NO820382L - PROCEDURE FOR THE PREPARATION OF Aqueous SALT SOLUTIONS OF MALEIC ACID ANHYDRIDE-DICYCLOPENTADIA COPOLYMERIZATE - Google Patents
PROCEDURE FOR THE PREPARATION OF Aqueous SALT SOLUTIONS OF MALEIC ACID ANHYDRIDE-DICYCLOPENTADIA COPOLYMERIZATEInfo
- Publication number
- NO820382L NO820382L NO820382A NO820382A NO820382L NO 820382 L NO820382 L NO 820382L NO 820382 A NO820382 A NO 820382A NO 820382 A NO820382 A NO 820382A NO 820382 L NO820382 L NO 820382L
- Authority
- NO
- Norway
- Prior art keywords
- aqueous
- maleic anhydride
- copolymer
- dicyclopentadiene
- solution
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- 239000012266 salt solution Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title 1
- 239000011976 maleic acid Substances 0.000 title 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title 1
- 229920001577 copolymer Polymers 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 12
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical class CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 27
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 12
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 8
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- VPLAKKIIYHIFQG-UHFFFAOYSA-N 5-methylhexan-2-one Chemical compound CC(C)CCC(C)=O.CC(C)CCC(C)=O VPLAKKIIYHIFQG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- -1 vinylcyclohexene cumene Chemical compound 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
-
- 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Gjennomfører man den radikalisk inisierte kopolymerisasjonThe radical-initiated copolymerization is carried out
av maleinsyreanhydrid med dicyklopentadien i aromatiske oppløsningsmidler faller polymerisatene ut tungtoppløselig. of maleic anhydride with dicyclopentadiene in aromatic solvents, the polymers precipitate out sparingly soluble.
Om denne arbeidsmåte finnes i litteraturen mange publikasjoner. Således omtales i US patent 3 188 303 å polymerisere maleinsyreanhydrid med dicyklopentadien i benzen. Videre fremgår det av DE-OS 27 27 510 at man kan fremstille kopolymerisater av maleinsyreanhydrid og dicyklopentadien i toluen. Ifølge DE-OS 29 43 980 anvendes ved kopolymerisasjon av maleinsyreanhydrid, dicyklopentadien og cyklooktadien og ifølge DE-OS 29 39 293 ved kopolymerisasjon av maleinsyreanhydrid, dicyklopentadien og vinylcykloheksen cumol som oppløsningsmiddel. There are many publications in the literature about this way of working. Thus US patent 3,188,303 describes polymerizing maleic anhydride with dicyclopentadiene in benzene. Furthermore, it appears from DE-OS 27 27 510 that it is possible to prepare copolymers of maleic anhydride and dicyclopentadiene in toluene. According to DE-OS 29 43 980 in the copolymerization of maleic anhydride, dicyclopentadiene and cyclooctadiene and according to DE-OS 29 39 293 in the copolymerization of maleic anhydride, dicyclopentadiene and vinylcyclohexene cumene is used as solvent.
Fra alle disse aromatiske oppløsningsmidler faller kopolymerisatene av maleinsyreanhydrid med dicyklopentadien eventuelt under tilsetning av olefiner, riktignok ut fast, imidlertid sterkt svellet og det er vanskelig å fjerne oppløsningsmiddelet godt herifra. Forsøker man å oppløse det svellede polymerisat i vandige alkalier, får man ikke skillbare emulsjoner hvori det dessuten er inneholdt betraktelige mengder halvfast stoff. From all these aromatic solvents, the copolymers of maleic anhydride with dicyclopentadiene, possibly with the addition of olefins, fall out solid, however strongly swollen and it is difficult to remove the solvent well from this. If one tries to dissolve the swollen polymerizate in aqueous alkalis, one does not obtain separable emulsions in which considerable quantities of semi-solid matter are also contained.
