NO153594B - PROCEDURE FOR THE PREPARATION OF A PREPARATION BASED ON PSYLLIUM SEEDS AND LATE FRUITS. - Google Patents
PROCEDURE FOR THE PREPARATION OF A PREPARATION BASED ON PSYLLIUM SEEDS AND LATE FRUITS. Download PDFInfo
- Publication number
- NO153594B NO153594B NO810133A NO810133A NO153594B NO 153594 B NO153594 B NO 153594B NO 810133 A NO810133 A NO 810133A NO 810133 A NO810133 A NO 810133A NO 153594 B NO153594 B NO 153594B
- Authority
- NO
- Norway
- Prior art keywords
- parts
- vinyl chloride
- weight
- product
- maleimide
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 16
- 101100020619 Arabidopsis thaliana LATE gene Proteins 0.000 title 1
- 241001499733 Plantago asiatica Species 0.000 title 1
- 235000003421 Plantago ovata Nutrition 0.000 title 1
- 239000009223 Psyllium Substances 0.000 title 1
- 235000013399 edible fruits Nutrition 0.000 title 1
- 229940070687 psyllium Drugs 0.000 title 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 47
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 18
- -1 N-(2-substituted phenyl)-maleimide Chemical class 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000004800 polyvinyl chloride Substances 0.000 description 15
- 229920000915 polyvinyl chloride Polymers 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- 229920002689 polyvinyl acetate Polymers 0.000 description 8
- 239000011118 polyvinyl acetate Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012686 granular polymerization Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000012815 thermoplastic material Substances 0.000 description 4
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PCJGHYSTCBLKIA-UHFFFAOYSA-N (1-acetylcyclohexyl)sulfonyloxy 1-acetylcyclohexane-1-sulfonate Chemical compound C1CCCCC1(C(C)=O)S(=O)(=O)OOS(=O)(=O)C1(C(=O)C)CCCCC1 PCJGHYSTCBLKIA-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 description 1
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/48—Fabaceae or Leguminosae (Pea or Legume family); Caesalpiniaceae; Mimosaceae; Papilionaceae
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
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Description
Sampolymer av vinylklorid og N-arylmaleimid. Copolymer of vinyl chloride and N-arylmaleimide.
Denne oppfinnelse angår nye polymere produkter, særlig de som er fremstilt ved å poly-merisere N-substituerte maleimider med vinylklorid. This invention relates to new polymeric products, particularly those prepared by polymerizing N-substituted maleimides with vinyl chloride.
I henhold til oppfinnelsen tilveiebringes en ny klasse termoplastiske materialer som er polymere produkter inneholdende fra 99 til 60 vektprosent vinylkloridenheter, fra 1 til 40 vektprosent N-aryl-maleimid-enheter og fra 0 til 20 vektprosent enheter avledet fra minst én annen sampolymerisbar, ethylenumettet forbindelse. According to the invention, there is provided a new class of thermoplastic materials which are polymeric products containing from 99 to 60 weight percent vinyl chloride units, from 1 to 40 weight percent N-aryl maleimide units and from 0 to 20 weight percent units derived from at least one other copolymerizable, ethylenically unsaturated compound .
Disse produkter er termoplastiske, sterke og påvirkes ikke av vann, og er ofte mer stabile mot avbygning ved forhøyet temperatur enn homopolymerer av vinylklorid. De produkter som er sampolymere av vinylklorid med N-aryl-maleimider alene eller med en tredje monomer hvis homopolymer har et minst like høyt mykningspunkt som et polyvinylklorid med lignende molekylvekt, har de fleste av de egenskaper man vanligvis forbinder med vinylkloridplaster, men i tillegg har de hensiktsmessig økte mykningspunkter, ofte av en størrelsesorden som er tilstrekkelig til å tillate kontinuerlig kontakt med kokende vann uten alvorlig deformering. Denne forbedring oppnåes videre uten noen vesentlig økning i vann-følsomheten og liten eller ingen nedsettelse av termisk stabilitet. These products are thermoplastic, strong and unaffected by water, and are often more stable against degradation at elevated temperatures than homopolymers of vinyl chloride. The products which are copolymers of vinyl chloride with N-aryl maleimides alone or with a third monomer whose homopolymer has a softening point at least as high as a polyvinyl chloride of similar molecular weight have most of the properties usually associated with vinyl chloride plasters, but in addition have the appropriately increased softening points, often of an order of magnitude sufficient to permit continuous contact with boiling water without severe deformation. This improvement is further achieved without any significant increase in water sensitivity and little or no reduction in thermal stability.
Det skal legges merke til at produktets na-tur i det minste delvis vil bestemmes av de rela-tive mengdeforhold av monomerene, og at en rekke forskjellige nye termoplastiske materialer kan oppnåes. For at det polymere produkt skal være støpbart eller på annen måte formbart omtrent som polyvinylklorid, må mengdefor-holdet av vinylklorid ikke være under 60 vektprosent. Por på den annen side å oppnå en nyt-tig økning i mykningspunktet må minst 1 vektprosent av N-aryl-maleimid være sampolymerisert med vinylkloridet. It should be noted that the nature of the product will be at least partially determined by the relative proportions of the monomers, and that a number of different new thermoplastic materials can be obtained. In order for the polymeric product to be castable or otherwise moldable approximately like polyvinyl chloride, the amount of vinyl chloride must not be below 60 percent by weight. On the other hand, in order to achieve a useful increase in the softening point, at least 1 percent by weight of N-arylmaleimide must be copolymerized with the vinyl chloride.
Det er funnet som en generell regel at etter-som N-aryl-maleimid-innholdet økes, økes strekkflytespenningen, men støpebarheten ned-settes. For å få den beste kombinasjon av gode støpeegenskaper og høy strekkstyrke, foretrekkes produkter som inneholder fra 70 til 90 vektprosent vinylkloridrester, 10 til 30 vektprosent N-aryl-maleimid-rester og 0 til 20 vektprosent av rester avledet fra andre monomerer som er sampolymeriserbare med både vinylklorid og N-aryl-maleimid, til sammen 100 pst. It has been found as a general rule that as the N-aryl maleimide content is increased, the tensile yield strength is increased, but the castability is reduced. In order to obtain the best combination of good casting properties and high tensile strength, products containing from 70 to 90 weight percent of vinyl chloride residues, 10 to 30 weight percent of N-aryl maleimide residues and 0 to 20 weight percent of residues derived from other monomers that are copolymerizable with both vinyl chloride and N-aryl maleimide, a total of 100 per cent.
