USRE32250E - Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates - Google Patents
Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates Download PDFInfo
- Publication number
- USRE32250E USRE32250E US06/512,306 US51230683A USRE32250E US RE32250 E USRE32250 E US RE32250E US 51230683 A US51230683 A US 51230683A US RE32250 E USRE32250 E US RE32250E
- Authority
- US
- United States
- Prior art keywords
- composition
- siliconate
- alkali metal
- coom
- group
- 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
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- 125000005625 siliconate group Chemical group 0.000 title claims abstract description 129
- 150000004760 silicates Chemical class 0.000 title claims abstract description 31
- 150000003839 salts Chemical class 0.000 title abstract description 10
- 229910052717 sulfur Chemical class 0.000 title abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000011593 sulfur Chemical class 0.000 title abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 title abstract description 4
- 150000002829 nitrogen Chemical class 0.000 title abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title abstract description 3
- 230000006641 stabilisation Effects 0.000 title description 4
- 238000011105 stabilization Methods 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims description 112
- 238000000034 method Methods 0.000 claims description 51
- 239000011734 sodium Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 229910052783 alkali metal Inorganic materials 0.000 claims description 45
- 150000001340 alkali metals Chemical class 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 28
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 27
- 238000005260 corrosion Methods 0.000 claims description 27
- 230000007797 corrosion Effects 0.000 claims description 27
- -1 alkali metal cations Chemical class 0.000 claims description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 230000002401 inhibitory effect Effects 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000012736 aqueous medium Substances 0.000 claims description 9
- 230000000087 stabilizing effect Effects 0.000 claims description 9
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910020381 SiO1.5 Inorganic materials 0.000 claims 14
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000002528 anti-freeze Effects 0.000 abstract description 11
- 239000003381 stabilizer Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 230000001476 alcoholic effect Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- JZDHUYKBYNFYAB-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(C)C JZDHUYKBYNFYAB-UHFFFAOYSA-N 0.000 description 1
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910004742 Na2 O Inorganic materials 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ABIUHPWEYMSGSR-UHFFFAOYSA-N bromocresol purple Chemical compound BrC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(Br)C(O)=C(C)C=2)=C1 ABIUHPWEYMSGSR-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 239000007793 ph indicator Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ACECBHHKGNTVPB-UHFFFAOYSA-N silylformic acid Chemical class OC([SiH3])=O ACECBHHKGNTVPB-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
- C01B33/325—After-treatment, e.g. purification or stabilisation of solutions, granulation; Dissolution; Obtaining solid silicate, e.g. from a solution by spray-drying, flashing off water or adding a coagulant
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/162—Organic compounds containing Si
Definitions
- This invention deals with novel salts of substituted nitrogen or sulfur containing siliconates which are effective stabilizers for aqueous silicates, silica sols and other silica containing water, such as boiler water, geothermal water, antifreeze and coolant solutions.
- Aqueous silicates are known as metal corrosion inhibitors for aqueous systems.
- One of the major disadvantages of such silicates has been the fact that they are unstable and after prolonged use at elevated temperatures they tend to gel and eventually precipitate out of solution. There have been many efforts, therefore, to stabilize silicates so that they could be more persistant in their corrosion inhibiting properties.
- Such materials are discussed as enhancing the corrosion inhibition of common antifreeze compositions and as overcoming disadvantages of other prior art corrosion inhibitors such as handling and dispensing of the antifreezes; selective corrosion inhibition of certain metals, poor shelf life, tendency to attack rubber hoses, excessive foaming in use and the causing of alcohols to decompose.
- the invention disclosed herein consists of a method of stabilizing soluble silicates comprising adding to the soluble silicates a siliconate selected from a group consisting essentially of (I) a siliconate having the general formula ##STR1## and (II) a siliconate having the general formula ##STR2## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein in formula (I), R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR3## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR4## and --(CH 2 ) z
- This invention also consists of an improved corrosion inhibiting alcohol composition
- a corrosion inhibiting amount of a composition which is selected from (I) a siliconate having the general formula ##STR8## and (II) a siliconate having the general formula ##STR9## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein in formula (I), R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR10## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR11## and --(CH 2 ) z N(
- This invention further deals with a composition of matter which comprises (A) 0.1 to 20 mole percent of a siliconate selected from a group consisting essentially of (I) a siliconate having the general formula ##STR14## and (II) a siliconate having the general formula ##STR15## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein in formula (I), R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR16## and wherein the formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR17## and --(CH 2 ) z N(CH 2 COOM
- This invention also deals with a method of inhibiting metal corrosion in an aqueous medium by adding to the aqueous medium a composition consisting of a siliconate selected from a group consisting of (I) a siliconate having the general formula ##STR20## and (II) a siliconate having the general formula ##STR21## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein formula (I), R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR22## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR23## and --(CH 2
- this invention deals with a method of inhibiting metal corrosion in an aqueous medium wherein the siliconate salts described above are used in conjunction with soluble silicates, that is, where the siliconate salts and the soluble silicate are combined and used to treat aqueous systems to prevent metal corrosion.
- this invention deals with aqueous alcohol compositions which are antifreezes, coolants and concentrates for use in engines having water cooling systems.
- siliconate salts shown by the above formulas. It should be noted that there are two formulas used to describe the siliconate salts that are useful in this invention. The formula for the siliconate salts differs depending on whether the siliconate salt contains a sulfur atom or a nitrogen atom.
- M can be selected from two different cationic groups which are the alkali metal cations and the tetraorganoammonium cations.
- M for purposes of this invention can be selected from sodium, potassium, lithium and rubidium while the tetraorganoammonium cations can be selected from tetra(alkyl)ammonium cations; tetra-(mixed aryl-alkyl and mixed aralkyl-alkyl ammonium cations and the tetra(hydroxyalkyl) ammonium cations.
- polyvalent cations produced by converting polyamines such as quanidine or ethylenediamine to poly ammonium hydroxides (See U.S. Pat. No. 3,341,469, supra).
- the unoccupied valences (not shown in the formulae for the sake of simplicity) of the oxygen atoms attached to the silicon atoms of the siliconate salts can be occupied by M or hydrogen or another silicon atom as long as there is at least one oxygen atom on the silicon atom occupied by an alkali metal cation or a tetraorganoammonium cation.
- the siliconate salts of this invention can be prepared prior to their use in the inventive compositions herein or the siliconate salts can be prepared in situ.
- the group --CH 2 ) z represents an alkylene bridge.
- the value of z is either 2 or 3. It will be noted that this value is critical for purposes of this invention since siliconate salts wherein z has a greater or lesser value than 2 or 3 do not work exceptionally well in this invention.
- a further critical aspect of this invention is the type of functional groups which are substituted on the sulfur and nitrogen atoms of the inventive siliconate salts.
- sulfur containing siliconate salts useful herein are ##STR29## Especially preferred are the sodium and potassium salts of the specific siliconates set forth just above.
- n has a value of 0 or 1 and m has a value of 1 or 2. In all cases, the sum of n+m has to be 2.
- R represents the functional groups of the molecule and R changes when n and m are changed. For purposes of this invention, when n is 0 and m is 2, the R group is selected from the groups --CH 2 COOM, --CH 2 CH 2 COOM, ##STR31##
- the siliconate salts ##STR32##
- Preferred for this invention are the sodium and potassium salts of the siliconates set forth just above.
- R group is selected from the groups ##STR33## and --CH 2 ) z NH p R' q wherein z has a value of 2 or 3, and wherein q has a value of 1 or 2 and p has a value of 0 or 1 and the sum of q+p is 2.
- R' is selected from a group consisting of ##STR34## when p is 1 and q is 1 and R' is selected from a group consisting of --CH 2 COOM, --CH 2 CH 2 COOM, ##STR35## when p is 0 and q is 2.
- siliconate salts useful in this invention include ##STR36##
- siliconate salts of this invention include ##STR37##.Iaddend.
