JP4000377B2 - Organoclay composite and method for producing the same - Google Patents
Organoclay composite and method for producing the same Download PDFInfo
- Publication number
- JP4000377B2 JP4000377B2 JP2004039072A JP2004039072A JP4000377B2 JP 4000377 B2 JP4000377 B2 JP 4000377B2 JP 2004039072 A JP2004039072 A JP 2004039072A JP 2004039072 A JP2004039072 A JP 2004039072A JP 4000377 B2 JP4000377 B2 JP 4000377B2
- Authority
- JP
- Japan
- Prior art keywords
- dispersed
- mpa
- solution
- thickener
- quaternary ammonium
- 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.)
- Expired - Lifetime
Links
- 239000002131 composite material Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000004927 clay Substances 0.000 claims description 95
- 239000002562 thickening agent Substances 0.000 claims description 73
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 61
- 239000003960 organic solvent Substances 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- -1 ammonium ions Chemical class 0.000 claims description 21
- 230000008719 thickening Effects 0.000 claims description 21
- 229910000275 saponite Inorganic materials 0.000 claims description 20
- 238000005341 cation exchange Methods 0.000 claims description 19
- 229910052899 lizardite Inorganic materials 0.000 claims description 19
- IBPRKWGSNXMCOI-UHFFFAOYSA-N trimagnesium;disilicate;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IBPRKWGSNXMCOI-UHFFFAOYSA-N 0.000 claims description 19
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 18
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 239000002635 aromatic organic solvent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 219
- 239000000243 solution Substances 0.000 description 168
- 239000003350 kerosene Substances 0.000 description 90
- 239000010410 layer Substances 0.000 description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 83
- 238000004062 sedimentation Methods 0.000 description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000000047 product Substances 0.000 description 27
- 238000001027 hydrothermal synthesis Methods 0.000 description 25
- 239000011777 magnesium Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000011734 sodium Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 150000002892 organic cations Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 229910021647 smectite Inorganic materials 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 7
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 7
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 7
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 235000019353 potassium silicate Nutrition 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002704 decyl 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])* 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
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 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 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 125000000913 palmityl 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])C([H])([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 description 2
- 125000002958 pentadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl 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])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])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 2
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GPBUTTSWJNPYJL-UHFFFAOYSA-N 2,2-dimethyloctane Chemical compound CCCCCCC(C)(C)C GPBUTTSWJNPYJL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 108700042658 GAP-43 Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
本発明は、有機溶媒中で増粘する機能を発揮する新規の有機粘土複合体、その製造方法及び増粘剤に関するものであり、更に詳しくは、膨潤性混合層ケイ酸塩の層間に特定の第四級アンモニウムイオンを導入した有機粘土複合体からなる増粘剤、その製造方法及び直鎖脂肪族炭化水素類等の有機溶媒の増粘剤に関するものである。
本発明は、有機溶媒の増粘剤として工業的に生産され、製品化されている、有機粘土複合体からなる、増粘剤の技術分野において、従来、直鎖脂肪族炭化水素に対して、活性剤を使用することなく増粘性を示す有機粘土複合体製品は開発されてなかったことを踏まえて、それを製品化することを可能とする新規有機粘土複合体からなる増粘剤の製造方法、及びその製品、特に、ケロシンやヘキサン等の直鎖脂肪族炭化水素等の有機溶媒の増粘剤として有用な有機粘土複合体からなる増粘剤を提供するものとして有用である。
The present invention relates to a novel organoclay composite that exhibits a function of thickening in an organic solvent , a method for producing the same, and a thickener, and more specifically , a specific layer between layers of a swellable mixed layer silicate . thickener consisting of organic clay complex by introducing quaternary ammonium ions, to a thickener of an organic solvent such as their preparation and linear aliphatic hydrocarbons.
The present invention is an industrially produced and commercialized thickening agent for organic solvents, and consists of an organoclay complex. In the technical field of thickening agents, Based on the fact that no organoclay complex product that exhibits thickening without using an activator has been developed, a method for producing a thickener comprising a novel organoclay complex that makes it possible to commercialize it. , and its products, in particular, is useful for providing a thickener consisting of useful organic clay complex as increasing Nebazai organic solvents such as straight-chain aliphatic hydrocarbons such as kerosene and hexane.
膨潤性層状ケイ酸塩の一種であるスメクタイト系粘土は、陽イオン交換能を有する微粒子であり、層間が広がり易く、水中では分散してチクソトロピー性を有するゾルを形成し、濃度を高くするとゲルを形成する性質を持っている。 Smectite clay, which is a kind of swellable layered silicate, is a fine particle with cation exchange capacity, easily spreads between layers, and forms a sol having thixotropic properties by dispersing in water. Has the property of forming.
膨潤性層状ケイ酸塩は、種々のカチオン性の有機化合物と反応させることにより有機粘土複合体とすることができる。このような有機粘土複合体の例として、例えば、特定の第四級アンモニウム塩（商品名：アーカード２ＨＴ）を用いて、スメクタイトの層間にジメチル・ジオクタデシル・第四級アンモニウムイオンを陽イオン交換によって導入した製品が工業的に生産され、塗料の増粘剤として商品化されている。しかし、この製品が分散、増粘可能な有機溶媒は、トルエン、キシレン等の芳香族炭化水素に限定されている。そのため、エチレンオキシド基やプロピレンオキシド基を含む第四級アンモニウム塩を用いた有機粘土複合体が開発され、アルコール類、ケトン類等の高極性有機溶媒の増粘剤として提案されている（特許文献１、特許文献２及び非特許文献１参照）。 Swellable layered silicate can be made into an organoclay complex by reacting with various cationic organic compounds. As an example of such an organoclay complex, for example, a specific quaternary ammonium salt (trade name: ARCARD 2HT) is used, and dimethyl, dioctadecyl, and quaternary ammonium ions are exchanged between the smectite layers by cation exchange. The introduced products are produced industrially and commercialized as thickeners for paints. However, organic solvents in which this product can be dispersed and thickened are limited to aromatic hydrocarbons such as toluene and xylene. Therefore, an organoclay complex using a quaternary ammonium salt containing an ethylene oxide group or a propylene oxide group has been developed and proposed as a thickener for highly polar organic solvents such as alcohols and ketones (Patent Document 1). Patent Document 2 and Non-Patent Document 1).
しかしながら、従来、直鎖脂肪族炭化水素に対して、活性剤を使用することなく増粘性を示す有機粘土複合体からなる増粘剤は知られていない。これまで、ケロシンやヘキサン等の直鎖脂肪族炭化水素溶媒中で好適に増粘する有機粘土複合体からなる増粘剤は未だ開発されていない。また、単独の有機粘土複合体からなる増粘剤で、例えば、直鎖脂肪族炭化水素と芳香族炭化水素を好適に増粘できる製品はみあたらず、当技術分野では、その開発が強く求められていた。
一方、従来、水熱方法により、膨潤性混合層ケイ酸塩を製造する方法（特許文献３〜８及び非特許文献２参照）、また、その構成原子のＭｇの一部あるいは全てをＮｉ，Ｃｏ，Ｚｎなどの２価重金属で置換した膨潤性混合層ケイ酸塩（特許文献９）、が知られている。
However, conventionally, there is no known thickener made of an organoclay complex that exhibits thickening without using an activator for straight-chain aliphatic hydrocarbons. So far, a thickener composed of an organoclay complex that can be suitably thickened in a linear aliphatic hydrocarbon solvent such as kerosene or hexane has not been developed yet. In addition, there are no products that can thicken linear aliphatic hydrocarbons and aromatic hydrocarbons with a thickener consisting of a single organoclay complex, and there is a strong demand for development in this technical field. It was.
On the other hand, conventionally, a method for producing a swellable mixed layer silicate by a hydrothermal method (see Patent Documents 3 to 8 and Non-Patent Document 2), and a part or all of Mg of its constituent atoms is converted to Ni, Co. , A swellable mixed layer silicate substituted with a divalent heavy metal such as Zn (Patent Document 9) is known.
このような状況下にあって、本発明者らは、上記従来技術に鑑みて、ケロシンやヘキサン等の直鎖脂肪族炭化水素の増粘剤として有用な有機粘土複合体からなる増粘剤を開発するため長年鋭意研究を重ねた結果、膨潤性混合層ケイ酸塩の層間に、特定の第四級アンモニウムイオンを導入した有機粘土複合体からなる増粘剤は、ケロシンやヘキサン等の直鎖脂肪族炭化水素類との親和性が優れ、且つ芳香族炭化水素に対しても親和性を示し、これらの有機溶媒中で好適な増粘効果を示すことを見出した。本発明は、これらの知見に基づいてなされたものである。
本発明は、従来、開発することが難しかった、直鎖脂肪族炭化水素類等の有機溶媒中で好適に使用することが可能な新規の有機粘土複合体からなる増粘剤、その製造方法及びその製品を提供することを目的とするものである。
Under such circumstances, the present inventors have found that in view of the above prior art, a thickener consisting of useful organic clay complex as thickeners linear aliphatic hydrocarbons such as kerosene and hexane As a result of many years of intensive research to develop, thickeners consisting of organoclay composites with specific quaternary ammonium ions introduced between swellable mixed layer silicate layers are linear chains such as kerosene and hexane. It has been found that it has an excellent affinity with aliphatic hydrocarbons and also has an affinity for aromatic hydrocarbons, and exhibits a suitable thickening effect in these organic solvents. The present invention has been made based on these findings.
The present invention is a thickener comprising a novel organoclay complex that can be suitably used in organic solvents such as linear aliphatic hydrocarbons, which has been difficult to develop in the past, a production method thereof, and it is an object of the present invention is to provide the products.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）膨潤性混合層ケイ酸塩の層間に、第四級アンモニウムイオンが導入された有機粘土複合体からなる有機溶媒中で増粘性を示す増粘剤であって、第四級アンモニウムイオンが、一般式（１）
The present invention for solving the above-described problems comprises the following technical means.
(1) Swellable mixed layer A thickener that exhibits thickening in an organic solvent composed of an organoclay complex in which quaternary ammonium ions are introduced between silicate layers, wherein quaternary ammonium ions are General formula (1)
（式中、Ｒ1 及びＲ2 は水素原子、炭素数１〜３０のアルキル基又はベンジル基を表し、Ｒ3 及びＲ4
は炭素数１〜３０のアルキル基、ｎが１〜３０の（ＣＨ2 ＣＨ2 Ｏ）n Ｈ基、ｍが１〜５０の（ＣＨ2
ＣＨ（ＣＨ3 ）m Ｈ基、又は（ＣＨ2 ＣＨ2 ＣＨ2
）m Ｈ基を表す。）で示される第四級アンモニウムイオンであることを特徴とする増粘剤。
（２）膨潤性混合層ケイ酸塩が、リザルダイトとサポナイトからなる成る合成混合層ケイ酸塩であることを特徴とする前記（１）に記載の増粘剤。
（３）リザルダイトが、一般式（２）
(Wherein R 1 and R 2 represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a benzyl group, R 3 and R 4
The alkyl group having 1 to 30 carbon atoms, n is 1 to 30 (CH 2 CH 2 O) n H group, m is 1 to 50 (CH 2
CH (CH 3 ) m H group or (CH 2 CH 2 CH 2
) Represents an m H group. A thickener characterized by being a quaternary ammonium ion.
(2) The thickener as described in (1) above, wherein the swellable mixed layer silicate is a synthetic mixed layer silicate composed of lizardite and saponite.
( 3 ) Rizardite is represented by general formula (2)
（式中、ａ及びｂの値は０≦ａ≦１及び０≦ｂ≦４である）で表され、及びサポナイトが、一般式（３） (Wherein the values of a and b are 0 ≦ a ≦ 1 and 0 ≦ b ≦ 4), and the saponite is represented by the general formula (3)
（式中、ｃ、ｄ、ｅ及びｆの値は０＜ｃ≦１、０≦ｄ≦１、０≦ｅ≦２及び１≦ｆ≦２とし、Ｍはアルカリ金属イオン、アルカリ土類金属イオン及びアンモニウムイオンからなる群から選んだ少なくとも１個の陽イオンである。）で表され、及びリザルダイトｘ層とサポナイトｙ層とから基本構造が構成され、０＜ｘ／ｙ≦１００の値であることを特徴とする前記（２）に記載の増粘剤。
（４）膨潤性混合層ケイ酸塩の陽イオン交換容量が０．３〜１．３ｍｅｑ・ｇ-1であることを特徴とする前記（１）に記載の増粘剤。
（５）直鎖脂肪族有機溶媒、芳香族有機溶媒及び水含有極性有機溶媒類に用いるための増粘剤であることを特徴とする前記（１）から（４）のいずれかに記載の増粘剤。
（６）膨潤性混合層ケイ酸塩の層間に、第四級アンモニウムイオンを含有する第四級アンモニウム塩を反応させる、有機粘土複合体からなる増粘剤の製造方法であって、第四級アンモニウムイオンが、上記一般式（１）で示される第四級アンモニウムイオンであることを特徴とする増粘剤の製造方法。
（７）膨潤性混合層ケイ酸塩の陽イオン交換容量に対して０．５〜２．０倍量（ミリ当量換算）の第四級アンモニウム塩を反応させることを特徴とする前記（６）に記載の増粘剤の製造方法。
（８）第四級アンモニウムイオンとして、アーカード２ＨＴ、アデカコールＣＣ３６及びエソカードＣ／２５の群から選ばれた少なくとも１種類の第四級アンモニウム塩を用いることを特徴とする前記（６）又は（７）に記載の増粘剤の製造方法。
（９）膨潤性混合層ケイ酸塩が、リザルダイトとサポナイトからなる成る合成混合層ケイ酸塩であることを特徴とする前記（６）に記載の増粘剤の製造方法。
（１０）リザルダイトが、上記一般式（２）、及びサポナイトが上記一般式（３）で表され、リザルダイトｘ層とサポナイトｙ層の比の値が０．０１≦ｘ／ｙ≦１０である膨潤性混合層ケイ酸塩を用いることを特徴とする前記（６）又は（７）に記載の増粘剤の製造方法。
（１１）前記（１）から（５）のいずれかに記載の増粘剤を、有機溶媒及び／又は水含有有機溶媒中で増粘させたことを特徴とする有機粘土複合体組成物。
(Where c, d, e and f have values of 0 <c ≦ 1, 0 ≦ d ≦ 1, 0 ≦ e ≦ 2 and 1 ≦ f ≦ 2, and M is an alkali metal ion or alkaline earth metal ion And at least one cation selected from the group consisting of ammonium ions), and the basic structure is composed of the lizardite x layer and the saponite y layer, and 0 <x / y ≦ 100. The thickener as described in (2) above,
( 4 ) The thickener according to (1) above, wherein the swellable mixed layer silicate has a cation exchange capacity of 0.3 to 1.3 meq · g −1 .
(5) The thickening agent according to any one of (1) to (4), wherein the thickening agent is used for a linear aliphatic organic solvent, an aromatic organic solvent, and a water-containing polar organic solvent. Sticky.
(6) between the layers of swellable mixed layer silicates, Ru reacting the quaternary ammonium salt containing a quaternary ammonium ion, a process for the preparation of thickeners consisting of organic clay complex, the A method for producing a thickener , wherein the quaternary ammonium ion is a quaternary ammonium ion represented by the general formula (1) .
(7) The quaternary ammonium salt in an amount of 0.5 to 2.0 times (in terms of milliequivalents) is reacted with the cation exchange capacity of the swellable mixed layer silicate (6) A method for producing a thickener according to 1.
(8) The above (6) or (7), wherein the quaternary ammonium ion is at least one quaternary ammonium salt selected from the group consisting of Arcade 2HT, Adeka Coal CC36, and Esocard C / 25. A method for producing a thickener according to 1.
(9) The method for producing a thickener as described in (6) above, wherein the swellable mixed layer silicate is a synthetic mixed layer silicate composed of lizardite and saponite .
