CN104371291A - High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof - Google Patents
High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN104371291A CN104371291A CN201410706220.6A CN201410706220A CN104371291A CN 104371291 A CN104371291 A CN 104371291A CN 201410706220 A CN201410706220 A CN 201410706220A CN 104371291 A CN104371291 A CN 104371291A
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- 239000000835 fiber Substances 0.000 title claims abstract description 73
- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000004626 polylactic acid Substances 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- -1 poly(lactic acid) Polymers 0.000 claims description 56
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 48
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 230000002787 reinforcement Effects 0.000 claims description 27
- 235000014655 lactic acid Nutrition 0.000 claims description 24
- 239000004310 lactic acid Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 239000003112 inhibitor Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- WSEFPKKOUNRCAJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;octadecanoic acid Chemical group OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O WSEFPKKOUNRCAJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229920000388 Polyphosphate Polymers 0.000 claims description 5
- 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 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 229940059574 pentaerithrityl Drugs 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 239000001205 polyphosphate Substances 0.000 claims description 5
- 235000011176 polyphosphates Nutrition 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 240000000797 Hibiscus cannabinus Species 0.000 claims description 3
- 244000198134 Agave sisalana Species 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 240000000491 Corchorus aestuans Species 0.000 claims description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 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
- 238000002791 soaking Methods 0.000 abstract 4
- 229920005604 random copolymer Polymers 0.000 abstract 1
- 229920001431 Long-fiber-reinforced thermoplastic Polymers 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and a preparation method thereof. The preparation method includes that polylactic acid is adopted as matrix resin, processing temperature of the polylactic acid is increased by adding chain extender, a ternary random copolymer of styrene-acrylonitrile-glycidyl methacrylate is taken as a compatilizer, the compatilizer can improve bonding force between the matrix resin and fibers, and compatibility between the matrix resin and flexibilizer is improved; a one-step method is adopted to prepare the high-performance halogen-free flame-retardant long fiber reinforced (PLC) polylactic acid composite material, in other words, soaking of continuous fibers by the matrix resin is completed through a soaking die, coating of matrix fused mass with halogen-containing flame retardant on a soaking material strip is completed in a coating die, cooling and traction are performed, and the soaking material strip is cut into needed length through a granulator. Compared with an existing two-step method, the preparation method is simple in process, and the high-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material is excellent in mechanical performance and good in 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 lactic acid composite material and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) is a kind of biodegradable polymer, due to poly(lactic acid) abundance, cheap, and has good mechanical property, and increasing experts and scholars are very interested in the research and apply of poly(lactic acid).But poly-lactic acid material poor heat stability, easy firing, and during burning, molten drop phenomenon is serious, restriction poly(lactic acid) has the application in flame-retardancy requirements field in electronic product, automotive upholstery, electron electric power equipment, traffic etc., therefore need to carry out flame-retardant modified to it; Society, the awareness of safety of people improves, and the environmental protection concept of country is constantly strengthened, and therefore, using halogen-free flame retardants to prepare fire retardant material is very important problem.Because the requirement of people to quality product is more and more higher, the performance of common short fiber reinforced PLA material can not meet the demands, long fiber reinforcement PLA has the excellent performance such as high strength, high-modulus, high thermal stability and can meet people to high-performance and pursue, when preparing fire-retardant long fiber reinforced thermoplastic composites, traditional method is that two-step approach (that is: prepares fire-retardant master granule and long fiber reinforcement master batch first respectively, then mix and carry out injection moulding), and single stage method prepares fire-retardant long fiber reinforced thermoplastic composites technique simply, 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 method thereof is provided, it solves poly(lactic acid) poor heat stability, be easy to the problems such as burning, and improve the mechanical property of product, environment-friendly type is good, and 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, calculate according to the mass fraction, comprise 75-95 part poly(lactic acid), 15-25 part toughner, 40-50 part fiber, 6-10 part compatilizer, 0.8-1.2 part chainextender, 0.8-1.2 part oxidation inhibitor, 15-25 part halogen-free flame retardants, 3-5 portions of synergist, 12-17 part char-forming agent and 1-3 part dispersion agent.
Described toughner is TPU or PBS.