- the salts of this invention can be prepared prior to use in the inventive compositions of this invention or the salts can be made in situ in the inventive compositions.
- the salts are prepared from the precurser carboxyorganosiliconates which in turn are prepared by a variety of reactions.
- the carboxyfunctional thioethers can be prepared by the methods set forth in U.S. Pat. No. 3,627,806, issued Dec. 14, 1971.
- the nitrogen containing siliconate salt precursors are well known and can be prepared by a variety of methods. For example, the reaction of (CH 3 O) 3 Si(CH 2 ) 3 NH(CH 2 ) 2 NH 2 and 2 moles of acrylic acid yield the precursor dicarboxylic acid. This material can, in turn, be converted to the soluble salt form.
- the acids are converted to the soluble salt form by neutralizing with, for example, aqueous NaOH to form the sodium salt.
- the carboxylic acids or their esters are prepared and then hydrolyzed and saponified in the same reaction by using aqueous alkali solutions or the carboxylic acids or their esters are treated with tetraorganoammonium compounds.
- the resulting products are then used alone or they can be used in conjunction with a silicate as will be explained infra.
- the soluble silicates useful in this invention are such materials as alkali metal orthosilicates, alkali metal metasilicates, alkali metal tetrasilicates, the alkali metal disilicates and the tetraorganoammonium silicates.
- this invention deals with a method of stabilizing silicates which are soluble in aqueous systems (whenever solubility of the silicates is referred to in this application, it is intended that the inventor is referring to those known silicates which are soluble in water).
- inventive method herein for stabilizing soluble silicates requires that certain defined siliconate salts be used in aqueous or aqueous-alcoholic systems that already contain soluble silicates but it is also contemplated within the scope of this invention to form a composition from a siliconate salt of this invention and a soluble silicate and use this combination to treat aqueous or aqueous alcoholic systems.
- siliconate salts or combination of such siliconate salts and soluble silicates to treat aqueous or aqueous alcoholic systems to enhance, in the former case, the stabilization of soluble silicates and in the latter case to prevent corrosion of metals.
- Such uses therefore include antifreezes, coolants and concentrates for use in automotive engine cooling systems, controlling scale in geothermal power plants, controlling scale in conventional heat exchange systems and the like. Also contemplated within the scope of this invention is the use of the siliconates in household cleaning compositions.
- the amount of siliconate salt required to carry out the inventive method herein is dependent on the system in which the siliconate salt is used. Ordinarily, the siliconate salts are useful at a few parts per million concentration to a few weight percent concentration.
- the two components are mixed in a ratio of about 0.1 to 20 mole percent of the siliconate salt based on the silicate. Quantities less than 0.1 mole percent have been found to give less than optimum results while quantities greater than about 20 mole percent have been found to be wasteful. For automotive antifreeze applications, it is best to use about 1 part of the siliconate-silicate mixture, based on 100 parts of the aqueous alcohol system, to prevent corrosion.
- the amount of siliconate salt that is used when it is not required to premix the siliconate salt with the silicate is about 50 ppm to 5 weight percent based on the weight of the total system it is being used in.
- the siliconate salt is used to stabilize soluble silicates in geothermal steam, one only needs to ascertain the amount of soluble silicate that is present in such steam and add an amount of siliconate salt equivalent to 0.1 to 20 mole percent of the siliconate salt based on the silicate present in the steam water. In other water systems, larger quantities may be required.
- the preferred range of use of the siliconates for all systems within the scope of this invention is about 100 parts per million parts of the total system to 5 parts of the siliconate per 100 parts of the total system.
- the siliconate salt When used with the soluble silicate, there must be water present in the system. Relatively large amounts of water can be used in alcoholic systems or, small amounts, i.e. 80-98 weight percent, of alcohol can be used in the alcohol systems.
- the aqueous alcoholic compositions may be "concentrates", coolants, or antifreeze compositions.
- the alcohols that are useful in this invention include both monomeric alcohols such as methanol, ethanol, propanol and butanol and polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerol, mixtures of the above and mixtures of the above alcohols with their ethers.
- monomeric alcohols such as methanol, ethanol, propanol and butanol
- polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerol, mixtures of the above and mixtures of the above alcohols with their ethers.
- the siliconate salt-soluble silicate combination can be easily prepared by simply mixing the siliconate salt with the soluble silicate. It should be noted that the siliconate salt, when used to stabilize systems already containing the soluble silicate, is simply added to such systems and stirred to homogenize.
- the siliconate salt-soluble silicate combination can also be formed in-situ, that is the carboxylic acid or the ester precursor of the siliconate salt can be added to an aqueous or aqueous alcoholic system and the system can be treated with, for example NaOH to saponify and yield the siliconate salt. Sometimes, there may be enough cationic material already in such a system to accomplish the saponification.
- additives which impart special properties such as anti-foam agents, both organic and siloxane based dyes, pH indicators, other inhibitors such as corrosion inhibitors, thickeners and the like.
- the residue was a clear oil (230 gms) comprising partially hydrolyzed (CH 3 O) 3 Si(CH 2 ) 2 SCH 2 COOH and CH 2 ⁇ CHSi(OCH 3 ) 3 .
- the product had an acid equivalent weight of 285 which indicates about 85 percent desired product and 15 percent vinylsiloxanes.
- the product retained a faint mercaptan odor.
- a solution of 28.5 gms of product in water was neutralized with NaOH and diluted to 100 gms to provide a 1 molal solution of (Na)O 1 .5 SiCH 2 CH 2 SCH 2 COONa.
- Aminoalkylsilanes were carboxylated by reaction with sodium chloroacetate in the presence of NaOH as the HCl acceptor or, by the addition of amino hydrogens to acrylate double bonds. Addition to acrylates is very rapid without additional catalyst, but addition to methacrylates and itaconates was much slower. Cyclic anhydrides react rapidly and completely with primary or secondary amines to form the corresponding acid amides. The following preparations are illustrative of such preparations.
- the product was a 1.37 molal solution of ##STR42## containing some ##STR43## having a density of 1.125 g/mol at 20° C., and a viscosity of 50 cs. (0.5 Pa.s) at 25° C.
- a 73 gm portion was diluted to 100 gms with water to give a 1 molal solution of the acid adduct.
- 1 molal solutions of the acid were mixed with excess sodium silicate solutions in order to form the alkali metal salt in-situ. After aging one hour, the solutions were neutralized to pH 8.
- the siliconate-silicates of this invention are stable even when the aqueous solution is treated with a neutralizing amount of mineral acid. Minimum stability of such materials is observed at a pH of about 8.
- Sodium silicate "G” (a polysilicate having an SiO 2 /Na 2 O weight ratio of 3.22, manufactured by Philadelphia Quartz, Philadelphia, PA) was used in the following manner:
- the siliconate salts were evaluated as additives to antifreeze systems by utilizing the ASTM test method D-1384.
- Prestone® II, Union Carbide commercial antifreeze was used as a comparative example.
- ASTM D-1384 test method requires that each test be run in triplicate. For the purposes herein, the test was run only once as a rough screening test.
- the corrosive water used in the test consisted of 100 ppm each of sodium sulfate, sodium chloride and sodium bicarbonate. Metals tested included copper, solder, brass, steel, cast iron and cast aluminum. A control was run using each of these metals without any additive. Test solutions were prepared using 250 gms of ethylene glycol and 500 gms of the corrosion water prepared as above.
- the metal strips were as assembled as set forth in the ASTM test procedure and these assembled metals were immersed in the test solution.
- the beakers containing the test solutions and metal assemblies were heated to 88° C. and aerated at 100 ml/min. for a period of two weeks.
- the pH of the test solution was determined both before and after the test.
- Weight measurements were taken on each metal to the nearest milligram after the test strips were cleaned with water and pumice soap and an acetone rinse. After the testing, weight loss calculations were made on the samples after they were cleaned with water and pumice soap using a soft brass bristle brush and acetone rinse. In some cases, the weight was recorded as a gain because of inadequate cleaning techniques.
