NO169132B - MIXTURE INCLUDING PIGMENT, ORGANIC FLUID AND A BLOCK POLYMER - Google Patents
MIXTURE INCLUDING PIGMENT, ORGANIC FLUID AND A BLOCK POLYMER Download PDFInfo
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- NO169132B NO169132B NO880738A NO880738A NO169132B NO 169132 B NO169132 B NO 169132B NO 880738 A NO880738 A NO 880738A NO 880738 A NO880738 A NO 880738A NO 169132 B NO169132 B NO 169132B
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- block
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- copolymer
- alkyl
- methacrylate
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- 239000000049 pigment Substances 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 27
- 229920000642 polymer Polymers 0.000 title description 8
- 239000012530 fluid Substances 0.000 title 1
- 229920001400 block copolymer Polymers 0.000 claims description 22
- 125000003010 ionic group Chemical group 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 15
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 150000005215 alkyl ethers Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003999 initiator Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- -1 glycidyl- Chemical group 0.000 description 3
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- JNOGVQJEBGEKMG-UHFFFAOYSA-N (1-methoxy-2-methylprop-1-enoxy)-trimethylsilane Chemical compound COC(=C(C)C)O[Si](C)(C)C JNOGVQJEBGEKMG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005653 Brownian motion process Effects 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000005537 brownian motion Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 1
- IGAWKPMXUGZZIH-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)C=C IGAWKPMXUGZZIH-UHFFFAOYSA-N 0.000 description 1
- ZSPOJBDHHFFJAP-UHFFFAOYSA-M 3-chlorobenzoate;tetrabutylazanium Chemical compound [O-]C(=O)C1=CC=CC(Cl)=C1.CCCC[N+](CCCC)(CCCC)CCCC ZSPOJBDHHFFJAP-UHFFFAOYSA-M 0.000 description 1
- HZHPOJPIGFWDTD-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C=C HZHPOJPIGFWDTD-UHFFFAOYSA-N 0.000 description 1
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MNRGFUBMMILKAL-UHFFFAOYSA-N methyl phenylmethanesulfonate Chemical compound COS(=O)(=O)CC1=CC=CC=C1 MNRGFUBMMILKAL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Description
Oppfinnelsens bakgrunn The background of the invention
Polymere materialer som er effektive for å dispergere pigmenter i organiske oppløsningsmidler har tidligere vært kjente. Slike polymere dispergeringsmidler er typisk av AB- eller BAB-typene, hvor en polar gruppe som er kjent som A-segmentet er tilstede i molekylet for å lette tilfestning til en pigmentoverflate/ og hvor minst én ikke-polar del som er kjent som B-segmentet er tilstede for å øke stearin-stabilisering av pigmentpartiklene i en dispersjon. Polymeric materials effective for dispersing pigments in organic solvents have previously been known. Such polymeric dispersants are typically of the AB or BAB types, where a polar group known as the A segment is present in the molecule to facilitate attachment to a pigment surface/ and where at least one non-polar portion known as the B- the segment is present to increase stearin stabilization of the pigment particles in a dispersion.
I US patent 3912677 (Baker et al) er fordelene ved polymerer som inneholder ioniske grupper beskrevet, i spesifikke tilfeller hvor de ioniske grupper er i form av et salt med en saltdannende komponent eller motion. Den saltdannende komponent har affinitet overfor organiske pig-mentpartiklers overflate og er istand til å reagere med den polart bundne ioniske gruppe under dannelse av et salt. Fort-satte anstrengelser har imidlertid gått ut på å forbedre opp-førselen til polymere dispergeringsmidler og å komme frem til effektive dispergeringsmidler som ikke krever anvendelse av spesielle saltdannende komponenter hvis anvendelse kom-pliserer produksjonen av dispergeringsmidlene og kan innføre uønsket farve. In US patent 3912677 (Baker et al) the advantages of polymers containing ionic groups are described, in specific cases where the ionic groups are in the form of a salt with a salt-forming component or counterion. The salt-forming component has affinity towards the surface of organic pigment particles and is capable of reacting with the polar bound ionic group to form a salt. However, continued efforts have been made to improve the behavior of polymeric dispersants and to arrive at effective dispersants that do not require the use of special salt-forming components, the use of which complicates the production of the dispersants and can introduce unwanted color.