Med et N-aryl-maleimid skal her forståes en forbindelse som begrepsmessig er avledet ved å erstatte hydrogenatomet som er knyttet til imidnitrogenatomet i maleimid, med et enverdig aromatisk radikal. Det enverdige aromatiske radikal kan være avledet fra et fullstendig aromatisk hydrokarbon som er usubstituert, f. eks. benzen, difenyl eller naftalen, eller som har ett eller flere av hydrogenatomene erstattet med andre enverdige atomer eller grupper; f. eks. halogenatomer (så som klor, brom, fluor), hydroksylgrupper, nitrogrupper, alkyl-, aralkyl-og cykloalkylgrupper (særlig som inneholder opptil 4 alifatiske karbonatomer), og grupper med strukturen -NH2, -NHR, -NRR', -OR, -CN, Here, an N-aryl maleimide is to be understood as a compound which is conceptually derived by replacing the hydrogen atom which is linked to the imide nitrogen atom in maleimide, with a monovalent aromatic radical. The monovalent aromatic radical may be derived from a fully aromatic hydrocarbon which is unsubstituted, e.g. benzene, diphenyl or naphthalene, or having one or more of the hydrogen atoms replaced by other monovalent atoms or groups; e.g. halogen atoms (such as chlorine, bromine, fluorine), hydroxyl groups, nitro groups, alkyl, aralkyl and cycloalkyl groups (especially containing up to 4 aliphatic carbon atoms), and groups of the structure -NH2, -NHR, -NRR', -OR, - CN,
-MOR, -SR, -COOR,"-COOH, -OCOR, -NHCOR -MOR, -SR, -COOR,"-COOH, -OCOR, -NHCOR
og -CONHR hvor M er et toverdig alifatisk hy-drokarbonradikal, f. eks. alkylen, og R og R' er hver enverdige hydrokarbonradikaler som f. eks. alkyl, cykloalkyl, aryl, alkaryl eller aralkyl, fortrinnsvis inneholdende ikke mer enn åtte karbonatomer, eller halogenerte (f. eks. bro-merte, klorerte eller fluorerte) derivater derav. To av hydrogenatomene i det aromatiske hydrokarbon kan være erstattet med et toverdig radikal slik at man f. eks. får forbindelser så som inden eller cumaron. Det foretrekkes at substituenten ikke inneholder noen aktive hydrogenatomer da disse kan ta del i reaksjoner som er skadelige for polmerisasjonsreaksjonen. Eksempler på slike substituenter er -OH, -NH, og and -CONHR where M is a divalent aliphatic hydrocarbon radical, e.g. alkylene, and R and R' are each monovalent hydrocarbon radicals such as e.g. alkyl, cycloalkyl, aryl, alkaryl or aralkyl, preferably containing no more than eight carbon atoms, or halogenated (e.g. brominated, chlorinated or fluorinated) derivatives thereof. Two of the hydrogen atoms in the aromatic hydrocarbon can be replaced by a divalent radical so that, for example, get compounds such as indene or coumarone. It is preferred that the substituent does not contain any active hydrogen atoms as these can take part in reactions that are harmful to the polymerization reaction. Examples of such substituents are -OH, -NH, and
-COOH-grupper. N-maryl-maleimider som er funnet å være særlig egnet for anvendelse i henhold til oppfinnelsen, er N-fenyl-maleimider og substituerte derivater derav i hvilke minst ett av de aromatisk bundede hydrogenatomer er substituert med et halogenatom, en nitrogruppe, en nitrilgruppe eller en alkyl- eller alkoksygruppe inneholdende fra 1 til 4 karbonatomer. . Eksempler på foretrukne aromatiske og substituerte aromatiske radikaler er fenyl, p-difenyl, a-nafthyl, |3-nafthyl, o-, m- og p-tolyl, 2, 3, og 4-klorfenyl, 4-bromfenyl, 2, 3 og 4-nitrofenyl 2,4,5-triklorfenyl, 2.4,6-tribromfenyl, 2,3 og 4-t-butylfenyl, 2,4-dinitrofenyl, 4-benzylfenyl, 2 og •3-methoksyfenyl, 4-ethoksyfenyl, 4-fenoksyfenyl, 2-klor-4-fenoksy-methylfenyl, 4-cyanfenyl og 2-methyl-4-klorfenyl. -COOH groups. N-maryl maleimides which have been found to be particularly suitable for use according to the invention are N-phenyl maleimides and substituted derivatives thereof in which at least one of the aromatically bonded hydrogen atoms is substituted with a halogen atom, a nitro group, a nitrile group or an alkyl or alkoxy group containing from 1 to 4 carbon atoms. . Examples of preferred aromatic and substituted aromatic radicals are phenyl, p-diphenyl, a-naphthyl, |3-naphthyl, o-, m- and p-tolyl, 2, 3, and 4-chlorophenyl, 4-bromophenyl, 2, 3 and 4-nitrophenyl 2,4,5-trichlorophenyl, 2,4,6-tribromophenyl, 2,3 and 4-t-butylphenyl, 2,4-dinitrophenyl, 4-benzylphenyl, 2 and •3-methoxyphenyl, 4-ethoxyphenyl, 4 -phenoxyphenyl, 2-chloro-4-phenoxy-methylphenyl, 4-cyanophenyl and 2-methyl-4-chlorophenyl.
"Det foretrekkes videre at substituenten ikke er slik at den øker den basiske karakter av imjdo-nitrogenatomet, ■. da produktene man får ved.--polymerisering av disse monomerer med vinylklorid, vil kunne ha redusert varmestabili-tet. Eksempler' på slike substituenter er halo- It is further preferred that the substituent is not such that it increases the basic character of the imido nitrogen atom, as the products obtained by polymerizing these monomers with vinyl chloride may have reduced heat stability. Examples of such substituents is halo-
genatomer og alkoksy gr upper. I noen tilfelle er det imidlertid ønskelig å anvende N-(halo-gen-tubstituert aryl)-maleimider fordi de i alminnelighet gir produkter med god farge. I disse tilfelle foretrekkes å anvende de brom- eller klor-substituerte derivater på grunn av deres tilgjengelighet. gene atoms and alkoxy groups. In some cases, however, it is desirable to use N-(halogen-substituted aryl)-maleimides because they generally give products with a good color. In these cases, it is preferred to use the bromine- or chlorine-substituted derivatives due to their availability.
Når N-(substituert fenyl)-maleimider anvendes, foretrekkes de som har en substituent i 2-stilling på fenylradikalet, da bruken av slike forbindelser i alminnelighet fører til polymere produkter med mindre farge enn man oppnår med andre substituerte N-fenyl maleimidér.'When N-(substituted phenyl)-maleimides are used, those having a substituent in the 2-position on the phenyl radical are preferred, as the use of such compounds generally leads to polymeric products with less color than is obtained with other substituted N-phenyl maleimides.'
Eksempler på monomerer som kan utgjøre enheter som danner opptil 49 vektprosent av sampolymeren, er ethylenumettede hydrokarboner (f. eks. alkener, diener og aralkener) og deres halogenerte derivater; ethylenumettede estere, f. eks. estere av mettede alkoholer og ethylenumettede karboksylsyrer og estere av ethylenumettede alkoholer og mettede karboksylsyrer, ethylenumettede etere og anhydrider av ethylenumettede syrer. Spesielle eksempler omfatter styren, halogensubstituerte styrener, a-alkyl (f. eks. a-methyl) styren, umettede (f. eks. vinyl eller allyl) estere av fettsyrer (særlig eddiksyre), alkylestere av akrylsyre (f. eks. methyl-, ethyl-, n-butyl-, 2-ethyl-heksyl- og octa-decyl-akrylat), alkylestere av methakrylsyre (f. eks. methylmethakrylat, butylmethakrylat, 2-ethylheksyl- og octadecylmethakrylat), alken-yletere så som vinyletere av alkoholer inneholdende opp til 4 karbonatomer, akrylnitril, me-thakrylnitril, vinylidenklorid, dialkylestere av monoethylenisk umettede dikarboksylsyrer så som diethylfumarat og dimethylmaleat, maleinsyreanhydrid, diener så som butadien, isopren og divinylbenzen, eller andre multiethylenisk umettede forbindelser så som glycoldimethakry-lat. Monomeren er fortrinnsvis én som ikke har noen skadelig virkning på sampolymerens egenskaper. Examples of monomers which may constitute units forming up to 49% by weight of the copolymer are ethylenically unsaturated hydrocarbons (eg alkenes, dienes and aralkenes) and their halogenated derivatives; ethylenically unsaturated esters, e.g. esters of saturated alcohols and ethylenically unsaturated carboxylic acids and esters of ethylenically unsaturated alcohols and saturated carboxylic acids, ethylenically unsaturated ethers and anhydrides of ethylenically unsaturated acids. Specific examples include styrene, halogen-substituted styrenes, α-alkyl (e.g. α-methyl) styrene, unsaturated (e.g. vinyl or allyl) esters of fatty acids (especially acetic acid), alkyl esters of acrylic acid (e.g. methyl- , ethyl, n-butyl, 2-ethylhexyl and octadecyl acrylate), alkyl esters of methacrylic acid (e.g. methyl methacrylate, butyl methacrylate, 2-ethylhexyl and octadecyl methacrylate), alkenyl ethers such as vinyl ethers of alcohols containing up to 4 carbon atoms, acrylonitrile, methacrylonitrile, vinylidene chloride, dialkyl esters of monoethylenically unsaturated dicarboxylic acids such as diethyl fumarate and dimethyl maleate, maleic anhydride, dienes such as butadiene, isoprene and divinylbenzene, or other polyethylenically unsaturated compounds such as glycol dimethacrylate. The monomer is preferably one which has no detrimental effect on the properties of the copolymer.
