CN104371291B - The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material - Google Patents
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 57
- 239000003063 flame retardant Substances 0.000 title claims abstract description 36
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 230000002787 reinforcement Effects 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 239000004310 lactic acid Substances 0.000 title claims abstract description 18
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 238000006424 Flood reaction Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 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 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 28
- 239000002270 dispersing agent Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920001431 Long-fiber-reinforced thermoplastic Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Abstract
The invention discloses a kind of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material and preparation method thereof, the present invention adopts PLA as matrix resin, add chain extender to improve the processing temperature of PLA, using the ternary atactic copolymer of styrene-acrylonitrile-GMA as compatilizer, this compatilizer not only strengthens the adhesion between matrix resin and fiber, but also improve the compatibility between matrix resin and flexibilizer, and adopt one-step method to prepare halogen-free flameproof long fiber reinforcement PLC composite, complete the dipping of matrix resin to fiber by continuous fiber by impregnation mold, then in coating mould, complete matrix melt being coated in dipping material strip with halogen containing flame-retardant, then carry out cooling, traction, finally be cut into Len req by pelleter, compared with existing two-step method, such mode not only technique is simple, and the product mechanical property excellence making, and there is good flame retardant effect.
Description
Technical field
The present invention relates to technical field of polymer materials, especially a kind of high-performance halogen-free flame retardant long fiber reinforcement PLAComposite and preparation method thereof.
Background technology
PLA (PLA) is a kind of biodegradable polymer, because PLA source is abundant, cheap, and toolHave good mechanical property, increasing experts and scholars are very interested in application the research of PLA. But PLAMaterial poor heat stability, easy firing, and when burning molten drop phenomenon serious, restriction PLA is at electronic product, automotive upholstery, electricitySub-power equipment, traffic etc. have the fire-retardant application that requires field, therefore need it to carry out flame-retardant modified; Society, peopleAwareness of safety improve, and country environmental protection concept constantly strengthen, therefore, use halogen-free flame retardants prepare fire proofing right and wrongNormal important problem. Because people are more and more higher to the requirement of product quality, the performance of common short fiber enhancing PLA material is notCan meet the demands, the performance that long fiber reinforcement PLA has the excellences such as high strength, high-modulus, high thermal stability can meet peopleHigh-performance is pursued, in preparation when fire-retardant long fiber reinforced thermoplastic composites, traditional method be two-step method (that is: firstPrepare respectively fire-retardant master granule and long fiber reinforcement master batch, then mix and carry out injection moulding), and one-step method is prepared fire-retardant long fibreStrengthen thermoplastic composite technique simple, excellent performance.
Summary of the invention
The object of the invention is: a kind of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material and preparation thereof are providedMethod, it has solved PLA poor heat stability, is easy to the problems such as burning, and has improved the mechanical property of product, and environment-friendly type is good,Technique is simple, to overcome the deficiencies in the prior art.
The present invention is achieved in that high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, by mass fractionCalculate, comprise 75-95 part PLA, 15-25 part flexibilizer, 40-50 part fiber, 6-10 part compatilizer, 0.8-1.2 part chain extensionAgent, 0.8-1.2 part antioxidant, 15-25 part halogen-free flame retardants, 3-5 portions of synergist, 12-17 part carbon forming agent and 1-3 part are disperseedAgent.
Described flexibilizer is TPU or PBS.
Described fiber is ramee, tossa, flax fiber, hemp, glass fibre, kenaf, swordAny combination of one or more in flaxen fiber or bamboo fibre.
Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-GMA.
Described halogen-free flame retardants is melamine polyphosphate.
Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite, and described carbon forming agent is pentaerythrite, and described dispersant isPentaerythrite stearate.
