US1963065A - manufacture of thickened - Google Patents
manufacture of thickened Download PDFInfo
- Publication number
- US1963065A US1963065A US1963065DA US1963065A US 1963065 A US1963065 A US 1963065A US 1963065D A US1963065D A US 1963065DA US 1963065 A US1963065 A US 1963065A
- Authority
- US
- United States
- Prior art keywords
- oil
- soap
- thickened
- products
- fatty
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title description 42
- 239000000047 product Substances 0.000 description 134
- 239000003921 oil Substances 0.000 description 122
- 235000019198 oils Nutrition 0.000 description 122
- 239000000344 soap Substances 0.000 description 114
- 238000000034 method Methods 0.000 description 80
- 239000010685 fatty oil Substances 0.000 description 74
- 239000000944 linseed oil Substances 0.000 description 70
- 235000021388 linseed oil Nutrition 0.000 description 70
- 238000010438 heat treatment Methods 0.000 description 64
- 239000003795 chemical substances by application Substances 0.000 description 58
- 239000000203 mixture Substances 0.000 description 50
- 230000000051 modifying Effects 0.000 description 48
- 238000002156 mixing Methods 0.000 description 36
- 235000014113 dietary fatty acids Nutrition 0.000 description 34
- 239000000194 fatty acid Substances 0.000 description 34
- 150000004665 fatty acids Chemical class 0.000 description 34
- 239000007789 gas Substances 0.000 description 34
- 238000001035 drying Methods 0.000 description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 32
- 239000005864 Sulphur Substances 0.000 description 30
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 30
- 229910052708 sodium Inorganic materials 0.000 description 30
- 239000011734 sodium Substances 0.000 description 30
- 239000002253 acid Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000004073 vulcanization Methods 0.000 description 26
- 229910052783 alkali metal Inorganic materials 0.000 description 24
- 239000002966 varnish Substances 0.000 description 24
- 150000001340 alkali metals Chemical class 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- 239000007858 starting material Substances 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- -1 dinitraniline Chemical compound 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 10
- 238000007792 addition Methods 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000006011 modification reaction Methods 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- FWMUJAIKEJWSSY-UHFFFAOYSA-N Sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating Effects 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 150000007522 mineralic acids Chemical class 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- ACJCWXDMBFPZQI-UHFFFAOYSA-N 6,6-dimethyl-4-methylidenebicyclo[3.1.1]heptane;hydrochloride Chemical compound Cl.C1C2C(C)(C)C1CCC2=C ACJCWXDMBFPZQI-UHFFFAOYSA-N 0.000 description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N Acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 229960002327 Chloral Hydrate Drugs 0.000 description 4
- RNFNDJAIBTYOQL-UHFFFAOYSA-N Chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N Dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 4
- NQRLPDFELNCFHW-UHFFFAOYSA-N Nitroacetanilide Chemical compound CC(=O)NC1=CC=C([N+]([O-])=O)C=C1 NQRLPDFELNCFHW-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N Pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- VRYIUQTXEWDFQI-UHFFFAOYSA-N S(=O)(=O)(O)O.NC1=C(C=CC=C1)N=NC1=CC=CC=C1 Chemical compound S(=O)(=O)(O)O.NC1=C(C=CC=C1)N=NC1=CC=CC=C1 VRYIUQTXEWDFQI-UHFFFAOYSA-N 0.000 description 4
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N Thiocarbanilide Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 4
- 229960004319 Trichloroacetic Acid Drugs 0.000 description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N Trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N Triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- DOUCHCULYHWMTQ-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].C1=CC=CC2=CC=CC=C12 Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].C1=CC=CC2=CC=CC=C12 DOUCHCULYHWMTQ-UHFFFAOYSA-J 0.000 description 4
- 239000012346 acetyl chloride Substances 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229960003172 iodoform Drugs 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 231100000489 sensitizer Toxicity 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-Dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-Dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-Naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-Naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- IQGMRVWUTCYCST-UHFFFAOYSA-N 3-Aminosalicylic acid Chemical compound NC1=CC=CC(C(O)=O)=C1O IQGMRVWUTCYCST-UHFFFAOYSA-N 0.000 description 2
- FWUUMDDHHPVSPL-UHFFFAOYSA-N 3-nitroaniline;hydrochloride Chemical compound [Cl-].[NH3+]C1=CC=CC([N+]([O-])=O)=C1 FWUUMDDHHPVSPL-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Nitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-Nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-Toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-Sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 2
- KRBZPDUCRARLKM-UHFFFAOYSA-N 5-amino-1,6-dimethylcyclohexa-2,4-diene-1-sulfonic acid Chemical compound CC1C(N)=CC=CC1(C)S(O)(=O)=O KRBZPDUCRARLKM-UHFFFAOYSA-N 0.000 description 2
- WBSMIPLNPSCJFS-UHFFFAOYSA-N 5-chloro-2-methoxyaniline Chemical compound COC1=CC=C(Cl)C=C1N WBSMIPLNPSCJFS-UHFFFAOYSA-N 0.000 description 2
- CSKNSYBAZOQPLR-UHFFFAOYSA-N Benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N Benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N Benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N Benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- IENFPADQGCKHJK-UHFFFAOYSA-N C(O)(=O)OC1=CC=CC(=C1C)[N+](=O)[O-] Chemical class C(O)(=O)OC1=CC=CC(=C1C)[N+](=O)[O-] IENFPADQGCKHJK-UHFFFAOYSA-N 0.000 description 2
- AWDPHQCYNXHDPB-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)O.[Cl].[Cl] Chemical compound C1(=CC=CC=C1)S(=O)(=O)O.[Cl].[Cl] AWDPHQCYNXHDPB-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N Chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940117389 Dichlorobenzene Drugs 0.000 description 2
