GB2061980A - Method for the preparation of vinyl chloride resins by suspension polymerization - Google Patents
Method for the preparation of vinyl chloride resins by suspension polymerization Download PDFInfo
- Publication number
- GB2061980A GB2061980A GB8033747A GB8033747A GB2061980A GB 2061980 A GB2061980 A GB 2061980A GB 8033747 A GB8033747 A GB 8033747A GB 8033747 A GB8033747 A GB 8033747A GB 2061980 A GB2061980 A GB 2061980A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- polymerization
- direct
- water
- red
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229920005989 resin Polymers 0.000 title claims abstract description 26
- 239000011347 resin Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 19
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical group 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 14
- -1 alkali metal salt Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- 239000004800 polyvinyl chloride Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 9
- 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 claims description 8
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 7
- 150000003567 thiocyanates Chemical group 0.000 claims description 6
- AOMZHDJXSYHPKS-UHFFFAOYSA-L disodium 4-amino-5-hydroxy-3-[(4-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(N=NC=3C=CC=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 AOMZHDJXSYHPKS-UHFFFAOYSA-L 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- CEQFOVLGLXCDCX-UHFFFAOYSA-N 2-[[4-(dimethylamino)phenyl]diazenyl]benzoic acid Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-UHFFFAOYSA-N 0.000 claims description 3
- YCMOBGSVZYLYBZ-UHFFFAOYSA-L disodium 5-[[4-[4-[(2-amino-8-hydroxy-6-sulfonatonaphthalen-1-yl)diazenyl]phenyl]phenyl]diazenyl]-2-hydroxybenzoate Chemical compound NC1=CC=C2C=C(C=C(O)C2=C1N=NC1=CC=C(C=C1)C1=CC=C(C=C1)N=NC1=CC=C(O)C(=C1)C(=O)O[Na])S(=O)(=O)O[Na] YCMOBGSVZYLYBZ-UHFFFAOYSA-L 0.000 claims description 3
- VSSMQLIMSVAUDK-UHFFFAOYSA-L disodium;5-[(4-ethoxyphenyl)diazenyl]-2-[4-[(4-ethoxyphenyl)diazenyl]-2-sulfonatophenyl]sulfanylbenzenesulfonate Chemical compound [Na+].[Na+].C1=CC(OCC)=CC=C1N=NC(C=C1S([O-])(=O)=O)=CC=C1SC1=CC=C(N=NC=2C=CC(OCC)=CC=2)C=C1S([O-])(=O)=O VSSMQLIMSVAUDK-UHFFFAOYSA-L 0.000 claims description 3
- LDIDZFWGINXVSD-UHFFFAOYSA-N sodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C4=C(C=C(C=C4C=C3S(=O)(=O)O)S(=O)(=O)O)N)O)N=NC5=C(C6=C(C=C(C=C6C=C5S(=O)(=O)O)S(=O)(=O)O)N)O.[Na+] LDIDZFWGINXVSD-UHFFFAOYSA-N 0.000 claims description 3
- BLFZMXOCPASACY-UHFFFAOYSA-N 1,4-bis(propan-2-ylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC(C)C)=CC=C2NC(C)C BLFZMXOCPASACY-UHFFFAOYSA-N 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical class CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 2
- SEXWRZHFWPOWFA-VAWYXSNFSA-N 5-(phenylcarbamoylamino)-2-[(e)-2-[4-(phenylcarbamoylamino)-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC(=O)NC=3C=CC=CC=3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(=O)NC1=CC=CC=C1 SEXWRZHFWPOWFA-VAWYXSNFSA-N 0.000 claims description 2
- WRSWXNQFTKCPHT-UHFFFAOYSA-N 5-bromo-2-(9-chloro-3-hydroxybenzo[g][1]benzothiol-2-yl)indol-3-one Chemical compound [O-]c1c(sc2c1ccc1cccc(Cl)c21)C1=[NH+]c2ccc(Br)cc2C1=O WRSWXNQFTKCPHT-UHFFFAOYSA-N 0.000 claims description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 claims description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-N 0.000 claims description 2
- JQYMGXZJTCOARG-UHFFFAOYSA-N Reactive blue 2 Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S(O)(=O)=O)C=C1NC(C=C1S(O)(=O)=O)=CC=C1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(O)(=O)=O)=C1 JQYMGXZJTCOARG-UHFFFAOYSA-N 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
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 238000005282 brightening Methods 0.000 claims description 2
- BEQIIZJSZSVJJK-UHFFFAOYSA-M chembl2028372 Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1N=NC1=C(O)C=CC2=CC=CC=C12 BEQIIZJSZSVJJK-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- VDRKHPFIMDTBNX-UHFFFAOYSA-L disodium 7-amino-8-[[4-[4-[(2-amino-8-oxido-6-sulfonaphthalen-1-yl)diazenyl]phenyl]phenyl]diazenyl]-3-sulfonaphthalen-1-olate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=CC4=CC(=CC(=C43)[O-])S(=O)(=O)O)N)N=NC5=C(C=CC6=CC(=CC(=C65)[O-])S(=O)(=O)O)N.[Na+].[Na+] VDRKHPFIMDTBNX-UHFFFAOYSA-L 0.000 claims description 2
