CN105694405A - Halogen-free flame retardant polylactic acid toughening modification composite material and preparing method thereof - Google Patents
Halogen-free flame retardant polylactic acid toughening modification composite material and preparing method thereof Download PDFInfo
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- CN105694405A CN105694405A CN201610272620.XA CN201610272620A CN105694405A CN 105694405 A CN105694405 A CN 105694405A CN 201610272620 A CN201610272620 A CN 201610272620A CN 105694405 A CN105694405 A CN 105694405A
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 66
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 7
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title abstract description 6
- 238000012986 modification Methods 0.000 title abstract 4
- 230000004048 modification Effects 0.000 title abstract 4
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 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 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 229920000704 biodegradable plastic Polymers 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- -1 Methylethyl phosphinic acid aluminum Chemical compound 0.000 claims description 26
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 229920001610 polycaprolactone Polymers 0.000 claims description 12
- 239000004632 polycaprolactone Substances 0.000 claims description 12
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 229920001897 terpolymer Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000006735 epoxidation reaction Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- JPJFHIRXDWEERX-UHFFFAOYSA-N [La].[PH2](=O)O Chemical compound [La].[PH2](=O)O JPJFHIRXDWEERX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 4
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 4
- 229910001376 inorganic hypophosphite Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 4
- DBKFYOISCCPYTQ-UHFFFAOYSA-K C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O Chemical compound C1(=CC=CC=C1)P([O-])=O.[Al+3].C1(=CC=CC=C1)P([O-])=O.C1(=CC=CC=C1)P([O-])=O DBKFYOISCCPYTQ-UHFFFAOYSA-K 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 230000000979 retarding effect Effects 0.000 abstract description 7
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 2
- 229920013730 reactive polymer Polymers 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000005452 bending Methods 0.000 description 24
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 22
- 238000002485 combustion reaction Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000004310 lactic acid Substances 0.000 description 11
- 235000014655 lactic acid Nutrition 0.000 description 11
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis 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
- 229920005601 base polymer Polymers 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a halogen-free flame retardant polylactic acid toughening modification composite material.The composite material is mainly composed of 50.0-80 wt% of polylactic acid, 5.0-20.0 wt% of biodegradable plastic, 10.0-20.0 wt% of phosphorus based flame retardant, 0.5-20.0 wt% of reactive compatibilizer and 0.2-1.0 wt% of antioxidant.Hypophosphite and phosphonate with different ratios are taken as the flame retardant to achieve flame retarding of polylactic acid, polylactic acid is toughened through a bio-based elastomer, a reactive polymer is added to serve as the reactive compatibilizer, and the halogen-free flame retardant biodegradable polylactic acid toughening modification composite material is prepared through melting reaction and blending.The composite material has excellent flame retarding property, elongation at break and toughness.The biodegradable halogen-free flame retardant polylactic acid toughening modification composite material is efficient and low in toxicity and is an environment-friendly biodegradable flame retardant plastic.The composite material has excellent flame retarding property and mechanical property and can be used in the fields such as packaging, film, textile and automobiles.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of environmentally friendly halogen-free flame-proof polylactic acid toughening modifying composite and preparation method thereof。
Background technology
