CN1465621A - Polyester/lamellar silicate nano composite material and preparation method thereof - Google Patents
Polyester/lamellar silicate nano composite material and preparation method thereof Download PDFInfo
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- CN1465621A CN1465621A CNA02123499XA CN02123499A CN1465621A CN 1465621 A CN1465621 A CN 1465621A CN A02123499X A CNA02123499X A CN A02123499XA CN 02123499 A CN02123499 A CN 02123499A CN 1465621 A CN1465621 A CN 1465621A
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229920000728 polyester Polymers 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- -1 polyethylene terephthalate Polymers 0.000 claims description 55
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 39
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 38
- 239000012065 filter cake Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000005119 centrifugation Methods 0.000 claims description 31
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 30
- 239000006228 supernatant Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000138 intercalating agent Substances 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000275 saponite Inorganic materials 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- DTOOTUYZFDDTBD-UHFFFAOYSA-N 3-chloropropylsilane Chemical group [SiH3]CCCCl DTOOTUYZFDDTBD-UHFFFAOYSA-N 0.000 claims description 2
- RXGZYBRXWQMEFT-UHFFFAOYSA-N 4-(2-dodecylphenyl)sulfonylaniline Chemical compound NC1=CC=C(C=C1)S(=O)(=O)C1=C(C=CC=C1)CCCCCCCCCCCC RXGZYBRXWQMEFT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001634 Copolyester Polymers 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- SPBMDAHKYSRJFO-UHFFFAOYSA-N didodecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCOP(O)OCCCCCCCCCCCC SPBMDAHKYSRJFO-UHFFFAOYSA-N 0.000 claims description 2
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N monofluoroacetic acid Natural products OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 230000002687 intercalation Effects 0.000 abstract description 21
- 238000009830 intercalation Methods 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 20
- 239000002131 composite material Substances 0.000 abstract description 19
- 239000000835 fiber Substances 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 2
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 abstract 1
- 238000009775 high-speed stirring Methods 0.000 description 43
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 238000010792 warming Methods 0.000 description 26
- 238000001291 vacuum drying Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 241000446313 Lamella Species 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 235000013405 beer Nutrition 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 150000004760 silicates Polymers 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- NNKSCESTDPOUKU-UHFFFAOYSA-N trioxidanylbenzene Chemical class OOOC1=CC=CC=C1 NNKSCESTDPOUKU-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Images
Abstract
The present invention relates to a kind of polyester/laminate silicate nano composite material and its preparation method. Said preparation method includes the following steps: making organic intercalation agent for silicate and auxiliary treatment agent to make intercalation reaction, then making the above-mentioned material and polyester undergo the process of mechanical melting and co-mixing or melt co-mixing in reactor and dispersing the laminate silicate in the polyester resin base body in nano size so as to obtain the invented nano composite material. Said invented composite material has good physical mechanical property, can be used for making high-choking packaging bottle and packaging bag, and functional fibre, etc.
Description
Technical field:
The present invention relates to a kind of polyester composite, particularly a kind of nano composite material of forming by polyethylene terephthalate (PET) and layered silicate.
Background technology:
PET is a kind of polymkeric substance of high comprehensive performance, can be made into goods such as trevira, biaxially oriented film, packing bottle, engineering plastics, and Application Areas is extensive.But, in fast development of new products, also show PET in recent years and still be weak at some aspect of performance, for example: (1) is not enough aspect resistance to air loss, can not reach the requirement that beer is guaranteed the quality to the resistance ability of oozing of oxygen, carbonic acid gas etc.When making Beer Bottle with it, the outer oxygen infiltration of bottle makes beer oxidation rotten by PET bottle wall, and beer shelf-life is short, and (mould makes 2001,4:31).(2) as the PET engineering plastics time, crystallization velocity is slow, and melt strength is low, require during the machine-shaping product that higher die temperature is arranged (J Appl Polym Sci, 1999,71:1139).