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, get respectively 35-45 part PLA,8-12 part flexibilizer and 3-5 part compatilizer drying for standby, by above-mentioned dried PLA, compatilizer and flexibilizer and 0.4-0.6 part of chain extender and 0.4-0.6 part antioxidant mix, and then carry out blending extrusion, and processing temperature is 150-200 DEG C, willThe melt of extruding floods 40-50 part fiber by dipping runner, obtains fiber impregnation material strip; Get again the poly-breast of 40-50 partAcid, 7-13 part flexibilizer, 15-25 part halogen-free flame retardants, 3-5 portions of synergist, 12-17 part carbon forming agent, 1-3 part dispersant and 3-5Part compatilizer is dried, and above-mentioned dried material and 0.4-0.6 part chain extender and 0.4-0.6 part antioxidant are mixedClose, mixing of materials added in extruder after evenly, in the time extruding, the mixed material of melting is coated in fiber impregnation material strip,Cooling rear pelletizing becomes the particle of 8～12mm, obtains high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material.
Described baking temperature is 60-80 DEG C, and be 5-8h drying time.
In the present invention, flood runner and the mixed material of melting is coated on to establishing of adopting in fiber impregnation material stripStandby, disclosed device in the application for a patent for invention that the application number that is applicant's earlier application is " 201110453139.8 ",Realize the device that continuous roving glass fiber is extruded.
Owing to having adopted technique scheme, compared with prior art, the present invention adopts PLA as matrix resin, addsEnter the processing temperature that chain extender improves PLA, random common with the ternary of styrene-acrylonitrile-GMAPolymers is as compatilizer, and this compatilizer not only strengthens the adhesion between matrix resin and fiber, but also has improved matrix treeCompatibility between fat and flexibilizer, and adopt one-step method to prepare halogen-free flameproof long fiber reinforcement PLC composite, be about to continuouslyFiber complete the dipping of matrix resin to fiber by impregnation mold, then in coating mould, complete with halogen containing flame-retardantMatrix melt at dipping coated in material strip, then carry out cooling, traction, be finally cut into Len req by pelleter, withExisting two-step method is compared, and such mode not only technique is simple, and the product mechanical property excellence making, and has goodFlame retardant effect. The present invention is simple, material source is extensive, with low cost, result of use is good.
Brief description of the drawings
Accompanying drawing 1 is flow chart of the present invention.
Detailed description of the invention
Embodiments of the invention 1: high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, according to the mass fractionCalculate, comprise 86 parts of PLAs, 20 parts of flexibilizer, 45 parts of fibers, 8 parts of compatilizers, 1 part of chain extender, 1 part of antioxidant, 20 parts of HalogensFire retardant, 4 portions of synergist, 15 parts of carbon forming agents and 2 parts of dispersants; Described flexibilizer is TPU; Described fiber is glass fibersDimension; Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-GMA; Described nothingHalogen fire retardant is melamine polyphosphate; Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite; Described carbon forming agent is season pentaTetrol; Described dispersant is pentaerythrite stearate;
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, gets respectively 40 parts of PLAs, 10Part flexibilizer and 4 parts of compatilizer drying for standby, by above-mentioned dried PLA, compatilizer and flexibilizer and 0.5 part of chain extenderAnd 0.5 part of antioxidant mixes, then carry out blending extrusion, processing temperature is 175 DEG C, and the melt of extruding is flowed by dippingRoad floods 45 parts of fibers, obtains fiber impregnation material strip; Get again 46 parts of PLAs, 10 parts of flexibilizer, 20 parts of halogen-free flameproofsAgent, 4 portions of synergist, 15 parts of carbon forming agents, 2 parts of dispersants and 4 parts of compatilizers are dried, by above-mentioned dried material and 0.5Part chain extender and 0.5 part of antioxidant mix, and mixing of materials are added in extruder to mixed by melting in the time extruding after evenlyCompound material is coated in fiber impregnation material strip, and cooling rear pelletizing becomes the particle of 8～12mm, obtains high-performance halogen-free flame retardantLong fiber reinforcement lactic acid composite material.