( 10 ) Swelling in which the lizardite is represented by the above general formula (2) and the saponite is represented by the above general formula (3), and the value of the ratio of the lizardite x layer and the saponite y layer is 0.01 ≦ x / y ≦ 10. The method for producing a thickener as described in (6) or (7) above, wherein an ionic mixed layer silicate is used.
(11) wherein (1) from the thickener according to any one of (5), an organic clay complex composition characterized in that is thickened with an organic solvent and / or water-containing organic solvent.
次に、本発明について更に詳細に説明する。
本発明の説明を容易にするために、以下、水熱法により製造したリザルダイトとサポナイトを種々の割合で含有した混合層構造を有する合成粘土と特定の第四級アンモニウム塩（アーカード２ＨＴ）を複合させた有機粘土複合体からなる増粘剤の場合を例にとって説明する。
本発明者らが、種々の実験を経て開発した本発明の増粘剤を構成する有機粘土複合体は、例えば、天然あるいは合成のスメクタイト層間にアーカード２ＨＴの主成分であるジメチル・ジオクタデシル・アンモニウムカチオンを導入した従来の有機粘土複合体では使用困難であったケロシン等の直鎖脂肪族炭化水素系溶媒に対して、本発明の、アーカード２ＨＴを複合させた有機粘土複合体からなる増粘剤は、直鎖脂肪族炭化水素系溶媒に対して好適に分散して良好なゲル組成物を形成することを可能とするものである。
Next, the present invention will be described in more detail.
In order to facilitate the explanation of the present invention, a composite clay and a specific quaternary ammonium salt (Arcade 2HT) having a mixed layer structure containing risardite and saponite produced in various proportions by a hydrothermal method will be described below. The case of a thickener comprising an organoclay composite made will be described as an example.
The organoclay complex constituting the thickener of the present invention developed by the present inventors through various experiments is, for example, dimethyl dioctadecyl ammonium which is a main component of arcade 2HT between natural or synthetic smectite layers. A thickener comprising an organoclay complex obtained by complexing archad 2HT of the present invention with a linear aliphatic hydrocarbon solvent such as kerosene which has been difficult to use with a conventional organoclay complex into which a cation has been introduced. Can be suitably dispersed in a linear aliphatic hydrocarbon solvent to form a good gel composition.
本発明で用いられる合成粘土は、膨潤性混合層ケイ酸塩であり、基本構造が以下の一般式（２）、 The synthetic clay used in the present invention is a swellable mixed layer silicate, and the basic structure is the following general formula (2),
で示されるリザルダイト層ｘ枚と、以下の一般式（３）、 X lizardite layers indicated by the following general formula (3),
で示されるサポナイト層ｙ枚とから成る基本構造を有する。
この膨潤性混合層ケイ酸塩は、天然では存在しないため、水熱方法による製造方法が提案されている（特許文献３〜８及び非特許文献２参照）。また、上記の一般式（２）と一般式（３）に示されているＭｇの一部あるいは全てをＮｉ，Ｃｏ，Ｚｎなどの２価重金属で置換した膨潤性混合層ケイ酸塩についても文献に掲載されている（特許文献９参照）。これらの膨潤性混合層ケイ酸塩は、本発明に好適に用いることができる。
It has the basic structure which consists of y saponite layers shown.
Since this swellable mixed layer silicate does not exist in nature, a production method using a hydrothermal method has been proposed (see Patent Documents 3 to 8 and Non-Patent Document 2). Further, a swellable mixed layer silicate in which a part or all of Mg shown in the above general formulas (2) and (3) is substituted with a divalent heavy metal such as Ni, Co, Zn is also described. (See Patent Document 9). These swellable mixed layer silicates can be suitably used in the present invention.
ｘ／ｙは、通常、０＜ｘ／ｙ≦１００の範囲の値であるが、好適には０．０１≦ｘ／ｙ≦１０の範囲の値であり、より好適には０．０５≦ｘ／ｙ≦５の範囲の値であり、及び最も好適には０．０５≦ｘ／ｙ≦３の範囲の値である。 x / y is usually a value in the range of 0 <x / y ≦ 100, but is preferably a value in the range of 0.01 ≦ x / y ≦ 10, and more preferably 0.05 ≦ x. / Y ≦ 5 and most preferably 0.05 ≦ x / y ≦ 3.
一般式（２）及び一般式（３）におけるａ、ｂ、ｃ、ｄ、ｅ、ｆ及びリザルダイト層とサポナイト層の割合を決めるｘとｙの値を設定することにより、合成粘土の膨潤性混合層ケイ酸塩におけるケイ素、マグネシウム、アルミニウム、フッ素及びナトリウムなど、陽イオンあるいは陰イオンの構成元素の組成を設計できる。上記に示したように、Ｍｇの一部あるいは全てをＮｉ，Ｃｏ，Ｚｎなどの２価重金属で置換した膨潤性混合層ケイ酸塩についても、同様に構成元素の組成を設計できる。 Swellable mixing of synthetic clay by setting a, b, c, d, e, f in general formula (2) and general formula (3) and the values of x and y that determine the ratio of the lizardite layer and the saponite layer The composition of cation or anion constituent elements such as silicon, magnesium, aluminum, fluorine and sodium in the layer silicate can be designed. As described above, the composition of the constituent elements can be similarly designed for the swellable mixed layer silicate in which a part or all of Mg is substituted with a divalent heavy metal such as Ni, Co, or Zn.
本発明に用いる膨潤性混合層ケイ酸塩は、以下の工程で製造される。第一に、ケイ素、マグネシウム及びアルミニウムの複合含水酸化物を調製し、第二に、この複合含水酸化物にナトリウムなどの陽イオン、水及び必要に応じてフッ素イオンを添加して出発原料組成物スラリーとし、第三に、該スラリーを水熱反応により膨潤性混合層ケイ酸塩を生成させ、第四に、この水熱反応物を必要に応じて乾燥し、粉砕することによって膨潤性混合層ケイ酸塩の合成粘土製品を得ることができ、この粉末製品を、本発明の有機粘土複合体を製造するための原料として使用できる。あるいは乾燥する前の水熱反応物を、直接、本発明の有機粘土複合体の原料として用いることもできる。 The swellable mixed layer silicate used in the present invention is produced by the following steps. First, a composite hydrated oxide of silicon, magnesium and aluminum is prepared, and secondly, a cation such as sodium, water and, if necessary, fluorine ions are added to the composite hydrated oxide to start a raw material composition Thirdly, the swellable mixed layer silicate is formed by hydrothermal reaction to form a swellable mixed layer silicate, and fourthly, the hydrothermal reactant is dried and pulverized if necessary. Silicate synthetic clay products can be obtained and this powder product can be used as a raw material for producing the organoclay composites of the present invention. Or the hydrothermal reaction material before drying can also be directly used as a raw material of the organoclay complex of this invention.
第一工程では、ケイ酸、マグネシウム塩及びアルミニウム塩を混合して作製した酸性均質混合液とアルカリ溶液を混合して沈殿させて複合含水酸化物を得ることができる。また、ケイ酸ナトリウムとアルカリ溶液を混合して得られたアルカリ性溶液を、マグネシウム塩とアルミニウム塩の酸性水溶液と混合して複合含水酸化物を得ることもできる。第三工程では、出発原料スラリーを、オートクレーブに仕込み、好適には１００〜５００℃、より好適には２００〜３５０℃及び最も好適には２２０〜３００℃の温度で反応させて膨潤性混合層ケイ酸塩の合成粘土を製造できる。得られた膨潤性混合層ケイ酸塩は、Ｘ線回折、示差熱分析、赤外吸収スペクトル、化学分析、陽イオン交換容量、分散水溶液の粘性特性などによって評価できる。 In the first step, a composite hydrous oxide can be obtained by mixing and precipitating an acidic homogeneous mixed solution prepared by mixing silicic acid, magnesium salt and aluminum salt and an alkali solution. Alternatively, an alkaline solution obtained by mixing sodium silicate and an alkaline solution can be mixed with an acidic aqueous solution of magnesium salt and aluminum salt to obtain a composite hydrous oxide. In the third step, the starting material slurry is charged into an autoclave and reacted at a temperature of preferably 100 to 500 ° C., more preferably 200 to 350 ° C. and most preferably 220 to 300 ° C. A synthetic clay of acid salts can be produced. The obtained swellable mixed layer silicate can be evaluated by X-ray diffraction, differential thermal analysis, infrared absorption spectrum, chemical analysis, cation exchange capacity, viscosity characteristics of aqueous dispersion, and the like.
本発明の有機粘土複合体を製造するのに使用される膨潤性混合層ケイ酸塩の陽イオン交換容量は、粘土１ｇ当り０．１ミリ当量以上であり、好ましくは０．３ミリ当量以上であり、より好ましくは０．５ミリ当量以上であり、最も好ましくは０．６ミリ当量以上であり、一般的には、交換容量が大きいほど良い。膨潤性混合層ケイ酸塩の合成粘土は、５０％以下の非粘土不純物を含有しても良いが、非粘土不純物の量は１０％以下が望ましい。 The cation exchange capacity of the swellable mixed layer silicate used to produce the organoclay composite of the present invention is at least 0.1 milliequivalent per gram of clay, preferably at least 0.3 milliequivalent. Yes, more preferably 0.5 milliequivalents or more, and most preferably 0.6 milliequivalents or more. In general, the larger the exchange capacity, the better. The synthetic clay of the swellable mixed layer silicate may contain 50% or less of non-clay impurities, but the amount of non-clay impurities is preferably 10% or less.
一般式（１）の第四級アンモニウムイオンにおけるＲ1 及びＲ2 は、水素原子、炭素数１〜３０のアルキル基又はベンジル基を表し、アルキル基はＣx Ｈ2x+1で示され、具体例として、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、オクタデシル等のアルキル基が挙げられる。
Ｒ3 及びＲ4 は炭素数１〜３０のアルキル基、ｎが１〜３０の（ＣＨ2ＣＨ2 Ｏ）n Ｈ基又はｍが１〜５０の（ＣＨ2 ＣＨ（ＣＨ3 ））mＨ基あるいは（ＣＨ2 ＣＨ2 ＣＨ2 ）m Ｈ基である）で示される。アルキル基はＣxＨ2x+1で示され、具体例として、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、オクタデシル等のアルキル基が挙げられる。（ＣＨ2ＣＨ2 Ｏ）n Ｈ基はポリオキシエチレン基とも称され、ｎ＝１〜３０であり、好ましくは１２〜２０である。（ＣＨ2ＣＨ（ＣＨ3 ））m Ｈ基はポリオキシイソプロピレン基、及び（ＣＨ2 ＣＨ2ＣＨ2 ）m Ｈ基はポリオキシプロピレン基とも称され、ｍ＝１〜５０であり、好ましくは１０〜４０であり、及び最も好ましくは１０〜２０である。
R 1 and R 2 in the quaternary ammonium ion of the general formula (1) represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a benzyl group, and the alkyl group is represented by C x H 2x + 1 , Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and the like.
R 3 and R 4 are alkyl groups having 1 to 30 carbon atoms, (CH 2 CH 2 O) n H group having 1 to 30 carbon atoms, or (CH 2 CH (CH 3 )) m H group having 1 to 50 carbon atoms. Or (CH 2 CH 2 CH 2 ) m H group). The alkyl group is represented by C x H 2x + 1 , and specific examples thereof include, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Alkyl groups such as hexadecyl and octadecyl. The (CH 2 CH 2 O) n H group is also called a polyoxyethylene group, and n = 1 to 30, preferably 12 to 20. The (CH 2 CH (CH 3 )) m H group is also called a polyoxyisopropylene group, and the (CH 2 CH 2 CH 2 ) m H group is also called a polyoxypropylene group, and m = 1 to 50, preferably 10 to 40, and most preferably 10 to 20.
第四級アンモニウムイオンとして、第四級アンモニウムイオンを含有する第四級アンモニウム塩として商品化されている、アーカード（Ａｒｑｕａｄ）２ＨＴ、アーカード２ＨＴ−７５、アーカード２Ｃ−７５、アーカード２Ｓ−７５、アーカードＴ−２Ｃ−５０、アーカードＳ−２Ｃ−５０、アーカード１２−５０、アーカード１６−５０、アーカード１８−５０、アーカードＣ−５０、アーカードＳ−５０、アーカードＴ−５０、アーカードＣＢ−５０、エソカード（Ｅｔｈｏｑｕａｄ）Ｃ／１２、エソカードＣ／２５、エソカードＯ／１２、エソカードＯ／２５、エソカード１８／１２、エソカード１８／２５、エソミン（Ｅｔｈｏｍｉｎ）Ｃ／１５、エソミンＴ／２５、ブラウノン（Ｂｌａｕｎｏｎ）Ｌ−２１０、ブラウノンＬ−２２０、コータミン２４Ｐ、コータミン８６Ｐコンク、コータミン６０Ｗ、コータミン８６Ｗ、コータミンＤ８６Ｐ、サニゾールＣ、サニゾールＢ−５０、アデカコールＣＣ２５、アデカコールＣＣ３６は、いずれも本発明に用いることができる。 As quaternary ammonium ions, Arquad 2HT, Arquad 2HT-75, Arcade 2C-75, Arcade 2S-75, Arcade T, which are commercialized as quaternary ammonium salts containing quaternary ammonium ions -2C-50, Arcade S-2C-50, Arcade 12-50, Arcade 16-50, Arcade 18-50, Arcade C-50, Arcade S-50, Arcade T-50, Arcade CB-50, Esoquad (Ethoquad) ) C / 12, Esocard C / 25, Esocard O / 12, Esocard O / 25, Esocard 18/12, Esocard 18/25, Ethomin C / 15, Esomin T / 25, Blaunon L-210 , Brownon L-2 0, QUARTAMIN 24P, QUARTAMIN 86P Conc, Quartamin 60 W, QUARTAMIN 86W, Quartamin D86P, SANISOL C, SANISOL B-50, ADEKA COL CC25, ADEKA COL CC36 are all can be used in the present invention.
一般式（１）の第四級アンモニウムイオンを導入するには、該イオンを含む第四級アンモニウム塩が用いられるが、そのような塩としては、該イオンと、例えば、Ｃｌイオン、Ｂｒイオン、ＮＯ3 イオン、ＣＨ3 ＣＯＯイオン等の陰イオンとの塩を挙げることができる。なお、本発明の有機粘土複合体は、一般式で示される１種類以上の第四級アンモニウムイオンを膨潤性混合層ケイ酸塩の層間に導入することで得られるが、更に、上記以外の種々の第四級アルキルアンモニウムイオンや、種々の無機イオンを同時に導入しても、本発明の目的を損なうことはない。 In order to introduce the quaternary ammonium ion of the general formula (1), a quaternary ammonium salt containing the ion is used. As such a salt, for example, Cl ion, Br ion, Mention may be made of salts with anions such as NO 3 ions and CH 3 COO ions. The organoclay composite of the present invention can be obtained by introducing one or more quaternary ammonium ions represented by the general formula between the layers of the swellable mixed layer silicate. Even if quaternary alkylammonium ions and various inorganic ions are simultaneously introduced, the object of the present invention is not impaired.
通常、ベントナイト等のスメクタイトを用いた有機粘土複合体においては、ベントナイトの陽イオン交換容量と等量の第四級アンモニウムイオンを複合させたものの特性が一番良いとされている。本発明では、例えば、ジメチル・ジオクタデシル基を主成分とするアーカード２ＨＴを複合させた有機粘土複合体の５％分散ケロシン溶液の粘性特性は、１．１倍量程度の有機イオンを用いた場合は、見掛粘度が最高値になっていることが示されている。一般式（１）で示される第四級アンモニウムイオンの合計導入量の値は、膨潤性混合層ケイ酸塩の陽イオン交換容量に対して０．５〜２．０倍量（ミリ当量換算）が好適であり、より好適には０．５〜１．８倍量あり、及び最も好適には０．５〜１．５倍量である。 In general, an organoclay composite using a smectite such as bentonite is said to have the best characteristics when it is combined with an equal amount of quaternary ammonium ions to the cation exchange capacity of bentonite. In the present invention, for example, the viscosity characteristic of a 5% dispersion kerosene solution of an organoclay complex in which archard 2HT mainly composed of a dimethyl-dioctadecyl group is combined is about 1.1 times the amount of organic ions. Shows that the apparent viscosity is the highest value. The value of the total introduction amount of the quaternary ammonium ions represented by the general formula (1) is 0.5 to 2.0 times the cation exchange capacity of the swellable mixed layer silicate (in milliequivalents). Is preferred, more preferably 0.5 to 1.8 times, and most preferably 0.5 to 1.5 times.
