NO165757B - Fremgangsmaate til fremstilling av polyvinylklorid. - Google Patents
Fremgangsmaate til fremstilling av polyvinylklorid. Download PDFInfo
- Publication number
- NO165757B NO165757B NO852907A NO852907A NO165757B NO 165757 B NO165757 B NO 165757B NO 852907 A NO852907 A NO 852907A NO 852907 A NO852907 A NO 852907A NO 165757 B NO165757 B NO 165757B
- Authority
- NO
- Norway
- Prior art keywords
- poly
- dyes
- methyl
- polymers
- vinyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 35
- 238000002360 preparation method Methods 0.000 title description 3
- 229920000915 polyvinyl chloride Polymers 0.000 title description 2
- 239000004800 polyvinyl chloride Substances 0.000 title description 2
- -1 zinc metals Chemical class 0.000 claims description 346
- 239000000975 dye Substances 0.000 claims description 97
- 238000006116 polymerization reaction Methods 0.000 claims description 89
- 239000000049 pigment Substances 0.000 claims description 67
- 239000000178 monomer Substances 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 52
- 229920000642 polymer Polymers 0.000 claims description 47
- 230000015572 biosynthetic process Effects 0.000 claims description 42
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 32
- 150000002484 inorganic compounds Chemical class 0.000 claims description 26
- 229910010272 inorganic material Inorganic materials 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 25
- 239000003112 inhibitor Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 239000000084 colloidal system Substances 0.000 claims description 17
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 16
- 150000001491 aromatic compounds Chemical class 0.000 claims description 13
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229920005615 natural polymer Polymers 0.000 claims description 5
- QWUFXJHVFNRNCU-UHFFFAOYSA-N phenazin-1-amine Chemical class C1=CC=C2N=C3C(N)=CC=CC3=NC2=C1 QWUFXJHVFNRNCU-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229930192627 Naphthoquinone Natural products 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 239000000987 azo dye Substances 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002791 naphthoquinones Chemical class 0.000 claims description 4
- PLOCPSZUSGEEMU-UHFFFAOYSA-N phenanthridin-1-amine Chemical compound C1=CC=CC2=C3C(N)=CC=CC3=NC=C21 PLOCPSZUSGEEMU-UHFFFAOYSA-N 0.000 claims description 4
- RHQTYDDJBYBCQV-UHFFFAOYSA-N phenazin-2-amine Chemical compound C1=CC=CC2=NC3=CC(N)=CC=C3N=C21 RHQTYDDJBYBCQV-UHFFFAOYSA-N 0.000 claims description 4
- VZPGINJWPPHRLS-UHFFFAOYSA-N phenazine-2,3-diamine Chemical compound C1=CC=C2N=C(C=C(C(N)=C3)N)C3=NC2=C1 VZPGINJWPPHRLS-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- QTNIZGZNNIWTGC-UHFFFAOYSA-N 1,5-naphthyridin-3-amine Chemical compound C1=CC=NC2=CC(N)=CN=C21 QTNIZGZNNIWTGC-UHFFFAOYSA-N 0.000 claims description 3
- HOLGXWDGCVTMTB-UHFFFAOYSA-N 2-(2-aminophenyl)aniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1N HOLGXWDGCVTMTB-UHFFFAOYSA-N 0.000 claims description 3
- QWAGALBSTFENEE-UHFFFAOYSA-N 4-aminoacridine Chemical compound C1=CC=C2N=C3C(N)=CC=CC3=CC2=C1 QWAGALBSTFENEE-UHFFFAOYSA-N 0.000 claims description 3
- IUHYFLKPKSFRCT-UHFFFAOYSA-N 5-phenyl-1,3-oxazol-2-amine Chemical compound O1C(N)=NC=C1C1=CC=CC=C1 IUHYFLKPKSFRCT-UHFFFAOYSA-N 0.000 claims description 3
- LSLUWQIENURREM-UHFFFAOYSA-N 5-phenyl-1,3-thiazol-2-amine Chemical compound S1C(N)=NC=C1C1=CC=CC=C1 LSLUWQIENURREM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- WDVSHHCDHLJJJR-UHFFFAOYSA-N Proflavine Chemical compound C1=CC(N)=CC2=NC3=CC(N)=CC=C3C=C21 WDVSHHCDHLJJJR-UHFFFAOYSA-N 0.000 claims description 3
- LOMMDWBTANPFEJ-UHFFFAOYSA-N acridin-1-amine Chemical compound C1=CC=C2C=C3C(N)=CC=CC3=NC2=C1 LOMMDWBTANPFEJ-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000001000 anthraquinone dye Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical class C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001005 nitro dye Substances 0.000 claims description 3
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 claims description 3
- 239000001007 phthalocyanine dye Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000000985 reactive dye Substances 0.000 claims description 3
- 150000004760 silicates Chemical class 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 2
- UTXPWBKKZFLMPZ-UHFFFAOYSA-N 2-aminoacridine Chemical compound C1=CC=CC2=CC3=CC(N)=CC=C3N=C21 UTXPWBKKZFLMPZ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000005022 aminoacridines Chemical class 0.000 claims description 2
- QYOFUVIUFNSMFM-UHFFFAOYSA-N anthracene-1,4-diamine Chemical class C1=CC=C2C=C3C(N)=CC=C(N)C3=CC2=C1 QYOFUVIUFNSMFM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920001795 coordination polymer Polymers 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000007850 fluorescent dye Substances 0.000 claims description 2
- 229920000592 inorganic polymer Polymers 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- VPRFQZSTJXHBHL-UHFFFAOYSA-N phenanthrene-9,10-diamine Chemical compound C1=CC=C2C(N)=C(N)C3=CC=CC=C3C2=C1 VPRFQZSTJXHBHL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 125000005624 silicic acid group Chemical class 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 229920001959 vinylidene polymer Polymers 0.000 claims description 2
- MXCFPBMPIORJIR-UHFFFAOYSA-N 4-phenyltriazol-2-amine Chemical compound NN1N=C(C=N1)C1=CC=CC=C1 MXCFPBMPIORJIR-UHFFFAOYSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 70
- 239000011248 coating agent Substances 0.000 description 68
- 239000000243 solution Substances 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 239000002904 solvent Substances 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 23
- 241000218691 Cupressaceae Species 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- 235000010980 cellulose Nutrition 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 8
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HSHXDCVZWHOWCS-UHFFFAOYSA-N N'-hexadecylthiophene-2-carbohydrazide Chemical compound CCCCCCCCCCCCCCCCNNC(=O)c1cccs1 HSHXDCVZWHOWCS-UHFFFAOYSA-N 0.000 description 6
- 235000012745 brilliant blue FCF Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 6
- 229940097275 indigo Drugs 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 5
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 5
- 125000005605 benzo group Chemical group 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 229940050176 methyl chloride Drugs 0.000 description 5
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 5
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 4
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 4
- 241000251468 Actinopterygii Species 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229940067157 phenylhydrazine Drugs 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- MDYOLVRUBBJPFM-UHFFFAOYSA-N tropolone Chemical compound OC1=CC=CC=CC1=O MDYOLVRUBBJPFM-UHFFFAOYSA-N 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 3
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 3
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- NETSNTQRMHVIEK-UHFFFAOYSA-M sodium;2-[n-butyl-4-[[4-[butyl(2-sulfonatoethyl)azaniumylidene]cyclohexa-2,5-dien-1-ylidene]-[4-(4-ethoxyanilino)phenyl]methyl]anilino]ethanesulfonate Chemical compound [Na+].C1=CC(N(CCS([O-])(=O)=O)CCCC)=CC=C1C(C=1C=CC(NC=2C=CC(OCC)=CC=2)=CC=1)=C1C=CC(=[N+](CCCC)CCS([O-])(=O)=O)C=C1 NETSNTQRMHVIEK-UHFFFAOYSA-M 0.000 description 1
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- AXMCIYLNKNGNOT-UHFFFAOYSA-M sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfonatophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-M 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
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- KQRZWHVIXVADGL-UHFFFAOYSA-M sodium;4-[[4-(dibenzylamino)phenyl]-(4-dibenzylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]benzene-1,3-disulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC(S(=O)(=O)[O-])=CC=C1C(C=1C=CC(=CC=1)N(CC=1C=CC=CC=1)CC=1C=CC=CC=1)=C(C=C1)C=CC1=[N+](CC=1C=CC=CC=1)CC1=CC=CC=C1 KQRZWHVIXVADGL-UHFFFAOYSA-M 0.000 description 1
- UWGCNDBLFSEBDW-UHFFFAOYSA-M sodium;4-[[4-(diethylamino)phenyl]-(4-diethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]naphthalene-2,7-disulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C2=CC=C(C=C2C=C(C=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 UWGCNDBLFSEBDW-UHFFFAOYSA-M 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-N sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonic acid Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S(O)(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-N 0.000 description 1
- FTUYQIPAPWPHNC-UHFFFAOYSA-M sodium;4-[[4-[benzyl(ethyl)amino]phenyl]-[4-[benzyl(ethyl)azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]benzene-1,3-disulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=CC=CC=2)C=2C(=CC(=CC=2)S([O-])(=O)=O)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC=C1 FTUYQIPAPWPHNC-UHFFFAOYSA-M 0.000 description 1
- RBYJOOWYRXEJAM-UHFFFAOYSA-M sodium;5,9-dianilino-7-phenylbenzo[a]phenazin-7-ium-4,10-disulfonate Chemical compound [Na+].C=1C=CC=CC=1[N+]1=C2C=C(NC=3C=CC=CC=3)C(S(=O)(=O)[O-])=CC2=NC(C2=CC=CC(=C22)S([O-])(=O)=O)=C1C=C2NC1=CC=CC=C1 RBYJOOWYRXEJAM-UHFFFAOYSA-M 0.000 description 1
- WQZNLMYQHGWSHK-UHFFFAOYSA-M sodium;5-[[4-(dimethylamino)phenyl]-(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]-4-ethoxy-2-(4-methyl-2-sulfonatoanilino)benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(C)C)C(OCC)=CC=1NC1=CC=C(C)C=C1S([O-])(=O)=O WQZNLMYQHGWSHK-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- YZMCKZRAOLZXAZ-UHFFFAOYSA-N sulfisomidine Chemical compound CC1=NC(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 YZMCKZRAOLZXAZ-UHFFFAOYSA-N 0.000 description 1
- 229960001975 sulfisomidine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RQBFBRABPQPCHC-UHFFFAOYSA-N tetrabenz(a,c,h,j)anthracene Chemical compound C1=CC=CC2=C(C=C3C4=CC=CC=C4C=4C(=CC=CC=4)C3=C3)C3=C(C=CC=C3)C3=C21 RQBFBRABPQPCHC-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- AEQDJSLRWYMAQI-KRWDZBQOSA-N tetrahydropalmatine Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3C[C@H]2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-KRWDZBQOSA-N 0.000 description 1
- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- YXVCLPJQTZXJLH-UHFFFAOYSA-N thiamine(1+) diphosphate chloride Chemical compound [Cl-].CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N YXVCLPJQTZXJLH-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- MDYPJPPXVOPUNX-UHFFFAOYSA-N thiochromen-2-one Chemical compound C1=CC=C2SC(=O)C=CC2=C1 MDYPJPPXVOPUNX-UHFFFAOYSA-N 0.000 description 1
- JADVWWSKYZXRGX-UHFFFAOYSA-M thioflavine T Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C1=[N+](C)C2=CC=C(C)C=C2S1 JADVWWSKYZXRGX-UHFFFAOYSA-M 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 210000001541 thymus gland Anatomy 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- DOKTZMKBGPRAPB-UHFFFAOYSA-N trimethyl(naphthalen-1-yl)azanium Chemical class C1=CC=C2C([N+](C)(C)C)=CC=CC2=C1 DOKTZMKBGPRAPB-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- YQEHHPFEQLDFCN-UHFFFAOYSA-K trisodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-[(2-sulfonatophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].Oc1c(N=Nc2ccccc2S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O YQEHHPFEQLDFCN-UHFFFAOYSA-K 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XAPNKXIRQFHCHN-QGOAFFKASA-N violacein Chemical compound O=C\1NC2=CC=CC=C2C/1=C(C(=O)N1)/C=C1C1=CNC2=CC=C(O)C=C21 XAPNKXIRQFHCHN-QGOAFFKASA-N 0.000 description 1
- LEJQUNAZZRYZKJ-UHFFFAOYSA-N violacein Natural products Oc1ccc2NCC(C3=CC(=C4/C(=O)Nc5ccccc45)C(=O)N3)c2c1 LEJQUNAZZRYZKJ-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
- 235000019143 vitamin K2 Nutrition 0.000 description 1
- 239000011728 vitamin K2 Substances 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
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
- C08F2/00—Processes of polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
Den foreliggende oppfinnelse vedrører en fremgangsmåte
til fremstilling av en vinylkloridpolymer ved suspensjonspolymerisasjon eller emulsjonspolymerisasjon av vinylkloridmonomer eller en blanding av vinylkloridmonomer og en vinylmonomer som er kopolymeriserbar med vinylkloridmonomeren i et vandig medium, hvor polymerisasjonen utføres i en polymerisasjonsreaktor hvis innervegg og deler av utstyr i denne som kan komme i kontakt med monomeren under polymerisasjonen på forhånd belegges med en flakdanningshindrer som inneholder fargestoff, og/eller pigment og/eller aromatisk eller heterocyklisk forbindelse som har minst 5 konjugert indinger.
Ved fremgangsmåter til suspensjonspolymerisasjon eller emulsjonspolymerisasjon av vinylkloridmonomer eller en blanding av vinykloridmonomer og andre vinylmonomerer i nærvær av en polymerisas jonskatalysator er det et problem at polymerflak kleber til polymerisasjonsreaktorens innervegg eller til de deler av utstyret i reaktoren som kan komme i kontakt med monomeren, såsom omrører, under polymerisasjon. Flak som kleber til polymerisasjonsreaktorens innervegg etc. vil resultere i et lavere polymerutbytte og lavere kjølekapasitet hos polymerisasjonsreaktoren, og kan også forårsake såkalte fiskeøyne dannet ved at vedheftende flak skaller av polymerisasjonsreaktorens innervegg og blander seg med produktet, hvorved produktets kvalitet nedsettes. Dessuten krever fjerningen av vedheftende flak mye arbeid og tid. I tillegg absorberes ureagerte mono-
merer (vinyklorid etc.) i flakene, noe som på ufordelaktig måte kan medføre fare for at det oppstår risiko for menneskekroppen.
Når det gjelder hindring av beleggsdannelse av polymer er
det kjent på området å påføre et belegg av et kjemisk middel (heretter benevnt "flakdanningshindrer") på polymerisasjonsreaktorens innervegg. Det er foreslått forskjellige slike flak-danningshindrere. Blant de forskjellige kjente fremgangsmåter er det kjent en særlig god fremgangsmåte hvor et fargestoff og/eller pigment anvendes som flakdanningshindrer (japansk patentpublikasjon 30835/1970). Men denne fremgangsmåte er ikke alltid effektiv og sikker når det gjelder å hindre beleggsdannelse og er derved ikke alltid tilfredsstillende.
Følgelig er det et formål med den foreliggende opp-
finnelse å frembringe fremgangsmåte til fremstilling en vinylkloridpolymer, hvorved det på sikker måte kan hindres beleggs-
dannelse i løpet av polymerisasjon av vinykloridmonomer eller en blanding av vinykloridmonomer med andre vinylmonomerer.
I forsøk på å bedre fremgangsmåten ifølge ovennevnte
japanske patentpublikasjon 30835/1970 har det ifølge den foreliggende oppfinnelse vist seg at beleggsdannelse kan hindres effektivt og sikkert ved anvendelse av et fargestoff, et pigment eller en spesifikk forbindelse, som har minst 5 konjugerte 7?-bindinger, og ved styring av konsentrasjonen av kloridioner (Cl~) i reaks jonsbl?.idingen under polymerisas jonen.
Ifølge oppfinnelsen er det frembrakt en fremgangsmåte til fremstilling av en vinylkloridpolymer ved suspensjonspolymerisasjon eller emulsjonspolymerisasjon av vinykloridmonomer eller en blanding av vinylkloridmonomer og en vinylmonomer som er kopolymeriserbar med vinylkloridmonomeren i et vandig medium,
hvor polymerisasjonen utføres i en polymerisasjonsreaktor hvis innervegg og deler av utstyr av denne som kan komme i kontakt med monomeren under polymerisasjonen på forhånd er belagt med en flakdanningshindrer som inneholder fargestoff, og/eller pigment og/eller aromatisk eller heterocyklisk forbindelse som har minst 5 konjugerte rr-b indinger, og den s;r karakterisert ved at kloridionekonsentrasjonen i reaksjonsblandingen styres slik at den er høyst 100 ppm.
Ytterligere trekk ved fremgangsmåten fremgår av krav 2-14.
Ved fremgangsmåten ifølge oppfinnelsen kan den beleggs-hindrende virkning ved hjelp av flakdanningshindreren utføres sikkert og kraftig, hvorved beleggsdannelse kan hindres på
effektiv måte. Følgelig er det ikke nødvendig med arbeid eller tid for fjerning av flak eller belegg, noe som muliggjør kontinuerlig anvendelse av polymerisasjonsreaktoren og særlig god driftseffektivitet. Dessuten kan polymerisasjonsreaktorens kjølekapasitet holdes konstant uten fare for at flakene skal komme inn i produktet, hvorved polymerens kvalitet kan bedres.
Generelt vil kloridionekonsentrasjonen i reaksjonsblandingen under polymerisasjon av vinykloridmonomer eller en vinylmonomerblanding som inneholder vinylkloridmonomer øke brått i innledende stadium av polymerisasjonen, hvoretter den har en tendens til å øke svakt eller bli værende på samme nivå inntil polymerisasjonen er fullført. Konsentrasjonen av klorid-ionene kan anses for å bli påvirket av forskjellige faktorer såsom innholdet av metylklorid og saltsyre i vinylmonomeren som anvendes som utgangsmateriale, temperaturen til vannet som anvendes ved chargering, graden av vakuum etter chargering etc. Det har ifølge den foreliggende oppfinnelse vist seg at den beleggsdannende virkning ved hjelp av fargestoffer, pigmenter og nevnte forbindelser som har minst 5 konjugerte ^-bindinger på sikker måte kan oppnås ved å regulere kloridionekonsentrasjonen i reaksjonsblandingen under hele polymerisasjonen til 100 ppm eller mindre, fortrinnsvis til 50 ppm eller mindre. Dersom kloridionekonsentrasjonen i reaksjonsblandingen eller polymerisasjonen overskrider 100 ppm, selv om ovennevnte flakdanningshindrer kan være påført på polymerisasjonsreaktorens innervegg etc. kan ikke dens virkning som flakdanningshindrer oppnås fullstendig, slik at beleggsdannelse ikke kan hindres på effektiv måte.
