CN101280097A - Nano flame-retardant polyethylene terephthalate engineering plastics and preparation method thereof - Google Patents
Nano flame-retardant polyethylene terephthalate engineering plastics and preparation method thereof Download PDFInfo
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- CN101280097A CN101280097A CNA2008100377375A CN200810037737A CN101280097A CN 101280097 A CN101280097 A CN 101280097A CN A2008100377375 A CNA2008100377375 A CN A2008100377375A CN 200810037737 A CN200810037737 A CN 200810037737A CN 101280097 A CN101280097 A CN 101280097A
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- polyethylene terephthalate
- nano
- flame
- engineering plastics
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- 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 claims abstract description 40
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims description 39
- 239000005020 polyethylene terephthalate Substances 0.000 title claims description 39
- -1 polyethylene terephthalate Polymers 0.000 title claims description 27
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002667 nucleating agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 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 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- DHTGRDDBCWWKQJ-UHFFFAOYSA-N 2-(2,2-dihydroxyethoxy)ethane-1,1-diol Chemical compound OC(O)COCC(O)O DHTGRDDBCWWKQJ-UHFFFAOYSA-N 0.000 claims description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 2
- 241001112258 Moca Species 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000001845 chromium compounds Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 229910021419 crystalline silicon Inorganic materials 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 6
- 239000004594 Masterbatch (MB) Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 101150074899 gpa-10 gene Proteins 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- 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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- 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
- B29C2948/9259—Angular velocity
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- 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
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- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
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- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92866—Inlet shaft or slot, e.g. passive hopper; Injector, e.g. injector nozzle on barrel
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- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种纳米阻燃PET工程塑料。它是由PET、复配阻燃剂、增强剂、成核剂、润滑剂、复配抗氧剂、增韧剂、增容剂和扩链剂组成，其中复配阻燃剂为纳米氢氧化镁、纳米蒙脱土与氰尿酸三聚氰胺的混合物。其制备方法是将干燥好的PET母粒与各种助剂在高速混合机中充分混合后，加入双螺杆挤出机中，熔融挤出的同时，在双螺杆的第二个加料口加入增强剂熔融挤出，挤出造粒。本发明的产品具有阻燃性能优良，良好的光泽、尺寸稳定、低翘曲、高模量、高抗冲击等性能，该产品属于本色，使得再后续加工不会受到颜色的限制，可广泛应用于电子、电气、汽车等领域。The invention relates to a nano flame-retardant PET engineering plastic. It is composed of PET, compound flame retardant, reinforcing agent, nucleating agent, lubricant, compound antioxidant, toughening agent, compatibilizer and chain extender, among which the compound flame retardant is nano-hydrogen A mixture of magnesium, nano-montmorillonite and melamine cyanurate. Its preparation method is to fully mix the dried PET masterbatch and various additives in a high-speed mixer, then add it to a twin-screw extruder, and at the same time of melting and extruding, add reinforcement to the second feeding port of the twin-screw. Agent melt extrusion, extrusion granulation. The product of the present invention has excellent flame retardant performance, good gloss, stable size, low warpage, high modulus, high impact resistance and other properties. The product belongs to the original color, so that subsequent processing will not be limited by color, and can be widely used In electronics, electrical, automotive and other fields.
Description
技术领域technical field
本发明涉及一种纳米阻燃聚对苯二甲酸乙二醇酯(PET)工程塑料及其制备方法，属于改性工程塑料技术领域。The invention relates to a nano flame-retardant polyethylene terephthalate (PET) engineering plastic and a preparation method thereof, belonging to the technical field of modified engineering plastics.