Normalt innføres en slik tredje sampoly-meriserbar bestanddel for å modifisere egenska-pene på en ønsket måte, f. eks. for å forbedre flyteegeneskapene under de betingelser man har ved fabrikasjonen, eller for å redusere gjenvæ-rende . farge i sampolymeren, eller for å inn-føre umettede grupper for senere fornetning. Tilsetningen av noen av disse monomerer kan imidlertid nedsette eller ødelegge den forbedring med hensyn til mykningspunkt som opp-nås ved innføring av N-arylmaleimidet. Når det ønskes å beholde forbedringen med hensyn til mykningspunkt, er egnede sammonomerer de hvis homopolymerer har minst like høyt mykningspunkt som et polyvinylklorid med samme molekylvekt. Mykningspunktene for homopolymeren og polyvinylkloridet kan sammenr lignes ved enhver egnet prøve, som f. eks. 1/10 Vicat-mykningspunktet eller varmedeforma-sjonstemperaturen. Eksempler på slike monomerer er vinylidenklorid, akrylnitril, methylmethakrylat, styren, a-methylstyren, o-klorstyren og maleinsyreanhydrid. I andre tilfelle hvor man ønsker å øke mykningspunktet, forerekkes det i alminnelighet ikke å anvende en tredje monomer. Normally, such a third copolymerizable component is introduced to modify the properties in a desired way, e.g. to improve the flow properties under the conditions of manufacture, or to reduce residual . color in the copolymer, or to introduce unsaturated groups for later crosslinking. The addition of some of these monomers may, however, reduce or destroy the improvement in softening point achieved by introducing the N-arylmaleimide. When it is desired to retain the improvement in terms of softening point, suitable comonomers are those whose homopolymers have at least as high a softening point as a polyvinyl chloride of the same molecular weight. The softening points of the homopolymer and the polyvinyl chloride can be compared by any suitable test, such as e.g. 1/10 Vicat softening point or heat deformation temperature. Examples of such monomers are vinylidene chloride, acrylonitrile, methyl methacrylate, styrene, α-methylstyrene, o-chlorostyrene and maleic anhydride. In other cases where it is desired to increase the softening point, it is generally not preferred to use a third monomer.
Produktet kan fremstilles ved hvilken som helst av de velkjente polymeriseringsproses-ser som anvendes for vinylklorid, dvs. i bulk, i oppløsning, i vandig emulsjon eller i vandig suspensjon (f. eks. ved det som vanligvis beteg-nes som en granularprosess i vinylkloridpoly-meriseringsteknikken). Når man anvender en oppløsningsmiddelprosess, bør den organiske forbindelse som anvendes som oppløsningsmid-del, ikke reagere med noen av monomerene, og bør fortrinnsvis ha liten eller ingen kjedeover-føringsvirkning på polymeriseringsreaksjonen. Egnede oppløsningsmidler er hydrokarboner så som heksan, heptan, octan, benzen eller toluen, alkoholer så som methanol eller ethanol, etere så som diethyleter, eller ketoner så som ace-ton. Klorerte hydrokarboner kan også anvendes, men disse har en tendens til å ha en kjedeover-føringsvirkning på polymerisasjonen. Eksempler er 1,1-diklorethan, tetraklorethan, methyl-endiklorid, kloroform og karbontetraklorid. The product can be produced by any of the well-known polymerization processes used for vinyl chloride, i.e. in bulk, in solution, in aqueous emulsion or in aqueous suspension (e.g. by what is usually referred to as a granular process in vinyl chloride poly -merization technique). When using a solvent process, the organic compound used as a solvent should not react with any of the monomers, and should preferably have little or no chain transfer effect on the polymerization reaction. Suitable solvents are hydrocarbons such as hexane, heptane, octane, benzene or toluene, alcohols such as methanol or ethanol, ethers such as diethyl ether, or ketones such as acetone. Chlorinated hydrocarbons can also be used, but these tend to have a chain transfer effect on the polymerization. Examples are 1,1-dichloroethane, tetrachloroethane, methyl dichloride, chloroform and carbon tetrachloride.
Polymerisasjonen kan igangsettes ved hjelp av enhver egnet kilde for frie radikaler, men frembringes fortrinnsvis. i nærvær av en fri-radikal-avgivende katalysator som er aktiv ved polymerisasj onstemperaturen. The polymerization can be initiated by means of any suitable source of free radicals, but is preferably produced. in the presence of a free-radical-releasing catalyst which is active at the polymerization temperature.
Polymerisasjon utføres fortrinnsvis i et vandig medium da dette gir god spredning av polymerisasj onsvarmen, og man unngår anven-delsen av kostbar apparatur for gjenvinning av oppløsningsmiddel. Emulsjonspolymerisasjon i vandig medium utføres ved å omsette de reagerende bestanddeler dispergert i vann i nærvær av en vannoppløselig fri-radikal-katalysator, i alminnelighet i nærvær av et overflateaktivt middel. Det overflateaktive middel kan være anionisk (f. eks. et salt av en langkjedet alkylsulfonsyre), ikke-ionisk (f. eks. en vann-oppløselig polymer så som polyethylenoksyd) eller kationisk (f. eks. et kvartært ammonium - salt), og kan utvelges fra dem som var almin-nelig kjente for polymerisasjon av vinylklorid. Ved granularpolymerisasjon anvendes et dispergeringsmiddel (f. eks. et beskyttende kolloid så som methylcellulose eller hydrolysert polyvinylacetat) og en monomeroppløselig katalysator. Temperaturer som vanligvis anvendes for fremstilling av polyvinylklorid (dvs. fra 25 til 80°C) kan anvendes for polymerisasjon, og et meget egnet temperaturområde er fra 25 til 65°C selv om høyere eller lavere temperaturer eventuelt kan anvendes. Polymerization is preferably carried out in an aqueous medium as this provides good dispersion of the polymerization heat, and the use of expensive equipment for solvent recovery is avoided. Emulsion polymerization in an aqueous medium is carried out by reacting the reacting components dispersed in water in the presence of a water-soluble free-radical catalyst, generally in the presence of a surface-active agent. The surfactant may be anionic (e.g. a salt of a long-chain alkylsulfonic acid), non-ionic (e.g. a water-soluble polymer such as polyethylene oxide) or cationic (e.g. a quaternary ammonium salt), and can be selected from those which were generally known for the polymerization of vinyl chloride. In granular polymerization, a dispersant (e.g. a protective colloid such as methylcellulose or hydrolyzed polyvinyl acetate) and a monomer-soluble catalyst are used. Temperatures that are usually used for the production of polyvinyl chloride (ie from 25 to 80°C) can be used for polymerisation, and a very suitable temperature range is from 25 to 65°C, although higher or lower temperatures can possibly be used.
Egnede katalysatorer utvelges fra dem som vanligvis .anvendes for homopolymerisasjon av vinylklorid. For granularpolymerisasjon anvendes f. eks. azo-nitriler så som a a'-azodiisobu-tyronitril, og monomeroppløselige peroksyder så som lauroylperoksyd, benzoylperoksyd og andre organiske forbindelser inneholdende peroksyd-O-O-leddet. Når det gjelder emulsjonspolymerisasjon anvendes i alminnelighet hydrogenper-oksyd eller vannoppløselige salter av peroksysy-rer. Et eksempel er ammoniumpersulfat. Det er funnet at tilstedeværelsen av N-aryl-maleimidet kan øke reaksjonstiden og også nedsette molekylvekten av produktet. Den førstnevnte virkning kan minskes ved å velge en mer aktiv katalysator, og den sistnevnte virkning kan unngås til en viss grad ved å senke polymerisasj onstemperaturen. Hvis ytterligere økning i reaksjonstid skal unngås, kan det være ønskelig i dette tilfelle også å kompensere dette ved å veige en mer aktiv katalysator. Den mengde katalysator som er nødvendig for å gi ønskede resultater, ligger vanligvis mellom 0,01 og 2 pst. basert på vekten av de polymeriserbare monomerer. Suitable catalysts are selected from those commonly used for the homopolymerization of vinyl chloride. For granular polymerization, e.g. azo nitriles such as α α'-azodiisobutyronitrile, and monomer soluble peroxides such as lauroyl peroxide, benzoyl peroxide and other organic compounds containing the peroxide O-O link. When it comes to emulsion polymerization, hydrogen peroxide or water-soluble salts of peroxyacids are generally used. An example is ammonium persulfate. It has been found that the presence of the N-aryl maleimide can increase the reaction time and also decrease the molecular weight of the product. The former effect can be reduced by choosing a more active catalyst, and the latter effect can be avoided to a certain extent by lowering the polymerization temperature. If a further increase in reaction time is to be avoided, it may also be desirable in this case to compensate for this by weighing a more active catalyst. The amount of catalyst required to give the desired results is usually between 0.01 and 2 percent based on the weight of the polymerizable monomers.
