CN102134379B - 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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- CN102134379B CN102134379B CN201110044688XA CN201110044688A CN102134379B CN 102134379 B CN102134379 B CN 102134379B CN 201110044688X A CN201110044688X A CN 201110044688XA CN 201110044688 A CN201110044688 A CN 201110044688A CN 102134379 B CN102134379 B CN 102134379B
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 41
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title description 9
- 239000003063 flame retardant Substances 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 29
- 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
- -1 poly butylene succinates Polymers 0.000 claims description 16
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 13
- 229920002961 polybutylene succinate Polymers 0.000 claims description 12
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 4
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 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 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 21
- 229920005989 resin Polymers 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation 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 11
- 229920000728 polyester Polymers 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000004631 polybutylene succinate Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 239000000203 mixture Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 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
- 238000005453 pelletization Methods 0.000 description 5
- 239000004632 polycaprolactone Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000000979 retarding effect Effects 0.000 description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 229920000379 polypropylene carbonate Polymers 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 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
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 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
- 150000001408 amides Chemical class 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 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
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 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
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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 method of manufacture thereof.
Background technology
POLYACTIC ACID derives from corn, is degredation plastic, and 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 Antimony Trioxide: 99.5Min 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 white lake [Al (OH) of 70%-100% (than the mass fraction of base-material)
3] or Marinco H [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, and research shows that 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, and the further polymerization of metaphosphoric acid generates and gathers metaphosphoric acid; In this process, the tectum that is not only generated by phosphoric acid plays coating effect, and because the metaphosphoric acid that gathers 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; Like 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 like zinc borate.Mostly source of the gas (foaming source) is amine or amides, like 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: the deficiency that remedies above-mentioned prior art; A kind of halogen-free flame-proof polylactic acid material and method of manufacture 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 adopts following technical scheme:
Said halogen-free flame-proof polylactic acid material comprises following component: by weight percentage, and the POLYACTIC 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 POLYACTIC 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 POLYACTIC 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, said processing aid dispersing auxiliary is at least a in ethylene bis stearamide, Triple Pressed Stearic Acid, stearate (for example StNa, potassium, calcium etc.), the organosilicon (like silicone oil).
Preferably, said degradable toughened resin is poly butylene succinate (PBS), gathers hexanodioic acid terephthalic acid copolymerization fourth diester (PBAT), polyhydroxyalkanoate (PHA), poly (propylene carbonate) (PPC), at least a in the polycaprolactone (PCL).
Preferably, said POLYACTIC ACID base-material is that weight percent is the mixture of high fondant-strength POLYACTIC ACID of poly-lactic acid in high molecular weight and the 10%-40% of 60%-90%.In general, molecular weight and melt index are inversely proportional to, and are directly proportional with melt strength; The poly-lactic acid in high molecular weight performance is good, but will make relatively difficulty of high molecular weight polylactic acid, and cost is high; And the POLYACTIC ACID of high fondant-strength processes, and cost is low relatively, realizes relatively easy; Can realize through modification technology,, both mixed use in order to satisfy the balance relation of cost, performance, processing.
Preferably, the viscosity-average molecular weight of said poly-lactic acid in high molecular weight is more than 100,000, and/or the melt index of said high fondant-strength POLYACTIC ACID is at 2-5g/10min.
Preferably, said 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 the bridge formation compatible role with POLYACTIC 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 POLYACTIC ACID are very poor, and the consistency that is not so good as adding powder polyester is good.
Preferably; Said 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%; Said organophosphate or ester are at least a in phosphate compounds (like tripolyphosphate), ammonium phosphate salt, ammonium polyphosphate, sodium phosphate and the potassiumphosphate, and said rich carbon polyol is at least a in tetramethylolmethane and two acetals, three acetals, polycaprolactone divalent alcohol, polyoxyethylene glycol, USP Kosher and the starch.
Preferably, said powder polyester is poly butylene succinate (PBS), gathers hexanodioic acid terephthalic acid copolymerization fourth diester (PBAT), polyhydroxyalkanoate (PHA), poly (propylene carbonate) (PPC), at least a in the polycaprolactone (PCL).
The method of manufacture of halogen-free flame-proof polylactic acid material of the present invention adopts following technical scheme:
A kind of method of manufacture of above-mentioned halogen-free flame-proof polylactic acid material is that each component extruding pelletization after mix of halogen-free flame-proof polylactic acid material in above-mentioned any obtains, and comprises the steps:
1) with POLYACTIC ACID base-material, halogen-free flame retardants at 85-90 ℃ of dry 2-3 hour;
2) the dried POLYACTIC 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% POLYACTIC ACID base-material, 5%-40% halogen-free flame retardants, 0.1%-1.5% dispersing auxiliary, 10%-30% degradable toughened resin.
Preferably; Said step 3) melt extrudes the air-dry pelletizing of postcooling through twin screw extruder, and the processing parameter of said 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 correlated beneficial effect of the present invention and prior art is: select for use halogen-free flame retardants and POLYACTIC ACID base-material to carry out compound; Reduced the addition of fire retardant; Influence to material is less; Add dispersing auxiliary simultaneously and improve the dispersion of halogen-free flame retardants in POLYACTIC 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 POLYACTIC ACID base-material as carrier in order to improve into charcoal, dispersion, cost.