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 claims description 2
- DXRWYIKGBIPGAG-UHFFFAOYSA-N sodium 3-hydroxy-4-[(2-hydroxynaphthalen-1-yl)diazenyl]-7-nitronaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(=C1)C=CC(=C2N=NC3=C4C=CC(=CC4=C(C=C3O)S(=O)(=O)O)[N+](=O)[O-])O.[Na+] DXRWYIKGBIPGAG-UHFFFAOYSA-N 0.000 claims description 2
- SZKZLHLJJLRYKJ-UHFFFAOYSA-N sodium 4-amino-3-[[4-[4-[(2,4-diaminophenyl)diazenyl]phenyl]phenyl]diazenyl]-5-hydroxy-6-phenyldiazenylnaphthalene-2,7-disulfonic acid Chemical compound C1=CC=C(C=C1)N=NC2=C(C3=C(C(=C(C=C3C=C2S(=O)(=O)O)S(=O)(=O)O)N=NC4=CC=C(C=C4)C5=CC=C(C=C5)N=NC6=C(C=C(C=C6)N)N)N)O.[Na+] SZKZLHLJJLRYKJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000375 suspending agent Substances 0.000 claims description 2
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 claims description 2
- 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 claims description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 claims description 2
- PEAGNRWWSMMRPZ-UHFFFAOYSA-L woodstain scarlet Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 PEAGNRWWSMMRPZ-UHFFFAOYSA-L 0.000 claims description 2
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 22
- 230000008021 deposition Effects 0.000 abstract description 11
- 239000012736 aqueous medium Substances 0.000 abstract description 7
- 238000004040 coloring Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- 238000000151 deposition Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012934 organic peroxide initiator Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ALWXETURCOIGIZ-UHFFFAOYSA-N 1-nitropropylbenzene Chemical compound CCC([N+]([O-])=O)C1=CC=CC=C1 ALWXETURCOIGIZ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- ASDREVVGQFYRTH-UHFFFAOYSA-N 3-[[2-acetamido-4-[(4-amino-6-chloro-1,3,5-triazin-2-yl)amino]phenyl]diazenyl]naphthalene-1,5-disulfonic acid Chemical compound C=1C=C(N=NC=2C=C3C(=CC=CC3=C(C=2)S(O)(=O)=O)S(O)(=O)=O)C(NC(=O)C)=CC=1NC1=NC(N)=NC(Cl)=N1 ASDREVVGQFYRTH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- AZOPGDOIOXKJRA-UHFFFAOYSA-L chembl1817788 Chemical compound [Na+].[Na+].C1=C(C([O-])=O)C(O)=CC=C1N=NC1=CC=C(C=2C=CC(=CC=2)N=NC=2C=C(C(O)=CC=2)C([O-])=O)C=C1 AZOPGDOIOXKJRA-UHFFFAOYSA-L 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KJPDHFPPVKRMMG-UHFFFAOYSA-L disodium 2,4-diamino-3-[[4-[4-[(2,6-diamino-3-methyl-5-sulfonatophenyl)diazenyl]-3-methylphenyl]-2-methylphenyl]diazenyl]-5-methylbenzenesulfonate Chemical compound [Na+].[Na+].CC1=CC(S([O-])(=O)=O)=C(N)C(N=NC=2C(=CC(=CC=2)C=2C=C(C)C(N=NC=3C(=C(C=C(C)C=3N)S([O-])(=O)=O)N)=CC=2)C)=C1N KJPDHFPPVKRMMG-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910021432 inorganic complex Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 235000012731 ponceau 4R Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- FZUOVNMHEAPVBW-UHFFFAOYSA-L quinoline yellow ws Chemical compound [Na+].[Na+].O=C1C2=CC=CC=C2C(=O)C1C1=NC2=C(S([O-])(=O)=O)C=C(S(=O)(=O)[O-])C=C2C=C1 FZUOVNMHEAPVBW-UHFFFAOYSA-L 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- MTNKEJFOGYPHON-AAKIMCHBSA-N sodium;5-[(z)-(3-carboxy-5-methyl-4-oxocyclohexa-2,5-dien-1-ylidene)-(2,6-dichlorophenyl)methyl]-2-hydroxy-3-methylbenzoic acid Chemical compound [Na+].C1=C(C(O)=O)C(=O)C(C)=C\C1=C(C=1C(=CC=CC=1Cl)Cl)/C1=CC(C)=C(O)C(C(O)=O)=C1 MTNKEJFOGYPHON-AAKIMCHBSA-N 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides means for preventing polymer scale deposition on the reactor walls during the suspension polymerization of vinyl chloride monomer in an aqueous medium.The method of the invention comprises (a) coating of the reactor walls, prior to polymerization, with an aqueous coating solution containing an organic dye having sulfonic acid groups or carboxylic acid groups in the alkali metal or ammonium salt form or an alkali metal or ammonium salt of an organic sulfonic acid or carboxylic acid having at least one pair of conjugated double bonds per molecule, followed by drying, and (b) adding a water-soluble thiocyanate to the polymerization mixture. Previously, the use of an organic peroxide with a relatively large solubility in water as initiator in the reaction had led to large scale deposition on the reactor walls but this is avoided under the conditions specified above. Use of such an organic peroxide is advantageous in improving the thermal stability and initial colouring of the resin products.