Described fiber is the arbitrary combination of one or more in ramee, jute fibre, flax fiber, hemp fibre, glass fibre, kenaf, sisal fibers or bamboo fibers.
Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-glycidyl methacrylate.
Described halogen-free flame retardants is melamine polyphosphate.
Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite, and described char-forming agent is tetramethylolmethane, and described dispersion agent is tetramethylolmethane stearate.
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, get 35-45 part poly(lactic acid), 8-12 part toughner and 3-5 part compatilizer drying for standby respectively, above-mentioned dried poly(lactic acid), compatilizer and toughner are mixed with 0.4-0.6 part chainextender and 0.4-0.6 part oxidation inhibitor, then blending extrusion is carried out, processing temperature is 150-200 DEG C, the melt extruded is flooded 40-50 part fiber by dipping runner, obtains fiber impregnation material strip; Get 40-50 part poly(lactic acid), 7-13 part toughner, 15-25 part halogen-free flame retardants, 3-5 portions of synergist, 12-17 part char-forming agent, 1-3 part dispersion agent and 3-5 part compatilizer again and carry out drying, above-mentioned dried material is mixed with 0.4-0.6 part chainextender and 0.4-0.6 part oxidation inhibitor, add in forcing machine after mixing of materials is even, when extruding, the mixture of melting is coated in fiber impregnation material strip, after cooling, pelletizing becomes the particle of 8 ~ 12 mm, obtains high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material.
Described drying temperature is 60-80 DEG C, and time of drying is 5-8h.
In the present invention, flood runner and the mixture of melting be coated on the equipment that fiber impregnation material strip adopts, be the application number of applicant's earlier application for device disclosed in the application for a patent for invention of " 201110453139.8 ", namely realize the device that continuous roving glass fiber is extruded.
Owing to have employed technique scheme, compared with prior art, the present invention adopts poly(lactic acid) as matrix resin, add the processing temperature that chainextender improves poly(lactic acid), using the ternary atactic copolymer of styrene-acrylonitrile-glycidyl methacrylate as compatilizer, this compatilizer not only strengthens the bonding force between matrix resin and fiber, but also the consistency that improve between matrix resin and toughner, and adopt single stage method to prepare halogen-free flameproof long fiber reinforcement PLC matrix material, the dipping of matrix resin to fiber is completed by impregnation mold by continuous print fiber, then complete in coating mould with halogen containing flame-retardant matrix melt dipping material strip on coated, then cool, traction, desired length is cut into finally by dicing machine, compared with existing two-step approach, such mode not only technique is simple, and obtained product excellent in mechanical performance, and there is good flame retardant effect.The present invention is simple, material source is extensive, with low cost, result of use is good.
Accompanying drawing explanation
Accompanying drawing 1 is schema of the present invention.
Embodiment
Embodiments of the invention 1: high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, calculate according to the mass fraction, comprise 86 parts of poly(lactic acid), 20 parts of toughner, 45 parts of fibers, 8 parts of compatilizers, 1 part of chainextender, 1 part of oxidation inhibitor, 20 parts of halogen-free flame retardantss, 4 portions of synergist, 15 parts of char-forming agents and 2 parts of dispersion agents; Described toughner is TPU; Described fiber is glass fibre; Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-glycidyl methacrylate; Described halogen-free flame retardants is melamine polyphosphate; Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite; Described char-forming agent is tetramethylolmethane; Described dispersion agent is tetramethylolmethane stearate;
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, get 40 parts of poly(lactic acid), 10 parts of toughner and 4 parts of compatilizer drying for standby respectively, above-mentioned dried poly(lactic acid), compatilizer and toughner are mixed with 0.5 part of chainextender and 0.5 part of oxidation inhibitor, then blending extrusion is carried out, processing temperature is 175 DEG C, the melt extruded is flooded 45 parts of fibers by dipping runner, obtains fiber impregnation material strip; Get 46 parts of poly(lactic acid) again, 10 parts of toughner, 20 parts of halogen-free flame retardantss, 4 portions of synergist, 15 parts of char-forming agents, 2 parts of dispersion agents and 4 parts of compatilizers carry out drying, above-mentioned dried material is mixed with 0.5 part of chainextender and 0.5 part of oxidation inhibitor, add in forcing machine after mixing of materials is even, when extruding, the mixture of melting is coated in fiber impregnation material strip, after cooling, pelletizing becomes the particle of 8 ~ 12 mm, obtains high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material.