Ved den foretrukne prosess tilsettes vannet, katalysator, overflateaktivt middel (dvs. emul-geringsmiddel eller dispergeringsmiddel) og N-aryl-maleimid til et reaksjonskar fra hvilket iuit deretter fjernes, f. eks. ved spyling med en inert gass, f. eks. nitrogen, eller ved evakuering eller begge deler. Vinylkloridet innføres deretter i karet, og de reagerende stoffer brin-ges til reaksj onstemperaturen for å igangsette polymerisasjon. Denne prosess kan av og til frembringe et ikke-homogent produkt, og for å forbedre homogeniteten kan det være ønskelig å tilsette den ønskede mengde N-aryl-maleimid kontinuerlig eller diskontinuerlig under reaksjonen. I et slikt tilfelle tilsettes forbin-delsen hensiktsmessig som en oppløsning i et egnet oppløsningsmiddel eller som en dispersjon i vann. In the preferred process, the water, catalyst, surfactant (ie emulsifier or dispersant) and N-aryl-maleimide are added to a reaction vessel from which water is then removed, e.g. when flushing with an inert gas, e.g. nitrogen, or by evacuation or both. The vinyl chloride is then introduced into the vessel, and the reacting substances are brought to the reaction temperature to initiate polymerisation. This process can occasionally produce a non-homogeneous product, and to improve the homogeneity it may be desirable to add the desired amount of N-arylmaleimide continuously or discontinuously during the reaction. In such a case, the compound is suitably added as a solution in a suitable solvent or as a dispersion in water.
Da den mengde N-aryl-maleimid man fin-ner i polymeren, vanligvis er høyere enn man skulle vente etter monomertilførselen, kan det være nødvendig å tilsette N-aryl-maleimidet til polymerisasjonen i et mengdeforhold noe under det man ønsker for det polymere produkt. En reduksjon på opptil ca. 5 eller 10 vektprosent er vanligvis tilstrekkelig, selv om en høyere reduksjon i noen tilfelle kan være nødvendig. As the amount of N-aryl-maleimide found in the polymer is usually higher than one would expect after the monomer addition, it may be necessary to add the N-aryl-maleimide to the polymerization in a quantity ratio slightly below that desired for the polymeric product . A reduction of up to approx. 5 or 10 percent by weight is usually sufficient, although a higher reduction may be necessary in some cases.
Etter polymerisasjonen kan det polymere produkt adskilles fra reaksj onsvæsken på enhver egnet måte som f. eks. ved filtrering eller sentrifugering, ved varme eller ved en kombinasjon av disse metoder. Produktet kan deretter renses, f. eks. ved vasking med et egnet selek-tivt oppløsningsmiddel så som vann, en eter eller en alkohol. Til slutt kan det tørkes f. eks. i et fluidisert lag eller ved forstøvningstørkning eller ved tørkning i en ovn. After the polymerisation, the polymeric product can be separated from the reaction liquid in any suitable way such as e.g. by filtration or centrifugation, by heat or by a combination of these methods. The product can then be cleaned, e.g. by washing with a suitable selective solvent such as water, an ether or an alcohol. Finally, it can be dried, e.g. in a fluidized bed or by spray drying or by drying in an oven.
Mindre viktige bestanddeler kan tilsettes til produktet, og eksempler på slike bestanddeler omfatter fyllstoffer (f. eks. glassfiber), pigmen-ter, varme- og lysstabiliseringsmidler,' myknere, smøremidler og formfrigjøringsmidler. Sampo-lymerene kan også blandes med annet polymert materiale, f. eks. termoplastiske materialer så som polyvinylklorid eller syntetiske gummier så som de som er avledet fra butadien. Less important components can be added to the product, and examples of such components include fillers (e.g. fiberglass), pigments, heat and light stabilizers, plasticizers, lubricants and mold release agents. The copolymers can also be mixed with other polymeric material, e.g. thermoplastic materials such as polyvinyl chloride or synthetic rubbers such as those derived from butadiene.
Da produktene ifølge oppfinnelsen i alminnelighet er i besittelse av de fleste egenskaper man i alminnelighet forbinder med polyvinylklorid, kan de anvendes med god virkning til anvendelser hvor et polyvinylklorid ville bli anvendt. De foretrukne produkter i henhold til oppfinnelsen kan dessuten anvendes for mange formål hvor polyvinylklorid ikke kan anvendes på grunn av sin dårlige dimensjonsstabilitet ved høye temperaturer. De foreliggende materialer er således særlig egnet for fremstilling av stive støpestykker ved hjelp av hvilken som helst av de fabrikasjonsprosesser som anvendes for termoplastiske materialer, så som profilsprøyt-ning, sprøytestøpning, press-støpning eller trans-press-støpning. De polymerer som har reduserte viskositeter (målt for en oppløsning av 0,5 g polymer i 100 ml dimethylformamid ved 25°C) på minst 0,3, er særlig egnet for slike formål. As the products according to the invention generally possess most of the properties that are generally associated with polyvinyl chloride, they can be used with good effect for applications where a polyvinyl chloride would be used. The preferred products according to the invention can also be used for many purposes where polyvinyl chloride cannot be used due to its poor dimensional stability at high temperatures. The present materials are thus particularly suitable for the production of rigid castings using any of the manufacturing processes used for thermoplastic materials, such as profile injection, injection molding, compression molding or trans-compression molding. The polymers which have reduced viscosities (measured for a solution of 0.5 g of polymer in 100 ml of dimethylformamide at 25°C) of at least 0.3 are particularly suitable for such purposes.
De formede gjenstander som er fremstilt av mange av de polymere produkter, kan utsettes for høye temperaturer som i alminnelighet er over mykningspunktene for homopolymerer av vinylklorid. Anvendelser omfatter rør og skjøte-ledd for anvendelse til varmtvannsrør. Andre anvendelser vil være åpenbare for en polymer-fabrikant. The shaped articles made from many of the polymeric products can be subjected to high temperatures that are generally above the softening points of homopolymers of vinyl chloride. Applications include pipes and joints for use in hot water pipes. Other applications will be obvious to a polymer manufacturer.
Oppfinnelsen skal illustreres ved de følgen-de eksempler hvor alle deler er vektdeler. I alle eksemplene ble de reduserte viskositeter målt i oppløsninger av 0,5 g polymer i 100 ml dimethylformamid ved 25°C, hvis ikke annet er angitt. The invention shall be illustrated by the following examples where all parts are parts by weight. In all examples, the reduced viscosities were measured in solutions of 0.5 g of polymer in 100 ml of dimethylformamide at 25°C, unless otherwise stated.
Eksempel 1. Example 1.
Et hundre deler vinylklorid ble dispergert i 200 deler vann under anvendelse av 0,5 del delvis hydrolysert polyvinylacetat som dispergeringsmiddel. Én del lauroylperoksyd ble tilsatt som katalysator, og dispersjonen ble om-rørt under en atmosfære av nitrogen ved 7—14 kg/cm.2 og ved en temperatur på 45 °C i 66 timer. Den resulterende oppslemming av polymer 1 vann ble sentrifugert for å atskille det faste produkt som deretter ble vasket omhyggelig med vann og tørket i vakuum. Utbyttet var 98 deler polyvinylklorid med en redusert viskositet på 1,2 og 1/10 og 10/10 Vicat-mykningspunkter på 76 og 103 °C målt på en prøve stabilisert med 2 vektprosent av et kommersielt tilgjengelig organo-tinn stabiliseringsmiddel og utpresset fra polymeren uten forutgående bearbeidning. One hundred parts of vinyl chloride was dispersed in 200 parts of water using 0.5 part of partially hydrolyzed polyvinyl acetate as dispersant. One part of lauroyl peroxide was added as a catalyst, and the dispersion was stirred under an atmosphere of nitrogen at 7-14 kg/cm 2 and at a temperature of 45°C for 66 hours. The resulting slurry of polymer 1 water was centrifuged to separate the solid product which was then washed thoroughly with water and dried in vacuo. The yield was 98 parts polyvinyl chloride with a reduced viscosity of 1.2 and 1/10 and 10/10 Vicat softening points of 76 and 103°C measured on a sample stabilized with 2% by weight of a commercially available organotin stabilizer and extruded from the polymer without prior processing.