Description
SPECIFICATION
Method for the preparation of vinyl chloride resins by suspension polymerization
The present invention relates to the preparation of a polyvinyl chloride resin by suspension polymerization.
At least in its preferred forms, it provides a method for the preparation of a polyvinyl chloride resin, having
excellent heat stability as well as remarkably decreased initial coloring in molding, by the suspension
polymerization of the vinyl chloride monomer in an aqueous medium, in which the efficiency of the
polymerization can be markedly improved owing to the substantially reduced amount of polymer scale
build-up on the walls of the polymerization reactor.
Needless to say, polyvinyl chloride resins are in most cases prepared by the suspension polymerization of
vinyl chloride monomer in an aqueous medium. One of the greatest technical problems in the suspension
polymerization of vinyl chloride monomer in an aqueous polymerization medium is the polymer scale
build-up on the walls of the polymerization reactor. In the suspension polymerization of vinyl chloride
monomer in an aqueous medium contained in a polymerization reactor of stainless steel or other materials,
polymer scale deposits on the inner walls of the reactor or other surfaces coming into contact with the
monomer such as the stirrer installed in the reactor result in not only a decrease of the polymer yield but also
a reduction of the cooling capacity of the reactor with consequent decrease of the overall production
capacity.In addition, the polymer scale often comes off from the reactor walls and enters the resin product
leading to lowered product quality due to the increased amount of so-called fish-eyes, which is a problem in
the molding fabrication of polyvinyl chloride resins. Even worse, removal of the polymer scale after each run
of the polymerization takes much labor and time causing decreased productivity as well as the serious
problem of the danger to workers' health brought about by the toxicity of the vinyl chloride monomer which
is contained in the polymer scale in large amounts.
On the other hand, it is also known in the art that some of the factors determining the product quality of the
polyvinyl chloride resins are influenced by several parameters in the polymerization reaction. For example,
heat resistance and initial coloring in molding fabrication of the resin are substantially affected by the kind of
polymerization initiator used in the polymerization reaction. As is well known, the polymerization initiators
used in the suspension polymerization of vinyl chloride monomer are always monomer-soluble ones. These
monomer-soluble polymerization initiators are almost insoluble or hardly soluble in water but it should be
noted that even these monomer-soluble polymerization initiators have a solubility in water even though the
solubility may be very small.It has come to be known in the art that the solubility of the polymerization
initiator in water is a parameter affecting the heat resistance and initial coloring of the polyvinyl chloride
resin products polymerized therewith and, in this respect, an organic peroxide initiator having a relatively
large solubility in water, say 0.2 % by weight or more at 20"C, is advantageous in improving the heat
resistance and initial coloring of the resin products in comparison with an organic peroxide having a lower
solubility in water.
Despite the above described advantages in the thermal stability of the resin products polymerized
therewith, such organic peroxides having a relatively large solubility in water are, in practice, not used
widely in the industrial production of polyvinyl chloride resins. This is partly due to the undesirable fact that
the use of such an organic peroxide results in much larger amounts of polymer scale deposition on the
reactor walls than is the case with less water-soluble organic peroxides.
Of course, various attempts have been made to decrease the amount of polymer scale deposition in the
suspension polymerization of vinyl chloride monomer in an aqueous medum. Generally, there have been
two approaches, i.e. that of providing the reactor walls with a coating layer of a material less susceptible to
deposition of polymer scale prior to polymerization and that of adding certain specific additives to the
polymerization mixture under reaction.
As the coating materials used in the first approach, there have been proposed, for example, polar organic
compounds, organic dyes and pigments including amine compounds, quinone compounds, aldehyde
compounds and the like (see, for example, Japanese Patent Publication 45-30343, 45-30835 and so on), polar organic compounds or organic dyes treated with a metal salt (see Japanese Patent Publication 52-24953),
mixtures of an electron donor compound and an electron acceptor compound (see Japanese Patent
Publication 53-28347) and certain inorganic salts and inorganic complex compounds (see Japanese Patent ,Publication 52-24070).
The above mentioned coating methods are effective when the polymerization initiator used in the reaction
is an azo compound or an organic peroxide having long-chain alkyl groups and consequently a very small
solubility in water. Unfortunately, these methods are almost ineffective in decreasing the polymer scale
deposition when the polymerization is carried out by use of an organic peroxide having a relatively large
solubility in water. Thus, no effective means have been developed for polymer scale prevention in the
polymerization of vinyl chloride monomer using an organic peroxide having a solubility in water of 0.2 % by
weight or larger as the polymerization initiator.
The present invention consists in an improvement in the suspension polymerization of vinyl chloride
monomer or a monomer mixture mainly composed of vinyl chloride in an aqueous polymerization medium
by use of a monomer-soluble organic peroxide having a solubility in water of at least 0.2 % by weight at 20"C as a polymerization initiator, which improvement comprises (a) prior to the introduction of the polymerization mixture into the polymerization reactor, coating the inner walls of the polymerization reactor with an aqueous coating solution containing an organic dye having a sulfonic acid group -SO3H or carboxylic acid group -COOH in the molecule in the form of an alkali metal or ammonium salt or an alkali metal salt or ammonium salt of an organic sulfonic acid or carboxylic acid having at least one pair of conjugated double bonds in the molecule, followed by drying, and (b) adding a water-soluble thiocyanate into the polymerization mixture in an amount of at least 1 p.p.m. based on the amount of the monomer or monomers.
