CN1125115C - 层状矿物及其组合物 - Google Patents
层状矿物及其组合物 Download PDFInfo
- Publication number
- CN1125115C CN1125115C CN96106007A CN96106007A CN1125115C CN 1125115 C CN1125115 C CN 1125115C CN 96106007 A CN96106007 A CN 96106007A CN 96106007 A CN96106007 A CN 96106007A CN 1125115 C CN1125115 C CN 1125115C
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- China
- Prior art keywords
- positively charged
- heteroatoms
- composition
- charged ion
- layer mineral
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims description 58
- 239000011707 mineral Substances 0.000 title claims description 58
- 125000005842 heteroatom Chemical class 0.000 claims abstract description 43
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- -1 heteroaromatic cation Chemical class 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims description 59
- 125000002091 cationic group Chemical group 0.000 claims description 20
- 229920001955 polyphenylene ether Polymers 0.000 claims description 20
- 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 18
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 16
- 229920002601 oligoester Polymers 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 229920000515 polycarbonate Polymers 0.000 claims description 13
- 239000004417 polycarbonate Substances 0.000 claims description 13
- 125000004429 atom Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229920001601 polyetherimide Polymers 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 4
- 229910000271 hectorite Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052902 vermiculite Inorganic materials 0.000 claims description 4
- 239000010455 vermiculite Substances 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 229910001594 brammallite Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910001649 dickite Inorganic materials 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000002475 indoles Chemical class 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 239000008239 natural water Substances 0.000 claims description 3
