CN102134379A - Halogen-free antiflaming polylactic acid material and produciotn method of same - Google Patents
Halogen-free antiflaming polylactic acid material and produciotn method of same Download PDFInfo
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- CN102134379A CN102134379A CN201110044688XA CN201110044688A CN102134379A CN 102134379 A CN102134379 A CN 102134379A CN 201110044688X A CN201110044688X A CN 201110044688XA CN 201110044688 A CN201110044688 A CN 201110044688A CN 102134379 A CN102134379 A CN 102134379A
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- Prior art keywords
- halogen
- free flame
- poly
- polylactic acid
- proof polylactic
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- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 71
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 61
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 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 claims abstract description 23
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- -1 poly(lactic acid) Polymers 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 12
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229920002961 polybutylene succinate Polymers 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 10
- 239000004631 polybutylene succinate Substances 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001241 acetals Chemical class 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 229940059574 pentaerithrityl Drugs 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 229940093916 potassium phosphate Drugs 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000000979 retarding effect Effects 0.000 description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001896 polybutyrate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a halogen-free antiflaming polylactic acid material which comprises the following components according to weight percentage: 50 to 80 percent of polyactic acid base stock, 5 to 40 percent of halogen-free flame retardant, 0.1 to 1.5 percent of dispersing aid, and 10 to 30 percent of degradable toughening resin. The invention also discloses a production method of the halogen-free antiflaming polylactic acid material, which comprises the steps of blending all the components of the halogen-free antiflaming polylactic acid material and then extruding for granulation. The polylactic acid material reduces the flame retardant additive amount of an antiflaming system, ensures the antiflaming effect and simultaneously guarantees the mechanical property of the material, and can be used for injection molding type electronic products, sheet grade decoration boards and the like.
Description
Technical field
The present invention relates to the polymer new material technology field, particularly relate to a kind of halogen-free flame-proof polylactic acid material and manufacture method thereof.
Background technology
Poly(lactic acid) derives from corn, it is degredation plastic, environment is not polluted and resistates, be one of green plastic kind, have higher rigidity and intensity, near the mechanical property of engineering plastics, its degraded needs under given conditions, and under common daily condition, can keep performance for a long time not change, and be applied to easily-consumed products fields such as electronic product, can solve the problem of environmental pollution that present electronic waste day by day increases.And poly-lactic acid material is applied to electronic product, needs the halogen-free flameproof test report mostly.Common flame-retardant additive method commonly used is added halogenide and the antimonous oxide contain halogen exactly, and the amount of being fuming was big when the shortcoming of these fire retardants was burning, produce poisonous, be harmful to, have the corrosive halogenide of strong row.In order to reach the purpose of the low mutual resistance combustion of low cigarette, domestic and international many experts are devoted to sending out of low smoke and low halogen material and open.A kind of in the not halogen-containing poly-lactic acid material is to add inorganic combustion inhibitor, generally adds the mass fraction of 70%-100%(than base-material) aluminium hydroxide [Al (OH)
3] or magnesium hydroxide [Mg (OH)
2] wait inorganic combustion inhibitor just to reach certain fire-retardant requirement, but the heavy addition of inorganic combustion inhibitor can reduce the mechanical property of material significantly, studies show that, and the tensile strength of material, elongation at break, flexibility etc. are all with Mg (OH)
2Or Al (OH)
3Consumption increases and reduces gradually.Another kind of halogen-free flame-retardant system is to contain the organophosphorus flame-retardant system, and its key is to improve the quality of expansion charcoal layer to greatest extent.Contain acid source in this flame-retardant system, carbon source, foaming source (source of the gas), and wherein acid source is an organophosphorus, and when burning, phosphorus compound decomposes the non-ignitibility liquid film that generates phosphoric acid, and its boiling point can reach 300 ℃.Simultaneously, phosphoric acid further dewaters again and generates metaphosphoric acid, the further polymerization of metaphosphoric acid generates poly-metaphosphoric acid, in this process, not only the tectum that is generated by phosphoric acid plays coating effect, and because the poly-metaphosphoric acid that generates is a strong acid, it is very strong dewatering agent, polymkeric substance is dewatered and charing, changed the pattern of polymer combustion process and formed carbon film with secluding air on its surface, thus the stronger flame retardant effect of performance.Carbon source (char-forming agent) is the basis that forms the foam charring layer, be generally the polyol of rich carbon, as starch, tetramethylolmethane and its dipolymer, trimer and the organic resin etc. that contains light base, can suitably add fire retarding synergist, strengthen the effect of acid source as zinc borate.Source of the gas (foaming source) mostly is amine or amides, as trimeric cyanamide, Dyhard RU 100, polyphosphoric acid amine etc.Though add the organophosphorus flame-retardant system poly-lactic acid material is carried out flame-retardant modifiedly obtaining flame retardant effect preferably to a certain extent, owing to these fire retardants bad dispersibility in poly-lactic acid material needs heavy addition.