Oppsummering av oppfinnelsen Summary of the invention
Den foreliggende oppfinnelse er basert på den erkjenn-else at blokkopolymerer som er sammensatt av lignende monomerer, men som oppviser vesentlig forskjellig polaritet, idet én av blokkene har kationiske ammonium-, fosfonium- The present invention is based on the recognition that block copolymers which are composed of similar monomers, but which exhibit significantly different polarity, with one of the blocks having cationic ammonium, phosphonium
eller sulfoniumgrupper, gir utmerket oppførsel som pigmentdispergeringsmidler uten at det er nødvendig med spesielle saltdannende komponenter. or sulfonium groups, provide excellent behavior as pigment dispersants without the need for special salt-forming components.
Det tilveiebringes nærmere bestemt ved hjelp av den foreliggende oppfinnelse en blanding som omfatter pigment, organisk væske og en blokkopolymer som i det vesentlige består av Specifically, the present invention provides a mixture comprising pigment, organic liquid and a block copolymer which essentially consists of
(a) 0,1-50 vekt%, basert på kopolymeren, av minst en blokk med en antallsmidlere molekylvekt av fra 200 til 10000 og fremstilt fra minst én monomer valgt fra for- (a) 0.1-50% by weight, based on the copolymer, of at least one block having a number average molecular weight of from 200 to 10,000 and prepared from at least one monomer selected from
bindelser med de generelle formler CH2=CHC02R og CH2=CCH3C02R, hvori R er alkyl eller alkylether med 1-20 carbonatomer, idet blokken ytterligere inneholder minst 2 ioniske deler som er uthengende deler fra R-gruppene og har den generelle formel ~A(Rl,mX/ hvori A er valgt fra N, P og S, ^ er uavhengig valgt fra alkyl eller alkylether med 1-20 carbonatomer, fenyl eller substituert fenyl, m er 3 når A er N eller P, og m er 2 når A er S, og X er valgt fra halogenider og konjugerte baser av organiske syrer, og idet blokkens ryggrad er fremstilt fra ethylenisk umettede enheter, og (b) 99,9-50 vekt%, basert på kopolymeren, av minst én blokk med en antallsmidlere molekylvekt av fra 500 til 100000 og fremstilt fra monomerer valgt fra forbindelser med de generelle formler CH2=CHC02R og CH2=CCH3C02R, hvori R er alkyl eller alkylether med 1-20 carbonatomer, og blandingen er særpreget ved at den er en ikke-vandig dispersjon. bonds with the general formulas CH2=CHC02R and CH2=CCH3C02R, in which R is alkyl or alkyl ether with 1-20 carbon atoms, the block further containing at least 2 ionic parts which are protruding parts from the R groups and have the general formula ~A(Rl ,mX/ wherein A is selected from N, P and S, ^ is independently selected from alkyl or alkyl ether of 1-20 carbon atoms, phenyl or substituted phenyl, m is 3 when A is N or P, and m is 2 when A is S, and X are selected from halides and conjugate bases of organic acids, and the backbone of the block is prepared from ethylenically unsaturated units, and (b) 99.9-50% by weight, based on the copolymer, of at least one block having a number average molecular weight of from 500 to 100,000 and prepared from monomers selected from compounds with the general formulas CH2=CHC02R and CH2=CCH3C02R, in which R is alkyl or alkyl ether of 1-20 carbon atoms, and the mixture is characterized by the fact that it is a non-aqueous dispersion.
Disse blokkopolymerer kan og blir fortrinnsvis fremstilt ved gruppeoverføringspolymerisasjonsmetoder, de oppviser utmerket oppførsel som dispergeringsmidler, og de krever ikke saltdannende motioner for å gi en tilfredsstillende opp-førsel . These block copolymers can and are preferably prepared by group transfer polymerization methods, they exhibit excellent behavior as dispersants, and they do not require salt-forming counterions to provide satisfactory behavior.