Preferred embodiments of the invention will now be described.
The suspension polymerization of vinyl chloride monomer according to the invention is applicable not only to the homopolymerization of vinyl chloride monomer but also to the copolymerization of vinyl chloride monomer with one or more copolymerizable ethylenically unsaturated monomers provided that the main component, say, 50 % by weight or more, is vinyl chloride. The comonomers copolymerizable with vinyl chloride are exemplified by vinyl esters such as vinyl acetate, vinyl propionate and the like, vinyl ethers, acrylic and methacylic acids and esters thereof, acrylonitrile, vinylketones, vinylidene halides such as vinylidene chloride, vinylidene fluoride and the like and olefins such as ethylene, propylene and the like.
The procedure for the polymerization may be conventional and the same as the prior art method excepting the coating of the reactor walls and the addition of the thiocyanate as mentioned above. For example, the dispersing agents used for suspending the monomer or monomer mixture in the aqueous medium include water-soluble synthetic and natural polymeric substances such as completely or partially saponified polyvinyl alcohol, cellulose ethers, e.g. methylcellulose, hydroxypropylmethylcellulose and the like, polyacrylic acid, copolymers of vinyl acetate and maleic anhydride, gelatin and starch, nonionic surface active agents such as sorbitan monolaurate, sorbitan trioleate and the like and dispersion aids such as carboxymethylcellulose and the like.
As has been mentioned before, the method of the invention is specifically applicable to the suspension polymerization of vinyl chloride in an aqueous medium in which the polymerization initiator used is a monomer-soluble organic peroxide having a solubility in water of at least 0.2 % by weight at 200C although no adverse effects are produced even when the method is applied to the polymerization of vinyl chloride with a polymerization initiator which is an azo compound or an organic peroxide having a greater solubility in water.
Examples of the above mentioned relatively water-soluble organic peroxides are di-2-ethoxyethylperoxy dicarbonate, bis-3-methoxybutylperoxy dicarbonate and dibutoxyethylperoxy dicarbonate, referred to hereinafter as EEP, MC and BEP, respectively, for brevity, although the applicability of the method is not limited to these three initiators.
The coating solution to be applied to the inner walls ofthe polymerization reactor and, according to need, to the surfaces of other parts such as stirrer of the reactor coming into contact with the monomer or monomers during polymerization, is prepared by dissolving the above mentioned alkali or ammonium salts of organic dyes or acids in water.
The organic dyes having a sulfonic acid group or carboxylic acid group in the molecule in the form of an alkali metal salt or ammonium salt are exemplified by: C.I. Direct Yellow 1; C.I. Acid Yellow 38; C.l. Acid
Yellow 3; C.I. Reactive Yellow 3; C.I. Direct orange 2; C.I. Direct Orange 10; C.l. Direct Red 1; C.l. Acid Red 2;
C.i. Acid Red 18; C.l. Acid Red 52; C.l. Acid Red 73; C.l. Direct Red 186; C.l. Direct Red 92; C.l. Basic Red 2; C.l.
Direct Violet 1; C.l. Direct Violet 22; C.l. Basic Violet 10; C.l. Acid Violet 11; C.l. Acid Violet 78; C.I. Mordant
Violet 5; C.l. Direct Blue 6; C.I. Direct Blue 71; C.l. Direct Blue 106; C.I. Reactive Blue 2; C.l. Reactive Blue 4; 0.1 Reactive Blue 18; C.I. Acid Blue 116; C.l. Acid Blue 158; C.I. Mordant Blue 1;C.I. Mordant Black 1; C.l.
Mordant Black 5; C.l. Acid Black 2; C.l. Direct Black 38; C.I. Solubilized Vat Black 1; C.l. Fluorescent
Brightening Agent 30; C.l. Fluorescent Brightening Agent 32; C.I. Azoic Brown 2 and the like.
The organic sulfonic acids or carboxylic acids having at least one part of conjugated double bonds in the molecule to be used as the solute in the coating solution in the form of an alkali metal or ammonium salt are exemplified by : toluidines; a-naphthalenesulfonic acid, anthraquinonesulfonic acids; dodecylbenzenesulfonic acid; p-toluenesulfonic acid; abietic acid; isonicotinic acid; benzoic acid; phenylglycine; 3-hydroxy-2naphthoic acid and the like.
The coating solution is prepared by dissolving one or more of the above specified organic dyes or organic sulfonic acids or carboxylic acids, all in the form of the salts, in water. The concentration of the coating solution is not important in so far as the coating can be performed without inconvenience to give a suitable coating amount on the reactor walls.
The coating solution prepared as above is usually more or less alkaline but it is preferable that the coating solution is used after adjusting the pH value of the solution so that it does not exceed 7 by adding a small amount of an acid after dissolution of the salts of the organic dyes or organic sulfonic acids or carboxylic acids. Suitable acids include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, carbonic acid, perchloric acid, molybdic acid, tungstic acid, formic acid, acetic acid, oxalic acid, lactic acid, maleic acid, glycolic acid, thioglycolic acid, phytic acid and the like. It is convenient to add these acids to the coating solution as an aqueous solution prepared in advance.