Described drying temperature is 60-80 DEG C, and time of drying is 5-8h.
Embodiments of the invention 2: high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, calculate according to the mass fraction, comprise 75 parts of poly(lactic acid), 25 parts of toughner, 50 parts of fibers, 10 parts of compatilizers, 1.2 parts of chainextenders, 1.2 parts of oxidation inhibitor, 15 parts of halogen-free flame retardantss, 5 portions of synergist, 12 parts of char-forming agents and 1 part of dispersion agent; Described toughner is TPU; Described fiber is glass fibre; Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-glycidyl methacrylate; Described halogen-free flame retardants is melamine polyphosphate; Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite; Described char-forming agent is tetramethylolmethane; Described dispersion agent is tetramethylolmethane stearate;
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, get 35 parts of poly(lactic acid), 12 parts of toughner and 5 parts of compatilizer drying for standby respectively, above-mentioned dried poly(lactic acid), compatilizer and toughner are mixed with 0.6 part of chainextender and 0.6 part of oxidation inhibitor, then blending extrusion is carried out, processing temperature is 150 DEG C, the melt extruded is flooded 50 parts of fibers by dipping runner, obtains fiber impregnation material strip; Get 40 parts of poly(lactic acid) again, 13 parts of toughner, 15 parts of halogen-free flame retardantss, 5 portions of synergist, 12 parts of char-forming agents, 1 part of dispersion agent and 5 parts of compatilizers carry out drying, above-mentioned dried material is mixed with 0.6 part of chainextender and 0.6 part of oxidation inhibitor, add in forcing machine after mixing of materials is even, when extruding, the mixture of melting is coated in fiber impregnation material strip, after cooling, pelletizing becomes the particle of 8 ~ 12 mm, obtains high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material.
Described drying temperature is 60-80 DEG C, and time of drying is 5-8h.
Embodiments of the invention 3: high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, calculate according to the mass fraction, comprise 95 parts of poly(lactic acid), 15 parts of toughner, 40 parts of fibers, 6 parts of compatilizers, 0.8 part of chainextender, 0.8 part of oxidation inhibitor, 25 parts of halogen-free flame retardantss, 3 portions of synergist, 17 parts of char-forming agents and 3 parts of dispersion agents; Described toughner is PBS; Described fiber is kenaf; Described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-glycidyl methacrylate; Described halogen-free flame retardants is melamine polyphosphate; Described synergist is quaternary alkylphosphonium salt intercalated montmorillonite; Described char-forming agent is tetramethylolmethane; Described dispersion agent is tetramethylolmethane stearate;
The preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, get 45 parts of poly(lactic acid), 8 parts of toughner and 3 parts of compatilizer drying for standby respectively, above-mentioned dried poly(lactic acid), compatilizer and toughner are mixed with 0.4 part of chainextender and 0.4 part of oxidation inhibitor, then blending extrusion is carried out, processing temperature is 200 DEG C, the melt extruded is flooded 40 parts of fibers by dipping runner, obtains fiber impregnation material strip; Get 50 parts of poly(lactic acid) again, 7 parts of toughner, 25 parts of halogen-free flame retardantss, 3 portions of synergist, 17 parts of char-forming agents, 3 parts of dispersion agents and 3 parts of compatilizers carry out drying, above-mentioned dried material is mixed with 0.4 part of chainextender and 0.4 part of oxidation inhibitor, add in forcing machine after mixing of materials is even, when extruding, the mixture of melting is coated in fiber impregnation material strip, after cooling, pelletizing becomes the particle of 8 ~ 12 mm, obtains high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material.
Described drying temperature is 60-80 DEG C, and time of drying is 5-8h.
In above-described embodiment, the trade mark of poly(lactic acid) is 4042D; The trade mark of toughner is WB271; The trade mark of glass fibre is ER4301H; The trade mark of compatilizer is SAG-008; The trade mark of chainextender is ADR4380; The trade mark of oxidation inhibitor is AS4500.
Salient features is tested: the product produced makes standard testing batten according to standard, carries out every test, and its performance test results is as shown in table 1.