Polymerisasjonen ble gjentatt under anvendelse av 90 deler vinylklorid og 10 deler N-fenyl-maleimid. Utbyttet av produktet etter 66 timers reaksjon ved 45 °C, fulgt av atskillelse, rensning og tørkning, var ca. 100 pst. av det teoretiske. Det var i form av hvitaktige korn og hadde en redusert viskositet på 0,94. Produktet ble blandet med 2 vektprosent av et kommersielt tilgjengelig organo-tinn stabiliseringsmiddel ved å tilsette en oppløsning av stabiliseringsmidlet og inndampe oppløsningsmidlet, og støpt ved 170°C for å gi lyst brune plater med et 1/10 Vicat-mykningspunkt, målt under de samme betingelser som for homopolymeren av vinylklorid, på 79,5°C, 3,5°C høyere enn for polyvinylklorid. 10/10 Vicat-mykningspunktet var 113°C. The polymerization was repeated using 90 parts of vinyl chloride and 10 parts of N-phenylmaleimide. The yield of the product after 66 hours of reaction at 45 °C, followed by separation, purification and drying, was approx. 100 percent of the theoretical. It was in the form of whitish granules and had a reduced viscosity of 0.94. The product was mixed with 2% by weight of a commercially available organotin stabilizer by adding a solution of the stabilizer and evaporating the solvent, and cast at 170°C to give light brown sheets with a 1/10 Vicat softening point measured under the same conditions as for the homopolymer of vinyl chloride, at 79.5°C, 3.5°C higher than for polyvinyl chloride. 10/10 Vicat softening point was 113°C.
Analyse av sampolymeren etter klorinnhol-det viste at den inneholdt 89 vektprosent vinylkloridenheter og 11 vektprosent N-fenyl-maleimid-enheter. Analysis of the copolymer according to the chlorine content showed that it contained 89 weight percent vinyl chloride units and 11 weight percent N-phenyl-maleimide units.
Eksempel 2. Example 2.
Fremgangsmåten ifølge eksempel 1 ble gjentatt under anvendelse av 80 deler vinylklorid og 20 deler N-fenyl-maleimid, og etter 46 timers polymerisasjon og påfølgende atskillelse, rensning og tørkning, fikk man 95,2 deler polymert produkt i form av hvitaktige korn med en redusert viskositet på 0,80. The procedure according to example 1 was repeated using 80 parts of vinyl chloride and 20 parts of N-phenyl-maleimide, and after 46 hours of polymerization and subsequent separation, purification and drying, 95.2 parts of polymeric product were obtained in the form of whitish grains with a reduced viscosity of 0.80.
Etter sammenblanding med 2 vektprosent av et kommersielt tilgjengelig organo-tinn stabiliseringsmiddel på samme måte som beskrevet i eksempel 1, ble produktet støpt ved 170°C for å gi lyst brune plater med 1/10 og 10/10 Vicat-mykningspunkter, målt som i" eksempel 1, på 103°C (27°C høyere enn for polyvinylklorid) og 121,5°C. After admixture with 2% by weight of a commercially available organotin stabilizer in the same manner as described in Example 1, the product was cast at 170°C to give light brown plates with 1/10 and 10/10 Vicat softening points, measured as in " example 1, at 103°C (27°C higher than for polyvinyl chloride) and 121.5°C.
Analyse-av produktet etter klorinnhold viste at det inneholdt 78,5 vektprosent vinylkloridenheter og 21,5 vektprosent N-fenyl-maleimid-enheter. Analysis of the product by chlorine content showed that it contained 78.5 weight percent vinyl chloride units and 21.5 weight percent N-phenyl-maleimide units.
Som en sammenligning ble prosessen gjentatt under anvendelse av 20 deler N-benzyl-maleimid, 80 deler vinylklorid, 285 deler vann, én del lauroyl peroksyd og 0,7 del delvis hydrolysert polyvinylacetat. Polymerisasjonen ble ut-ført ved 45°C i 29 timer, og produktet ble filtrert, vasket med vann og tørket omhyggelig slik at man fikk 45,5 deler polymert materiale inneholdende 26,2 vektprosent N-benzyl-maleimid, som vist ved nitrogenanalyse. Produktet ble blandet med et stabiliseringsmiddel som i eksempel 1 og press-støp for å gi plater med et 1/10 Vicat-mykningspunkt på bare 73°C (lavere enn for polyvinylklorid), og var også uoppløse-lig i alle vanlige oppløsningsmidler. As a comparison, the process was repeated using 20 parts of N-benzyl maleimide, 80 parts of vinyl chloride, 285 parts of water, one part of lauroyl peroxide and 0.7 part of partially hydrolyzed polyvinyl acetate. The polymerization was carried out at 45°C for 29 hours, and the product was filtered, washed with water and carefully dried to give 45.5 parts of polymeric material containing 26.2% by weight of N-benzyl maleimide, as shown by nitrogen analysis. The product was mixed with a stabilizer as in Example 1 and compression molded to give sheets with a 1/10 Vicat softening point of only 73°C (lower than polyvinyl chloride), and was also insoluble in all common solvents.
Som et ytterligere sammenlignende forsøk ble 80 deler vinylklorid polymerisert med 20 deler maleimid i 200 deler vann og i nærvær av én del lauroylperoksyd og 0,5 del delvis hydrolysert polyvinylacetat. Polymerisasjonen ble utført i 17 timer ved 45°C, og produktet ble filtrert, vasket og tørket for å gi 56,2 deler polymert materiale med en redusert viskositet på 0,7 og inneholdende 44,7 vektprosent maleimid. Presstøpte plater av den stabiliserte polymer hadde et 1/10 Vicat-mykningspunkt på bare 61,8°C og var merkbart ustabile. Etter noen få dager oppviste den beholder i hvilken prøvene ble lagret, tegn på korrosjon av hydrogenklorid. Etter neddypning i vann ved 55—60 °C ble produktet videre funnet å være betraktelig mer føl-somt for vann enn polyvinylklorid. Dette er vist i den følgende tabell. As a further comparative experiment, 80 parts of vinyl chloride were polymerized with 20 parts of maleimide in 200 parts of water and in the presence of one part of lauroyl peroxide and 0.5 part of partially hydrolyzed polyvinyl acetate. The polymerization was carried out for 17 hours at 45°C, and the product was filtered, washed and dried to give 56.2 parts of polymeric material having a reduced viscosity of 0.7 and containing 44.7 weight percent maleimide. Die-cast sheets of the stabilized polymer had a 1/10 Vicat softening point of only 61.8°C and were noticeably unstable. After a few days, the container in which the samples were stored showed signs of corrosion by hydrogen chloride. After immersion in water at 55-60 °C, the product was further found to be considerably more sensitive to water than polyvinyl chloride. This is shown in the following table.
Vektreduksjonen etter den opprinnelige økning tyder på at vinylklorid/maleimid-polyme-risasjonsproduktet oppløses. The weight reduction after the initial increase indicates that the vinyl chloride/maleimide polymerization product is dissolving.
Eksempel 3. Example 3.
Fremgangsmåten. ifølge eksempel 1 ble gjentatt under anvendelse av 30 deler N-fenyl-maleimid, 70 deler vinylklorid og en temperatur på 40 °C slik at man fikk 68 deler blek-gule korn med en redusert viskositet på 0,87. Produktet ble blandet med 2 vektprosent av et kommersielt tilgjengelig organo-tinn stabiliseringsmiddel og utpresset ved 170°C for å gi brune, opake plater med 1/10 og 10/10 Vicat-mykningspunkter på 130 og 147°C. Analyse viste at produktet inneholdt 63 vektprosent vinylklorid og 37 vektprosent N-fenyl-maleimid. En sammenligning mellom produktet ifølge dette eksempel og produktene ifølge eksempel 1 og 2 er vist i den følgende tabell. The procedure. according to example 1 was repeated using 30 parts of N-phenyl-maleimide, 70 parts of vinyl chloride and a temperature of 40°C so that 68 parts of pale yellow grains with a reduced viscosity of 0.87 were obtained. The product was mixed with 2% by weight of a commercially available organotin stabilizer and extruded at 170°C to give brown, opaque plates with 1/10 and 10/10 Vicat softening points of 130 and 147°C. Analysis showed that the product contained 63 weight percent vinyl chloride and 37 weight percent N-phenyl-maleimide. A comparison between the product according to this example and the products according to examples 1 and 2 is shown in the following table.