背景技术Background technique
PET工程塑料具有良好的力学性能、电绝缘性、耐化学药品性、耐蠕变形、耐疲劳性等，PET作为工程塑料用途，绝大部分是使用改性PET，其主要目的是提高强度，耐热性，耐燃烧性等。特别是随着PET广泛应用于电子、电气、汽车等行业，这些行业对燃烧、安全性能有严格的要求，所在在该聚酯中添加阻燃剂以提高材料的阻燃性，保证产品的使用安全性，成为近年来聚酯研发的一个重要课题。在PET工程塑料中添加有效的阻燃剂是目前提高阻燃性的最有效、最经济的手段之一。最常应用的阻燃剂主要份三大类：卤素类、磷氮类以及无机纳米粉体类。对于卤素类的阻燃剂在燃烧过程中会生成大量的烟和有毒、有腐蚀性的气体，对环境造成严重的污染，因此磷氮类和无机纳米粉体成为绿色阻燃剂逐渐受到人们的亲睐，特别是21世纪以来，纳米技术的普遍推广，纳米材料被认为是21世纪最有前途的材料，并已经成为世界性的研究热潮，因此制备添加纳米阻燃剂是获得高性能阻燃复合材料的重要方法之一。PET engineering plastics have good mechanical properties, electrical insulation, chemical resistance, creep resistance, fatigue resistance, etc. PET is used as engineering plastics, and most of them use modified PET. The main purpose is to improve the strength. Heat resistance, combustion resistance, etc. Especially as PET is widely used in electronics, electrical, automobile and other industries, these industries have strict requirements on combustion and safety performance, so flame retardants are added to the polyester to improve the flame retardancy of the material and ensure the use of the product Safety has become an important topic in the research and development of polyester in recent years. Adding effective flame retardants to PET engineering plastics is currently one of the most effective and economical means to improve flame retardancy. The most commonly used flame retardants are mainly divided into three categories: halogens, phosphorus nitrogen and inorganic nanopowders. For halogen-based flame retardants, a large amount of smoke and toxic and corrosive gases will be generated during combustion, which will cause serious pollution to the environment. Therefore, phosphorus-nitrogen and inorganic nano-powders have gradually become green flame retardants and are gradually favored by people. Pros, especially since the 21st century, with the widespread promotion of nanotechnology, nanomaterials are considered to be the most promising materials in the 21st century, and have become a worldwide research boom. One of the important methods of composite materials.
氢氧化镁(MH)是无机纳米阻燃剂中最常见的一种，具有较好的阻燃协同性和抑烟效果。MH开始脱水温度340℃，PET的熔点在250℃左右，因此可添加纳米MH来承受较高的加工温度。此外MH粒径细，对设备磨损小，还利于加快挤塑速度，缩短模塑时间，同时有利于利于延长加工设备使用寿命。MH在生产、使用和废弃过程中均无有害物质排放，而且还能中和燃烧过程中产生的酸性与腐蚀性气体。通过改性的纳米MH作为阻燃剂单独使用时，虽可均匀分散，但用量一般在40-60％，这严重影响了材料的机械性能。因此在制备阻燃PET工程塑料时加工的过程当中不能单独使用MH，在本发明当中，我们采用MH与含氮阻燃剂氰尿酸三聚氰胺和纳米蒙脱土复配，从而使PET阻燃性能和力学性能同时达到提高。Magnesium hydroxide (MH) is the most common kind of inorganic nano-flame retardant, which has good flame-retardant synergy and smoke suppression effect. The dehydration temperature of MH starts at 340°C, and the melting point of PET is around 250°C, so nano-MH can be added to withstand higher processing temperatures. In addition, the particle size of MH is fine, which has little wear and tear on equipment, and is also beneficial to speed up extrusion, shorten molding time, and prolong the service life of processing equipment. MH has no harmful substance emission in the process of production, use and disposal, and it can also neutralize the acid and corrosive gases produced in the combustion process. When the modified nano-MH is used alone as a flame retardant, although it can be uniformly dispersed, the dosage is generally 40-60%, which seriously affects the mechanical properties of the material. Therefore, in the process of preparing flame-retardant PET engineering plastics, MH cannot be used alone. In the present invention, we use MH to compound with nitrogen-containing flame retardant melamine cyanurate and nano-montmorillonite, so that the flame-retardant properties of PET and The mechanical properties are improved at the same time.
纳米蒙脱土用作阻燃材料具有添加量小，阻燃协同能力好，除了具有较好的阻燃能力之外还能提高聚合物的物理性能，改善物料的加工性能。Nano-montmorillonite used as a flame-retardant material has a small amount of addition and good flame-retardant synergistic ability. In addition to having good flame-retardant ability, it can also improve the physical properties of the polymer and improve the processing performance of the material.