- 229910000273 nontronite Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- 229910000276 sauconite Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical group CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910052626 biotite Inorganic materials 0.000 claims description 2
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 6
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical class [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 229910052604 silicate mineral Inorganic materials 0.000 abstract description 3
- 238000005341 cation exchange Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- PCVVBHUFWPHCAL-UHFFFAOYSA-N butane-1,4-diol;terephthalic acid Chemical compound OCCCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 PCVVBHUFWPHCAL-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 150000002390 heteroarenes Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-O dodecylazanium Chemical group CCCCCCCCCCCC[NH3+] JRBPAEWTRLWTQC-UHFFFAOYSA-O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical class [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 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 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical class C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZDPRGVZJAFZMPE-UHFFFAOYSA-N n,n,1-tributylpyridin-1-ium-4-amine Chemical compound CCCCN(CCCC)C1=CC=[N+](CCCC)C=C1 ZDPRGVZJAFZMPE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical class CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical class CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/20—Mica; Vermiculite
- C04B14/206—Mica or vermiculite modified by cation-exchange; chemically exfoliated vermiculate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
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Abstract
本发明描述的是一种与至少一种杂芳族阳离子进行阳离子交换的新的硅酸盐矿物及其组合物，该阳离子是含一个带正电荷的有机取代的杂原子和/或至少一个带正电荷的杂原子，该杂原子不在芳族环上，该环具有至少一个键序大于1的键。