- 229940116901 Diethyldithiocarbamate Drugs 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N Diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N Diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229940035422 Diphenylamine Drugs 0.000 description 2
- 229920001875 Ebonite Polymers 0.000 description 2
- 229940013317 Fish Oils Drugs 0.000 description 2
- 240000007842 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 240000008528 Hevea brasiliensis Species 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N Hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920000126 Latex Polymers 0.000 description 2
- KBOPZPXVLCULAV-UHFFFAOYSA-N Mesalazine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 description 2
- 229960004011 Methenamine Drugs 0.000 description 2
- ADWDNOJZWIDEOT-UHFFFAOYSA-N N-phenylaniline;hydrobromide Chemical compound [Br-].C=1C=CC=CC=1[NH2+]C1=CC=CC=C1 ADWDNOJZWIDEOT-UHFFFAOYSA-N 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N Phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 229940079877 Pyrogallol Drugs 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- DCKMSBIWTITCME-UHFFFAOYSA-N S(=O)(=O)(O)O.NC=1C(=C(C=CC1)NC1=CC=CC=C1)N Chemical compound S(=O)(=O)(O)O.NC=1C(=C(C=CC1)NC1=CC=CC=C1)N DCKMSBIWTITCME-UHFFFAOYSA-N 0.000 description 2
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- JBWKIWSBJXDJDT-UHFFFAOYSA-N Triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000012237 artificial material Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ASKHTHDBINVNFJ-UHFFFAOYSA-N chlorosulfonyloxyethane Chemical compound CCOS(Cl)(=O)=O ASKHTHDBINVNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulant Effects 0.000 description 2
- 230000001427 coherent Effects 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylazanium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GFTHTGSSEPPTQV-UHFFFAOYSA-N diphenylazanium;2,2,2-trichloroacetate Chemical compound [O-]C(=O)C(Cl)(Cl)Cl.C=1C=CC=CC=1[NH2+]C1=CC=CC=C1 GFTHTGSSEPPTQV-UHFFFAOYSA-N 0.000 description 2
- IPZMDJYHJNHGML-UHFFFAOYSA-N diphenylazanium;hydrogen sulfate Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1NC1=CC=CC=C1 IPZMDJYHJNHGML-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 230000002708 enhancing Effects 0.000 description 2
- 230000002349 favourable Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- NTOLGSSKLPLTDW-UHFFFAOYSA-N hydrogen sulfate;phenylazanium Chemical compound OS(O)(=O)=O.NC1=CC=CC=C1 NTOLGSSKLPLTDW-UHFFFAOYSA-N 0.000 description 2
- JEFJSEIUEJBMSR-UHFFFAOYSA-N hydron;N-phenylaniline;chloride Chemical compound Cl.C=1C=CC=CC=1NC1=CC=CC=C1 JEFJSEIUEJBMSR-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000004972 metal peroxides Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- XFSXWFOXECTCPD-UHFFFAOYSA-N naphthalen-1-ylsulfamic acid Chemical compound C1=CC=C2C(NS(=O)(=O)O)=CC=CC2=C1 XFSXWFOXECTCPD-UHFFFAOYSA-N 0.000 description 2
- DASJFYAPNPUBGG-UHFFFAOYSA-N naphthalene-1-sulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1 DASJFYAPNPUBGG-UHFFFAOYSA-N 0.000 description 2
- AYDPPJFUTOOTRP-UHFFFAOYSA-N naphthalene;sulfurochloridic acid Chemical compound OS(Cl)(=O)=O.C1=CC=CC2=CC=CC=C21 AYDPPJFUTOOTRP-UHFFFAOYSA-N 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000010665 pine oil Substances 0.000 description 2
- 239000010491 poppyseed oil Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 230000001131 transforming Effects 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000010698 whale oil Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F242/00—Copolymers of drying oils with other monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F7/00—Chemical modification of drying oils
- C09F7/06—Chemical modification of drying oils by polymerisation
Definitions
- This invention relates to the manufacture of thickened, bodied oil products from fatty oils, and it comprises methods of making such oil products wherein certain soaps are dissolved or dispersed in the said fatty oil, advantageously by heating a mixture of the fatty oil and soap to temperatures sufficient to effect a thickened or bodying of the oil, the temperatures being advantageously about 200 C. or higher, until said oil in the present inas tung oil, linseed oil, fish oils (train oils), poppyseed oil, sunflower oil, cottonseed oil, rapeseed oil, soya bean oil, pine oil, corn oil, olive oil, castor oil, etc. Products containing the acids of fatty oils may also be used.
- This invention is particularly adaptable to making the said oil products from drying oils; linseed oil and the like.
- Laszld Auer By the previous investigations of one of us, Laszld Auer, there has been developed various methods of producing thickened, bodied oil products from fatty oils and the like, with the aid of certain polar compounds or electrolytes (called modifying agents) under a wide range of conditions; all of those methods involve changes in the lsocolloid system of the fatty oil.
- the oil products so obtained are thickened, modified fatty oils.
- modifying agents are e. g.
- an acidic'inorganlc residue we mean such an inorganic residue as can be converted by the addition of one or more hydrogen atoms into an inorganic acid (including carbonic acid as inorganic). It will be seen that this definition includes such compounds as organic halogen derivatives (e. g. trichloroacetic acid, chloral hydrate, iodoform, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, mono-chloracetic acid,
- organic halogen derivatives e. g. trichloroacetic acid, chloral hydrate, iodoform, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, mono-chloracetic acid
- methyl ester of p-toluene sulphonic acid ethyl chlorsulphonate (esters of inorganic acids) e. g. 'dimethylsulphate, triphenyl or tricresyl phosphate, nitrocresol carbonates, and inorganic salts of organic bases e. g. m-nitroaniline hydrochloride, diaminodiphenylamine sulphate, aminoazo-benzene sulphate, diphenylamine hydrochloride, diphenyl-amine, hydrobromide, diphenylamine trichloracetate, trichloraniline hydrochloride.
- modifying agents are certain metallic peroxides
- modifying agents e. g. peroxides of magnesium,zink, barium, strontium, calcium, sodium etc., alkali metals, their oxides and hydroxides etc.