氰尿酸三聚氰胺(又称为三聚氰胺氰尿酸酯MC)，英文名称为MelamineCyanurate，外观为白色结晶粉末。因此作为阻燃剂与MH复配较适合制备本色的PET工程塑料。MC在250～450℃发生分解反应，吸收大量的热，并放出氮气，冲淡了氧和高聚物分解产生的可然气浓度，并且气体的对流带走部分热量；在高温时能够脱水成炭，具有隔热、隔氧的作用。MC的阻燃制品具有很多优点：低烟、无毒，制品的力学性能好，冲击强度可以提高一倍左右；制品的阻燃效果好，价格低廉，添加量少。Melamine cyanurate (also known as melamine cyanurate MC), the English name is MelamineCyanurate, and its appearance is white crystalline powder. Therefore, it is more suitable to prepare natural-color PET engineering plastics as a flame retardant compounded with MH. MC decomposes at 250-450°C, absorbs a large amount of heat, and releases nitrogen gas, which dilutes the concentration of combustible gas produced by the decomposition of oxygen and polymers, and the convection of the gas takes away part of the heat; it can be dehydrated into charcoal at high temperatures , has the function of heat insulation and oxygen insulation. MC's flame retardant products have many advantages: low smoke, non-toxic, good mechanical properties of the product, and the impact strength can be doubled; the product has good flame retardant effect, low price, and less added amount.
利用上述三者组成的复合阻燃剂对PET具有良好的阻燃性能，同时由于三种阻燃剂均属于白色粉末，因此适合本色无卤阻燃PET工程塑料的生产。The composite flame retardant composed of the above three has good flame retardant performance on PET. At the same time, because the three flame retardants are all white powders, they are suitable for the production of natural halogen-free flame-retardant PET engineering plastics.
发明内容Contents of the invention
本发明的目的在于提供一种纳米阻燃聚对苯二甲酸乙二醇酯(PET)工程塑料。The object of the present invention is to provide a kind of nano flame-retardant polyethylene terephthalate (PET) engineering plastics.
本发明的另一目的在于提供一种纳米阻燃聚对苯二甲酸乙二醇酯工程塑料的制备方法。Another object of the present invention is to provide a preparation method of nano flame-retardant polyethylene terephthalate engineering plastics.
为达到上述目的，本发明采用下述技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种纳米阻燃聚对苯二甲酸乙二醇酯工程塑料，其特征在于其组成按重量份数计为：A kind of nano-flame-retardant polyethylene terephthalate engineering plastics is characterized in that its composition is calculated in parts by weight:
(1)聚对苯二甲酸乙二醇酯 60～80份(1) Polyethylene terephthalate 60-80 parts
(2)增强剂 25～40份(2) Enhancer 25-40 parts
(3)复配阻燃剂 1～20份(3) Compound flame retardant 1 to 20 parts
(4)成核剂 0.2～2份(4) Nucleating agent 0.2～2 parts
(5)润滑剂 0.1～0.5份(5) Lubricant 0.1～0.5 parts
(6)复配抗氧剂 0.1～0.3份(6) Compound antioxidant 0.1～0.3 parts
(7)增韧剂 1～5份(7) Toughening agent 1~5 parts
(8)增容剂 10～20份(8) Compatibilizer 10-20 parts
(9)扩链剂 0.1～0.3份(9) Chain extender 0.1～0.3 parts
所述的增强剂为无碱长玻璃纤维、碳纤维、晶硅须中的一种或几种，其中无碱长玻璃纤维、碳纤维、晶硅须需经过碳链脂肪酸、硅烷类化合物、有机铬化合物、钛酸酯类化合物中的一种表面改性处理，使之挤出时能充分、均匀分布在PET中。The reinforcing agent is one or more of alkali-free long glass fibers, carbon fibers, and crystal silicon whiskers, wherein the alkali-free long glass fibers, carbon fibers, and crystal silicon whiskers need to pass through carbon chain fatty acids, silane compounds, and organic chromium compounds. , A surface modification treatment of titanate compounds, so that they can be fully and evenly distributed in PET during extrusion.