Description
本发明涉及新的硅酸盐矿物及其包含它们的组合物。特别是本发明涉及与至少一种杂芳族阳离子进行阳离子交换的层状矿物，该阳离子是由一带正电荷的有机取代的杂原子和/或至少一种带正电荷的杂原子组成，该杂原子不在芳族环上，该环具有至少一个键序大于1的键。
由聚碳酸酯、聚酯和聚亚苯基醚组成的组合物可制成例如价值很高的工程热塑塑料。它们的特征在于化学、物理、电学的独特结合。例如，它们具有化学稳定性并且通常又具有高的冲击强度。
人们逐渐关心制备一种聚合物组合物，这种组合物在保持它们的特性的同时，又具有高的热偏差温度。特别是需要具有增加热偏差温度的聚碳酸酯、聚酯和聚亚苯基醚的组合物，这是因为它们通常被用于暴露在高温下的工业应用中。此外，为了改性，例如把填料加到聚合物组合物中。
因此，本发明发现了一种可以被用作为组合物的组份的新的层状矿物和可由低粘度大环低聚物制备的新组合物。
人们已经公开了制备聚合纳米级复合材料的成果。在国际专利申请WO94/11430中，描述了有两种必要组份的纳米级复合材料和这两种必要组份是γ相聚酰胺和层状纤丝状的无机材料，该材料是经季铵阳离子处理的。
制备含层状硅酸盐的复合材料也取得了其它成果。在美国专利4889885中，描述了具有高机械强度和耐热性的复合材料，该材料适用于汽车部件、飞机部件和建筑材料。
本发明与上述的成果具有专利区别，这是因为连同其它原因在内，本发明涉及的新的层状矿物是与至少一种杂芳族阳离子进行阳离子交换的层状矿物，该阳离子是由一带正电荷的有机取代杂原子和/或至少一种带正电荷的杂原子组成，该杂原子不在芳族环上，该环具有至少一个键序大于1的键，以及由它们制成的组合物。另外，本发明涉及由低粘度大环低聚物制备的新的组合物。
第一方面，本发明涉及与选自下述组的至少一种阳离子进行离子交换的新的层状矿物：
(a)含至少一个带正电荷的有机取代杂的原子的杂芳族阳离子，
(b)含至少一个带正电荷的有机杂原子阳离子，该杂原子不在芳族环上，该环具有至少一个键序大于1的键。
第二方面，本发明涉及含至少一种有机体系的组合物，该有机体系是大环聚合物和/或直链聚合物和/或支链聚合物以及前面提到的与(a)和(b)中所述的至少一种阳离子进行阳离子交换的层状矿物。
第三方面，本发明涉及含大环低聚物和层状矿物的组合物，该层状矿物与鎓类化合物进行阳离子交换。
第四方面，本发明涉及在层状矿物的存在下通过聚合大环低聚物制备聚合物的方法。
第五方面，本发明涉及大环低聚物组成的聚合产品。
这里所述的组合物优选的常常包含与在(a)和(b)中所述的阳离子进行阳离子交换的层状矿物，因为这类组合物明显地提高了刚度，它是通过弹性模量的增加来表示的，和/或明显地提高了稳定性，它是通过分子量来表示的。此外，把聚合物和层状矿物混合之后，可将组合物称之为纳米级复合材料，本文中纳米级复合材料被定义为有机体系和分散在其中的层状矿物(粘土)组份的组合物，且层状矿物至少有一维是纳米级大小。
就本发明中所使用的层状矿物而言，除了它们能与上述的阳离子和/或鎓类化合物进行阳离子交换外，对其没有限制。本发明中可使用的这类层状矿物的实例包括例如高岭石类和蒙脱石类。前者可包括高岭石、多水高岭石、地开石和珍珠陶土等。后者包括蒙脱石、囊脱石、贝得石、水辉石和滑石粉等。
使用伊利石的矿物也在本发明的范围之内，它们包括水云母、多硅白云母、钠伊利石、海绿石和绿鳞石等。此外层状矿物包括水羟硅钠石、天然水玻璃、白云母、锌蒙脱石、蛭石、铬岭石以及在本发明中也可以使用的
叶蜡石类、云母类或绿土类；条件是它们能与上述提及的阳离子进行阳离子交换。
此外，分类为层状双氢氧化物的层状矿物以及在层上带有少量或不带电荷的层状矿物也包括在本发明的范围之内，只要该层状矿物与上述的阳离子和鎓类化合物接触时能够膨胀。
但是，优选的层状矿物常常包括那些称之为2∶1的层状硅酸盐矿物，象白云母、蛭石、贝得石、滑石粉、水辉石和蒙脱石，其中，常常优选蒙脱石。
除了上述粘土外，也能使用由它们制成的混合物以及副矿物，例如石英、黑云母、褐铁矿、水云母和长石等。
上述矿物可以人工合成制造。但大多数是天然存在的和从市场上买到的。一般通过许多方法制备，包括硅酸盐的水解和水合、页岩风蚀以及酸性粘土、腐殖土和无机酸对原生硅酸盐的作用。
这里所使用的阳离子定义为例如从杂芳族化合物、杂脂环族化合物、或被取代的或未被取代的杂芳族化合物衍生的带正电荷的化合物，包括单环、双环、三环和多环化合物。