The aqueous coating solution is applied to the inner walls of the polymerization reactor and other surfaces coming into contact with the monomer or monomers by a suitable method, e.g. spraying, brush coating and the like, and the thus coated surface is then thoroughly dried, if necessary, by heating. The surface to be coated with the coating solution may be heated in advance at a temperature of 40 to 100"C before coating. In any case, the coated and dried surface is washed with water, if necessary.
The aqueous coating solution may be prepared by use of a mixed solvent of water and a water-miscible organic solvent, if desired. An advantage is obtained in this way in that the drying of the coated surface is accelerated necessitating no heating for drying in some cases. Suitable organic solvents include alcoholic solvents, ester solvents and ketone solvents.
The coating amount with the coating solution is preferably such that the amount as dried is at least 0.001 g/m2 on the coated surface, as in the prior art coating methods for polymer scale prevention.
After completion of the coating of the reactor walls in the above described manner, the polymerization reaction is started in the usual manner by introducing water for the polymerization medium, dispersing or suspending agent, polymerization initiator and the vinyl chloride monomer or monomers as well as other optional ingredients to form the polymerization mixture. It is essential that at least water-soluble thiocyanate is added to the polymerization mixture.
The water-soluble thiocyanates suitable for use in the method of the invention are exemplified by thiocyanates of an alkali metal such as sodium, potassium and cesium, ammonium thiocyanate and thiocyanates of alkaline earth metals such as magnesium, calcium, strontium and barium. These thiocyanates may be added directly to the polymerization mixture to be dissolved in the aqueous medium, preferably before the start of the polymerization run, although about the same degree of the desired effects can be obtained even when the thiocyanate is added after the polymerization has been started (if not too late).
The amount of the thiocyanate to be added to the polymerization mixture is desirably at least 1 p.p.m. by weight based on the amount of the vinyl chloride monomer or monomer mixture. The upper limit of the amount of the thiocyanate is 500 p.p.m. by weight or, preferably, 100 p.p.m. by weight based on the monomer or monomer mixture. This upper limit is determined by the adverse effects on the quality of the resin products with an excessively large amount of the thiocyanate whereas no particular additional effects can be obtained with regard to polymer scale prevention.
Although the method of the invention is applicable to the suspension polymerization of vinyl chloride not only with an organic peroxide initiator having a solubility in water of at least 0.2 % by weight but also with such an initiator having a solubility in water smaller than 0.2 % by weight at 20"C, the organic peroxide cannot have an excessively large solubility in water since the polymerization in such a mixture containing an excessively water-soluble organic peroxide initiator proceeds rather like an emulsion polymerization so that the desired suspension polymerizate of the polyvinyl chloride resin is not obtained.In this regard, the polymerization according to the present invention should be carried out by use of an organic peroxide polymerization initiator having a solubility in water not exceeding 10 % by weight or, preferably, not exceeding 5 % by weight at 20"C.
The method of the present invention wll now be illustrated in further detail by way of examples.
Example 1 (Experiments No. 1 to No. 29).
Four series of polymerization tests were undertaken each using 7 kinds of monomer-soluble organic peroxides as the polymerization initiator. The organic peroxides were: di-2-ethylhexylperoxy dicarbonate, lauroyl peroxide, 3,5,5-trimethyl hexanoyl peroxide and a-cumylperoxy neodecanoate, referred to hereinafter as OPP, LPO, L-355 and L-188, respectively, for brevity, in addition to the aforementioned EEP, MC and
BEP.
The solubility of these peroxides in water was determined by dispersing an excess amount of each of the peroxides in water at 20"C and, after establishment of the equilibrium, iodometrically titrating the aqueous solution obtained by centrifugal separation of the dispersion. The results were: OPP 0.04 % by weight; LPO 0.003 % by weight; L-355 0.05 % by weight; L-1 88 0.01 % by weight; EEP 0.41 % by weight; MC 0.24 % by weight; and BEP 0.20 % by weight.
The procedure for each of the polymerization runs was as follows. In the first place, three kinds of coating solutions were prepared with the formulations given below and the inner walls of a 1000-liter capacity polymerization reactor made of stainless steel and the surface of the stirrer installed in the reactor were coated with either one of the coating solutions followed by drying of the coated surfaces by heating for 10 minutes at 90"C. The formulations of the coating solutions were:
.Coating solution A : 0.1 % by weight of methyl alcohol solution of C.l. Solvent Black 7;
Coating solution B : 0.1 % by weight methyl alcohol solution of sodium thiocyanate; and
Coating solution C : 0.1 % by weight aqueous solution of C.l. Acid Black 2 having a pH value of 3.0 as
adjusted by adding sulfuric acid.
The coating amount with each of the coating solutions was 0.1 gim2 as dried.
Into the thus surface-treated polymerization reactor were introduced 500 kg of water containing 150 g of a partially saponified polyvinyl alcohol, one of the above named organic peroxides in an amount of 500 g for
LPO or 100 g for each of the other peroxides and 250 kg of vinyl chloride monomer together with or without the addition of 2.5 g of ammonium thiocyanate and polymerization run was carried out by heating at 50"C for 10 hours in the usual manner. After completion of the polymerization reaction, the polymerizate slurry was discharged out of the polymerization reactor and the amount of the polymer scale deposited on the reactor walls was examined to give the results set out in Table 1 below. For comparison, an additional polymerization run was undertaken without the coating treatment of the reactor walls to give the results also given in the table.