Forutsetning til fremstilling av vandige alkaliske oppløs-ninger av kopolymerisater ifølge disse fremgangsmåter var hittil en best mulig fjerning av aromatene, f.eks. ved 35- A prerequisite for the preparation of aqueous alkaline solutions of copolymers according to these methods has so far been the best possible removal of the aromatics, e.g. at 35-
til 45-timers tørkning ved ca. 140°C og 40 mbar, eventuelt under gjennomføring av vanndamp, respektiv indifferente gasser. Selv deretter kan man ennå påvise 1-2% aromater som f.eks. cumol i kopolymerisat av maleinsyreanhydrid med dicyklopentadien som restfuktighet. Da det opptrer en beskad-igelse av polymerisatet ved den høye temperaturbelastning måtte tørketemperaturen settes ned til maksimalt 120°C. to 45-hour drying at approx. 140°C and 40 mbar, possibly during the passage of steam or inert gases. Even then, one can still detect 1-2% aromatics such as e.g. cumol in copolymer of maleic anhydride with dicyclopentadiene as residual moisture. As the polymer is damaged by the high temperature load, the drying temperature had to be reduced to a maximum of 120°C.
Derved økes imidlertid betraktelig den nødvendige tørketid.This, however, considerably increases the required drying time.
Som alternativ til tørkning byr det seg vanndampdestillasjonSteam distillation is an alternative to drying
av det filterfuktige maleinsyreanhydrid-dicyklopentadien-kopolymerisat. For å unngå stoffbeskadigelser kan man hen-,' of the filter-wet maleic anhydride-dicyclopentadiene copolymer. To avoid fabric damage, you can
siktsmessig arbeide under normale betingelser. Dertil er det for 10 g filterfuktig kopolymerisat nødvendig å destillere over 3,5-4 liter vann for å senke aromatinnholdet i kopolymerisatet såvidt at det med vandig alkalier lar seg fremstille en til en viss grad klar oppløsning. Ved polymerisasjon i aromater bør konsentrasjonen av de anvendte monomere ikke overskride en viss grad. Polymeriserer man maleinsyreanhydrid og dicyklopentadien i forholder <~1:1, danner det seg ved anvendelse av høyere samlet monomerkonsentrasjoner enn 23 vekt% allerede betraktelige organiske oppløsningsmidler og vandige alkalier ikke mer oppløselige deler. termly work under normal conditions. In addition, for 10 g of filter-wet copolymer, it is necessary to distill over 3.5-4 liters of water in order to lower the aromatic content in the copolymer to such an extent that a clear solution to a certain extent can be produced with aqueous alkali. In the case of polymerization in aromatics, the concentration of the monomers used should not exceed a certain degree. If maleic anhydride and dicyclopentadiene are polymerized in ratios <~1:1, when using higher total monomer concentrations than 23% by weight, already considerable organic solvents and aqueous alkalis form no more soluble parts.
Utbyttet ved kopolymerisasjon av maleinsyreanhydrid med dicyklopentadien i molforhold~l:1 og cumol som oppløsnings-middel beveger seg mellom 68 og 76 vekt%. The yield by copolymerization of maleic anhydride with dicyclopentadiene in a molar ratio ~1:1 and cumene as solvent ranges between 68 and 76% by weight.
I alifatiske og cykloalifatiske oppløsningsmidler er en kopolymerisasjon riktignok mulig, fører imidlertid til urene mørke materialer (US-PS 3 188 303). In aliphatic and cycloaliphatic solvents, a copolymerization is indeed possible, but leads to impure dark materials (US-PS 3,188,303).
Fra litteraturen er det også kjent at maleinsyreanhydrid-dicyklopentadien-kopolymerisater å oppløse seg i bestemte opp-løsningsmidler. Således finner man henvisninger til dioksan, aceton og cykloheksanon. I disse medier er det også allerede blitt utført radikalisk insierte kopolymerisasjoner av maleinsyreanhydrid og dicyklopentadien (US-PS 3 188 303; J.Polym. Sei., A 11, 1795, (1977). It is also known from the literature that maleic anhydride-dicyclopentadiene copolymers dissolve in certain solvents. Thus, one finds references to dioxane, acetone and cyclohexanone. Radically initiated copolymerizations of maleic anhydride and dicyclopentadiene have also already been carried out in these media (US-PS 3 188 303; J.Polym. Sei., A 11, 1795, (1977).