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Abstract
Salts of substituted nitrogen or sulfur containing siliconates are effective stabilizers for aqueous silicates in such applications as treating boiler water, geothermal water and other aqueous silicates. They are also useful in antifreeze and cooland solutions.
Description
This invention deals with novel salts of substituted nitrogen or sulfur containing siliconates which are effective stabilizers for aqueous silicates, silica sols and other silica containing water, such as boiler water, geothermal water, antifreeze and coolant solutions.
Aqueous silicates are known as metal corrosion inhibitors for aqueous systems. One of the major disadvantages of such silicates, however, has been the fact that they are unstable and after prolonged use at elevated temperatures they tend to gel and eventually precipitate out of solution. There have been many efforts, therefore, to stabilize silicates so that they could be more persistant in their corrosion inhibiting properties.
Arthur N. Pines et al. in U.S. Pat. Nos. 3,312,622 and 3,198,820 describe combinations of siliconate-silicate polymers as corrosion inhibitors. Although the patent does not specifically describe the stabilization of silicates, it is very obvious from the specification that the so-called "novel organosilicon polymer" does in fact contribute to the persistency of the corrosion inhibition of the siliconate-silicate polymers of that invention. The novelty, as pointed out therein, is the use of silyl carboxylate salts in conjunction with the silicates. Such materials are discussed as enhancing the corrosion inhibition of common antifreeze compositions and as overcoming disadvantages of other prior art corrosion inhibitors such as handling and dispensing of the antifreezes; selective corrosion inhibition of certain metals, poor shelf life, tendency to attack rubber hoses, excessive foaming in use and the causing of alcohols to decompose.
In later issued patents, U.S. Pat. Nos. 3,341,469 and 3,337,496, Pine et al. describe another system that was found useful for inhibiting corrosion in aqueous alcohol compositions. It consisted of a mixture of an alkyl silsesquioxane, a siloxane modified with a cyanoalkyl or carbinol group and, a silicate. There materials are stated as being "remarkably soluble in aqueous liquids". Further, the compositions are alleged to overcome many of the above mentioned disadvantages.
Another U.S. Pat. No. 3,948,964, issued Apr. 6, 1976, describes the stabilization of partially hydrolyzed silicic acid esters using stabilizers selected from the organic compounds such as cyclic ethers, ether alcohols, carboxylic acid esters and ketones. Such stabilized materials are described as binders for zinc dust pigments and the like.
In U.S. Pat. No. 3,960,576, issued June 1, 1976, there is disclosed the use of organic phosphonates in conjunction with alkaline oxide silicates as corrosion inhibitors for metal surfaces. It is stated therein that in addition to its corrosion inhibiting properties, the materials have the advantage of preventing the crystallization and deposition of dissolved solids which tend to precipitate on hot heat transfer surfaces.
Finally, there is a disclosure in a co-pending U.S. patent application Ser. No. 891,584, filed Mar. 30, 1978, now abandoned in the name of Edwin P. Plueddemann, showing the use of siliconates of silylalkyl phosphonates to stabilize aqueous silicates.
Thus, what has now been discovered is the use of certain sulfur or nitrogen containing siliconate salts to stabilize soluble silicates in order to overcome the problems associated with the prior art products.
The invention disclosed herein consists of a method of stabilizing soluble silicates comprising adding to the soluble silicates a siliconate selected from a group consisting essentially of (I) a siliconate having the general formula ##STR1## and (II) a siliconate having the general formula ##STR2## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein in formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR3## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR4## and --(CH2)z N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR5## and --(CH2)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2 wherein R' is selected from a group consisting of ##STR6## when p is 1 and q is 1 and R' is selected from a group consisting of --CH2 COOM, --CH2 CH2 COOM, ##STR7## when p is 0 and q is 2, wherein M and z have the same meaning as set forth above.
This invention also consists of an improved corrosion inhibiting alcohol composition comprising a combination of (A) an alcohol; (B) a corrosion inhibiting amount of a composition which is selected from (I) a siliconate having the general formula ##STR8## and (II) a siliconate having the general formula ##STR9## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein in formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR10## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR11## and --(CH2)z N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR12## and --(CH2)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2, and (C) a soluble silicate .[.represented by the general formula ##STR13## wherein M has the meaning above and a has a value of 1-3.]..
This invention further deals with a composition of matter which comprises (A) 0.1 to 20 mole percent of a siliconate selected from a group consisting essentially of (I) a siliconate having the general formula ##STR14## and (II) a siliconate having the general formula ##STR15## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein in formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR16## and wherein the formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR17## and --(CH2)z N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR18## and --(CH2)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2, and (B) 80 to 99.9 mole percent of a soluble silicate .[.represented by the general formula ##STR19## wherein M has the meaning above and a has a value of 1-3.]..
This invention also deals with a method of inhibiting metal corrosion in an aqueous medium by adding to the aqueous medium a composition consisting of a siliconate selected from a group consisting of (I) a siliconate having the general formula ##STR20## and (II) a siliconate having the general formula ##STR21## wherein, in both formulas, M is selected from a group consisting essentially of (i) alkali metal cations and (ii) tetraorganoammonium cations and z has a value of 2 or 3, wherein formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR22## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR23## and --(CH2)z N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR24## and --(CH2)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2 wherein R' is selected from a group consisting of ##STR25## when p is 1 and q is 1 and R' is selected from a group consisting of --CH2 COOM, --CH2 CH2 COOM, ##STR26## when p is 0 and q is 2, wherein M and z have the same meaning as set forth above.
Further, this invention deals with a method of inhibiting metal corrosion in an aqueous medium wherein the siliconate salts described above are used in conjunction with soluble silicates, that is, where the siliconate salts and the soluble silicate are combined and used to treat aqueous systems to prevent metal corrosion.
Finally, this invention deals with aqueous alcohol compositions which are antifreezes, coolants and concentrates for use in engines having water cooling systems.
As can be observed from the above disclosure, the key to the inventive concepts herein is the use of certain, specifically defined, siliconate salts shown by the above formulas. It should be noted that there are two formulas used to describe the siliconate salts that are useful in this invention. The formula for the siliconate salts differs depending on whether the siliconate salt contains a sulfur atom or a nitrogen atom.
In the above formulas, M can be selected from two different cationic groups which are the alkali metal cations and the tetraorganoammonium cations. Thus, M for purposes of this invention can be selected from sodium, potassium, lithium and rubidium while the tetraorganoammonium cations can be selected from tetra(alkyl)ammonium cations; tetra-(mixed aryl-alkyl and mixed aralkyl-alkyl ammonium cations and the tetra(hydroxyalkyl) ammonium cations. Preferred are tetra(methyl)ammonium, tetra(ethyl)ammonium, phenyltrimethyl ammonium, benzyltrimethyl ammonium and tetra(hydroxyethyl) ammonium cations. Also considered within the scope of this invention are the polyvalent cations produced by converting polyamines such as quanidine or ethylenediamine to poly ammonium hydroxides (See U.S. Pat. No. 3,341,469, supra).
The unoccupied valences (not shown in the formulae for the sake of simplicity) of the oxygen atoms attached to the silicon atoms of the siliconate salts can be occupied by M or hydrogen or another silicon atom as long as there is at least one oxygen atom on the silicon atom occupied by an alkali metal cation or a tetraorganoammonium cation.
The siliconate salts of this invention can be prepared prior to their use in the inventive compositions herein or the siliconate salts can be prepared in situ.
In both formulas, the group --CH2)z represents an alkylene bridge. For purposes of this invention, the value of z is either 2 or 3. It will be noted that this value is critical for purposes of this invention since siliconate salts wherein z has a greater or lesser value than 2 or 3 do not work exceptionally well in this invention.
A further critical aspect of this invention is the type of functional groups which are substituted on the sulfur and nitrogen atoms of the inventive siliconate salts.
Turning first to the sulfur containing siliconate salts represented by the general formula ##STR27## it should be noted that only the groups --CH2 COOM, --CH2 CH2 COOM, ##STR28## are effective herein.
