CN107151430B - 一种用于3d打印的阻燃抗菌pla生物降解复合材料 - Google Patents
一种用于3d打印的阻燃抗菌pla生物降解复合材料 Download PDFInfo
- Publication number
- CN107151430B CN107151430B CN201710387027.4A CN201710387027A CN107151430B CN 107151430 B CN107151430 B CN 107151430B CN 201710387027 A CN201710387027 A CN 201710387027A CN 107151430 B CN107151430 B CN 107151430B
- Authority
- CN
- China
- Prior art keywords
- pla
- flame
- composite material
- printing
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 28
- 238000010146 3D printing Methods 0.000 title claims abstract description 24
- 239000003063 flame retardant Substances 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 20
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 18
- 229920005615 natural polymer Polymers 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000002667 nucleating agent Substances 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920001661 Chitosan Polymers 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 6
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 claims description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000013508 migration Methods 0.000 claims description 4
- 230000005012 migration Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- FKPUYTAEIPNGRM-UHFFFAOYSA-N 1-(diaminomethylidene)guanidine;hydron;chloride Chemical compound [Cl-].N\C([NH3+])=N/C(N)=N FKPUYTAEIPNGRM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 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 group 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 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical group C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 230000002045 lasting effect Effects 0.000 abstract description 4
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 239000012757 flame retardant agent Substances 0.000 abstract description 3
- 229940126572 wide-spectrum antibiotic Drugs 0.000 abstract description 2
- 239000004626 polylactic acid Substances 0.000 description 27
- 229920000747 poly(lactic acid) Polymers 0.000 description 25