Det har nu overraskende vist seg at alifatiske monoketonerIt has now surprisingly been shown that aliphatic monoketones
i området på 5 til 8 C-atomer har en fullstendig oppløselig-het for kopolymerisat av maleinsyreanhydrider og dicyklopentadien når ketogruppen er anordnet i molekylets to- eller trestilling. De viser, i motsetning til de i litteraturen omtalte overnevnte oppløsningsmidler dioksan, aceton og cykloheksanon, bare en liten oppløselighet i vann. De ifølge oppfinnelsen anvendte metyl- eller etylketoner har i det over- in the range of 5 to 8 C atoms has a complete solubility for copolymers of maleic anhydrides and dicyclopentadiene when the keto group is arranged in the two or three position of the molecule. They show, in contrast to the above-mentioned solvents dioxane, acetone and cyclohexanone mentioned in the literature, only a small solubility in water. The methyl or ethyl ketones used according to the invention generally have
nevnte molekylvektsområde evne til å oppløse sågar inntil konsentrasjoner over 40 vekt% kopolymerisat• I dem kan det direkte fremstilles over 40%-ige oppløsninger av et ufor-nettet maleinsyreanhydrid-dicyklopentadien-kopolymerisat med radikaliske katalysatorer. I aromater derimot opptrer ved anvendelse av samlet monomere på mer enn 23 vekt% allerede nettdannede deler som er uoppløselige i vandige alkalier. said molecular weight range, the ability to dissolve even up to concentrations above 40% by weight copolymer• In them, above 40% solutions of an uncrosslinked maleic anhydride-dicyclopentadiene copolymer can be directly prepared with radical catalysts. In aromatics, on the other hand, when using total monomers of more than 23% by weight, already net-formed parts appear which are insoluble in aqueous alkalis.
Anvender man andre olefiner som partnere for maleinsyreanhydrid som f.eks. styren, vinylcykloheksen, cyklooctadien eller blandinger av dicyklopentadien med andre olefiner utskiller polymerisatet seg helt eller delvis fra de ifølge oppfinnelsen anvendte metyl- eller etylketoner. Other olefins are used as partners for maleic anhydride, such as e.g. styrene, vinylcyclohexene, cyclooctadiene or mixtures of dicyclopentadiene with other olefins, the polymer separates completely or partially from the methyl or ethyl ketones used according to the invention.
Som egnede ketoner kommer f.eks. på tale dietylketon, metyl-isopropylketon, metylbutylketon, metylisobutylketon, etylprop-ylketon, metylpentylketon, etylbutylketon, metylheksylketon, metylisoamylketon, metylamylketon osv. Ketonenes oppløselig-het med vann synker med økende kjedelengde og er ved de ifølge oppfinnelsen anvendte ketoner så lav at det er mulig herav overraskende umiddelbart med kort tidsforbruk og på en enkel måte å fremstille oppløsningsmiddelfattig klare, lyse alkalisk-vandige oppløsninger direkte av den organiske polymerisatopp-løsning f.eks. ved utrystning. ER ketogruppen anordnet i en annen stilling eller har den anvendte monoketon mer enn 8 C-atomer, avsetter kopolymerisatet av maleinsyreanhydrid og dicyklopentadien seg helt eller delvis ofte i seig form fra oppløsningsmiddelet allerede under polymerisasjonen. Det er mulig til ifølge oppfinnelsen anvendte ketoner å sette indifferente oppløsningsmidler som f.eks. aromater og/eller alifater inntil 40 volum% uten at det foregår en utfelling. Suitable ketones include e.g. namely diethyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, ethyl propyl ketone, methyl pentyl ketone, ethyl butyl ketone, methyl hexyl ketone, methyl isoamyl ketone, methyl amyl ketone, etc. The solubility of the ketones in water decreases with increasing chain length and is so low with the ketones used according to the invention that it is possible of this surprisingly immediately with a short consumption of time and in a simple way to produce solvent-poor clear, bright alkaline-aqueous solutions directly from the organic polymerization solution e.g. upon disarmament. IF the keto group is arranged in a different position or the monoketone used has more than 8 C atoms, the copolymer of maleic anhydride and dicyclopentadiene often deposits in whole or in part in a viscous form from the solvent already during the polymerization. It is possible to add indifferent solvents such as e.g. to the ketones used according to the invention. aromatics and/or aliphatics up to 40% by volume without precipitation taking place.