本発明の有機粘土複合体は、膨潤性混合層ケイ酸塩の層間の陽イオン交換により得られるが、例えば、以下の方法で製造することができる。第１段階として、前記した水熱合成法で得られた膨潤性混合層ケイ酸塩を水中に分散させる。その固体分散濃度は、通常、１〜２０重量％が望ましいが、膨潤性混合層ケイ酸塩が十分分散可能な濃度の範囲であれば自由に設定することができる。次に、この膨潤性混合層ケイ酸塩懸濁液に、前述の第四級アンモニウム塩溶液を添加するか、逆に、前述の第四級アンモニウム塩溶液に膨潤性混合層ケイ酸塩懸濁液を添加することによっても、本発明の有機粘土複合体を製造することが可能である。 The organoclay composite of the present invention is obtained by cation exchange between layers of the swellable mixed layer silicate, and can be produced, for example, by the following method. As a first step, the swellable mixed layer silicate obtained by the hydrothermal synthesis method described above is dispersed in water. The solid dispersion concentration is usually preferably 1 to 20% by weight, but can be freely set as long as the swellable mixed layer silicate is in a concentration range in which it can be sufficiently dispersed. Next, the quaternary ammonium salt solution is added to the swellable mixed layer silicate suspension, or conversely, the swellable mixed layer silicate suspension is added to the quaternary ammonium salt solution. The organoclay composite of the present invention can also be produced by adding a liquid.
第四級アンモニウム塩は、通常、５〜５０重量％の混合水溶液として膨潤性混合層ケイ酸塩懸濁液と混合する。なお、混合時、アルコール等の有機溶媒を加え、有機溶媒含有水溶液中で反応させても良い。 The quaternary ammonium salt is usually mixed with the swellable mixed layer silicate suspension as a mixed aqueous solution of 5 to 50% by weight. In addition, you may make it react in organic solvent containing aqueous solution by adding organic solvents, such as alcohol, at the time of mixing.
反応は室温で充分進行するが、加温しても良い。加温の最高温度は、用いる第四級アンモニウム塩の分解温度以下であれば任意に設定が可能であり、一般的には１０〜１００℃、好ましくは５０〜１００℃である。反応時間は、数分〜数時間と反応条件によって異なるが、一般的には１０分〜１０時間であり、好ましくは１０分〜５時間であり、より好ましくは２０分〜３時間であり、及び最も好ましくは３０分〜２時間である。 The reaction proceeds sufficiently at room temperature, but may be warmed. The maximum temperature for heating can be arbitrarily set as long as it is not higher than the decomposition temperature of the quaternary ammonium salt to be used, and is generally 10 to 100 ° C., preferably 50 to 100 ° C. The reaction time varies from several minutes to several hours depending on the reaction conditions, but is generally 10 minutes to 10 hours, preferably 10 minutes to 5 hours, more preferably 20 minutes to 3 hours, and Most preferably, it is 30 minutes to 2 hours.
次いで、固液を分離し、生成した有機粘土複合体を水洗浄して副生溶解質を充分に除去する。この有機粘土複合体の液からの分離、洗浄は、極めて容易であり、ごく一般的な濾過分離機で十分である。例えば、実験室規模では、ブフナー漏斗（濾紙を敷く）を用いた減圧濾過・洗浄あるいは遠心分離機による濾過・洗浄で容易に行われる。 Next, the solid and liquid are separated, and the produced organic clay complex is washed with water to sufficiently remove the by-product solute. Separation and washing of the organoclay complex from the liquid is extremely easy, and an ordinary filter separator is sufficient. For example, in the laboratory scale, it is easily performed by vacuum filtration / washing using a Buchner funnel (laying filter paper) or filtration / washing by a centrifuge.
このようにして得られた有機粘土複合体を乾燥し、必要に応じて粉砕して最終製品とする。乾燥温度は、通常、１００℃以下が望ましく、３０〜１００℃が好適であり、５０〜１００℃がより好適であり、及び６０〜９５℃が最も好適である。 The organoclay composite thus obtained is dried and pulverized as necessary to obtain a final product. The drying temperature is usually desirably 100 ° C. or less, preferably 30 to 100 ° C., more preferably 50 to 100 ° C., and most preferably 60 to 95 ° C.
最終製品である有機粘土複合体からなる増粘剤を有機溶媒に添加し、撹拌等によって有機溶媒中で増粘させた有機粘土複合体組成物を容易に得ることができる。攪拌しうる量であれば、添加量は多いほど増粘効果が高い。添加量は、用途により大きく異なるが、一般的には有機溶媒に対し、０．１〜３０重量％の範囲で、各種の用途に用いることができる。 A thickener consisting of an organic clay compound which is the final product was added to an organic solvent, an organic clay complex composition increased by viscosity in organic solvents by the agitation or the like can be easily obtained. If the amount can be stirred, the thickening effect increases as the amount added increases. Although the addition amount varies greatly depending on the application, it can generally be used for various applications in the range of 0.1 to 30% by weight with respect to the organic solvent.
最終製品として得られた有機粘土複合体からなる増粘剤は、有機溶媒に分散させるとチクソトロピックな粘性を示すため、有機溶媒用の増粘剤、ゲル化剤又は沈降防止剤として、塗料、グリース、インク、化粧品、医農薬品、洗剤等の用途に好適に用いることができる。また、フィラーとしてナイロン、プロピレン、エチレン、ビニール等の高分子材料（プラスチックス）の機械的特性の改善やガス透過性の制御に用いても良い。本発明の有機粘土複合体からなる増粘剤は、有機溶媒に対し、０．１〜３０重量％の範囲で用いることができる。 The thickener consisting of the organoclay composite obtained as the final product exhibits a thixotropic viscosity when dispersed in an organic solvent, and therefore, as a thickener, gelling agent or anti-settling agent for organic solvents, It can be suitably used for applications such as grease, ink, cosmetics, medicines and agricultural chemicals, and detergents. Moreover, you may use for improvement of the mechanical characteristic and control of gas permeability of polymer materials (plastics), such as nylon, propylene, ethylene, and vinyl, as a filler. Thickener comprising an organic clay complex of the present invention, in organic solvents, it can have use in the range of 0.1 to 30 wt%.
なお、有機溶剤としては、直鎖脂肪族炭化水素、高極性溶媒、低極性あるいは無極性溶媒、中極性溶媒等の各種有機溶媒を用いることができる。具体的には、ケロシン、鉱物油、ペンタン、ヘキサン、ヘプタン、オクタン等の直鎖脂肪族炭化水素、メチルヘプタン、ジメチルヘキサン、トリメチルヘプタン、シクロヘキサン、シクロヘプタン等の炭化水素、メタノール、エタノール、プロパノール、イソプロパノール等のアルコール類、アセトン等のケトン類、ジメチルホルムアミドのようなアミド類、テトラヒドロフラン、メチルセロソルブ、メチルエーテル、エチルエーテル等のエーテル類、ベンゼン、トルエン、キシレン、シンナー等の芳香族炭化水素類、四塩化炭素、クロロホルム、ジクロロメタン、パークロロエチレン、クロロベンゼン等のハロゲン化炭化水素類及びジメチルスルホキシド、Ｎ−メチル−２−ピロリドン等の溶剤中で、本発明の有機粘土複合体からなる増粘剤は、良好な増粘効果を示す。 In addition, as an organic solvent, various organic solvents, such as a linear aliphatic hydrocarbon, a highly polar solvent, a low polarity or nonpolar solvent, and a medium polarity solvent, can be used. Specifically, linear aliphatic hydrocarbons such as kerosene, mineral oil, pentane, hexane, heptane, octane, hydrocarbons such as methylheptane, dimethylhexane, trimethylheptane, cyclohexane, cycloheptane, methanol, ethanol, propanol, Alcohols such as isopropanol, ketones such as acetone, amides such as dimethylformamide, ethers such as tetrahydrofuran, methyl cellosolve, methyl ether, and ethyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, thinner, carbon tetrachloride, chloroform, dichloromethane, perchlorethylene, halogenated hydrocarbons and dimethyl sulfoxide as chlorobenzene, in a solvent such as N- methyl-2-pyrrolidone, thickening made of an organic clay complex of the present invention Shows a good thickening effect.
また、溶媒として、上記の２つ以上を混合したもの、あるいは水などの他の無機溶媒と上記溶媒を混合した各種溶媒を用いることもできる。例えば、前記のアーカード２ＨＴを複合させた有機粘土複合体からなる増粘剤は、ケロシンとトルエン中で増粘性を示すが、エタノール中では沈降して増粘性を示さない。しかしながら、この有機粘土複合体からなる増粘剤は、例えば、（５％水−９５％エタノール）で示される様な水を混合した極性溶媒等の混合溶液中で使用可能となる。 As the solvent, a mixture of two or more of the above, or various solvents obtained by mixing the above solvent with other inorganic solvents such as water can be used. For example, a thickener composed of an organoclay complex obtained by combining the above-mentioned Arcard 2HT exhibits thickening in kerosene and toluene , but does not exhibit thickening due to precipitation in ethanol. However, the thickener composed of the organoclay complex can be used in a mixed solution such as a polar solvent mixed with water as shown by (5% water-95% ethanol).
また、通常、本発明製品は、粘性を高めるために極性溶媒を特に添加する必要はないが、使用に当って、水、メタノール、エタノール、アセトン等の極性溶媒を添加することは一向に差し支えない。 Usually, in the product of the present invention, it is not necessary to add a polar solvent in order to increase the viscosity, but in use, it is possible to add a polar solvent such as water, methanol, ethanol, acetone or the like.
アーカード２ＨＴを、膨潤性ケイ酸塩であるベントナイトや合成ヘクトライト等のスメクタイトに複合させた従来のアーカード２ＨＴ−スメクタイト型有機粘土複合体は、トルエン等の低極性有機溶媒しか使用できなかった。ところが、膨潤性混合層ケイ酸塩にアーカード２ＨＴを複合させた本発明のアーカード２ＨＴ−膨潤性混合層ケイ酸塩型有機粘土複合体からなる増粘剤は、トルエン等の低極性有機溶媒中において前記のスメクタイト型有機粘土複合体と同様な増粘性を示すが、これまで全く使用しえなかった、ケロシン等の直鎖脂肪族炭化水素中で好適に増粘する機能を発現し、更に、水含有エタノール混合溶液中においても使用できることが判明した。 The conventional arcard 2HT-smectite type organic clay complex obtained by combining arcard 2HT with smectite such as swellable silicate bentonite or synthetic hectorite can only use a low polar organic solvent such as toluene. However, the thickener composed of the archard 2HT-swellable mixed layer silicate type organic clay complex of the present invention in which arcad 2HT is combined with the swellable mixed layer silicate is used in a low polar organic solvent such as toluene . Although it exhibits thickening similar to that of the smectite-type organoclay complex, it has a function of suitably thickening in straight chain aliphatic hydrocarbons such as kerosene that could not be used at all, It was found that it can be used in a mixed ethanol solution.
上記の様に、本発明製品が多くの有機溶媒に対して使用できることは、好適であり、従来の有機粘土複合体より優れている点である。従来の有機粘土複合体製品に用いられているベントナイトや合成スメクタイト等の膨潤性ケイ酸塩の層面にはシロキサンが存在し、疎水性を形成しているのに対して、膨潤性混合層ケイ酸塩のリザルダイト層面にはＯＨ基が存在して、親水性表面となっていることが影響していると考えられる。本発明で得られるアーカード２ＨＴ有機粘土複合体からなる増粘剤は、ケロシン等の直鎖脂肪族炭化水素に対し、親和性を有し、増粘効果を示すのは、リザルダイト層面、サポナイト層面、層間有機物及び直鎖脂肪族炭化水素溶媒との親水性、疎水性バランスの一致により、溶媒分子が膨潤性混合層ケイ酸塩の層間に侵入して層間を押し広げ、更に積層した混合層ケイ酸塩層を分離させることによる、と考えられる。分離した混合層ケイ酸塩層は、層面に残る陰電荷や端面の陽電荷により相互に不規則な結合をして、ゾル・ゲル構造を形成するものと推測される。 As described above, it is preferable that the product of the present invention can be used for many organic solvents, which is superior to conventional organic clay composites. Siloxane is present on the layer surface of swellable silicates such as bentonite and synthetic smectite used in conventional organoclay composite products, forming hydrophobicity, while swellable mixed layer silicic acid It is considered that an OH group is present on the surface of the salt lizardite layer, and that it has a hydrophilic surface. Thickener consisting of Arquad 2HT organoclay composite obtained by the present invention, with respect to a straight-chain aliphatic hydrocarbons kerosene has an affinity, exhibit thickening effect, lizardite layer surface, saponite layer surface, Due to the matching of hydrophilicity and hydrophobicity between the interlayer organic material and the linear aliphatic hydrocarbon solvent, the solvent molecules penetrated between the layers of the swellable mixed layer silicate, spread the layer, and further laminated the mixed layer silicic acid This is thought to be due to separation of the salt layer. The separated mixed-layer silicate layer is presumed to form a sol-gel structure by irregularly bonding to each other due to the negative charge remaining on the layer surface and the positive charge on the end surface.
本発明で得られる有機粘土複合体からなる増粘剤は、混合層ケイ酸塩の構造や化学組成を変化させることによって、疎水性ー親水性を制御できるため、一種類の第四級アンモニウムイオンに対して種々の特性が異なる混合層ケイ酸塩と複合させることができ、種々の有機溶媒に親和性を持たせることが可能となり、例えば、これまで増粘させることができなかった直鎖脂肪族炭化水素に対して増粘効果を示す特定の有機粘土複合体からなる増粘剤の開発を可能とするものである。更に、第四級アンモニウムイオンの種類を変えたり、２種類以上の第四級アンモニウムイオンを混合したりすることにより、特定の有機溶媒に対する最適な有機粘土複合体からなる増粘剤を設計・開発することが可能となる。 The thickener composed of the organoclay composite obtained in the present invention can control hydrophobicity and hydrophilicity by changing the structure and chemical composition of the mixed layer silicate, so that one kind of quaternary ammonium ion Can be combined with mixed-layer silicates with different properties, making it possible to give affinity to various organic solvents, for example, linear fats that could not be thickened so far It is possible to develop a thickener composed of a specific organoclay complex that exhibits a thickening effect on a group hydrocarbon. In addition, by designing different types of quaternary ammonium ions or mixing two or more types of quaternary ammonium ions, we can design and develop thickeners consisting of an optimal organoclay complex for a specific organic solvent. It becomes possible to do.