所述的复配阻燃剂为包含3～8份纳米氢氧化镁、2～5份纳米蒙脱土和3～10份氰尿酸三聚氰胺的混合物；纳米氢氧化镁和纳米蒙脱土要经过改性处理。The compound flame retardant is a mixture comprising 3-8 parts of nano-magnesium hydroxide, 2-5 parts of nano-montmorillonite and 3-10 parts of melamine cyanurate; nano-magnesium hydroxide and nano-montmorillonite are modified sexual processing.
所述的成核剂为二氧化硅、滑石、云母、碳酸钙中的一种或几种。The nucleating agent is one or more of silicon dioxide, talc, mica, and calcium carbonate.
所述的的润滑剂为季戊四醇硬脂酸酯(PETS)。Described lubricant is pentaerythritol stearate (PETS).
所述的抗氧剂为市售Irganox 245和Irganox1010的复配抗氧剂，重量比为1∶1；Described antioxidant is the composite antioxidant of commercially available Irganox 245 and Irganox1010, and the weight ratio is 1: 1;
所述的增韧剂为MBS、EVA、ABS中的一种或几种。The toughening agent is one or more of MBS, EVA and ABS.
所述的增容剂为POE-g-MAH，PPO-g-MAH，PP-g-MAH中的一种或几种。The compatibilizer is one or more of POE-g-MAH, PPO-g-MAH, and PP-g-MAH.
所述的扩链剂为均苯二酐(PMDA)、对苯酚二羟基乙醚(HQEE)、1，4-丁二醇(1，4-BD)、3，3’-二氯-4，4’-二氨基-二苯基甲烷(MOCA)中的一种或几种。The chain extender is pyrophthalic anhydride (PMDA), p-phenol dihydroxyethyl ether (HQEE), 1,4-butanediol (1,4-BD), 3,3'-dichloro-4,4 One or more of '-diamino-diphenylmethane (MOCA).
一种用于纳米阻燃聚对苯二甲酸乙二醇酯工程塑料的制备方法，其特征在于该方法具有如下工艺过程：将干燥好的聚对苯二甲酸乙二醇酯母粒、阻燃剂、成核剂、润滑剂、抗氧剂、增韧剂、增容剂和扩链剂助剂在高速混合机中充分混合后，加入双螺杆挤出机中，熔融挤出的同时，在双螺杆的第二个加料口加入增强剂熔融挤出，挤出机的温度设定为如下：A preparation method for nano-flame-retardant polyethylene terephthalate engineering plastics, characterized in that the method has the following process: the dried polyethylene terephthalate masterbatch, flame-retardant Agents, nucleating agents, lubricants, antioxidants, toughening agents, compatibilizers and chain extender additives are fully mixed in a high-speed mixer, then added to a twin-screw extruder, and melt-extruded at the same time The second feed port of the twin-screw is added to the reinforcing agent for melt extrusion, and the temperature of the extruder is set as follows:
一区温度：240～260℃，二区温度：245～265℃，三区温度：250～270℃，Zone 1 temperature: 240～260℃, Zone 2 temperature: 245～265℃, Zone 3 temperature: 250～270℃,
四区温度：255～275℃，五区温度：255～280℃，六区温度：255～280℃Temperature in Zone 4: 255～275℃, Temperature in Zone 5: 255～280℃, Temperature in Zone 6: 255～280℃
七区温度：255～280℃，八区温度：255～280℃，九区温度：255～280℃，Temperature in zone seven: 255～280℃, temperature in zone eight: 255～280℃, temperature in zone nine: 255～280℃,
机头温度245～265℃；真空度-0.08Pa；挤出时的主机转速：15～20r/min；喂料速度7～10r/min。挤出物料经冷却、风干、切粒，干燥后，即得纳米阻燃聚对苯二甲酸乙二醇酯工程塑料。挤出物料经冷却、风干、切粒，干燥后，即得纳米阻燃聚对苯二甲酸乙二醇酯工程塑料。The head temperature is 245-265°C; the vacuum degree is -0.08Pa; the speed of the main machine during extrusion is 15-20r/min; the feeding speed is 7-10r/min. The extruded material is cooled, air-dried, pelletized, and dried to obtain nano flame-retardant polyethylene terephthalate engineering plastics. The extruded material is cooled, air-dried, pelletized, and dried to obtain nano flame-retardant polyethylene terephthalate engineering plastics.