Det er bemerkelsesverdig at utbyttene av polymerisat kanIt is noteworthy that the yields of polymerizate can
ligge betraktelig høyere i de ifølge oppfinnelsen anvendte ketoner enn i de aromatiske oppløsningsmidler i henhold til teknikkens stand. Mens ifølge den kjente fremgangsmåte, altså lie considerably higher in the ketones used according to the invention than in the aromatic solvents according to the state of the art. While according to the known method, that is
ved kopolymerisasjon av maleinsyreanhydrid med dicyklopentadien i molforhold 1:1 i aromatene ble funnet et utbytte mellom 68-76%, lykkes i oppløsningsmidlene ifølge oppfinnelsen en økning til 85 til over 99 vekt%. in the copolymerization of maleic anhydride with dicyclopentadiene in a molar ratio of 1:1 in the aromatics, a yield of between 68-76% was found, in the solvents according to the invention an increase to 85 to over 99% by weight is achieved.
Oppfinnelsens gjenstand er følgelig en fremgangsmåte til fremstilling av vandige saltoppløsninger av maleinsyreanhydrid-dicyklopentadien-kopolymerisat idet fremgangsmåten erkarakterisert vedat den radikaliske kopolymerisasjon gjennomføres i med vann ikke blandbare alifatiske metyl- og/eller etylketoner med 5 til 8 C-atomer, deretter ekstraheres den dannede kopolymerisatoppløsning med vandige alkalier og den vandige alkaliske fase adskilles fra oppløsningsmiddelet. The object of the invention is therefore a method for the production of aqueous salt solutions of maleic anhydride-dicyclopentadiene copolymer, the method being characterized in that the radical copolymerization is carried out in water-immiscible aliphatic methyl and/or ethyl ketones with 5 to 8 C atoms, then the formed copolymer solution is extracted with aqueous alkalis and the aqueous alkaline phase is separated from the solvent.
I praksis kan man f.eks. gå frem således at man omrører denIn practice, one can e.g. proceed in such a way as to stir it
ca. 30-40 vekt%-ige kopolymerisatoppløsning, fremstilt av maleinsyreanhydrid og dicyklopentadien i f.eks. heptanon-2 about. 30-40% by weight copolymer solution, prepared from maleic anhydride and dicyclopentadiene in e.g. heptanone-2
ved temperaturer mellom ca. 40-95°C med den for saltdannelse tilstrekkelige alkalimengde i vann i h- 2 timer. De to sjikt adskiller seg deretter ganske fort. Det nedre vandige sjikt består av den umiddelbart anvendbare polymere saltoppløsning. Det øvre organiske sjikt er praktisk talt fritt for polymeri-sater, syrer og anhydrider. Den kan etter egnet tørkning anvendes umiddelbart som oppløsningsmiddel for neste poly-merisasj on. at temperatures between approx. 40-95°C with the amount of alkali sufficient for salt formation in water for 2 hours. The two layers then separate quite quickly. The lower aqueous layer consists of the immediately usable polymeric salt solution. The upper organic layer is practically free of polymers, acids and anhydrides. After suitable drying, it can be used immediately as a solvent for the next polymerization.