Detaljert beskrivelse av oppfinnelsen Detailed description of the invention
Monomerer som kan anvendes for fremstillingen av blandingene ifølge den foreliggende oppfinnelse, innbefatter de acrylater og methacrylater som er beskrevet i US patent nr. 4508880 (Webster), spalte 8, linjene 4-58, bortsett fra 3-methacryloxypropylacrylat, og 2-methacryloxy-ethylacrylat og -linalat. Monomerer som er foretrukne for den første blokk for kopolymeren og som inneholder de uthengende ioniske grupper, innbefatter dimethylaminoethylmethacrylat og diethylaminoethylmethacrylat. Monomerer som er foretrukne for den annen (b) blokk av copolymerene, innbefatter methylmethacrylat, butylmethacrylat og 2-ethylhexylmethacrylat. Monomers which can be used for the preparation of the compositions according to the present invention include the acrylates and methacrylates described in US Patent No. 4508880 (Webster), column 8, lines 4-58, except for 3-methacryloxypropyl acrylate, and 2-methacryloxy- ethyl acrylate and -linalate. Monomers preferred for the first block of the copolymer and which contain the pendant ionic groups include dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. Monomers preferred for the second (b) block of the copolymers include methyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
Polymerene for blandingen ifølge oppfinnelsen kan fremstilles ved anvendelse av vanlige anioniske polymerisasjons-metoder, hvor en første blokk av kopolymeren dannes, og når den første blokk er ferdig, igangsettes en annen monomer-strøm for å danne en påfølgende blokk av polymeren. Reak-sjonstemperaturene under anvendelse av slike metoder bør imidlertid holdes på" et lavt nivå, for eksempel fra 0 til -40°C, slik at bireaksjoner minimeres og de ønskede blokker, med de spesifiserte molekylvekter, oppnås. The polymers for the mixture according to the invention can be prepared using common anionic polymerization methods, where a first block of the copolymer is formed, and when the first block is finished, another monomer flow is initiated to form a subsequent block of the polymer. However, the reaction temperatures using such methods should be kept at a low level, for example from 0 to -40°C, so that side reactions are minimized and the desired blocks, with the specified molecular weights, are obtained.
For å oppnå den ønskede molekylvekt for hver blokk såvel som jevnhet i blokkene blir gruppeoverføringspolymerisasjons-metoder med fordel og fortrinnsvis anvendt, som de som er beskrevet i det ovennevnte US patent nr. 4508880 (Webster), herved inkorporert ved henvisning. I henhold til denne fremgangsmåte blir en umettet monomer bragt i kontakt med en initiator og et katalysatorsystem som inneholder silicium, tinn eller germanium, og i løpet av dette forløper polymerisa-sjonen på regulert måte, i motsetning til den vilkårlige måte som er typisk for polymerisasjonsreaksjoner, slik at en i det vesentlige lineær polymer kan fremstilles med polymer-kjeder som er jevne og har den ønskede molekylvekt. To achieve the desired molecular weight for each block as well as block uniformity, group transfer polymerization methods are advantageously and preferably used, such as those described in the above-mentioned US Patent No. 4,508,880 (Webster), hereby incorporated by reference. According to this method, an unsaturated monomer is brought into contact with an initiator and a catalyst system containing silicon, tin or germanium, during which the polymerization proceeds in a regulated manner, in contrast to the arbitrary manner typical of polymerization reactions , so that an essentially linear polymer can be produced with polymer chains that are uniform and have the desired molecular weight.
Ved fremstillingen av blandingene i henhold til In the preparation of the mixtures according to
den foreliggende oppfinnelse er den rekkefølge med hvilken blokkene fremstilles ikke av kritisk betydning. Blokken som inneholder de uthengende ioniske deler eller blokken som ikke inneholder disse deler, kan fremstilles først. the present invention the order in which the blocks are produced is not of critical importance. The block containing the protruding ionic moieties or the block that does not contain these moieties can be produced first.