Det skal legges merke til at Vicat-mykningspunktene viser en jevn økning med økning i N-aryl-maleimid-innholdet, mens molekylvek-tene (som vist ved redusert viskositet) avtar. Denne avtagning er til en viss grad oppveiet i eksempel 3 ved den densatte polymerisasj ons-temperatur. It should be noted that the Vicat softening points show a steady increase with increasing N-aryl maleimide content, while the molecular weights (as shown by reduced viscosity) decrease. This reduction is to some extent offset in example 3 by the dense polymerization temperature.
Eksempel 4. Example 4.
En serie granularpolymerisasjoner av vinylklorid og N-fenyl-maleimid ble utført ved 50 °C i en omrørt autoklav inneholdende 4000 deler vann med åtte deler lauroylperoksyd som katalysator og 10 deler delvis hydrolysert polyvinylacetat som dispergeringsmiddel. I hvert tilfelle ble alle bestanddelene bortsett fra vinylkloridet tilført til karet som deretter langsomt ble evakuert, spylt to ganger med nitrogen og deretter evakuert på nytt før innføring av vinylkloridet. Monomerer ble anvendt i mengder på til sammen 2000 deler i hvert tilfelle. A series of granular polymerizations of vinyl chloride and N-phenyl-maleimide were carried out at 50 °C in a stirred autoclave containing 4000 parts of water with eight parts of lauroyl peroxide as catalyst and 10 parts of partially hydrolyzed polyvinyl acetate as dispersant. In each case, all components except the vinyl chloride were added to the vessel which was then slowly evacuated, flushed twice with nitrogen and then evacuated again before introducing the vinyl chloride. Monomers were used in amounts totaling 2000 parts in each case.
Etter atskillelse, vasking og tørkning, ble produktene malt med 1 vektprosent toverdig blystearat på en tovalsemølle og deretter press-støpt ved 215°C til prøvestykker hvis Vicat-mykningspunkter ble målt. Fikentscher K-verdien for hvert produkt ble notert for å gi en indika-sjon på molekylvekten. K-verdien ble beregnet fra viskositetsmålinger av oppløsninger av 0,25 g polymer i 50 ml ethylendiklorid ved 25°C. For noen av prøvestykkene fikk man Macklow-Smith flytetrykk som angir produktenes støpbarhet. Økning av f lyte trykket angir en reduksjon av støpbarheten. After separation, washing and drying, the products were ground with 1% by weight divalent lead stearate on a two roll mill and then compression molded at 215°C into test pieces whose Vicat softening points were measured. The Fikentscher K value for each product was noted to give an indication of the molecular weight. The K-value was calculated from viscosity measurements of solutions of 0.25 g of polymer in 50 ml of ethylene dichloride at 25°C. For some of the test pieces, the Macklow-Smith yield pressure was obtained, which indicates the castability of the products. An increase in flow pressure indicates a reduction in castability.
Den generelle avtagning i molekylvekt og økning i Macklow-Smith flytetrykk med økning i N-aryl-maleimid-innhold skal legges merke til. Den tilsynelatende reduksjon av 1/10 Vicat-mykningspunkt antas å skyldes de malebetin-gelser som anvendes før utpressing. Tallene re-presenterer ikke en virkelig verdi for den temperatur ved hvilken produktet blir plastisk, da det under fremstillingen ble lagt merke til at med økende N-aryl-maleimid-innhold ble produktet vanskeligere å danne til gel under de betingelser som normalt anvendes for polyvinylklorid. For forsøk E måtte maletemperaturen til og med heves til 170°C før man kunne få en tilfredsstillende krepp. Dette tyder på at det virkelige mykningspunkt for produktet faktisk øker med økning i N-aryl-maleimid-innholdet. The general decrease in molecular weight and increase in Macklow-Smith yield pressure with increase in N-aryl maleimide content should be noted. The apparent reduction of 1/10 Vicat softening point is believed to be due to the milling conditions used before extrusion. The figures do not represent a real value for the temperature at which the product becomes plastic, as it was noticed during production that with increasing N-aryl-maleimide content the product became more difficult to gel under the conditions normally used for polyvinyl chloride . For trial E, the grinding temperature even had to be raised to 170°C before a satisfactory crimp could be obtained. This suggests that the true softening point of the product actually increases with increasing N-aryl maleimide content.
Eksempel 5. Example 5.
En ytterligere serie granularpolymerisasjoner av vinylklorid med N-fenyl-maleimid ble utført ved 60 °C under anvendelse av lauroylperoksyd som katalysator og delvis hydrolysert polyvinylacetat som dispergeringsmiddel. I de fleste tilfelle utgjorde monomertilsatsen 2000 deler og 4000 deler vann ble anvendt. I eksempel F var imidlertid vanntilsatsen 2000 deler og monomertilsatsen 1000 deler. A further series of granular polymerizations of vinyl chloride with N-phenyl-maleimide was carried out at 60 °C using lauroyl peroxide as catalyst and partially hydrolysed polyvinyl acetate as dispersant. In most cases, the monomer addition amounted to 2000 parts and 4000 parts of water were used. In example F, however, the water addition was 2000 parts and the monomer addition 1000 parts.
Under malingen ble produktet blandet med 1 vektprosent toverdig blystearat, og for Vicat-forsøkene ble prøvestykker press-støpt ved 215°C. During painting, the product was mixed with 1% by weight divalent lead stearate, and for the Vicat tests, test pieces were pressure-molded at 215°C.
Mens økningen i 1/10 Vicat-mykningspunkt er meget liten, når innholdet av N-aryl-maleimid øker, tyder den økende vanskelighet ved maling av materialet på at den temperatur ved hvilken materialet blir plastisk, var økt betraktelig. Dette var særlig merkbart for det materiale som inneholdt 33,3 vekt-pst. N-fenyl-maleimid. While the increase in 1/10 Vicat softening point is very small as the N-aryl maleimide content increases, the increasing difficulty in painting the material suggests that the temperature at which the material becomes plastic was increased considerably. This was particularly noticeable for the material which contained 33.3% by weight. N-phenyl-maleimide.
Eksempel 6. Example 6.
En ytterligere serie granularpolymerisasjoner av vinylklorid og N-fenyl-maleimid ble ut-ført ved 70°C under anvendelse av 4000 deler vann, tilsammen 2000 deler monomer, 2 deler lauroylperoksyd og 5 deler dispergeringsmiddel. Forsøkbetingelser og resultater er angitt i den følgende tabell: A further series of granular polymerizations of vinyl chloride and N-phenyl-maleimide was carried out at 70°C using 4000 parts water, a total of 2000 parts monomer, 2 parts lauroyl peroxide and 5 parts dispersant. Test conditions and results are indicated in the following table:
Eksempel 7. Example 7.
Til en autoklav ble tilsatt 3500 deler destil-lert vann, 8 deler lauroylperoksyd, 10 deler delvis hydrolysert polyvinylacetat og 200 deler N-fenyl-maleimid som en oppløsning med en styrke på 40 g/100 ml etylendiklorid. Karet ble deretter evakuert, spylt to ganger med nitrogen, evakuert på nytt og tilført 1800 deler vinylklorid, og polymerisasjon ble utført ved 60°C for å gi 1728 deler hvitaktig produkt. To an autoclave were added 3500 parts of distilled water, 8 parts of lauroyl peroxide, 10 parts of partially hydrolyzed polyvinyl acetate and 200 parts of N-phenylmaleimide as a solution with a strength of 40 g/100 ml of ethylene dichloride. The vessel was then evacuated, flushed twice with nitrogen, evacuated again and 1800 parts of vinyl chloride was added and polymerization was carried out at 60°C to give 1728 parts of whitish product.
Eksempel 8. Example 8.