本発明は、有機溶媒中で増粘性を示す有機粘土複合体からなる増粘剤に係るものであり、本発明により、（１）膨潤性混合層ケイ酸塩を用いることにより、これまで増粘させることができなかった直鎖脂肪族炭化水素溶媒中で増粘効果を示す有機粘土複合体からなる増粘剤が得られる、（２）膨潤性混合層ケイ酸塩の構造と化学組成を制御することにより、種々の有機溶媒に使用可能な有機粘土複合体からなる増粘剤が得られる、（３）一種類の有機粘土複合体からなる増粘剤に複数の機能を持たせることができる、（４）有機物の種類を変えることによっても有機粘土複合体からなる増粘剤の特性を制御できる、（５）膨潤性混合層ケイ酸塩に、第四級アンモニウム塩を反応させることを特徴とする有機粘土複合体からなる増粘剤の新規製造方法を提供できる、（６）種々の有機溶媒に親和性を有し、良好な増粘効果を示す増粘剤を提供できる、（７）種々の有機溶媒中で有機粘土複合体からなる増粘剤を増粘させた組成物を提供できる、という格別の効果が奏される。 The present invention according to a thickener consisting of an organic clay complex showing a thickening in an organic solvent, the present invention, by using (1) swellable mixed layer silicate, which until thickening thickener consisting of organic clay complex shows the thickening effect is obtained in a linear aliphatic hydrocarbon solvents that could not be, (2) structure and chemical composition of the swellable mixed layer silicate By controlling the viscosity, a thickener composed of an organoclay complex that can be used in various organic solvents can be obtained. (3) A thickener composed of one kind of organoclay complex can have multiple functions. (4) It is possible to control the properties of thickeners composed of organoclay composites by changing the type of organic matter. (5) Reacting quaternary ammonium salt with swellable mixed layer silicate. made of an organic clay complex features novel made thickener The method can provide, (6) have various organic solvents affinity may provide a thickening agent showing a good good thickening effect, increasing consisting of an organic clay compound (7) in various organic solvents The special effect that the composition which thickened the adhesive can be provided is produced.
以下、本発明を実施例により具体的に説明する。しかしながら、本実施例は、本発明の好適な例を説明したものであり、本発明は、これらの実施例のみに限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples. However, the present embodiment describes preferred examples of the present invention, and the present invention is not limited to only these embodiments.
参考例１
１０００ｍｌのビーカーに水４００ｍｌを入れ、これに３号水ガラス（ＳｉＯ2 ２８重量％、Ｎａ2 Ｏ ９重量％、ＳｉＯ2 ／Ｎａ2 Ｏ モル比 ３．２２）６８．７ｇを溶解した後、これに１６規定硝酸水溶液１８ｍｌをかき混ぜながら加えて、ケイ酸水溶液を得た。このケイ酸水溶液に、塩化マグネシウム六水和物一級試薬（純度９８％）５９．８ｇ及び塩化アルミニウム六水和物一級試薬（純度９８％）７．９ｇを加えて作製したケイ酸−マグネシウム−アルミニウム均質溶液を、２規定水酸化ナトリウム溶液４００ｍｌ中に撹拌しながら５分間で滴下した。沈殿のｐＨは１０．６であった。直ちに、得られた複合含水酸化物を濾過し、充分に水洗した後、２規定水酸化ナトリウム溶液１６ｍｌを加えてスラリーとし、オートクレーブに移し、３００℃、２４時間反応させた。原料スラリーのｐＨは１１．５であり、水熱合成後のｐＨは１２．０であった。生成物をオートクレーブから取り出し、水洗しないでろ過して水分を除去した後、磁性皿に移して乾燥器中において８０℃で乾燥し、秤量後粉砕して粉末試料３０．７ｇを得た。
Reference example 1
400 ml of water was put into a 1000 ml beaker, and after dissolving 68.7 g of No. 3 water glass (SiO 2 28 wt%, Na 2 O 9 wt%, SiO 2 / Na 2 O molar ratio 3.22), A 16N aqueous nitric acid solution (18 ml) was added with stirring to obtain an aqueous silicic acid solution. Silicate-magnesium-aluminum prepared by adding 59.8 g of magnesium chloride hexahydrate primary reagent (purity 98%) and 7.9 g of aluminum chloride hexahydrate primary reagent (purity 98%) to this silicic acid aqueous solution. The homogeneous solution was dropped into 400 ml of 2N sodium hydroxide solution over 5 minutes with stirring. The pH of the precipitate was 10.6. Immediately, the obtained composite hydrous oxide was filtered, washed thoroughly with water, added with 16 ml of 2N sodium hydroxide solution to form a slurry, transferred to an autoclave, and reacted at 300 ° C. for 24 hours. The pH of the raw material slurry was 11.5, and the pH after hydrothermal synthesis was 12.0. The product was taken out of the autoclave, filtered without washing with water to remove moisture, transferred to a magnetic dish, dried in a dryer at 80 ° C., weighed and ground to obtain 30.7 g of a powder sample.
本試料を用いて、スライドガラス上に定方位試料を作成し、エチレングリコール処理した後、Ｘ線回折の測定をした。得られた（００５）、（００１１）、（００１６）、（００２１）及び（００２７）ピークは、それぞれ１８．０Å、８．５９Å、５．７２Å、４．４０Å及び３．４０Åであった。これらの５ピークから計算される（００１）ピークの平均値は９２．０Åであり、リザルダイト層１枚とサポナイト層５枚からなる理想的な混合層鉱物の（００１）ピークの値は９２．５Åであり、ほぼ想定した合成粘土（Ｎｏ．１）が製造されたと考えられる。 Using this sample, an orientation sample was prepared on a slide glass, treated with ethylene glycol, and then measured for X-ray diffraction. The obtained (005), (0011), (0016), (0021), and (0027) peaks were 18.0Å, 8.59Å, 5.72Å, 4.40Å, and 3.40Å, respectively. The average value of the (001) peak calculated from these 5 peaks is 92.0Å, and the value of the (001) peak of an ideal mixed layer mineral consisting of one lizardite layer and five saponite layers is 92.5Å. It is considered that the synthetic clay (No. 1) almost assumed was produced.
得られた合成粘土（Ｎｏ．１）はａ＝０、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５で設計して作製したものであり、得られた化学組成はＳｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．８０：７．２０：０．８０であり、及びメチレンブルー吸着量から得られた陽イオン交換容量は１．００ ｍｅｑ／ｇであった。２．５％水溶液はゲルを形成し、ファンＶＧメーターで測定した見掛粘度は１０２２／ｓ＝７．５ ｍＰａ・ｓ及び１０．２／ｓ＝１５０ ｍＰａ・ｓであった。 The obtained synthetic clay (No. 1) was prepared by designing with a = 0, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 5. The chemical composition obtained was Si: Al: Mg: Na = 8.00: 0.80: 7.20: 0.80, and the cation exchange capacity obtained from the amount of adsorbed methylene blue was 1. 0.000 meq / g. The 2.5% aqueous solution formed a gel, and the apparent viscosities measured with a fan VG meter were 1022 / s = 7.5 mPa · s and 10.2 / s = 150 mPa · s.
２０００ｍｌのビーカーに水８００ｍｌを入れ、参考例１で作製した合成粘土１０ｇを加えて分散させ、加熱してＡ液を調製した。一方、５００ｍｌのビーカーにアーカード２ＨＴ（純度９３％）６．２ｇを採取し、７０℃の加熱水２００ｍｌを加えてＢ液を調製した。有機陽イオンの使用量は１．００ ｍｅｑ／ｇ（合成粘土）であった。７５℃程度の温度になったＡ液にＢ液を撹拌しながら加えて混合し、更に加熱して９５℃で３０分間反応させた。反応後ろ紙を用いてろ過し、硝酸銀溶液で塩素が認められなくなるまで水洗した。得られた反応物を磁製皿に移し、８０℃で乾燥した後、粉砕して有機粘土複合体１３．４ｇを得た。 800 ml of water was put into a 2000 ml beaker, 10 g of the synthetic clay prepared in Reference Example 1 was added and dispersed, and heated to prepare A liquid. On the other hand, 6.2 g of Arcard 2HT (purity 93%) was collected in a 500 ml beaker, and 200 ml of 70 ° C. heated water was added to prepare B liquid. The amount of organic cation used was 1.00 meq / g (synthetic clay). The liquid B was added to the liquid A at a temperature of about 75 ° C. with stirring and mixed, and further heated and reacted at 95 ° C. for 30 minutes. It filtered using the reaction back paper, and washed with water until chlorine was not recognized with a silver nitrate solution. The obtained reaction product was transferred to a porcelain dish, dried at 80 ° C., and then pulverized to obtain 13.4 g of an organic clay complex.
内容積１０ｍｌの栓付きのメスフラスコに、本発明製品０．１ｇを採取し、ケロシンを添加して１％分散ケロシン溶液を作製し、３０分間振とうさせた後、静置して２４時間後の沈降状態を調べた。同様に、本発明製品の試料量を変化させて、２％、３％及び５％分散ケロシン溶液を作製し、２４時間後の沈降状態を観察した。沈降体積は１％分散ケロシン溶液＝１００％、２％分散ケロシン溶液＝１００％、３％分散ケロシン溶液＝１００％及び５％分散ケロシン溶液＝１００％であった。５％分散ケロシン溶液はゲル化していた。同様にして調べた１％分散ヘキサン溶液及び１％分散ヘプタン溶液の沈降体積は、それぞれ１００％であった。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は、それぞれ１００％であった。 Collect 0.1 g of the product of the present invention in a volumetric flask with a stopper having an internal volume of 10 ml, add kerosene to make a 1% dispersed kerosene solution, shake for 30 minutes, and then let stand for 24 hours. The sedimentation state of was investigated. Similarly, 2%, 3% and 5% dispersed kerosene solutions were prepared by changing the sample amount of the product of the present invention, and the sedimentation state after 24 hours was observed. The sedimentation volumes were 1% dispersed kerosene solution = 100%, 2% dispersed kerosene solution = 100%, 3% dispersed kerosene solution = 100% and 5% dispersed kerosene solution = 100%. The 5% dispersed kerosene solution was gelled. The sedimentation volumes of the 1% dispersed hexane solution and the 1% dispersed heptane solution examined in the same manner were 100%, respectively. Moreover, the sedimentation volumes of the 1% dispersed toluene solution and the 5% dispersed toluene solution were 100%, respectively.
沈降体積の測定を行った後、デジタル粘度計（東機産業（株）製ＤＶＭ−Ｂ型）を用いて、５％分散ケロシン溶液の粘度測定を行った。ローターＨＭ−２を用いて得られたずり速度と見掛粘度の関係は１．０／ｓ＝２０８０ ｍＰａ・ｓ、２．０／ｓ＝１０５０ ｍＰａ・ｓ、４．１／ｓ＝５２１ ｍＰａ・ｓ、１０．２／ｓ＝２２８ ｍＰａ・ｓ及び２０．４／ｓ＝１２５ ｍＰａ・ｓであった。更に、ローターをＨＭ−１に変えて測定した５％分散トルエン溶液の見掛粘度は０．８／ｓ＝４９１ ｍＰａ・ｓ、２．０／ｓ＝３０３ ｍＰａ・ｓ、４．０／ｓ＝１９９ ｍＰａ・ｓ、７．９／ｓ＝１１３ ｍＰａ・ｓ、１５．８／ｓ＝６５ ｍＰａ・ｓ、３９．６／ｓ＝３１ ｍＰａ・ｓ、及び７９．２／ｓ＝１８ ｍＰａ・ｓであった。 After measuring the sedimentation volume, the viscosity of the 5% dispersed kerosene solution was measured using a digital viscometer (DVM-B type manufactured by Toki Sangyo Co., Ltd.). The relationship between the shear rate and the apparent viscosity obtained using the rotor HM-2 is 1.0 / s = 2080 mPa · s, 2.0 / s = 1050 mPa · s, 4.1 / s = 521 mPa · s. s, 10.2 / s = 228 mPa · s and 20.4 / s = 125 mPa · s. Furthermore, the apparent viscosity of the 5% dispersed toluene solution measured by changing the rotor to HM-1 is 0.8 / s = 491 mPa · s, 2.0 / s = 303 mPa · s, 4.0 / s = 199 mPa · s, 7.9 / s = 113 mPa · s, 15.8 / s = 65 mPa · s, 39.6 / s = 31 mPa · s, and 79.2 / s = 18 mPa · s there were.
参考例２
参考例１と同様な操作で、化学組成及び合成条件を下記の条件に変更して、合成粘土（Ｎｏ．２）３１．８ｇを作製した。
（合成条件）
３号水ガラス：６８．７ｇ
塩化マグネシウム六水和物一級試薬（純度９８％）：５７．７ｇ
塩化アルミニウム六水和物一級試薬（純度９８％）：８．３ｇ
沈殿用２規定水酸化ナトリウム溶液量：３９０ｍｌ
沈殿ｐＨ：１０．５
合成用２規定水酸化ナトリウム溶液量：１７ｍｌ
水熱合成温度：３００℃
水熱合成反応時間：２４時間
原料スラリーｐＨ：１１．５
水熱合成後ｐＨ：１１．９
Reference example 2
In the same manner as in Reference Example 1, the chemical composition and synthesis conditions were changed to the following conditions to produce 31.8 g of synthetic clay (No. 2).
(Synthesis conditions)
No.3 water glass: 68.7g
Magnesium chloride hexahydrate primary reagent (purity 98%): 57.7 g
Aluminum chloride hexahydrate primary reagent (purity 98%): 8.3 g
2N sodium hydroxide solution for precipitation: 390 ml
Precipitation pH: 10.5
2N sodium hydroxide solution for synthesis: 17 ml
Hydrothermal synthesis temperature: 300 ° C
Hydrothermal synthesis reaction time: 24 hours Raw material slurry pH: 11.5
PH after hydrothermal synthesis: 11.9
本試料を用いて、エチレングリコール処理定方位試料を作製し、Ｘ線回折の測定をした。得られた（００１１）、（００２１）、（００２４）、（００３１）（００４０）、（００５２）及び（００６２）ピークは、それぞれ１６．１Å、８．４５Å、７．４０Å、５．７３Å， ４．４４Å， ３．４１Å及び２．８６Åであった。これらの７ピークから計算される（００１）ピークの平均値は１７７．８Åであり、リザルダイト層１枚とサポナイト層１０枚からなる理想的な混合層鉱物の（００１）ピークの値は１７７．５Åと計算され、ほぼ想定した合成粘土（Ｎｏ．２）が製造されたと考えられる。 Using this sample, an ethylene glycol-treated fixed orientation sample was prepared and measured for X-ray diffraction. The obtained (0011), (0021), (0024), (0031) (0040), (0052) and (0062) peaks were 16.1Å, 8.45Å, 7.40Å, 5.73Å, 4 respectively. 44 mm, 3.41 mm and 2.86 mm. The average value of the (001) peak calculated from these 7 peaks is 177.8%, and the value of the (001) peak of an ideal mixed layer mineral consisting of one lizardite layer and 10 saponite layers is 177.5%. It is calculated that synthetic clay (No. 2) almost assumed was produced.
得られた合成粘土（Ｎｏ．２）はａ＝０、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝１０で設計して作製したものであり、得られた化学組成はＳｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．８４：６．９５：０．８４であり、及びメチレンブルー吸着量から得られた陽イオン交換容量は１．１２ ｍｅｑ／ｇであった。２．５％水溶液はゲルを形成し、ファンＶＧメーターで測定した見掛粘度は１０２２／ｓ＝７ ｍＰａ・ｓ及び１０．２／ｓ＝１００ ｍＰａ・ｓであった。 The obtained synthetic clay (No. 2 ) was prepared by designing with a = 0, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 10. The chemical composition obtained was Si: Al: Mg: Na = 8.00: 0.84: 6.95: 0.84, and the cation exchange capacity obtained from the amount of adsorbed methylene blue was 1. .12 meq / g. The 2.5% aqueous solution formed a gel, and the apparent viscosities measured with a fan VG meter were 1022 / s = 7 mPa · s and 10.2 / s = 100 mPa · s.
