof polylactic acid that step (3) is obtained and step (1) successively joins and carries out Compound Machining in the twin screw extruder, heat-stable flame-proof polylactic acid/glass fiber compound material is enhanced, wherein the weight ratio of flame-proof polylactic acid and glass fibre is 1: 1, screw speed is 35rpm, and extrusion temperature is 200 ℃.
Flame retardant resistance UL94V experiment is identical with embodiment one.
Polylactic acid modified material that previous embodiment obtains and existing poly-lactic acid material mechanical property, heat-drawn wire and flame retardant properties see the following form:
| Embodiment one | Embodiment two | Embodiment three | Embodiment four | Existing poly(lactic acid) | |
| Tensile strength | ??52.3MPa | ??71.5MPa | ??68.2MPa | ??61.6MPa | ??40Mpa |
| Heat-drawn wire | ??70℃ | ??87℃ | ??103℃ | ??122℃ | ??60℃ |
| Flame retardant properties | ??V-2 | ??V-1 | ??V-1 | ??V0 | ??-- |
Annotate:--expression does not possess flame retardant properties
Claims (13)
1. the preparation method of a glass fibre reinforced flame retardant heat-resistance polylactic acid composite material is characterized in that:
Step 1: glass fibre is carried out modification with silane coupling agent handle;
Step 2: poly(lactic acid) and fire retardant are carried out vacuum-drying;
Step 3: after dried poly(lactic acid) and fire retardant and softening agent, expanding material, oxidation inhibitor mixed, in twin screw extruder, react, obtain flame-proof polylactic acid;
Step 4: aforementioned flame-proof polylactic acid and aforementioned modified glass-fiber joined carry out Compound Machining in the twin screw extruder.
2. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 1 is characterized in that: the concentration of silane coupling agent is 0.1%-1%.
3. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 2, it is characterized in that: the shared parts by weight of each composition of poly(lactic acid), fire retardant, softening agent, expanding material and oxidation inhibitor are, poly(lactic acid) 60-95, fire retardant 3-18, softening agent 1-10, expanding material 1-10, oxidation inhibitor 0.1-2.
4. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 3 is characterized in that: the weight ratio of flame-proof polylactic acid and modified glass-fiber is 9 in the step 4: 1-1: 1.
5. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 4 is characterized in that: the operating parameter of twin screw extruder is in the step 3, and screw speed is 15rpm-180rpm, and extrusion temperature is 150 ℃-190 ℃.
6. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 5 is characterized in that: the operating parameter of twin screw extruder is in the step 4, and screw speed is 35rpm-200rpm, and extrusion temperature is 160 ℃-200 ℃.
7. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 6 is characterized in that: the length-to-diameter ratio of glass fibre is 5-30.
8. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 7 is characterized in that: the poly(lactic acid) weight-average molecular weight is 3-30 ten thousand.
9. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 8, it is characterized in that: silane coupling agent can be γ-r-chloropropyl trimethoxyl silane, vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy Trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(beta-aminoethyl)-γ TSL 8330, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane or γ-methyl mercapto propyl trimethoxy silicane.
10. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 9, it is characterized in that: fire retardant can be wherein a kind of of triphenyl phosphite, ammonium polyphosphate, melamine, triphenylphosphate, phosphoric acid salt, melamine cyanurate, magnesium hydroxide, aluminium hydroxide, trioctyl phosphate, tributyl phosphate, zinc borate, tetramethylolmethane, polynite, or aforementioned several combination.
11. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 10 is characterized in that: softening agent can be dioctyl phthalate (DOP), polyoxyethylene glycol, diethyl phthalate, tributyl citrate, acetylize triethyl citrate or methane amide acetylize tributyl citrate.
12. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 11 is characterized in that: expanding material can be polycaprolactone, polyhydroxyalkanoate or Resins, epoxy.
13. the preparation method of glass fibre reinforced flame retardant heat-resistance polylactic acid composite material according to claim 12, it is characterized in that: oxidation inhibitor can be four (β-(3,5 di-tert-butyl-hydroxy phenyls) pentaerythritol ester, (3 propionic acid), the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) cyclohexyl propionate or Tyox B.
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