Thus, representative examples of the sulfur containing siliconate salts useful herein are ##STR29## Especially preferred are the sodium and potassium salts of the specific siliconates set forth just above.
Now turning to the nitrogen containing siliconate salts represented by the general formula ##STR30## it should be noted that the effective groups herein are determined by the values of n and m in the formula. n has a value of 0 or 1 and m has a value of 1 or 2. In all cases, the sum of n+m has to be 2. R represents the functional groups of the molecule and R changes when n and m are changed. For purposes of this invention, when n is 0 and m is 2, the R group is selected from the groups --CH2 COOM, --CH2 CH2 COOM, ##STR31## Thus, contemplated within the scope of this invention are the siliconate salts ##STR32## Preferred for this invention are the sodium and potassium salts of the siliconates set forth just above. When n is 1 and m is 1, the R group is selected from the groups ##STR33## and --CH2)z NHp R'q wherein z has a value of 2 or 3, and wherein q has a value of 1 or 2 and p has a value of 0 or 1 and the sum of q+p is 2. R' is selected from a group consisting of ##STR34## when p is 1 and q is 1 and R' is selected from a group consisting of --CH2 COOM, --CH2 CH2 COOM, ##STR35## when p is 0 and q is 2. Thus, examples of siliconate salts useful in this invention include ##STR36##
Most preferred are the sodium and potassium salts of the siliconates set forth just above. .Iadd.
Additional examples of siliconate salts of this invention include ##STR37##.Iaddend.
As indicated above, the salts of this invention can be prepared prior to use in the inventive compositions of this invention or the salts can be made in situ in the inventive compositions. The salts are prepared from the precurser carboxyorganosiliconates which in turn are prepared by a variety of reactions. Thus, for example, the carboxyfunctional thioethers can be prepared by the methods set forth in U.S. Pat. No. 3,627,806, issued Dec. 14, 1971.
The nitrogen containing siliconate salt precursors are well known and can be prepared by a variety of methods. For example, the reaction of (CH3 O)3 Si(CH2)3 NH(CH2)2 NH2 and 2 moles of acrylic acid yield the precursor dicarboxylic acid. This material can, in turn, be converted to the soluble salt form.
The acids are converted to the soluble salt form by neutralizing with, for example, aqueous NaOH to form the sodium salt.
In practice, the carboxylic acids or their esters are prepared and then hydrolyzed and saponified in the same reaction by using aqueous alkali solutions or the carboxylic acids or their esters are treated with tetraorganoammonium compounds. The resulting products are then used alone or they can be used in conjunction with a silicate as will be explained infra.
The soluble silicates useful in this invention are such materials as alkali metal orthosilicates, alkali metal metasilicates, alkali metal tetrasilicates, the alkali metal disilicates and the tetraorganoammonium silicates.
As mentioned above, this invention deals with a method of stabilizing silicates which are soluble in aqueous systems (whenever solubility of the silicates is referred to in this application, it is intended that the inventor is referring to those known silicates which are soluble in water).
The inventive method herein for stabilizing soluble silicates requires that certain defined siliconate salts be used in aqueous or aqueous-alcoholic systems that already contain soluble silicates but it is also contemplated within the scope of this invention to form a composition from a siliconate salt of this invention and a soluble silicate and use this combination to treat aqueous or aqueous alcoholic systems.
Thus, what is contemplated in this invention is the use of the above defined siliconate salts or combination of such siliconate salts and soluble silicates to treat aqueous or aqueous alcoholic systems to enhance, in the former case, the stabilization of soluble silicates and in the latter case to prevent corrosion of metals.
Such uses therefore include antifreezes, coolants and concentrates for use in automotive engine cooling systems, controlling scale in geothermal power plants, controlling scale in conventional heat exchange systems and the like. Also contemplated within the scope of this invention is the use of the siliconates in household cleaning compositions.
The amount of siliconate salt required to carry out the inventive method herein is dependent on the system in which the siliconate salt is used. Ordinarily, the siliconate salts are useful at a few parts per million concentration to a few weight percent concentration.
When the system requires the addition of the siliconate salts to the soluble silicates before use, the two components are mixed in a ratio of about 0.1 to 20 mole percent of the siliconate salt based on the silicate. Quantities less than 0.1 mole percent have been found to give less than optimum results while quantities greater than about 20 mole percent have been found to be wasteful. For automotive antifreeze applications, it is best to use about 1 part of the siliconate-silicate mixture, based on 100 parts of the aqueous alcohol system, to prevent corrosion.
The amount of siliconate salt that is used when it is not required to premix the siliconate salt with the silicate is about 50 ppm to 5 weight percent based on the weight of the total system it is being used in. For example, if the siliconate salt is used to stabilize soluble silicates in geothermal steam, one only needs to ascertain the amount of soluble silicate that is present in such steam and add an amount of siliconate salt equivalent to 0.1 to 20 mole percent of the siliconate salt based on the silicate present in the steam water. In other water systems, larger quantities may be required. The preferred range of use of the siliconates for all systems within the scope of this invention is about 100 parts per million parts of the total system to 5 parts of the siliconate per 100 parts of the total system.
When the siliconate salt is used with the soluble silicate, there must be water present in the system. Relatively large amounts of water can be used in alcoholic systems or, small amounts, i.e. 80-98 weight percent, of alcohol can be used in the alcohol systems. Thus, the aqueous alcoholic compositions may be "concentrates", coolants, or antifreeze compositions.
The alcohols that are useful in this invention include both monomeric alcohols such as methanol, ethanol, propanol and butanol and polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerol, mixtures of the above and mixtures of the above alcohols with their ethers.
The siliconate salt-soluble silicate combination can be easily prepared by simply mixing the siliconate salt with the soluble silicate. It should be noted that the siliconate salt, when used to stabilize systems already containing the soluble silicate, is simply added to such systems and stirred to homogenize.
The siliconate salt-soluble silicate combination can also be formed in-situ, that is the carboxylic acid or the ester precursor of the siliconate salt can be added to an aqueous or aqueous alcoholic system and the system can be treated with, for example NaOH to saponify and yield the siliconate salt. Sometimes, there may be enough cationic material already in such a system to accomplish the saponification.
It is within the scope of this invention to add various additives which impart special properties such as anti-foam agents, both organic and siloxane based dyes, pH indicators, other inhibitors such as corrosion inhibitors, thickeners and the like.
Now, so that those skilled in the art understand and appreciate the invention, the following examples are offered. These examples should not be construed as limiting that which is set out and claimed as the invention in the appended claims.
A mixture of 26 gms of methyl acrylate (0.3 mols) and 36.4 gms of (CH3 O)3 SiCH2 CH2 SH was catalyzed by adding 1 ml. of N/2 alcoholic KOH into a 250 ml., round bottomed glass flask, with stirring. An exothermic reaction raised the temperature to 60° C. The mixture was refluxed for 30 minutes and then distilled under vacuum to recover 46 gms of water-white product with a boiling point at 0.7 mm Hg pressure of 115°-125° C. for an 87 percent yield of (CH3 O)3 Si(CH2)2 S(CH2)2 COOCH3.d4 20 =1.115, ND 25 =1.4546. One tenth gram mol (26.8 gms) of this product was saponified by refluxing for one hour with 4 grams of NaOH (0.1 mol) in 80 gms of H2 O. Methanol and other volatiles were taken off until the temperature, with auxiliary heating, reached 100° C. The residue was diluted to 100 gms with water to give a 1 molal solution of (Na)O1.5 Si(CH2)2 S(CH2)2 COONa.
Dimethylitaconate 24 gms (0.15 mol) and 18.2 gms of (CH3 O)3 Si(CH2)2 SH (0.1 mol) and 0.23 gms Na° in 10 ml of methanol were warmed to 100° C. for 1 hour after initially exotherming. The mixture was distilled under vacuum to give 21 gms (65 percent yield) of ##STR38## with a boiling point at 0.3 mm Hg pressure of 145°-155° C., d4 21 =1.55 and ND 25 =1.4572.