実施例１と同様にして、合成粘土（Ｎｏ．２）１０ｇから有機粘土複合体を作製した。但し、アーカード２ＨＴの量を６．９ｇにして実施し、有機粘土複合体１３．９ｇが得られた。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．２）： ａ＝０、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝１０ 合成粘土（Ｎｏ．２）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．８４：６．９５：０．８４
合成粘土（Ｎｏ．２）の２．５％水溶液の見掛粘度：１０２２／ｓ＝７ ｍＰａ・ｓ及び１０．２／ｓ＝１００ ｍＰａ・ｓ
有機陽イオンの使用量：１．１２ ｍｅｑ／ｇ
In the same manner as in Example 1, an organoclay composite was prepared from 10 g of synthetic clay (No. 2). However, the experiment was carried out with the amount of Arcade 2HT set to 6.9 g, and 13.9 g of an organoclay composite was obtained.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 2): a = 0, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 10 Composition of synthetic clay (No. 2) : Si: Al: Mg: Na = 8.00: 0.84: 6.95: 0.84
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 2): 1022 / s = 7 mPa · s and 10.2 / s = 100 mPa · s
Amount of organic cation used: 1.12 meq / g
実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％、２％、３％及び５％の有機粘土複合体をケロシンに分散させた溶液の沈降体積は、１％分散ケロシン溶液＝１００％、２％分散ケロシン溶液＝１００％、３％分散ケロシン溶液＝１００％及び５％分散ケロシン溶液＝１００％であった。５％分散ケロシン溶液はゲル化していた。また、同様に測定した、有機粘土複合体分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝１００％及び５％分散トルエン溶液＝１００％であった。５％分散トルエン％溶液はゲル化していた。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume of a solution obtained by dispersing 1%, 2%, 3% and 5% organoclay complex in kerosene is 1% dispersed kerosene solution = 100%, 2% dispersed kerosene solution = 100%, 3% dispersed kerosene. Solution = 100% and 5% dispersed kerosene solution = 100%. The 5% dispersed kerosene solution was gelled. Moreover, the sedimentation volume of the organoclay complex-dispersed toluene solution measured in the same manner was 1% dispersed toluene solution = 100% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene% solution was gelled.
５％分散ケロシン溶液の粘度測定を実施例１と同様に行った。ローターＨＭ−２を用いて得られた、ずり速度と見掛粘度の関係は１．０／ｓ＝ ４９３ ｍＰａ・ｓ、２．０／ｓ＝１９４ ｍＰａ・ｓ、４．１／ｓ＝１０２ ｍＰａ・ｓ、１０．２／ｓ＝４９ ｍＰａ・ｓ及び２０．４／ｓ＝２８ ｍＰａ・ｓであった。
更に、ローターをＨＭ−１に変えて実施例１と同様に測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝４３６ ｍＰａ・ｓ、２．０／ｓ＝２７６ ｍＰａ・ｓ、４．０／ｓ＝１７６ ｍＰａ・ｓ、７．９／ｓ＝１０７ ｍＰａ・ｓ、１５．８／ｓ＝６６ ｍＰａ・ｓ、３９．６／ｓ＝３５ ｍＰａ・ｓ、及び７９．２／ｓ＝２１ ｍＰａ・ｓであった。
The viscosity of the 5% dispersed kerosene solution was measured in the same manner as in Example 1. The relationship between the shear rate and the apparent viscosity obtained using the rotor HM-2 is 1.0 / s = 493 mPa · s, 2.0 / s = 194 mPa · s, 4.1 / s = 102 mPa. S, 10.2 / s = 49 mPa · s and 20.4 / s = 28 mPa · s.
Further, the apparent viscosity of the 5% dispersed toluene solution measured in the same manner as in Example 1 with the rotor changed to HM-1 was 0.8 / s = 436 mPa · s, 2.0 / s = 276 mPa · s. 4.0 / s = 176 mPa · s, 7.9 / s = 107 mPa · s, 15.8 / s = 66 mPa · s, 39.6 / s = 35 mPa · s, and 79.2 / s = 21 mPa · s.
参考例３
参考例１と同様な操作で、化学組成及び合成条件を下記の条件に変更して、合成粘土（Ｎｏ．３）３４．４ｇを作製した。
（合成条件）
３号水ガラス：６８．７ｇ
塩化マグネシウム六水和物一級試薬（純度９８％）：５８．２ｇ
塩化アルミニウム六水和物一級試薬（純度９８％）：７．０ｇ
沈殿用２規定水酸化ナトリウム溶液量：３８０ｍｌ
沈殿ｐＨ：１０．５
合成用２規定水酸化ナトリウム溶液量：２４ｍｌ
水熱合成温度：２７０℃
水熱合成反応時間：２時間
原料スラリーｐＨ：１１．３
水熱合成後ｐＨ：９．７
Reference example 3
In the same manner as in Reference Example 1, the chemical composition and synthesis conditions were changed to the following conditions to produce 34.4 g of synthetic clay (No. 3 ).
(Synthesis conditions)
No.3 water glass: 68.7g
Magnesium chloride hexahydrate primary reagent (purity 98%): 58.2 g
Aluminum chloride hexahydrate primary reagent (purity 98%): 7.0 g
2N sodium hydroxide solution for precipitation: 380 ml
Precipitation pH: 10.5
2N sodium hydroxide solution for synthesis: 24 ml
Hydrothermal synthesis temperature: 270 ° C
Hydrothermal synthesis reaction time: 2 hours Raw material slurry pH: 11.3
PH after hydrothermal synthesis: 9.7
得られた合成粘土（Ｎｏ．３）はａ＝０．１５、ｂ＝０、ｃ＝０．３、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５で設計して作製したものであり、得られた組成はＳｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７１：７．０２：０．５９であり、及びメチレンブルー吸着量から得られた陽イオン交換容量は１．０７ｍｅｑ／ｇであった。２．５％水溶液はゲルを形成し、ファンＶＧメーターで測定した見掛粘度は１０２２／ｓ＝１６ ｍＰａ・ｓ及び１０．２／ｓ＝８７５ ｍＰａ・ｓであった。 The resulting synthetic clay (No. 3) was designed with a = 0.15, b = 0, c = 0.3, d = 0, e = 0, f = 1, x = 1 and y = 5. The composition obtained was Si: Al: Mg: Na = 8.00: 0.71: 7.02: 0.59, and the cation exchange capacity obtained from the amount of adsorbed methylene blue was It was 1.07 meq / g. The 2.5% aqueous solution formed a gel and the apparent viscosities measured by a fan VG meter were 1022 / s = 16 mPa · s and 10.2 / s = 875 mPa · s.
実施例１と同様にして、合成粘土（Ｎｏ．３）１０ｇから有機粘土複合体を作製した。但し、アーカード２ＨＴの量を６．６ｇにして実施し、有機粘土複合体１３．３ｇが得られた。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．３）： ａ＝０．１５、ｂ＝０、ｃ＝０．３、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５
合成粘土（Ｎｏ．３）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７１：７．０２：０．５９
合成粘土（Ｎｏ．３）の２．５％水溶液の見掛粘度：１０２２／ｓ＝１６ ｍＰａ・ｓ及び１０．２／ｓ＝８７５ ｍＰａ・ｓ
有機陽イオンの使用量：１．０７ｍｅｑ／ｇ
In the same manner as in Example 1, an organoclay composite was prepared from 10 g of synthetic clay (No. 3). However, the experiment was carried out with an amount of Arcade 2HT of 6.6 g, and 13.3 g of an organoclay composite was obtained.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 3): a = 0.15, b = 0, c = 0.3, d = 0, e = 0, f = 1, x = 1 and y = 5
Composition of synthetic clay (No. 3): Si: Al: Mg: Na = 8.00: 0.71: 7.02: 0.59
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 3): 1022 / s = 16 mPa · s and 10.2 / s = 875 mPa · s
Amount of organic cation used: 1.07 meq / g
実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％及び５％の有機粘土複合体をケロシンに分散させた溶液の沈降体積は、１％分散ケロシン溶液＝１００％及び５％分散ケロシン溶液＝１００％であった。５％分散ケロシン溶液はゲル化していた。また、同様に測定した、有機粘土複合体分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝１００％及び５％分散トルエン溶液＝１００％であった。５％分散トルエン溶液はゲル化していた。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume of a solution in which 1% and 5% organoclay complex was dispersed in kerosene was 1% dispersed kerosene solution = 100% and 5% dispersed kerosene solution = 100%. The 5% dispersed kerosene solution was gelled. Moreover, the sedimentation volume of the organoclay complex-dispersed toluene solution measured in the same manner was 1% dispersed toluene solution = 100% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene solution was gelled.
実施例１と同様に、ローターＨＭ−１を用いて測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝７６５ ｍＰａ・ｓ、２．０／ｓ＝４３６ ｍＰａ・ｓ、４．０／ｓ＝２６４ ｍＰａ・ｓ、７．９／ｓ＝１４９ ｍＰａ・ｓ、１５．８／ｓ＝８５ ｍＰａ・ｓ、３９．６／ｓ＝４０ ｍＰａ・ｓ、及び７９．２／ｓ＝２３ ｍＰａ・ｓであった。 As in Example 1, the apparent viscosities of the 5% dispersed toluene solution measured using the rotor HM-1 were 0.8 / s = 765 mPa · s, 2.0 / s = 436 mPa · s, 4 0.0 / s = 264 mPa · s, 7.9 / s = 149 mPa · s, 15.8 / s = 85 mPa · s, 39.6 / s = 40 mPa · s, and 79.2 / s = It was 23 mPa · s.
１％有機粘土複合体分散エタノール溶液及び１％有機粘土複合体分散（５％水＋９５％エタノール）混合溶液の２４時間後の沈降体積は、１％分散エタノール溶液＝６％及び１％分散（５％水＋９５％エタノール）混合溶液＝３５％であった。水は、エタノール膨潤の活性剤として作用すると考えられる。 The sedimentation volume after 24 hours of the mixed solution of 1% organoclay complex dispersed ethanol and 1% organoclay complex dispersed (5% water + 95% ethanol) was 1% dispersed ethanol solution = 6% and 1% dispersed (5 % Water + 95% ethanol) mixed solution = 35%. Water is thought to act as an activator of ethanol swelling.
参考例４
参考例１と同様な操作で、化学組成及び合成条件を下記の条件に変更して、合成粘土（Ｎｏ．４）３４．４ｇを作製した。
（合成条件）
３号水ガラス：６８．７ｇ
塩化マグネシウム六水和物一級試薬（純度９８％）：６０．７ｇ
塩化アルミニウム六水和物一級試薬（純度９８％）：７．３ｇ
沈殿用２規定水酸化ナトリウム溶液量：３８０ｍｌ
沈殿ｐＨ：１０．５
合成用２規定水酸化ナトリウム溶液量：２２ｍｌ
水熱合成温度：２７０℃
水熱合成反応時間：２時間
原料スラリーｐＨ：１１．２
水熱合成後ｐＨ：１１．３
Reference example 4
In the same manner as in Reference Example 1, the chemical composition and synthesis conditions were changed to the following conditions to produce 34.4 g of synthetic clay (No. 4).
(Synthesis conditions)
No.3 water glass: 68.7g
Magnesium chloride hexahydrate primary reagent (purity 98%): 60.7 g
Aluminum chloride hexahydrate primary reagent (purity 98%): 7.3 g
2N sodium hydroxide solution for precipitation: 380 ml
Precipitation pH: 10.5
2N sodium hydroxide solution for synthesis: 22 ml
Hydrothermal synthesis temperature: 270 ° C
Hydrothermal synthesis reaction time: 2 hours Raw material slurry pH: 11.2
PH after hydrothermal synthesis: 11.3
得られた合成粘土（Ｎｏ．４）はａ＝０．１５、ｂ＝０、ｃ＝０．３、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝３で設計して作製したものであり、得られた組成はＳｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７４：７．３２：０．５６であり、及びメチレンブルー吸着量から得られた陽イオン交換容量は０．９８ｍｅｑ／ｇであった。２．５％水溶液はゲルを形成し、ファンＶＧメーターで測定した見掛粘度は１０２２／ｓ＝１９ ｍＰａ・ｓ及び１０．２／ｓ＝９００ ｍＰａ・ｓであった。 The resultant synthetic clay (No. 4) was designed with a = 0.15, b = 0, c = 0.3, d = 0, e = 0, f = 1, x = 1 and y = 3. The composition obtained was Si: Al: Mg: Na = 8.00: 0.74: 7.32: 0.56, and the cation exchange capacity obtained from the adsorbed amount of methylene blue was It was 0.98 meq / g. The 2.5% aqueous solution formed a gel, and the apparent viscosities measured with a fan VG meter were 1022 / s = 19 mPa · s and 10.2 / s = 900 mPa · s.
実施例１と同様にして、合成粘土（Ｎｏ．４）１０ｇから有機粘土複合体を作製した。但し、アーカード２ＨＴの量を６．６ｇにして実施し、有機粘土複合体１３．３ｇが得られた。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．４）： ａ＝０．１５、ｂ＝０、ｃ＝０．３、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝３
合成粘土（Ｎｏ．４）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７４：７．３２：０．５６
合成粘土（Ｎｏ．４）の２．５％水溶液の見掛粘度：１０２２／ｓ＝１９ ｍＰａ・ｓ及び１０．２／ｓ＝９００ ｍＰａ・ｓ
有機陽イオンの使用量：０．９８ｍｅｑ／ｇ
In the same manner as in Example 1, an organoclay composite was prepared from 10 g of synthetic clay (No. 4). However, the experiment was carried out with an amount of Arcade 2HT of 6.6 g, and 13.3 g of an organoclay composite was obtained.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 4): a = 0.15, b = 0, c = 0.3, d = 0, e = 0, f = 1, x = 1 and y = 3
Composition of synthetic clay (No. 4): Si: Al: Mg: Na = 8.00: 0.74: 7.32: 0.56
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 4): 1022 / s = 19 mPa · s and 10.2 / s = 900 mPa · s
Amount of organic cation used: 0.98 meq / g
実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％及び５％の有機粘土複合体をケロシンに分散させた溶液の２４時間後の沈降体積は、１％分散ケロシン溶液＝２９％及び５％分散ケロシン溶液＝１００％であった。５％分散ケロシン溶液はゲル化していた。また、同様に測定した、有機粘土複合体分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝１００％及び５％分散トルエン溶液＝１００％であった。５％分散トルエン溶液はゲル化していた。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume after 24 hours of the solution in which 1% and 5% organoclay complex was dispersed in kerosene was 1% dispersed kerosene solution = 29% and 5% dispersed kerosene solution = 100%. The 5% dispersed kerosene solution was gelled. Moreover, the sedimentation volume of the organoclay complex-dispersed toluene solution measured in the same manner was 1% dispersed toluene solution = 100% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene solution was gelled.
実施例１と同様に、ローターＨＭ−１を用いて測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝６４４ ｍＰａ・ｓ、２．０／ｓ＝３９２ ｍＰａ・ｓ、４．０／ｓ＝２４４ ｍＰａ・ｓ、７．９／ｓ＝１４１ ｍＰａ・ｓ、１５．８／ｓ＝８４ ｍＰａ・ｓ、３９．６／ｓ＝４２ ｍＰａ・ｓ、及び７９．２／ｓ＝２５ ｍＰａ・ｓであった。 As in Example 1, the apparent viscosities of the 5% dispersed toluene solution measured using the rotor HM-1 were 0.8 / s = 644 mPa · s, 2.0 / s = 392 mPa · s, 4 0.0 / s = 244 mPa · s, 7.9 / s = 141 mPa · s, 15.8 / s = 84 mPa · s, 39.6 / s = 42 mPa · s, and 79.2 / s = 25 mPa · s.
１％有機粘土複合体分散エタノール溶液及び１％有機粘土複合体分散（５％水＋９５％エタノール）混合溶液の２４時間後の沈降体積は、１％分散エタノール溶液＝７％及び１％分散（５％水＋９５％エタノール）混合溶液＝１００％であった。本発明製品に対して、水はエタノール膨潤の活性剤として特に有効に作用して、１％分散（５％水＋９５％エタノール）混合溶液では完全分散していると考えられる。従って、本製品は、水を用いることによって、アルコール等の極性溶媒に対して有効に用いることができる。 The sedimentation volume after 24 hours of 1% organoclay complex dispersed ethanol solution and 1% organoclay complex dispersed (5% water + 95% ethanol) mixed solution was 1% dispersed ethanol solution = 7% and 1% dispersed (5 % Water + 95% ethanol) mixed solution = 100%. For the product of the present invention, water acts particularly effectively as an activator of ethanol swelling, and is considered to be completely dispersed in a 1% dispersion (5% water + 95% ethanol) mixed solution. Therefore, this product can be effectively used for polar solvents such as alcohol by using water.