Owing to macromolecular material is cheap, the excellent properties such as light weight and scale batch production; and widely use in all trades and professions and daily life; but; a large amount of worldwide public hazards using produced " white pollution " to become harm social environment of petroleum base macromolecular material, seriously hinder the sustainable development of social economy and environment。What bio-based degradable poly condensation material can solve petroleum base polymer is difficult to recovery problem。In the last few years, Biodegradable material is competitively developed in countries in the world, the biological plastics market in the whole world quickly increases, biodegradable plastic market estimates that the output value will increase to 3,400,000,000 dollars of the year two thousand twenty from 2,000,000,000 dollars of 2015, average annual growth rate is up to 8%-10%, by 2025, Asia will become the main force in biological plastics market。Domestic also greatly developing Biodegradable material, Jilin Province takes the lead in forcing to use biodegradable plastic, disabling non-degradable plastic bag and tableware。
At present, biodegradable polymer mainly includes polylactic acid (PLA), poly butylene succinate (PBS) and copolymer, polycaprolactone (PCL), PHA (PHA) etc., and wherein polylactic acid causes pay close attention to widely with its biodegradability, abundant available resource and superior mechanical performance。And the raw material of polylactic acid can be obtained on a large scale by cereal crops such as fermented maizes, is independent of petroleum resources, the sustainable development of the mankind is had great importance by this, it is believed that be the recyclable organism plastics of most competitiveness。
Poly-adipic acid/butylene terephthalate (PBAT, Poly (butyleneadipate-co-terephalate)) it is the copolymer of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, with the characteristic of poly adipate succinic acid ester (PBA) and polybutylene terephthalate (PBT) (PBT), not only there is excellent biological degradability。Existing good thermostability and impact property, it may have good ductility and elongation at break, be one of biodegradation material very active in the research of current biological plastics。
From disclosed patent both at home and abroad, polylactic acid is mainly used in medical field, relates generally to medicine microsphere carrier, antiadhesion barrier, biological duct, orthopaedics fixture, bone surgery device, medicine composite macromolecular support, artificial bone etc.。Biodegradable plastic is also applied to the fields such as packaging, fiber, agricultural, injection moulding, wherein being most widely used at packaging industry。
Polylactic acid has hardness height, optical property, air barrier, biocompatibility are excellent, the characteristic such as surface smoothness is good and typographical display is effective, and its mechanical strength is better than the performance of the general-purpose plastics such as polyethylene (PE), polypropylene (PP), polystyrene (PS), suitable with the performance of the engineering plastics such as ABS。Therefore, polylactic acid is expected to become general and engineering plastics substitute products, is applied to electronics industry, construction material, textile material。These fields require that material has good impact flexibility, requires have anti-flammability on the other hand on the one hand, but owing to polylactic acid impact property is poor, and flammable, the therefore restriction polylactic acid application in fields such as electronics, building, weavings。Therefore the improvement of the toughness reinforcing of polylactic acid and fire resistance is extremely urgent。
At present, conventional flame-retardant modified main of polymer adopts the method adding fire retardant, and halogen containing flame-retardant addition is few, and flame retarding efficiency is high, but the toxic gas such as two English produced in combustion due to halogen flame, environment is caused secondary pollution。Therefore, the halogen-free flameproof of polymer modifiies is the main flow of market development。Halogen-free flame retardants mainly includes inorganic hydroxide, phosphorus flame retardant, nitrogenated flame retardant, Intumescent Retardant System。For the inorganic filler fire retardant such as magnesium hydroxide, aluminium hydroxide, addition can be only achieved flame-retardancy requirements up to more than 50%, and the Effect on Mechanical Properties of material is bigger。And conventional Intumescent Retardant System, phosphorus system and nitrogenated flame retardant to also tend to there is addition many, mechanics and physical property impact on polylactic acid are bigger。