Alt etter type og molforhold av de anvendte monomere kan det under tiden opptre en liten skumdannelse av polymerenes vandige alkaliske oppløsning. Man kan unngå den når man vasker den organiske oppløsning av kopolymerisatene i første rekke med vann og deretter ekstraherer med de vandige alkalier. Derved fjernes bl.a. eventuelt denne tilstedeværende maleinsyreanhydrid i monomer eller polymer form under hydrolyse fra reaksjonsoppløsningen, mens kopolymerisatet blir tilbake i det organiske sjikt. Depending on the type and molar ratio of the monomers used, a slight foaming of the polymers' aqueous alkaline solution may occur during this time. It can be avoided when the organic solution of the copolymers is first washed with water and then extracted with the aqueous alkalis. This removes, among other things, optionally this present maleic anhydride in monomeric or polymeric form during hydrolysis from the reaction solution, while the copolymer remains in the organic layer.
Av den ca. 40%-ige oppløsning i de ifølge oppfinnelsen anvendte ketoner faller etter polymerisasjonen ved avkjøling til værelsetemperatur ikke ut noe kopolymerisat. Of the approx. A 40% solution in the ketones used according to the invention does not precipitate any copolymer after polymerization when cooled to room temperature.
Som alkaliske reaksjonspartnere for kopolymerisatet kan det anvendes vandige oppløsninger av primære, sekundære eller tertiære aminer, qarternære ammoniumhydroksyder, ammoniakk samt hydroksydene fra det periodiske systems første hoved-gruppe, enkelvis eller i blandinger. As alkaline reaction partners for the copolymer, aqueous solutions of primary, secondary or tertiary amines, quaternary ammonium hydroxides, ammonia and the hydroxides from the first main group of the periodic table can be used, singly or in mixtures.
De vandige alkaliske oppløsninger ifølge oppfinnelsen kan man f.eks. anvende som anioniske overflatelimingsmidler for papir, fortykningsmidler, emulgatorer osv. The aqueous alkaline solutions according to the invention can be e.g. use as anionic surface sizing agents for paper, thickeners, emulsifiers, etc.
EksemplerExamples
1) Metylpentylketon (heptanon-2) som polymerisatoppløsnings-middel. 1) Methylpentyl ketone (heptanone-2) as a polymerizate solvent.
En oppløsning av 161g maleinsyreanhydrid og 289g dicyklopentadien i 680 ml metylpentylketon oppvarmes til ca. 9 3°C, reak-sjonsgodset avdekkes med nitrogen og en oppløsning av 30,3g benzoylperoksyd i 320 ml metylpentylketon inndryppes således at det ikke overskrides temperaturen på 95°C. Hertil kreves ca. 3 timer. Deretter foregår en etterreaksjon på ca. 2 timer ved samme temperatur, hvoretter det ikke mer er påvisbart peroksyd. Deretter avkjøles til ca. 80°C. Noen utskillelse av fast produkt foregår da ikke. For fjerning av ikke omsatt meleinsyreanhydrid fra den organiske oppløsning vaskes nu med 600 ml vann. Deretter emulgeres den organiske fase i 998 ml av en 5,6%-ig vandig NH^-oppløsning og blandes deretter med 929 ml vann. Emulsjonshøyden utgjør ca. 13 cm. Etter ca. 15 minutter ved en temperatur på ca. 80°C er adskillelsen fullstendig. I den klare vandige svakt gule fase befinner det seg det samlede kopolymerisat som ammoniumsalt. A solution of 161g maleic anhydride and 289g dicyclopentadiene in 680 ml methylpentyl ketone is heated to approx. 9 3°C, the reaction material is uncovered with nitrogen and a solution of 30.3g of benzoyl peroxide in 320 ml of methylpentyl ketone is added dropwise so that the temperature of 95°C is not exceeded. This requires approx. 3 hours. An after-reaction of approx. 2 hours at the same temperature, after which peroxide is no longer detectable. Then cool to approx. 80°C. No excretion of solid product then takes place. To remove unreacted maleic anhydride from the organic solution, wash now with 600 ml of water. The organic phase is then emulsified in 998 ml of a 5.6% aqueous NH 3 solution and then mixed with 929 ml of water. The emulsion height is approx. 13 cm. After approx. 15 minutes at a temperature of approx. At 80°C the separation is complete. In the clear aqueous slightly yellow phase, the combined copolymer is found as an ammonium salt.