Embodiment
Below in conjunction with preferred embodiment the present invention is carried out detailed elaboration (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 POLYACTIC ACIDs of preferred 5g/10min, 0.2 part of StNa (dispersing auxiliary); Poly butylene succinate (degradable toughened resin) places on the high-speed mixer for 20 parts and stirs, and it is subsequent use to obtain mixed resin.With 42 parts of ammonium polyphosphates (ammonium polyphosphate, initialism are APP), 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.The mixed resin and the halogen-free flame retardants of gained are put into mixing in the high-speed mixer respectively by 6: 4 (mass ratio); Be put in then in the twin screw extruder, 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 POLYACTIC ACIDs 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 subsequent use to obtain mixed resin.With 42 parts of ammonium polyphosphates (ammonium polyphosphate, initialism are APP), 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.The mixed resin and the halogen-free flame retardants of gained are put into mixing in the high-speed mixer respectively by 7: 3 (mass ratio); Be put in then in the twin screw extruder, 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 POLYACTIC ACIDs 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 subsequent use to obtain mixed resin.With 52.5 parts of ammonium polyphosphates (ammonium polyphosphate, initialism are APP), 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.The base-material and the halogen-free flame retardants of gained are put into mixing in the high-speed mixer respectively by 8: 2 (mass ratio); Be put in then in the twin screw extruder, 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, 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 are seen table 1, table 2.
Table 1 different hydro Natural manganese dioxide 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
Find out from table 1; When the addition of Marinco H reaches 100wt%; Its tensile strength and elongation at break have only 10MPa and 1%, and oxygen index just reaches 27, and oxygen index is being called fire retardant material more than 27 usually; So test-results shows that the flame retarding efficiency of Marinco H is lower, need great addition could satisfy fire-retardant requirement.
Find out that 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%, its oxygen index can reach 27.
The halogen-free flame-proof polylactic acid material that embodiment 4 obtains, see shown in the table 3 through detecting each item index:
The The performance test results of table 3 halogen-free flame-proof polylactic acid material
| Interventions Requested | Unit | Testing method | Standard-required | Assay |
| Oxygen index | ％ | ASTMF?1955-99 | ≥30 | 30～31 |
| Melt flow rate(MFR) | g/10min | ASTMD1238 | ≤20 | 15-18 |
| Tensile strength | MPa | ASTMD638 | ≥20 | 25-28 |
| Elongation at break | ％ | ASTM?D882-02 | ≥10 | 12-15 |
| Notched Izod impact strength | KJ/m 2 | ASTM?D256 | ≥6 | 6-8 |
Content of halogen test result (unit: mg/kg) in table 4 poly-lactic acid material
| Test event | Standard value | Test result |
| F | 50 | N.D. |
| Cl | 50 | N.D. |
| Br | 50 | N.D. |
| I | 50 | N.D. |
Annotate: (1) mg/kg=ppm
(2) N.D.=does not detect and contains halogen (＜standard value)
The combustion testing result of table 5 Halogen poly-lactic acid material (result shows: after fire, in 10 seconds, extinguishes, do not have drip phenomenon, qualified basically)
Annotate: (1) .t1, after t2 is 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. after time under the test conditions of regulation.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, do not breaking away under the prerequisite of the present invention design, make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be regarded as belonging to protection scope of the present invention.
Claims (3)
1. halogen-free flame-proof polylactic acid material; It is characterized in that: in weight part; It consists of: viscosity-average molecular weight is 60 parts of poly-lactic acid in high molecular weight more than 100,000; Melt index is 40 parts of the high fondant-strength POLYACTIC ACIDs of 2-5g/10min, 0.2 part of StNa, 20 parts of poly butylene succinates and halogen-free flame retardants; Wherein halogen-free flame retardants is 42 parts of ammonium polyphosphates, 28 parts of tetramethylolmethanes, 20 parts of poly butylene succinates, 10 parts of zinc borates.
2. halogen-free flame-proof polylactic acid material; It is characterized in that: in weight part; It consists of: 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 POLYACTIC ACIDs of 5g/10min, 0.2 part of calcium stearate, 20 parts of poly butylene succinates and halogen-free flame retardants; Wherein halogen-free flame retardants is 42 parts of ammonium polyphosphates, 28 parts of tetramethylolmethanes, 20 parts of polyhydroxyalkanoates, 10 parts of zinc borates.
3. halogen-free flame-proof polylactic acid material; It is characterized in that: in weight part; It consists of: 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 POLYACTIC ACIDs of 5g/10min, 0.2 part of calcium stearate, 20 parts of poly butylene succinates and halogen-free flame retardants; Wherein halogen-free flame retardants is 52.5 parts of ammonium polyphosphates, 17.5 parts of tetramethylolmethanes, 20 parts of polycaprolactones, 10 parts of zinc borates.
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| CN116218180B (en) * | 2023-05-09 | 2023-10-10 | 北京微构工场生物技术有限公司 | Flame-retardant material |
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| CN101260227B (en) * | 2008-04-24 | 2012-05-23 | 同济大学 | Method for preparing halogen-free flame-proof polylactic acid |
| CN101831156B (en) * | 2010-05-07 | 2012-11-07 | 四川大学 | Toughened halogen-free flame-retardant polylactic acid blending material |
| CN101880448A (en) * | 2010-07-06 | 2010-11-10 | 奇瑞汽车股份有限公司 | Nano modified polylactic acid and preparation method thereof |
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