Summary of the invention
Technical problem to be solved by this invention is: remedy above-mentioned the deficiencies in the prior art, a kind of halogen-free flame-proof polylactic acid material and manufacture method thereof are proposed, can reduce the fire retardant addition of flame-retardant system, when guaranteeing flame retardant effect, guarantee the mechanical property of material.
Halogen-free flame-proof polylactic acid material of the present invention is by the following technical solutions:
Described halogen-free flame-proof polylactic acid material comprises following component: by weight percentage, and the poly(lactic acid) base-material of 50%-80%, the halogen-free flame retardants of 5%-40%, the dispersing auxiliary of 0.1%-1.5%, the degradable toughened resin of 10%-30%.
The effect of dispersing auxiliary improves the flowability of blend, dispersiveness, lubrication, promptly improve the flowability of the poly(lactic acid) course of processing, prevent the sticking to mould tool, reduce and use outer remover, reduce cost, improve the dispersion of halogen-free flame retardants in poly(lactic acid), to reduce the consumption of fire retardant.
The toughness reinforcing resin of degradable generally is granular, adds plasticizing mother particle and improves toughness, avoids because fragility increases after adding fire retardant.
Preferably, described processing aid dispersing auxiliary is at least a in ethylene bis stearamide, stearic acid, stearate (for example sodium stearate, potassium, calcium etc.), the organosilicon (as silicone oil).
Preferably, described degradable toughened resin is poly butylene succinate (PBS), poly-hexanodioic acid terephthalic acid copolymerization fourth diester (PBAT), polyhydroxyalkanoate (PHA), polymerized thylene carbonate second (third) ester (PPC), at least a in the polycaprolactone (PCL).
Preferably, described poly(lactic acid) base-material is that weight percent is the mixture of the high fondant-strength poly(lactic acid) of the poly-lactic acid in high molecular weight of 60%-90% and 10%-40%.In general, molecular weight and melt index are inversely proportional to, and are directly proportional with melt strength, and the poly-lactic acid in high molecular weight performance is good, but make relatively difficulty of high molecular weight polylactic acid, the cost height, and the poly(lactic acid) of high fondant-strength processes, cost is low relatively, realize relatively easy, can realize by modification technology,, both be mixed use in order to satisfy the balance relation of cost, performance, processing.
Preferably, the viscosity-average molecular weight of described poly-lactic acid in high molecular weight is more than 100,000, and/or the melt index of described high fondant-strength poly(lactic acid) is at 2-5g/10min.
Preferably, described halogen-free flame retardants is to comprise that weight percent is the mixture of 70%-90% organophosphate or ester/rich carbon polyol compound flame retardant, 5%-10% zinc borate and 5%-20% powder polyester.The organic resin carrier that wherein pulverous polyester is a halogen-free flame-retardant system, and play bridge formation compatible role with poly(lactic acid), consistency is good, and generally be to add nylon, PP etc. as carrier in the existing flame-retardant system, the such carrier and the consistency of poly(lactic acid) are very poor, and the consistency that is not so good as adding powder polyester is good.
Preferably, described compound flame retardant is to comprise that weight percent is organophosphate or the ester of 60%-85%, mixture with the rich carbon polyol of 15%-40%, described organophosphate or ester are at least a in phosphate compounds (as tripolyphosphate), ammonium phosphate salt, ammonium polyphosphate, sodium phosphate and the potassiumphosphate, and described rich carbon polyol is at least a in tetramethylolmethane and two acetals, three acetals, polycaprolactone dibasic alcohol, polyoxyethylene glycol, glycerol and the starch.
Preferably, described powder polyester is poly butylene succinate (PBS), poly-hexanodioic acid terephthalic acid copolymerization fourth diester (PBAT), polyhydroxyalkanoate (PHA), polymerized thylene carbonate second (third) ester (PPC), at least a in the polycaprolactone (PCL).