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 alkene Hydrocarbon Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
- C08L2205/24—Crystallisation aids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及高分子材料领域,具体涉及一种用于3D打印的阻燃抗菌PLA生物降解复合材料,由以下原料按重量份制备而成:PLA 100份、成核剂2~10份、天然高分子抗菌剂5~10份、增韧剂1‑5份、抗氧剂0.3~0.8份、相容剂0.5~1份、润滑剂0.5~1.5份、DOPO衍生物阻燃剂5~10份。本发明的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,在PLA复合材料体系中添加了DOPO衍生物阻燃剂和天然高分子抗菌剂,一方面选用的天然高分子抗菌剂赋予PLA复合材料较持久和广谱的抗菌性,杀菌力强,性能稳定,易生物降解,不会造成二次污染;另一方面,当阻燃剂含量达到5‑10%时,固化物可以达到UL94,V‑0级。
Description
技术领域
本发明涉及高分子材料领域,具体涉及一种用于3D打印的阻燃抗菌PLA生物降解复合材料。
背景技术
3D打印技术又称叠层制造技术,是快速成型领域的一种新兴技术,它是一种以数字模型文件为基础,运用粉末状金属或塑料等可粘合材料,通过逐层打印的方式来构造物体的技术。基本原理是叠层制造,逐层增加材料来生成三维实体的技术。目前,3D打印技术主要被应用于产品原型、模具制造以及艺术创作、珠宝制作等领域,替代这些传统依赖的精细加工工艺。另外,3D打印技术逐渐应用于医学、生物工程、建筑、服装、航空等领域,为创新开拓了广阔的空间。
目前市场上熔融挤压堆积成型技术较常用的聚合物材料是丙烯腈一丁二烯一苯乙烯三元共聚物(ABS)、聚乳酸(PLA)、尼龙(PA)和聚碳酸酯(PC),其中PLA是一种可降解的打印原材料。聚乳酸(PLA)是近年发展出来的综合物性最好的生物可降解塑料,对环境完全没有污染,其具有良好的生物可降解性,使用后能被自然界中微生物完全降解,最终生成二氧化碳和水,不污染环境,符合当今世界对环保的要求。但是,聚乳酸的缺陷,如热变形温度低、冲击强度低、韧性不好、不具有阻燃性且抗菌性较差等问题,达不到工程塑料的物性要求,这极大的限制了其应用。在许多场合应用中,防火阻燃是一个至关重要的因素,另外,在许多场合适当地使用抗菌产品,可以有效地抑制细菌的生长,防止细菌的传播和感染,加入适当的阻燃剂和抗菌剂可以提高它的阻燃性能和抗菌性能。高分子抗菌剂是近些年兴起的抗菌剂品种,目前研究和使用主要集中于高分子季铵盐、季鏻盐等。高分子抗菌剂主要是通过带官能团单体的聚合反应或以接枝的方式在高分子链上引入抗菌官能团而获得抗菌性能的。高分子抗菌剂由于其高效杀菌、杀菌时效性长等优点,日益受到人们的广泛关注。早期使用的含卤的阻燃剂由于生产过程中,对设备腐蚀性很大,同时产生粉尘和废液污染,并且在使用过程中易析出,产生二噁英等有毒物,污染环境。目前阻燃剂的研究主要集中于含磷、氮、硫等元素的有机物或低聚物的设计合成,以及通过共混或共聚的方法使高分子材料具有阻燃性。
壳聚糖具有广谱抗菌性,生物可降解性,纯天然无污染;在壳聚糖的胺基上接上了不同长度的烷基,制备了一系列的壳聚糖季铵盐衍生物。由于壳聚糖的衍生物在酸性和碱性条件下都可溶,因此有着更广泛的应用。对抗菌性能的研究表明经过改性的壳聚糖抗菌活性有所提高,而且抗菌活性随着烷基链的增长而增加(孙洪,夏英,陈莉,谭振宇,孟令懿.国内外抗菌剂的研究现状及发展趋势.塑料工业,2006,34(9):1-4.)。
9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,简称DOPO,其结构中含有P-H键,对烯烃、环氧化合物和羰基化合物极具活性,可反应生成许多衍生物。DOPO及其衍生物由于分子结构中含有联苯环、菲环、O=P-O键,所以比普通的有机磷酸酯具有更强的阻燃性能。由Saito于1972年首次报道其合成路线。DOPO及其衍生物可作为反应型和添加型阻燃剂,其合成的阻燃剂无卤、无烟、无毒,不迁移,阻燃性能持久。在提高材料的阻燃性能的同时,不影响材料的力学强度等机械性能。
发明内容
本发明的目的在于针对现有技术的不足,提供一种用于3D打印的阻燃抗菌PLA生物降解复合材料,在PLA复合材料体系中添加了DOPO衍生物阻燃剂和天然高分子抗菌剂,一方面选用的天然高分子抗菌剂赋予PLA复合材料较持久的抗菌性;另一方面,当阻燃剂含量达到5-10%时,固化物可以达到UL94,V-0级。
为实现本发明的目的,本发明采用如下技术方案:
一种用于3D打印的阻燃抗菌PLA生物降解复合材料,由以下原料按重量份制备而成:
PLA 100份、成核剂2~10份、天然高分子抗菌剂5~10份、增韧剂1-5份、抗氧剂0.3~0.8份、相容剂0.5~1份、润滑剂0.5~1.5份、DOPO衍生物阻燃剂5~10份。
具体地,上述的PLA的重均分子量为1×105~1×106g/mol。
具体地,上述的成核剂为碳酸氢钠、苯甲酸钠、乙烯-甲基丙烯酸钠中的一种或几种。
具体地,上述的天然高分子抗菌剂为壳聚糖、羧甲基壳聚糖、壳聚糖季铵盐、壳聚糖双胍盐酸盐中的一种或几种。
具体地,上述的增韧剂为羧基液体丁腈橡胶、聚硫橡胶、聚酰胺树脂、聚乙烯醇叔丁醛中的一种或几种。
具体地,上述的抗氧剂为复合抗氧剂,由主抗氧剂和辅助抗氧剂组成,主抗氧剂为抗氧剂1010,辅助抗氧剂为亚磷酸二苯辛酯,主抗氧剂与辅助抗氧剂的重量组成比例为(3~5)∶1
具体地,上述的相容剂为乙烯-甲基丙烯酸酯-缩水甘油酯。
具体地,上述的润滑剂为硅酮粉、季戊四醇硬脂酸酯、乙撑双脂肪酸酰胺中的一种。
具体地,上述的DOPO衍生物阻燃剂的结构式为:
其中,DOPO衍生物阻燃剂的制备方法,包括如下步骤:
(1)将联苯基氨基磷酸酯和8-三氟甲基喹啉-2-甲醛在溶剂中加热,反应结束后,得含有中间产物I的反应体系;
(2)将DOPO加入到步骤(1)得到的含有中间产物I的反应体系中加热,反应结束后,洗涤、干燥,得具有表面迁移性的阻燃剂。
其反应过程为:
具体地,上述步骤(1)中联苯基氨基磷酸酯和8-三氟甲基喹啉-2-甲醛的摩尔比为1:1。
具体地,上述步骤(1)中反应时间为6-10h。
具体地,上述步骤(1)中加热温度为70℃。
具体地,上述步骤(1)中溶剂为乙醇、DMF或DMSO。
具体地,上述步骤(1)中溶剂的加入量为联苯基氨基磷酸酯和8-三氟甲基喹啉-2-甲醛质量和的6-12倍。
具体地,上述步骤(2)中的DOPO和步骤(1)中的8-三氟甲基喹啉-2-甲醛的摩尔比为1:1。
具体地,上述步骤(2)中的反应温度为70℃。
具体地,上述步骤(2)中的反应时间为5-8h。
上述一种用于3D打印的阻燃抗菌PLA生物降解复合材料的制备方法,具体包括如下步骤:
(1)按重量份,将已干燥的PLA 100份、成核剂2~10份、天然高分子抗菌剂5~10份、增韧剂1-5份、抗氧剂0.3~0.8份、相容剂0.5~1份、润滑剂0.5~1.5份、DOPO衍生物阻燃剂5~10份投入高速混合机中;混合均匀后投放进锥形双螺杆挤出机,双螺杆挤出机的挤出温度为160~220℃,机头160~200℃,双螺杆挤出机转速为100~300r/min;
(2)将步骤(1)得到的粒料冷却后用球磨机粉碎,转速为200~500r/min,球磨时间3~5h,然后在50~150目的筛网中进行筛分;
(3)将步骤(2)得到的物料加入到真空干燥箱中,在60~80℃条件下,干燥4~6h后得到阻燃抗菌PLA生物降解复合材料。
本发明具有的有益效果:
(1)本发明的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,随着PLA复合材料中磷含量的增加,PLA复合材料的阻燃性增大;当阻燃剂含量达到5-10%(含磷量为0.46wt%-0.92wt%)时,固化物可以达到UL-94,V-0级。
(2)本发明的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,由于氟较低的表面能,具有较好的表面迁移性,使得阻燃剂在使用过程中易迁移到材料表面富集,在量很少的条件下就具有高阻燃性、并且低烟、低毒害、无腐蚀性气体产生。
(3)本发明的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,选用的天然高分子抗菌剂赋予PLA复合材料较持久和广谱的抗菌性,杀菌力强,性能稳定,易生物降解,不会造成二次污染。
(4)本发明所使用的原料易得、工艺简单、成本低、易于工业化生产。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明具体实施例1的DOPO衍生物阻燃剂核磁谱图。
具体实施方式
现在结合实施例对本发明作进一步详细的说明。
实施例1
一种用于3D打印的阻燃抗菌PLA生物降解复合材料,由以下原料按重量份制备而成:
重均分子量为5×105g/molPLA 100份
碳酸氢钠5份
壳聚糖双胍盐酸盐10份
羧基液体丁腈橡胶3份
抗氧剂1010与亚磷酸二苯辛酯质量比为4:1组成的抗氧剂0.5份
乙烯-甲基丙烯酸酯-缩水甘油酯0.5份
季戊四醇硬脂酸酯1份
DOPO衍生物阻燃剂5~10份
其中,DOPO衍生物阻燃剂的结构式为:
所述DOPO衍生物阻燃剂的合成步骤为:
(1)将7.5g的联苯基氨基磷酸酯和6.8g的8-三氟甲基喹啉-2-甲醛在70℃的85.5g乙醇中加热6h,反应结束后,得含有中间产物I的反应体系;
(2)将6.5g的DOPO加入到步骤(1)得到的含有中间产物I的反应体系中在70℃条件下5h加热,反应结束后,洗涤、干燥,得具有表面迁移性的阻燃剂,产率84.5%。
其红外测试结果如下:
FTIR(KBr):N-H伸缩振动峰3410cm-1,C-H伸缩振动峰3070cm-1,C-N特征峰1288cm-1,C-F特征峰1100cm-1,P-O-C特征峰1032cm-1,P-O-Ph特征峰1231cm-1,P-Ph特征峰1595cm-1,P=O特征峰1212cm-1,芳氢的面外弯曲振动峰900cm-1。
核磁谱图如图1所示,核磁测试结果如下:
1H-NMR(400MHz,DMSO-d6)δ8.27(1H),8.17(1H),7.87(1H),7.54(2H),7.2-7.35(5H),7.09(4H),7.05(1H),6.88(1H),6.82(2H),6.79(1H),6.73(4H),3.90(1H),2.00(1H)。
一种用于3D打印的阻燃抗菌PLA生物降解复合材料的制备方法,具体包括如下步骤:
(1)按重量份,将已干燥的PLA、成核剂、天然高分子抗菌剂、增韧剂、抗氧剂、相容剂、润滑剂、DOPO衍生物阻燃剂投入高速混合机中;混合均匀后投放进锥形双螺杆挤出机,双螺杆挤出机的挤出温度为160~220℃,机头160~200℃,双螺杆挤出机转速为100~300r/min;
(2)将步骤(1)得到的粒料冷却后用球磨机粉碎,转速为200~500r/min,球磨时间3~5h,然后在50~150目的筛网中进行筛分;
(3)将步骤(2)得到的物料加入到真空干燥箱中,在60~80℃条件下,干燥4~6h后得到阻燃抗菌PLA生物降解复合材料。
实施例2-5与实施例1基本相同,不同之处在于表1;对比例1-4与实施例1基本相同,不同之处在于表1:
表1:
将实施例1-5及对比例1-4中PLA生物降解复合材料粒子料在60~80℃条件下,干燥4~6h,然后使用3D打印机打印成测试样条,在室温充分稳定化后,进行各项性能测试,测试结果如表2所示。
表2
对实施例1-5和对比例1-4的用于3D打印的阻燃抗菌PLA生物降解复合材料进行UL94垂直燃烧试验,结果表3所示:
表3:
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (7)
1.一种用于3D打印的阻燃抗菌PLA生物降解复合材料,其特征在于,由以下原料按重量份制备而成:
PLA 100份、成核剂2~10份、天然高分子抗菌剂5~10份、增韧剂1-5份、抗氧剂0.3~0.8份、相容剂0.5~1份、润滑剂0.5~1.5份、DOPO衍生物阻燃剂5~10份。
所述的PLA的重均分子量为1×105~1×106g/mol;
其中,DOPO衍生物阻燃剂的制备方法,包括如下步骤:
(1)将联苯基氨基磷酸酯和8-三氟甲基喹啉-2-甲醛在溶剂中加热,反应结束后,得含有中间产物I的反应体系;
(2)将DOPO加入到步骤(1)得到的含有中间产物I的反应体系中加热,反应结束后,洗涤、干燥,得具有表面迁移性的阻燃剂;
所述的天然高分子抗菌剂为壳聚糖、羧甲基壳聚糖、壳聚糖季铵盐、壳聚糖双胍盐酸盐中的一种或几种。
2.如权利要求1所述的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,其特征在于,所述的成核剂为碳酸氢钠、苯甲酸钠、乙烯-甲基丙烯酸钠离子聚合物中的一种或几种。
3.如权利要求1所述的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,其特征在于,所述的增韧剂为羧基液体丁腈橡胶、聚硫橡胶、聚酰胺树脂、聚乙烯醇叔丁醛中的一种或几种。
4.如权利要求1所述的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,其特征在于,所述的抗氧剂为复合抗氧剂,由主抗氧剂和辅助抗氧剂组成,主抗氧剂为抗氧剂1010,辅助抗氧剂为亚磷酸二苯辛酯,主抗氧剂与辅助抗氧剂的重量组成比例为(3~5)∶1。
5.如权利要求1所述的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,其特征在于,所述的相容剂为乙烯-甲基丙烯酸酯-缩水甘油酯。
6.如权利要求1所述的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,其特征在于,所述的润滑剂为硅酮粉、季戊四醇硬脂酸酯、乙撑双脂肪酸酰胺中的一种。