- more than one of the modifying agents may be used such, for instance, favorable results are obtained by treating the starting material with an alkali metal, its oxide or hydroxide and with a metal peroxide.
- Aromatic amines, especially diamines and amines with high molecular weight are also suitable modifying agents.
- the given list of modifying agents shall not be a complete one as other agents giving the desired results may be used for the said purpose.
- the modifying agents starting material in a dry should be added to the form (without the presence of water) and-in relatively small quantities. In order to ensure complete dissolution or disper- .110
- sion of the modifying agent the operation of dissolving or dispersing the latter should be carried out under application of heat.
- the degree of heat necessary depends upon the nature of the substance under treatment and also of the modifying agent used. Generally temperatures from 100 to 300 C. or more will give satisfactory results.
- the heat treatment promotes the complete (molecular or colloidal) dissolution of the modifying agent in the substance to be treated. In some cases it may be advisable to continue the heat treatment after the dissolution or dispersion of the modifying agent is substantially complete.
- the pressure conditions may also be alternated during the gas treatment which, of course may be carried out together with the dissolution or dispersion of the modifying agent in the substance to be treated or as an aftertreatment.
- the gas treatment may be carried out by blowing the gas through the reaction mixture or simply by passing it over the mass contained in the reaction chamber.
- the gas may be further produced in situ in the reaction mass by using substances which under the conditions of the reaction develop gases as desired. Such, for instance by using peroxides, carbonates, sulphides, sulphites and the like the corresponding gases may v be developed in the reaction mass.
- the process as described may be made to effect a solidification or a liquefaction of the initial material.
- thickened products and even solid substances like hard rubber may be obtained from thin oils.
- the results obtained depend in any given case upon the conditions of the reaction, e. g. upon the duration of the heat-treatment of the material, the duration of the gas-treatment, the quantity of the dissolved Generally speaking the products obtained were, from liquids, solid or semi-solid thermoplastic masses, and from solids,
- the dissolution or dispersion of the modifying agents in .the starting material may be favorably udiuenced by the addition of certain "auxiliary agents or sensitizers.
- auxiliary agents or sensitizers include the purely inorganic (e. g. silica gel, vfullers earth), and the purely organic (e. g. formaldehyde, phenol, thiocarbanilide, benzidine, hexamethylenetetramine, 2 :3-hydroxy-naphthoic acid, a-naphthol, quinoline, pyrogallol, benzene, glycerol and phthalimide).
- the purely inorganic e. g. silica gel, vfullers earth
- the purely organic e. g. formaldehyde, phenol, thiocarbanilide, benzidine, hexamethylenetetramine, 2 :3-hydroxy-naphthoic acid
- auxiliary agents here mentioned are to be taken as typical of the substances which have been successfully used for this purpose and not as comprising all the effective substances. It should be mentioned that quite a number of the modifying agents comprising within the molecule an acidic inorganic residue and an organic residue are auxiliary agents (sensitizers) when used in conjunction with other modifying agents.
- an acidic inorganic residue we mean such an inorganic residue as can be converted by the addition of one or more hydrogen atoms, into an inorganic acid (includin carbonic acid as inorganic).
- the sulphur may be added as such or in the form of a sulphur compound (e. g. sulphur chloride) which under the conditions of the process decomposes with liberation of nascent sulphur. It would appear that the action of the sulphur is analogous to that which takes place in the vulcanization of rubber.
- the sulphur or sulphur compounds may be added either at the beginning of the process or so as to act only during the gas treatment part of the process.
- the sulphur or sulphur compounds may be added to the material after the main reaction of the process has been completed.
- Alternating treatment with sulphur dioxide and hydrogen sulphide has been found to be specially useful in certain cases.
- the vulcanizing treatment results carbamate, diethylammonium, diethyl-dithiocarbamate etc.) 'are added. vulcanization occurs below 100 C.
- the modified materials produced by these processes may be used in a variety of industries, e. g.
- a very important application of the new products is the manufacture of new artificial materials by emulsification of organic isocolloids.
- One of the emulsification processes consists in subjecting the isocolloid first to a treatment with modifying agents of the kind described and thereafter effecting further transformation by emulsification or dispersion in an aqueous medium.
- the isocolloid may be first emulsified or dispersed in an aqueous medium and thereafter treated with one or more of the above characterized agents which are capable of modifying the physical properties of the starting material.
- the emulsions or dispersions may be vulcanized or sulphurized by one of the above sions obtained, whether vulcanized or not, are valuable in the art for a variety of purposes.
- the disperse phase may be separated in solid form by means of the usual coagulating agents, or by drying (as e. g. when the aqueous dispersions are used for varnishes), or it may be deposited in forms by dipping (in which case it is advantageous to cover the form with a coat containing a coagulant) or by electrophoresis; or the disperse phase may be separated from the dispersing medium by ultrafiltration.
- the emulsion may be used alone or in admixture with natural rubber latex or an artificially prepared emulsion of rubber, which may or may not have been previously vulcanized, in any or all of the above treatments, and for any of the purposes mentioned.
- the treatment may be profitably influenced byexposing the materials undergoing treatment to oscillating energy (X-rays, ultraviolet rays, infrared rays etc.) or by including the reaction chamber in an electric circuit.
- oscillating energy X-rays, ultraviolet rays, infrared rays etc.
- Filling materials, pigments and the like may be added at any stage of the processes.
- the isocolloidal system does not contain a sufiiciently high concentration of the disperse phase to enable colloidal changes to take place, and for instance heating at higher temperatures is necessary to increase the concentration of the disperse phase. This heating frequently causes a darkening of the products and it is very desirable to devise methods which enable in all cases a modifying action at comparatively lower temperatures and with shorter heat treatment.
- the present inventions are improvements upon those processes and may be used in conjunction they being likewise based upon changes in the isocolloid system of the fatty oil.
- the present invention accordingly comprises a process for the modification of fatty. oils, thickened, modified fatty oils and the like, wherein the modification is efiected' by dispersing or ing material by heating at comparatively low The emulsions or disper-l temperatures until a considerable modification of the physical properties of the starting material has been obtained.