The product, 17 gms (0.05 mol) was saponified by refluxing with 4 gms of NaOH in 50 ml of H2 O until a temperature of 100° C. was reached. The material was diluted to 50 gms with H2 O to obtain 1 molal solution of ##STR39## A titration indicated 0.02 equivalents of excess alkali.
An excess of CH2 ═CHSi(OCH3)3 (200 gms, 1.35 mols) was stirred at 100°-110° C. while dropping in 100 gms (technical grade, 96-98 percent purity) of thioglycolic acid containing 1 gm of Vazo® (azobisisobutyrolnitrile DuPont) free radical initiator. The reaction was exothermic. After one hour at 100°-110° C. the product was stripped to remove methanol (about 15 ml) and excess CH2 ═CHSi(OCH3)3 to 100° C. The residue was a clear oil (230 gms) comprising partially hydrolyzed (CH3 O)3 Si(CH2)2 SCH2 COOH and CH2 ═CHSi(OCH3)3. The product had an acid equivalent weight of 285 which indicates about 85 percent desired product and 15 percent vinylsiloxanes. The product retained a faint mercaptan odor. A solution of 28.5 gms of product in water was neutralized with NaOH and diluted to 100 gms to provide a 1 molal solution of (Na)O1.5 SiCH2 CH2 SCH2 COONa.
A solution of 15 gms of thiomalic acid (technical grade) (0.1 mol) in 30 gms of 1-methoxy-2-propanol and 15 gms of .[.CH2 CH═Si(OCH3)3.]. CH2 ═CHSi(.Iadd.OCH3)3 .Iaddend. with 0.5 gms of Luazo 82 (2-t-butylazo-2-cyanobutane) (Lucidol Div. of Pennwalt Corp., Buffalo, NY 14240) free radical initiator was warmed to 105° C. for one hour. There was a mild exotherm. The product was diluted with water to 100 gms to give a 1 molal solution of the free acid which was neutralized with 2 mol equivalents of NaOH to give the Na salt ##STR40##
Aminoalkylsilanes were carboxylated by reaction with sodium chloroacetate in the presence of NaOH as the HCl acceptor or, by the addition of amino hydrogens to acrylate double bonds. Addition to acrylates is very rapid without additional catalyst, but addition to methacrylates and itaconates was much slower. Cyclic anhydrides react rapidly and completely with primary or secondary amines to form the corresponding acid amides. The following preparations are illustrative of such preparations.
To a solution of 22 gms of (CH3 O)3 Si(CH2)3 NH(CH2)2 NH2 (0.1 mol) in 100 ml. of water was added 28.5 gms of ClCH2 COOH (0.3 mols). To the stirred mixture was added 48 gms of 50 percent aqueous NaOH (0.6 mols) with cooling to keep the temperature below 50° C. The course of the reaction was followed by titrating 5 ml of product (0.5 molal) against 0.5 molal CaCl2 with ammonium oxalate indicator to a cloudy end point.
______________________________________
equivalent Ca.sup.++
Time of Reaction
ml CaCl.sub.2
Product
______________________________________
After mixing 1 0.2
6 hours at 50° C.
5 1.0
______________________________________
Chelation of 1 mole of Ca++ per mole of product indicated complete reaction to the compound. ##STR41##
To a solution of 144 gms of acrylic acid in 364 gms of water was added 220 gms of technical grade (CH3 O)3 Si(CH2)3 NH(CH2)2 NH2 and the mixture was refluxed for six hours. The course of the reaction was followed by thin layer chromatography on adsorbasil-1 silica. A spot of 1 percent aqueous product was eluted with methanol and sprayed with bromcresol-purple indicator. The initial mix showed an immobile alkaline spot (purple in color) of unreacted amine and an eluted band of the acid (yellow color). After 6 hours reflux there was only an immobile acid spot indicating that the acid was now part of the silane. The product was a 1.37 molal solution of ##STR42## containing some ##STR43## having a density of 1.125 g/mol at 20° C., and a viscosity of 50 cs. (0.5 Pa.s) at 25° C. A 73 gm portion was diluted to 100 gms with water to give a 1 molal solution of the acid adduct. 1 molal solutions of the acid were mixed with excess sodium silicate solutions in order to form the alkali metal salt in-situ. After aging one hour, the solutions were neutralized to pH 8.
In U.S. Pat. No. 3,337,496, there is disclosed mixtures of various siliconates with silicates as corrosion inhibitors in antifreeze solutions. It was observed that certain mixtures had improved stability to gelation. Ratios of siliconate to potassium silicate were relatively high ranging from 1:1 to 1:5 (50 to 20 mol percent siliconate). The pH was maintained at 10-11 and reserve alkalinity was maintained.
It has now been observed that the siliconate-silicates of this invention are stable even when the aqueous solution is treated with a neutralizing amount of mineral acid. Minimum stability of such materials is observed at a pH of about 8.
Sodium silicate "G" (a polysilicate having an SiO2 /Na2 O weight ratio of 3.22, manufactured by Philadelphia Quartz, Philadelphia, PA) was used in the following manner:
A simple test was developed to compare the stabilizing capability of molal solutions of siliconate salts. One molal solutions of siliconate salt were mixed with 1 molal solutions of sodium silicate "G" and allowed to age for 16 hours at room temperature. They were then neutralized to pH 8 with 10 percent aqueous HCl and the time for gelation was observed. Compositions that did not gel in seven days were generally stable indefinitely. These materials are designated with an asterik in Table I below. Some compositions gave a delayed initial gelation, but the gel re-liquified to give stable solutions. They are shown in parentheses in the table below. A number of siliconate salts of the prior art were also evaluated. Samples B-I of Table I fall within the scope of this invention. Samples A and J-R fall outside the scope of this invention.
TABLE I
__________________________________________________________________________
Stabilizing Capability of Siliconate Salts
Time to gellation at a mole ratio of
siliconate to silicate
Ref.
Siliconate 1:5 1:7.5 1:10
1:15
1:20
__________________________________________________________________________
A silicate alone** -- -- -- -- --
B NaOOCCH.sub.2 SCH.sub.2 CH.sub.2 SiO.sub.1.5 (Na)
* * * 21/2min.
90 sec
C NaOOCCH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2 SiO.sub.1.5 (Na)
2 days
30 sec. 30 sec.
-- --
D NaOOCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 SiO.sub.1.5 (Na)
" 12 hrs. 30 sec.
20 sec.
15 sec.
E NaOOCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2 SiO.sub.1.5
2days
25 min. 30 sec.
-- --
##STR44## * * * 10 min.
90 sec.
G
##STR45## *
##STR46##
90 sec.
-- --
H
##STR47## * * * 11/2hr.
1 min.
I
##STR48## * * * 11/2hr.
40 sec.
J CH.sub.3 SiO.sub.1.5 (Na)
35 sec.
-- -- -- --
K C.sub.6 H.sub.5 SiO.sub.1.5 (Na)
15 sec.
-- -- -- --
L HSCH.sub.2 CH.sub.2 SiO.sub.1.5 (Na)
40 sec.
-- -- -- --
M CNCH.sub.2 CH.sub.2 SiO.sub.1.5 (Na)
20 sec.
-- -- -- --
N
##STR49## 2 min.
-- -- -- --
O
##STR50## 3 min.
-- -- -- --
P NaOOCCH.sub.2 CH.sub.2 CH.sub.2 SiO.sub.1.5 (Na)
* 30 min. 4 min.
-- --
Q NaOPO(CH.sub.3)OCH.sub.2 CH.sub.2 CH.sub.2 SiO.sub.1.5 (Na)
* 9 min. 2 min.
-- --
R .[.NaO.sub.2 C(CH.sub.2).sub.2 S(CH.sub.2).sub.3 SiO.sub.1.5 (Na).].
45 sec.