The melt strength of the compound PET of phyllosilicate nano is good, crystallization rate big, easily machine-shaping, help making the engineering plastics product of heat-drawn wire height, dimensional stabilizing, also can be made into packing bottle, the packaging film of high obstructing performance, be used for the compound BOPET film of Beer Bottle and the high resistant of anti-boiling Turner rice (bag) (plastics, 2001,30 (1): 9).But PET and layered silicate adhere to organism and inorganics separately, and physics between them and chemical property difference are big, and it is quite difficult preparing its nano composite material.
Layered silicate has laminated structure, includes three subgrades, is embedded an alumina octahedral subgrade in the middle of two silicon-oxy tetrahedron subgrades, connect with covalent linkage by shared Sauerstoffatom between the subgrade, and the about 1nm of bed thickness, in conjunction with very firm, the about 100nm of length and width.Because the part aluminium atom in the alumina octahedral subgrade is replaced by the low price atom, lamella has negative charge.Superfluous negative charge is by being free on the Na of interlayer
+, Ca
2+And Mg
2+Deng cation balance.The lamella that is being maintained by the interlayer positively charged ion can be opened or part is opened under suitable ambient conditions, forms lamination.The thickness of lamination has just reached nano level dispersion (Chinese plastics, 2001,15 (6): 29) in 100nm.
For the lamination that makes layered silicate (if you would take off soil) is dispersed in the macromolecule matrix, generally all use some positively charged organic molecules both at home and abroad, as alkyl quaternary ammonium salts or other organic cation, carry out ion exchange reaction with interlayer cation and generate organic montmorillonoid.World patent WO 00/78540 A1 report is with organic quaternary amine, season phosphonium salt, sulfur organic, U.S. Pat 005962553A is with organic season phosphonium salt, Japanese patent laid-open 11-1605 is with organic season phosphonium salt, and Japanese Patent organosilicon (Japanese patent laid-open 11-12451, Te Kaiping 11-71509, spy open flat 11-323102) handle layered silicate such as polynite.Because the cationic bulk of organic molecule is more much bigger than metallic cation, interlamellar spacing is strengthened in the organic montmorillonoid.The consistency of organic montmorillonoid and organic polymer matrix is greatly improved, and the interlamellar spacing that has strengthened helps polymer and enters interlayer space, makes laminate structure be easy to disperse.
In the nano-dispersed technology of concrete enforcement layered silicate, there are two technological lines to walk, be respectively intercalation polymeric method and melting intercalation method.
The intercalation polymeric legal system is equipped with the compound PET of phyllosilicate nano, be to contact with polynite mixing earlier through the compatible processing that organises with the monomer (being terephthalic acid, dimethyl terephthalate (DMT), ethylene glycol) of pet polymer, catalysis monomer generation polycondensation again, make polynite peel off structure lamella into nanoscale, evenly spread in the polymeric matrix, thereby form nano combined PET.The intercalation polymeric ratio juris is earlier polymer monomer dispersion, intercalation to be entered in the layered silicate lamella, in-situ polymerization then, a large amount of heats of emitting when utilizing polymerization, overcome the Coulomb's force of silicate plate interlayer, it is peeled off, thereby make silicate lamella and polymeric matrix with nanoscale mutually compound (nanometer organic composite material utilisation technology collection of thesis (Beijing), 1999:10).This method is finished intercalation dispersive energy and is come from the chemical energy that the chemosynthesis process is discharged.The shortcoming of this method is a complex process, the development cost height, and the product limitation is big.
Melting intercalation method is that polymer melt is mixed with layered silicate, utilizes mechanics or thermodynamics effect to make layered silicate peel off into the lamella of nanoscale and be dispersed in and forms the nano composite polymeric material in the polymeric matrix.Melt intercalation compounding technology does not need new high facility investment, environmental friendliness based on traditional blending technology.Compare with the intercalation polymeric method, melting intercalation method can be controlled the molecular weight of PET in advance, simultaneously can require the compound different multiple product trade mark of nanometer component concentration that goes out according to product design, the design grace period is big, controllable product quality is strong, the big I of industrial scale according to market at that time amount of capacity in time adjust.Particularly to obtain the nanometer PET of high barrier, it seems at present and have only feasibility higher (plastics, 2001,30 (6): 25) (technological line is seen Fig. 1) of selecting the melting intercalation method technology of preparing.