The manufacture method of halogen-free flame-proof polylactic acid material of the present invention is by the following technical solutions:
A kind of manufacture method of above-mentioned halogen-free flame-proof polylactic acid material is that each component of halogen-free flame-proof polylactic acid material in above-mentioned any obtains through mixing back extruding pelletization, comprises the steps:
1) with poly(lactic acid) base-material, halogen-free flame retardants at 85-90 ℃ of dry 2-3 hour;
2) the dried poly(lactic acid) base-material of dispersing auxiliary, degradable toughened resin and step 1) is mixed in stirrer, obtain mixed resin;
3) with step 2) in mixed resin and the dried halogen-free flame retardants of step 1) in stirrer, mix, melt extrude granulation then and obtain the halogen-free flame-proof polylactic acid material, the weight percent of each component is: 60%-85% mixed resin, 15%-40% halogen-free flame retardants;
The halogen-free flame-proof polylactic acid material that wherein obtains, by weight percentage, each components contents is: 50%-80% poly(lactic acid) base-material, 5%-40% halogen-free flame retardants, 0.1%-1.5% dispersing auxiliary, 10%-30% degradable toughened resin.
Preferably, described step 3) melt extrudes the air-dry pelletizing of postcooling through twin screw extruder, the processing parameter of described twin screw extruder is provided with as follows: each section temperature is set to: spout room temperature-50 ℃, 160-165 ℃ of feeding section, compression section 165-170 ℃, metering zone 170-175 ℃, adapter 175-180 ℃, 180-185 ℃ of die head section; The main-machine screw rotating speed is 150-220rpm, and the conveying screw rod rotating speed is 20-40rpm, and the barrel rate of feeding is 13-19rpm.
The beneficial effect that the present invention is compared with the prior art is: select for use halogen-free flame retardants and poly(lactic acid) base-material to carry out compound, reduced the addition of fire retardant, mechanical property influence to material is less, add dispersing auxiliary simultaneously and improve the dispersion of halogen-free flame retardants in poly(lactic acid), add the degradable toughened resin and guarantee that poly-lactic acid material also can keep toughness preferably simultaneously containing fire retardant.
In addition,, preferably add a certain amount of powder polyester, improve the consistency of fire retardant and poly(lactic acid) base-material as carrier in order to improve into charcoal, dispersion, cost.
Embodiment
Below in conjunction with preferred embodiment the present invention is explained in detail (described part is weight part).
Embodiment 1: with viscosity-average molecular weight more than 100,000,60 parts of preferred 120,000 poly-lactic acid in high molecular weight, melt index is 2-5g/10min, 40 parts of the high fondant-strength poly(lactic acid) of preferred 5g/10min, 0.2 part of sodium stearate (dispersing auxiliary), poly butylene succinate (degradable toughened resin) places on the high-speed mixer for 20 parts and stirs, and it is standby to obtain mixed resin.With ammonium polyphosphate (ammonium polyphosphate, initialism is APP) 42 parts, 28 parts of tetramethylolmethanes, 20 parts of poly butylene succinates (powder polyester), zinc borate (fire retarding synergist) places high-speed mixer to stir for 10 parts, obtains halogen-free flame retardants.With the mixed resin of gained and halogen-free flame retardants by the 6:4(mass ratio) be put into respectively in the high-speed mixer and mix, be put in the twin screw extruder then, each section temperature is set to: spout room temperature-50 ℃, 160-165 ℃ of feeding section, compression section 165-170 ℃, metering zone 170-175 ℃, adapter 175-180 ℃, 180-185 ℃ of die head section; The main-machine screw rotating speed is 150-220rpm, and the conveying screw rod rotating speed is 20-40rpm, and the barrel rate of feeding is 13-19rpm, and air-dry pelletizing after the material water-cooled of extruding at last obtains required halogen-free flame-proof polylactic acid material.
Embodiment 2: with viscosity-average molecular weight is 60 parts of 120,000 poly-lactic acid in high molecular weight, melt index is 40 parts of the high fondant-strength poly(lactic acid) of 5g/10min, 0.2 part of calcium stearate (dispersing auxiliary), poly butylene succinate (degradable toughened resin) places on the high-speed mixer for 20 parts and stirs, and it is standby to obtain mixed resin.With ammonium polyphosphate (ammonium polyphosphate, initialism is APP) 42 parts, 28 parts of tetramethylolmethanes, 20 parts of polyhydroxyalkanoates (powder polyester), zinc borate (fire retarding synergist) places high-speed mixer to stir for 10 parts, obtains halogen-free flame retardants.With the mixed resin of gained and halogen-free flame retardants by the 7:3(mass ratio) be put into respectively in the high-speed mixer and mix, be put in the twin screw extruder then, each section temperature is set to: spout room temperature-50 ℃, 160-165 ℃ of feeding section, compression section 165-170 ℃, metering zone 170-175 ℃, adapter 175-180 ℃, 180-185 ℃ of die head section; The main-machine screw rotating speed is 150-220rpm, and the conveying screw rod rotating speed is 20-40rpm, and the barrel rate of feeding is 13-19rpm, and air-dry pelletizing after the material water-cooled of extruding at last obtains required halogen-free flame-proof polylactic acid material.