Ifølge oppfinnelsen kan en eller flere av forbindelsene fargestoffer, pigmenter og aromatiske eller heterocykliske forbindelser som inneholder minst 5 konjugerte tr-bindinger (heretter benevnt forbindelser som inneholder konjugerte Tf-bindinger) anvendes alene eller i kombinasjon. Det foretrekkes imidlertid å anvende et fargestoff eller et pigment, særlig et azinfargestoff.
Fargestoffene og pigmentene som kan anvendes som flakdanningshindrer til fremgangsmåten ifølge oppfinnelsen kan eksemplifiseres ved: azofargestoffer, såsom monoazo- og polyazofargestoffer og -pigmenter, metallkompleksazofargestoffer og -pigmenter, stil-benazopigmenter, tiazolazofargestoffer o.likn.,
antrakinonfargestoffer- og pigmenter såsom antrakinon-derivater,'antronderivater o.likn.,
indigoidfargestoffer og -pigmenter, såsom indigoderivater, tioindigoderivater o.likn.,
ftalocyaninfargestoffer og -pigmenter,
karboniumfargestoffer og -pigmenter, såsom difenylmetanfargestoffer, trifenylmetanfargestoffer og -pigmenter, zanten-fargestoffer, akridinfargestoffer o.likn.,
kinoniminfargestoffer, såsom azinfargestoffer,
oksazinfargestoffer, tiazinfargestoffer o.likn.,
metinfargestoffer, såsom polymetin- eller cyaninfarge-stoffer o.likn.,
kinolinfargestoffer,
nitrofargestoffer,
benzokinon- og naftokinonfargestoffer,
naftalimidfargestoffer og -pigmenter,
perinonfargestoffer,
sulfidfargestoffer,
fluorreseren^e fargestoffer,
azoinfargestoffer, samt
reaktive fargestoffer.
Disse kan anvendes enten alene eller ved vilkårlig ønsket kombinasjon med to eller flere forbindelser. Av de ovenfor eksemplifiserte fargestoffer og pigmenter er de ovennevnte azinfargestoffer særlig foretrukne. Typiske eksempler på disse fargestoffer og pigmenter er angitt nedenfor.
Azofargestoffer og pigmenter omfatter følgende forbindelser : Monoazo- polyzaofargestoffer som f.eks. basisk gult 32, 34 og 36, basisk orange 2, 32, 33 og 34, basisk rødt 17, 18, 22, 23, 24, 32, 34, 33, 39 og 40, basisk fiolett 26 og 28, basisk blått 58, 59, 64, 65, 66, 67 og 68, basisk brun 1, 4, 11 og 12, basisk svart 8, azoindiazokomponent 4, 32, 27 og 38, dispersgult 3, 4, 5, 7, 8, 23, 50, 60, 64, 66, 71, 72, 76, 78 og 79, dispersorange 1, 3, 5, 13, 20, 21, 30, 32, 41, 43, 45, 46, 49, 50 og 51, dispersrødt 1, 5, 7, 12, 13, 17, 43, 52, 54, 56, 58, 60, 72, 73, 74, 75, 76, 80, 82, 84, 88, 90, 97, 99, 101, 103, 113, 117, 122, 125, 126, 128 og 129, dispersfiolett 10, 24, 33, 38, 41, 43 og 96, dispersblått 85, 92, 94 og 106, dispersbrunt 3 og 5, disperssvart 1, 2, 10, 26, 27, 28, 29, 30 og 31, løsningsmiddelsgult ("Solvent Yellow") 2, 6, 14, 15, 16, 19, 21 og 56, løsningsmiddelsorange 1, 2, 5, 6, 14 og 45, dispersrødt 1, 3, 23, 24, 25, 27 og 30, dispersbrunt 3, 5 og 20, disperssvart 3, pigmentgult 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73 og 83, pigmentorange 1, 2, 5, 13, 14, 15, 16, 17, 24 og 31, pigmentrødt 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 112, 114 og 168, pigmentblått 25, pigmentgrønt 10, pigmentbrunt 1 og 2, pigmentsvart 1, direktegult 1, 8, 11, 12, 24, 26, 27, 28, 33, 44, 50, 58, 85,
.86, 87, 88, 89, 98, 100 og 110, direkteorange 1, 6, 8, 10, 26, 29, 39, 41, 49, 51, 57, 102 og 107, direkterødt 1, 2, 4, 13,
17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230 og 231, direktefiolett 1, 7, 9, 12, 22, 35, 51, 63, 90, 94 og 98, direkteblått 1, 2, 6, 8, 15, 22, 25, 71, 76, 77, 78, 80, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 203, 207, 225, 236, 237, 246, 248 og 249, direktegrønt 1, 6, 8, 28, 30, 31, 33, 37, 59, 63, 64 og 74, direktebrunt IA, 2, 6, 25, 27, 44, 58, 59, 101, 106, 173, 195, 195, 209, 210 og 211, direktesvart 17, 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 94, 105, 106, 107, 108, 112, 113, 117, 118,
132, 133 og 146, syregult 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 61, 70, 72, 75, 76, 78, 79, 110, 127, 131, 135, 1541, 142, 164 og 165, syreorange 1, 7, 8, 10, 19, 20, 24, 28, 33, 41, 43, 45, 51, 56, 63, 64, 65, 67 og 95, syrerødt 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 57, 75, 77, 85, 88, 89, 97,106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 249, 252, 254, 257, 262,
265, 266, 274, 276, 282, 283 og 303, syrefiolett 7, 11, 97 og 106, syreblått 29, 60, 92, 113,, 117 og 120, syregrønt 19, 20
og 48, syrebrunt 2, 4, 13, 14, 20, 53, 92, 100, 101, 236, 247, 266, 268, 276, 277, 282, 289, 301 og 302, syresvart 1, 7, 24, 26, 29, 431, 44, 76, 77, 94, 109 og 110, beisfargestoffgult 1, 3, 5, 23, 26, 30, 38 og 59, beisfargestoffgult 1, 3, 5, 23, 26, 30, 38 og 59, beisfargestofforange 1, 4, 5, 6, 8, 29 og 37, beisfargestoffrødt 7, 9, 17, 19, 21, 26, 30, 63 og 89, beisfargestofffiolett 5 og 44, beisfargestoffblått 7, 13, 44, 75 og 76, beisfargestoffgrønt 11, 15, 17 og 47, beisfarge-stoffbrunt 1, 14, 15, 19, 21, 33, 38, 40, 52 og 87, beis-fargestoffsvart 1, 3, 7, 9, 11, 17, 26, 32, 38, 43, 44, 51, 54, 65, 75, 77, 84, 85, 86 og 87, matfargestoffgult 3 og 4, matfargestoffrødt 7 og 9.
Metallkoraplekszaofargestoffer som f.eks. løsnings-middelsgult 61 og 80, løsningsmiddelsorange 37, 40 og 44, løsningsmiddelsrødt 8, 21, 83, 84, 100, 109 og 121, løsningsmiddelsbrunt 37, løsningsmiddelssvart 23, syresvart 51, 52, 58, 60, 62, 63, 64, 67, 72, 107, 108, 112, 115, 118, 119, 121, 122, 123, 131, 132, 139, 140, 155, 156, 157, 158, 159 og 191, syregult 59, 98, 99, 111, 112, 114, 116, 118, 119, 128, 161, 162 og 163, syreorange 74, 80, 82, 85, 86, 87, 88, 122, 123 og 124, syrerødt 180, 183, 184, 186,, 194, 198, 199, 209, 211, 215, 216, 217, 219, 256, 317, 318, 320, 321 og 322, syrefiolett 75 og 78, syreblått 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 184, 187, 192, 199, 229, 234 og 236, syregørnt 7, 12, 35, 43, 56, 57, 60, 61, 65, 73, 75, 76, 78 og 79, syrebrunt 19, 28, 30, 31, 39, 44, 45, 46, 48, 224, 225, 226, 231, 256, 257, 294, 295, 296, 297, 299 og 300, direktegult 39, direktefiolett 47 og 48, direkteblått 90, 98, 200, 201, 202 og 226 samt direktebrunt 95, 100, 112 og 170. Stilbenazofargestoff som f.eks. er direktesvart 62, og tiazolazofargestoffer som f.eks. er direkterødt 9 og 11.
Antrakinonfargestoff er og -pigmenter omfatter følgende forbindelser.
Antrakinonderivater som f.eks. basisk fiolett 25, basisk blått 21, 22, 44, 45, 47, 54 og 60, azoindiazokomponent 36, kypegult ("Vat Yellow") 2, 3, 10, 20, 22 og 33, kypeorange 13 og 15, kyperødt 10, 13, 16, 31, 35 og 52, kypefiolett 13 og 21, kypeblått 4, 6, 8, 12, 14, 64, 66, 67 og 72, kypegrønt 8, 13, 43, 44 og -45, kypebrunt 1, 3, 22, 25, 39, 41, 44, 46, 57, 68, 72 og 73, kypesvart 8, 14, 20, 25, 27, 36, 56, 59 og 60, dispersorange 11, dispersrødt 4, 9, 11, 15, 53, 55, 65, 91, 92, 100, 104, 116 og 127, dispersfiolett 1, 4, 8, 23, 26, 28, 30 og 37, dispersblått 1, 3, 5, 6, 7, 20, 26, 27, 54, 55, 56, 60, 61, 62, 64, 72, 73, 75, 79, 81, 87, 90, 91, 97, 98, 99, 103, 104 og 105, dispersgult 51, løsningsmiddelsgrønt 3, pigmentrødt 83 og 89, pigmentblått 22, syrefiolett 31, 34, 35, 41, 43, 47, 48, 51, 54, 66 og 68, syreblått 23, 25, 27, 40, 41, 43, 45, 54, 62, 72, 78, 80, 82, 112, 126, 127, 129, 130, 131, 138, 140, 142, 143, 182, 183, 203, 204 og 205, syregrønt 25, 27, 28, 36, 40, 41 og 44, syrebrunt 27, syresvart 48 og 50, beisfargestoffrødt 3 og 11, beisfargestoff blått 8 og 48, beisfargestoff 13, pigmentfiolett 5.
Antronderivater som f.eks. kypegult 1 og 4, kypeorange 1, 2, 3, 4 og 9, kypefiolett 1, 9 og 10, kypeblått 18, 19 og 20, kypegrønt 1, 2, 3 og 9, kypesvart 9, 13, 29 og 57, kyperødt 13, syrerødt 80, 82 og 83.
Indigoidfargestoffer og -pigmenter som omfatter følgende forbindelser.
Indigoderivater som f.eks. kypeblått 1, 3, 5, 35 og 41, redusert kypeblått 1, pigmentfiolett 19 og 122, syreblått 74 og 102, løseliggjort kypeblått 5 og 41, løseliggjort kypesvart 1, matevareblått 1 og'
tioindigoderivater som kypeorange 5, kyperødt 1, 2 og 61, kypefiolett 2 og 3, pigmentrødt 87 og 88, kypebrunt 3.
Ftaloncyaninfargestoffer og -pigmenter kan f.eks. omfatte løsningsmiddelsblått 55, pigmentblått 15, 16 og 17, pigment-grønt 36, 37 og 38, direkteblått 86 og 199, samt beisblått ("Mordant blue") 58.
Karbonfargestoffer og -pigmenter omfatter følgende forbindelser: Difenylmetanfargestoffer som f.eks. basisk gult 2,
trif e.nylmetanf argestof fer som f. eks. basisk rødt 9, basisk fiolett 1, 3 og 14, basisk blått 1, 5, 7, 19, 26, 28,
29, 40 og 41, basisk grønt 1 og 4, løsningsmiddelsfiolett 8, løsningsmiddelsblått 2 og 73, pigmentfiolett 3, pigmentblått 1, 2 og 3, pigmentgrønt 1, 2 og 7, direkteblått 41, syrefiolett 15 og 49, syreblått 1, 7, 9, 15, 22, 83, 90, 93, 100, 103 og 104, syregrønt 3, 9 og 16, kypefiolett 1, kypeblått 1, 29 og 4.7, matvarefiolett 2, matvareblått 2, matvaregrønt 2,
xantenfargestoffer som f.eks. basisk rødt 1, løsnings-middelsrødt 49, pigmentrødt 81 og 90, pigmentfiolett 1, 2 og 23, syrerødt 51, 52, 87, 92 og 94, kyperødt 15 og 27, samt matvarerødt 14,
akridinfargestoffer som f.eks. basisk orange 14 og 15. Kinoiminfargestoffer omfatter følgende forbindelser:
Azinfargestoffer som f.eks. basisk rødt 2, basisk svart
2, løsningsmiddelssvart 5 og 7, syreblått 59, syresvart 2, oksi azinfargestoffer som f.eks. basisk blått 3, direkteblått 106 og 108,
tiazinfargestoffer som f.eks. basisk gult 1, basisk blått 9, 24 og 25.
Metinfargestoffer omfatter følgende forbindelser: Polymetin-(eller cyanin-) fargestoffer som f.eks. basisk gult 11, 13, 14, 19, 21, 25, 28, 33 og 35, basisk orange 21 og 22, basisk rødt 12, 13, 14, 15, 27, 29, 35, 36 og 37 og basisk fiolett 7, 15, 21 og 27.
Kinonlinfargestoffer som f.eks. basisk grønt 6, dispersgult 54 og 56, løsningsmiddelsgult 33 og syregult 3.
Nitrofargestoffer som f.eks. dispersgult 1, 33, 39, 42, 49 og 54, samt syregult 1.
Benzokinon- og naftokinonfargestoffer som f.eks. dispersblått 58 og 108, og syrebrunt 103, 104, 106, 160, 161, 165 og 188.
Naftalimidfargestoffer og -pigmenter som f.eks. pigment-rødt 123, kypefiolett 23 og 39, samt syregult 7.
Perinonfargestoffer som f.eks. kypeorange 7 og 15.
Sulfidfargestoffer kan f.eks. omfatte løseliggjort svovelgult 2, svovelgult 4, svovelorange 3, svovelrødt 2, 3, 5 og 7, løseliggjort svovelblått 15, svovelblått 2, 3, 4, 6, 7, 9 og 13, svovelgjørnt 2, 3, 6, 14 og 27, løseliggjort svovelbrunt 1 og 51, svovelbrunt 7, 12, 15 og 31, svovelsvart 1, 2, 5, 6, 10, 11 og 15, kypegult 35, 42 og 43, samt kypeblått 43 og 56.
Fluorescerende fargestoffer kan f.eks. omfatte de fluorescerende oppfriskningsmidler 14, 22, 24, 30, 32, 37, 45, 52, 54, 55, 56, 84, 85, 86, 87, 90, 91, 104, 112, 121, 134, 135, 153, 162, 163, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 og 177.
Azoinfargestoffer kan f.eks. omfatte azoindiazokomponent 17, 20, 22, 24, 26, 31, 35, 41, 47, 48, 109 og 121, azoin-koplingskomponent 2, 3, 4, 5, 7, 8, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20, 23, 26, 28, 29, 35, 36, 37, 41 og 108, azoinbrunt 2, 7, 11 og 15, azoinsvart 1 og 5, azoingult 1 og 2, azoin-orange 2, 3 og 7, azoinrødt 1, 2, 6, 9, 16 og 24, azoinfiolett 1, 2, 6, 7, 9 og 10, samt azoingrønt 1.
Reaktive fargestoffer kan f.eks. omfatte reaktivt gult 1, 2, 3, 4, 6, 7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37 og 42, reaktivt orange 1, 2, 4, 5, 7, 13, 14, 15,
16, 18, 20, 23 og 24, reaktivt rødt 1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 49, 50, 58, 59, 63 og 64, reaktivt fiolettt 1, 2, 4, 5, 8, 9 og 10, reaktivt
blått 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21,
25, 26, 27, 28, 29, 31, 32, 33, 34, 37, 38, 39, 40, 41, 43, 44 og 46, reaktivt grønt 5, 6, 7 og 8, reaktivt brunt 1, 2, 5, 7, 8, 9, 10, 11, 14 og 16, reaktivt svart 1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14 og 18.
Ytterligere eksempler på pigmenter er uorganiske pigmenter som kromgult, sinkkromattype ZTO, blymønje, jernoksyd-pulver, sinkhvitt, aluminiumpulver og sinkpulver.
Den konjugerte w-binding i forbindelsen med konjugerte Tr-bindinger, som kan anvendes som bakdanningshindrer til fremgangsmåten ifølge oppfinnelsen omfatter to eller flere dobbelt-hindringer og/eller trippelbindinger i konjugert forhold. Og de aromatiske forbindelser som har minst 5 konjugerte V-bindinger som kan anvendes ifølge den foreliggende oppfinnelse kan omfatte benzenderivater, naftalenderivater, aromatiske forbindelser med flere ringer, kinoner, aromatiske forbindelser som ikke er av benzentype etc. som har minst fem konjugerte ^-bindinger. Heterocykliske forbindelser som inneholder minst 5 ^-bindinger kan. f.eks. være oksygenholdige heterocykliske forbindelser, nitrogenholdige heterocykliske forbindelser, svovelholdige heterocykliske forbindelser, bicykliske forbindelser som har ett nitrogenatom felles, alkaloider etc, som har minst 5 konjugerte ir-bindinger. Spesielle eksempler på disse forbindelser er angitt nedenfor.