比較例１
有機溶剤系添加剤商品のＳ−ＢＥＮ（エスベン、株式会社ホージュン）を用いて、実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％及び５％分散ケロシン溶液の沈降体積は、１％分散ケロシン溶液＝３％、及び５％分散ケロシン溶液＝１７％であった。５％分散ケロシン溶液は分離していた。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝２３％、及び５％分散トルエン溶液＝１００％であった。５％分散トルエン溶液はゲル化していた。
Comparative Example 1
Using S-BEN (Esven, Hojun Co., Ltd.), an organic solvent-based additive product, the sedimentation volume after 24 hours of the dispersed organic solvent was measured in the same manner as in Example 1. The sedimentation volumes of the 1% and 5% dispersed kerosene solutions were 1% dispersed kerosene solution = 3% and 5% dispersed kerosene solution = 17%. The 5% dispersed kerosene solution was separated. The sedimentation volumes of the 1% dispersed toluene solution and the 5% dispersed toluene solution were 1% dispersed toluene solution = 23% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene solution was gelled.
更に、実施例１と同様に、ローターＨＭ−１を用いて測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝５３９ ｍＰａ・ｓ、２．０／ｓ＝２６３ ｍＰａ・ｓ、４．０／ｓ＝１７７ ｍＰａ・ｓ、７．９／ｓ＝１３５ ｍＰａ・ｓ、１５．８／ｓ＝１１１ ｍＰａ・ｓ 、３９．６／ｓ＝６６ ｍＰａ・ｓ、及び７９．２／ｓ＝４０ ｍＰａ・ｓであった。 Further, as in Example 1, the apparent viscosity of the 5% dispersed toluene solution measured using the rotor HM-1 was 0.8 / s = 539 mPa · s, 2.0 / s = 263 mPa · s. 4.0 / s = 177 mPa · s, 7.9 / s = 135 mPa · s, 15.8 / s = 111 mPa · s, 39.6 / s = 66 mPa · s, and 79.2 / s = 40 mPa · s.
比較例２
有機溶剤系添加剤商品のＳ−ＢＥＮ７４（エスベン７４、株式会社ホージュン）を用いて実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％及び５％分散ケロシン溶液の沈降体積は、１％分散ケロシン溶液＝８％、及び５％分散ケロシン溶液＝２９％であった。５％分散ケロシン溶液は分離していた。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝３８％、及び５％分散トルエン溶液＝１００％であった。５％分散トルエン溶液はゲル化していた。
Comparative Example 2
The sedimentation volume of the dispersed organic solvent after 24 hours was measured in the same manner as in Example 1 using S-BEN74 (Esven 74, Hojun Co., Ltd.), an organic solvent additive product. The sedimentation volumes of 1% and 5% dispersed kerosene solutions were 1% dispersed kerosene solution = 8% and 5% dispersed kerosene solution = 29%. The 5% dispersed kerosene solution was separated. The sedimentation volumes of the 1% dispersed toluene solution and the 5% dispersed toluene solution were 1% dispersed toluene solution = 38% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene solution was gelled.
更に、実施例１と同様に、ローターＨＭ−１を用いて測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝５１００ ｍＰａ・ｓ、２．０／ｓ＝２０５７ ｍＰａ・ｓ、４．０／ｓ＝１０２７ ｍＰａ・ｓ、７．９／ｓ＝５１３ ｍＰａ・ｓ、１５．８／ｓ＝２５７ ｍＰａ・ｓ、３９．６／ｓ＝１０７ ｍＰａ・ｓ、及び７９．２／ｓ＝５１ ｍＰａ・ｓであった。 Further, in the same manner as in Example 1, the apparent viscosity of the 5% dispersed toluene solution measured using the rotor HM-1 was 0.8 / s = 5100 mPa · s, 2.0 / s = 2005 mPa · s. 4.0 / s = 1027 mPa · s, 7.9 / s = 513 mPa · s, 15.8 / s = 257 mPa · s, 39.6 / s = 107 mPa · s, and 79.2 / s = 51 mPa · s.
比較例３
有機溶剤系添加剤商品のＯＲＧＡＮＩＴＥ（オーガナイト、株式会社ホージュン）を用いて、実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％及び５％分散ケロシン溶液の沈降体積は１％分散ケロシン溶液＝８％、及び５％分散ケロシン溶液＝２９％であった。５％分散ケロシン溶液は分離していた。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝３５％、及び５％分散トルエン溶液＝１００％であった。５％分散トルエン溶液はゲル化していた。
Comparative Example 3
The sedimentation volume of the dispersed organic solvent after 24 hours was measured in the same manner as in Example 1 using ORGANITE (Organite, Hojun Co., Ltd.), an organic solvent additive product. The sedimentation volumes of 1% and 5% dispersed kerosene solutions were 1% dispersed kerosene solution = 8% and 5% dispersed kerosene solution = 29%. The 5% dispersed kerosene solution was separated. The sedimentation volumes of the 1% dispersed toluene solution and the 5% dispersed toluene solution were 1% dispersed toluene solution = 35% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene solution was gelled.
更に、実施例１と同様に、ローターＨＭ−１を用いて測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝１０９０ ｍＰａ・ｓ、２．０／ｓ＝６４０ ｍＰａ・ｓ、４．０／ｓ＝４７０ ｍＰａ・ｓ、７．９／ｓ＝４１０ ｍＰａ・ｓ、１５．８／ｓ＝２１０ ｍＰａ・ｓ、３９．６／ｓ＝８７ ｍＰａ・ｓ、及び７９．２／ｓ＝４６ ｍＰａ・ｓであった。 Further, as in Example 1, the apparent viscosity of the 5% dispersed toluene solution measured using the rotor HM-1 was 0.8 / s = 1090 mPa · s, 2.0 / s = 640 mPa · s. 4.0 / s = 470 mPa · s, 7.9 / s = 410 mPa · s, 15.8 / s = 210 mPa · s, 39.6 / s = 87 mPa · s, and 79.2 / s = 46 mPa · s.
比較例４
合成ヘクトライトから製造した有機溶剤系添加剤製品のＳＡＮ（コープケミカル株式会社）を用いて、実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％及び５％分散ケロシン溶液の沈降体積は１％分散ケロシン溶液＝８％、及び５％分散ケロシン溶液＝２２％であった。５％分散ケロシン溶液は分離していた。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝１００％、及び５％分散トルエン溶液＝１００％であった。５％分散トルエン溶液はゲル化していた。なお、ＳＡＮはアーカード２ＨＴを複合させた商品である。
Comparative Example 4
Using SAN (Coop Chemical Co., Ltd.), an organic solvent additive product produced from synthetic hectorite, the sedimentation volume after 24 hours of the dispersed organic solvent was measured in the same manner as in Example 1. The sedimentation volumes of the 1% and 5% dispersed kerosene solutions were 1% dispersed kerosene solution = 8% and 5% dispersed kerosene solution = 22%. The 5% dispersed kerosene solution was separated. The sedimentation volumes of the 1% dispersed toluene solution and the 5% dispersed toluene solution were 1% dispersed toluene solution = 100% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene solution was gelled. Note that SAN is a product in which ARCARD 2HT is combined.
更に、実施例１と同様に、ローターＨＭ−２を用いて測定した、５％分散トルエン溶液のずり速度と見掛粘度の関係は０．８／ｓ＝８４４ ｍＰａ・ｓ、２．０／ｓ＝４５５ ｍＰａ・ｓ、４．１／ｓ＝ ２６２ ｍＰａ・ｓ、１０．２／ｓ＝１２８ ｍＰａ・ｓ及び２０．４／ｓ＝７４ ｍＰａ・ｓであった。 Further, as in Example 1, the relationship between the shear rate of the 5% dispersed toluene solution and the apparent viscosity measured using the rotor HM-2 was 0.8 / s = 844 mPa · s, 2.0 / s. = 455 mPa · s, 4.1 / s = 262 mPa · s, 10.2 / s = 128 mPa · s and 20.4 / s = 74 mPa · s.
参考例５
参考例１と同様な操作で、化学組成及び合成条件を下記の条件に変更して、合成粘土（Ｎｏ．５）２９．７ｇを作製した。
（合成条件）
３号水ガラス：６８．７ｇ
塩化マグネシウム六水和物一級試薬（純度９８％）：５９．７ｇ
塩化アルミニウム六水和物一級試薬（純度９８％）：９．６ｇ
沈殿用２規定水酸化ナトリウム溶液量：４１０ｍｌ
沈殿ｐＨ：１０．６
合成用２規定水酸化ナトリウム溶液量：１６ｍｌ
水熱合成温度：３００℃
水熱合成反応時間：２４時間
原料スラリーｐＨ：１１．５
水熱合成後ｐＨ：１２．０
Reference Example 5
In the same manner as in Reference Example 1, the chemical composition and synthesis conditions were changed to the following conditions to produce 29.7 g of synthetic clay (No. 5).
(Synthesis conditions)
No.3 water glass: 68.7g
Magnesium chloride hexahydrate primary reagent (purity 98%): 59.7 g
Aluminum chloride hexahydrate primary reagent (purity 98%): 9.6 g
2N sodium hydroxide solution for precipitation: 410ml
Precipitation pH: 10.6
2N sodium hydroxide solution for synthesis: 16 ml
Hydrothermal synthesis temperature: 300 ° C
Hydrothermal synthesis reaction time: 24 hours Raw material slurry pH: 11.5
PH after hydrothermal synthesis: 12.0
本試料を用いて、エチレングリコール処理定方位試料を作製し、Ｘ線回折の測定をした。得られた（００５）、（００１１）、（００１６）、（００２１）及び（００２７）ピークは、それぞれ１９．２Å、８．６７Å、５．７５Å、４．３５Å及び３．４０Åであった。この５ピークから計算される（００１）ピークの平均値は９３．３Åであり、リザルダイト層１枚とサポナイト層５枚からなる理想的な混合層鉱物の（００１）ピークの値は９２．５Åと計算され、ほぼ想定した合成粘土（Ｎｏ．５）が製造されたと考えられる。 Using this sample, an ethylene glycol-treated fixed orientation sample was prepared and measured for X-ray diffraction. The obtained (005), (0011), (0016), (0021) and (0027) peaks were 19.2．, 8.67Å, 5.75Å, 4.35Å and 3.40Å, respectively. The average value of the (001) peak calculated from these 5 peaks is 93.3Å, and the value of the (001) peak of an ideal mixed layer mineral consisting of one lizardite layer and five saponite layers is 92.5Å. It is considered that synthetic clay (No. 5) calculated and almost assumed was produced.
得られた合成粘土（Ｎｏ．５）はａ＝０．２、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５で設計して作製したものであり、得られた組成はＳｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．９７：７．１９：０．８１であり、及びメチレンブルー吸着量から得られた陽イオン交換容量は０．８３ｍｅｑ／ｇであった。２．５％水溶液はゲルを形成し、ファンＶＧメーターで測定した見掛粘度は１０２２／ｓ＝４．５ ｍＰａ・ｓ及び１０．２／ｓ＝５０ ｍＰａ・ｓであった。 The resultant synthetic clay (No. 5) was designed with a = 0.2, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 5. The composition obtained was Si: Al: Mg: Na = 8.00: 0.97: 7.19: 0.81, and the cation exchange capacity obtained from the amount of adsorbed methylene blue was It was 0.83 meq / g. The 2.5% aqueous solution formed a gel, and the apparent viscosities measured with a fan VG meter were 1022 / s = 4.5 mPa · s and 10.2 / s = 50 mPa · s.
実施例１と同様にして、合成粘土（Ｎｏ．５）１０ｇから有機粘土複合体を作製した。但し、アーカード２ＨＴの量を５．１ｇにして実施し、有機粘土複合体１２．４ｇが得られた。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．５）： ａ＝０．２、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５
合成粘土（Ｎｏ．５）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．９７：７．１９：０．８１
合成粘土（Ｎｏ．５）の２．５％水溶液の見掛粘度：１０２２／ｓ＝４．５ ｍＰａ・ｓ及び１０．２／ｓ＝５０ ｍＰａ・ｓ
有機陽イオンの使用量：０．８３ ｍｅｑ／ｇ
In the same manner as in Example 1, an organoclay composite was prepared from 10 g of synthetic clay (No. 5). However, it was carried out with the amount of Arcade 2HT set to 5.1 g, and 12.4 g of an organoclay complex was obtained.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 5): a = 0.2, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 5
Composition of synthetic clay (No. 5): Si: Al: Mg: Na = 8.00: 0.97: 7.19: 0.81
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 5): 1022 / s = 4.5 mPa · s and 10.2 / s = 50 mPa · s
Amount of organic cation used: 0.83 meq / g
実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％、２％、３％及び５％の有機粘土複合体をケロシンに分散させた溶液の沈降体積は、１％分散ケロシン溶液＝２７％、２％分散ケロシン溶液＝４０％、３％分散ケロシン溶液＝６２％及び５％分散ケロシン溶液＝１００％であった。５％分散ケロシン溶液はゲル化していた。また、同様に測定した、有機粘土複合体分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝１００％及び５％分散トルエン溶液＝１００％であった。５％分散トルエン％溶液はゲル化していた。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume of a solution in which 1%, 2%, 3% and 5% organoclay complex was dispersed in kerosene was 1% dispersed kerosene solution = 27%, 2% dispersed kerosene solution = 40%, 3% dispersed kerosene. Solution = 62% and 5% dispersed kerosene solution = 100%. The 5% dispersed kerosene solution was gelled. Moreover, the sedimentation volume of the organoclay complex-dispersed toluene solution measured in the same manner was 1% dispersed toluene solution = 100% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene% solution was gelled.
５％分散ケロシン溶液の粘度測定を、実施例１と同様に行った。ローターＨＭ−２を用いて得られた、ずり速度と見掛粘度の関係は１．０／ｓ＝３４０ ｍＰａ・ｓ、２．０／ｓ＝２３１ ｍＰａ・ｓ、４．１／ｓ＝１４９ ｍＰａ・ｓ、１０．２／ｓ＝７９ ｍＰａ・ｓ及び２０．４／ｓ＝４９ ｍＰａ・ｓであった。
更に、ローターをＨＭ−１に変えて、実施例１と同様に測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝５２７ ｍＰａ・ｓ、２．０／ｓ＝２５８ ｍＰａ・ｓ、４．０／ｓ＝１６７ ｍＰａ・ｓ、７．９／ｓ＝９６ ｍＰａ・ｓ、１５．８／ｓ＝５３ ｍＰａ・ｓ、３９．６／ｓ＝２３ ｍＰａ・ｓ、及び７９．２／ｓ＝１３ ｍＰａ・ｓであった。
The viscosity of the 5% dispersed kerosene solution was measured in the same manner as in Example 1. The relationship between the shear rate and the apparent viscosity obtained using the rotor HM-2 is 1.0 / s = 340 mPa · s, 2.0 / s = 231 mPa · s, 4.1 / s = 149 mPa. S, 10.2 / s = 79 mPa · s and 20.4 / s = 49 mPa · s.
Further, the apparent viscosity of the 5% dispersed toluene solution measured in the same manner as in Example 1 with the rotor changed to HM-1 was 0.8 / s = 527 mPa · s, 2.0 / s = 258 mPa · s. s, 4.0 / s = 167 mPa · s, 7.9 / s = 96 mPa · s, 15.8 / s = 53 mPa · s, 39.6 / s = 23 mPa · s, and 79.2 / S = 13 mPa · s.