-- -- -- --
##STR51##
__________________________________________________________________________
**control no siliconate present gelled in 2 sec.
*indicates at least 7 days stability parentheses indicates initial
gellation, but reliquification to give a stable solution.
In a manner similar to Example 7, the salts of the nitrogen containing siliconates were evaluated using sodium silicate "G" (see Table II). Samples B-I fall within the scope of this invention while Samples A and J-O show similar materials but they fall outside the scope of this invention.
TABLE II
__________________________________________________________________________
Stabilizing Capability of Salts of Nitrogen Containing Siliconates
Time to gellation at mole ratio of
siliconate to silicate
Ref.
Siliconate 1:5
.[.1:75.]..Iadd.1:7.5.Iaddend.
1:10
1:15 1:20
__________________________________________________________________________
A silicate alone -- -- -- -- --
B (NaOOCCH.sub.2).sub.2 N(CH.sub.2).sub.3 SiO.sub.1.5 (Na)
*
##STR52##
45 sec.
-- --
##STR53## * 8 hr. 2 min.
15 sec. --
D (NaOOCCH.sub.2 CH.sub.2).sub.2 N(CH.sub.2).sub.3 SiO.sub.1.5 (Na)
* * 2 min
-- --
E (NaOOCCH.sub.2).sub.2 N(CH.sub.2).sub.2 NH(CH.sub.2).sub.3 SiO.sub.1.5
(Na) * 6 min. 90 sec.
-- --
F
##STR54## * * *
##STR55##
--
G .[.(NaOOCH.sub.2 CH.sub.2).sub.2 NCH.sub.2 CH.sub.2 NH(CH.sub.2).sub.3
SiO.sub.1.5 (Na).]. * * * 1 min. 10 sec.
.Iadd.(NaOOCCH.sub.2 CH.sub.2).sub.2 NCH.sub.2 CH.sub.2 NH(CH.sub.2).s
ub.3 SiO.sub.1.5 (Na).
H
##STR56## * 8 hrs. 2 min.
15 sec. --
.Iaddend.#
I
##STR58## * * *
##STR59##
90 sec.
J NaOOCCH.sub.2 NH(CH.sub.2).sub.3 SiO.sub.1.5 (Na)
9 -- -- -- --
min.
K NaOOC(CH.sub.2).sub.2 NH(CH.sub.2).sub.3 SiO.sub.1.5 (Na)
+ -- -- -- --
L
##STR60## + -- -- -- --
##STR61##
M NaOOCCH.sub.2 NH(CH.sub.2).sub.2 NH(CH.sub.2).sub.3 SiO.sub.1.5
10a)
-- -- -- --
sec.
N .[.NaOOCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH(CH.sub.2).sub.3
SiO.sub.1.5 (Na).]. + -- -- -- --
.Iadd.NaOOCCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH(CH.sub.2).sub.3
SiO.sub.1.5 (Na).Iaddend.
O
##STR62## * 3 min. 1 min.
-- --
__________________________________________________________________________
*indicates at least 7 days stability
**control no siliconate present gelled in 2 seconds parentheses
indicates initial gellation, but reliquification to give a stable
solution.
.[." ".]..Iadd."+".Iaddend. indicates initial incompatibility
The siliconate salts were evaluated as additives to antifreeze systems by utilizing the ASTM test method D-1384. Prestone® II, Union Carbide commercial antifreeze was used as a comparative example. ASTM D-1384 test method requires that each test be run in triplicate. For the purposes herein, the test was run only once as a rough screening test. The corrosive water used in the test consisted of 100 ppm each of sodium sulfate, sodium chloride and sodium bicarbonate. Metals tested included copper, solder, brass, steel, cast iron and cast aluminum. A control was run using each of these metals without any additive. Test solutions were prepared using 250 gms of ethylene glycol and 500 gms of the corrosion water prepared as above.
The metal strips were as assembled as set forth in the ASTM test procedure and these assembled metals were immersed in the test solution. The beakers containing the test solutions and metal assemblies were heated to 88° C. and aerated at 100 ml/min. for a period of two weeks. The pH of the test solution was determined both before and after the test. Weight measurements were taken on each metal to the nearest milligram after the test strips were cleaned with water and pumice soap and an acetone rinse. After the testing, weight loss calculations were made on the samples after they were cleaned with water and pumice soap using a soft brass bristle brush and acetone rinse. In some cases, the weight was recorded as a gain because of inadequate cleaning techniques.
__________________________________________________________________________
Siliconate
weight percent
weight loss by corrosion in mg
reference
type of Siliconate
amount used
copper
solder
brass
steel
cast iron
cast
__________________________________________________________________________
aluminum
Control 0 27.5
117.2
57.7
434.3
535.9
28.7
(Prestone ® II)
-- -- 0.5
2.8 0.9 0.9
1.4 0.3
Control 0 0.7
102.1
+0.1
792.6
694.7
27.5
B (Na).sub.1.5 OSiCH.sub.2 CH.sub.2 --
0.5 14.1
12.2 0.4 0.7
0.5 +4.6
SCH.sub.2 COONa
Control 0 0.8
99.1 0.2 317.2
406.5
12.8
C* (Na).sub.1.5 OSi(CH.sub.2).sub.3 --
NHCH.sub.2 CH.sub.2 N(CH.sub.2 CH.sub.2 COONa).sub.2
0.5 32.3
24.6 0.2 +1.6
+3.2 +52.9
__________________________________________________________________________
*some precipitate noted at the end of the test
Claims (120)
1. A method of stabilizing soluble silicates comprising adding to the soluble silicates a siliconate selected from a group consisting essentially of
(I) a siliconate having the general formula ##STR63## and
(II) a siliconate having the general formula ##STR64## wherein in both formulas, M is selected from a group consisting essentially of
(i) alkali metal cations and
(ii) tetraorganoammonium cations and z has a value of 2 or 3,
wherein in formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR65## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and .Iadd.each .Iaddend.R is .Iadd.independently .Iaddend.selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR66## and --(CH2)2 N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR67## and (CH2)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2 wherein R' is selected from a group consisting of ##STR68## when p is 1 and q is 1 and R' is selected from a group consisting of --CH2 COOM, --CH2 CH2 COOM, ##STR69## when p is 0 and q is 2, wherein M and z have the same meaning as set forth above.
2. A method as claimed in claim 1 wherein the siliconate has the formula ##STR70##
3. A method as claimed in claim 2 wherein M is an alkali metal and z is 2.
4. A method as claimed in claim 3 wherein M is an alkali metal and z is 3.
5. A method as claimed in claim 3 wherein the alkali metal is sodium.
6. A method as claimed in claim 3 wherein the alkali metal is potassium.
7. A method as claimed in claim 4 wherein the alkali metal is sodium.
8. A method as claimed in claim 4 wherein the alkali metal is potassium.
9. A method as claimed in claim 2 wherein M is a tetraorganoammonium radical.
10. A method as claimed in claim 9 wherein the tetraorganoammonium radical is a tetraalkylammonium radical.
11. The method as claimed in claim 10 wherein the tetraalkylammonium radical is tetramethylammonium.
12. A method as claimed in claim 1 wherein the siliconate has the formula ##STR71##
13. A method as claimed in claim 12 wherein M is an alkali metal and z is 2.
14. A method as claimed in claim 12 wherein M is an alkali metal and z is 3.
15. A method as claimed in claim 13 wherein the alkali metal is sodium.
16. A method as claimed in claim 13 wherein the alkali metal is potassium.
17. A method as claimed in claim 14 wherein the alkali metal is sodium.
18. A method as claimed in claim 14 wherein the alkali metal is potassium.
19. A method as claimed in claim 12 wherein M is a tetraorganoammonium radical.
20. A method as claimed in claim 19 wherein the tetraorganoammonium radical is a tetraalkylammonium radical.
21. A method as claimed in claim 20 wherein the tetraalkylammonium radical is tetramethylammonium.
22. A method as claimed in claim 1 wherein M in each case is sodium.
23. A method as claimed in claim 1 wherein M in each case is potassium.
24. A method as claimed in claim 1 wherein M in each case is a tetraalkylammonium cation.
25. A method as claimed in claim 24 wherein the tetraalkylammonium cation is a tetra(methyl)ammonium cation.
26. An alcohol composition comprising a combination of
(A) an alcohol;
(B) a corrosion inhibiting amount of a composition which is selected from a group consisting of
(I) a siliconate having the general formula ##STR72## and (II) a siliconate having the general formula ##STR73## wherein in both formulas, M is selected from a group consisting essentially of
(i) alkali metal cations and
(ii) tetraorganoammonium cations and z has a value of 2 or 3,
wherein in formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR74## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and .Iadd.each .Iaddend.R is .Iadd.independently .Iaddend.selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR75## and --(CH2)2 N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR76## and (CH2)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2, .[.and.].