- the above specified soaps act partly as modifying agents, partly as a new disperse phase in the system.
- the proportion of soaps to be added lies between 5 and 20% generally. In certain cases, however, satisfactory results can be obtained by using less than 5% or more than 20% of soaps.
- the melting point of the product depends upon the quantity of the soap dissolved and to a smaller extent upon the duration of heating. It has been found that the dispersion of such soaps in the isocolloids to be treated can be very advantageously carried out by rubbing or kneading of the soaps into the material to be modified in the presence of water when the soap is water-soluble, or in the presence of an organic solvent when the soap is soluble in an organic solvent, for instance benzene.
- the rubbing or kneading is carried out generally at room temperatures, and after the water or organic solvent has been driven oif by drying the mixture, a modified product results without the use of heat to any considerable extent.
- Especially alkali soaps yield very light-colored products according to the present invention.
- reaction product may be used either unvulcanized or vulcanized for varnish purposes.
- accelerators and/or activators may be used.
- Fillers or pigments may be incorporated at any stage into the reaction mass.
- the modifying process according to the present invention may be carried out under the influence of radiations such as infra-red rays, ultra-violet rays, X-rays etc., or by making the reaction mass part of an electric circuit.
- radiations such as infra-red rays, ultra-violet rays, X-rays etc.
- the properties of the products may further be infinanced by concomitant or subsequent treatment with gases.
- Example 1 100 parts linseed oil and 5 parts of the potassium soap of the acids of linseed oil, are heated for 1 hour at 200 C. The viscous mass resulting from the reaction is cooled to 16 C. and treated with 5 parts of sulphur chloride under constant stirring, yielding a very viscous, tacky,
- Example 3 parts linseed oil and 5 parts sodium soap of the acids of linseed oil are heated for 40 minutes at 200 C.
- the product is cooled to 160 C. and vulcanized with the aid of 3 parts sulphur, 1 zinc oxide and 0.7 mercaptobenzthiazole, yielding a viscous oil product for varnish purposes.
- 13.11 the manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing 100 parts of linseed oil with 10 parts of a sodium soap of the fatty acids of linseed oil, heating the mixture to between 200 and 220 C. for approximately one hour, cooling the mixture thus obtained, adding about 10 per cent of sulphur and maintaining the mixture at about 180 C. until complete vulcanization is effected and recovering the modified products thus obtained, said modified products being useful as a rubber substitute.
- said soap being a salt of fatty acids and a metal of the class consisting of alkali metals, alkaline earth metals, magnesium and zinc, heating the mixture to a temperature of at least 200 C. until a thickened, bodied oil product is obtained, adding to the bodied oil thus obtained, a vulcanizing agent of the class consisting of sulphur and sulphur chloride, and then subjecting said mixsaidsoap being a salt of fatty acids and a metal 5 to 20 per cent of an alkali metal soap of the fatty acids of linseed oil, the said soap enhancing the body obtained by heat-bodying said oil.
- a non-oxidized, vulcanized, heat-bodied faty oil, heat-bodied at temperatures of at least 200 C. obtained from a mix ture of a fatty oil and a soap by the process of claim 16, the body of said oil being due partly to heat-bodying, partly to the presence of said soap and partly to vulcanization.
- the two step process which comprises mixing a drying fatty oil with a soap, said soap being an alkali metal salt of the fatty acids of a drying fatty oil, heating the mixture at temperatures sufiicient to thicken and'heat-body the same until a thickened, heat-bodied oil is obtained, said temperature being at 200 C. and then mixing the bodied oil thus obtained with a vulcanizing agent and heating the mixture of bodied oil and vulcanizing agent to temperatures sufiicient to effect reaction and vulcanization and recovering the vulcanized and thickened heat-bodied oil product thus obtained.
- the 2-step process which comprises mixing a soap with a drying fatty oil, heating the mixture to at least 200 C. until a thickened bodied oil is obtained and then mixing said thickened bodied oil with sulphur and a vulcanization accelerator, heating the vulcanizable mass thus obtained to vulcanizing temperatures and recovering said oil products.
- the'2- step process which comprises first producing a thickened bodied oil by mixing a drying fatty oil with alkali metal soap of the fatty acids of a drying oil and heating the mixture to at least 200 C. until a thickened bodied oil is produced, and then vulcanizingsaid thickened bodied oil by mixing said bodied oil with sulphur, an activator and a vulcanization accelerator and heating the vulcanizable mass thus obtained to vulcaniz temperatures, thereby producing said bodied oil products.
- the 2- step process which comprises first producing a thickened bodied oil containing dispersed therein an alkali metal soap of the fatty acids of a drying oil by heating a mixture of said fatty oil and said soap to at least 200 C. and then vulcanizing said thickened bodied oil with sulphur in the presence of an organic vulcanization accelerator thereby producing said bodied oil products.
- the improvement which comprises substantially bodying the fatty oil, prior to vulcanization, by mixing 100 parts of said oil with 2 to 10 parts of a soap and heating the mixture to at least 200 0.
Description
Patented June ll-9 34 1 ACTURE F rmcnanan. BODIED OIL PRODUCTS FROM FATTY OILS Laszl Auer and Lajos Susztek, Budapest, Hungary No Drawing. Application April 21, 1930, Serial No. 446,173. in
30 Claims.
This invention relates to the manufacture of thickened, bodied oil products from fatty oils, and it comprises methods of making such oil products wherein certain soaps are dissolved or dispersed in the said fatty oil, advantageously by heating a mixture of the fatty oil and soap to temperatures sufficient to effect a thickened or bodying of the oil, the temperatures being advantageously about 200 C. or higher, until said oil in the present inas tung oil, linseed oil, fish oils (train oils), poppyseed oil, sunflower oil, cottonseed oil, rapeseed oil, soya bean oil, pine oil, corn oil, olive oil, castor oil, etc. Products containing the acids of fatty oils may also be used.