Embodiment 3: be with the difference of embodiment one, the mixed resin and the halogen-free flame retardants of gained are pressed 8.5:1.5 (mass ratio) mixing.
Embodiment 4: with viscosity-average molecular weight is 60 parts of 120,000 poly-lactic acid in high molecular weight, melt index is 40 parts of the high fondant-strength poly(lactic acid) of 5g/10min, 0.2 part of calcium stearate (dispersing auxiliary), poly butylene succinate (degradable toughened resin) places on the high-speed mixer for 20 parts and stirs, and it is standby to obtain mixed resin.With ammonium polyphosphate (ammonium polyphosphate, initialism is APP) 52.5 parts, 17.5 parts of tetramethylolmethanes, 20 parts of polycaprolactones (powder polyester), zinc borate (fire retarding synergist) places high-speed mixer to stir for 10 parts, obtains halogen-free flame retardants.With the base-material of gained and halogen-free flame retardants by the 8:2(mass ratio) be put into respectively in the high-speed mixer and mix, be put in the twin screw extruder then, each section temperature is set to: spout room temperature-50 ℃, 160-165 ℃ of feeding section, compression section 165-170 ℃, metering zone 170-175 ℃, adapter 175-180 ℃, 180-185 ℃ of die head section; The main-machine screw rotating speed is 150-220rpm, and the conveying screw rod rotating speed is 20-40rpm, and the barrel rate of feeding is 13-19rpm, and air-dry pelletizing after the material water-cooled of extruding at last obtains required halogen-free flame-proof polylactic acid material.
Halogen-free flame-proof polylactic acid material with embodiment 4 gained is that example is carried out the material property sign, and is as follows:
The proportioning of each component is identical, and processing units is also identical with processing condition, and test one is to adopt Mg (OH)
2As main flame retardant, test two is to adopt low price organophosphate system as main flame retardant, investigates Mg (OH)
2The mechanical property of flame-retardant system and organophosphate flame-retardant system of the present invention and flame retardant properties, concrete contrast test data see Table 1, table 2.
Table 1 different hydro magnesium oxide addition is the fire retardant material Mechanics Performance Testing and the oxygen index data of preparation down
The different lower valency organophosphate of table 2 flame retardant addition is the fire retardant material data of mechanical and the oxygen index of preparation down
As seen from Table 1, when the addition of magnesium hydroxide reaches 100wt%, its tensile strength and elongation at break have only 10MPa and 1%, oxygen index just reaches 27, usually oxygen index is being called fire retardant material more than 27, so test-results shows that the flame retarding efficiency of magnesium hydroxide is lower, need great addition could satisfy fire-retardant requirement.
As seen from Table 2, when the addition of lower valency organophosphate/tetramethylolmethane (3:1) reached 15wt%, its tensile strength and elongation at break can remain on 38MPa and 13%, and its oxygen index can reach 27.
The halogen-free flame-proof polylactic acid material that embodiment 4 obtains, every after testing index is shown in Table 3:
The The performance test results of table 3 halogen-free flame-proof polylactic acid material
Content of halogen test result (unit: mg/kg) in table 4 poly-lactic acid material
Annotate: (1) mg/kg=ppm
(2) N.D.=does not detect and contains halogen (＜standard value)
(result shows the combustion testing result of table 5 Halogen poly-lactic acid material: extinguished in 10 seconds after fire, do not have
Drip phenomenon, qualified substantially)
Annotate: (1). after t1, t2 are meant that Ignition sources is removed, the time that the material residual flame continues under prescribed condition, i.e. residual flame time;
(2). t3 is meant after flame stops, when perhaps not producing flame, remove Ignition sources after, material continues the time of aura, i.e. time of persistence under the test conditions of regulation.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. halogen-free flame-proof polylactic acid material is characterized in that: comprise following component: by weight percentage, and the poly(lactic acid) base-material of 50%-80%, the halogen-free flame retardants of 5%-40%, the dispersing auxiliary of 0.1%-1.5%, the degradable toughened resin of 10%-30%.
2. halogen-free flame-proof polylactic acid material as claimed in claim 1 is characterized in that: described processing aid dispersing auxiliary is at least a in ethylene bis stearamide, stearic acid, stearate, the organosilicon.