Can learn according to table 1, adopt the preparation-obtained sample of technical scheme of the present invention, compared with the PLA short fiber material of routine, its performance improves greatly, and owing to adding chainextender and compatilizer, therefore solves PLA poor heat stability.Prepared by obtain Flame Retardancy can reach V0 rank.
Claims (8)
1. a high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material, it is characterized in that: calculate according to the mass fraction, comprise 75-95 part poly(lactic acid), 15-25 part toughner, 40-50 part fiber, 6-10 part compatilizer, 0.8-1.2 part chainextender, 0.8-1.2 part oxidation inhibitor, 15-25 part halogen-free flame retardants, 3-5 portions of synergist, 12-17 part char-forming agent and 1-3 part dispersion agent.
2. high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material according to claim 1, is characterized in that: described toughner is TPU or PBS.
3. high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material according to claim 1, is characterized in that: described fiber is the arbitrary combination of one or more in ramee, jute fibre, flax fiber, hemp fibre, glass fibre, kenaf, sisal fibers or bamboo fibers.
4. high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material according to claim 1, is characterized in that: described compatilizer is the ternary atactic copolymer of styrene-acrylonitrile-glycidyl methacrylate.
5. high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material according to claim 1, is characterized in that: described halogen-free flame retardants is melamine polyphosphate.
6. high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material according to claim 1, it is characterized in that: described synergist is quaternary alkylphosphonium salt intercalated montmorillonite, described char-forming agent is tetramethylolmethane, and described dispersion agent is tetramethylolmethane stearate.
7. the preparation method of a high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material as claimed in claim 1, it is characterized in that: get 35-45 part poly(lactic acid), 8-12 part toughner and 3-5 part compatilizer drying for standby respectively, above-mentioned dried poly(lactic acid), compatilizer and toughner are mixed with 0.4-0.6 part chainextender and 0.4-0.6 part oxidation inhibitor, then blending extrusion is carried out, processing temperature is 150-200 DEG C, the melt extruded is flooded 40-50 part fiber by dipping runner, obtains fiber impregnation material strip; Get 40-50 part poly(lactic acid), 7-13 part toughner, 15-25 part halogen-free flame retardants, 3-5 portions of synergist, 12-17 part char-forming agent, 1-3 part dispersion agent and 3-5 part compatilizer again and carry out drying, above-mentioned dried material is mixed with 0.4-0.6 part chainextender and 0.4-0.6 part oxidation inhibitor, add in forcing machine after mixing of materials is even, when extruding, the mixture of melting is coated in fiber impregnation material strip, after cooling, pelletizing becomes the particle of 8 ~ 12 mm, obtains high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material.
8. the preparation method of high-performance halogen-free flame retardant long fiber reinforcement lactic acid composite material according to claim 7, it is characterized in that: described drying temperature is 60-80 DEG C, time of drying is 5-8h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176032A (en) * | 2015-08-08 | 2015-12-23 | 同济大学 | Halogen-free flame retardant polylactic acid nanocomposite and preparation method thereof |
| CN106147156A (en) * | 2016-08-31 | 2016-11-23 | 江林（贵州）高科发展股份有限公司 | Halogen-free flame-retardant long fiber glass reinforced PBT composite and preparation method thereof |
| 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 |
| CN106280341A (en) * | 2016-08-31 | 2017-01-04 | 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 |
| CN106398137A (en) * | 2016-09-04 | 2017-02-15 | 康命源（安徽）塑料科技发展股份有限公司 | Halogen-free inflaming-retarding long glass fiber reinforced PET (Polyethylene Terephthalate) 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 |
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| 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 |
| CN111793338A (en) * | 2020-08-17 | 2020-10-20 | 郑州大学 | Compound halogen-free flame-retardant plant fiber reinforced polylactic acid material and preparation method thereof |
| CN114905808A (en) * | 2022-04-22 | 2022-08-16 | 醴陵千汇实业有限公司 | Paper-surface gypsum board and preparation method thereof |
| CN117229589A (en) * | 2023-11-10 | 2023-12-15 | 云南邦辉新材料科技有限公司 | Impact-resistant polyethylene composite material and preparation process 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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