This invention is particularly adaptable to making the said oil products from drying oils; linseed oil and the like.
By the previous investigations of one of us, Laszld Auer, there has been developed various methods of producing thickened, bodied oil products from fatty oils and the like, with the aid of certain polar compounds or electrolytes (called modifying agents) under a wide range of conditions; all of those methods involve changes in the lsocolloid system of the fatty oil. The oil products so obtained are thickened, modified fatty oils. Such modifying agents are e. g. salts of organic and inorganic acids, metallic derivatives of organic compounds, certain organic acids, compounds comprising within the molecule an acidic inorganic residue and an organic residue: By an acidic'inorganlc residue we mean such an inorganic residue as can be converted by the addition of one or more hydrogen atoms into an inorganic acid (including carbonic acid as inorganic). It will be seen that this definition includes such compounds as organic halogen derivatives (e. g. trichloroacetic acid, chloral hydrate, iodoform, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, mono-chloracetic acid,
4-chloro-o-anisidine, pinene hydrochloride,
naphthalene tetrachloride, p-nitrochlorobenzene,
benzyl chloride, triphenylchloro-methane, acetyl chloride, benzoyl chloride) organic sulphonic acids and their halides and esters, e. g.-
Great Britain April 24, 1929 Sodium 2 6 :8 naphthylaminedisulphonate Sodium 2 6: 8 naphtholdisulphonate Sodium 1 8 z 3 :6 aminonaphtholdisulphonate Sodium 1:5 naphtholsulphonate Sodium 2:3 :6 naphtholdisulphonate Sodium 2: 6 naphtholsulphonate Sodium 2:6 naphthylaminesulphonic acid Sodium 2:1 naphthylaminesulphonic acid 2-phenylamino-8-naphthol-6-6 sulphonic acid, Beta-naphthylamine 3:6:8 trisulphonic acid, Beta naphtol- 3 6 i 8 trisulphonic acid, Beta-naphthol 1:5 disulphonic acid, Naphthalene 2:6 disulphonic acid, Naphthalene 1 sulphonyl chloride, Alpha-naphthyl sulphamic acid,
m-xylidine sulphonic acid,
Benzene sulphonic acid,
p-toluene sulphonic acid,
p-toluene sulphonyl chloride,
5-sulpho salicylic acid,
p-toluldine m-sulphonic acid,
Benzene sulphonyl chloride,
2:5 dichlor benzene sulphonic acid,
methyl ester of p-toluene sulphonic acid, ethyl chlorsulphonate (esters of inorganic acids) e. g. 'dimethylsulphate, triphenyl or tricresyl phosphate, nitrocresol carbonates, and inorganic salts of organic bases e. g. m-nitroaniline hydrochloride, diaminodiphenylamine sulphate, aminoazo-benzene sulphate, diphenylamine hydrochloride, diphenyl-amine, hydrobromide, diphenylamine trichloracetate, trichloraniline hydrochloride.
Further examples are o-nitrophenol, p-nitrophenol, p-nitro acetanilide, dinitraniline, fluoresceine, eosin, thiocarbanilide, 4:4 -diaminodiphenyl sulphide, diphenyl sulphone. Further diphenylamine sulphate,
modifying agents are certain metallic peroxides,
e. g. peroxides of magnesium,zink, barium, strontium, calcium, sodium etc., alkali metals, their oxides and hydroxides etc. In certain cases more than one of the modifying agents may be used such, for instance, favorable results are obtained by treating the starting material with an alkali metal, its oxide or hydroxide and with a metal peroxide. Aromatic amines, especially diamines and amines with high molecular weight are also suitable modifying agents. The given list of modifying agents shall not be a complete one as other agents giving the desired results may be used for the said purpose.
The modifying agents starting material in a dry should be added to the form (without the presence of water) and-in relatively small quantities. In order to ensure complete dissolution or disper- .110
sion of the modifying agent, the operation of dissolving or dispersing the latter should be carried out under application of heat. The degree of heat necessary depends upon the nature of the substance under treatment and also of the modifying agent used. Generally temperatures from 100 to 300 C. or more will give satisfactory results. The heat treatment promotes the complete (molecular or colloidal) dissolution of the modifying agent in the substance to be treated. In some cases it may be advisable to continue the heat treatment after the dissolution or dispersion of the modifying agent is substantially complete.
It has been further found that the results of the process vary with the nature and/or with the physical condition (pressure) of the gas (air or other gas) present in the reaction chamber. Thus, it has been found that a certain given starting material which is initially liquid will become viscous only as the result of the electrolyte treatment, if the latter is effected under atmospheric pressure (e. g. in an open vessel), but solid if the gas is rarified by the employment of a partial vacuum. In other cases the converse applies. When plus pressure was used (e. 3. caused by the tension of the starting materials at higher temperatures), the results diifer again from both of those of the treatments under atmospheric pressure and vacuum. Also, as to the nature of the gas present, an" gives for in= stance a different result from another gas, or mixture of gases. The pressure conditions may also be alternated during the gas treatment which, of course may be carried out together with the dissolution or dispersion of the modifying agent in the substance to be treated or as an aftertreatment.
It may be stated with reference to the action of gases that generally speaking rarifaction or the gases present in the reaction chamber by reduction of pressure tends to intensify their action in the process both in the case of solidification of the starting material and also in the case of liquefaction thereof.
The gas treatment may be carried out by blowing the gas through the reaction mixture or simply by passing it over the mass contained in the reaction chamber. The gas may be further produced in situ in the reaction mass by using substances which under the conditions of the reaction develop gases as desired. Such, for instance by using peroxides, carbonates, sulphides, sulphites and the like the corresponding gases may v be developed in the reaction mass.
The process as described may be made to effect a solidification or a liquefaction of the initial material. Thus, for instance, thickened products and even solid substances like hard rubber may be obtained from thin oils. The results obtained depend in any given case upon the conditions of the reaction, e. g. upon the duration of the heat-treatment of the material, the duration of the gas-treatment, the quantity of the dissolved Generally speaking the products obtained were, from liquids, solid or semi-solid thermoplastic masses, and from solids,
pasty or thin liquids.