在本发明中对含至少一种带正电荷的有机取代的杂原子的杂芳族化合物阳离子，或含至少一个带正电荷的杂原子的阳离子没有限制，该杂原子不在芳族环上，该环具有至少一个键序大于1的键。本文中大于1的键序被称之为大于单键的任何键，包括部分双键和双键。条件是只要能够与本发明所使用的层状矿物进行阳离子交换。
除了有机取代的杂原子外，本发明中所使用的杂芳族阳离子，也可以在原子上是被取代或未被取代的，并且它们能包含多于1个的杂原子。因此，从C3-14芳族衍生的阳离子包括在本发明的范围之内，包括苯、萘、蒽或菲等，通篇所用“从……衍生”词意指用至少一个杂原子代替至少一个骨架碳原子。
含至少一个带正电荷的原子(该原子具有至少一个键序大于1的键)的阳离子包括例如：亚胺(席夫碱类)和由其衍生的inium阳离子，例如包含阳离子的吖、噻、磷杂和噁。因此，含至少一个带正电荷的有机取代的杂原子，和含至少一个带正电荷的杂原子的阳离子的(该杂原子不在芳族环上，该环具有至少一个键序大于1的键)杂芳族阳离子，在本文中称之为inium型阳离子，这是因为它们的性质是三角平面形，与性质是四面体的鎓型阳离子有区别。
对本发明中所使用的杂原子没有限制，它们常常选自N、P、O和S，特另是N。
本发明所使用的含至少一种带正电荷的有机取代的杂原子的通常优选的杂芳族阳离子包括例如吡咯、咪唑、噻唑、噁唑、吡啶、嘧啶、喹啉、异喹啉、吲哚、嘌呤、苯并咪唑、苯并三唑、苯并噁唑、吡嗪、喹喔啉、吖啶、吩嗪、咪唑并吡啶和联吡啶等的N-有机取代的盐。
在有机取代的杂原子上的有机取代基常常是C1-25脂肪族基、脂环族基或芳族基，优选C1-18基团，通常优选的阳离子是N-C10-18吡啶鎓阳离子。举例说明包括例如N-十二烷基吡啶鎓阳离子、N、N′-双十四烷基苯并咪唑鎓盐阳离子和4-(二烷基氨基)-N-烷基吡啶鎓阳离子如4-(二丁基氨基)-N-丁基吡啶鎓阳离子等。
含至少一个杂原子(该原子具有一个键序大于1的键)，组成的离子常常包括例如具有下式的离子其中R1、R2、R3和R4分别独立地表示氢、C1-20烷基、芳香基、取代的杂原子或
和R5是氢或C1-10烷基，或至少R1和R2、R3和R4、R1和R3以及R2和R4之一与连接它们的原子一起能形成4-10节的单环或双环。本发明常常使用的优选阳离子包括胍盐和脒盐；因此，胍盐型和脒盐型离子，举例说明包括六烷基胍盐如N，N，N′，N′，N″，N″六丁基胍盐离子以及在美国专利5132423中所述的胍盐离子，这里引入本文作为参考。
含至少一个杂原子(该原子具有一个键序大于1的键)的其它阳离子包括例如从C1-14杂脂环族链烯衍生的阳离子例如二环十二碳烯、二环壬烯、二环十一碳烯、三环十四碳烯等以及由二环和螺二环化合物衍生的阳离子。
当用大环低聚物制备组合物时，可以使用与鎓类化合物进行阳离子交换的层状矿物。这种鎓类化合物包括铵、磷鎓和锍型盐例如有下式的盐其中每个R6独立地表示氢、C1-20烷基或取代或非取代的芳香基或两个R6与连接它们的原子一起能形成4-12节的单环或双环和X代表N、P或S以及Y代表阴离子常常是Cl或Br。至少一种R6包含反应的官能团也属于本发明的范围之内，例如不饱和烃基、包含羧基的羧酸衍生物，包含氮的衍生物例如胺等以及环氧基和原酸酯基等。
可以使用的其它鎓类阳离子包括例如吡咯烷、哌啶、哌嗪和吗啉的盐以及从二环十二烷、二环壬烷、二环十一烷和三环十四烷等衍生的杂阳离子。
包含与至少一种杂芳族阳离子进行阳离子交换的层状矿物(该阳离子含一个带正电荷的有机取代的杂原子和/或至少一个带正电荷的杂原子，该杂原子不在芳族环上，该环具有至少一个键序大于1的键)的本发明组合物也包含有机体系，该有机体系被定义为能够与层状矿物结合的任何聚合物或低聚物。这种有机体系常常包括大环低聚物以及直链和支链的聚合物。对本发明使用的有机体系是没有限制的，它们是在工业上已知和按传统法生产。它们常常包括由聚碳酸酯、聚酯、聚亚苯基醚、聚酰亚胺、烯烃、聚醚酰亚胺、酰胺、聚亚芳基硫化物、聚砜、聚醚酮、丙烯腈丁二烯苯乙烯共聚物、聚苯乙烯组成的直链和支链的聚合物和由它们制成的混合物组合物或共聚物。
另外，本发明使用的有机体系常常可包括大环低聚物，它们选自大环聚碳酸酯、聚酯、聚酰亚胺、聚醚酰亚胺、聚亚苯基醚聚碳酸酯共低聚物、聚醚酰亚胺聚碳酸酯共低聚物和由它们制备的混合物，组合物和共低聚物。此外，常常优选包括聚酯、聚碳酸酯或聚亚苯基醚的有机体系。这类有机体系典型地包括例如聚酯如聚(1，2-对苯二酸-乙二醇)、聚(1，4-对苯二酸-丁二醇)、聚(1，2-亚乙基2，6-萘二羧酸酯)等和它们的共聚物，聚碳酸酯如双酚A聚碳酸酯等和聚亚苯基醚，包括含2，6-二甲基-1，4-亚苯基醚单元或2，3，6-三甲基-1，4-亚苯基醚单元的高聚物以及它们的共聚物。这里应注意的是所有的有机体系通过本领域已知的方法，包括本领域通用的酸、酐和原酸酯型官能化作用可以使其具有官能化的或非官能化的作用。