7.如权利要求1所述的一种用于3D打印的阻燃抗菌PLA生物降解复合材料,其特征在于,所述的DOPO衍生物阻燃剂的结构式为:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710387027.4A CN107151430B (zh) | 2017-05-26 | 2017-05-26 | 一种用于3d打印的阻燃抗菌pla生物降解复合材料 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710387027.4A CN107151430B (zh) | 2017-05-26 | 2017-05-26 | 一种用于3d打印的阻燃抗菌pla生物降解复合材料 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107151430A CN107151430A (zh) | 2017-09-12 |
CN107151430B true CN107151430B (zh) | 2019-06-28 |
Family
ID=59794481
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710387027.4A Active CN107151430B (zh) | 2017-05-26 | 2017-05-26 | 一种用于3d打印的阻燃抗菌pla生物降解复合材料 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107151430B (zh) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108285557A (zh) * | 2017-12-31 | 2018-07-17 | 芜湖林电子科技有限公司 | 一种具有抗菌性能的3d打印材料及其制备方法 |
CN110003629A (zh) * | 2019-04-26 | 2019-07-12 | 安徽农业大学 | 一种生物基高韧聚乳酸组合物及其制备方法 |
CN110468463B (zh) * | 2019-07-30 | 2021-08-31 | 福建省百凯经编实业有限公司 | 一种高端针织面料及其加工方法 |
CN112745456B (zh) * | 2019-10-30 | 2022-07-12 | 中国石油化工股份有限公司 | 一种阻燃抗菌剂及其制法和应用及阻燃抗菌热塑性树脂组合物 |
CN110903512B (zh) * | 2019-11-21 | 2021-12-17 | 浙江大学宁波理工学院 | 高效无卤的磷系气相阻燃剂及含有该阻燃剂的高分子材料 |
CN111334016A (zh) * | 2020-04-16 | 2020-06-26 | 广东特莱福生物科技有限公司 | 一种可降解自增效抑菌生物基聚酯合金材料及其制备方法和应用 |
CN111718537B (zh) * | 2020-07-28 | 2022-12-13 | 黎明职业大学 | 一种抗菌改性塑料 |
CN112175368A (zh) * | 2020-10-10 | 2021-01-05 | 福建省支点三维科技有限公司 | 一种抗菌pla3d打印复合材料 |
CN112210199A (zh) * | 2020-10-10 | 2021-01-12 | 福建师范大学泉港石化研究院 | 一种抗菌pla3d打印复合材料 |
CN113045855A (zh) * | 2021-05-10 | 2021-06-29 | 中山大学孙逸仙纪念医院 | 一种用于阻断卵巢性索间质肿瘤扩散的薄膜材料及其制备方法 |
CN114133715A (zh) * | 2021-11-05 | 2022-03-04 | 北方华锦化学工业股份有限公司 | 一种3d打印用高光泽抗菌pla材料及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102746625A (zh) * | 2012-07-02 | 2012-10-24 | 同济大学 | 一种无卤阻燃天然纤维增强聚乳酸复合材料及其制备方法 |
CN105713043A (zh) * | 2009-05-19 | 2016-06-29 | 雅宝公司 | Dopo衍生物阻燃剂 |
CN106189319A (zh) * | 2016-07-21 | 2016-12-07 | 芜湖凯奥尔环保科技有限公司 | 一种秸秆复合阻燃3d打印材料及其制备方法 |
CN106832836A (zh) * | 2017-03-02 | 2017-06-13 | 张家港市五湖新材料技术开发有限公司 | 一种用于3d打印的阻燃增强pla复合材料 |
-
2017