TABLE 1
(Polymer scale deposition g/m2) Coating Ammonium Organic peroxide
solution thiocyanate
OPP LPO L-355 L-188 EEP,,,. MC BEP
A Yes 1 2 1 3 450 400 250
B Yes 12 18 25 33 550 600 320
C Yes 1 2 1 4 0 0 0
C No 1 3 3 8 300 100 85
None No - - - - 1500 -
As is clear from the results shown in Table 1, of which the experiments initiated by EEP, MC or BEP and with the coating solution C for the coating treatment and addition of ammonium thiocyanate are the examples in accordance with the invention, the polymer scale deposition in the polymerization with EEP, MC or BEP can be almost completely eliminated only when both the two measures of coating and thiocyanate addition are takeri in accordance with the invention.
Example 2 fExperiments No. 30 to No. 41).
Aqueous coating solutions were prepared each by dissolving one of the coating compounds indicated in
Table 2 below in a concentration of 1 % by weight with subsequent adjustment of the value of pH to 4.0 with addition of acetic acid. The inner walls of a 1000-liter capacity polymerization reactor made of stainless steel and the surface ofthe stirrer installed in the reactor were coated with the coating solutions in a coating amount of 0.1 g/m2 as dried followed by drying by heating at 90"C for 10 minutes and washing with water.
Into the thus treated polymerization reactor were introduced 400 kg of water, 250 g of a partially saponified polyvinyl alcohol, 25 g of a hydroxypropylmethylcellulose, 75 g of EEP and 200 kg of vinyl chloride monomer without or with addition of ammonium thiocyanate in an amount as indicated in Table 2 and the polymerization was carried out by heating the polymerization mixture at 570C for 12 hours.
After completion of the polymerization reaction, the polymerizate slurry was discharged out of the reactor and the amount of the polymer scale deposition on the reactor walls was examined to give the results set out in the table. In parallel, the dried polyvinyl chloride resin product obtained in each of the polymerization runs was examined for the amount of fish-eyes and the thermal stability in the test procedures given below to give the results shown in Table 2. The thermal stability of the resin product obtained in the last-given experiment was somewhat inferior to those obtained in the other polymerization runs indicating that an excessively large amount of the thiocyanate was disadvantageous to the thermal stability of the resin product.
Testing of fish-eyes: a resin compound composed of 100 parts by weight of the resin product, 50 parts by weight of dioctyl phthalate, 1 part by weight of dibutyltin dilaurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of titanium dioxide and 0.05 part by weight of carbon black was kneaded in a two-roller mill at 1500for 7 minutes and then shaped into a sheet of 0.2 mm thickness, of which the number of pieces of fish-eyes was counted for 100 cm2 area of the sheet under illumination with transmitted light.
Testing of thermal stability: a resin compound composed of 100 parts by weight of the resin product, 1 part by weight of stearic acid and 1 part by weight of dibutyltin maleate was kneaded in a two-roller mill at 17000 with a roll gap of 0.7 mm for 10 minutes and then shaped into a sheet of 0.7 mm thickness. The test pieces taken from this sheet were heated in a Geer's oven at 180 C and the time to the blackening of the test piece in minutes was taken as a measure of the thermal stability of the resin product.
TABLE 2
Ammonium Fish- Thermal Polymer
Coating compound thiocyanate eyes, stabil- scale
added, p.p.m. pieces ity, deposi
by weight minutes tion,
per monomer g/m2 None None 60 120 1600
None 10 55 120 1500 C.l.AcidBlue116 None 40 120 350 C.l.AcidBlue116 10 8 120 0
Ammonium abietate 10 10 120 3
Sodium a-napthalenesulfonate 10 10 120 2 C.l. Direct blue 6 20 6 120 0 0.1. Acid Violet 78 1 10 120 3 C.l. Acid Violet 78 10 6 120 1 C.l. Acid Violet 78 50 4 120 0 0.1. Acid Violet78 100 4 120 0 0.1. Acid Violet 78 1000 4 80 0
Example 3 (Experiments No. 42 to No. 48).
Aqueous coating solutions were prepared each by dissolving one of the coating compounds indicated in
Table 3 below in a concentration of 1 % by weight with subsequent adjustment of the value of pH to 2.5 with addition of phosphoric acid. The inner walls of a 100-liter capacity polymerization reactor made of stainless steel and the surface of the stirrer installed in the reactor were coated with the thus prepared coating solutions in a coating amount of 0.1 g/m2 as dried followed by drying with heating at 900C for 10 minutes and washing with water.
Into the thus coated polymerization reactor were introduced 40 kg of water, 17 kg of vinyl chloride monomer, 3 kg of vinyl acetate monomer, 12 g of a partially saponified polyvinyl alcohol, 4 g of a hydroxypropylmethylcellulose, 6 g of MC and 200 g oftrichloroethylene without or with addition of a thiocyanate of the kind and in an amount as indicated in Table 3 and, after 15 minutes of preliminary agitation, polymerization was carried out by heating the polymerization mixture to a temperature of 58"C for 12 hours.