Being engaged in nano composite polymer/laminated silicate material at present both at home and abroad develops, only be equipped with and got some progress aspect layered silicate/PET nano composite material in the intercalation polymeric legal system, as: Institute of Chemistry, Academia Sinica adopts in-situ inserted polymerization, with the PET polycondensation monomer is feedstock production polyester/phyllosilicate nano-composite material (Chinese patent application number 97104055.9), obtain the PET nano composite material of polynite, Meccah stone, improved crystallization rate, heat-drawn wire; Yizheng Fiber Optical plant company has also obtained PET/ laminated nm-silicate composite material (Chinese patent publication number CN1324890) with in-situ inserted polymerization; China Textile Science Inst. also reports and has obtained PET/ Nano composite material of montmorillonite (polymer journal, 1999 (3): 15); Japanese patent laid-open 11-130951 has reported thermoplastic polyester/layered silicate matrix material.But, in conventional P ET polymeric kettle, add layered silicate and produce nano combined PET, be subjected to polymerization process complexity in the still, influence that the factor of polyreaction is many etc. to be influenced, former PET polymerization technique is changed big, production efficiency reduces, the variable range of nano-component content is narrow in the matrix material, and intercalation polymeric reaction can only bigger, the single kind of industrial scale, and the product limitation is big.In addition, (250 ℃-290 ℃) also can cause the degraded of layered silicate intercalator in long high temperature polymerization process, and then influence the color and luster of product.
Though fusion mechanical blending method is at the alloy of polymkeric substance, blend, widespread use in composite modified, as prepare the polymer/polymer alloy, filler/polymkeric substance weighting material, glass/polymkeric substance strongthener etc., technology is simple, controllability is strong, suitability is wide, but this method is only seen at present and is used to prepare polyamide/laminated silicate, polypropylene/layered silicate (J Appl Polym Sci, 2000,78:1918), nano composite materials such as poletene/lamina silicate, hydroxyl phenoxy ethers or polyester polymers/layered silicate (Chinese patent publication number CN1212716A) do not obtain polyester/phyllosilicate nano-composite material.U.S. Pat 6287992 B1 have reported that also layered silicate is dispersed in the thermoset nano composite material of epoxy group(ing) Vinylite or unsaturated polyester.
Summary of the invention:
The present invention's's " a kind of polyester/phyllosilicate nano-composite material and preparation method thereof " the component that polyester/phyllosilicate nano-composite material comprised is:
Polyester: 80-99 part, intercalator: 0.001-50 part, layered silicate (montmorillonite or saponite): 0.5-50 part, dispersion medium: 10-1000 part, protonating agent: 0.005-50 part, auxiliary treatment agent: 0.001-50 part, additive: 0.001-1.0 part.
Described polyester is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC), copolyester, and two or more mixture.
Described intercalator is a lauryl amine, hexadecylamine, hexanediamine, lauric acid amine, trolamine, Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, octadecyl benzyl dimethyl brometo de amonio.
Described dispersion medium is deionized water, acetone, ethanol, methyl alcohol, butanols, toluene, dimethylbenzene etc.
Described protonating agent is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetate, phenylformic acid etc.
The ion exchange capacity (CEC) of described polynite (calcium base, lithium base or sodium base) or saponite is 80-120meq./100g.
Described auxiliary treatment agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, Resins, epoxy, or their two or more mixtures wherein; As the chloropropyl silane coupling agent, epoxy silane coupling, methacrylate based silane coupling agent, the amino containing silane coupling agent, cationic silane coupling agent, or their two or more mixtures wherein, sec.-propyl three isophthaloyl titanic acid ester, sec.-propyl dodecyl benzene sulfonyl titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, two (dioctyl phosphorous acid ester) titanic acid ester of tetra isopropyl, two (two (dodecyl) phosphorous acid ester) titanic acid ester of four octyl groups, four (2,2-two allyloxys-1-butyl) two (two (tridecyl) phosphorous acid ester) titanic acid ester, two (dioctylphyrophosphoric acid ester) fluoroacetic acid ester titanic acid ester, isopropyl stearyl two acryloyl titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester) titanic acid ester, sec.-propyl two (dodecyl benzene sulfonyl)-4-amino-benzene sulfonyl titanic acid ester, sec.-propyl three (methacryloyl) titanic acid ester, dilauryl phosphorite type titanic acid ester, isopropyl stearyl two (4-aminobenzoyl) titanic acid ester, sec.-propyl three acryloyl titanic acid ester, epoxy 628, epoxy E-51,1050,1051,4051, polyethylene oxide, poly(propylene oxide), and their two or more mixtures wherein.