Utbyttet av kopolymerisat er 9 8,7% av det teoretiske referert The yield of copolymer is 98.7% of the theoretical reference
til anvendt maleinsyreanhydrid.to used maleic anhydride.
For å fjerne en liten ketonlukt kan den vandige oppløsning behandles med vanndamp ved 100°C. Derved synker oppløs-ningens pH fra 8 til ca. 5. Etter avkjøling oppstår derved en liten utfelling som igjen forsvinner ved tilsetning av ammoniakkoppløsning. To remove a slight ketone smell, the aqueous solution can be treated with steam at 100°C. Thereby, the solution's pH drops from 8 to approx. 5. After cooling, a small precipitate is thereby produced, which again disappears when ammonia solution is added.
Ketonfasen inneholder etter ammoniakkbehandlingen over-skytende dicyklopentadien, vann og ammoniakk. For igjen å kunne føre oppløsningsmiddelblandingen i kretsen er det nødvendig at oppløst vann og ammoniakk fjernes på kjent måte. After the ammonia treatment, the ketone phase contains excess dicyclopentadiene, water and ammonia. In order to be able to feed the solvent mixture into the circuit again, it is necessary that dissolved water and ammonia are removed in a known manner.
Under samme betingelser kan heptanonoppløsningen rystes med vandige oppløsninger av 4,5%-ig litiumhydroksyd, 9,5%-ig kaliumhydroksy, 6,7%-ig natriumhydroksyd, 11%-ig aminoetanol eller 14%-ig morfolin, idet kopolymerisatet går kvantitativt i den vandige fase. Sjiktadskillelsen er i alle tilfeller fullendt, senest etter 40 minutter (80°C). 2) Metylisobutylketon som kopolymerisatoppløsningsmiddel. 680 ml metylisobutylketon has i 169g maleinsyreanhydrid og 273g dicyklopentadien og oppvarmes til ca. 93°C, idet det inntrer fullstendig oppløsning. Nu dekkes med nitrogen og en oppløsning av 25,5g benzoylperoksyd i 320 ml metylisobutylketon tildryppes således at 95°C ikke overskrides. Derved holdes temperaturen ennu så lenge inntil det ikke mer er påvisbart peroksyd. Deretter avkjøles til 80°C den klare oppløsning, rystes med 1047 ml 5,6%-ig vandig ammoniakkoppløsning kraftig, blandes med 9 75 ml vann og rystes igjen (emulsjonshøyde: 13 cm). Deretter foregår hurtig i løpet av 20 min. adskillelsen. Ved alle disse trinn holdes en temperatur på ca. 8 0°C. 1 den vandige fase befinner det seg nu ammoniumsaltet av den kopolymere. Utbytte 99,7% av det teoretiske referert til maleinsyreanhydrid. 3) Metylisoamylketon (5-metyl-heksan-2-on) som kopolymerisa-sjonsoppløsningsmiddel. Under the same conditions, the heptanone solution can be shaken with aqueous solutions of 4.5% lithium hydroxide, 9.5% potassium hydroxide, 6.7% sodium hydroxide, 11% aminoethanol or 14% morpholine, the copolymer being quantitative in the aqueous phase. The layer separation is complete in all cases, after 40 minutes (80°C) at the latest. 2) Methyl isobutyl ketone as copolymer solvent. 680 ml methyl isobutyl ketone is mixed with 169 g maleic anhydride and 273 g dicyclopentadiene and heated to approx. 93°C, as complete dissolution occurs. Now cover with nitrogen and a solution of 25.5 g of benzoyl peroxide in 320 ml of methyl isobutyl ketone is added dropwise so that 95°C is not exceeded. Thereby, the temperature is maintained for a longer time until there is no more detectable peroxide. The clear solution is then cooled to 80°C, shaken vigorously with 1047 ml of 5.6% aqueous ammonia solution, mixed with 9 75 ml of water and shaken again (emulsion height: 13 cm). Then takes place quickly within 20 min. the separation. During all these steps, a temperature of approx. 80°C. In the aqueous phase, there is now the ammonium salt of the copolymer. Yield 99.7% of the theoretical referred to maleic anhydride. 3) Methyl isoamyl ketone (5-methyl-hexan-2-one) as copolymerization solvent.