Described baking temperature is 60-80 DEG C, and be 5-8h drying time.
Embodiments of the invention 2: high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, according to the mass fractionCalculate, comprise 75 parts of PLAs, 25 parts of flexibilizer, 50 parts of fibers, 10 parts of compatilizers, 1.2 parts of chain extenders, 1.2 parts of antioxidant, 15 partsHalogen-free flame retardants, 5 portions of synergist, 12 parts of carbon forming agents and 1 part of dispersant; Described flexibilizer is TPU; Described fiber is glassGlass fiber; Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-GMA; DescribedHalogen-free flame retardants be melamine polyphosphate; Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite; Described carbon forming agent isPentaerythrite; Described dispersant is pentaerythrite stearate;
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, gets respectively 35 parts of PLAs, 12Part flexibilizer and 5 parts of compatilizer drying for standby, by above-mentioned dried PLA, compatilizer and flexibilizer and 0.6 part of chain extenderAnd 0.6 part of antioxidant mixes, then carry out blending extrusion, processing temperature is 150 DEG C, and the melt of extruding is flowed by dippingRoad floods 50 parts of fibers, obtains fiber impregnation material strip; Get again 40 parts of PLAs, 13 parts of flexibilizer, 15 parts of halogen-free flameproofsAgent, 5 portions of synergist, 12 parts of carbon forming agents, 1 part of dispersant and 5 parts of compatilizers are dried, by above-mentioned dried material and 0.6Part chain extender and 0.6 part of antioxidant mix, and mixing of materials are added in extruder to mixed by melting in the time extruding after evenlyCompound material is coated in fiber impregnation material strip, and cooling rear pelletizing becomes the particle of 8～12mm, obtains high-performance halogen-free flame retardantLong fiber reinforcement lactic acid composite material.
Described baking temperature is 60-80 DEG C, and be 5-8h drying time.
Embodiments of the invention 3: high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, according to the mass fractionCalculate, comprise 95 parts of PLAs, 15 parts of flexibilizer, 40 parts of fibers, 6 parts of compatilizers, 0.8 part of chain extender, 0.8 part of antioxidant, 25 partsHalogen-free flame retardants, 3 portions of synergist, 17 parts of carbon forming agents and 3 parts of dispersants; Described flexibilizer is PBS; Described fiber is oceanFlaxen fiber; Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-GMA; DescribedHalogen-free flame retardants be melamine polyphosphate; Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite; Described carbon forming agent isPentaerythrite; Described dispersant is pentaerythrite stearate;
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, gets respectively 45 parts of PLAs, 8 partsFlexibilizer and 3 parts of compatilizer drying for standby, by above-mentioned dried PLA, compatilizer and flexibilizer and 0.4 part of chain extender and0.4 part of antioxidant mixes, and then carries out blending extrusion, and processing temperature is 200 DEG C, and the melt of extruding is passed through to dipping runner40 parts of fibers are flooded, obtain fiber impregnation material strip; Get again 50 parts of PLAs, 7 parts of flexibilizer, 25 parts of halogen-free flame retardants, 3Portions of synergist, 17 parts of carbon forming agents, 3 parts of dispersants and 3 parts of compatilizers are dried, by above-mentioned dried material and 0.4 part of expansionChain agent and 0.4 part of antioxidant mix, mixing of materials is added in extruder after evenly, in the time extruding by the mixture of meltingMaterial is coated in fiber impregnation material strip, and cooling rear pelletizing becomes the particle of 8～12mm, obtains high-performance halogen-free flame retardant long fineDimension strengthens lactic acid composite material.
Described baking temperature is 60-80 DEG C, and be 5-8h drying time.
In above-described embodiment, the trade mark of PLA is 4042D; The trade mark of flexibilizer is WB271; The trade mark of glass fibre isER4301H; The trade mark of compatilizer is SAG-008; The trade mark of chain extender is ADR4380; The trade mark of antioxidant is AS4500.