De aromatiske forbindelser som inneholder minst 5 ir-bindinger omfatter følgende forbindelser: For det første benzenderivater som f.eks. fenoler og derivater derav, såsom 2,6-di-tert-butylfenylfenol, katekol-ftalin, 2,2-difenylolpropan, 3,7-dioksy-10-metylxanten, fenol-ftalein, 7-oksy-2,4-dimetylbenzopyrooksoniumklorid, oksyan-trakinon, purpurogallin, gallein, difenyleter, a-metoksyfenazin, klorglukosid, 2,3-dioksyantrakinon, 5,7-dioksy-4-metylkumarin, dioksyakridon, salicylsyre, a-hydrindon, B-fenyl-butyrofenyl, N-2,4-dinitrofenyl-N-fenylhydroksylamin, 1-(4-nitrofenyl)-3,5-dimetylpyrazol, 9,10-difenylfenantren og acetofenon,
aromatiske aminer og derivater derav, såsom N-fenyl-p-benzokinondiamin, kinolin, safranin B, rosanilin, utløselig indiurin, analinsvart, para-rosanilin, metylfiolett, metyl-orange, metylrødt, indigo, karbazol, metylenblått,
o-fenantrolin,. p-fenantrolin, 3,6-diaminoakridin, "Indanthrene Scarlet" 2G, 4-aminodifenylamin, akridingult, 3-aminofeno-tiazin, N'-difenyl-p-fenylendiamin, rodarain, 7-amino-4-metylkumarin, 2-aminofenazin, fenotiazin, difenylamin, N-metylfenylamin, N-fenyltolylamin, ditolylamin, 2-oksy-4-metylkinonlin, hansagult G, N,N'-difenylformamidin, fenan-trofenazin, bismarckbrunt G, 2,3-diaminofenazin, 2-aminodifenylamin, krysodin R, 2,3,7,8-tetraaminofenanzin, amino-fenoksazon, oksyfenok^azon, trifenylendioksazin, 2,4-dinitro-fenoksazin, 2<*>,4'-dinitro-4-oksy-3-aminofenylamin,
nitro- og nitrosoderivater som p-nitrosodifenylhydroksy-lamin, fenanzin, fenazinoksyd, l-fenylazo-2-naftol, 4-nitro-xanton, 4'-nitroso-2-nitrodifenylamin,
fenylhydroksylaminderivater som 4,4 *-dinitrodifenylamin, oksalsyre-bis(e-fenylhydrazin), malonsyre-bis(B-fenylhydrazin), ravsyre-bis(B-fenylhydrazin), ftalsyre-bis(B-fenylhydrazin),
aromatiske halogenider som bifenylklorid,
aromatiske aldehyder som 2-fenyl-l-benzyl-benzimidazol, leukomalakitgrønt, malakitgrønt, tetraklorhydrokinonmono-benzoat, benzoflavin, 2-fenylbenztiazol, 4-benzhydrylbenzal-dehyd, bisfenylhydrazon, bis(4-nitrofenylhydrazon),
aromatiske ketoner som trifenylisooksazol, bensofenon-kalium, 4-metylbenzofenon, p-tolylsyreanilid, benzosyretolui-did, durylfenylketon, 2,4,2',4•-tetrametylbenzofenon, kalkon-fenylhydrazon, 1,3,5-trifenylpyrazolin, dinitrobenzyl,
benzosyrer, ftalsyrer og derivater derav, såsom kinizalin og nitrodifenyleter,
benzenderivater som inneholder en substituent i tillegg til aldehydgruppen, såsom disalicylaldehyd, koumarin, 2-ben-zoylkoumaron, l-oksy-2,4-dimetylfluoron, 3-fenylkoumaron, etylkoumarin-3-karboksylat, 3-acetylkoumarin, hydrovaniloin, 4-oksy-3-metoksy- n)-nitrostyren, a- (nitrofenyl) -6-benzoyl-etylenoksyd, dinitrofenylindazol, 5-klor-3-(4-oksyfenyl)-antranil, 3-nitroakridon, 6-nitro-3-fenylantranil, 2,8-dimetyl-1,9-antrazolin, karbostyril, 1,3-dioksyakridin, oksykinakridin, florkinyl, 2-metyl-kinazolin, 3-acetyl-2-metylkinolin, l-oksy-3-fenylkinolin, 3-nitrokinolin, kinolin-2,3-dikarboksylsyreester,
benzenderivater som har en ytterligere substituent som er
forskjellig fra acylgruppen, såsom 7-oksyflavanon, 7-oksy-flavon, 7,8-dioksyflavon, 7-acetoksy-4-metyl-3-fenylkoumarin, 7,8-diacetoksy-4-metyl-3-fenyl-koumarin, o-oksybenzofenon, xanton, 2-fenylbenzoaoksazol, m-oksybenzofenon, p-oksybenzofenon, 2-benzoylxanton, 2,4-dioksybenzofenon, 2,5-dioksybenzofenon, 2,2'-dioksybenzofenon, xanten, aurin, trioksy-benzofenon, 6,7-dimetoksy-3-fenylkoumaron, o-nitrobenzofenon, m-nitrobenzofenon, 4,4'-dibenzoylazoksybenzen, 2-(2-amino-f enyl)-4-metylkinon, 2-oksy-4-metylk.inon, akridon, 2,4-dimetyl-kinazolin, 3-cyan-2-oksy-4-metylkinolin, fluoren, anhydro-(2-aminobenzofenon)dimer, 2-oksy-3-fenylindazol, 3-fenyl-indazol, 2-fenylbenzimidazol, 2-metyl-8-benzoylkinolin, 2-metyl-4-fenykinolin, 4-fenyl-2-kinazolon, aminobenzofenon, klorbenzofenon, 4-fenylbenzo-1,2,3-triazin-3-oksyd, diamino-benzofenon, 7-metyl-3-fenyl-4,5-benzo-l,2,6-oksydiazin, 4,4'-bisdimetylaminobenzofenon, 4,4'-bisdimetylaminobenzofenon-imid, 2,4-dinitro-9-fenylakridin og 4,4'-dibenzoyldifenyl,
benzen- og toluenderivater som har tre eller flere forskjellige substituenter, såsom tetrametoksyindigo, 5,6,5',6'-bismetylendioksyindigo, 7-acetoksy-8-metoksy-3-(2-nitrofenyl)karbostyril, 2,2'-dinitrodifenyldisulfid-4,4'-dialdehyd, 6-klor-3-benzoylflavon og 1,3,8-trinitrofenoksazin,
aralkylforbindelser som 9-benzylakridin,
diazo- og azoforbindelser som azobenzen, azotoluen, 2,2-dimetoksyazobenzen, 4,4'-diklorazobenzen, 1,1'-azonaftalen, 2,2<*->dioksyazobenzen, 2,2'-dioksy-5,5'-dimetylazobenzen, p-bromazobenzen, p-nitroazobenzen, fenoazoksyd,
aroma.tiske umettede forbindelser som 2,3,4,5-tetrafeny1-cyklopentan-2-en-l-on, 1,2,3-trifenylenazulen, 2,2<1->dimetyl-difenylacetylen, 4,4<1->dietyldifenylacetylen, 3,4,3',4'-tetra-metyldifenylacetylen, 2,2'-diklordifenylacetylen, 2,2'-dibrom-difenylacetylen, 2-nitrodifenylacetylen, 2,2'-dinitrodifenyl-acetylen, 2,2<1->diaminodifenylacetylen, 2,2'-dimetoksy-di-fenylacetylen, stilben, a-metylstilben, a-etylstilben, a,B-dimetylstilben, a,8-dietylstilben, a,B-diklorstilben, a,3-dibromstilben, 2-klorstilben, 4,4'-dijodstilben, a-nitro-stilben,a,B-dinitrostilben, 2,4,6-trinitrostilben, 2-aminostilben, 2,2'-diaminostilben,
4,4'-di(dimetylamino)stilben, 2,2'-dicyanostilben,
2-oksystilben, 2-metoksystilben, 2,2'-dioksystilben, 2,2'-dimetoksystilben, 4,4<1->dialkoksystilben og 3,5,2',4'-tetra-oksystilben, samt
polyfenyler og derivater derav, såsom bifenyl, trifenyl, tetrafenyl, pentafenyl, heksafenyl, heptafenyl, oktafenyl, novafenyl, dekafenyl etc.
Deretter naftalenderivater som:
Alkyl, alkenyl- og fenylnaftalener, såsom 1-metyl-naftalen, 2-metylnaft^len, 1-etylnaftalen, 2-etylnaftalen, 1,2-dimetylnaftalen, 1,4-dimetylnaftalen, 1,5-dimetylnaftalen, 1,6-dimetylnaftalen, 1,7-dimetylnaftalen, 2,3-dimetylnaftalen, 2,6-dimetylnaftalen, 2,7-dimetylnaftalen, 1-propylnaftalen, 1-isopropylnaftalen, 2-isopropylnaftalen, trimetylnaftalen, diisopropylnaftalen, 1-vinylnaftalen, 2-vinylnaftalen, 1- propenylnaftalen, 1-allylnaftalen, 1-isopropenylnaftalen, 2- isopropenylnaftalen, 1-fenylnaftalen, 2-fenylnaftalen, 1,4-difenylnaftalen, 1,2,4-trifenylnaftalen,
dinaftyler som 1,1'-dinaftyl, 1,2'-dinaftyl og 2,2'-dinaftyl,
naftylarylmetaner som 1-benzylnaftalen, 2-benzylnaftalen, 1-(a-klorbenzyl)naftalen, 1-(a,a-diklorbenzyl)naftalen, difenyl-a-naftylmetan, difenyl-8-naftylmetan, 1,8-dibenzyl-naftalen, di-a-naftylmetan,a-naftyl-Bnaftylmetan, di-S -naftyl-metan,
naf tylaryletaner som 1-f enetylnaf talen, 1, 2-di-a-naftyletan, 1,2-di-a-naftyletan, 1,1-a-dinaftyletan,
hydronaftalener som 1,2-dihydronaftalen, 1,4-dihydronaftalen og 1,2,3,4-tetrahydronaftalen,
nitronaftalener og derivater derav såsom dinaftyl-pyridanzin, 7,8-benzokinon, 5,6-benzokinon, naftazarin, di-perimidin, nitrometylnaftalen.- nitrofenyl-
naftalen, halogen-nitronaftalen, halogen-dinitronaftalen, nitrosonaftalen, dinitrotetralin, dibenzofenazin, metylbenzo-indol, 9-klor-l-azaantracen, kinolylkinolin, 1,2,3-triaza-fenaren, perimidon, perimidin, dibenzoakridin, benzofenazin-12-oksyd, diaminonaftalen, triaminonaftalen, tetraamino-naftalen, N-etyl-a-naftylamin, N-metylnaftylamin, N,N-dimetyl-naftylamin, N-mety1-N-etylnaftylamin, M-metyl-N-etylnaftylamin, trimetylnaftylammoniumsalt, N-fenylnaftylamin, N-benzylnaftyl-
amin, N-naftyletylendiamin, N-naftylglysin, N-e-cyanometyl-naftylamin, N-acetylnaftylamin, N-formylnaftylamin, N-ben-zoylnaftylamin, N-ftaloylnaftylamin, aminometylnaftalen, nitronaftylamin, dinitronaftylamin, halogen-nitronaftylamin, aminotetralin og diaminotetralin,
halogenerte naftalener som 1-fluornaftalen, 1-klornaf-talen, l-klor-3,4-dihydronaftalen, 1-jodnaftalen, 1-bromnaf-talen, l-klor-4-klormetylnaftalen, l-brom-2-(brommetyl)naftalen, 1,4-difluornaftalen, 1,2-diklornaftalen, 1,6-diklornaftalen, 1,7-diklornaftalen, 1,5-diklornaftalen, 1,3-diklornaftalen, 2.3- diklornaftalen, 1,4-dibromnaftalen, 1,4-dijodnaftalen, perylen, 1,2,3-triklornaftalen, 1,2,4-tribromnaftalen, 1,2, 3.4- tetraklornaftalen, 1,4,5-tribrdm-3,8-dimetylnaftalen, 1,3,6,7-tetraklornaftalen, 1,3,5,8-tetrabromnaftalen, 1,2,3,4,5-pentaklornaftalen,
naftylhydroksylaminer, naftylpyraziner og naftylureaer, såsom a-naftylhydroksylamin, N'-fenyl-N-a-naftyl-N-oksyurea, B-naftyltiohydroksylamin, N-nitroso-a-naftylhydroksylamin, neokupferron, 2-oksy-l,1'-azonaftalen, a-naftylhydrazin, 1,2-dibenzokarbazol, 4,4-diamino-l,1 *-binaftyl, 3,4-benzokarbazol, 2,2'-diamino-1,1'-binaftyl, N'-acetyl-N-e-naftylhydrazin, N'-lauroyl -N-B~naftoylnydrazin, N'-fenyl-N-a-naftylhydrazin, N'-(2,4-dinitrofenyl)-N-a-naftylhydrazin, 2-a-nafty1-5-nitrobenztriazol, N,N<1->di-a-naftylhydrazin, 1,1'-diamino-2,2'-binaftyl, N,N'-di-5-tetralylhydrazin, N'-(2,4-dinitrofenyl)-N-fi-naftylhydrazin, 2-B-naftyl-5-nitrobenztriazol, N'-trifenylmetyl-N-B-naftylhydrazin, N,N'-8-di-8-naftylhydrazin, N-metyl-N-(2,4-dinitro-l-nafty1)-hydrazin, 2-amino(nafto-1',2'-:4,5-tiazol), 1,2:5,6-dibenzofenazin, 2-amino-(nafto-2',1':4,5-tiazol), 2,3-dihydrazinonaftalen, 2-fenyl-1,3-bisbenzylidenamino)nafto-2',3':4,5-imidazolin), N-acetyl-anaftylnitrosoamin, N-etyl-a-naftylnitrosoamin, N-fenyl-a-naftylnitrosoamin, a,a'-dinaftylnitrosoamin, ravsyre-bis(B~ naftylnitrosoamid) , N-etyl-enaftylnitrosoamin, N-fenyl-8-naftylnitrosoamin, N-acetyl-2-metyl-l-naftylnitrosoamin, 4,5-benzindazol, naftylnitrosoamin, l-nitro-2-naftylamin, a-naftyl-urea, N,N<1->di-a-naftylurea, 4-klor-l-naftylkarbamoylklorid, 2,4'-diklor(nafto-1',2':4,5-tiazol), 2-merkapto(nafto-1<1>,2': 4.5- tiazol), 2-klor(nafto-1',2':4,5-tiazol), 2-merkapto(nafto-2',1':4,5-tiazol), 2-klor(nafto-2•,1':4,5-tiazol),
aralkylforbindelser av naftalentype, såsom dibenzoantracen, acenaften, a-kloretylnaftalen, fenylnaftylklormetan, di-fenylnaftylklormetan, nitrometylnaftalen, aminometylnaftalen, (naftylmetyl)amin, a-fenyl(naftylmetyl)amin, N-benzyl(naftyl-metyDamin, tr imetyl (naf tylmetyl) ammoniumsalt, tri(naftyl-metyljamin, di(naftylmetyl)amin, ( B-naftyletyl)alkohol, di-metylnaftylkarbinol, fenylnaftylkarbinol, difenylnaftyl-karbinol, 9-fenylbenzofluoren, naftylpropylenoksyd, etyl-(naftylmetyl)eter, ff.nyl(naftylmetyl)eter, naftylacetal-dehyd, naftylaceton, w-naftylacetofenon, acenaftenon, di-hydrofenaron, fenarone, benzoindanon, naftylacetonitril, 9,9' -diklordibenzof luoren, a -n.itro-8 -naf tyletylen, Y—naf tyl-ally1alkohol,6-naftylakrolein, metyl(8-naftylvinyl)keton, naftylfenantrendikarboksylsyreanhydrid,
nafto, naftalensulfonsyrer, såsom 9-oksynaftacenkinon, 2'-naftalen-2-indoleindigo, 1-metoksynaftalen, 1-etoksynaftalen, 1-fenoksynaftalen, a-naftolsalicylsyreester, 8-naftol, a-naftol, a-naftolbenzosyreester, a-naftoleddiksyreester, fenyl-B-oksynaftylbenzaliminometan, B-naftolfenylmetylamin, metylen-di-B-naftol, dinaftopyran, 1'-naftol-2-indolindigo, 2-metoksynaftalen, 2-etoksynaftalen, N-p-oksyfenyl-2-naftyl-aminbase, 3-naftolsalicylsyreester, 2-metyl-l-naftol, 1,2-naftametylenkinon, 1,2-dioksynaftalen, naftalenindolindigo, a,B-naftofenoksazin, B,Y-naftofenoksazin, 4-oksy-10-metyl-1',2'-benzokarbazol, dioksynaftfluoran, dinaftokinon, 2,6-naftokinon, oksybenzoakridin, 9-oksy-3-dimetylaminonafto-fenoksazin, 1,2,4-trioksynaftalen, 1,4,5,6-tetraoksynaftalen, tio-a-naftol, 4-merkapto-l-naftol, 1,5-naftalenditiol, metyl-a-naftylsulfid, 1,1'-naftylsulfid, 1,1'-tiodi-2-naftol, 1,1'-naftyldisulfid, 1,1'-tiodi-l-naftol, tio-B-naftol, naftotio-indigo, l-amino-2-naftalentiol, naftotiantren, 2-merkapto-1,2-naftotiazol,
ne.f coaldehyder og derivater derav, såsom a-naftoaldehyd, 2-(2,4-dinitrofenyl)-1-(a-naftyl)etylen, 2-metyl-l-naftoaldehyd, 2,3-dimetyl-l-naftoaldehyd, 4-brom-l-naftoaldehyd, 4-nitro-l-naftoaldehyd, 2,4-dinitro-l-naftoaldehyd, 4-amino-l-naftoaldehyd, 2-oksy-l-naftoaldehyd, 1-naftalen-2'-indolindigo, 1,2-bis(2-oksy-l-naftyl)etylen, 1,2:7,8-dibenzoxantiliumklorid, 2-oksy-l-naftyletenylpyryliumsalt, 5,6-benzokoumarin, bis(2-
metyl-3-indolyl)(2-oksy-l-naftyl)metan, 4,5-benzindoksazen, 2-acetoksy-l-naftonitril, 4-metoksy-l-naftoaldehyd, l,4-bis(4-metoksy-l-naftyl)-1,3-butadien, 2-naftalen-2'-indolindigo, 3-acetyl-6,7-benzokoumarin, 4-klor-l-oksy-2-naftoaldehyd, naftalendialdehyd, 5-oksy-2-naftalenindolindigo, 5,6,7,8-tetrahydro-2-naftoaldehyd, imidklorid, naftoamid, naftoanilid, naftonitril, etyl-6-naftomidat,s-naftamidin, a-naftamidin,a-naftoamidoksim, a-naftohydrazid, naftostyryl, oksynaftonitril, 1,2:7,8-dibenzoxanton, 1,2-benzoxanton, 1,1 *-binaftylen-2,8: 8,2'-dioksyd, 2,3:6,7-dibenzoxanton, 3-oksy-2-naftoanilid, 1,3-bis(3-oksy-2-naftoyloksy)benzen, 2,4-dioksyfenyl-3-oksy-2-naftylketon, 4-arylazo-3-oksy-2-naftoanilid, 3,4-dihydronaftalen-1,2-dikarboksylsyreanhydrid, 2-aminonaftalimid, naftalo-hydrazid, a-pyridonaftalon, N-metylnaftalimid, samt
acetonaftener, benzoylnaftener, såsom 1,2:5,6-dibenzan-tracene, 2'-metyl-2,1'-metyl-2,1'-dinaftylketon, 2-metyl-l,1<1->dinaftylketon, styryl-2-naftylketon, B-naftoylaceton, 8-naf-toylacetopfenon, 1-(B-naftyl)-1-kloretylen, 2-[tris(B-cyano-etyl)acetyl]naftalen, 1,3,5-tris(B-naftyl)benzen, dimetyl-2-naftylkarbinol, 4,5:4',5'-dibenzotioindigo, styryl-l-naftylketon, B-acetonafton, 1-propionylnaftalen, 1-butylnaftalen, 1-isobutylnaftalen, 1-stearoylnaftalen, 1-benzoylnaftalen, l-o-toluylnaftalen, p-bifenyl-l-naftylketon, 1,2,5,6-dibenzan-tracen, l-acetyl-3,4-dihydronaftalen, l-acetyl-7-bromnaftalen-1-aminoacetylnaftalen, 2-aminobenzoylnaftalen, l-acetyl-2-oksynaftalen, l-acetyl-2-metoksynaftalen, l-acetyl-4-etoksynaftalen, 2-cinnamoyl-l-naftol, 7,8-benzokromon, 3-acetyl-2-metyl-7,8-benzokromon, 3,4-dimetyl-7,8-benzokoumarin, 4-metyl-3-fenyl-7,8-benzokoumarin, l-benzoyl-2-oksynaftalen, 4-oksybenzantron, 4-benzoyl-l-naftol, 3-oksy-l,2-benzofluo-renon, 2-acetyl-4-klor-l-oksynaftalen, a-naftylglyoksal, 8-naftylglyoksal, 1,4-dibenzoylnaftalen, fenyl-4-metyl-l-naftyl-diketon o.l.