本发明将纳米技术与高分子材料结合，利用纳米改性氢氧化镁、纳米改性蒙脱土与氰尿酸三聚氰胺作为复配阻燃剂与PET熔融共混并通过双螺杆挤出，得到纳米阻燃聚对苯二甲酸乙二醇酯工程塑料。The present invention combines nanotechnology with polymer materials, uses nano-modified magnesium hydroxide, nano-modified montmorillonite and melamine cyanurate as compound flame retardants and melts blends with PET and extrudes through twin-screws to obtain nano-resistors. Burning polyethylene terephthalate engineering plastics.
本发明的优点是采用无卤抑烟阻燃技术，产品具有优良的阻燃性能，达到UL 94V-0，且在燃烧的过程中无融滴现象。此外，该产品具有良好的光泽、尺寸稳定、低翘曲、高模量、高耐热、高抗冲击等性能，且属本色，对于后续加工不会受到颜色的限制，同时价格低廉，可以广泛应用于电子、电气、汽车等领域。The advantage of the invention is that it adopts the halogen-free smoke suppression and flame retardant technology, and the product has excellent flame retardant performance, reaching UL 94V-0, and there is no melting drop phenomenon during the combustion process. In addition, the product has good gloss, dimensional stability, low warpage, high modulus, high heat resistance, high impact resistance and other properties, and is of natural color, and will not be restricted by color for subsequent processing. At the same time, it is cheap and can be widely used Used in electronics, electrical, automotive and other fields.
具体实施方式Detailed ways
结合实施例，对本发明做详细说明。The present invention is described in detail with reference to the embodiments.
实施例1Example 1
按下表样品的配方进行备料；将干燥好的聚对苯二甲酸乙二醇酯母粒、阻燃剂、成核剂、润滑剂、抗氧剂、增韧剂、增容剂和扩链剂助剂在高速混合机中充分混合后，加入双螺杆挤出机中，熔融挤出的同时，在双螺杆的第二个加料口加入增强剂熔融挤出，挤出机的温度设定为如下：一区240；二区245；三区250；四区255；五区260；六区260；七区260；八区260；九区260；机头加热温度(℃)：250，真空度-0.08Pa，挤出造粒。挤出时的主机转速：15～20r/min；喂料速度7～10r/min。挤出物料经冷却、风干、切粒，干燥后，即得纳米阻燃聚对苯二甲酸乙二醇酯工程塑料。样品的配方如下表：Prepare materials according to the formula of the sample in the table below; mix the dried polyethylene terephthalate masterbatch, flame retardant, nucleating agent, lubricant, antioxidant, toughener, compatibilizer and chain extender After the additives and additives are fully mixed in the high-speed mixer, they are added to the twin-screw extruder, and at the same time of melt extrusion, the reinforcing agent is added to the second feeding port of the twin-screw for melt extrusion, and the temperature of the extruder is set to As follows: 240 for the first zone; 245 for the second zone; 250 for the third zone; 255 for the fourth zone; 260 for the fifth zone; 260 for the sixth zone; 260 for the seventh zone; 260 for the eighth zone; -0.08Pa, extrusion granulation. Main engine speed during extrusion: 15~20r/min; feeding speed 7~10r/min. The extruded material is cooled, air-dried, pelletized, and dried to obtain nano flame-retardant polyethylene terephthalate engineering plastics. The formula of the sample is as follows:
上述实施例的样品性能如下表：The sample performance of above-mentioned embodiment is as following table:
上述实施例只为说明本发明的技术构思及特点，并非用以限制本发明的专利范围。凡根据本发明精神实质所作的等效变化或改进，都应包含在本发明的保护范围之内。The above-mentioned embodiments are only for illustrating the technical concepts and features of the present invention, and are not intended to limit the patent scope of the present invention. All equivalent changes or improvements made according to the spirit of the present invention shall be included in the protection scope of the present invention.
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