Ved en blanding bearbeidet analogt eksempel 2 med metylisoamylketon som oppløsningsmiddel fåes ammoniumsaltet av den kopolymere med et utbytte på 97,5% av det teoretiske, referert til anvendt maleinsyreanhydrid. Faseadskillelsen etter ekstrahering med 5,6%-ig vandig ammoniakk er oppnådd etter 2 timer (den emulgerte fases høyde: 14 cm.). 4) Etylbutylketon (heptanon-3) som polymerisatoppløsnings- middel. Under ellers like betingelser som i eksempel 2 gjennomføres kopolymerisasjonen i etylbutylketon og saltoppløsningen til-beredes deretter ved omsetning av vandig ammoniakkoppløs-ning. Adskillelsen fullstendiggjøres ved en emulsjonshøyde på 14 cm i løpet av 45 minutter ved 80°C. Utbytte av ko-polymeren utgjør 90,1% referert til anvendt maleinsyreanhydrin. 5) Dietylketon (pentanon-3) som polymerisatoppløsningsmiddel. With a mixture processed analogously to example 2 with methyl isoamyl ketone as solvent, the ammonium salt of the copolymer is obtained with a yield of 97.5% of the theoretical, referred to maleic anhydride used. The phase separation after extraction with 5.6% aqueous ammonia is achieved after 2 hours (height of the emulsified phase: 14 cm.). 4) Ethyl butyl ketone (heptanone-3) as a polymerizing agent medium. Under otherwise similar conditions as in example 2, the copolymerization is carried out in ethyl butyl ketone and the salt solution is then prepared by reacting an aqueous ammonia solution. The separation is completed at an emulsion height of 14 cm within 45 minutes at 80°C. Yield of the copolymer amounts to 90.1% referred to maleic anhydrin used. 5) Diethyl ketone (pentanone-3) as polymerizate solvent.
Under ellers samme betingelser som omtalt i eksempel 2 poly-meriseres maleinsyreanhydrid med dicyklopentadien i dietylketon som oppløsningsmiddel og omsettes deretter ved rysting med den vandige ammoniakkoppløsning ved 80°C. I løpet av 15 minutter inntrer ved en emulsjonshøyde på 14 cm klar fase-adskillelse. Utbytte av kopolymerisatets ammoniumsalt er 84,3% av det teoretiske referert til anvendt maleinsyreanhydrid. 6) Metylheksylketon (octanon-2) som polymerisatoppløsnings-middel . Under otherwise the same conditions as described in example 2, maleic anhydride is polymerized with dicyclopentadiene in diethyl ketone as solvent and is then reacted by shaking with the aqueous ammonia solution at 80°C. Clear phase separation occurs within 15 minutes at an emulsion height of 14 cm. Yield of the ammonium salt of the copolymer is 84.3% of the theoretical referred to maleic anhydride used. 6) Methylhexyl ketone (octanone-2) as polymer solvent.