Som aromatiske forbindelser med flere ringer kan det anvendes: Antracener og derivater derav, såsom antracen, 1,2-dihydroantracen, 1-klorantracen, 1,4-diklorantracen, 1,2,7-triklorantracen, 1,2,3,4-tetraklorantracen, 1-nitro-antracen, 9,10-dinitroantracen, 1-aminoantracen, 2-dimetyl-
aminoantracen, 2-anilinoantracen, 9-metylaminoantracen, 1,4-diarainoantracen, 1-oksyantracen, 9,10-dihydroantrol, 10-metylantranol, 10-fenylantranol, 10-nitroantranol, 2-amino-I-antranol, 1,2-dioksyantracen, 9,10-dioksyantracendiacetat, 1-metylantracen, 4-klor-l-metylantracen, 1,5-diklor-2-metylantracen, 9-etylantracen, 9-vinylantracen, 9-propylantracen, 9-isopropylantracen, 9-butylantracen, 9-isobutylantracen, 9-isoamylantracen, 1,3-dimetylantracen, 9,10-dietylantracen, 1-fenylantracen, 9-fenylantracen, 1,5-diklor-9-fenylantracen, 10-nitro-9-fenylantracer, 9-benzylantracen, 1-benzylhydrylantra-cen, 9,10-difenylantracen, 9,10-dibenzylantracen, 9,10-difenyl-9,10-dihydroantracen, 1-(g-naftyl)antracen, 9-(a-naftyl)-10-fenylantracen, 9,10-di(a-naftyl)antracen, 1,1'-biantryl, 2,2'-biantryl, 9,9'-biantryl, antracen-9-aldehyd, 1-acetylantracen, 9-benzoylantracen, 10-nitroantrafenon, 9,10-dibenzoylantracen, antron, 9-merkaptoantracen, 9,10-dinatrium-9,10-dihydroantra-cen, 10-broin-9-antrylaragnesiuinbromid, antryl-kvikksølvklorid,
fenantrener og derivater derav, såsom fenantren, 9,10-dihydrofenantren, 1,2,3,4-tetrahydrofenantren, 1-klorfenan-tren, fenantren-9,10-diklorid, 1-bromfenantren, 1-jodfenan-tren, 9-(klormetyl)fenantren, 1-(brommetyl)fenantren, 4,5-bis-(brometyl)fenantren, 1-nitrofenantren, 10-brom-9-nitrofenantren, 1-aminofenantren, 9,10-diaminofenantren, 9,9'-azoksy-fenantren, 9,9'-azofenantren, 1-oksyfenantren, kolesterol, estron, androsteron, 10-brom-9-fenantrol, 9-nitro-3-fenantrol, 4-amino-l-fenantrol, 10-benzoazo-9-fenantrol, 1,2-dioksyfenantren, reten-3,8-diol, 2,3,5,6-tetraoksyfenantren, 1- metylfenantren, 1-etylfenantren, 1-vinylfenantren, 1,2-di-metylfenantren, 9,10-dietylfenantren, 9,10-dipropylfenantren, 2- etyl-l-metylfenantren, 7-isopropy1-1-metylfenantren, 9,10-dihydroreten, aminoreten, 3-acetoaminoreten, 6-acylamino-reten, 9-fenylfenantren, 9-benzylfenantren, 1-(a-naftyl)-fenantren, 1,1'-bifenantryl, 9,9'-bifenantryl, 1-fenantraldehyd, 2-fenantraldehyd, 9-fenantraldehyd, 1-acetylfenantren, 2- propionylfenantren, 3-acetylreten, 1-benzoylfenantren,
fenantrenkinoner, såsom fenantren-1,2-kinon, fenantren-1,4-kinon, fenantren-3,4-kinon, fenantren-9,10-kinon, 2-fenyl-3- acetoksy-4,5-bifenylfuran, 7-isopropy1-1-metylfenantrenkinon, 1-klorfenantrenkinon, 2-bromfenantrenkinon, 2-jodfenantren-
kinon, 2,7-dibromfenantrenkinon, 2-nitrofenantrenkinon, 2,5-dinitrofenantrenkinon, 2-amino-fenantrenkinon, 2,7-diamino-fenantrenkinon, 3,6-diarainofenantrenkinon, 2,5-diaminofenan-trenkinon, 2-oksyfenantren-1,4-kinon, 3-oksyfenantrenkinon, 2- oksyretenkinon, 3-oksyretenkinon, 6-oksyretenkinon, 2-oksy-3,4-dinitrofenantrenkinon, 2-amino-3-oksyfenantrenkinon, samt
aromatiske forbindelser med flere kjerner, og derivater derav, såsom pentacen, heksacen, benzofenantren, benzo [a]-antracen, naftol[2,1,alpyren, dibenzo [a,jlantracen, pyren, koronen, 1,12-benzopyren, ovalen, dibenzoantracen, naftacen, terramycin, aureomycin, rubren, a-toluoyl-l-naftalen, benzo-antrakinon, 5,6-dioksy-5,6-dihydrobenzoantracen, krysen, tri-fenylen, dibenzonaftacen, heksahydropyren, perylen, 3,9-diklorperylen, tetraklorperylen, 3,9-dibromperylen, 3,10-dinitroperylen, 4,6-dibenzoyl-l,3-dimetylbenzen, 6,13-dihydro-pentacen, nafto [2,3-aJ-antracen, dispiran, dibenzo [a,hlantra-cen, piken, pikylenketon, piken-5,6-kinon, dibenzo[c,gj-fenantren, benzo[a]pyren-1,6-kinon, mesobenzoantronperikar-bpkssyreanhydrid, antracen[ 2,1-aJantracen, dibenzo [a,1]naftacen, fenantren[2,3-a]antracen, nafto[2,3-alpyren, dibenzo-£a,h]pyren, dibenzo fa, 1] pyren, zetren, antantren, benzorifl2]-perylen, heptacen, tetrabenzo[a,c,h,j]antracen, tribenzo |.a, i, li,pyren, tetrahydrodimetyldinaftyl, mesonnaftodiantren, meso-antraodiantren, 2,3:8,9-dibenzokoronen, pyrantren, o.l.
Som kinoner og derivater derav kan det anvendes: benzokinoner og derivater derav, såsom dibenzokinoyldi-sulfid, 2,5-bis(fenyltio)-p-benzokinon, dibenzokinon, ditolu-kinon, føenicin, cosporein, indofenol, indoanilin, hydronblått, indamin, Meldolas blått, Wursters blått, Wursters rødt, 4,4-difenokinon, 4,4 *-stilbenkinon, 3,5,3',5'-tetrametyl-4,4'-di-fenokinon, 3,5,3',5'-tetra-tert-butyl-4,4'-difenokinon, 3,5, 3',5'-tetrametyl-4,4'-stilbenkinon, 3,5,3',5'-tetra-tert-butyl-4,4 *-stilbenkinon,
naftokinoner og derivater derav, såsom 1,2-naftokinon, 3- oksy-2,2'-binafty1-1,4,3',4'-dikinon, 5,6-benzokinoksalin, 1,2-benzofenazin, 2-benzoazo-l-naftol, 4-(2,4-dioksyfenyl)-1,2-dioksynaftalen, 4-(3,4,5-trioksyfenyl)-1,2-dioksynaftalen, 1,2-naftokinon-l-fenylimid, 1,2-benzofenoksazin, 1,2-naftokinon-2-klorimid, 1,2-naftokinon-bis-klorimid, 2-anilin-l,4-
naftokinon-4-anil, 2-oksy-l,4-naftokinon-4-anil, 1,2-naftokinon-l-oksimbenzoat, 1,2-naftokinon-l-oksimmetyleter, 1- nitroso-2-naftol, 2-nitroso-l-naftol, naftolp.',2':3,4]L_ furazan, 1,2-naftokinon-2-oksimbenzoat, 1,2-naftokinon-2-oksimmetyleter, 3-anilin-l,2:8,9-dibenzofenazin, naftylblått, naftylfiolett, 1,2:5,6-dibenzofenazin, nafto Q.',2':3,4}furazan-2-oksyd, triftaloylbenzen, heksaoksynaftalenanhydrid, 2,2'-binaftyl-1,4:1<1>,4'-dikinon, 1',4'-dioksynafto(2',3': 3,4)pyrazol, 4, 1- d?oksy-3,3-difenyl-5,6-benzindiazen, 2-difenylmetyl-i,4-naftokinon, metylnafto[2',3':4,5j-triazol-1',4'-kinon, 1,2,4-triacetoksynaftalen, 1,4-naftokinonfenyl-imid, 1,4-naftokinon-mono(p-dimetylaminoanil), 1,4-nafto-kinonalkylimid, 4-nitroso-l-naftol, fenylkarbamat, 4-nitroso-l-naftylamin, 4-benzhydryl-l,2-naftokinon, 2-benz-hydry1-1,4-naftokinon, 3-benzhydryl-2-metyl-l,4-naftokinon, 3- gerany1-2-metyl-l,4-naftokinon, 3-farnesyl-2-metyl-l,4-naftokinon, 2-metyl-3-fytyl-1,4-naftokinon, vitamin Kl, vitamin K2, 3-allyl-2,6-dimetyl-l,4-naftokinon, 2,6-dimetyl-3-fytyl-1,4-naftokinon, 2,3-diallyl-6,7-dimetyl-l,4-naftokinon, 2-fenyl-1,4-naftokinon, 2-metyl-l,4-naftokinon, 2,6-dimetyl-3-fenyl-1,4-naftokinon, 3-benzyl-2-metyl-l,4-naftokinon, 2-metyl-3-(S-fenyletyl)-1,4-naftokinon, 3-cinnamyl-2-metyl-1,4-naftokinon, 2-benzhydryl-l,4-naftokinon, 4,7-diketo-t-di fenyImety1-4,7,8,9-tetrahydro-5,6-benzindiazen, 2-metyl-3-difenylmetyl-1,4-naftokinon, 2,3-difenyl-l-naftol, naftc—
[2 ' , 3 ' : 3 , 4j -pyrazol-1' , 4 ' -kinion, 3 , 4-diklor-l, 2 — benzof enazin, 2- jod-1,4-naftokinon,1,4,5,8-tetraoksy-2,3;6,7— dibenzo-tiantren, 5,8-dioksy-2,3;6,7-dibenzotiantrene-l,4-kinon, 2.3- difenoksy-1,4-naftokinon, dinafto Q',3':2,3} £l'', 2'' :5,|-furan-1',4'kinon, 2,3,5,8-tetraklor-l,4-naftokinon, N,N'-bis-(1,4-naftokinon-2-yl)-benzidin, 2-anilin-l,4-naftokinon-4-anil, 4- anilino-l,2-naftokinon-2-anil, fenylrosindarin, 2-anilino-1.4— naftokinon-4-(p-dimetylaminoanil), 2-anilino-l,4-naftokinon- dianil, 2-anilino-3-fenyl-1,4— naftokinon, 2-anilino-■3-brom-l,4 -naftokinon, 2-anilino-4-klor-l,4-naftokinon, 2,3-dianilino-l,4— naftokinon, 2,3-dianilion-l,4-naftokinon-dianil, nitrosoaminonaftokinon, 3-klor-2-fenylnitroso-amino-1,4— naftokinon, fenyl-bis-(3-anilino-l,4-naftokinon-2-yl)amin, 3-klor-2—(p-tolylnitrosoamino)-1,4-naftokinon,
2,7-dioksy-l— nitrosonaftalen, 4-benzenazo-l,3-dioksynaftalen, di-(3-oksy-l, 4-naftokinyl-2-)-metan, anhydroalkanin, di-kinoksalino-j2',3': 1, 2 : 2 * ' , 3 ' ' : 3, 4] -naf talen, 3 , 4-f taloyl-furazan, samt
antrakinoner og derivater derav, såsom 1,2-antrakinon, 2,3-antrakinon, 1,4-antrakinon, 9,10-antrakinon, 1,5-antrakinon, 2,6-antrakinon, 1,10-antrakinon, 9,9-bis(p-oksy-fenyl)antron, antrakinonbisdifenylmetid, bisfenyl-hydrozon,benzantrone, antrahydrokinon, B-etylantrakinon, 1,3,5,7-tetrametylantrakinon, 2,2'-diantrakinonyletan, 2,2'-diantrakinonyletylen, 1,2,3- trioksyantrakinon, antrakryson, erytrooksyantrakinon, alizarin, kinizarin, antrarufin, krysazin, hystazarin, antraflavin, isoantraflavin, antragallol, purpurin, oksyantrarufin, antrapurpurin, oksykrysazin, oksy-flavopurpurin, rufiopin, kinazarin, alizarinpentacyanin, rufi-gallol, antracenblått WR, alizarinheksacyanin, 2-klorkinizarin, 1-nitroantrakinon, 2,4,6,8-tetrabromantrakryson, 3-aminoantrapurpurin, 1,8-dinitroantrakinon, B-aminoantrakinon, 1,1'-diantrakinonylj diantrakinoninid, 1,4-dimetylamino-antrakinon, 5-amino-l-nitro-6,8-dibromantrakinon, 1,5-tetra-metyldiaarino-4,8-dinitroantrakinon, antrakinonakridon, bis-N-(2-oksyantrakinolyl)-p-fenylendiamin, leukokinazarin, kinazaringrønt, l-amino-2,4-dibromantrakinon, 1,4-diacylamino-antrakinon, antrakinon-B-aldehyd, o-diazin,. 6,7-ftaloyl-1,9-benzantron, oksynitrosoantrakinon, 1,1'-diantrakinolyl, azoksyantrakinon, 8-klorpyrazolantron, 2,6-dihydrazinantra-kinon, antrakinondiazoniumsalt, B-antrakinonhydrazin, azoksyantrakinon, pyrazolantron, 1-(antrakin-2-yl)-3-metyl-pyrazolone, 1-hydroksylaminoantrakinon, 1,5-dihydroksyl-aminoantrakinon, 1-nitrosoantrakinon, 1-hydrazinantrakinon, 1,5-dihydrazinoantrakinon, 1-azidoantrakinon, 2-azidoantrakinon, antrakinonmetylsulfoksyd, 1,4-dirodanantrakinon,
6,B'-diantrakinolylsulfid, antrakinonsulfenylklorid, 2,2'-diantrakinonyl, 1,1<1->diantrakinonoyl, heliantron, meso-benzodiantron, 2,2<1->diamino-1-1'-diantrakinolyl, flavantrone, 2,2<1->diantryl, mesonaftodiantrone, 1,1'-diantrakinolylamin, kinizarinkinon, hystazarinkinon, alizarinkinon, 6-oksykini-zarinkinon, o.l.
Dessuten kan det anvendes aromatiske forbindelser av ikke-benzentype, såsom f.eks. azulen, cyklodekapentan, cyklo-tetradekaheptan, cyklooktadekanonaen, cyklotetrakosadodekaen, heptalen, fulvalen, sesku-fluvalen, heptafluvalen, perinaften, indenoT2, l-a] perinaften, dibenzo [ bf] oksepin, dibenzo [bf Itiepin, indolizin, cykloT3,2,2jazin, 4,5-benzotropolon, 3,4-benzotropolon, 5H-benzocyklohepten, 7H-benzocyklohepten, colchicin, colchicein, colchinolmetyleter, ditropyleter, ditropylsulfid, cyklopentadienyltropyliden, benzoazulen, karbinol, 4,5-benzo-tropon, 2-fenyltropon, naftocykloheptadienon, naftotropon, tri-benzotropon, 1-amino-l,3-dicyanoazulen, benzoylhydrazon, 3-f enyl-l-oksazuranon-2, 2-benzy.ltropon, 3-metyl-2-f enyltropon, 2,7-difenyltropon, 2-(g-naftyl)tropon, 2,7-tetrametylen-4,5-benzotropon, 2,7-difenyl-4,5-benzotropon, nafto£2 ',3 *-4,5]-tropon, naftol2',1'-2,3]-tropon, dibenzosuberan, nafto-[1',2<1->2,3]tropon, dibenzosuberol, 4-oksy-2-fenyltropon, 4,5,7-tribrom-2-fenyltropon, 3,5'-ditropolon, 3-(p-metoksy-fenyl)tropolon, 4-oksy-2-fenyltropon, 3-(s-naftyl)tropolon, 3,4-difenyltropolon, 3,7-dibenzyltropolon, 4-( y- fenylpropyl)-tropolon, 3,5 *-bitropolonyl, 4-(p-nitrostyryl)tropolonmetyl-eter, 2-amino-l,3-dicyanoazuren, benzo[b]tropotiazin, 5-brom-2-fenyltropon, 4-brom-2,7-difenyltropon, difenylbifenylkarbinol, tiazinotrcpon, o.l. <1>
Typiske eksempler på de heterocykliske forbindelser som har 5 eller flere konjugerte ti-bindinger omfatter følgende forbindelser: For det første dé oksygenholdige heterocykliske forbindelser, såsom
furan og derivater derav, såsom 2,5-difenylfuran, 2-fenylfuran, 3-metyl-difenylfuran, lepiden, pyridoksin og 2,4-difenylfuran,
benzofuran, isobenzofuran, dibenzofuran og derivater derav, såsom dibenzofuran, furano-] 21,3'-7,8]flavon, egonol, euparin, 1,3-difenylisobenzofuran, tetrafenylglykol, tetra-fenylftalan, 9-fenylantracen, o-oksymetyltrifenylkarbinol, 3,3'-difenylftalid, 1-fenylftalan, 1,1-fenylftalan, 3,3-difenylftalid, rubren, a-sorinin, dibenzofuran, 2,2'-dioksybi-fenyl, 2,2'-diaminobifenyl, fenanzon, dibenzokinon, 2-hydroksy-benzofuran, 2-metylbenzofuran, benzo[aj-benzofuran, benzo[b]-benzofuran, dibenzota,f]dibenzofuran, dibenzo[c,dldibenzofuran,
dibenzo[c,ejdibenzofuran, bis(2-dibenzofuryl) og bis(3-dibenzo-furyl),
pyran- og pyronderivater, såsom 2-p-oksyfenyl-4,6-di-fenylpyryliumjern-III-klorid, anhydrobase, benzopyran, 4-p-oksyfenyl-2,6-difenylpyrylium-jern-III-klorid og 6-fenyl-koumarin,
kromenol- og kromenderivater, såsom 6-metyl-2,3-difenyl-kromon, 6-metyl-2,3-difenyl-4-(p-tolyl)-1,4-benzopyran-4-ol, kromanol, Y-kromen, oksykmaron, kromen, cyanizinklorid, fisetin, 6-oksy-3-metoksy-5,7-dimetylflaviriumklorid, 4,4'-diflavilen-3,3'-oksyd, krysinidin, apigenidin, rotoflavinidin, lutosonidin, galanginidin, fisenidin, molinidin, flavoneimin, peralgonidin, cyanidin, delfinidin, petunidin, syringidin, hir-sutidin, apigenidin, karajurin, drakorodin, drakorubin,
flavon, flavonol- og isoflavonderivater, såsom flavonol, flavone og fukugetin,
koumarin- og isokoumarinderivater, såsom 7-oksy-3,4-benzokoumarin, dikoumarol, angelisin, psoralen, bergapten, bergaptol, xantotoksin, xantotoksal, isopimpinellin, pimpi-nellin, oroselol, oroselon, peusedanin, oksypeusedanin, ostrutol, medakenin, nodakenetin, seselin, xantyletin, xant-oksyletin, samt
xanton- og beslektede forbindelser, såsom dizantylen, 9-fenylxanten, isoksxanton, 1,2,7,8-dibenzoxanten, 3,9-difenylxanten, 9,9-difenylxanten, o.l.