Described auxiliary treatment agent addition is the 10-100% of polynite (calcium base, lithium base or sodium base) or saponite quality.
Described additive is oxidation inhibitor, lubricant, fire retardant, static inhibitor, antiseptic-germicide etc.
The preparation method of polyester/phyllosilicate nano-composite material of the present invention follows these steps to carry out:
1, the modification of layered silicate (1) earlier is that layered silicate 0.5-10 part of 80-120meq./100g is stirred and risen to 50-100 ℃ of temperature in the dispersion medium high speed of 10-1000 part with the cationic exchange total volume, forms stable suspensoid.(2) with intercalator 0.001-10 part, protonating agent 0.001-10 part is distributed to earlier in 0.05-50 part dispersion medium, slowly adds in the above-mentioned suspensoid again and carries out violent stirring, and centrifugation after 1-3 hour discards supernatant liquid, obtains filter cake.(3) with filter cake in 50-100 ℃ of oven dry, pulverize, again the dispersion medium high speed that is dispersed in 10-1000 part again stirs, the dispersion medium high speed that perhaps filter cake directly is dispersed in 10-1000 part stirs, the auxiliary treatment agent that adds 0.05-10 part again, continuing to rise to 50-100 ℃ of temperature stirred 0.5-3 hour, centrifugation goes out solid matter in 50-100 ℃ of oven dry again, pulverizes, and obtains modified layered silicate.
2, the modified sheet silicate after the preparation of matrix material will be pulverized mixes through 2-5 hour vibrin high-speed stirring of 100-150 ℃ of oven dry with 80-99 part, and the twin screw extruder extruding pelletization obtains polyester/phyllosilicate nano-composite material.Modified Portland and polyester after perhaps will pulverizing are earlier made the master batch that contains the 4-25% modified Portland through melt blending, with master batch and the further melt blending of polyester, obtain polyester/phyllosilicate nano-composite material again.Or modified sheet silicate joined in the pet reaction still that polymerization finishes mix with polyester fondant, obtain polyester/phyllosilicate nano-composite material.
The present invention's " a kind of polyester/phyllosilicate nano-composite material and preparation method thereof " uses compound organic intercalation agent, the auxiliary treatment agent organises natural layered silicate, enlarge the interlamellar spacing of layered silicate earlier, and then under molten state, pass through in mechanical blending or the reactor melt blended with polyester, layered silicate is dispersed in the vibrin matrix with nanoscale obtains nano composite material, can regulate and control nanophase component concentration in the matrix material on a large scale, thereby make the physical and mechanical properties of the polyester/phyllosilicate nano-composite material that makes good, variable range is wide, can be applicable to respectively and make high gas barrier property packing bottle and packing bag, heat-resistant engineering plastic and packing articles, functional fiber etc. (seeing Fig. 2, table 1).
The present invention's " a kind of polyester/phyllosilicate nano-composite material and preparation method thereof " is although difficulty is big aspect formulating, and to the degree height of equipment technology innovation requirement, technological operation is more convenient, and cost is low, realizes the feasibility height of suitability for industrialized production.Table 2 is listed in the technical characterstic contrast that the fusion intercalation preparation method of polyester/phyllosilicate nano-composite material of the present invention and intercalation polymeric prepare method.