Metal phosphinate and alkylphosphinic acid metal salts are as the environmental protection halogen-free flame retardants of a new generation, owing in secondary phosphine/phosphate, phosphorus content is significantly high, have fire resistance is good, flame retarding efficiency is high, heat-resist advantage and are subject to the favor of domestic and international flame retardant area。Metal phosphinate is mainly with hypo-aluminum orthophosphate, magnesium hypophosphite, calcium hypophosphite, hypophosphorous acid lanthanum etc. for representative；Therefore, it is flame-retardant modified that modified time phosphine/phosphate that one aspect of the present invention adopts flame retarding efficiency high carries out polylactic acid, needs on the other hand, to polylactic acid toughening modifying, to improve the combination property of flame-retardant polylactic acid material。
Summary of the invention
It is an object of the invention to the shortcoming that the impact property for Biodegradable material polylactic acid is poor, inflammable, a kind of biodegradable halogen-free flame-proof polylactic acid toughening modifying composite is provided, use the secondary phosphine/phosphate of high fire-retardance efficiency as fire retardant on the one hand, the few poison of low cigarette, is a class environment friendly phosphorus flame retardant；Adopt degradable biological plastics such as poly-adipic acid/butylene terephthalate and the polycaprolactone of good toughness that polylactic acid is carried out toughening modifying on the other hand, and adopt the modifying agent of response type as bulking agent, and then promote the toughness of biodegradation halogen-free flame-proof polylactic acid modified composite material。
A kind of halogen-free flame-proof polylactic acid toughening modifying composite provided by the invention, this material is mainly made up of following component:
Above component is all weight percentage。
It is preferably in a proportion of:
Above component is all weight percentage。
Further, described phosphine/phosphate flame retardants includes one or more in inorganic hypophosphites, organic secondary phosphine acid salt。Further, described inorganic hypophosphites is one or more in hypo-aluminum orthophosphate, calcium hypophosphite, hypophosphorous acid lanthanum；Described organic secondary phosphine acid salt is one or more in aluminum diethylphosphinate, Methylethyl phosphinic acid aluminum, methylphenylphosphinic acid aluminum, aluminum phenylphosphinate。
Further, described biodegradable plastic modifying agent is one or more in polycaprolactone, polyvinyl alcohol, poly-adipic acid/butylene terephthalate (PBAT) copolymer。
Further, described reactive compatibilizer is one or more in butyl acrylate-methyl ester-glycidyl methacrylate, epoxidation EP rubbers, ethylene-acrylate-glycidyl methacrylate terpolymer。
Further, described antioxidant is one or both in antioxidant 1010, irgasfos 168。
Further, the preparation method of a kind of halogen-free flame-proof polylactic acid toughening modifying composite provided by the invention is the method adopting melt blending reactive extrursion, and concrete technical process and blending condition are as follows:
(1) it is by powder and pellet mix homogeneously, reach best mixed effect, dry secondary phosphine/phosphate flame retardants, biodegradable plastic modifying agent, reactive compatibilizer and antioxidant are formed flame-retardant mixture by proportioning mix homogeneously in mixer；
(2) polylactic acid and flame-retardant mixture being added melting mixing in banbury, the processing temperature of banbury is at 170-200 DEG C；The rotating speed of banbury is at 50-150 rev/min, and mixing time is at 5-15min；Or the extrusion that is fed in double screw extruder by polylactic acid and flame-retardant mixture melt blending, temperature range 170-210 DEG C of each section of double screw extruder, rotating speed, at 40-100 rev/min, melt extrudes rear cooling granulation。
The method have the benefit that: adopt the secondary phosphor/phosphine hydrochlorate that flame retarding efficiency is high that polylactic acid is fire-retardant, adopt biodegradable plastic and reactive compatibilizer that flame-retardant polylactic acid material coordination plasticizing is modifiied simultaneously, obtain the biodegradable halogen-free flame-proof polylactic acid toughening modifying composite of a kind of good combination property。The halogen-free flameproof Biodegradable polylactic acids toughening modifying composite of the present invention is not showed only as the fire resistance of excellence, also has elongation at break and the toughness of excellence。Notch impact strength brings up to 2-4 times of pure polyacids, and elongation at break improves 7.3-27.3 times。This halogen-free flameproof Biodegradable polylactic acids toughening modifying composite has important using value in fields such as electronic apparatus, automobile, packaging, thin film, weavings。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details。