アルミニウム含有量の異なる合成混合層粘土を用いた本発明のアーカード２ＨＴ−有機粘土複合体（実施例１〜５）及び商品として用いられている従来の有機粘土複合体（比較例１〜４）のケロシン及びトルエン分散溶液の沈降体積及び見掛粘度の値を表１に示す。従来のスメクタイト系粘土より製造した比較例１〜４の有機粘土複合体は、トルエンには分散し、５％分散トルエン溶液はゲル化するが、ケロシンには分散しなかった。一方、本発明の実施例１〜５のアーカード２ＨＴ−有機粘土複合体は、トルエン及びケロシンの両方の有機溶媒に対して良好な分散性を示し、特にケロシンに対しては、メタノール等の活性剤を使用することなく、単独で調粘性のゲル溶液を形成して有用であることが判明した。
アーカード２ＨＴ−有機粘土複合体における混合層粘土のｘ／ｙ＝１／５の場合には、ケロシンに対する分散性は、アルミニウム含有量が多くなると低下し、１％分散ケロシン溶液の沈降体積は小さくなる傾向が認められた。１％分散ケロシン溶液の沈降体積が２０％程度以上の値であれば、５％分散ケロシン溶液は、ほぼゲル化することが認められた。アーカード２ＨＴ−有機粘土複合体のケロシン及びトルエン分散溶液の沈降体積及び見掛粘度の変化を表１に示す。
Of the arcade 2HT-organoclay composites (Examples 1-5) of the present invention using synthetic mixed layer clays with different aluminum contents and the conventional organoclay composites (Comparative Examples 1-4) used as commercial products Table 1 shows the sediment volume and apparent viscosity values of the kerosene and toluene dispersions. The organoclay composites of Comparative Examples 1 to 4 produced from conventional smectite clay were dispersed in toluene and a 5% dispersed toluene solution was gelled, but was not dispersed in kerosene. On the other hand, the arcade 2HT-organoclay composites of Examples 1 to 5 of the present invention show good dispersibility in both toluene and kerosene organic solvents, and particularly for kerosene, an activator such as methanol. It was found that it is useful to form a viscous gel solution by itself without using
In the case of x / y = 1/5 of the mixed layer clay in the arcade 2HT-organoclay composite, the dispersibility with respect to kerosene decreases as the aluminum content increases, and the sedimentation volume of the 1% dispersed kerosene solution decreases. A trend was observed. When the sedimentation volume of the 1% dispersed kerosene solution was about 20% or more, it was confirmed that the 5% dispersed kerosene solution was almost gelled. Table 1 shows changes in the sedimentation volume and apparent viscosity of the kerosene and toluene dispersion of the arcade 2HT-organoclay clay complex.
実施例５と同様に操作して、有機粘土複合体１３．０ｇを作製した。但し、アーカード２ＨＴの量を５．６ｇに変更して実施した。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．５）： ａ＝０．２、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５ 合成粘土（Ｎｏ．５）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．９７：７．１９：０．８１
合成粘土（Ｎｏ．５）の２．５％水溶液の見掛粘度：１０２２／ｓ＝４．５ ｍＰａ・ｓ及び１０．２／ｓ＝５０ ｍＰａ・ｓ
有機陽イオンの使用量：０．９０ ｍｅｑ／ｇ
In the same manner as in Example 5, 13.0 g of an organoclay composite was produced. However, the amount of Arcard 2HT was changed to 5.6 g.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 5): a = 0.2, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 5 Synthetic clay (No. 5) Composition: Si: Al: Mg: Na = 8.00: 0.97: 7.19: 0.81
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 5): 1022 / s = 4.5 mPa · s and 10.2 / s = 50 mPa · s
Amount of organic cation used: 0.90 meq / g
実施例１と同様に分散有機溶媒の２４時間後の沈降体積を測定した。１％、２％、３％及び５％分散ケロシン溶液の２４時間後の沈降体積は、１％分散ケロシン溶液＝４１％、２％分散ケロシン溶液＝１００％、３％分散ケロシン溶液＝１００％及び５％分散ケロシン溶液＝９５％であった。５％分散ケロシン溶液はゲル化していた。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は１００％であった。 The sedimentation volume after 24 hours of the dispersed organic solvent was measured in the same manner as in Example 1. The sedimentation volume after 24 hours of 1%, 2%, 3% and 5% dispersed kerosene solutions is 1% dispersed kerosene solution = 41%, 2% dispersed kerosene solution = 100%, 3% dispersed kerosene solution = 100% and 5% dispersed kerosene solution = 95%. The 5% dispersed kerosene solution was gelled. Moreover, the sedimentation volume of the 1% dispersed toluene solution and the 5% dispersed toluene solution was 100%.
５％分散ケロシン溶液の粘度測定を、実施例１と同様に行った。ローターＨＭ−２を用いて得られた、ずり速度と見掛粘度の関係は１．０／ｓ＝１６２０ ｍＰａ・ｓ、２．０／ｓ＝８２４ ｍＰａ・ｓ、４．１／ｓ＝４３３ ｍＰａ・ｓ、１０．２／ｓ＝１７３ ｍＰａ・ｓ及び２０．４／ｓ＝７５ ｍＰａ・ｓであった。
更に、ローターをＨＭ−１に変えて、実施例１と同様に測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝２５２ ｍＰａ・ｓ、２．０／ｓ＝１５２ ｍＰａ・ｓ、４．０／ｓ＝９１ ｍＰａ・ｓ、７．９／ｓ＝５５ ｍＰａ・ｓ、１５．８／ｓ＝３２ ｍＰａ・ｓ、３９．６／ｓ＝１６ ｍＰａ・ｓ、及び７９．２／ｓ＝１０ ｍＰａ・ｓであった。
The viscosity of the 5% dispersed kerosene solution was measured in the same manner as in Example 1. The relationship between the shear rate and the apparent viscosity obtained using the rotor HM-2 is 1.0 / s = 1620 mPa · s, 2.0 / s = 824 mPa · s, 4.1 / s = 433 mPa. S, 10.2 / s = 173 mPa · s and 20.4 / s = 75 mPa · s.
Furthermore, the apparent viscosity of the 5% dispersed toluene solution measured in the same manner as in Example 1 with the rotor changed to HM-1 was 0.8 / s = 252 mPa · s, 2.0 / s = 152 mPa · s. s, 4.0 / s = 91 mPa · s, 7.9 / s = 55 mPa · s, 15.8 / s = 32 mPa · s, 39.6 / s = 16 mPa · s, and 79.2 / S = 10 mPa · s.
実施例５と同様に操作して、有機粘土複合体１３．２ｇを作製した。但し、アーカード２ＨＴの量を６．０ｇに変更して実施した。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．５）： ａ＝０．２、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５ 合成粘土（Ｎｏ．５）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．９７：７．１９：０．８１
合成粘土（Ｎｏ．５）の２．５％水溶液の見掛粘度：１０２２／ｓ＝４．５ ｍＰａ・ｓ及び１０．２／ｓ＝５０ ｍＰａ・ｓ
有機陽イオンの使用量：０．９８ ｍｅｑ／ｇ
In the same manner as in Example 5, 13.2 g of an organoclay composite was produced. However, the amount of Arcard 2HT was changed to 6.0 g.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 5): a = 0.2, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 5 Synthetic clay (No. 5) Composition: Si: Al: Mg: Na = 8.00: 0.97: 7.19: 0.81
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 5): 1022 / s = 4.5 mPa · s and 10.2 / s = 50 mPa · s
Amount of organic cation used: 0.98 meq / g
実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％、２％、３％及び５％分散ケロシン溶液の２４時間後の沈降体積は、１％分散ケロシン溶液＝９８％、２％分散ケロシン溶液＝１００％、３％分散ケロシン溶液＝１００％及び５％分散ケロシン溶液＝１００％であった。５％分散ケロシン溶液はゲル化していた。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は、それぞれ１００％であった。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume after 24 hours of 1%, 2%, 3% and 5% dispersed kerosene solutions is 1% dispersed kerosene solution = 98%, 2% dispersed kerosene solution = 100%, 3% dispersed kerosene solution = 100% and 5% dispersed kerosene solution = 100%. The 5% dispersed kerosene solution was gelled. Moreover, the sedimentation volumes of the 1% dispersed toluene solution and the 5% dispersed toluene solution were 100%, respectively.
実施例１と同様に、５％分散ケロシン溶液の粘度測定を行った。ローターＨＭ−２を用いて得られた、ずり速度と見掛粘度の関係は１．０／ｓ＝５６６ ｍＰａ・ｓ、２．０／ｓ＝２７６ ｍＰａ・ｓ、４．１／ｓ＝１５２ ｍＰａ・ｓ、１０．２／ｓ＝７４ ｍＰａ・ｓ及び２０．４／ｓ＝４３ ｍＰａ・ｓであった。
更に、ローターをＨＭ−１に変えて、実施例１と同様に測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝２７１ ｍＰａ・ｓ、２．０／ｓ＝１４９ ｍＰａ・ｓ、４．０／ｓ＝９５ ｍＰａ・ｓ、７．９／ｓ＝５６ ｍＰａ・ｓ、１５．８／ｓ＝３５ ｍＰａ・ｓ、３９．６／ｓ＝１９ ｍＰａ・ｓ、及び７９．２／ｓ＝１２ ｍＰａ・ｓであった。
As in Example 1, the viscosity of a 5% dispersed kerosene solution was measured. The relationship between the shear rate and the apparent viscosity obtained using the rotor HM-2 is 1.0 / s = 566 mPa · s, 2.0 / s = 276 mPa · s, 4.1 / s = 152 mPa. S, 10.2 / s = 74 mPa · s and 20.4 / s = 43 mPa · s.
Further, the apparent viscosity of the 5% dispersed toluene solution measured in the same manner as in Example 1 with the rotor changed to HM-1 was 0.8 / s = 271 mPa · s, 2.0 / s = 149 mPa · s. s, 4.0 / s = 95 mPa · s, 7.9 / s = 56 mPa · s, 15.8 / s = 35 mPa · s, 39.6 / s = 19 mPa · s, and 79.2 / S = 12 mPa · s.
実施例５と同様に操作して有機粘土複合体１３．４ｇを作製した。但し、アーカード２ＨＴの量を６．９ｇに変更して実施した。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．５）： ａ＝０．２、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝５ 合成粘土（Ｎｏ．５）の化学組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．９７：７．１９：０．８１
合成粘土（Ｎｏ．５）の２．５％水溶液の見掛粘度：１０２２／ｓ＝４．５ ｍＰａ・ｓ及び１０．２／ｓ＝５０ ｍＰａ・ｓ
有機陽イオンの使用量：１．１２ｍｅｑ／ｇ
The same operation as in Example 5 was performed to produce 13.4 g of an organoclay complex. However, the amount of Arcard 2HT was changed to 6.9 g.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 5): a = 0.2, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 1 and y = 5 Synthetic clay (No. 5) Chemical composition: Si: Al: Mg: Na = 8.00: 0.97: 7.19: 0.81
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 5): 1022 / s = 4.5 mPa · s and 10.2 / s = 50 mPa · s
Amount of organic cation used: 1.12 meq / g
実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。１％、２％、３％及び５％分散ケロシン溶液の２４時間後の沈降体積は、１％分散ケロシン溶液＝１００％、２％分散ケロシン溶液＝１００％、３％分散ケロシン溶液＝１００％及び５％分散ケロシン溶液＝１００％であった。５％分散ケロシン溶液はゲル化していた。また、１％分散トルエン溶液及び５％分散トルエン溶液の沈降体積は％１００であった。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume after 24 hours of 1%, 2%, 3% and 5% dispersed kerosene solutions is 1% dispersed kerosene solution = 100%, 2% dispersed kerosene solution = 100%, 3% dispersed kerosene solution = 100% and 5% dispersed kerosene solution = 100%. The 5% dispersed kerosene solution was gelled. Moreover, the sedimentation volume of the 1% dispersed toluene solution and the 5% dispersed toluene solution was 100%.
実施例１と同様に、５％分散ケロシン溶液の粘度測定を行った。ローターＨＭ−２を用いて得られた、ずり速度と見掛粘度の関係は１．０／ｓ＝２５３ ｍＰａ・ｓ、２．０／ｓ＝１３１ ｍＰａ・ｓ、４．１／ｓ＝８４ ｍＰａ・ｓ、１０．２／ｓ＝４６ ｍＰａ・ｓ及び２０．４／ｓ＝２９ ｍＰａ・ｓであった。
更に、実施例１と同様に、ローターをＨＭ−１に変えて測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝２６８ ｍＰａ・ｓ、２．０／ｓ＝１４５ ｍＰａ・ｓ、４．０／ｓ＝９５ ｍＰａ・ｓ、７．９／ｓ＝５５ ｍＰａ・ｓ、１５．８／ｓ＝３４ ｍＰａ・ｓ、３９．６／ｓ＝１８ ｍＰａ・ｓ、及び７９．２／ｓ＝１１ ｍＰａ・ｓであった。
As in Example 1, the viscosity of a 5% dispersed kerosene solution was measured. The relationship between the shear rate and the apparent viscosity obtained using the rotor HM-2 is 1.0 / s = 253 mPa · s, 2.0 / s = 131 mPa · s, 4.1 / s = 84 mPa. S, 10.2 / s = 46 mPa · s and 20.4 / s = 29 mPa · s.
Further, as in Example 1, the apparent viscosity of the 5% dispersed toluene solution measured by changing the rotor to HM-1 was 0.8 / s = 268 mPa · s, 2.0 / s = 145 mPa · s. s, 4.0 / s = 95 mPa · s, 7.9 / s = 55 mPa · s, 15.8 / s = 34 mPa · s, 39.6 / s = 18 mPa · s, and 79.2 / S = 11 mPa · s.
実施例１〜３に比べてケロシン対する分散性が良くない実施例５の合成混合層粘土を用いてアーカード２ＨＴの複合量を変化させて得たアーカード２ＨＴ―有機粘土複合体の沈降体積及び見掛粘度に及ぼす効果を表２に示す。１０８〜１３５％の範囲でアーカード２ＨＴの複合量を多くした本発明製品（実施例６〜８）はケロシンに対する分散性が実施例５より良くなり、実施例６〜７の発明製品では見掛粘度の値も増加している。一方、トルエン分散液の見掛粘度は、実施例６〜８の本発明製品で実施例５より小さい値となっていることが判明した。アーカード２ＨＴの複合量を変化させた場合のケロシン及びトルエン分散液の沈降体積及び見掛粘度の変化を表２に示す。 Sedimentation volume and apparent appearance of the arcade 2HT-organoclay complex obtained by changing the composite amount of arcade 2HT using the synthetic mixed layer clay of example 5, which has poor dispersibility for kerosene as compared with examples 1-3 Table 2 shows the effect on viscosity. The products of the present invention (Examples 6 to 8) in which the composite amount of Arcard 2HT is increased in the range of 108 to 135% have better dispersibility with respect to kerosene than Example 5, and the apparent viscosity of the inventive products of Examples 6 to 7 The value of has also increased. On the other hand, the apparent viscosity of the toluene dispersion was found to be smaller than that of Example 5 in the products of the present invention of Examples 6-8. Table 2 shows the changes in the sedimentation volume and apparent viscosity of the kerosene and toluene dispersions when the complex amount of Arcade 2HT is changed.
参考例６
参考例１と同様な操作で、化学組成及び合成条件を下記の条件に変更して、合成粘土（Ｎｏ．６）３５．２ｇを作製した。
（合成条件）
３号水ガラス：６８．７ｇ
塩化マグネシウム六水和物一級試薬（純度９８％）：６３．５ｇ
塩化アルミニウム六水和物一級試薬（純度９８％）：７．７ｇ
沈殿用２規定水酸化ナトリウム溶液量：３９８ｍｌ
沈殿ｐＨ：１０．５
合成用２規定水酸化ナトリウム溶液量：２１ｍｌ
水熱合成温度：２７０℃
水熱合成反応時間：２時間
原料スラリーｐＨ：１１．１
水熱合成後ｐＨ：１１．４
Reference Example 6
In the same manner as in Reference Example 1, the chemical composition and synthesis conditions were changed to the following conditions to produce 35.2 g of synthetic clay (No. 6).