本发明的层状矿物一般具有带负电荷层，该层中嵌有无机碱和/或碱土阳离子。结果在带电层和阳离子之间有强静电作用，致使层状矿物常常难以分散在非极性的有机体系中。在本发明中，层状矿物的制备例如是通过把它们置于阳离子作用下，该阳离子是由带正电荷的有机取代的杂原子和/或至少一个带正电荷的杂原子组成的，该杂原子不在芳族环上，该环具有至少一个键序大于1的键，通常分散在由水和包括醇类和酮类水溶的有机溶剂的均匀分散体中。
包含层状矿物的组合物例如是通过在聚合作用之前，将层状矿物与聚合物熔融混合/挤压或在低粘度大环低聚物混合层状矿物制备的，其中低粘度定义为小于2000厘泊。当层状矿物在低粘度大环低聚物中混合时，通常通过加入适当的催化剂如包含聚合催化剂的锌、钛或锡后形成聚合物。此外，本发明中包含层状矿物的组合物常常含不超过约70％(重量)，优选不超过约40％(重量)，更优选不超过20％(重量)的层状矿物(基于组合物的总重量)。
下面的实施例进一步说明和便于理解本发明。所得到的产品可以通过常规技术例如质子和碳13核磁共振分光镜和GPC分析得到证实。
实施例1：
把500毫升水、200毫升甲醇和11克钠蒙脱石(10％水119meq/100克)加入混合机中，加入部分钠蒙脱石是为了产生均匀的分散液。强力搅拌均匀的分散液，并同时向分散液中加入由4.85克(26.2毫摩尔)胺、2.64克37％盐酸溶液、25毫升水和25毫升甲醇组成的十二烷基氯化铵溶液。产生白色沉淀并通过过滤回收，接着用水冲洗。将所产生的经冲洗的沉淀物重新分散在700毫升水中。通过过滤和真空冷冻干燥重新回收得到的经冲洗的沉淀物(具有与铵阳离子进行阳离子交换的蒙脱石)。
实施例2：
在实施例2中，除了使用N-十六烷基吡啶鎓氯化物代替十二烷基氯化铵外用与实施例1中所述的相同方法制备层状矿物。回收与含带正电荷的有机取代杂的原子的阳离子进行阳离子交换的蒙脱石。
实施例3和4：
通过下列步骤制备大环低聚物组合物，将两个混合烧瓶都装入4.8克大环低聚物(乙二醇和丁二醇5∶95混合的环对苯二酸酯共低聚物，基于共低聚物的总重量)，一个(实施例3)具有实施例1中所述经过阳离子交换的蒙脱石(0.2克)，另一个(实施例4)具有实施例2中所述经过阳离子交换的蒙脱石(0.2克)。所得到的混合物用氮气冲洗，然后在0.05毫米汞柱的真空中在110℃干燥0.5小时。然后把烧瓶放在油浴中在真空下保持在190℃下熔化混合物。生成的低粘度半透明的液体在190℃下搅拌15分钟生成大环低聚物熔融组合物。接着冷却，将层状矿物的固态组合物物均匀地分散在其中。
实施例5：
将聚合催化剂二辛基锡dioctoxide(62μl，0.109毫摩尔)在190℃下加入到在实施例4中制备的大环低聚物熔融组合物中，聚合低聚物。在大约15秒钟内熔融体变为粘稠体，在大约2分钟内形成含具有进行阳离子交换的蒙脱石的固体聚合物组合物。通过凝胶渗透色谱法测定得到的聚合组合物的重均分子量(Mw)为103000。
实施例6：
除了使用环状对苯二酸丁二醇均低聚物代替由乙二醇和丁二醇的5∶95混合物组成的环对苯二酸酯共低聚物，使用2，2-二乙基-1，3-丙烯二氧钛酸二辛酯作为聚合催化剂代替二辛基锡dioctoxide外，按照与实施例5中所述的相同方法制备组合物。得到的聚合组合物的重均分子量为145000。
实施例7：
在本实施例中，除了使用实施例2中制备的蒙脱石代替实施例1中制备的蒙脱石和使用钛酸四辛酯聚合催化剂代替2，2-二乙基-1，3-丙烯二氧钛酸二辛酯外，按照与实施例6中所述的相同方法制备组合物。重均分子量为139000。
实施例8：
将聚亚苯基醚(包含2，6-二甲基-1，4-亚苯基醚单元的均聚物)(20份)和实施例2中制备的蒙脱石(1份)完全混合的干混合物，用双螺旋挤压机，在295℃下、喂料速度约为40克/分钟、400转/分钟的操作条件下挤压。使挤出物成粒，在真空烘箱里在90℃下干燥，在310℃下，用15吨注射模型成形机将测试样品注射模制。组合物在室温下具有的剪切模量为13.9×109达因/厘米2，比使用未改性的蒙脱石生产的组合物的模量增加29％。使用鎓盐改性蒙脱石生产的组合物的模量只提高15％。
实施例9：
在本实施例中，除了使用聚(1，4-对苯二酸丁二醇)粉代替聚亚苯基醚和挤压机温度为约260℃外，按照与实施例8中所述的相同方法制备组合物。将所得到的挤压物成粒、在空气循环烘箱中在120℃下干燥4小时，并在30吨注射模成形机上模制。组合物的重均分子量为97.2×103，而使用十二烷基铵阳离子改性的层状矿物制备的组合物的重均分子量为84.6×103。