Main performance test: the product of producing is made standard testing batten according to standard, carries out every test, its performanceTest result is as shown in table 1.
Can learn according to table 1, adopt the preparation-obtained sample of technical scheme of the present invention, with conventional PLA short fiberDimension material is compared, and its performance improves greatly, and owing to adding chain extender and compatilizer, has therefore solved PLA poor heat stability. InstitutePrepare Flame Retardancy and can reach V0 rank.
Claims (2)
1. a preparation method for high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, is characterized in that: get respectively35-45 part PLA, 8-12 part flexibilizer and 3-5 part compatilizer drying for standby, by above-mentioned dried PLA, compatilizer andFlexibilizer mixes with 0.4-0.6 part chain extender and 0.4-0.6 part antioxidant, then carries out blending extrusion, and processing temperature is150-200 DEG C, floods by dipping runner the melt of extruding to 40-50 part fiber, obtain fiber impregnation material strip; Get again40-50 part PLA, 7-13 part flexibilizer, 15-25 part halogen-free flame retardants, 3-5 portions of synergist, 12-17 part carbon forming agent, 1-3 partDispersant and 3-5 part compatilizer are dried, and above-mentioned dried material and 0.4-0.6 part chain extender and 0.4-0.6 part are resistedOxygen agent mixes, and mixing of materials is added in extruder after evenly, in the time extruding, the mixed material of melting is coated on to fiberIn dipping material strip, cooling rear pelletizing becomes the particle of 8～12mm, obtains high-performance halogen-free flame retardant long fiber reinforcement PLAComposite.
2. the preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material according to claim 1, itsBe characterised in that: described baking temperature is 60-80 DEG C, be 5-8h drying time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105176032A (en) * | 2015-08-08 | 2015-12-23 | 同济大学 | Halogen-free flame retardant polylactic acid nanocomposite and preparation method thereof |
| CN106280341B (en) * | 2016-08-31 | 2018-12-14 | 江林（贵州）高科发展股份有限公司 | Halogen-free flameproof long glass fiber reinforced lactic acid composite material and preparation method thereof |
| CN106147156B (en) * | 2016-08-31 | 2019-01-22 | 江林（贵州）高科发展股份有限公司 | Halogen-free flame-retardant long fiber glass reinforced PBT composite material and preparation method |
| CN106221096A (en) * | 2016-08-31 | 2016-12-14 | 贵州国塑科技管业有限责任公司 | Halogen-free flameproof long glass fiber reinforced composite material of polymethyl methacrylate and preparation method thereof |
| CN106398137B (en) * | 2016-09-04 | 2019-01-29 | 康命源（安徽）塑料科技发展股份有限公司 | A kind of halogen-free flameproof long glass fiber reinforced PET composite material and preparation method thereof |
| CN106633710A (en) * | 2016-09-30 | 2017-05-10 | 刘振 | Single-step-prepared halogen-free flame-resistant long glass fiber reinforced PLA composite material and preparation method thereof |
| CN110856690A (en) * | 2018-08-22 | 2020-03-03 | 深圳善康医疗健康产业有限公司 | Implant diolame and drying device |
| CN111087777A (en) * | 2020-02-10 | 2020-05-01 | 贵州富斯特化工材料科技有限公司 | Efficient halogen-free flame-retardant PLA composite material and preparation method thereof |
| CN111793338B (en) * | 2020-08-17 | 2023-06-23 | 郑州大学 | Compound halogen-free flame-retardant plant fiber reinforced polylactic acid material and preparation method thereof |
| CN114905808B (en) * | 2022-04-22 | 2023-04-07 | 醴陵千汇实业有限公司 | Paper-surface gypsum board and preparation method thereof |
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| CN101792602A (en) * | 2010-03-11 | 2010-08-04 | 四川大学 | Halogen-free expansible flame-retardant thermoplastic resin composition |
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