If desired, the modifying agentv may be produced in situ within the mass of the=substance under treatment by interaction within the substance, of substances capable of reacting under the conditions of the process to produce the modifying agent wanted.
The dissolution or dispersion of the modifying agents in .the starting material may be favorably iriiuenced by the addition of certain "auxiliary agents or sensitizers. These fall into two groups, namely the purely inorganic (e. g. silica gel, vfullers earth), and the purely organic (e. g. formaldehyde, phenol, thiocarbanilide, benzidine, hexamethylenetetramine, 2 :3-hydroxy-naphthoic acid, a-naphthol, quinoline, pyrogallol, benzene, glycerol and phthalimide). The specific examples of auxiliary agents here mentioned are to be taken as typical of the substances which have been successfully used for this purpose and not as comprising all the effective substances. It should be mentioned that quite a number of the modifying agents comprising within the molecule an acidic inorganic residue and an organic residue are auxiliary agents (sensitizers) when used in conjunction with other modifying agents. By an acidic inorganic residue we mean such an inorganic residue as can be converted by the addition of one or more hydrogen atoms, into an inorganic acid (includin carbonic acid as inorganic). Thus, e. g. the dissolution of 5% of sodium bisulphite in linseed oil is facilitated and the color of the product is'made lighter by the addition of say 2% of such compounds as aminoazobenzene sulphate, aniline sulphate, nitro cresyl carbonate, dimethyl sulphate, trichloroacetic acid, benzenesulphonicacid, iodoform, naphthalene tetrachloride, pinene hydrochloride, m-xylidinesulphonio acid, [i-naphthylamine-Sz'8-disulphonic acid, p-naphthylamine 6-sulphomc acid, acetyl chloride, p-nitroacetanilide, chloral hydrate, and triphenyl phosphate, naphthalene-sulphochloride, diphenyl-amine hydrobromide, 5 or 3-amino salicylic acid, 2:6-naphthalene disulphonic acid, 0- dichlorobenzene.
The advantages of a rapid dissolutionof the modifying agent are greatest in those cases where a clear, pale or colorless product is desired, especially' for example, for the varnish industry.
For the modification of the physical properties of the initial materials solutions or colloidal solutions of one or more electrolytes in an organic solvent may be used.
Solid coherent and elastic products may be obtained, similar in general characteristics to ordinary rubber, by adding sulphur to the initial sub= stance in addition to the agents already mentioned. The sulphur may be added as such or in the form of a sulphur compound (e. g. sulphur chloride) which under the conditions of the process decomposes with liberation of nascent sulphur. It would appear that the action of the sulphur is analogous to that which takes place in the vulcanization of rubber. The sulphur or sulphur compounds may be added either at the beginning of the process or so as to act only during the gas treatment part of the process. Alternatively, the sulphur or sulphur compounds may be added to the material after the main reaction of the process has been completed. Alternating treatment with sulphur dioxide and hydrogen sulphide has been found to be specially useful in certain cases. The vulcanizing treatment results carbamate, diethylammonium, diethyl-dithiocarbamate etc.) 'are added. vulcanization occurs below 100 C.
The modified materials produced by these processes may be used in a variety of industries, e. g.
described methods.
therewith,
in the rubber, linoleum, varnish, soap and candle industries and others.
A very important application of the new products is the manufacture of new artificial materials by emulsification of organic isocolloids. One of the emulsification processes consists in subjecting the isocolloid first to a treatment with modifying agents of the kind described and thereafter effecting further transformation by emulsification or dispersion in an aqueous medium. Or, the isocolloid may be first emulsified or dispersed in an aqueous medium and thereafter treated with one or more of the above characterized agents which are capable of modifying the physical properties of the starting material. The emulsions or dispersions may be vulcanized or sulphurized by one of the above sions obtained, whether vulcanized or not, are valuable in the art for a variety of purposes. They may be for example concentrated and used for impregnation of textiles; or the disperse phase may be separated in solid form by means of the usual coagulating agents, or by drying (as e. g. when the aqueous dispersions are used for varnishes), or it may be deposited in forms by dipping (in which case it is advantageous to cover the form with a coat containing a coagulant) or by electrophoresis; or the disperse phase may be separated from the dispersing medium by ultrafiltration. The emulsion may be used alone or in admixture with natural rubber latex or an artificially prepared emulsion of rubber, which may or may not have been previously vulcanized, in any or all of the above treatments, and for any of the purposes mentioned.
In all cases the treatment may be profitably influenced byexposing the materials undergoing treatment to oscillating energy (X-rays, ultraviolet rays, infrared rays etc.) or by including the reaction chamber in an electric circuit.
Filling materials, pigments and the like may be added at any stage of the processes.
In the case of most fatty oils the isocolloidal system does not contain a sufiiciently high concentration of the disperse phase to enable colloidal changes to take place, and for instance heating at higher temperatures is necessary to increase the concentration of the disperse phase. This heating frequently causes a darkening of the products and it is very desirable to devise methods which enable in all cases a modifying action at comparatively lower temperatures and with shorter heat treatment.
Such processes and products are described and claimed in the copending applications Ser. Nos. 143,786 and 359,425 filed by Laszlo Auer, one of the inventors.
The present inventions are improvements upon those processes and may be used in conjunction they being likewise based upon changes in the isocolloid system of the fatty oil.
We have now found that the addition of soaps of the alkali and alkaline earth metals and oi. zinc and magnesium to the isocolloids by dispersing or dissolving the former in the latter, brings about a modifying action at compartively low temperatures and with short treating periods.