.Iadd.wherein R' is selected from a group consisting of ##STR77##.Iaddend. when p is 1 and q is 1 and R' is selected from a group consisting of --CH2 COOM, --CH2 CH2 COOM, ##STR78## when p is 0 and q is 2, wherein M and z have the same meaning as set forth above;
(C) a soluble silicate .[.represented by the general formula ##STR79## wherein M has the meaning above and a has a value of 1-3.]. and (D) water.
27. An aqueous alcohol composition as claimed in claim 26 comprising
(A) 85 to 98 percent by weight of alkylene glycol,
(B) 0.01 to 0.5 percent by weight of a siliconate,
(C) 0.025 to 1.0 percent by weight of an alkali metal silicate, and
(D) the remainder being water.
28. An aqueous alcohol composition as claimed in claim 27 wherein the siliconate has the formula ##STR80##
29. An aqueous alcohol composition as claimed in claim 28 wherein M is an alkali metal.
30. An aqueous alcohol composition as claimed in claim 29 wherein the alkali metal is sodium.
31. An aqueous alcohol composition as claimed in claim 29 wherein the alkali metal is potassium.
32. A composition as claimed in claim 30 wherein the siliconate is .[.NaOOCH2 SCH2 CH2 SiO1.5 (Na)..]. .Iadd.NaOOCCH2 SCH2 CH2 SiO1.5 (Na). .Iaddend.
33. A composition as claimed in claim 30 wherein the siliconate is ##STR81##
34. A composition as claimed in claim 30 wherein the silconate is ##STR82##
35. A composition as claimed in claim 30 wherein the siliconate is ##STR83##
36. A composition as claimed in claim 30 wherein the siliconate is ##STR84##
37. A composition as claimed in claim 31 wherein the siliconate is KOOCCH2 SCH2 CH2 SiO1.5 (K).
38. A composition as claimed in claim 31 wherein the siliconate is ##STR85##
39. A composition as claimed in claim 31 wherein the siliconate is ##STR86##
40. A composition as claimed in claim 31 wherein the siliconate is ##STR87##
41. A composition as claimed in claim 31 wherein the siliconate is ##STR88##
42. An aqueous alcohol composition as claimed in claim 28 wherein M is a tetraorganoammonium radical.
43. An aqueous alcohol composition as claimed in claim 42 wherein the tetraorganoammonium radical is a tetraalkylammonium radical.
44. An aqueous alcohol composition as claimed in claim 43 wherein the tetraalkylammonium radical is tetramethylammonium and M is sodium.
45. An aqueous alcohol composition as claimed in claim 43 wherein the tetraalkylammonium radical is tetramethylammonium and M is potassium.
46. An aqueous alcohol composition as claimed in claim 28 wherein component (A) is ethylene glycol.
47. An aqueous alcohol composition as claimed in claim 29 wherein component (A) is ethylene glycol.
48. An aqueous alcohol composition as claimed in claim 30 wherein component (A) is ethylene glycol.
49. An aqueous alcohol composition as claimed in claim 31 wherein component (A) is ethylene glycol.
50. An aqueous alcohol composition as claimed in claim 28 wherein component (A) is propylene glycol.
51. An aqueous alcohol composition as claimed in claim 29 wherein component (A) is propylene glycol.
52. An aqueous alcohol composition as claimed in claim 30 wherein component (A) is propylene glycol.
53. An aqueous alcohol composition as claimed in claim 31 wherein component (A) is propylene glycol.
54. An aqueous alcohol composition as claimed in claim 27 wherein the siliconate has the formula ##STR89##
55. An aqueous alcohol composition as claimed in claim 54 wherein M is an alkali metal.
56. An aqueous alcohol composition as claimed in claim 55 wherein the alkali metal is sodium.
57. An aqueous alcohol composition as claimed in claim 55 wherein the alkali metal is potassium.
58. A composition as claimed in claim 56 wherein the siliconate is (NaOOCCH2)2 N(CH2)3 SiO1.5 (Na).
59. A composition as claimed in claim 56 wherein the siliconate is ##STR90##
60. A composition as claimed in claim 56 wherein the siliconate is (NaOOCCH2 CH2)2 N(CH2)3 SiO1.5 (Na).
61. A composition as claimed in claim 56 wherein the siliconate is (NaOOCCH2)2 N(CH2)2 NH(CH2)3 SiO1.5 (Na).
62. A composition as claimed in claim 56 wherein the siliconate is ##STR91##
63. A composition as claimed in claim 56 wherein the silconate is .[.(NaOOCH2 CH2)2 NCH2 CH2 NH(CH2)3 SiO1.5 (Na)..]. (.Iadd.NaOOCCH2)CH2)2 NCH2 CH2 NH(CH2)3 SiO1.5 (Na).Iaddend..
64. A composition as claimed in claim 56 wherein the siliconate is ##STR92##
65. .[.A composition as claimed in claim 56 wherein the siliconate is.]. .Iadd.An alcohol composition comprising a combination of
(A) an alcohol,
(B) a corrosion inhibiting amount of ##STR93## (C) a soluble silicate, and (D) water. .Iaddend.
66. A composition as claimed in claim 57 wherein the siliconate is (KOOCCH2)2 N(CH2)3 SiO1.5 (K).
67. A composition as claimed in claim 57 wherein the siliconate is .[.KOOCCHCH2 NH(CH2)3 SiO1.5 (K)..]. ##STR94##
68. A composition as claimed in claim 57 wherein the siliconate is (KOOCCH2 CH2)2 N(CH2)3 SiO1.5 K.
69. A composition as claimed in claim 57 wherein the siliconate is (KOOCCH2)2 N(CH2)2 NH(CH2)3 SiO1.5 K.
70. A composition as claimed in claim 57 wherein the siliconate is ##STR95##
71. A composition as claimed in claim 57 wherein the siliconate is .[.(KOOCH2 CH2)2 NCH2 CH2 NH(CH2)3 SiO1.5 (K).]. .Iadd.(KOOCCH2 CH2)2 NCH2 CH2 NH(CH2)3 SiO1.5 (K) .Iaddend..
72. A composition as claimed in claim 57 wherein the siliconate is ##STR96##
73. .[.A composition as claimed in claim 57 wherein the siliconate is.]. .Iadd.An alcohol composition comprising a combination of
(A) an alcohol,
(B) a corrosion inhibiting amount of ##STR97## (C) a soluble silicate, and (D) water. .Iaddend.
74. An aqueous alcohol composition as claimed in claim 54 wherein M is a tetraorganoammonium radical.
75. An aqueous alcohol composition as claimed in claim 74 wherein the tetraorganoammonium radical is a tetraalkylammonium radical.
76. An aqueous alcohol composition as claimed in claim 75 wherein the tetraalkylammonium radical is tetramethylammonium and M is sodium.
77. An aqueous alcohol composition as claimed in claim 75 wherein the tetraalkylammonium radical is tetramethylammonium and M is potassium.