For det andre de nitrogenholdige heterocykliske forbindelser, såsom: pyrroler, såsom 1-fenylpyrrol, 5-fenylpyrrol-2-aldehyd, fenyl-2-pyrrylketonoksim, 2-fenylpyrrol, 2-metyl-l-fenylpyrrol, 2-metyl-4-fenylpyrrol, 2-metyl-5-fenylpyrrol, 3-metyl-5-fenylpyrrol, 2,4-difenylpyrrol, 2,5-difenylpyrrol, 2,3-difenylpyrrol, 2,3,5-trifenylpyrrol, 1,2,3,5-tetrafynyl-pyrrol, 2,3,4,5-tetrafenylpyrrol, difenyl-2-pyrrolylkarbinol, pyrrolcyklotrimetynfargestoff, pyrrolpolymetylenfargestoff, biliverdin, bilirubin, prodigiosin og sterkobilin,
indoler, såsom 5,7-diklor-2-fenylindol, 7-klor-2-fenylindol, 5,7-dibrom-2-fenylindol, 7-brom-5-klor-2-fenylindol, 2-(3'-indolyl)-3-isonitroindolenin, roseindol, trip-tofblått, indolo£3 , 2-c^Jkinolin, indolo [1, 2-c] kinazolin, 2-
fenylindol, 3-nitro-2-fenylindol, 3-fenylindol, N-metyl-3-fenylindol, 3-(o-nitrofenyl)indol, 2,3-difenylindol, 3-trifenylmetylindol, 2-metyl-3-trifenylmetylindol, 2-fenyl-3- trifenylmetylindol, 2-(1-naftyl)-3-trifenylmetylindol, 2-(2-naftyl)-3-trifenylmetylindol, 3,3'-diindolyl, 3,2'-diindolyl, 3,3'-dehydrodiindol, roseindol, 3-nitroso-2-fenylindol, 3-nitro-2-fenylindol, 2-metyl-3-fenylazoindol, 2-f enyl-3-f enylazoindol, G.-oksy-3-f enylindol, triptofan, 4,5-benzotriptofan, 6,7-benzotriptofan, violasein,
oksoderivater av indol, såsom 3-(4-etoksy-l-naftyl)-oksyindol, indofenin, indigoazin og indigogult 3G,
isoindoler, såsom l-klor-4-metylftalazin, 1-ben-zilidenftalimidin, 2-metyl-3-fenylftalimidin, 2-metyl-1,3-difenylisoindol, 2,5-dlfenylisoindol, 6-isoindigo, dimetylimino-8-isoindigo,
karazoler, såsom 1-fenyl-1,2,3-benzotrizol, 2,2'-diaminodifenyl og 1,1'-dikarbazol,
forfyriner, såsom forfyrazin, magnesiumoktametyl-tetraazaporfyrin, azadipyrometin, ftalacyanin, diazako-proporfyrin, porfin, mesotetrafenylporfyrin, klorofyll-
b og klorofyll-a,
oksazoler, såsom 2-fenyloksazol, 4-fenyloksazol, 5-fenyloksazol, 2-metyl-4-fenyloksazol, 2-metyl-5-fenyloksazol, 4- metyl-2-fenyloksazol, 5-metyl-2-fenyloksazol, 4,5-dimetyl-2-fenyloksazol, 2,4-difenyloksazol, 2,5-difenyloksazol, 4,5-difenyloksazol, 2-metyl-4,5-difenyloksazol, 2,4,5-trifenyl-oksazol, 2-(o-nitrofenyl)oksazol, 2-(p-nitrofenyl)oksazol, 2-amino-5-fenyloksazol, 2-(p-aminofenyl)oksazol, 2-(o-amino-fenyl)oksazol, 4,5-dimetyl-2-fenyloksidooksazol, 4-metyl-2,5-difenyloksydoksazol, 2,4,5-trifenyloksydoksazol, 4-(o-metoksykarbonylbenzal)-2-fenyl-5-oksazolon, oksakarbo-cyaninfargestoff og fenantrooksazol,
isooksazoler, såsom 4-nitro-3-fenylisooksazol, 5-amino-3-metyl-4-fenylisooksazol og 5-benzoyl-3,4-difenyl-isooksazol ,
tiazoler, såsom 4-fenyltiazol, 5-fenyltiazol, 5-(p-fluorfenyl)tiazol, 2-metyl-4-fenyltiazol, 4-metyl-5-fenyltiazol, 5-metyl-4-fenyltiazol, 4,5-difenyltiazol, 2-metyl-4,5-difenyltiazol, 1,4-bis(4-mety1-2-tiazoly1)benzen.
p,p<1->bis(4-metyl-2-tiazolyl)bifenyl, 2-amino-4-fenyltiazol, 2- amino-5-fenyltiazol, 2-amino-4,5-difenyltiazol, 2-fenylazo-tiazol, 2-amino-4-metyl-5-fenylazotiazol, 4-metyl-2-fenylazo-tiazol, a-naftotiazol, B-naftotiazol, nafto\ 2, 3]tiazol, nafto-[1, 2J tiazol, 2-metyl T_l, 2ltiazol, 2-f enylnaf to [1, 2J tiazol, 2-metylnafto£2 ,1]-tiazol, 4-brom-2-fenylnafto [ 2,3]tiazol, 2-oksy-naf to [ 2 , lj tiazol, 2-aminonaf to [1, 2j tiazol, 2-aminonaf to [2 , lj - tiazol, 2-merkaptonaf to]~L, 2~[ tiazol, 2-mer kap tona f to [ 2 , 1} 'tiazol,
imidazoler, såsom 2-fenylimidazol, 4-fenylimidazol, 4-metyl-2-fenylimidazol, 2,4-difenylimidazol, 4,5-difenylimidazol, 2,4,5-trifenylimidazol, 2-brom-4-fenylimidazol, 5-klor-l-etyl-2-fenylimidazol, 5-klor-l,2-difenylimidazol, 2-fenylazo-imidazol, 2-metyl-4-fenylazoimidazol, 2-(o-aminofeny1)benzo-imidazol,
pyrazoler, såsom 3-fenylpyrazol, 5-fenylpyrazoi, 4-fenylpyrazol, 1-mety1-3-fenylpyrazol, 1-mety1-5-fenylpyrazol, 3- metyl-5-fenylpyrazol, 1,3-difenylpyrazol, 1,5-difenylpyrazol, 1,3,4-trifenylpyrazol, 1,3,5-trifenylpyrazol, 1,4,5-trifenylpyrazol, 5-amino-3-fenylpyrazol, 3-amino-5-fenylpyrazol, 5-metyl-1,3-difenylpyrazol-4-aldehyd, 3,5-diacety1-4-fenylpyrazol og 4-benzoyl-l,5-difenylpyrazol,
oksadizoler, såsom 3-fenylfurazan, 3,4-difenylfurazan, nafto £1,2jfurazan, fenylfuroksan, 3-metyi-5-fenyl-1,2,4-oksa-diazol og 2,5'-difenyl-1,3,4-oksadiazol,
tiadiazoler, såsom 5-fenyl-1,2,3-tiadiazol, 2-fenyl-l,3, 4- tiadiazol, 5,5'-difenyl-2,2'-bis(1,3,4-tiadiazol), 2-oksy-5-fenyl-1,3,4-tiadiazol og 2-metylsulfonyl-5-fenyl-1,3,4-tiadiazol,
triazoler, såsom 2-fenyl-1,2,3-triazol, 5-(p-aminofenyl)-3-markapto-l,2,4-triazol,
tetrazoler, såsom 5-fenyltetrazol, 1,5-difenyltetrazol, l-oksy-5-fenyltetrazol og l-amino-5-fenyltetrazol,
pyridinbeslektede forbindelser, såsom 2-fenylpyridin, 2,2'-dipyridyl, 2-klor-6-fenylpyridin, 2,6-diklor-3-fenylpyridin, 2,2<1->azopyridin, 3,3'-azopyridin, benzen-4-azopyridin, 5-klor-2,2'-azopyridin, 5,5'-diklor-2,2'-azopyridin, 4-pyridyl-azoresorcin, 4-pyridyl-m-fenylendiamin og 3-pyridyl-m-fenylendiamin,
kinolin og beslektede forbindelser, såsom kinolin, kinal-
din, kinaldin-N-oksyd, etylkinolin, 2-fenylkinolin, 3-metylkinolin, 3-fenylkinolin, 4-metylkinolin, 4-fenylkinolin, 6-metylkinolin, 6-etylkinolin, 6-fenylkinolin, 2,4-dimetyl-kinolin, 2,4-difenylkinolin, kinolin-4-metanol, kinolin-[6,5-fJkinolin, kinoftalon, flavaanilin, kinolinblått, etyl-rødt, pinacyanol, naftocyanol, kryptocyanin, xenocyanin, aza-cyanin, 6,6'-oktahydrokinon, Besthornrødt, 2,3'-bikinolin,
2,5<1->bikinolin, 2,6<1->bikinolin, 2,7<1->bikinolin, 3,3'-bikinolin, 4,5'-bikinolin, 4,6'-bikinolin, 5,5'-bikinolin, 6,6'-bikinolin, 6,7'-bikinolin, 6,8<1->bikinolin, 7,7'-bikinolin, 8,8<1->bikinolin, 2-fluorkinolin, 3-fluorkinolin, 4-fluorkinolin, 5-fluorkinolin, 6-fluorkinolin, 7-fluorkinolin, 8-fluorkinolin, 3-bromkinolin, 4- klorkinolin, 2,4-diklorkinolin, 3-nitrokinolin, 4-nitrokinolin, 2,3-kinolindio, kinolin-2-tiol, 2-oksykinolin-3-tiol, 2-aminokinolin, 8-aminokinolin, 2-hydrazikinolin, pyrolkinolin, tiazolkinolin, pyrimido[4, 5- b]kinolin og benzo ffjkinolin,
isokinolin og beslektede forbindelser, såsom 1-metyliso-kinolin, 3-brommetylisokinolin, 1-fenylisokinolin, 4-fenylisokinolin, 1,1-biisokinolin, 5,5'-biisokinolin, 1-klorisokinolin, 5- jodisokinolin, 5-bromisokinolin, 5-nitroisokinolin, isokinolin-1,3-diol, 6,7-metylendioksyisokinolin, 1-aminoisokinolin, 1-cyanoisokinolin, 1-f enylbenzo£g"] 3 , 4-dihydroisokinolin, 3- (p-aminof enyl) - 5 , 6-dihydro-8, 9-dimetoksyimidazo]j5, l-a"| isokinolin,
akridin og beslektede forbindelser, såsom akridin, 1-metylakridin, 9-fenylakridin, 9-(3-pyridinyl)-akridin, 2-klor-akridin, 2-bromakridin, 2-acridinol, acridin-3,6-diol, 4-nietoksyakridin, 9-fenoksyakridin, 1-nitroakridin, 4-aminoakridin, 1-aminoakridin, 9-fenylaminoakridin, 9-oksyakridin, krysanilin, akriflavin, 3,6-diamino-4,5-dimetylakridin og akrynol,
penantridiner, såsom 3,4-benzokinolin, 6-metylfenantri-din, 6-aminometylfenantridin, 6-fenylfenantridin, 6-klor-fenantridin, 6-bromfenantridin, 6-nitrofenantridin, 1-aminofenantridin, 3-oksyfenantridinon,
antrazoliner, såsom pyrido [2,3-g]kinolin, 2,7-difenyl-|_2 , 3-gJ kinolin, 2 , 8-dif enylpyrido £3 , 2-gJ kinolin,
fenantrolin og beslektede forbindelser, såsom 1,7-fenantrolin, 1,10-fenantrolin, 4,7-fenantrolin, 8-metyl-l,7-fenantrolin, 4,10-dioksy-l,7-fenantrolin, 3,5-diklor-l,10-
fénantrolin, 2-amino-l,10-fenantrolin, 5-oksy-4,7-fenantrolin og 5-amino-4,7-fenantrolin,
pyridoindoler, såsom 1,9-pyridoindol, 2,9-pyridoindol
og 4,9-pyridoindol,
naftyridin og beslektede forbindelser, såsom 1,5-naftyridin, 1,7-naftyridin, 1,8-naftyridin, 1,6-naftyridin, 2,6-naftyridin, 2,7-naftyridin, 1,5-naftyridin-4-ol, 3-amino-1,5-naftyridin, 2-amino-l,5-naftyridin og 2-oksy-l,7-naftyridin,
oksazin og beslektede forbindelser, såsom fenoksazinon, resazurin, karocyanin, nilblått A, meldorablått og brilliant-kresylblått,
tiazin og beslektede forbindelser, såsom o-benzamino-fenyl-e-fenoksykarbonyletersulfid, fenotiazin, nitrofenotia-zin, 3-klor-10-etylfenotiazin, 4-amino-4'-anilindifenyldisul-fid, 2-klor-10-(3-dimetylaminopropyl)fenotiazin, klorpromazin, 10-(2-dimetylamino-l-propyl)fenotiazinhydroklorid, 10-[ 2-(1-pyrrolidyl)etyl]fenotiazinhydroklorid, 10- [l-metyl-3-piperidyl-metyl)fenotiazin, 2-acetyl-10-(3-dimetylaminopropyl)fenotiazin, metylenblått,
pyridazin og beslektede forbindelser, såsom cinnolin, 3-metylcinnolin, 4-klorcinnolin, 3-bromcinnolin, 4-cinnolinol, 4-aminocinnolin, ftalazin, 4-etyl-2-fenylftalazinon, ftalazin-tiol, 1(2H)-ftalazinon, 3-fenylpseudoftalazin, 4-metyl-3-fenylpseudoftalazin, 2,3-dihydro-l,4-ftalazindion,
pyrimidin og beslektede forbindelser, såsom 2-cinnametyl-pyrimidin, 4,6-dimetyl-2-fenylpyrimidin, 2,4,6-trifenylpyri-midin, alloksantin, 2,6-dioksy-4-fenylpyrimidin, 4,6-dioksy-2-fenylpyrimidin, 5-klor-4,6-dioksy-2-fenylpyrimidin, sulfadi-azin, sulfisomidin, tonzylaminhydroklorid, vitamin Bl, tio-krom, ko-karboksylase, allomycin, 6-(2-furfuryl)aminopurin, pteridin, 2,4-pterindiol, 2-amino-6-metyl-4-pteridinol, xantopterin, leucopterin, isoxantopterin, kinazolin, 4-klor-kinazolin, 2,4-diklorkinazolin, 4-kinazolin, 2,3-difenyl-4-kinazolin,
pyrazinbeslektede forbindelser, såsom 3,6-difenyl-pyrazinol, kinoksalin, 2-metylkinoksalin, 2,3-dimetylkinoksa-lin, 2-klorkinoksalin, 2,3-diklorkinoksalin, 2-(o-amino-anilin)kinoksalin, N,N<1->difeny1-2,3-piperazion, 2-kinoksa-
linol, 2,3-kinoksalindiol, 2-aminokinoksalin, 2,3-diaminokin-oksalin, metylkinoksalin-2-karboksylsyreester, 2-(d-arabotetra-oksybutyl)kinoksalin, flavazol, glukazidon, fenazin, fenazin-5-oksyd, fenazin-5,10-dioksyd, 5-metylfenazinium-metylsulfat, 10-metyl-5,10-dihydro-2-fenazinkarbonitril, 2-fenazinkarbo-nitr.il, 1-fenazinol, 2-metoksyfenazin, 2-fenazinol, 1,6-dioksy-fenazin-5,10-dioksyd, 1-aminofenazin, 2-aminofenazin, 2,3-diaminofenazin, nøytral-, ødt, 5,10-dihydrofenanzin, 5-metyl-5,10-dihydrofenanzin, 1,2,3,4-tetrahydrofenazin,
seksleddete cykliske forbindelser med tre og fire heteroatomer, såsom 2,4,6-trifenyl-s-triazin, 2,4-diklor-6-o-klor-anilin-s-triazin, 5,6-difenyl-as-triazin, 2,6-difenyl-2,3,4,5-tetrahydro-as-triazin, 5,6-difenyl-as-triazin-3-ol, 1,2,4-benzotriazin, 1,2,4-benzotriazin-3-ol, 3-fenyl-1,2,3-benzotria-zin-4-(3H)-on, 1,2,3-benzotriazin-4-ol, 1,2,3-benzotriazin-4-tiol, 3-amino-l,2,3-benzotriazin, 2,3-disfenylosotetrazin, 5,6-dimetyl-2,3-difenylasotetrazin, 5-cyano-2,3-difenylosotetrazin, 5,6-dibenzoyl-2,3-difenylosotetrazin, 2,3-dibenzoyl-5-metyloso-tetrazin, 2,3-dibenzoyl-5,6-dimetylosotetrazin, 2,3-dibenzoyl-5„6-difenylosotetrazin, 2,3-bis(2,4-diklorfenyl)-5,6-difeny1-1,2,3,4-tetrahydro-Y-tetrazin, 1,2,3,4-tetraetoksykarbonyl-5,5-difenyl-1,2,3,4,5,6-heksahydro-r-tetrazin, 7-metyl-2-(4-mety1-fenyl)-i,2-dihydrobenzotetrazin, 3,6-difenyl-1,2-dihydro-s-tetrazin, 1,3-difenyl-1,4,5,6-tetrahydro-s-tetrazin, 3,3,6,6-tetrafenyl-1,2,3,6-tetrahydro-s-tetrazin, o.1.