下表中提供的数据表明：本发明具有意想不到的和优良的特性。所有数值是按照与实施例中所述的相同方法作出的。
表I
序号 有机体系a层状矿物b阳离子c T℃ 剪切模量d
1 PBT 无 无 60 4.59
150 0.86
200 0.51
2 PBT M Na+ 60 5.74
150 1.13
200 0.666
3 PBT m Na+ 60 7.88
200 0.87
4 c-PBT M′ DDA 60 6.80
150 1.79
200 0.82
5 PBT M DDA 60 9.04
6 PBT m DDA 60 15.6
7 PBT M DDA 200 0.88
8 PBT m DDA 200 1.38
9 PBT M HDA 60 9.8
200 0.97
10 PBT M HDP 60 8.27
200 0.85
11 PPE 无 无 25 10.2
12 PPE M Na+ 25 10.8
13 PPE M HDA 25 12.4
14 PPE M HDP 25 13.9aPBT＝聚(1，4-对苯二酸丁二醇)；c-PBT＝这里是大环对苯二酸丁二醇低聚物的开环聚合形成的聚合物；PPE＝聚亚苯基醚。bM＝蒙脱石，有机体系总重的5％。m＝蒙脱石，有机体系总重的15％；M′＝有机体系总重的4％。cNa+＝对照物；DDA＝十二烷基铵阳离子；HDA＝十六烷基铵阳离子；HDP＝N-十六烷基吡啶鎓阳离子。d(109达因/厘米2)。
表II序号 有机体系e 层状矿物f 阳离子g MWh1 PPE 无 无 74.02 PPE M Na+ 72.93 PPE M DDA 61.94 PPE M TDA 67.65 PPE M HDA 62.26 PPE M TDP 65.27 PPE M HDP 67.08 PBT 无 无 104.09 PBT M Na+ 94.910 PBT m Na+ 92.911 PBT M DDA 84.612 PBT m DDA 74.313 PBT M HDP 97.2e定义同表1。f定义同表1。g定义同表1和TDP＝N-十四烷基吡啶鎓；Na+＝对照物。h重均分子量×10-3。
Claims (22)
1.一种与选自下面至少一种阳离子进行阳离子交换的层状矿物：
(a)含至少一个带正电荷有机取代的杂原子的杂芳族阳离子；
(b)含至少一个带正电荷的杂原子的阳离子，该杂原子不在芳族环上，该环具有至少一个键序大于1的键；
其中所说的层状矿物为高岭石类、蒙脱石类、伊利石类或它们的混合物、水羟硅钠石、天然水玻璃、白云母、锌蒙脱石、蛭石、铬岭石、叶蜡石、云母或绿土；
其中在(a)和(b)中所说的阳离子包括选自N、P、O和S的杂原子；
其中所说的含至少一个带正电荷的杂原子，且该杂原子不在芳族环上，该所述的环具有至少一个键序大于1的键的阳离子具有下式：其中R1、R2、R3和R4分别独立地是氢、C1-20烷基、芳香基、取代的杂原子或
和R5是氢或C1-10烷基，或至少R1和R2、R3和R4、R1和R3以及R2和R4之一与连接它们的原子一起能形成4-10节的单环或双环。
2.按照权利要求1的层状矿物，其中所说的高岭石类包括高岭石、多水高岭土、地开石或珍珠陶土。
3.按照权利要求1的层状矿物，其中所说的蒙脱石类包括蒙脱石、囊脱石、贝得石、水辉石或滑石粉。
4.按照权利要求1的层状矿物，其中所说的伊利石类包括水云母、多硅白云母、钠伊利石、海绿石或绿鳞石。
5.按照权利要求1的层状矿物，其中所说的含至少一个带正电荷的有机取代的杂原子的杂芳族阳离子是吡咯、咪唑、噻唑、噁唑、吡啶、嘧啶、喹啉、异喹啉、吲哚、嘌呤、苯并咪唑、苯并三唑、苯并噁唑、吡嗪、喹喔啉、吖啶、吩嗪、咪唑并吡啶或联吡啶基的有机取代的盐。
6.按照权利要求5的层状矿物，其中所说的有机取代的杂原子是用C1-25脂肪族、脂环族或芳族基团取代的。
7.按照权利要求1的层状矿物，其中所说的含至少一种带正电荷的杂原子，该杂原子不在芳族环上的阳离子是弧盐或脒盐。
8.按照权利要求7的层状矿物，其中所说的胍盐是六烷基胍盐。
9.按照权利要求6的层状矿物，其中所说的杂芳族阳离子是N-C1-18吡啶鎓阳离子。
10.一种包含层状矿物的组合物，其含有：
(a)一种是与选自下面至少一种阳离子进行阳离子交换的层状矿物：
(i)含至少一个带正电荷有机取代的杂原子的杂芳族阳离子；
(ii)含至少一个带正电荷的杂原子，该杂原子不在芳族环上，该环具有至少一个键序大于1的键的阳离子；
(b)一有机体系，所说的有机体系包括
(i)大环低聚物；所说的大环低聚物选自大环聚碳酸酯、聚酯、聚酰亚胺、聚醚酰亚胺、聚亚苯基醚-聚碳酸酯低聚物、聚醚酰亚胺-聚碳酸酯低聚物；或