(Synthesis conditions)
No.3 water glass: 68.7g
Magnesium chloride hexahydrate primary reagent (purity 98%): 63.5 g
Aluminum chloride hexahydrate primary reagent (purity 98%): 7.7 g
2N sodium hydroxide solution for precipitation: 398 ml
Precipitation pH: 10.5
2N sodium hydroxide solution for synthesis: 21 ml
Hydrothermal synthesis temperature: 270 ° C
Hydrothermal synthesis reaction time: 2 hours Raw material slurry pH: 11.1
PH after hydrothermal synthesis: 11.4
得られた合成粘土（Ｎｏ．６）はａ＝０．１５、ｂ＝０、ｃ＝０．３、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝２で設計して作製したものであり、得られた組成はＳｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７８：７．６５：０．５２であり、及びメチレンブルー吸着量から得られた陽イオン交換容量は１．０５ ｍｅｑ／ｇであった。２．５％水溶液はゲルを形成し、ファンＶＧメーターで測定した見掛粘度は１０２２／ｓ＝１９．５ ｍＰａ・ｓ及び１０．２／ｓ＝１１２５ ｍＰａ・ｓであった。 The resultant synthetic clay (No. 6) was designed with a = 0.15, b = 0, c = 0.3, d = 0, e = 0, f = 1, x = 1 and y = 2. The composition obtained was Si: Al: Mg: Na = 8.00: 0.78: 7.65: 0.52, and the cation exchange capacity obtained from the adsorbed amount of methylene blue was It was 1.05 meq / g. The 2.5% aqueous solution formed a gel, and the apparent viscosities measured with a fan VG meter were 1022 / s = 19.5 mPa · s and 10.2 / s = 1125 mPa · s.
実施例１と同様にして、合成粘土（Ｎｏ．６）１０ｇから有機粘土複合体を作製した。但し、アーカード２ＨＴの量を６．５ｇにして実施し、有機粘土複合体１３．８ｇが得られた。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．６）： ａ＝０．１５、ｂ＝０、ｃ＝０．３、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝２
合成粘土（Ｎｏ．６）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７８：７．６５：０．５２
合成粘土（Ｎｏ．６）の２．５％水溶液の見掛粘度：１０２２／ｓ＝１９．５ ｍＰａ・ｓ及び１０．２／ｓ＝１１２５ ｍＰａ・ｓ
有機陽イオンの使用量：１．０５ｍｅｑ／ｇ
In the same manner as in Example 1, an organoclay composite was prepared from 10 g of synthetic clay (No. 6). However, it was carried out with an amount of Arcade 2HT of 6.5 g, and 13.8 g of an organoclay composite was obtained.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 6): a = 0.15, b = 0, c = 0.3, d = 0, e = 0, f = 1, x = 1 and y = 2
Composition of synthetic clay (No. 6): Si: Al: Mg: Na = 8.00: 0.78: 7.65: 0.52
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 6): 1022 / s = 19.5 mPa · s and 10.2 / s = 1125 mPa · s
Amount of organic cation used: 1.05 meq / g
実施例１と同様に測定した、有機粘土複合体分散トルエン溶液の沈降体積は、１％分散トルエン溶液＝１００％及び５％分散トルエン溶液＝１００％であった。５％分散トルエン溶液はゲル化していた。 The sedimentation volumes of the organoclay complex-dispersed toluene solution, measured in the same manner as in Example 1, were 1% dispersed toluene solution = 100% and 5% dispersed toluene solution = 100%. The 5% dispersed toluene solution was gelled.
実施例１と同様に、ローターＨＭ−１を用いて測定した、５％分散トルエン溶液の見掛粘度は０．８／ｓ＝２５４０ ｍＰａ・ｓ、２．０／ｓ＝１０３０ ｍＰａ・ｓ、４．０／ｓ＝４９２ ｍＰａ・ｓ、７．９／ｓ＝２３４ ｍＰａ・ｓ、１５．８／ｓ＝１２０ ｍＰａ・ｓ、３９．６／ｓ＝５７ ｍＰａ・ｓ、及び７９．２／ｓ＝３６ ｍＰａ・ｓであった。本発明製品で得られた見掛粘度の値は、市販されているエスベン（比較例１）、オーガナイト（比較例３）及びサン（比較例４）より高く、増粘効果が高いことがわかる。 In the same manner as in Example 1, the apparent viscosity of the 5% dispersed toluene solution measured using the rotor HM-1 was 0.8 / s = 2540 mPa · s, 2.0 / s = 1030 mPa · s, 4 0.0 / s = 492 mPa · s, 7.9 / s = 234 mPa · s, 15.8 / s = 120 mPa · s, 39.6 / s = 57 mPa · s, and 79.2 / s = 36 mPa · s. The value of the apparent viscosity obtained with the product of the present invention is higher than that of commercially available Esbene (Comparative Example 1), Organite (Comparative Example 3), and Sun (Comparative Example 4), indicating that the thickening effect is high. .
実施例１と同様にして、合成粘土（Ｎｏ．４）１０ｇから有機粘土複合体を作製した。但し、第四級アンモニウム塩としてアデカコールＣＣ−３６（純度９８％）１５．０ｇを用いて実施し、有機粘土複合体２０．３ｇが得られた。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．４）： ａ＝０．１５、ｂ＝０、ｃ＝０．３、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝１及びｙ＝３
合成粘土（Ｎｏ．４）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７４：７．３２：０．５６
合成粘土（Ｎｏ．４）の２．５％水溶液の見掛粘度：１０２２／ｓ＝１９ ｍＰａ・ｓ及び１０．２／ｓ＝９００ ｍＰａ・ｓ
有機陽イオンの使用量：０．９８ｍｅｑ／ｇ
In the same manner as in Example 1, an organoclay composite was prepared from 10 g of synthetic clay (No. 4). However, the reaction was carried out using 15.0 g of Adekacol CC-36 (purity 98%) as a quaternary ammonium salt, and 20.3 g of an organic clay complex was obtained.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 4): a = 0.15, b = 0, c = 0.3, d = 0, e = 0, f = 1, x = 1 and y = 3
Composition of synthetic clay (No. 4): Si: Al: Mg: Na = 8.00: 0.74: 7.32: 0.56
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 4): 1022 / s = 19 mPa · s and 10.2 / s = 900 mPa · s
Amount of organic cation used: 0.98 meq / g
実施例１と同様に分散有機溶媒の２４時間後の沈降体積を測定した。有機粘土複合体をエタノールに分散させた分散エタノール溶液の２４時間後の沈降体積は、１％分散エタノール溶液＝１００％、２％分散エタノール溶液＝１００％、３％分散エタノール溶液＝１００％及び５％分散エタノール溶液＝１００％であった。１〜５％分散エタノール溶液は、全て透明のゾル溶液で、サラサラした感じであった。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume after 24 hours of the dispersed ethanol solution in which the organoclay complex was dispersed in ethanol was 1% dispersed ethanol solution = 100%, 2% dispersed ethanol solution = 100%, 3% dispersed ethanol solution = 100% and 5%. % Dispersed ethanol solution = 100%. The 1 to 5% dispersed ethanol solution was a clear sol solution and felt smooth.
参考例７
参考例１と同様な操作で、化学組成及び合成条件を下記の条件に変更して、合成粘土（Ｎｏ．７）３９．９ｇを作製した。
（合成条件）
３号水ガラス：６８．７ｇ
塩化マグネシウム六水和物一級試薬（純度９８％）：７９．３ｇ
塩化アルミニウム六水和物一級試薬（純度９８％）：１３．１ｇ
沈殿用２規定水酸化ナトリウム溶液量：５３０ｍｌ
沈殿ｐＨ：１０．５
合成用２規定水酸化ナトリウム溶液量：９ｍｌ
水熱合成温度：３００℃
水熱合成反応時間：２４時間
原料スラリーｐＨ：１１．５
水熱合成後ｐＨ：１１．６
Reference Example 7
By the same operation as in Reference Example 1, the chemical composition and synthesis conditions were changed to the following conditions to produce 39.9 g of synthetic clay (No. 7).
(Synthesis conditions)
No.3 water glass: 68.7g
Magnesium chloride hexahydrate primary reagent (purity 98%): 79.3 g
Aluminum chloride hexahydrate primary reagent (purity 98%): 13.1 g
2N sodium hydroxide solution for precipitation: 530 ml
Precipitation pH: 10.5
2N sodium hydroxide solution for synthesis: 9 ml
Hydrothermal synthesis temperature: 300 ° C
Hydrothermal synthesis reaction time: 24 hours Raw material slurry pH: 11.5
PH after hydrothermal synthesis: 11.6
本試料を用いて、エチレングリコール処理定方位試料を作製し、Ｘ線回折の測定をした。得られた（００３）、（００４）、（００５）、（００９）及び（００１２）ピークは、それぞれ１２．１Å、８．１９Å、６．０９Å、３．４９Å及び２．６８Åであった。この５ピークから計算される（００１）ピークの平均値は３２．６Åであり、リザルダイト層２枚とサポナイト層１枚からなる理想的な混合層鉱物の（００１）ピークの値は３２．０Åと計算され、ほぼ想定した合成粘土（Ｎｏ．７）が製造されたと考えられる。 Using this sample, an ethylene glycol-treated fixed orientation sample was prepared and measured for X-ray diffraction. The obtained (003), (004), (005), (009) and (0012) peaks were 12.1Å, 8.19Å, 6.09６, 3.49Å and 2.68Å, respectively. The average value of the (001) peak calculated from these five peaks is 32.6 、, and the value of the (001) peak of an ideal mixed layer mineral consisting of two lizardite layers and one saponite layer is 32.0 Å. It is considered that synthetic clay (No. 7) calculated and almost assumed was produced.
得られた合成粘土（Ｎｏ．７）はａ＝０．２、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝２及びｙ＝１で設計して作製したものであり、得られた組成はＳｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：１．２９：９．０８：０．４５であり、及びメチレンブルー吸着量から得られた陽イオン交換容量は０．７１ｍｅｑ／ｇであった。２．５％水溶液はゲルを形成し、ファンＶＧメーターで測定した見掛粘度は１０２２／ｓ＝５．３ ｍＰａ・ｓ及び１０．２／ｓ＝５０ ｍＰａ・ｓであった。 The resulting synthetic clay (No. 7) was designed with a = 0.2, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 2 and y = 1. The composition obtained was Si: Al: Mg: Na = 8.00: 1.29: 9.08: 0.45, and the cation exchange capacity obtained from the methylene blue adsorption amount was It was 0.71 meq / g. The 2.5% aqueous solution formed a gel, and the apparent viscosities measured with a fan VG meter were 1022 / s = 5.3 mPa · s and 10.2 / s = 50 mPa · s.
実施例１と同様にして、合成粘土（Ｎｏ．７）１０ｇから有機粘土複合体を作製した。但し、エソカードｃ／２５（純度９５％）１．２ｇとアデカコールＣＣ−３６（純度９８％）１．９ｇを用いて、有機粘土複合体１２．１ｇが得られた。本発明製品には、エソカードｃ／２５とアデカコールＣＣ−３６が当量ずつ含有されている。
（有機粘土複合体の原料特性）
合成粘土（Ｎｏ．７）： ａ＝０．２、ｂ＝０、ｃ＝０．４、ｄ＝０、ｅ＝０、ｆ＝１、ｘ＝２及びｙ＝１
合成粘土（Ｎｏ．７）の組成：Ｓｉ：Ａｌ：Ｍｇ：Ｎａ＝８．００：０．７４：７．３２：０．５６
合成粘土（Ｎｏ．７）の２．５％水溶液の見掛粘度：１０２２／ｓ＝５．３ ｍＰａ・ｓ及び１０．２／ｓ＝５０ ｍＰａ・ｓ
有機陽イオンの使用量：０．４９ ｍｅｑ／ｇ
In the same manner as in Example 1, an organoclay composite was prepared from 10 g of synthetic clay (No. 7). However, 12.1 g of an organoclay complex was obtained using 1.2 g of Esocard c / 25 (purity 95%) and 1.9 g of Adekacol CC-36 (purity 98%). The product of the present invention contains Esocard c / 25 and Adeka Coal CC-36 in equivalent amounts.
(Raw material characteristics of organoclay complex)
Synthetic clay (No. 7): a = 0.2, b = 0, c = 0.4, d = 0, e = 0, f = 1, x = 2 and y = 1
Composition of synthetic clay (No. 7): Si: Al: Mg: Na = 8.00: 0.74: 7.32: 0.56
Apparent viscosity of 2.5% aqueous solution of synthetic clay (No. 7): 1022 / s = 5.3 mPa · s and 10.2 / s = 50 mPa · s
Amount of organic cation used: 0.49 meq / g
実施例１と同様に、分散有機溶媒の２４時間後の沈降体積を測定した。有機粘土複合体をエタノールに分散させた溶液の２４時間後の沈降体積は、１％分散エタノール溶液＝１００％及び５％分散エタノール溶液＝１００％であった。陽イオン交換容量の６９％しか有機陽イオンが置換していないが、極性溶媒であるエタノールに分散でき、経済的にも有利と考えられる。 In the same manner as in Example 1, the sedimentation volume after 24 hours of the dispersed organic solvent was measured. The sedimentation volume after 24 hours of the solution in which the organoclay complex was dispersed in ethanol was 1% dispersed ethanol solution = 100% and 5% dispersed ethanol solution = 100%. Although only 69% of the cation exchange capacity is replaced by the organic cation, it can be dispersed in ethanol, which is a polar solvent, and is considered economically advantageous.
以上詳述したように、本発明は、有機溶媒中で増粘性を示す有機粘土複合体からなる増粘剤及びその製造方法に係るものであり、本発明により、膨潤性混合層ケイ酸塩を用いることにより、これまで増粘させることができなかった直鎖脂肪族炭化水素に対して増粘効果を示す有機粘土複合体からなる増粘剤が得られる。膨潤性混合層ケイ酸塩の構造と化学組成を制御することにより、種々の有機溶媒に使用可能な有機粘土複合体からなる増粘剤が得られる。一種類の有機粘土複合体からなる増粘剤に複数の機能を持たせることができる。有機物の種類を変えることによっても有機粘土複合体からなる増粘剤の特性を制御できる。膨潤性混合層ケイ酸塩に、第四級アンモニウム塩を反応させることを特徴とする有機粘土複合体からなる増粘剤の新規製造方法を提供できる。種々の有機溶媒に親和性を有し、良好な増粘効果を示す増粘剤を提供できる。種々の有機溶媒中で有機粘土複合体からなる増粘剤を増粘させた組成物を提供できる。本発明は、上記の有機粘土複合体からなる増粘剤を利用した新しい技術・新産業の創出に資するものとして有用である。
As described above in detail, the present invention relates to a thickener composed of an organoclay complex exhibiting viscosity in an organic solvent and a method for producing the same, and according to the present invention, a swellable mixed layer silicate is obtained. by using this thickener consisting of increasing the viscosity effects indicate to organic clay complex relative linear aliphatic hydrocarbons which could not be thickened to obtain. By controlling the structure and chemical composition of the swellable mixed layer silicate, a thickener composed of an organoclay complex that can be used in various organic solvents can be obtained. A thickener composed of one kind of organic clay complex can have a plurality of functions. By changing the kind of organic matter, the properties of the thickener composed of the organoclay complex can be controlled. It is possible to provide a novel method for producing a thickener comprising an organoclay composite, characterized by reacting a swellable mixed layer silicate with a quaternary ammonium salt. Has an affinity to various organic solvents, it can provide a thickening agent showing a good good thickening effect. It can provide various compositions and the thickener consisting of an organic clay compound is thickened with an organic solvent. The present invention is useful as it will contribute to the creation of new technologies and new industries that use a thickener made from organic clay complexes of the above.
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