Embodiment 1
By the hypo-aluminum orthophosphate of 15.0wt%, the polycaprolactone of 10.0wt%, 0.5wt% butyl acrylate-methyl ester-glycidyl methacrylate, 0.5wt% antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (1010) puts into mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 74.0wt%, add in double screw extruder, melt extrude at 180-210 DEG C, rotating speed 100 revs/min, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 28.5, and vertical combustion grade is V-0。Flame-proof polylactic acid toughening modifying composite notch impact strength is 7.0kJ/m2, hot strength is 45.6MPa, and elongation at break is 32%, and bending strength is 68.5MPa, and bending modulus is 2.4GPa。
Embodiment 2
By the aluminum diethylphosphinate of 17.0wt%, 10.0wt% polyvinyl alcohol, 2.5wt% epoxidation EP rubbers, 0.5wt% antioxidant tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (168) puts into mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 70.0wt%, add in double screw extruder, melt extrude at 180-210 DEG C, rotating speed 50 revs/min, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 29.0, and vertical combustion grade is V-0。The notch impact strength of flame-proof polylactic acid toughening modifying composite is 8.5kJ/m2, hot strength is 42.3MPa, and elongation at break is 41%, and bending strength is 66.3MPa, and bending modulus is 2.2GPa。
Embodiment 3
By the hypo-aluminum orthophosphate of 12.5wt%, 15.0wt% poly-adipic acid/butylene terephthalate, 5.0wt% ethylene-acrylate-glycidyl methacrylate terpolymer, 0.5wt% antioxidant 1010 mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 67.0wt%, add in double screw extruder, rotating speed 50 revs/min, melt extrude at 180-210 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 27.5, and vertical combustion grade is V-0。The notch impact strength of flame-proof polylactic acid toughening modifying composite is 9.6kJ/m2, hot strength is 41.2MPa, and elongation at break is 50%, and bending strength is 62.0MPa, and bending modulus is 2.1GPa。
Embodiment 4
By 20.0wt% calcium hypophosphite, 12.5wt% polycaprolactone, 7.0wt% epoxidation EP rubbers, 0.5wt% irgasfos 168 mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 60.0wt%, put in double screw extruder blended, rotating speed 50 revs/min, melt extrude at 180-200 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 30.0, and vertical combustion grade is V-0。The notch impact strength of flame-proof polylactic acid toughening modifying composite is 10.2kJ/m2, hot strength is 40.5MPa, and elongation at break is 65%, and bending strength is 61.4MPa, and bending modulus is 2.1GPa。
Embodiment 5
By 15.0wt% aluminum diethylphosphinate, 5.0wt% polycaprolactone, 10.0wt% butyl acrylate-methyl ester-glycidyl methacrylate, 0.5wt% antioxidant four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (1010) and 0.5wt% antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester (168) mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 69.0wt%, add in double screw extruder, rotating speed 50 revs/min, melt extrude at 180-210 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 28.5, and vertical combustion grade is V-0。Flame-proof polylactic acid toughening modifying composite notch impact strength is 6.2kJ/m2, hot strength is 38.5MPa, and elongation at break is 28%, and bending strength is 55.6MPa, and bending modulus is 1.9GPa。
Embodiment 6
By 15.0wt% hypophosphorous acid lanthanum, 5.0wt% polycaprolactone, 12.5wt% ethylene-acrylate-glycidyl methacrylate terpolymer, 0.75wt% antioxidant four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (1010) and 0.75wt% antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester (168) mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 66.0wt%, add in double screw extruder, rotating speed 100 revs/min, melt extrude at 180-210 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 28.0, and vertical combustion grade is V-0。Flame-proof polylactic acid toughening modifying composite notch impact strength is 7.5kJ/m2, hot strength is 37.6MPa, and elongation at break is 32%, and bending strength is 55.0MPa, and bending modulus is 1.8GPa。
Embodiment 7