(ii)直链聚合物或支链聚合物；所说的直链或支链的聚合物选自聚碳酸酯、聚酯、聚亚苯基醚、聚酰亚胺、烯烃、聚醚酰亚胺、聚酰胺、聚亚芳基硫醚、聚砜、聚醚酮、丙烯腈丁二烯苯乙烯共聚物、聚苯乙烯；
其中所说的层状矿物为高岭石类、蒙脱石类或伊利石类、水羟硅钠石、天然水玻璃、白云母、锌蒙脱石、蛭石、铬岭石、叶蜡石、云母或绿土；
其中在(a)(i)和(a)(ii)中所说的阳离子包括选自N、P、O和S的杂原子；
其中所说的含至少一个带正电荷的杂原子，且该杂原子不在芳族环上，该所述的环具有至少一个键序大于1的键的阳离子具有下式：其中R1、R2、R3和R4分别独立地是氢、C1-20烷基、芳香基取代的杂原子或
和R5是氢或C1-10烷基，或至少R1和R2、R3和R4、R1和R3以及R2和R4之一与连接它们的原子一起能形成4-10节的单环或双环。
11.按照权利要求10的组合物，其中所说的高岭石类包括高岭石、多水高岭土、地开石或珍珠陶土。
12.按照权利要求10的组合物，其中所说的蒙脱石类包括蒙脱石、囊脱石、贝得石、水辉石或滑石粉。
13.按照权利要求10的组合物，其中所说的伊利石类包括水云母、多硅白云母、钠伊利石、海绿石或绿鳞石。
14.按照权利要求10的组合物，其中所说的含至少一种带正电荷的有机取代的杂原子的杂芳族阳离子是吡咯、咪唑、噻唑、噁唑、吡啶、嘧啶、喹啉、异喹啉、吲哚、嘌呤、苯并咪唑、苯并三唑、苯并噁唑、吡嗪、喹喔啉、吖啶、吩嗪、咪唑并吡啶或联吡啶基的有机取代的盐。
15.按照权利要求14的组合物，其中所说有机取代基杂原子是用C1-25脂肪族类、脂环族类或芳族类取代。
16.按照权利要求10的组合物，其中所说的含至少一种带正电荷的杂原子，该杂原子不在芳族环上的阳离子是胍盐或脒盐。
17.按照权利要求16的组合物，其中所说的胍盐是六烷基胍盐。
18.按权利要求10的组合物，其中所说的聚酯是聚(1，2-对苯二酸乙二醇)、聚(1，4-对苯二酸丁二醇)、聚(1，2-亚乙基2，6-萘联羧基酯)。
19.按照权利要求10的组合物，其中所说的聚亚苯基醚包括2，6-二甲基-1，4-亚苯基醚单元、2，3，6-三甲基-1，4-亚苯基醚单元的均聚物或它们的共聚物。
20.按照权利要求10的组合物，其中所说的聚碳酸酯是双酚A聚碳酸酯。
21.按照权利要求10的组合物，其中所说组合物还包括石英、黑云母、褐铁矿、水云母或长石。
22.按照权利要求15的组合物，其中所说的杂芳族阳离子是N-C10-18吡啶鎓阳离子。
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- 1996-03-25 DE DE69628496T patent/DE69628496T2/de not_active Expired - Fee Related
- 1996-04-01 JP JP07860596A patent/JP4100726B2/ja not_active Expired - Fee Related
- 1996-04-02 KR KR1019960009851A patent/KR100354308B1/ko not_active IP Right Cessation
- 1996-04-03 CN CN96106007A patent/CN1125115C/zh not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0736490A1 (en) | 1996-10-09 |
| US5707439A (en) | 1998-01-13 |
| DE69628496D1 (de) | 2003-07-10 |
| KR960037595A (ko) | 1996-11-19 |
| EP0736490B1 (en) | 2003-06-04 |
| KR100354308B1 (ko) | 2002-12-28 |
| CN1148060A (zh) | 1997-04-23 |
| CN1161420C (zh) | 2004-08-11 |
| DE69628496T2 (de) | 2004-04-15 |
| JPH08337414A (ja) | 1996-12-24 |
| JP4100726B2 (ja) | 2008-06-11 |
| CN1329108A (zh) | 2002-01-02 |
| US5530052A (en) | 1996-06-25 |
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