Til en autoklav ble tilsatt 200 deler vann, 6 deler ammoniumpersulfat, 3,33 deler av et salt To an autoclave were added 200 parts of water, 6 parts of ammonium persulfate, 3.33 parts of a salt
av et organisk sulfonat som et anionisk emul-geringsmiddel og 400 deler N-fenyl-maleimid. Etter evakuering og spyling ble det til karet tilsatt 1600 deler vinylklorid, og temperaturen ble hevet til 50°C. Etter 8 timer var polymerisasjonen fullstendig, og etter atskillelse, rensning og tørkning fikk man 1610 deler av et hvitaktig produkt. of an organic sulfonate as an anionic emulsifier and 400 parts of N-phenylmaleimide. After evacuation and flushing, 1,600 parts of vinyl chloride were added to the vessel, and the temperature was raised to 50°C. After 8 hours the polymerization was complete, and after separation, purification and drying, 1610 parts of a whitish product were obtained.
Eksempel 9. Example 9.
Fremgangsmåten ifølge eksempel 5K ble gjentatt under anvendelse av 8 deler lauroylperoksyd, 10 deler dispergeringsmiddel og N.-. klorfenyl-maleimid istedenfor N-fenyl-maleimid. Man fikk 1655 deler av et hvitt produkt med en Fikentscher K-verdi på 49,6. Etter maling ved 150 °C i 10 minutter ble det utpresset for å gi et prøvestykke med et 1/10 Vicat-mykningspunkt på 83°C. The procedure according to Example 5K was repeated using 8 parts lauroyl peroxide, 10 parts dispersant and N.-. chlorophenylmaleimide instead of N-phenylmaleimide. 1655 parts of a white product with a Fikentscher K value of 49.6 were obtained. After milling at 150°C for 10 minutes, it was extruded to give a specimen with a 1/10 Vicat softening point of 83°C.
Eksempel 10. Example 10.
Til et kar ble tilsatt 200 deler vann inneholdende 1 del lauroylperoksyd, 0,5 del delvis hydrolysert polyvinylacetat og 20 deler N-o-klorfenylmaleimid. Karet ble deretter satt under trykk med N2 og ventilert 3 ganger for å fjerne eventuell oppløst luft. 80 deler vinylklorid ble deretter tilsatt og trykket ble hevet til 8,5 kg/cm^ med nitrogen. Blandingen ble rystet ved 45°C i 24 timer. Produktet ble filtrert fra, vasket godt med varmt vann fulgt av etanol og deretter tørket i vakuum ved 70—75°C for å gi 67 deler med en redusert viskositet på 1,08. Produktet inneholdt 22,3 vektprosent N-o-klorfenyl-maleimid basert på nitrogenanalyse. Etter blanding med 2 vektprosent stabiliseringsmiddel på samme måte som beskrevet i eksempel 1, kunne det press-støpes til plater med 1/10 og 10/10 Vicat-mykningspunkter på henholdsvis 89 og 136,6°C. To a vessel was added 200 parts of water containing 1 part of lauroyl peroxide, 0.5 part of partially hydrolyzed polyvinyl acetate and 20 parts of N-o-chlorophenylmaleimide. The vessel was then pressurized with N2 and vented 3 times to remove any dissolved air. 80 parts vinyl chloride was then added and the pressure was raised to 8.5 kg/cm 2 with nitrogen. The mixture was shaken at 45°C for 24 hours. The product was filtered off, washed well with hot water followed by ethanol and then dried in vacuo at 70-75°C to give 67 parts with a reduced viscosity of 1.08. The product contained 22.3% by weight of N-o-chlorophenyl-maleimide based on nitrogen analysis. After mixing with 2% by weight stabilizer in the same way as described in example 1, it could be press-molded into sheets with 1/10 and 10/10 Vicat softening points of 89 and 136.6°C respectively.
Eksempel 11. Example 11.
Fremgangsmåten ifølge eksempel 10 ble gjentatt under anvendelse av N-o-tolylmaleimid istedenfor N-o-klorfenylmaleimid, og polymerisasjonen ble utført ved 45 °C i 23 timer. Produktet ble bearbeidet som beskrevet i eksempel 10 for å gi 55,3 deler polymert materiale med en redusert viskositet på 1,02 og inneholdende 62,5 vektprosent vinylklorid basert på kloranalyse. I dette og alle de følgende eksempler ble polymeren blandet med 2 vektprosent av et organo-tinn-stabiliseringsmiddel på samme måte som beskrevet i eksempel 1, og plater ble press-støpt fra blandingen. De presstøpte plater hadde i dette tilfelle 1/10 og 10/10 Vicat-mykningspunkter på 73,4 og 153,2°C. The procedure of Example 10 was repeated using N-o-tolylmaleimide instead of N-o-chlorophenylmaleimide, and the polymerization was carried out at 45°C for 23 hours. The product was processed as described in Example 10 to give 55.3 parts of polymeric material having a reduced viscosity of 1.02 and containing 62.5 weight percent vinyl chloride based on chlorine analysis. In this and all of the following examples, the polymer was mixed with 2 percent by weight of an organotin stabilizer in the same manner as described in Example 1, and plates were compression molded from the mixture. The die-cast plates in this case had 1/10 and 10/10 Vicat softening points of 73.4 and 153.2°C.
Eksempel 12. Example 12.
Fremgangsmåten ifølge eksempel 10 ble gjetatt under anvendelse av 20 deler N-fenyl-maleimid, 70 deler vinylklorid og 10 deler vi-nyleter. Polymerisasjon ble utført ved 55°C i 19 timer. Polymeren ble bearbeidet som beskrevet i det foregående for å gi 76,4 deler produkt med en redusert viskositet på 0,64. Press-støpte støpestykker hadde 1/10 og 10/10 Vicat mykningspunkter på 75,8 og 118,2°C. Produktet inneholdt 37 vektprosent klor, som tyder på tilstedeværelsen av 65,3 vektprosent vinylklorid. Nitrogenanalyse (2,1 vektprosent) tydet på tilstedeværelsen av 26 vektprosent N-fenyl-maleimid. The procedure of Example 10 was carried out using 20 parts of N-phenylmaleimide, 70 parts of vinyl chloride and 10 parts of vinyl ether. Polymerization was carried out at 55°C for 19 hours. The polymer was processed as described above to give 76.4 parts of product with a reduced viscosity of 0.64. Die cast castings had 1/10 and 10/10 Vicat softening points of 75.8 and 118.2°C. The product contained 37% by weight of chlorine, indicating the presence of 65.3% by weight of vinyl chloride. Nitrogen analysis (2.1 weight percent) indicated the presence of 26 weight percent N-phenyl-maleimide.
Eksempel 13. Example 13.
Til et kar ble tilført 160 deler metanol, 10 deler N-fenyl-maleimid og 1 del lauroylperoksyd. Karet ble deretter satt under trykk til 7,0 kg/cm<2> med nitrogen og ventilert 3 ganger, og 90 deler vinylklorid ble tilsatt. Blandingen ble rystet ved 50°C og 9,5 kg/cm^ i 3 dager, hvor-etter produktet ble filtrert fra, vasket godt med metanol og tørket i vakuum ved 60 °C for å gi 73,8 deler polymert materiale med en redusert viskositet på 0,38 og inneholdende 85 vektprosent vinylklorid. Press-støpte støpestykker oppviste 1/10 og 10/10 Vicat mykningspunkter på 70,8 og 100°C. Det ble antatt at disse lave avlesninger skyldtes produktets iave molekylvekt. 160 parts of methanol, 10 parts of N-phenylmaleimide and 1 part of lauroyl peroxide were added to a vessel. The vessel was then pressurized to 7.0 kg/cm<2> with nitrogen and vented 3 times, and 90 parts of vinyl chloride was added. The mixture was shaken at 50°C and 9.5 kg/cm^ for 3 days, after which the product was filtered off, washed well with methanol and dried in vacuo at 60°C to give 73.8 parts of polymeric material with a reduced viscosity of 0.38 and containing 85% vinyl chloride by weight. Die cast castings exhibited 1/10 and 10/10 Vicat softening points of 70.8 and 100°C. It was assumed that these low readings were due to the product's low molecular weight.
Eksempel 14. Example 14.
Fremgangsmåten ifølge eksempel 13 ble gjentatt med 10 deler N-fenylmaleimid, 90 deler vinylklorid, 240 deler methanol og 1 del acetyl-cykloheksyl-sulfonylperoksyd. Blandingen ble rystet ved 25°C i 3 dager, og de faste bestanddeler ble isolert for å gi 73 deler polymert produkt med en redusert viskositet på 0,4 og inneholdende 86,8 vektprosent vinylklorid basert på kloranalyse. The procedure according to example 13 was repeated with 10 parts of N-phenylmaleimide, 90 parts of vinyl chloride, 240 parts of methanol and 1 part of acetyl-cyclohexyl-sulphonyl peroxide. The mixture was shaken at 25°C for 3 days and the solids were isolated to give 73 parts of polymeric product having a reduced viscosity of 0.4 and containing 86.8 weight percent vinyl chloride based on chlorine analysis.