After completion of the polymerization reaction, the polymerizate slurry was discharged out of the polymerization reactor and the amount of the polymer scale deposition on the reactor walls was examined to give the results shown in Table 3.
TABLE 3
Thiocyanate added Polymer
Coating compound (p.p.m. by weight per scale
monomer) deposi
tion, glum2 None None 1800
None Ammonium thiocyanate 1600
(10) 0.1. Acid Black2 None 1300 C.l. Acid Black 2 Ammonium thiocyanate 3
(10) C.l. Acid Red 2 Sodium thiocyanate 2
(20) C.l. Acid Yellow 38 Calcium thiocyanate 1
(20) C.l. Direct Red 1 Potassium thiocyanate 1
(10)
Claims (8)
1. A method for the preparation of a polyvinyl chloride resin by the suspension polymerization of vinyl chloride monomer or a monomer mixture mainly composed of vinyl chloride monomer in an aqueous polymerization medium containing a suspending agent and a monomer-soluble polymerization initiator which is an organic peroxide having a solubility in water of at least 0.2 % by weight at 20"C in a polymerization reactor, which comprises (a) coating, priorto polymerization, the inner wall surfaces of the polymerization reactor with an aqueous coating solution containing, dissolved therein, at least one compound selected from (i) organic dyes having at least one sulfonic acid group or carboxylic acid group per molecule in the form of an alkali metal salt or ammonium salt, and (ii) alkali metal salts or ammonium salts of organic sulfonic acids and carboxylic acids having at least one pair of conjugated double bonds per molecule, followed by drying, and (b) including at least one water-soluble thiocyanate in the polymerization mixture in the polymerization reactor.
2. The method as claimed in claim 1 wherein acid is added if necessary to adjust the pH of the aqueous coating solution to a pH value not exceeding 7.
3. The method as claimed in claim 1 or 2 wherein the coating on the inner wall surfaces of the polymerization reactor deposited from the aqueous coating solution is at least 0.001 g/m2 as dried.
4. The method as claimed in claim 1, 2 or 3 wherein the water-soluble thiocyanate is selected from thiocyanates of alkali metals, ammonium thiocyanate and thiocyanates of alkaline earth metals.
5. The method as claimed in any preceding claim wherein the water-soluble thiocyanate is included in the polymerization mixture in an amount in the range from 1 to 500 p.p.m. by weight based on the vinyl chloride monomer or the monomer mixture.
6. The method as claimed in any preceding claim wherein the organic dye is selected from C.l. Direct
Yellow 1, C.l. Acid Yellow 38, C.l. Acid Orange 2, C.l. Direct Orange 10, C.l. Direct Red 1, C.l. Acid Red 2, C.l.
Acid Red 18, C.l. Acid Red 52, C.l. Acid Red 73, C.l. Direct Red 186, C.l. Direct Red, 92, C.l. Basic Red 2, C.l.
Direct Violet 1, C.l. Direct Violet 22, C.l. Basic Violet 10, C.l. Acid Violet 11,0.1. Acid Violet 78, C.l. Mordant Violet 5, C.l. Direct Blue 6, C.l. Direct Blue 71, C.l. Direct Blue 106, C.l. Reactive Blue 2, C.l. Reactive Blue 4, C.l.
Reactive Blue 18, C.l. Acid Blue 116, C.l. Acid Blue 158, C.i. Mordant Black 1, C.l. Mordant Black 5, C.l. Acid
Black 2, C.l. Direct Black 38, C.l. Solubilized Vat Black 1, C.l. Fluorescent Brightening Agent 30, C.l. Fluorescent
Brightening Agent 32 and C.l. Azoic Brown 2 and the organic sulfonic acid or carboxylic acid having at least one pair of conjugated double bonds per molecule is selected from toluidene, a-naphthalenesulfonic acid, anthraquinonesulfonic acids, dodecylbenzenesulfonic acids, p-toluenesulfonic acid, abietic acid, isonicotinic acid, benzoic acid, phenylglycine and 3-hydroxy-2-naphthoic acid.