Dessuten de svovelholdige heterocykliske forbindelser som kan omfatte: svovelholdige heterocykliske forbindelser som 2-fenyltio-fen, 2,4-difenyltiofen, 2,3,4,5-tetrafenyltiofen, metafenylen-hydroklorid, metapyrylenhydroklorid, klorotencitrat, tenyldi-aminhydroklorid, a-pentatienyl, a-heksatienyl,
kondenserte tiofenforbindelser, såsom 3,3'-diiminotio-indigo, indogoron, dihydronafto[2,1-bJ-tianaften, 1,3-difenyl-isotianaften, dibenzotiofen, 2-nitrodibenzotiofen, aminodi-benzotiofen, 2,8-diaminodibenzotiofen, dibenzotiofen-5-dioksyd, 4-oksydibenzotiofen, 2,8-dioksydibenzotiofen, 2-klordibenzotio-fen, 1-bromdibenzotiofen, 2,8-dibromdibenzotiofen, 2-jod-dibenzotiofen, 2,8-diacetyldibenzotiofen, naftotiofen, 3-oksytio-fantren, 2,3-tiofantren, nafto [2,3-c]tiofen, nafto [1,2-b]tio-
fen, naftoL2,l-b]-tiofen, naftoEl,2-c]tiofen, 1, 2-naftoE2,1-bl-tiofenkinon, l-oksy-2-nafto[2,1-b]tiofenaldehyd, nafto[l,2-c]-tiofen, 2H-nafto[l,8l-tiofen, benzo[b]tiofantren, 6,11-benzo-[b]-tiofantrakinon, benzo[gltiofantren, 4,5-benzotiofantren, 8,9-benzotiofantren,
femleddete mbnocykliske forbindelser som inneholder 2 heteroatomer, såsom 5-fenyl-1,2-ditiol-3-tion, 3,4-dihydro-nafto-2,1-trition, tiaflavon, tiakoumarin, tiaksanten, ti-aksantohydrol, tiaksanton, Milacil D, bistiaksantylen,
seksleddete cykliske forbindelser som inneholder to eller flere heteroatomer, såsom 2,5-difenyl-1,4-ditiadien, tiofen-aldehyd, tiantren, 2,7-dimetyltiantren, 1-tiantrenyllitium, 1- klortiantren, fenokstin, 2-vinylfenokstin, 2-aminofen-okstin, 2-nitrofenokstin, 3,7-dinitrofenokstin, 10,10-difenylfenokstin, 2,5-difenyltiofen, o.l.
Andre anvendbare forbindelsar kan være:
dicykliske forbindelser som har et felles nitrogenatom, såsom cinkonin, 2-fenylpyrrokolin, 3-etyl-2-fenylpyrrokolin, 3- benzyl-2-fenylpyrrokolin, 3-nitroso-2-fenylpyrrokolin, 2:3-benzopyrrokolin, 1,5,8-trimetyl-2:3-benzopyrrokolin, 1-etyl-5,8-dimetyl-2:3-benzopyrrokolin, 1,8-dimetyl-2:3-benzo-pyrrokolin, . 3-f eny 1-7: 8-benzopyrrokolin, cyklo["3 .3.3] azin,
cyklo[3.2.2]azin, 2-fenylcyklo-[3.2.2.Jazin, 2,3-difenyl-cykloL3.2.2]azin, tricykladin, 7-metylbenzo[a]kinolinium-bromid, 7-fenylbenzo£a]kinolidiniumbromid, benzo[b]kino-lidiniumsalt, tetrahydro-y-berberin, tetrahydroberberin, laud-anosolin, tetrahydro-2,3,9,10-tetraoksy-7-metyldibenzopyrro-koliumklorid, homolaudanosolin, oktadehydromatrin, kanadin-metojodid og tetrahydropalmatinmetojodid,
alkaloider, såsom nikotyrin, 3',2-dipyridyl, kusparin, galipolin, l-metyl-2-kinolin, kasimiroin, 2-pentylkinolin, 4- oksy-2-pentylkinolin, 4-metoksy-2-pentylkinolin, 1-metyl-2- pentyl-4-kinolin, 4-metoksy-2-fenylkinolin, 7-metoksy-l-metyl-2-fenyl-4-kinolin, kusparin, diktamnin, skimmianin, evolitrin, maklurin, kokusagin, kokusaginin, makulosidin, flindersiamin, evoksoidin, evoksin, evolatin, akronycidin, medikosmin, akronidin, Y-fagarin, cinkonin, kininon, kino-toksin, N-bromkinotoksin, dihydrocinkonicin, heterokinin, evoksantidin, xantokinolin, 1,3-dimetoksy-10-metylakridon,
evoxantin, xantevodin, melikopin, melikopidin, melikopicin, akronycin, flindersin, papaverin, papaveraldin, laudanosin, laudanin, kodamin, protopapaverin, almepavin, 4,4',5-tri-metoksy-2-vinylstilben, koklaurin, d-isokoklaurin, kok-lanolin, narkotin, narkotolin, aponarcein, cinkonin, cinko-toksin, dihydrohydrastin, bikukullin, adlumidin, korlumidin, kordrastin, magnolamin, berbarain, o-metylberamin etc.
Blant de ovenfor beskrevne forbindelser med konjugerte it-bindinger, foretrekkes de forbindelser som har minst en aminogruppe. Særlig foretrukne slike forbindelser er f.eks. aminonaftalener som diaminonaftalener, triaminonaftalener og tetraaminonaftalener, 1,4-diaminoantracener, 9,10-diaminofena-tren, 2,2<1->diaminodifenyl, 1,1'-diamino-2,2'-dinaftyl, 2-amino-5-fenyloksazol, 1-aminofenantridin, 2-amino-4-fenyltiazol, 2-amino-5-fenyltiazol, 3-amino-l,5-naftyridin, 1-aminofenantridin, aminoakridiner som 4-aminoakridin, 2-aminoakridin, 1-aminoakridin og 3,6-diaminoakridin, samt amino-fenaziner som 1-aminofenazin, 2-aminofenazin og 2,3-diaminofenazin.
Flakdanningshindreren som skal anvendes ifølge den foreliggende oppfinnelse inneholder i tillegg til minst ett av de anførte fargestoffer, pigmenter og forbindelser med konjugerte ir-bindinger, minst én uorganisk forbindelse. Selv om en uorganisk forbindelse som sådan ikke har noen beleggsdannelses-hindrende virkning, har det overraskende vist seg at den flakdanningshindrende virkning ved hjelp av fargestoffer, pigmenter eller forbindelser med konjugerte Ti-bindinger kan økes ytterligere når den uorganiske forbindelse anvendes sammen med fargestoff e.l. Det har også vist seg at denne virkning kan utøves på sikker måte dersom kloridionekonsentrajonen i reaksjonsblandingen styres.til 100 ppm eller mindre. Ved et kloridionekonsentrasjonsnivå på over 100 ppm er den beleggs-danningshindrende virkning ikke tilstrekkelig til å hindre effektiv beleggsdannelse.
Når et fargestoff, et pigment eller en forbindelse med konjugerte ir-bindinger i blanding med en uorganisk forbindelse skal påføres på innerveggen av en polymerisasjonsreaktor, vil andelen av begge komponenter fortrinnsvis være fra 0,1 til 2000 vektdeler av den uorganiske forbindelse, mer foretrukket fra 1 til 100 vektdeler, pr. 100 vektdeler av fargestoffet, pigmentet eller forbindelsen med konjugerte 7/-bindinger.
Slike uorganiske forbindelser kan være kiselsyrer eller silikater, såsom ortokiselsyre, metakiselsyre, mesodikiselsyre, mesotrikiselsyre, mesotetrakiselsyre, natriummetasilikat, natriumortosilikat, natriumdisilikat, natriumtetrasilikat, kaliummetasilikat, kaliumhydrogendisilikat, litiumortosilikat, heksalitiumortodisilikat, vannglass, 12-silisiumwolframsyré, iso-12-silisiumwolframsyre, 10-silisiumwolframsyre, kalium-12-silisiumwolf ramat , kalium-iso-12-silisiumwolframat, kalium-10-silisiumwolframat, natrium-12-silisiumwolframat, kalium-iso-12-silisiumwolframat, silisiummolybdensyre, kaliumsili-siummolybdat, natriumsilisiummolybdat, o.l.,
metallsalter, såsom oksysyresalter og acetater, nitrater, hydroksyder eller halogenider av forskjellige metaller, nemlig jordalkalimetaller som magnesium, kalsium, arium etc, aluminiummetaller som aluminium etc, tinnmetaller som titan, tinn, etc, jernmetaller som jern, nikkel etc, krommetaller som krom, molybden etc, manganmtaller som mangan etc, kooper-metaller som kopper, sølv etc samt platinametaller som platina etc.,
uorganiske kolloider fremstilt ved mekanisk formaling, bestråling eller ultralydbølger, elektrisk dispergering eller kjemiske metoder, såsom gullkolloid, sølvkolloid, svovel-kolloid, jern-III-hydroksydkolloid, tinn-IV-syrekolloid, kiselkolloid, mangandioksydkolloid, molybdenoksydkolloid, bariumsulfatkolloid, vanadiumpentoksydkolloid, aluminium-hydroksydkolloid, litiumsilikatkolloid osv.
Blant de ovenfor anførte uorganiske forbindelser er silikater, kiselsyrekolloid og jern-III-hydroksydkolloid særlig foretrukne.
For belegging av flakdanningshindrerén på innerveggen av en polymerisasjonsreaktor etc, kan den påføres som sådan eller som en beleggsløsning fremstilt ved å løse eller dispergere den i et egnet løsningsmiddel. Det foretrekkes vanligvis at flakdanningshindrerens konsentrasjon i beleggsløsningen er 0,01 vekt% eller mer.
Løsningsmidlet som kan anvendes ved fremstilling av be-leggsløsningen kan være vann eller forskjellige organiske
løsningsmidler, såsom f.eks.
alifatiske hydrokarboner som gasolin, petroleum, bensin, white spirit, petroleumnafta, W.M.&P. nafta, dekalin, tetralin, p-cymen, o.1.,
aromatiske hydrokarboner som benzen, toluen, xylen o.l.,
halogenerte hydrokarboner som trikloretylen, perkloretylen, klorform, karbontetraklorid, etylentriklorid, benzenmonobromid, benzenmonoklorid, benze.idiklorid o.l.,
alkoholer som ar.ylalkohol, etylalkohol, isopropylalkohol, 2-etylbutylalkohol, 2-etylheksylalkohol, cykloheksanol, metylalkohol, metylamylalkohol, benzylalkohol, butylalkohol o.l.,
ketoner som aceton, acetonylaceton, diisobutylketon, di-etylketon, dipropylketon, metylamylketon, metylbutylketon, metyl-cykloheksanon, metyldipropylketon, metyletylketon, metyl-n-heksyl-keton, metylisobutylketon, metylpropylketon, mesityloksyd o.l.,
estre som acetater, butyrater, propionater, formiater
o.l.,
alkoholestre som butyllaktat, isopropyllaktat, etyl-laktat, etyloksypropionat, dietylmaleat o.l.,
ketonestre som etylacetoacetat, etylpyruvat o.l.,
etre som isopropyleter, etyleter, dietylkarbitol, dietylcellosolve, butyleter o.l.,
ketonalkoholer som acetonylmetanol, diacetonalkohol, dihydroksylaceton, pyruvylalkohol o.l.,
eteralkoholer som isopropylcellosolve, karbitol,
glysidol, cellosolve, glykoleter, benzylcellosolve, butyl-karbitol, butylcellosolve, metylkarbitol, metylcellosolve, trietylenglykolmonoetyleter o.l.,
ketonetre som acetaletyleter, acetonylmetanoletyleter, metyletoksyetyleter o.l.,
esteretre som butylkarbitolacetat, butylcellosolveacetat, karbitolacetat, cellosolveacetat, 3-metoksybutylacetat, metyl-karbitolacetat, metylcellosolveacetat o.l.
Når det anvendes organiske løsningsmidler som er meget godt forenelige med vann, kan vann tilsettes til beleggs-løsningen i en mengde som ikke svekker flakdanningshindrerens løselighet eller dispergerbarhet, hvorved beleggsløsningen kan bedres når det gjelder økonomi og sikkerhet under transport og lagring. Slike løsningsmidler omfatter: alkoholer som metylalkohol, etylalkohol, allylalkohol, n-propylalkohol, isopropylalkohol o.l.,
ketoner som aceton, acetonylaceton, diacetonalkohol o.l.,
estre som etylenglykolmonometyleteracetat, dietylen-glykolmetyleteracetat, monoetyleteracetat o.l.,
etre som dioksan, etylenglykolmonometyleter, etylen-glykolmonoetyleter o.l.,
furaner som tetrahydrofuran, furfurylalkohol o.l.,
aprotiske løsningsmidler som acetonitril, N,N-dimetyl-formamid, N,N-dimetylacetamid o.l.
Når flakdanningshindreren som skal anvendes er et farge-s.toff av sulfonsyretype eller karboksylsyretype, som inneholder sulfonsyregrupper eller karboksylsyregrupper i form av et alkalimetallsalt eller ammoniumsalt, kan vannet anvendes som løsningsmiddel hvori flakdanningshindreren løses, slik som beskrevet i japansk patentpublikasjon 5442/1981, noe som er en fordel når det gjelder sikkerhet og hygiene ved at løsnings-midlet er ikke-toksisk og ufarlig. Dersom vann anvendes som løsningsmiddel slik som beskrevet ovenfor kan det oppnås bedre fukting av en polymerisasjonsreaktors innervegg med beleggs-løsningen ved tilsetning av alkoholer, fortrinnsvis C^-Cg-monoalkoholer, såsom n-propylalkohol, n-butylalkohol, iso-butylalkohol, sek-butylalkohol, tert-butylalkohol, n-amylalkohol, tert-amylaikohol, iso-amylalkohol, sek-amylalkonol, sek-heksylalkøhol etc, slik som beskrevet i japansk patent-publikas jon 5444/1981. Med det formål å gjøre tørring av be-leggsløsningen etter belegging enklere, kan som beskrevet i ovennevnte japanske patentpublikasjon 5442/1981 et organisk løsningsmiddel som er forenelig med vann, såsom alkoholiske løsningsmidler, estre og ketoner, tilsettes til beleggs-løsningen.
Ved påføring av beleggsløsningen som inneholder flakdanningshindreren, på innerveggen av en polymerisasjonsreaktor ved fremgangsmåten ifølge oppfinnelsen, kan det om ønskelig anvendes forskjellige festemidler for å øke vedheften. Festemidlet kan anvendes på forskjellige måter, f.eks. ved å tilsette det til beleggsløsningen som inneholder flakdanningshindreren, ved at festemidlet eller en løsning av denne på forhånd påføres på veggoverflaten før belegging med flakdanningshindreren, etterfulgt av anbringelse av flakdanningshindreren oppå festemidlet, hvorved den fremgangsmåte som er egnet velges avhengig av typen flakdanningshindrer og; typen festemiddel.