Eksempel 15. Example 15.
Fremgangsmåten ifølge eksempel 2 ble gjentatt, men i dette tilfelle ble N-fenyl-maleimidet tilsatt i 8 porsjoner med halvtimes mel-lomrom under polymerisasjonen i form av en dispersjon i vann. Utbyttet var 48,5 deler av et produkt med en redusert viskositet på 0,78. En porsjon ble blandet med 2 vektprosent av et organo-tinn-stabiliseringsmiddel og press-støpt ved 200 °C for å gi brune, opake prøvestykker med 1/10 og 10/10 Vicat-mykningspunkter på henholdsvis 114— 120°C og 139—143°C. Kloranalyse tydet på et vinylklorinnhold på 60 vektprosent. The procedure according to example 2 was repeated, but in this case the N-phenylmaleimide was added in 8 portions at half-hour intervals during the polymerization in the form of a dispersion in water. The yield was 48.5 parts of a product with a reduced viscosity of 0.78. A portion was mixed with 2% by weight of an organotin stabilizer and compression molded at 200°C to give brown, opaque specimens with 1/10 and 10/10 Vicat softening points of 114— 120°C and 139— 143°C. Chlorine analysis indicated a vinyl chlorine content of 60% by weight.
Claims (5)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3001357A DE3001357C2 (en) | 1980-01-16 | 1980-01-16 | Granulated laxative based on plantago seeds and senna pods and process for the manufacture of the same |
Publications (3)
Publication Number | Publication Date |
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NO810133L NO810133L (en) | 1981-07-17 |
NO153594B true NO153594B (en) | 1986-01-13 |
NO153594C NO153594C (en) | 1986-05-21 |
Family
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Application Number | Title | Priority Date | Filing Date |
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NO810133A NO153594C (en) | 1980-01-16 | 1981-01-15 | PROCEDURE FOR THE PREPARATION OF A PREPARATION BASED ON PSYLLIUM SEEDS AND LATE FRUITS. |
Country Status (26)
Country | Link |
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AR (1) | AR222269A1 (en) |
AT (1) | AT372280B (en) |
AU (1) | AU547152B2 (en) |
BE (1) | BE887111A (en) |
CA (1) | CA1167769A (en) |
CH (1) | CH650403A5 (en) |
CS (1) | CS227324B2 (en) |
DE (1) | DE3001357C2 (en) |
DK (1) | DK153774C (en) |
FI (1) | FI75095C (en) |
FR (1) | FR2473311A1 (en) |
GB (1) | GB2067402B (en) |
GR (1) | GR73649B (en) |
HK (1) | HK75984A (en) |
IE (1) | IE50621B1 (en) |
IT (1) | IT1135052B (en) |
LU (1) | LU83058A1 (en) |
MX (1) | MX7112E (en) |
NL (1) | NL188452C (en) |
NO (1) | NO153594C (en) |
NZ (1) | NZ196034A (en) |
PT (1) | PT72358B (en) |
SE (1) | SE454744B (en) |
SU (1) | SU1145911A3 (en) |
YU (1) | YU42551B (en) |
ZA (1) | ZA81254B (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4321263A (en) * | 1980-09-30 | 1982-03-23 | Rowell Laboratories, Inc. | Psyllium compositions |
DE3479630D1 (en) * | 1983-12-12 | 1989-10-12 | Procter & Gamble | Psyllium mucilloid products |
US5009916A (en) * | 1983-12-12 | 1991-04-23 | The Procter & Gamble Company | Psyllium mucilloid fiber food products |
US4950689A (en) * | 1987-03-31 | 1990-08-21 | Yang Robert K | Pectin delivery system |
EP0412604B1 (en) * | 1989-08-10 | 1993-08-04 | The Procter & Gamble Company | Agglomerated psyllium husk containing edible acid |
US5219570A (en) * | 1989-08-10 | 1993-06-15 | The Procter & Gamble Company | Agglomerated psyllium husk containing edible acid |
US5126150A (en) * | 1990-10-01 | 1992-06-30 | The Procter & Gamble Company | Compositions containing psyllium |
GB2272374B (en) * | 1992-11-13 | 1996-07-03 | Asta Medica Ag | Stable senna extract formulations |
FR2723318B1 (en) * | 1994-08-04 | 1999-09-03 | Chicouri Marcel | NOVEL LAXATIVE COMPOSITIONS AND THEIR PREPARATION PROCESS |
US20050053676A1 (en) * | 2003-09-05 | 2005-03-10 | Madaus Ag | Powdered composition for use as laxative |
ES2320827B1 (en) * | 2006-12-29 | 2010-03-03 | Madaus, S.A. | "PHARMACEUTICAL COMPOSITION CONTAINING PSYLLIUM AND SENNA". |
DE202007007143U1 (en) | 2007-05-02 | 2008-06-12 | Madaus Gmbh | New pharmaceutical composition for use as a laxative |
DE102007023397B4 (en) | 2007-05-02 | 2015-03-26 | Madaus Gmbh | New pharmaceutical composition for use as a laxative |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1847247A (en) * | 1931-02-14 | 1932-03-01 | Jones William Thomas | Mechanical laxative |
DE1003916B (en) * | 1954-05-12 | 1957-03-07 | Westminster Lab Ltd | Process for the production of Sennespraeparaten |
GB829068A (en) * | 1958-04-09 | 1960-02-24 | Mundipharma Ag | Improvements in novel laxative agents |
DE1103520B (en) * | 1959-08-12 | 1961-03-30 | Madaus & Co Dr | Process for making a laxative |
DE2629773C2 (en) * | 1976-07-02 | 1985-06-27 | Thiele, Henry, Dipl.-Ing. Dr., 7534 Birkenfeld | Product made from bran and pectin |
-
1980
- 1980-01-16 DE DE3001357A patent/DE3001357C2/en not_active Expired
-
1981
- 1981-01-13 CA CA000368439A patent/CA1167769A/en not_active Expired
- 1981-01-14 FI FI810095A patent/FI75095C/en not_active IP Right Cessation
- 1981-01-14 LU LU83058A patent/LU83058A1/en unknown
- 1981-01-14 GB GB8101047A patent/GB2067402B/en not_active Expired
- 1981-01-14 DK DK015181A patent/DK153774C/en not_active IP Right Cessation
- 1981-01-15 NO NO810133A patent/NO153594C/en unknown
- 1981-01-15 NL NLAANVRAGE8100167,A patent/NL188452C/en not_active IP Right Cessation
- 1981-01-15 IE IE74/81A patent/IE50621B1/en not_active IP Right Cessation
- 1981-01-15 GR GR63874A patent/GR73649B/el unknown
- 1981-01-15 IT IT19154/81A patent/IT1135052B/en active
- 1981-01-15 CS CS81297A patent/CS227324B2/en unknown
- 1981-01-15 SE SE8100207A patent/SE454744B/en not_active IP Right Cessation
- 1981-01-15 PT PT72358A patent/PT72358B/en not_active IP Right Cessation
- 1981-01-15 CH CH247/81A patent/CH650403A5/en not_active IP Right Cessation
- 1981-01-15 AU AU66241/81A patent/AU547152B2/en not_active Ceased
- 1981-01-15 AT AT0014681A patent/AT372280B/en not_active IP Right Cessation
- 1981-01-15 ZA ZA00810254A patent/ZA81254B/en unknown
- 1981-01-16 NZ NZ196034A patent/NZ196034A/en unknown
- 1981-01-16 BE BE0/203510A patent/BE887111A/en not_active IP Right Cessation
- 1981-01-16 MX MX819267U patent/MX7112E/en unknown
- 1981-01-16 FR FR8100819A patent/FR2473311A1/en active Granted
- 1981-01-16 SU SU813238931A patent/SU1145911A3/en active
- 1981-01-16 AR AR283983A patent/AR222269A1/en active
- 1981-01-16 YU YU95/81A patent/YU42551B/en unknown
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1984
- 1984-10-04 HK HK759/84A patent/HK75984A/en not_active IP Right Cessation
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