I metylheksylketon som oppløsningsmiddel kopolymeriseresIn methyl hexyl ketone as solvent, copolymerization is carried out
1 mol maleinsyreanhydrid med et mol dicyklopentadien som 30%-ig oppløsning ved 93°C og deretter fremstilles ved ekstrahering med vandig ammoniakk den vndige ammoniumsalt-oppløsning som omtalt under eksempel 2. Emulsjonshøyden utgjør 14 cm. Adskillelsen inntrer ved 80oC i l,øpet av 15 minutter. Kopolymerisatutbytte utgjør 98,8% av det teoretiske referert til maleinsyreanhydrid. 1 mole of maleic anhydride with one mole of dicyclopentadiene as a 30% solution at 93°C and then the aqueous ammonium salt solution described under example 2 is prepared by extraction with aqueous ammonia. The emulsion height is 14 cm. The separation occurs at 80°C over a period of 15 minutes. Copolymer yield is 98.8% of the theoretical referred to maleic anhydride.
7) Sammenligningsforsøk i cumol.7) Comparative experiment in cumol.
Et ifølge DE-OS 27 27 510 i cumol av et mol maleinsyreanhydrid og et mol dicyklopentadien fremstilt kopolymerisat har etter oppløsningsmiddelets adskillelse ennu en restfuktighet på 32% cumol. 30 g av dette filterfuktige kopolymerisat kan ved omrøring med 125 m 6%-ig ammoniakk-vann ved 80°C overføres i en suspensjon hvor det etter dag-lang henstand ved værelsetemperatur bare utskiller seg små cumolmengder. Det kan ikke fastslås noen oppløsning av det faste svellede stoff. A copolymer produced according to DE-OS 27 27 510 in cumol of one mole of maleic anhydride and one mole of dicyclopentadiene still has a residual moisture of 32% cumol after the separation of the solvent. 30 g of this filter-wet copolymer can be transferred by stirring with 125 ml of 6% ammonia water at 80°C into a suspension where, after a day-long standstill at room temperature, only small amounts of cumene are secreted. No dissolution of the solid swollen substance can be determined.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813104621 DE3104621A1 (en) | 1981-02-10 | 1981-02-10 | METHOD FOR PRODUCING AQUEOUS SALT SOLUTIONS FROM MALEIC ACID ANHYDRIDE DICYCLOPENTADIENE COPOLYMERISAT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO820382L true NO820382L (en) | 1982-08-11 |
Family
ID=6124455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO820382A NO820382L (en) | 1981-02-10 | 1982-02-09 | PROCEDURE FOR THE PREPARATION OF Aqueous SALT SOLUTIONS OF MALEIC ACID ANHYDRIDE-DICYCLOPENTADIA COPOLYMERIZATE |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0057961A3 (en) |
| AT (1) | AT371486B (en) |
| DE (1) | DE3104621A1 (en) |
| FI (1) | FI820407L (en) |
| NO (1) | NO820382L (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3188303A (en) * | 1961-03-17 | 1965-06-08 | Velsicol Chemical Corp | Process and product relating to the reaction of dicyclopentadiene and alpha, beta di-and tri-carboxylic acids |
-
1981
- 1981-02-10 DE DE19813104621 patent/DE3104621A1/en not_active Withdrawn
-
1982
- 1982-02-05 EP EP82200139A patent/EP0057961A3/en not_active Withdrawn
- 1982-02-05 AT AT0043682A patent/AT371486B/en not_active IP Right Cessation
- 1982-02-09 NO NO820382A patent/NO820382L/en unknown
- 1982-02-09 FI FI820407A patent/FI820407L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FI820407L (en) | 1982-08-11 |
| DE3104621A1 (en) | 1982-09-02 |
| ATA43682A (en) | 1982-11-15 |
| AT371486B (en) | 1983-06-27 |
| EP0057961A3 (en) | 1982-09-01 |
| EP0057961A2 (en) | 1982-08-18 |
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