Slike festemidler kan omfatte polymere forbindelser som anført nedenfor: olefinpolymerer som polyetylen, polyetylensulfonsyre, polypropylen, poly(1-buten), polyisobuten, polycyklopenten, polycyklopentyletylen, polycykloheksyletylen, poly(3-cyklo-heksyl-l-propen), poly(4-cykloheksyl-l-buten), poly(5-cyklo-heksyl-l-penten), poly(cyklotrifluoretylen), poly(tetrafluor-etylen),
dienpolymerer som polyallen, polybutadien, polyisopren, polykloropren, poly (1-metoksybuta.dien) , poly(2-tert-butyl-l,3-butadien), poly(cyklopentadien), poly(l,3-cykloheksadien), poly(dimetylfulven), poly(4-vinyl-l-cykloheksan), poly-(1, 5-heksadien) , poly (1, 5-cyklook.tadien), poly (bicyklo-(2,2, 1)-hepta-2,5-dien), poly(5,7-dimetyl-l,6-oktadien), poly(di-allylftalat), poly(diallylmetylsilan) og poly(diallyl-fenylfosfinoksyd),
acetylenpolymerer som polyacetylen, poly(cyanoacetylen), poly((hydroksymetyl)acetylen), poly(butoksyacetylen), poly-(fenylacetylen), poly(difenylacetylen) og poly(pyridyl-acetylen),
alifatiske vinylpolymerer og vinylidenpolymerer, såsom polyvinylalkohol, polyallylalkohol, poly(vinylformal), poly-(vinylacetal), poly(vinylbutyral), poly(vinylisobutyral), poly-(vinylcykloheksanonketal), poly(vinylacetat), poly(vinylklor-acetat), poly(vinylisobutyrat), poly(vinylpivalat), poly(vinyl-n-kaproat), poly(vinyl-kaprylat), poly(vinyllaurat), poly-(vinylpalmitat), poly(vinylbenzoat), poly(vinylsulfat), poly-vinylklorid), poly(vinylidenklorid), poly(vinylbromid), poly-(vinylmetyleter), poly(vinyletyleter), poly(vinyl-n-propyl-eter), poly(vinylisopropyleter), poly(vinyl-n-butyleter), poly-(vinylisobutyleter), poly(vinyl-tert-butyleter), poly(vinylneo-pentyleter), poly(vinylkarbometoksymetyleter), poly(vinyl-2-metoksyetyleter), poly(vinyl-2-kloretyleter), poly(vinyl-2,2, 2-trifluoretyleter), poly(vinylbenzyleter), poly(vinylmetyl-keton), poly(metylisopropenylketon), poly(1-nitropropylen),
poly(vinylsulfofluorid), poly(vinylsulfonsyre), poly(vinyldi-fenylfosfinoksyd), poly(vinyldifenylfosfinsulfid), poly(dimetyl-2-cyano-2-propen-l-fosfonat), poly(dietyl-2-cyano-2-propen-l-fosfonat og poly(maleinsyreanhydrid),
aromatiske vinylpolymerer som polysteren, poly(a-metylstyren), poly(4-klorstyren), poly(4-bromstyren), poly-(diklorstyren), poly(4-metoksystyren), poly(2,5-dimetoksy-styren), poly(vinyl-bis(1-etoksyetyl)hydrokinon), poly(4-vinylftalsyre), poly(4-vinylfenylsyre), poly(difenyl-4-styryl-fosfinoksyd), poly(difenyl-4-styrylfosfinsulfid), poly(9-vinylantracen), poly(4-vinylbifenyl), poly(acenaftylen) og polyinden,
heterocykliske vinylpolymerer som (N-vinylkarbazol), poly(9-£<5->pentenylkarbazol), poly(9-a -heksenylkarbazol), poly(N-vinylpyrrolidin), poly-(2-vinylpyridin), poly(4-vinyl-pyridin), poly(2-metyl-2-vinylpyridin), poly(2,4-dimetyl-6-. vinyl-S-triazin), poly(N-vinyl-1,2,4-triazin), poly(N-vinyl-benztriazol), poly(N-morfolino-(3)) og polykoumaron,
akryl- og metakrylpolymerer, såsom polyakrylsyre, poly-metakrylsyre, poly(metylakrylat), poly(etylakrylat), poly-(butylakrylat), poly(5-cyano-3-tia-fenylakrylat), poly(metyl-metakrylat), poly(etylmetakrylat), poly{n-propylmetakrylac), poly(n-butylmetakrylat), poly(isobutylmetakrylat), poly(n-heksylmetakrylat), poly(2-etylbutylmetakrylat), poly(n-oktylmetakrylat), poly(n-laurylmetakrylat), poly(4-(tert-butyl)fenylmetakrylat), poly(bornylmetakrylat), poly(@-(N-kara zyl)etylmetakrylat, poly(tert-butylkrotonat), polyakryl-nitril, polymetakrylnitril, polyakrylamid, poly(N,N-dimetyl-akrylamid), poly(N-(1,l-dimetyl-3-oksobutyl)akrylamid, poly-(akrylpiperidin), poly(akrylmorfolid), poly(9-akryloylkarba-zol), polymetakrylamid, polyakrolein, poly(o-metakrylakrolein), poly(diakryloylmetan), poly(akrylsyreanhydrid), poly(metakryl-syreanhydrid),
etre, såsom polyformaldehyd, polyacetaldehyd, poly(mono-kloracetaldehyd), polykloral, polypropionaldehyd, polyakrolein, poly(2-formyl-A^-dihydropyran), poly(trans-1,2-cykloheksandi-karboksyaldehyd(, poly(glutardialdehyd), poly(6-metylglutardi-aldehyd), poly(B~fenylglutardialdehyd), poly(dimetylketen), polyaceton, poly(monobromaceton), poly(7-oksa-bicyklo [2,2,l]-
heptan), poly(3-fenoksylen), poly(2,6-xylenol), poly(etylen-oksyd), poly(propylenoksyd), poly(cyklopentenoksyd), poly-(cykloheksenoksyd), poly(fenylglycidyleter), poly(l,2-di-(epoksyetyl)benzen), poly(3,3-bis(klormetyl)oksetan og poly-(tetrahydrofuran),
polysulfider og polysulfoner, såsom poly(tiokarboksyl-fluorid), poly(etylendikloridnatriumtetrasulfid), poly(di-klordietyleternatriumdisulfid), poly(diklordietyleternatrium-tetrasulf id) , poly ( f vjnylensulf id) , poly (etylensulf on) , poly-(propylensulfone, roly(1-butensulfon), poly(5-norbornensulfon), poly(styrensulfon), poly(1-pentylsulfon), poly(1-heksylsulfon), poly(1-heptylsulfon), poly(butadiensulfon), poly(isopren-sulfon), poly(dimetylbutadiensulfon), poly(1,5-heksadien-sulfon), poly(cis,cis-cyklooktadiensulfon), poly(norbornadien-sulfon),
forskjellige addisjonspolymerer, såsom poly(metylendi-isocyanat), poly(etylendiisocyanat), poly(trimetylendiiso-cyanat), poly(tetrametylendiisocyanat), poly(5-iminohydan-toin), poly(perfluorglutardinitril) og poly(1-(perfluor-butyryl)aziridin,
formaldehydharpikser som fenol-formaldehydharpiks, melamin-formaldehydharpiks, urea-formaldehydharpiks, anilin-formaldehydharpiks og p-toluensulfonamid-formaldehydharpiks,
polyestre som poly(11-oksyundekanoat), poly(heksa-metylensuccinat), poly(heksametylensebakat), poly(heksade-kametylensebakat), poly(heksametylen-a,a'-dibutylsebakat), poly(oktametylen-cis-heksahydrotereftalat), poly(okta-metylen-transheksahydrotereftalat), poly(heksametylen-maleat), poly(heksametylenfumarat), poly(heksametylenace-tylendikarboksylat), poly(etylenterftalat), poly(p-fenylen-isoftalat), poly(4,4'-bifenylenisoftalat), poly(heksa-metylenkarbonat), poly(p-fenylenkarbonat), poly(m-fenylen-karbonat), poly(4,4'-isopropylidendifenylenkarbonat), poly-(4,4'-(2-pentylen)difenylenkarbonat) , poly(1,2-bis(hydroksy-metyl)karboran-adipinsyre), poly(allylsulfonat), poly-(hydrokinon-aryloksyfosforyldiklorid), poly(hydrokinon-(klormetyl)-fosforyldiklorid og poly(hydrokinon-(N-dimetyl)-fosforamidsyre)diklarid,
polyamider som poly(isocyanat), poly(vinylisocyanat),
poly(butylisocyanat), poly(3-aminopropionsyre), poly(6-amino-propionsyre), poly(11-aminoundekansyre), poly(heksametylenadi-pamid), poly(dekametylenadipamid), poly(3,3'-(metylimin)-bistrimetylenadipamid), poly(benzidin-isoftalsyre), poly-(pyrromelliticsyredianhydrid-aromatisk diamin), poly(1,6-heksa-metylen-bis(karboksyetyl(sulfid), poly(1,6-heksametylendi-amin-benzen-1,3-bis-sulfonsyreklorid), poly(trans-2,5-dimetyl-piperazin-4,4'-sulfonyl-dibenzoylklorid), poly(bis(3-aminopropyl)fenylfosforin-adipinsyre), poly(bis(3-amino-propyl)fenylfosfin-tereftalsyre), poly(bis(3-aminopropyl)-metylfosfinoksyd-adipinsyre), poly(bis(3-aminopropyl)n-oktylfosfinsyre-adipinsyre, poly(bis(3-aminopropyl)fenyl-fosf inoksyd-adipinsyre) , poly(heksametylendiamin-bis(2-karboksyetylen)fenylfosfinoksyd), poly(heksametylendiamin-bisfp-karboksyfenyl) fenylfosf inoksyd) , poly(piperazin-bis-(2-karboksyetyL)fenylfosfinoksyd,
polyureaer og polyuretaner, såsom polyureaer, poly-(1,10-dekametylendiamin-l,6-heksametylen-bis-etyluretan), poly(difenylmetan-4,4'-diisocyanat-4,4 *-difenylmetan), poly(toluen-2,4-diisocyanat-N,N'-bis(trimetylsilyl-p,p'-diaminodifenyleter og polyuretan,
forskjellige lineære kondenserte polymerer, såsom poly(dietylkarbodiimid), poly(diallylkarbodiimid), poly-(di-n-butylkarbodiimid), poly(metylisopropylkarbodiimid), poly (di^-n-heksylkarbodiimid), poly (dif eny lkarbodiimid), poly(4,4'-difenylenmetankarbodiimid), poly(heksametylen-karbodiimid), poly(1,3-xylylenkarbodiimid), poly(3-metyl-1,4-fenylenkarbodiimid), poly(2,2•-dimetyl-bifenylenkarbodiimid), poly(2,2 *-dimetoksy-bifenylenkarbodiimid), poly-(1,5-naftylenkarbodiimid), poly(adipyldihydrazid-succinoyl-klorid), poly(adipyldihydrazid-isoftaloylklorid), poly-(isoftalsyredihydrazid-tereftaloylklorid), poly(2,5-dimetyl-benzylen), poly(p-xylylen), poly(2,5-dimetylxylylen), poly-(2,5-dimetoksy-p-xylylen), poly(p-xylyliden), poly {& -cyano-m-xylylidin), poly(^-cyano-p-xylylidin), poly(nitrofenylen), poly(tetrametyl-p-fenylen)dimetylen), poly(2,5-dihydroksy-p-fenylendimetylen), poly(4,4'-oksydifenylendimetylen), poly(2,5-dimetoksy-p-fenylendimetylen),
heterocykliske kondenserte polymerer som poly(benzoimidazol), poly(alkylen-5,5'-dibenzimidazol), poly(allylen-5,5<1->dibenzoimdazol), poly(pyromellitimid), poly(benzoksazol), poly(oksadiazol), poly-(oksadiazolidin), poly(ditiazol), poly(benzotiazol), poly(1,4-xylenyl)-2^metyl-p;iperazin) , poly(kinoksalin) og poly(S-triazinylen-imid),
naturlige polymerer og modifiserte naturlige polymerer, såsom naturgummi cyklisert kautsjuk, kautsjukhydroklorid, klorkautsjuk, guttaperka, cellulose, metylcellulose, etyl-cellulose, propylcellulose, butylcellulose, allylcellulose, benzylcellulose, hydroksyetylcellulose, karboksymetyl-cellulose, cyanoetylcellulose, cellulosetriformiat, cellulose-acetat, cellulosetriacetat, cellulosetripropionat, cellulose-tributyrat, cellulosetrikaproat, cellulosetrikarbaiiilat, cellulosenitrat, cellulosetrinitrat, stivelse, amylose, amyloseacetat, amylosekaranilat, amylopektin, alginsyre, kitin, glykogen, gummiarabikum, tragantgummi, heparin, pektin, kalafonium, kopal, skjellakk, kasein, kollagen(kalveskinn), kollagen(iktyokol), gelatin, jordnøttprotein, soyabønne-protein, nukleikprotein (kalvetymus), nukleikprotein (sperma fra sjøpinnsvin), poly(sarkosin), serisln, silke, ull, zein, polyadenylsyre, deoksyribonukleinsyre og ribonukleinsyre,
polysiloksaner som polysiloksan og polydimetylsiloksan
organiske metallpolymerer som poly(bis-(imidazolat)-metall((II)) og poly(aluminiumtriisopropylatetylendiamin), samt
uorganiske polymerer som polymetafosfat osv.
Ved fremgangsmåten ifølge oppfinnelsen påføres den ovenfor beskrevne flakdanningshindrer på innerveggen i en polymerisasjonsreaktor og på de partier av utstyr i polymerisasjonsreaktoren som flak kan bli hengende fast på, nemlig de partier som monomerene kan komme i kontakt med under polymerisasjonen (også de partier som monomerer eventuelt kan komme i kontakt med), f.eks. omrørerblader, omrøreraksel, kondensator, samletank, ledeplater, prøvespole, bolter, muttre etc. Fortrinnsvis påføres flakdanningshindreren også på de partier av gjenvinningssystem for ureagerte monomerer hvor flak kan bli hengende fast, f.eks. de innvendige flater i monomerdestillasjonkolonner, kondensatorer, monomerlagrings-beholdere, ventiler etc.
Materialene for den ovennevnte polymerisasjonsreaktor og nevnte papirer av utstyr i reaktoren er ikke spesielt begrenset, men et sådant materiale som rustfritt stål eller et materiale utstyrt med en glassforing kan være tilgjengelige. De partier hvor belegget skal påføres bør fortrinnsvis ha en overflateruhet (R-^^^if ølge JIS B 0016) på 10 um eller mindre, helst 5 um eller mindre.
Fremgangsmåten til påføring av flakdanningshindreren på innerveggen i en polymerisasjonsreaktor, slik som nevnt ovenfor, er ikke særlig kritisk og den kan typisk omfatte påføring med pensel, sprøyting, fylling av polymerisasjonsreaktoren med beleggsløsning etterfulgt av uttapping av løsningen, samt de automatiske beleggingsmetoder som er beskrevet i de offentlige tilgjengelige japanske patentpublikasjoner 61001/1981, 36288/1980, 501116/1981, 501117/1981 samt 11303/1984.
Fremgangsmåten ifølge oppfinnelsen er anvendbar for homopolymerisasjon av vinylkloridmonomer og kopolymerisasjon av vinylkloridmonomer ved andre vinylmonomerer i et vandig medium. Polymerisasjonen kan enten være suspensjonspolymerisasjon eller emulsjonspolymerisasjon. Vinylmonomerer kan anvendes for kopolymerisasjon eller f.eks. vinylestre som vinylacetat og vinylpropionat, akrylsyre, metakrylsyre og deres estre eller salter, maleinsyre eller fumarsyre og deres estre eller anhydrider, dienmonomerer som butadien, kloropren eller isopren og dessuten styren, akrylnitril, vinyliden-halogenid, vinyleter etc.
Ved suspensjons- og emulsjonspolymerisasjonene er polymerisasjonskatalysatorer som vanligvis anvendes f.eks. organiske peroksyder som tert-butylperoksyneodekanat, di-2-etylheksylperoksydikarbonat, 3,5,5-trimetylheksanoyl-peroksyd, a-kumylperoksyneodekanoat, kumenhydroperoksyd, cykloheksanonperoksyd, tert-butylperoksypivalat, di-2-etoksy-etylperoksydikarbonat, benzoylperoksyd, lauroylperoksyd, 2,4-diklorbenzoylperoksyd, diisopropylperoksydikarbonat og acetylcykloheksylperoksyd, azokatalysatorer som a ,a '-azobis-isobutyronitril, a,a'-azobis-2,4-dimetylvaleronitril, vann-løselige persulfater som kaliumpersulfat og ammoniumpersulfat. Dessuten kan det anvendes et dispergeringsmiddel, f.eks. naturlige eller syntetiske polymere forbindelser, f.eks. delvis forsåpet polyvinylacetat, polyakrylsyre, kopolymer av polyvinylacetat og maleinsyreanhydrid, cellulosederivater som hydroksypropylmetylcellulose og gelatin og emulgatorer som ikke-ioniske emulgatorer som sorbitanmonolaurat, sorbitan-trioleat, anioniske emulgatorer som natriumlaurylsulfonat og natriumalkylbenzensulfonat. Det kan også tilsettes andre hjelpestoffer, nemlig fyllstoffer som kalsiumkarbonat, titanoksyd etc, stabilisatorer som tribasisk blysulfat, kalsiumstearat, dibutyltinnlaurat og dioktyltinnmerkaptid, smøremidler som lusveks, stearinsyre og cetylalkohol, myknere som DOP og DBP, kjedeoverførere som trikloretylen og merkaptaner samt pH- reguleringsmidler. Ved fremgangsmåten ifølge oppfinnelsen kan beleggsdannelse hindres på effektiv måte i et hvert polymerisasjonssystem selv om katalysatorer, dispergeringsmidler og tilsetningsmidler ikke anvendes.
Oppfinnelsen vil bli beskrevet mer detaljert nedenfor under henvisning til de etterfølgende eksempler.
Anm.: I de etterfølgende eksempler er forsøkene 218-300 utelatt.
Eksempel 1
For hvert av de i tabell 1 viste forsøk ble et fargestoff eller pigment løst eller dispergert i et løsningsmiddel, eventuelt under tilsetning av en uorganisk forbindelse eller en polymer forbindelse, slik som vist i samme tabell for fremstilling av en beleggsløsning. Forholdet mellom den uorganiske forbindelse eller den polymere forbindelse og konsentrasjonen av fargetoffet eller pigmentet i beleggsløsningen er også vist i tabell 1. Beleggsløsningen ble påført på den polerte innervegg i en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1 og på de partier som kan komme i kontakt med monomerene, såsom omrører, hvoretter det påførte belegg ble tørket ved 8°C i 10 minutter og deretter vasket grundig med vann.
Deretter ble det i den således belagte polymerisasjonsreaktor innført 200 kg vinylkloridmonomer, 400 kg avionisert vann, 400 g delvis forsåpet "poval", 56 g hydroksypropylmetylcellulose og 60 g tert-butylperoksyneodekanat, og polymerisasjonen ble utført ved 52°C i 7 timer. Etter full-føring av polymerisasjonen ble polymerene uttatt, og polymerisas j onsreaktoren ble vasket innvendig med vann med en strømningsmengde pa 0,1 m 3 /m 2 h som vist i tabell 1. De ovenfor beskrevne operasjoner for belegging og chargering til vasking med vann ble utført på hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen i reaksjonsblandingen under polymerisasjonen i hvert forsøk ble regulert i hvert forsøk ved at forandringer av innholdet av metylklorid og hydrogen-kloridkomponenter i utgangsvinylkloridmonomeren, temperaturen 1 det tilførte avioniserte vann (i området fra 10 til 80°C) og graden av vakuum etter innføring av avionisert vann og dispergeringsmiddel (750-100 mmHg). Forskjellige vinylmonomer-materialer med forskjellige innhold av metylklorid og hydrogenklorid ble fremstilt ved blanding av to typer vinyl-klorid, nemlig (1) en som inneholdt 40-50 ppm metylklorid og 0-2 ppm hydrogenklorid og (2) en annen som inneholdt 1000-3000 ppm metylklorid og 1-10 ppm hydrogenklorid i forskjellige vektforhold i området fra 80:100 til 20:0.
Etter fullføring av polymerisasjonen av hver sats ble kloridionekonsentrasjonen i oppslemmingen målt ved metoden som er definert i JIS K 0102 (1974). Gjennomsnittsverdien og maksimums- og minimumsverdiene av disse målte verdier er vist for hvert forsøk i tabell 1. Dessuten ble beleggsdannelse etter fullføring av hver 10., 30., 50., 100., 150. og 200. vurdert visuelt og adhert som anført nedenfor, og mengden vedheftende flak (g/m ) ble også målt etter fullføring av den siste sats. Resultatene er også vist i tabell 1.
A: ingen vedheftende flak
B: betydelig prosentvis vedhengende sandaktige flak
C: flak som er tynt over en del av flaten (ca. 10%)
D: flak klebende tykt over deler av flaten (ca. 10%)
E: flak klebende tynt over en del av flaten (ca. 50%) F: flak klebende tykt over deler av flaten (ca. 5 0%)
G: flak klebende tynt over hele flaten
H: flak klebende tykt over hele flaten
I tabell 1 er de forsøksnumre som. er markert med en stjerne (<*>) sammenlikningseksempler. Særlig er forsøkene 1 og 2 eksempler hvor innerveggen i en polymerisasjonsreaktor ikke ble underkastet noen behandling med noen forbindelse. Beleggsløsningen som ble anvendt i forsøkene 33 og 34 ble fremstilt ved å løse 1 del natriumsulfid i 100 deler vann og tilsette 0,5 del av et fargestoff til den resulterende løsning, etterfulgt av oppvarming ved 80°C i 30 minutter.
Eksempel 2
Som vist i tabell 2 ble i hvert forsøk et fargestoff eller et pigment løst eller dispergert i et løsningsmiddel, eventuelt ved tilsetning a<y> en uorganisk forbindelse eller en polymer forbindelse som vist i samme tabell, for fremstilling av en beleggsløsning. Forholdet mellom den uorganiske forbindelse og den polymere forbindelse og konsentrasjonen av fargestoffet eller pigmentet i beleggsløsningen er også angitt i tabell 2. Beleggsløsningen ble påført på den polerte innervegg av en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1, og på de partier som kan komme i kontakt med monomerer, såsom omrører, tørket ved 70°C i 20 minutter og deretter vasket grundig med vann.
Deretter ble den således belagte polymerisasjonsreaktor chargert med 200 kg vinylkloridmonomer, 400 kg avionisert vann, 2,2 kg natriumlaurylsulfat, 3,2 kg cetylalkohol og 300 g a, a'— azobis-2,4-dimetylvaleronitril, og polymerisasjonen ble utført ved 50°C i 10 timer. Etter fullføring av polymerisasjonen ble polymeren uttatt, og polymerisasjonsreaktoren ble vasket innvendig med vann med en strømningsmengde på 0,1^m h, som vist i tabell 2. De ovenfor beskrevne operasjoner fra belegging og chargering til vasking med vann ble utført for hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen ble regulert, og beleggs-dannelsen ble vurdert på tilsvarende måte som beskrevet i eksempel 1. Betingelsene og resultatene er vist i tabell 2.