78. A composition as claimed in claim 54 wherein component (A) is ethylene glycol.
79. An aqueous alcohol composition as claimed in claim 55 wherein component (A) is ethylene glycol.
80. An aqueous alcohol composition as claimed in claim 56 wherein component (A) is ethylene glycol.
81. An aqueous alcohol composition as claimed in claim 57 wherein component (A) is ethylene glycol.
82. An aqueous alcohol composition as claimed in claim 54 wherein component (A) is propylene glycol.
83. An aqueous alcohol composition as claimed in claim 55 wherein component (A) is propylene glycol.
84. An aqueous alcohol composition as claimed in claim 56 wherein component (A) is propylene glycol.
85. An aqueous alcohol composition as claimed in claim 57 wherein component (A) is propylene glycol.
86. A method of inhibiting metal corrosion in an aqueous medium by adding to the aqueous medium a composition consisting of a siliconate selected from a group consisting of
(I) a siliconate having the general formula ##STR98## and (II) a siliconate having the general formula ##STR99## wherein in both formulas, M is selected from a group consisting essentially of
(i) alkali metal cations and
(ii) tetraorganoammonium cations and z has a value of 2 or 3,
wherein in formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR100## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and .Iadd.each .Iaddend.R is .Iadd.independently .Iaddend.selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR101## and --(CH2)2 N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR102## and (CHz)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2 wherein R' is selected from a group consisting of ##STR103## when p is 1 and q is 1 and R' is selected from a group consisting of --CH2 COOM, --CH2 CH2 COOM, ##STR104## when p is 0 and q is 2, wherein M and .[.Z.]. .Iadd.z .Iaddend.have the same meaning as set forth above.
87. A method as claimed in claim 86 wherein there is also present a soluble silicate .[.represented by the general formula ##STR105## wherein M has the meaning above and a has a value of 1-3.]..
88. A method as claimed in claim 86 wherein the siliconate has the formula ##STR106##
89. A method as claimed in claim 88 wherein M in the siliconate is an alkali metal.
90. A method as claimed in claim 89 wherein the alkali metal is sodium.
91. A method as claimed in claim 90 wherein the siliconate is ##STR107##
92. A method as claimed in claim 89 wherein the alkali metal is potassium.
93. A composition as claimed in claim 92 wherein the siliconate is ##STR108##
94. A method as claimed in claim 86 wherein the siliconate has the formula ##STR109##
95. A method as claimed in claim 94 wherein M in the siliconate is an alkali metal.
96. A method as claimed in claim 95 wherein the alkali metal is sodium.
97. A method as claimed in claim 95 wherein the alkali metal is potassium.
98. A .[.composition.]. .Iadd.method .Iaddend.as claimed in claim 96 wherein the siliconate is ##STR110##
99. A .[.composition.]. .Iadd.method .Iaddend.as claimed in claim 97 wherein the siliconate is ##STR111##
100. A composition of matter comprising
(A) 0.1 to 20 mole percent of a siliconate selected from a group consisting essentially of
(I) a siliconate having the general formula ##STR112## and (II) a siliconate having the general formula ##STR113## wherein in both formulas, M is selected from a group consisting essentially of
(i) alkali metal cations and
(ii) tetraorganoammonium cations and z has a value of 2 or 3,
wherein in formula (I), R is selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR114## and wherein in formula (II), n has a value of 0 or 1; m has a value of 1 or 2, the sum of n+m is 2 and .Iadd.each .Iaddend.R is .Iadd.independently .Iaddend.selected from a group consisting essentially of --CH2 COOM, --CH2 CH2 COOM, ##STR115## and --(CH2)2 N(CH2 COOM)2 when n is 0 and m is 2, and R is selected from a group consisting essentially of ##STR116## and (CH2)z NHp R'q when n is 1 and m is 1, p has a value of 0 or 1, q has a value of 1 or 2 and the sum of p+q is 2,
.Iadd.wherein R' is selected from a group consisting of ##STR117##.Iaddend. when p is 1 and q is 1 and R' is selected from a group consisting of --CH2 COOM, --CH2 CH2 COOM, ##STR118## when p is 0 and q is 2, wherein M and z have the same meaning as set forth above and
(B) 80 to 99.9 mole percent of a soluble silicate .[.represented by the general formula ##STR119## wherein M has the meaning above and a has a value of 1-3.]..
101. A composition of matter as claimed in claim 100 wherein the siliconate has the formula ##STR120##
102. A composition of matter as claimed in claim 101 wherein M is an alkali metal.
103. A composition of matter as claimed in claim 102 wherein the alkali metal is sodium.
104. A composition of matter as claimed in claim 102 wherein the alkali metal is potassium.
105. A composition as claimed in claim 103 wherein the siliconate is ##STR121##
106. A composition as claimed in claim 104 wherein the siliconate is ##STR122##
107. A composition as claimed in claim 100 wherein the siliconate has the formula ##STR123##
108. A composition as claimed in claim 107 wherein M in the siliconate is an alkali metal.
109. A composition as claimed in claim 108 wherein the alkali metal is sodium.
110. A composition as claimed in claim 108 wherein the alkali metal is potassium.
111. A composition as claimed in claim 109 wherein the siliconate is ##STR124##
112. A composition as claimed in claim 110 wherein the siliconate is ##STR125## .Iadd.
113. A method of stabilizing soluble silicates comprising adding ##STR126## to the soluble silicate. .Iaddend. .Iadd.
114. A method of inhibiting metal corrosion in an aqueous medium by adding to the aqueous medium a composition consisting of ##STR127## .Iaddend. .Iadd.
115. A composition of matter comprising
(A) 0.2 to 20 mole percent of ##STR128## and (B) 80 to 99.9 mole percent of a soluble silicate. .Iaddend. .Iadd.
116. A method of stabilizing soluble silicates comprising adding ##STR129## to the soluble silicate. .Iaddend. .Iadd.
117. A method of inhibiting metal corrosion in an aqueous medium by adding to the aqueous medium a composition consisting of ##STR130## .Iaddend. .Iadd.
118. A composition of matter comprising
(A) 0.2 to 20 mole percent of ##STR131## and (B) 80 to 99.9 mole percent of a soluble silicate. .Iaddend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/512,306 USRE32250E (en) | 1981-03-30 | 1983-07-11 | Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/248,131 US4344860A (en) | 1981-03-30 | 1981-03-30 | Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates |
| US06/512,306 USRE32250E (en) | 1981-03-30 | 1983-07-11 | Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/248,131 Reissue US4344860A (en) | 1981-03-30 | 1981-03-30 | Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE32250E true USRE32250E (en) | 1986-09-23 |
Family
ID=26939121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/512,306 Expired - Lifetime USRE32250E (en) | 1981-03-30 | 1983-07-11 | Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE32250E (en) |
Cited By (7)
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|---|---|---|---|---|
| US4863978A (en) | 1988-06-03 | 1989-09-05 | Dow Corning Corporation | Ionomeric silane coupling agents |
| US4871788A (en) | 1988-06-03 | 1989-10-03 | Dow Corning Corporation | Inomeric coupling agents based on amic acid-functional silanes |
| US5008349A (en) * | 1989-10-26 | 1991-04-16 | Dow Corning Corporation | Silicone primer compositions |
| US5045360A (en) * | 1989-10-26 | 1991-09-03 | Dow Corning Corporation | Silicone primer compositions |
| US20040037964A1 (en) * | 2000-09-13 | 2004-02-26 | Davies Gerald Howard | Primer coating of steel |
| US20050276923A1 (en) * | 2000-09-13 | 2005-12-15 | Davies Gerald H | Primer coating of steel |
| US7166328B1 (en) * | 1999-03-18 | 2007-01-23 | International Coatings Ltd. | Primer coating of steel |
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| US20050276923A1 (en) * | 2000-09-13 | 2005-12-15 | Davies Gerald H | Primer coating of steel |
| US8048215B2 (en) | 2000-09-13 | 2011-11-01 | Akzo Nobel N.V. | Primer coating of steel |
| US8128996B2 (en) | 2000-09-13 | 2012-03-06 | Akzo Nobel N.V. | Primer coating of steel |
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