The present invention accordingly comprises a process for the modification of fatty. oils, thickened, modified fatty oils and the like, wherein the modification is efiected' by dispersing or ing material by heating at comparatively low The emulsions or disper-l temperatures until a considerable modification of the physical properties of the starting material has been obtained. The above specified soaps act partly as modifying agents, partly as a new disperse phase in the system. The proportion of soaps to be added lies between 5 and 20% generally. In certain cases, however, satisfactory results can be obtained by using less than 5% or more than 20% of soaps.
The melting point of the product depends upon the quantity of the soap dissolved and to a smaller extent upon the duration of heating. It has been found that the dispersion of such soaps in the isocolloids to be treated can be very advantageously carried out by rubbing or kneading of the soaps into the material to be modified in the presence of water when the soap is water-soluble, or in the presence of an organic solvent when the soap is soluble in an organic solvent, for instance benzene. The rubbing or kneading is carried out generally at room temperatures, and after the water or organic solvent has been driven oif by drying the mixture, a modified product results without the use of heat to any considerable extent. Especially alkali soaps yield very light-colored products according to the present invention. Subsequent vulcanization leads to factice like products which show improved properties in rubber mixes, and the reaction product may be used either unvulcanized or vulcanized for varnish purposes. In the vulcanization, accelerators and/or activators may be used. Fillers or pigments may be incorporated at any stage into the reaction mass.
Besides unmodified isocolloids of the type described also those modifled by any method, described in said copending applications Ser. Nos. 143,786 and 359,425 may be used as starting materials for the process; the products of this double modification find application as raw materials for varnishes.
The modifying process according to the present invention may be carried out under the influence of radiations such as infra-red rays, ultra-violet rays, X-rays etc., or by making the reaction mass part of an electric circuit. The properties of the products may further be infinanced by concomitant or subsequent treatment with gases.
The following examples are given by way of 5 illustration and are in no way limitative. The parts are by weight.
Example 1 Example 2 100 parts linseed oil and 5 parts of the potassium soap of the acids of linseed oil, are heated for 1 hour at 200 C. The viscous mass resulting from the reaction is cooled to 16 C. and treated with 5 parts of sulphur chloride under constant stirring, yielding a very viscous, tacky,
oil product which can be advantageously used as varnish raw materials. When instead of potassium soap, a soap containing another metai tained.
Example 3 parts linseed oil and 5 parts sodium soap of the acids of linseed oil are heated for 40 minutes at 200 C. The product is cooled to 160 C. and vulcanized with the aid of 3 parts sulphur, 1 zinc oxide and 0.7 mercaptobenzthiazole, yielding a viscous oil product for varnish purposes.
. What we claim is:
1. As an improvement in the manufacture of thickened, heat-bodied oil products from fatty oils, the steps which comprise mixing together a fatty oil with a soap, said soap being a salt of fatty acids and a metal of the class consisting of alkali metals, alkaline earth metals, magnesium and zinc, and heating the mixture thus obtained, to a temperature of at least 200 C., untilv a thickened, heat-bodied oil product is obtained.
2. The process of claim 1 in which 5 to 20 parts of said soap are mixed with 100 parts of said fatty oil.
3. The process of claim 1 in which said fatty oil is linseed oil and said fatty acids are the fatty acids of linseed oil.
4. The process of claim 1 in which said soap is a soap of alkali metal.
5. The process of claim 1 in which said soap is a sodium soap.
6. The process of claim 1 in which said soap is a potassium soap.
'7. In the manufacture of thickened, heat-v bodied oil products from linseed oil, the process which comprises mixing together linseed oil with an alkali metal soap of theacids of linseed oil, heating the mixture to between 200 and 220 C., to distribute said soap in the linseed oil, the heating being continued until a thickened, bodied oil product is obtained and recovering the products thus produced.
8. In the manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing 100 parts of linseed oil with between 5 to 20 parts of an alkali metal soap of the fatty acids of linseed oil, heating the mixture to about 200 C., to distribute said soap in the linseed oil, the heating being continued until a thickened, bodied oil product is obtained and recovering the products thus obtained.
9. The process of claim 8 in which 10 parts of the sodium soap of the fatty acids of linseed oil is used.
10. The process of claim Bin which 5 parts of potassium soap of the fatty acids of linseed oil is used.
11. Intthe manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing linseed oil with an alkali soap of thefatty acids of linseed oil, heat-, ing the mixture at a temperature su l cient to thicken and heat-body said mixture, the temperature being at least 200 C., until said thickened, heat-bodied oil product is produced, adding a vulcanizing agent to said thickened, heatbodied oil, heating to a temperature and for a time sufficient to effect vulcanization, and recovering the vulcanized, thickened, heat-bodied oil products thus obtained.
12. In the manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing 100 parts of linseed oil with 10 parts of a sodium soap of the fatty acids of linseed oil, heating the mixture to between 200 and 220 C. for approximately one hour, cool is used, a somewhat different product is obing the mixture thus obtained, adding about 3 percent of sulphur and heating at 180 for about 'one hour and recovering the modified products thus obtained, said modified products being suitable as raw materials in the manufacture of varnish,
13.11: the manufacture of thickened, heatbodied oil products from linseed oil, the process which comprises mixing 100 parts of linseed oil with 10 parts of a sodium soap of the fatty acids of linseed oil, heating the mixture to between 200 and 220 C. for approximately one hour, cooling the mixture thus obtained, adding about 10 per cent of sulphur and maintaining the mixture at about 180 C. until complete vulcanization is effected and recovering the modified products thus obtained, said modified products being useful as a rubber substitute.
14. In the manufacture of modified products from linseed oil, the process which comprises mixing together 100 parts of linseed oil and 5 parts of the potassium soap of the fatty acids of linseed oil, heating the mixture thus obtained at 200 C. for about one hour, cooling the viscous mass so obtained to about 16 C., reacting the cooled mixture thus obtained with about 5 parts of sulphur chloride, recovering the very vlscous tacky product thus obtained, said product being useful as a raw material in the manufacture of varnish.