7. The method as claimed in claim 1, substantially as hereinbefore described in any of the Examples.
8. A polyvinyl chloride resin when prepared by a method according to any preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54136262A JPS606361B2 (en) | 1979-10-22 | 1979-10-22 | Polymerization method of vinyl chloride monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2061980A true GB2061980A (en) | 1981-05-20 |
| GB2061980B GB2061980B (en) | 1983-06-29 |
Family
ID=15171066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8033747A Expired GB2061980B (en) | 1979-10-22 | 1980-10-20 | Method for the preparation of vinyl chloride resins by suspension polymerization |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS606361B2 (en) |
| AT (1) | AT369755B (en) |
| BE (1) | BE885813A (en) |
| BR (1) | BR8006772A (en) |
| CA (1) | CA1193394A (en) |
| CH (1) | CH645392A5 (en) |
| CU (1) | CU21471A (en) |
| DE (1) | DE3039543A1 (en) |
| DK (1) | DK443880A (en) |
| ES (1) | ES8107254A1 (en) |
| FR (1) | FR2467860B1 (en) |
| GB (1) | GB2061980B (en) |
| HU (1) | HU191809B (en) |
| IN (1) | IN151895B (en) |
| IT (1) | IT1133972B (en) |
| MX (1) | MX155347A (en) |
| NL (1) | NL8005812A (en) |
| NO (1) | NO803099L (en) |
| PL (1) | PL227440A1 (en) |
| PT (1) | PT71944B (en) |
| SE (1) | SE8007331L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62176245A (en) * | 1986-01-29 | 1987-08-03 | Sekisui Chem Co Ltd | Telephone set |
| JPS62219736A (en) * | 1986-03-19 | 1987-09-28 | Matsushita Electric Works Ltd | Telephone set switching device |
| JPS62219737A (en) * | 1986-03-19 | 1987-09-28 | Matsushita Electric Works Ltd | Telephone set switching device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093788A (en) * | 1974-06-24 | 1978-06-06 | Stauffer Chemical Company | Method for the preparation of polyvinyl chloride by suspension or emulsion polymerization |
| JPS5212291A (en) * | 1975-07-18 | 1977-01-29 | Shin Etsu Chem Co Ltd | Process for polymerizing vinyl chloride |
| JPS5214688A (en) * | 1975-07-24 | 1977-02-03 | Shin Etsu Chem Co Ltd | A process for polymerizing vinyl chloride |
| JPS5224070A (en) * | 1975-08-19 | 1977-02-23 | Toshiba Corp | Productio method of magnetron anode |
| JPS5224953A (en) * | 1975-08-22 | 1977-02-24 | Osaka Transformer Co Ltd | Arc welding machine |
| JPS5228347A (en) * | 1975-08-29 | 1977-03-03 | Nippon Kogaku Kk <Nikon> | Position detector unit |
| LU76676A1 (en) * | 1977-02-01 | 1978-09-13 | ||
| JPS548690A (en) * | 1977-06-20 | 1979-01-23 | Goodrich Co B F | Method of preventing polymer from adhering on inner surface of polymerization reactor |
-
1979
- 1979-10-22 JP JP54136262A patent/JPS606361B2/en not_active Expired
-
1980
- 1980-10-14 IN IN1167/CAL/80A patent/IN151895B/en unknown
- 1980-10-17 NO NO803099A patent/NO803099L/en unknown
- 1980-10-17 CA CA000362647A patent/CA1193394A/en not_active Expired
- 1980-10-20 DE DE19803039543 patent/DE3039543A1/en not_active Withdrawn
- 1980-10-20 SE SE8007331A patent/SE8007331L/en unknown
- 1980-10-20 GB GB8033747A patent/GB2061980B/en not_active Expired
- 1980-10-20 DK DK443880A patent/DK443880A/en not_active Application Discontinuation
- 1980-10-21 MX MX184414A patent/MX155347A/en unknown
- 1980-10-21 ES ES496127A patent/ES8107254A1/en not_active Expired
- 1980-10-21 PT PT71944A patent/PT71944B/en unknown
- 1980-10-21 IT IT25487/80A patent/IT1133972B/en active
- 1980-10-21 BE BE0/202545A patent/BE885813A/en not_active IP Right Cessation
- 1980-10-21 BR BR8006772A patent/BR8006772A/en unknown
- 1980-10-21 CU CU35339A patent/CU21471A/en unknown
- 1980-10-21 FR FR8022441A patent/FR2467860B1/en not_active Expired
- 1980-10-22 AT AT0521080A patent/AT369755B/en not_active IP Right Cessation
- 1980-10-22 NL NL8005812A patent/NL8005812A/en not_active Application Discontinuation
- 1980-10-22 PL PL22744080A patent/PL227440A1/xx unknown
- 1980-10-22 CH CH788080A patent/CH645392A5/en not_active IP Right Cessation
- 1980-10-22 HU HU802567A patent/HU191809B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2467860A1 (en) | 1981-04-30 |
| SE8007331L (en) | 1981-04-23 |
| ES496127A0 (en) | 1981-10-01 |
| IN151895B (en) | 1983-08-27 |
| DE3039543A1 (en) | 1981-09-10 |
| ATA521080A (en) | 1982-06-15 |
| FR2467860B1 (en) | 1985-11-15 |
| JPS606361B2 (en) | 1985-02-18 |
| BR8006772A (en) | 1981-04-28 |
| BE885813A (en) | 1981-02-16 |
| NL8005812A (en) | 1981-04-24 |
| CU21471A (en) | 1983-10-04 |
| DK443880A (en) | 1981-04-23 |
| PL227440A1 (en) | 1981-07-10 |
| CA1193394A (en) | 1985-09-10 |
| IT1133972B (en) | 1986-07-24 |
| HU191809B (en) | 1987-04-28 |
| PT71944B (en) | 1981-08-31 |
| CH645392A5 (en) | 1984-09-28 |
| PT71944A (en) | 1980-11-01 |
| AT369755B (en) | 1983-01-25 |
| JPS5659808A (en) | 1981-05-23 |
| MX155347A (en) | 1988-02-22 |
| NO803099L (en) | 1981-04-23 |
| GB2061980B (en) | 1983-06-29 |
| IT8025487A0 (en) | 1980-10-21 |
| ES8107254A1 (en) | 1981-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19921020 |