3. halogen-free flame-proof polylactic acid material as claimed in claim 1 or 2 is characterized in that: described degradable toughened resin is at least a in poly butylene succinate, poly-hexanodioic acid terephthalic acid copolymerization fourth diester, polyhydroxyalkanoate, polymerized thylene carbonate second (third) ester, the polycaprolactone.
4. as claim 1 or 2 or 3 described halogen-free flame-proof polylactic acid materials, it is characterized in that: described poly(lactic acid) base-material is that weight percent is the mixture of the high fondant-strength poly(lactic acid) of the poly-lactic acid in high molecular weight of 60%-90% and 10%-40%.
5. halogen-free flame-proof polylactic acid material as claimed in claim 4 is characterized in that: the viscosity-average molecular weight of described poly-lactic acid in high molecular weight is more than 100,000, and/or the melt index of described high fondant-strength poly(lactic acid) is 2-5g/10min.
6. as claim 1 or 2 or 3 described halogen-free flame-proof polylactic acid materials, it is characterized in that: described halogen-free flame retardants is that weight percent is the mixture of compound flame retardant, 5%-10% zinc borate and the 5%-20% powder polyester of 70%-90% organophosphate or organophosphate and rich carbon polyol.
7. halogen-free flame-proof polylactic acid material as claimed in claim 6, it is characterized in that: described compound flame retardant is that weight percent is organophosphate or the organophosphate of 60%-85%, mixture with the rich carbon polyol of 15%-40%, described organophosphate or organophosphate be phosphate compounds preferably, ammonium phosphate salt, ammonium polyphosphate, at least a in sodium phosphate and the potassiumphosphate, described rich carbon polyol is tetramethylolmethane and two acetals thereof preferably, three acetals, the polycaprolactone dibasic alcohol, polyoxyethylene glycol, at least a in glycerol and the starch.
8. halogen-free flame-proof polylactic acid material as claimed in claim 6, it is characterized in that: described powder polyester is a poly butylene succinate, poly-hexanodioic acid terephthalic acid copolymerization fourth diester, polyhydroxyalkanoate, polymerized thylene carbonate second (third) ester, at least a in the polycaprolactone.
9. the manufacture method of a halogen-free flame-proof polylactic acid material is characterized in that, each component of halogen-free flame-proof polylactic acid material described in any one of the claim 1-8 is obtained through mixing back extruding pelletization, comprises the steps:
1) with poly(lactic acid) base-material, halogen-free flame retardants at 85-90 ℃ of dry 2-3 hour;
2) the dried poly(lactic acid) base-material of dispersing auxiliary, degradable toughened resin and step 1) is mixed in stirrer, obtain mixed resin;
3) with step 2) in mixed resin and the dried halogen-free flame retardants of step 1) in stirrer, mix, melt extrude granulation then and obtain the halogen-free flame-proof polylactic acid material, the weight percent of each component is: 60%-85% mixed resin, 15%-40% halogen-free flame retardants;
The halogen-free flame-proof polylactic acid material that wherein obtains, by weight percentage, each components contents is: 50%-80% poly(lactic acid) base-material, 5%-40% halogen-free flame retardants, 0.1%-1.5% dispersing auxiliary, 10%-30% degradable toughened resin.
10. the manufacture method of halogen-free flame-proof polylactic acid material as claimed in claim 9, it is characterized in that: described step 3) melt extrudes the air-dry pelletizing of postcooling through twin screw extruder, the processing parameter of described twin screw extruder is provided with as follows: each section temperature is set to: spout room temperature-50 ℃, 160-165 ℃ of feeding section, compression section 165-170 ℃, metering zone 170-175 ℃, adapter 175-180 ℃, 180-185 ℃ of die head section; The main-machine screw rotating speed is 150-220rpm, and the conveying screw rod rotating speed is 20-40rpm, and the barrel rate of feeding is 13-19rpm.
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Denomination of invention: Halogen-free antiflaming polylactic acid material and produciotn method of same Effective date of registration: 20160331 Granted publication date: 20120808 Pledgee: Shenzhen high tech investment and financing Company limited by guarantee Pledgor: SHENZHEN ESUN INDUSTRIAL CO., LTD. Registration number: 2016990000257 |
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Denomination of invention: Halogen-free antiflaming polylactic acid material and produciotn method of same Effective date of registration: 20170424 Granted publication date: 20120808 Pledgee: Shenzhen high tech investment and financing Company limited by guarantee Pledgor: SHENZHEN ESUN INDUSTRIAL CO., LTD. Registration number: 2017990000337 |