- 2017-05-26 CN CN201710387027.4A patent/CN107151430B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105713043A (zh) * | 2009-05-19 | 2016-06-29 | 雅宝公司 | Dopo衍生物阻燃剂 |
CN102746625A (zh) * | 2012-07-02 | 2012-10-24 | 同济大学 | 一种无卤阻燃天然纤维增强聚乳酸复合材料及其制备方法 |
CN106189319A (zh) * | 2016-07-21 | 2016-12-07 | 芜湖凯奥尔环保科技有限公司 | 一种秸秆复合阻燃3d打印材料及其制备方法 |
CN106832836A (zh) * | 2017-03-02 | 2017-06-13 | 张家港市五湖新材料技术开发有限公司 | 一种用于3d打印的阻燃增强pla复合材料 |
Also Published As
Publication number | Publication date |
---|---|
CN107151430A (zh) | 2017-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107151430B (zh) | 一种用于3d打印的阻燃抗菌pla生物降解复合材料 | |
CN106496975B (zh) | 一种聚乳酸/淀粉膨胀阻燃复合材料及其制备方法 | |
CN109912650A (zh) | 一种磷-氮系生物基阻燃剂及其合成方法和应用 | |
CN106832906B (zh) | 一种用于3d打印的高阻燃性尼龙复合材料 | |
CN105153462B (zh) | 大豆油基阻燃增塑剂及其制备方法和应用 | |
CN104119660B (zh) | 一种改性聚碳酸亚丙酯材料的制备方法 | |
CN104559100A (zh) | 功能化环糊精阻燃聚乳酸复合材料及其制备方法 | |
CN114133622A (zh) | 一种复合阻燃剂及其制备方法和应用 | |
CN110172244A (zh) | 一种改性磷酸锆阻燃复合材料及其制备方法 | |
CN106832836A (zh) | 一种用于3d打印的阻燃增强pla复合材料 | |
CN106589889A (zh) | 一种高性能聚碳酸酯复合材料及其制备方法及应用 | |
CN111363291A (zh) | 一种用于聚苯乙烯类硬塑玩具的抗菌色母粒 | |
CN102936403A (zh) | 一种无卤阻燃聚碳酸酯复合物及其制备方法 | |
CN112280270B (zh) | 一种阻燃聚乳酸增材及其制备方法 | |
CN106433055A (zh) | 一种具有良好阻燃性的高强度生物质板材的制备方法 | |
CN111363322B (zh) | 一种阻燃聚乳酸树脂组合物及其制备方法 | |
CN113603990A (zh) | 一种抗菌pe材料及其制备方法 | |
CN112321999A (zh) | 一种超支化聚己二酸对苯二甲酸丁二醇酯材料的制备方法 | |
CN106632703B (zh) | 一种生物基含磷淀粉及其制备方法和应用 | |
CN117304661B (zh) | 一种聚酯组合物、制备方法及其应用 | |
CN116875021B (zh) | 一种pc/abs合金材料及其制备方法和应用 | |
CN110981977A (zh) | 一种阻燃纤维素及其制备方法和应用 | |
CN113788799B (zh) | 一种抗菌阻燃剂的制备方法及其应用 | |
CN104877133A (zh) | 一种含苯并噁嗪环的芳腈基特种树脂和苯并噁嗪树脂的共聚树脂及其工业制备方法 | |
CN109280357A (zh) | 一种阻燃抗菌pc-abs合金及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20190626 Address after: 322000 No. 968 Xuefeng West Road, Yiwu City, Jinhua City, Zhejiang Province Patentee after: Yiwu build true Electronic Technology Co., Ltd. Address before: 215625 No. 3 Jinxiu Road, Jiangsu Yangzijiang International Metallurgical Industrial Park, Jinfeng Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee before: Wu Xinxian |
|
TR01 | Transfer of patent right |