I tabell 2 er de forsøk som er markert med en stjerne
(<*>) sammenlikningseksempler. Nærmere bestemt er forsøkene 91 og 92 eksempler hvor polymerisasjonsreaktorens innervegg ikke ble behandlet med noen forbindelse. Beleggsløsningen som ble anvendt i forsøkene 104 og 105 ble fremstilt ved å løse 1 del natriumsulfid i 100 deler vann og tilsette 0,5 del fargestoff til den resulterende løsning, etterfulgt av oppvarming ved 80°C i 3 0 minutter.
Eksempel 3
Som vist i tabell 3 ble i hvert forsøk et fargestoff eller et pigment løst eller dispergert i et løsningsmiddel, eventuelt ved tilsetning av en uorganisk forbindelse eller en polymer forbindelse som vist i samme tabell, for fremstilling av én beleggsløsning. Forholdet mellom den uorganiske forbindelse og den polymere forbindelse og konsentrasjonen av fargestoffet eller pigmentet i beleggsløsningen er også angitt i tabell 3. Beleggsløsningen ble påført på den polerte innervegg av en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1, og på de partier som kan komme i kontakt med monomerer, såsom omrører, tørket ved 70°C i 20 minutter og deretter vasket grundig med vann.
Deretter ble den således belagte polymerisasjonsreaktor chargert med 160 kg vinylkloridmonomer, 40 kg vinylacetat-monomer, 400 kg avionisert vann, 600 g gelatin, 2. kg "Trielene" og 350 g laurolperoksyd, og polymerisasjonen ble utført ved 70°C i 6 timer. Etter fullføring av polymerisasjonen ble polymeren uttatt, og polymerisasjonsreaktoren ble vasket innvendig med vann med en strømningsmengde på ■> 0,1 3 m /m <2 >h, som vist i tabell 3. De ovenfor beskrevne operasjoner frå belegging og chargering til vasking med vann ble utført for hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen ble regulert, og beleggs-dannelsen ble vurdert på tilsvarende måte som beskrevet i eksempel 1. Betingelsene og resultatene er vist i tabell 3.
I tabell 3 er de forsøk som er markert med en stjerne
(<*>) sammenlikningseksempler. Nærmere bestemt er forsøkene 158 og 159 eksempler hvor polymerisasjonsreaktorens innervegg ikke ble behandlet med noen forbindelse. Beleggsløsningen som ble anvendt i forsøkene 195 ble fremstilt ved å løse 1 del natriumsulfid i 100 deler vann og tilsette.0,5 del fargestoff til den resulterende løsning, etterfulgt av oppvarming ved 80°C i 30 minutter.
Eksempel 4
Som vist i tabell 4 ble i hvert forsøk et fargestoff eller et pigment løst eller dispergert i et løsningsmiddel, eventuelt ved tilsetning av en uorganisk forbindelse eller en polymer forbindelse som vist i samme tabell, for fremstilling av en beleggsløsning. Forholdet mellom den uorganiske forbindelse og den polymere forbindelse og konsentrasjonen av fargestoffet eller pigmentet i beleggsløsningen er også angitt i tabell 4. Beleggsløsningen ble påført på den polerte innervegg av en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1, og på de partier som kan komme i kontakt med monomerer, såsom omrører, tørket ved 70°C i 20 minutter og deretter vasket grundig med vann.
Deretter ble den således belagte polymerisasjonsreaktor chargert med 200 kg vinylkloridmonomer, 400 kg avionisert vann, 40 g delvis forsåpet polyvinylalkohol, 60 g hydroksypropylmetylcellulose og 80 g di-2-etylheksylperoksydkarbonat, og polymerisasjonen ble utført ved 57°C i 7 timer. Etter fullføring av polymerisasjonen ble polymeren uttatt, og polymerisasjonsreaktoren ble vasket innvendig med vann med en strømningsmengde på 0,1 m^/ iz^ h, som vist i tabell 4. De ovenfor beskrevne operasjoner fra belegging og chargering til vasking med vann ble utført for hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen ble regulert, og beleggs-dannelsen ble vurdert på tilsvarende måte som beskrevet i eksempel 1. Dessuten ble antallet "fiskeøyne" i produktene fra 10., 30., 50., 100., 150. og 200. sats i hvert forsøk bestemt på følgende måte: En blanding av 100 vektdeler polymer fremstilt ved avvanning og tørking av polymeroppslemmingen etter polymerisasjon, 50 vektdeler DOP, 1 vektdel dibutyltinnlavrat, 1 vektdel cetylalkohol, 0,25 vektdeler titanoksyd og 0,05 vektdeler carbon black, ble knadd mellom to valser ved 150°C i
7 minutter, og deretter formet til en plate med tykkelse 0,2 mm. Antall fiskeøyner per 100 cm av platen ble undersøkt ved lystransmisjonsmetoder. Betingelsene og resultatene er vist i tabell 4. I tabell 4 er de forsøk som er markert med en stjerne
(<*>) sammenlikningseksempler. Nærmere bestemt er forsøkene 185 og 186 eksempler hvor polymerisasjonsreaktorens innervegg ikke ble behandlet med noen forbindelse.
Eksempel 5
Som vist i tabell 5 ble i hvert forsøk et fargestoff eller et pigment løst eller dispergert i et løsningsmiddel, eventuelt ved tilsetning av en uorganisk forbindelse eller en polymer forbindelse som vist i samme tabell, for fremstilling av en beleggsløsning. Forholdet mellom den uorganiske forbindelse og den polymere forbindelse og konsentrasjonen av forbindelsen med konjugerte -bindinger i beleggsløsningen er også angitt i tabell 5. Beleggsløsningen ble påført på den polerte innervegg av en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1, og på de partier som kan komme i kontakt med monomerer, såsom omrører, tørket ved 70°C i 20 minutter og deretter vasket grundig med vann.
Deretter ble den således belagte polymerisasjonsreaktor chargert med 200 kg vinylkloridmonomer, 400 kg avionisert vann, 44 g delvis forsåpet polyvinylalkohol, 56 g hydroksypropylmetylcellulose og 60 g tert-butylperoksyneodekanat, polymerisasjonen ble utført ved 52°C i 7 timer. Etter fullføring av polymerisasjonen ble polymeren uttatt, og polymerisasjonsreaktoren ble vasket innvendig med vann med en strømningsmengde på 0,1 m /m h, som vist i tabell 5. De ovenfor beskrevne operasjoner fra belegging og chargering til vasking med vann ble utført for hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen ble regulert, og beleggs-dannelsen ble vurdert på tilsvarende måte som beskrevet i eksempel 1. Betingelsene og resultatene er vist i tabell 5.
I tabell 5 er de forsøk som er markert med en stjerne
(<*>) sammenlikningseksempler. Nærmere bestemt er forsøkene 3 01 og 302 eksempler hvor polymerisasjonsreaktorens innervegg ikke ble behandlet med noen forbindelse. Beleggsløsningen som ble anvendt i forsøkene 333 og 334 ble fremstilt ved å løse 1 del natriumsulfid i 100 deler vann og tilsette 0,5 del fargestoff til den resulterende løsning, etterfulgt av oppvarming ved 80°C i 30 minutter.
Eksempel 6
Som vist i tabell 6 ble i hvert forsøk en forbindelse med konjugerte W-bindinger løst eller dispergert i et løsnings-middel, eventuelt ved tilsetning av en uorganisk forbindelse eller en polymer forbindelse som vist i samme tabell, for fremstilling av en beleggsløsning. Forholdet mellom den uorganiske forbindelse og den polymere forbindelse og konsentrasjonen av forbindelsen med de konjugerte ir-bindinger i beleggsløsningen er også angitt i tabell 6. Beleggsløsningen ble påført på den polerte innervegg av en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1, og på de partier som kan komme i kontakt med monomerer, såsom omrører, tørket ved 70°C i 2 0 minutter og deretter vasket grundig med vann.
Deretter ble den således belagte polymerisasjonsreaktor chargert med 200 kg vinylkloridmonomer, 400 kg avionisert vann, 0,25 kg hydroksypropylmetylcellulose, 0,25 kg sorbitanmonooleat og 50 g a, a' -azobis-2 ,4-dimetylvaleronitril, og polymerisasjonen ble utført ved 70°C i 10 timer. Etter fullføring av polymerisasjonen ble polymeren uttatt, og polymerisasjonsreaktoren ble vasket innvendig med vann med en strømningsmengde på 0,1 nP/m^h, som vist i tabell 2. De ovenfor beskrevne operasjoner fra belegging og chargering til vasking med vann ble utført for hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen ble regulert, og beleggs-dannelsen ble vurdert på tilsvarende måte som beskrevet i eksempel 1. Betingelsene og resultatene er vist i tabell 6.
I tabell 6 er de forsøk som er markert med en stjerne
(<*>) sammenlikningseksempler. Nærmere bestemt er forsøkene 413 og 414 eksempler hvor polymerisasjonsreaktorens innervegg ikke ble behandlet med noen forbindelse.
Eksempel 7
Som vist i tabell 7 ble i hvert forsøk et fargestoff eller et pigment løst eller dispergert i et løsningsmiddel, eventuelt ved tilsetning av en uorganisk forbindelse eller en polymer forbindelse som vist i samme tabell, for fremstilling av en beleggsløsning. Forholdet mellom den uorganiske forbindelse og den polymere forbindelse og konsentrasjonen av forbindelsen med konjugerte 7T-bindinger i beleggsløsningen er også angitt i tabell 7. Beleggsløsningen ble påført på den polerte innervegg av en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1, og på de partier som kan komme i kontakt med monomerer, såsom omrører, tørket ved 60°C i 2 0 minutter og deretter vasket grundig med vann.
Deretter ble den således belagte polymerisasjonsreaktor chargert med 160 kg vinylkloridmonomer, 40 kg vinylacetat-monomer, 400 kg avionisert vann, 600 g gelatin, 2 kg "Trielene" og 350 g laurolperoksyd, og polymerisasjonen ble utført ved 70°C i 6 timer. Etter fullføring av polymerisa-sionen ble polymeren uttatt, og polymerisasjonsreaktoren ble vasket innvendig med vann med en strømningsmengde på 0,1 m 3 /m2 h, som vist i tabell 3. De ovenfor beskrevne operasjoner fra belegging og chargering til vasking med vann ble utført for hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen ble regulert, og beleggs-dannelsen ble vurdert på tilsvarende måte som beskrevet i eksempel 1. Betingelsene og resultatene er vist i tabell 7.
I tabell 7 er de forsøk som er markert med en stjerne
(<*>) sammenlikningseksempler. Nærmere bestemt er forsøkene 4 67 og 4 68 eksempler hvor polymerisasjonsreaktorens innervegg ikke ble behandlet med noen forbindelse.
Eksempel 8
Som vist i tabell 8 ble i hvert forsøk en forbndelse med konjugerte 7f-bindinger løst eller dispergert i et løsnings-middel, eventuelt ved tilsetning av en uorganisk forbindelse eller en polymer forbindelse som vist i samme tabell, for fremstilling av en beleggsløsning. Forholdet mellom den uorganiske forbindelse og den polymere forbindelse og konsentrasjonen av forbindelsen med konjugerte n-bindinger i be-leggsløsningen er også angitt i tabell 8. Beleggsløsningen ble påført på den polerte innervegg av en polymerisasjonsreaktor av rustfritt stål med et innvendig volum på 1000 1, og på de partier som kan komme i kontakt med monomerer, såsom omrører, tørket ved 80°C i 10 minutter og deretter vasket grundig med vann.
Deretter ble den således belagte polymerisasjonsreaktor chargert med 200 kg vinylkloridmonomer, 400 kg avionisert vann, 40 g delvis forsåpet polyvinylalkohol, 60 g hydroksypropylmetylcellulose og 80 g di-2-etylheksylperoksydkarbonat, og polymerisasjonen ble utført ved 57°C i 7 timer. Etter fullføring av polymerisasjonen ble polymeren uttatt, og polymerisasjonsreaktoren ble vasket innvendig med vann med en strømningsmengde på 0,1 m 3 /m 2h, som vist i tabell 8. De ovenfor beskrevne operasjoner fra belegging og chargering til vasking med vann ble utført for hver sats, og dette ble gjentatt for høyst 200 satser.
Kloridionekonsentrasjonen ble regulert, og beleggs-dannelsen ble vurdert på tilsvarende måte som beskrevet i eksempel 1. Dessuten ble antallet "fiskeøyne" i produktene som ble oppnådd i den 10., 30., 50., 100., 150. og 200. sats i hvert forsøk målt på tilsvarende måte som i eksempel 4. Betingelsene og resultatene er vist i tabell 8.
I tabell 8 er de forsøk som er markert med en stjerne
(<*>) sammenlikningseksempler. Nærmere, bestemt er forsøkene 507 og 508 eksempler hvor polymerisasjonsreaktorens innervegg ikke ble behandlet med noen forbindelse.
Claims (14)
1. Fremgangsmåte til fremstilling av en vinylkloridpolymer ved suspensjonspolymerisasjon eller emulsjonspolymerisasjon av vinylkloridmonomer eller en blanding av vinylkloridmonomer og en vinylmonomer som er kopolymeriserbar med vinylkloridmonomeren i et vandig medium, hvor polymerisasjonen utføres i en polymerisasjonsreaktor hvis innervegg og deler av utstyr i denne som kan komme i kontakt med monomeren under polymerisasjonen på forhånd belegges med en flakdanningshindrer som inneholder fargestoff, og/eller pigment og/eller aromatisk eller heterocyklisk forbindelse som har minst 5 konjugerte •'/' -bindinger, karakterisert ved at klorid-ionekonsentras jonen i reaksjonsblandingen styres slik at den er høyst 100 ppm.
2. Fremgangsmåte i samsvar med krav 1, karakterisert ved at flakdanningshindreren dessuten inneholder en uorganisk forbindelse.
3. Fremgangsmåte i samsvar med krav 2, karakterisert ved at den uorganiske forbindelse velges blant kiselsyrer, silikater, salter av jordalkalimetaller, sinkmetaller, aluminiummetaller, tinnmetaller, jernmetaller, krommetaller, manganmetaller, kobbermetaller og platinametaller, samt uorganiske kolloider.
4. Fremgangsmåte i samsvar med krav 3, karakterisert ved at det som uorganisk forbindelse anvendes et silikat, et kiselsyrekolloid eller jern-III-hydroksydkolloid.
5. Fremgangsmåte i samsvar med krav 1 eller 2, karakterisert ved at flakdanningshindreren inneholder et fargestoff og/eller et pigment.
6. Fremgangsmåte i samsvar med krav 5, karakterisert ved at flakdanningshindreren inneholder fargestoff eller pigment valgt blant azofargestoffer og -pigmenter, antrakinonfargestoffer og -pigmenter, indigoidfargestoffer og -pigmenter, ftalocyaninfargestoffer og -pigmenter, karbonfargestoffer og -pigmenter, kinoniminfargestoffer, metinfargestoffer, kinolinfargestoffer, nitrofargestoffer, benzokinonfargestoffer og naftokinonfargestoffer, naftalimidfargestoff og -pigmenter, perinonfargestoffer, sulfidfargestoffer, fluorescerende fargestoffer, azoinfargestoffer og reaktive fargestoffer.
7. Fremgangsmåte i samsvar med krav 6, karakterisert ved at flakdanningshindreren inneholder et azinfargestoff.
8. Fremgangsmåte i samsvar med krav 1 eller 2, karakterisert ved at flakdanningshindreren inneholder en aromatisk eller heterocyklisk forbindelse som har minst 5 konjugerte'//'-bindinger.
9. Fremgangsmåte i samsvar med krav 8, karakterisert ved at den aromatiske eller heterocykliske forbindelse som har minst 5 konjugerte 7^-bindinger er en forbindelse som inneholder minst én aminogruppe.
10. Fremgangsmåte i samsvar med krav 9, karakterisert ved at forbindelsen som inneholder minst én aminogruppe er valgt blant aminonaftalener, såsom diaminonaftalener, triaminonaftalener og tetraaminonaftalener, 1,4-diaminoantracener, 9,10-diaminofenantren, 2,2'-diamino-difenyl, 1,1'-diamino-2,2'-dinaftyl, 2-amino-5-fenyloksazol, 1-amionfenantridin, 2-amino-4-fenyltriazol, 2-amino-5-fenyltiazol, 3-amino-l,5-naftyridin, 1-aminofenantridin, aminoakridiner som 4-aminoakridin, 2-aminoakridin, 1-aminoakridin, og 3,6-diaminoakridin, samt aminofenanziner som 1-aminofenazin, 2-aminofenazin og 2,3-diaminofenazin.
11. Fremgangsmåte i samsvar med krav 1, karakterisert ved at det anvendes et festemiddel for økning av flakdanningshindrerens festeegenskaper.
12. Fremgangsmåte i samsvar med krav 11, karakterisert ved at festemidlet er valgt blant olefinpolymerer, dienpolymerer, acetylenpolymerer, alifatiske vinyl- eller vinylidenpolymrer, aromatiske vinylpolymerer, heterocykliske vinylpolymerer, akryl- eller metakrylpolymerer, polyetre, polysulfider, polysulfoner, addisjonspolymrer, polyestre, polyamider, polyureaer, polyuretaner, lineære kondenserte polymerer, heterocykliske kondenserte polymerer, naturlige polymerer, modifiserte naturlige polymerer, polysiloksaner, organiske metallpolymerer og uorganiske polymerer.
13. Fremgangsmåte i samsvar med krav 1, karakterisert ved at deler av gjenvinningssystemet for ureagerte monomerer hvor flak kan festes, behandles på forhånd med flakdanningshindreren.
14. Fremgangsmåte i samsvar med krav 1, karakterisert ved at innerveggen og de deler av utstyret i polymerisasjonsreaktoren som kan komme i kontakt med monomeren har en overflateruhet på 10 um eller mindre.
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JP15252284A JPS6131406A (ja) | 1984-07-23 | 1984-07-23 | 塩化ビニル系重合体の製造方法 |
JP15596784A JPS6134006A (ja) | 1984-07-26 | 1984-07-26 | 塩化ビニル系重合体の製造方法 |
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NO165757B true NO165757B (no) | 1990-12-27 |
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NO852907A NO165757C (no) | 1984-07-23 | 1985-07-22 | Fremgangsmaate til fremstilling av polyvinylklorid. |
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US5817830A (en) * | 1992-08-14 | 1998-10-06 | Trustees Of The University Of Pennsylvania | Pyrrolic compounds |
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JP2678711B2 (ja) * | 1992-08-28 | 1997-11-17 | 信越化学工業株式会社 | 重合体スケール付着防止剤及びそれを使用する重合体製造方法 |
GB9312853D0 (en) * | 1993-06-22 | 1993-08-04 | Euro Celtique Sa | Chemical compounds |
US5607503A (en) * | 1993-09-03 | 1997-03-04 | Refract-A-Gard Pty Limited | Silica-based binder |
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US5922751A (en) * | 1994-06-24 | 1999-07-13 | Euro-Celtique, S.A. | Aryl pyrazole compound for inhibiting phosphodiesterase IV and methods of using same |
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