15. In the manufacture of modified products from linseed oil, the process which comprises mixing 100 parts of linseed oil and 5 parts of a sodium soap of the fatty acids of linseed oil, heating the mixture to 200 C. for about 40 minutes, cooling the product thus obtained to about 160 C., mixing the cooled product with approximately 3 parts of sulphur, zinc oxide and mercaptobenzthiazole and heating the vulcanizable mass thus obtained at the vulcanizing temperature and recovering the viscous oily product thus obtained, said product being suitable in the manufacture of varnish.
16. As an improvement in the manufacture of vulcanized products from fatty oils, the process which comprises mixing together 100 parts of a fatty oil with between 5 to 20 parts of a soap,'
said soap being a salt of fatty acids and a metal of the class consisting of alkali metals, alkaline earth metals, magnesium and zinc, heating the mixture to a temperature of at least 200 C. until a thickened, bodied oil product is obtained, adding to the bodied oil thus obtained, a vulcanizing agent of the class consisting of sulphur and sulphur chloride, and then subjecting said mixsaidsoap being a salt of fatty acids and a metal 5 to 20 per cent of an alkali metal soap of the fatty acids of linseed oil, the said soap enhancing the body obtained by heat-bodying said oil.
20. As a new product, a non-oxidized, vulcanized, heat-bodied faty oil, heat-bodied at temperatures of at least 200 C., obtained from a mix ture of a fatty oil and a soap by the process of claim 16, the body of said oil being due partly to heat-bodying, partly to the presence of said soap and partly to vulcanization. V
21. As an improvement in themanufacture of thickened heat-bodied oil products from fatty oils, the process which comprises mixing a drying fatty oil with a soap, said soap being an alkali metal salt of the fatty acids of a drying fatty oil, heating the mixture at temperatures sufiicient to thicken and heat-body the same until .said thickened, heat-bodied oil products are produced, said temperature being at least 200 C.
22. As an improvement in the manufacture of vulcanized and thickened, heat-bodied oil products from fatty oils of the drying type, the two step process which comprises mixing a drying fatty oil with a soap, said soap being an alkali metal salt of the fatty acids of a drying fatty oil, heating the mixture at temperatures sufiicient to thicken and'heat-body the same until a thickened, heat-bodied oil is obtained, said temperature being at 200 C. and then mixing the bodied oil thus obtained with a vulcanizing agent and heating the mixture of bodied oil and vulcanizing agent to temperatures sufiicient to effect reaction and vulcanization and recovering the vulcanized and thickened heat-bodied oil product thus obtained.
23. As an improvement in the manufacture of oil products from drying oils, said oil products being suitable for making quick drying varnishes, the 2-step process which comprises mixing a soap with a drying fatty oil, heating the mixture to at least 200 C. until a thickened bodied oil is obtained and then mixing said thickened bodied oil with sulphur and a vulcanization accelerator, heating the vulcanizable mass thus obtained to vulcanizing temperatures and recovering said oil products.
24. As an improvement in the manufacture of bodied oil products from drying fatty oils, the'2- step process which comprises first producing a thickened bodied oil by mixing a drying fatty oil with alkali metal soap of the fatty acids of a drying oil and heating the mixture to at least 200 C. until a thickened bodied oil is produced, and then vulcanizingsaid thickened bodied oil by mixing said bodied oil with sulphur, an activator and a vulcanization accelerator and heating the vulcanizable mass thus obtained to vulcaniz temperatures, thereby producing said bodied oil products.
25. As an improvement in the manufacture of bodied oil products from drying fatty oils, the 2- step process which comprises first producing a thickened bodied oil containing dispersed therein an alkali metal soap of the fatty acids of a drying oil by heating a mixture of said fatty oil and said soap to at least 200 C. and then vulcanizing said thickened bodied oil with sulphur in the presence of an organic vulcanization accelerator thereby producing said bodied oil products.
26. As an improvement in the manufacture of vulcanized bodied oil products useful as rubber substitutes, varnish ingredients and the like from fatty oils, the improvement which comprises substantially bodying the fatty oil, prior to vulcanization, by mixing 100 parts of said oil with 2 to 10 parts of a soap and heating the mixture to at least 200 0.
27. As an improvement in the manufacture of vulcanized bodied oil products from fatty oils, the
ing the fatty oil, prior to vulcanization, by means of heat in the presence of a soap, the amount of soap, temperature and time of heating being sufficient to substantially body said oil, said temperatures being at least 200 C., thus producing vulcanized bodied oil products having a greater body.
28. The process of claim 1 wherein said soap is a soap of an alkaline earth metal. a
29. The process of claim 1 wherein said fatty oil is a thickened, modified fatty oil, thickened and modified prior to admixture with said soap. 30. The process of claim 16 wherein said fatty oil is a thickened, modified fatty oil.
miszn AUER. LAJOS SUSZ'I'IEIK.
, improvement which comprises substantially body-
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US1963065A true US1963065A (en) | 1934-06-19 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2428901A (en) * | 1947-10-14 | Polymerization nucleus fob | ||
US2433831A (en) * | 1942-12-04 | 1948-01-06 | Auer Laszlo | Aqueous dispersions of vulcanized fatty oils |
US2498133A (en) * | 1950-02-21 | Treatment of polyene compounds | ||
US20070209552A1 (en) * | 2004-08-12 | 2007-09-13 | Wacker Chemie Ag | Rheology control of pickering emulsions by electrolytes |
-
0
- US US1963065D patent/US1963065A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2428901A (en) * | 1947-10-14 | Polymerization nucleus fob | ||
US2498133A (en) * | 1950-02-21 | Treatment of polyene compounds | ||
US2433831A (en) * | 1942-12-04 | 1948-01-06 | Auer Laszlo | Aqueous dispersions of vulcanized fatty oils |
US20070209552A1 (en) * | 2004-08-12 | 2007-09-13 | Wacker Chemie Ag | Rheology control of pickering emulsions by electrolytes |
US8586639B2 (en) * | 2004-08-12 | 2013-11-19 | Wacker Chemie Ag | Rheology control of Pickering emulsions by electrolytes |
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