The Figure of description explanation
Fig. 1, fusion intercalation prepare the technological line block diagram of nanometer PET and goods thereof
Fig. 2, the transmission electron microscope photo of the compound PET of polyester/phyllosilicate nano
Polyester/phyllosilicate nano-composite material laminate silicate content 5%, what photo represented is the lamella and the stepped construction thereof of layered silicate
Embodiment:
Embodiment 1 is the polynite 5g of 120meq./100g with the cationic exchange total volume, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 0.6ml and 2.6g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 300ml ethanol again, again stir, be warming up to backflow, add 1g epoxy 628 (Shell companies), refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake was in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 2 is the polynite 5g of 120meq./100g with the cationic exchange total volume, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 0.6ml and 2.6g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 200ml ethanol again, again stir, be warming up to 60 ℃, add 0.2g silane coupling agent (Z6030 of Dow Corning Corporation), stirred 1 hour, discard supernatant liquid after the centrifugation, filter cake was in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 3 is the polynite 10g of 100meq./100g with the cationic exchange total volume earlier, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 1.0ml and 4.2g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 100ml ethanol again, again stir, be warming up to backflow, add 1g epoxy 628 (Shell companies), 0.2g silane coupling agent (Z6030 of Dow Corning Corporation), refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 4 is the polynite 10g of 100meq./100g with the cationic exchange total volume earlier, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 1.0ml and 5.0g octadecyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours discards supernatant liquid, and filter cake is dispersed in the 100ml ethanol again, again stir, be warming up to backflow, add 4g epoxy 1051, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake was in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 5 is the polynite 10g of 100meq./100g with the cationic exchange total volume earlier, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 1.0ml and 5.0g octadecyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 100ml ethanol again, again stir, be warming up to backflow, add 2g epoxy 1051 and 0.1g silane coupling agent (Z6030 of Dow Corning Corporation) respectively, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake was in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 6 is the polynite 15g of 80meq./100g with the cationic exchange total volume earlier, add deionized water 400ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 1.2ml and 5.0g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours discards supernatant liquid, filter cake is dispersed in the 300ml acetone again, again stir, rise to backflow, add 5g epoxy 4050, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is pulverized in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 7 is the polynite 25g of 100meq./100g with the cationic exchange total volume earlier, add deionized water 400ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 2.34ml and 10.2g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 300ml ethanol again, again stir, be warming up to backflow, add 10g epoxy 1050, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is pulverized in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 8 is the polynite 25g of 100meq./100g with the cationic exchange total volume earlier, add deionized water 400ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 2.34ml and 10.2g octadecyl benzyl dimethyl brometo de amonio are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 300ml deionized water again, again stir, be warming up to backflow, add 10g epoxy ME-2, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is pulverized in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 9 is the polynite 50g of 80meq./100g with the cationic exchange total volume earlier, add deionized water 1000ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 7.8ml and 50.2g octadecyl benzyl dimethyl brometo de amonio are added in the 500ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 500ml deionized water again, again stir, be warming up to backflow, add 30g epoxy ME-2, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is pulverized in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 10 is the saponite 5g of 120meq./100g with the cationic exchange total volume, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 0.6ml and 2.6g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 300ml ethanol again, again stir, be warming up to backflow, add 1g epoxy 628 (Shell companies), refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake was in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPET high-speed stirring of 120 ℃ of oven dry again, obtain the PET/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 11 is the polynite 5g of 120meq./100g with the cationic exchange total volume, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 0.6ml and 2.6g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 300ml ethanol again, stirs again, be warming up to backflow, add 1g epoxy 628 (Shell companies), refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours.Add in the polymeric kettle that contains 500gPET that new polymerization finishes, high-speed stirring was mixed 30 minutes, obtained the PET/ laminated nm-silicate composite material with screw rod discharging machine extruding pelletization again.