By 19.5wt% aluminum diethylphosphinate, 10.0wt% polycaprolactone (PCL), 20.0wt% ethylene-acrylate-glycidyl methacrylate terpolymer, 0.5wt% antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (1010) mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 50.0wt%, add in double screw extruder, rotating speed 100 revs/min, melt extrude at 180-210 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 30.0%, and vertical combustion grade is V-0。Flame-proof polylactic acid toughening modifying composite notch impact strength is 12.8kJ/m2, hot strength is 37.9MPa, and elongation at break is 75%, and bending strength is 52.3MPa, and bending modulus is 1.9GPa。
Embodiment 8
By 10.0wt% hypo-aluminum orthophosphate, 20.0wt% poly-adipic acid/butylene terephthalate (PBAT), 4.0wt% epoxidation EP rubbers, 0.5wt% antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (1010) and 0.5wt% antioxidant tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (168) mix homogeneously in high-speed mixer, then after mixing homogeneously with 65.0wt% polylactic resin, add in double screw extruder, rotating speed 100 revs/min, melt extrude at 180-210 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 26.5%, and vertical combustion grade is V-1。The notch impact strength of flame-proof polylactic acid toughening modifying composite is 9.8kJ/m2, hot strength is 41.6MPa, and elongation at break is 65%, and bending strength is 55.0MPa, and bending modulus is 2.2GPa。
Embodiment 9
By 20.0wt% Methylethyl phosphinic acid aluminum, 20.0wt% pla-pcl, 4.0wt% ethylene-acrylate-glycidyl methacrylate terpolymer, 0.5wt% antioxidant four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (1010) and 0.5wt% antioxidant tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester (168) mix homogeneously in high-speed mixer, then after mixing homogeneously with 55.0wt% polylactic resin, add in double screw extruder, rotating speed 50 revs/min, melt extrude at 180-210 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 30.5, and vertical combustion grade is V-0。Flame-proof polylactic acid toughening modifying composite notch impact strength is 8.9kJ/m2, hot strength is 40.6MPa, and elongation at break is 52%, and bending strength is 54.5MPa, and bending modulus is 2.1GPa。
Embodiment 10
By 14.0wt% aluminum phenylphosphinate, 5.0wt% poly-adipic acid/butylene terephthalate (PBAT), 0.5wt% ethylene-acrylate-glycidyl methacrylate terpolymer, 0.5wt% irgasfos 168 mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 80.0wt%, add in double screw extruder, rotating speed 100 revs/min, melt extrude at 180-210 DEG C, and cooling granulation。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 27.5, and vertical combustion grade is V-0。Flame-proof polylactic acid toughening modifying composite notch impact strength is 6.4kJ/m2, hot strength is 53.0MPa, and elongation at break is 25%, and bending strength is 69.1MPa, and bending modulus is 2.4GPa。
Embodiment 11
By 15.0wt% aluminum diethylphosphinate, 15.0wt% pla-pcl (PCL), 15.0wt% glycidyl methacrylate modified EPT rubber, 1.0wt% antioxidant 1010 and 1.0wt% irgasfos 168 mix homogeneously in high-speed mixer, then after mixing homogeneously with the polylactic resin of 53.0wt%, add in banbury at 180 DEG C of melt blendings, rotating speed 100 revs/min, mixing time 10 minutes, then 180 DEG C of mold pressings。The LOI of the lactic acid composite material of the halogen-free flameproof of gained is 28.5, and vertical combustion grade is V-0。Flame-proof polylactic acid toughening modifying composite notch impact strength is 11.4kJ/m2, hot strength is 39.6MPa, and elongation at break is 64%, and bending strength is 57.6MPa, and bending modulus is 2.0GPa。
A kind of biodegradable halogen-free flame-proof polylactic acid toughening modifying composite of the present invention, flame-proof polylactic acid toughening modifying composite is injection molded into the standard batten of test by standard size, and wherein in reference examples and embodiment, PLA resin is U.S. Natureworks2003D。Its physical property is respectively by China's national standard test, as shown in table 1。In reference examples and flame-proof polylactic acid toughening modifying composite each component and parts by weight thereof in Table 2, corresponding mechanical property and combustibility in Table 3。
The mechanical performance of table 1 reference examples PLA of the present invention and embodiment 1-11 composite and combustibility testing standard
| Performance | Method of testing | Unit |
| Hot strength | GB/T1040-1992 | MPa |
| Elongation at break | GB/T1040-1992 | % |
| Bending strength | GB/T9341-2000 | MPa |
| Bending modulus | GB/T9341-2000 | MPa |
| Notch impact strength | GB/T1043.1-2008 | kJ/m2 |