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 12 is the saponite 5g of 120meq./100g with the cationic exchange total volume, add deionized water 200ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 0.6ml and 2.6g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 300ml ethanol again, again stir, be warming up to backflow, add 1g epoxy 628 (Shell companies), refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake was in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPC high-speed stirring of 120 ℃ of oven dry again, obtain the PC/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 13 is the polynite 15g of 80meq./100g with the cationic exchange total volume earlier, add deionized water 400ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 1.2ml and 5.0g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours discards supernatant liquid, filter cake is dispersed in the 300ml acetone again, again stir, rise to backflow, add 5g epoxy 4050, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is pulverized in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPBT high-speed stirring of 120 ℃ of oven dry again, obtain the PBT/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Embodiment 14 is the polynite 25g of 100meq./100g with the cationic exchange total volume earlier, add deionized water 400ml, high-speed stirring was uniformly dispersed in 0.5 hour, obtain stable suspensoid, again concentrated hydrochloric acid 2.34ml and 10.2g cetyl trimethylammonium bromide are added in the 100ml deionized water, slowly add the latter in the suspensoid, continue high-speed stirring and be warming up to 80 ℃, centrifugation after 2 hours, discard supernatant liquid, filter cake is dispersed in the 300ml ethanol again, again stir, be warming up to backflow, add 10g epoxy 1050, refluxed 1 hour, discard supernatant liquid after the centrifugation, filter cake is pulverized in 50 ℃ of air blast oven dry 10 hours, again with it in 80 ℃ of vacuum dryings 3 hours, mix with 5 hours 500gPBT high-speed stirring of 120 ℃ of oven dry again, obtain the PBT/ laminated nm-silicate composite material with Φ 30 twin screw extruder blend granulations.In matrix material, layered silicate disperse phase yardstick is 3～100nm.
Table 1, the physical and mechanical properties of polyester/phyllosilicate nano-composite material
| Embodiment | Laminar silicic acid salts contg (%) | X-ray diffraction is surveyed D001 interplanar distance (nm) | Tensile break strength (MPa) | Elongation at break (%) | Modulus in flexure (MPa) | Notched Izod impact strength (J.M -1) | Heat-drawn wire (1.84 MPa, ℃) |
| ????PET | ????0 | ????- | ????65 | ????300 | ????1600 | ????30 | ????78 |
| ????1 | ????1 | ????3.1 | ????65 | ????60 | ????2200 | ????25 | ????80 |
| ????5 | ????2 | ????≥3.1 | ????66 | ????60 | ????2350 | ????18 | ????85 |
| ????6 | ????3 | ????≥3.1 | ????66 | ????40 | ????2840 | ????16 | ????91 |
| ????7 | ????5 | ????≥3.1 | ????67 | ????30 | ????3600 | ????10 | ????109 |
| ????10 | ????1 | ????3.0 | ????65 | ????60 | ????2150 | ????26 | ????79 |
| ????11 | ????1 | ????3.1 | ????65 | ????120 | ????2250 | ????25 | ????82 |
| ????PBT | ????0 | ????- | ????61 | ????40 | ????2100 | ????28 | ????- |
| ????13 | ????3 | ????≥3.0 | ????61 | ????40 | ????2400 | ????30 | ????- |
| ????14 | ????5 | ????≥3.0 | ????56 | ????30 | ????2700 | ????32 | ????- |
Table 2, intercalation polymeric method and melt intercalated method prepare nano combined PET
The technical economical analysis contrast
| Project | The intercalation polymeric method | Melt intercalated method | Remarks |
| Technological layer | Complex process | Technology is simple | |
| Facility investment is big | Facility investment is less | ||
| The development cost height | The development cost height | ||
| Nanometer PET product aspect | Industrial scale is big | Scale is changeable | |
| Nano-component content is lower | Nano-component content is higher | ||
| Cost is lower | Cost is low slightly | ||
| Nanometer PET Beer Bottle aspect | Barrier can not reach requirement | Barrier can reach requirement | |
| Thermotolerance is relatively poor | Good heat resistance | ||
| Easily processing | Easily processing |
Claims (10)
1, a kind of polyester/phyllosilicate nano-composite material, it is characterized in that described matrix material comprises polyester: 80～99 parts, intercalator: 0.001～50 part, the disperse phase yardstick is the layered silicate of 3～100nm: 0.5～50 part, dispersion medium: 10～1000 parts, protonating agent: 0.005～50 part, the auxiliary treatment agent: 0.001～50 part, additive: 0.001～1.0 part.