| UL-94 grade | GB/T2508-1996 | - |
| Oxygen index (OI) | GB/T2406.1-2008 | % |
The concrete formula of composite corresponding in table 2 reference examples PLA and embodiment 1-11
The mechanical performance of table 3 reference examples PLA sample and embodiment 1-11 composite and fire resistance
The physical and mechanical properties of the halogen-free flameproof Biodegradable polylactic acids toughening modifying composite listed by table 3 being and fire resistance, be can be seen that the halogen-free flameproof Biodegradable polylactic acids toughening modifying composite of the present invention is not showed only as the fire resistance (V-0) of excellence by table, also there is elongation at break and the toughness of excellence。The present invention adopts the secondary phosphor/phosphine hydrochlorate flame-proof polylactic acid of different proportion, and adopt bio-based elastomer to carry out toughness reinforcing to polylactic acid, and adding reactive polymer as reactive compatibilizer and toughener, notch impact strength brings up to 2-4 times of pure polyacids, and elongation at break improves 7.3-27.3 times。This halogen-free flameproof Biodegradable polylactic acids toughening modifying composite has important using value in fields such as electronic apparatus, automobile, packaging, thin film, weavings。
Claims (8)
1. a halogen-free flame-proof polylactic acid toughening modifying composite, it is characterised in that this material is mainly made up of following component:
2. halogen-free flame-proof polylactic acid toughening modifying composite according to claim 1, it is characterised in that be mainly made up of following component:
3. halogen-free flame-proof polylactic acid toughening modifying composite according to claim 1 and 2, it is characterised in that described time phosphine/phosphate flame retardants includes one or more in inorganic hypophosphites, organic secondary phosphine acid salt。
4. halogen-free flame-proof polylactic acid toughening modifying composite according to claim 3, it is characterised in that described inorganic hypophosphites is one or more in hypo-aluminum orthophosphate, calcium hypophosphite, hypophosphorous acid lanthanum；Described organic secondary phosphine acid salt is one or more in aluminum diethylphosphinate, Methylethyl phosphinic acid aluminum, methylphenylphosphinic acid aluminum, aluminum phenylphosphinate。
5. halogen-free flame-proof polylactic acid toughening modifying composite according to claim 1 and 2, it is characterised in that described biodegradable plastic modifying agent is one or more in polycaprolactone, polyvinyl alcohol, poly-adipic acid/butylene terephthalate。
6. halogen-free flame-proof polylactic acid toughening modifying composite according to claim 1 and 2, it is characterized in that, described reactive compatibilizer is one or more in butyl acrylate-methyl ester-glycidyl methacrylate, epoxidation EP rubbers, ethylene-acrylate-glycidyl methacrylate terpolymer。
7. halogen-free flame-proof polylactic acid toughening modifying composite according to claim 1 and 2, it is characterised in that described antioxidant is one or both in antioxidant 1010, irgasfos 168。
8. the preparation method of the arbitrary described halogen-free flame-proof polylactic acid toughening modifying composite of claim 1-7, it is characterised in that the method adopting melt blending reactive extrursion, concrete technical process and blending condition are as follows:
(1) dry secondary phosphine/phosphate flame retardants, biodegradable plastic modifying agent, reactive compatibilizer and antioxidant are formed flame-retardant mixture by proportioning mix homogeneously in mixer；
(2) polylactic acid and flame-retardant mixture being added melting mixing in banbury, the processing temperature of banbury is at 170-200 DEG C；The rotating speed of banbury is at 50-150 rev/min, and mixing time is at 5-15min；Or the extrusion that is fed in double screw extruder by polylactic acid and flame-retardant mixture melt blending, temperature range 170-210 DEG C of each section of double screw extruder, rotating speed, at 40-100 rev/min, melt extrudes rear cooling granulation。
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| CN112759905A (en) * | 2019-11-01 | 2021-05-07 | 南通林格橡塑制品有限公司 | Halogen-free flame-retardant polylactic acid mixture |
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| CN114634691B (en) * | 2022-03-17 | 2023-05-23 | 华南师范大学 | Full-biodegradation composite material and preparation method thereof |
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