2, a kind of polyester/phyllosilicate nano-composite material according to claim 1, it is characterized in that described polyester is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC), copolyester, and two or more mixture.
3, a kind of polyester/phyllosilicate nano-composite material according to claim 1, it is characterized in that described intercalator is a lauryl amine, hexadecylamine, hexanediamine, lauric acid amine, trolamine, Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, or octadecyl benzyl dimethyl brometo de amonio.
4, a kind of polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that described dispersion medium is water, acetone, ethanol, methyl alcohol, ethylene glycol, toluene, or dimethylbenzene.
5, a kind of polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that described layered silicate is polynite (calcium base, lithium base or sodium base) or saponite, and ion exchange capacity (CEC) is 80meq～120meq/100g.
6, a kind of polyester/phyllosilicate nano-composite material according to claim 1, it is characterized in that described auxiliary treatment agent is a silane coupling agent, titanate coupling agent, aluminate coupling agent, or Resins, epoxy, and their two or more mixtures wherein.
7, a kind of polyester/phyllosilicate nano-composite material according to claim 6, it is characterized in that described silane coupling agent is chloropropyl silane coupling agent, epoxy silane coupling, methacrylate based silane coupling agent, amino containing silane coupling agent or cationic silane coupling agent, and their two or more mixtures wherein.
8, a kind of polyester/phyllosilicate nano-composite material according to claim 6, it is characterized in that described titanate coupling agent is sec.-propyl three isophthaloyl titanic acid ester, sec.-propyl dodecyl benzene sulfonyl titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, two (dioctyl phosphorous acid ester) titanic acid ester of tetra isopropyl, two (two (dodecyl) phosphorous acid ester) titanic acid ester of four octyl groups, four (2,2-two allyloxys-1-butyl) two (two (tridecyl) phosphorous acid ester) titanic acid ester, two (dioctylphyrophosphoric acid ester) fluoroacetic acid ester titanic acid ester, isopropyl stearyl two acryloyl titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester) titanic acid ester, sec.-propyl two (dodecyl benzene sulfonyl)-4-amino-benzene sulfonyl titanic acid ester, sec.-propyl three (methacryloyl) titanic acid ester, dilauryl phosphorite type titanic acid ester, isopropyl stearyl two (4-aminobenzoyl) titanic acid ester, or sec.-propyl three acryloyl titanic acid ester, and their two or more mixtures wherein.
9, a kind of polyester/phyllosilicate nano-composite material according to claim 6 is characterized in that described Resins, epoxy is epoxy 628, epoxy E-51,1050,1051,4051, polyethylene oxide, or poly(propylene oxide), and their two or more mixtures wherein.
10, the preparation method of a kind of polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that following these steps to carrying out:
Earlier be that 0.5～10 part of dispersion medium high speed at 10～1000 parts of layered silicate of 80～120meq/100g stirs and rises to 50-100 ℃ of temperature, form stable suspensoid the cationic exchange total volume; To be distributed to 0.001～10 part of 0.05～50 part of intercalator in the dispersion medium more in advance, 0.001～10 part of protonating agent slowly adds in the above-mentioned suspensoid and carries out violent stirring; Centrifugation after 1～3 hour, discard supernatant liquid, with behind the filtration cakes torrefaction or filter cake directly be dispersed in 10～1000 parts dispersion medium high speed again and stir, add 0.05～10 part auxiliary treatment agent again, continue to rise to 50-100 ℃ of temperature and stirred 1～3 hour; Centrifugal again or filter to isolate solid matter in 50-100 ℃ of oven dry, pulverize, obtain modified sheet silicate; Modified sheet silicate and vibrin after pulverizing are mixed,, obtain polyester/phyllosilicate nano-composite material at twin screw extruder melting mixing extruding pelletization; Or make the master batch that contains the 4-25% layered silicate earlier, obtain polyester/phyllosilicate nano-composite material with the granulation of polyester melt blending again; Or modified sheet silicate joined in the pet reaction still that polymerization finishes mix with polyester fondant, obtain polyester/phyllosilicate nano-composite material.
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