Katalysatorer som kan anvendes, innbefatter dem som er beskrevet i US patent nr. 4508880, spalte 11, linjene 42-68, såvel som dem som er beskrevet i den samtidig svevende US patentsøknad nr. 707190 (Dicker et al.), inngitt 1. mars 1985, hverved inkorporert ved henvisning. Catalysts that can be used include those described in US Patent No. 4,508,880, column 11, lines 42-68, as well as those described in co-pending US Patent Application No. 707,190 (Dicker et al.), filed 1 March 1985, hereby incorporated by reference.
Initiatorer som kan anvendes, innbefatter dem som er angitt i det ovennevnte Webster-patent i spalte 9, linje 25 -spalte 10, linje 13. Foretrukne initiatorer innbefatter 1-(2-trimethyl-siloxyethoxy)-l-trimethylsiloxy-2-methyl-propen> 1-(2-[1-ethoxyethoxy]-ethoxy-l-trimethylsiloxy-2-methylpropen og l-methoxy-l-trimethylsiloxy-2-methylpropen. Initiators which may be used include those set forth in the above Webster patent at column 9, line 25 -column 10, line 13. Preferred initiators include 1-(2-trimethyl-siloxyethoxy)-1-trimethylsiloxy-2-methyl- propene > 1-(2-[1-ethoxyethoxy]-ethoxy-1-trimethylsiloxy-2-methylpropene and 1-methoxy-1-trimethylsiloxy-2-methylpropene.
Dersom dispergeringsmidlet fremstilles ved først å If the dispersant is prepared by first
danne blokken uten de uthengende ioniske grupper, blir disse blokker derefter reagert, under anvendelse av de samme generelle metoder, for å danne blokkene som inneholder de uthengende ("pendant") ioniske grupper. De samme generelle reaktanter anvendes for disse andre blokker, bort- form the block without the pendant ionic groups, these blocks are then reacted, using the same general methods, to form the blocks containing the pendant ("pendant") ionic groups. The same general reactants are used for these other blocks, except
sett fra at monomerene og deres relative mengder velges slik at de har et gjennomsnitt på minst to kationiske enheter, eller deres utgangsmaterialer, i hver blokk. De kationiske enheter kan ha den nødvendige kvartære eller tertiære kon-figurasjon som polymerisert, eller de kan, mer typisk og fortrinnsvis, være primære, sekundære eller tertiære amin-, fosfin- eller thioetherforbindelser som omvandles til den kvartære eller tertiære tilstand efter dannelsen av den grunnleggende polymerstruktur. Selv om en rekke forskjellige monomerer kan anvendes for dette formål, har methacrylater vist seg å være spesielt tilfredsstillende, innbefattende for eksempel provided that the monomers and their relative amounts are chosen to have an average of at least two cationic units, or their starting materials, in each block. The cationic units may have the required quaternary or tertiary configuration as polymerized, or they may, more typically and preferably, be primary, secondary or tertiary amine, phosphine or thioether compounds which are converted to the quaternary or tertiary state upon formation of the basic polymer structure. Although a number of different monomers can be used for this purpose, methacrylates have been found to be particularly satisfactory, including for example
2-(dimethylamino)ethylmetacrylat, 2-(dimethylamino)ethyl methacrylate,
2-(diethylamino)ethylmethacrylat, glycidyl- 2-(diethylamino)ethyl methacrylate, glycidyl-
methacrylat og t-butylaminoethylmethacrylat. methacrylate and t-butylaminoethyl methacrylate.
Lignende monomerer kan-anvendes for å innføre .ioniske grupper basert på fosfor og svovel, hvilket vil være selvklart for gjennomsnittsfagmannen. Similar monomers can be used to introduce ionic groups based on phosphorus and sulphur, which will be obvious to the average person skilled in the art.
De uthengende ioniske deler har den generelle formel -A(R^) X, hvori A er valgt fra N, P og S, R, er uavhengig valgt fra alkyl eller alkylether med 1-2 0 carbonatomer, The leading ionic moieties have the general formula -A(R^) X, wherein A is selected from N, P and S, R is independently selected from alkyl or alkyl ether of 1-20 carbon atoms,
fenyl eller substituert fenyl, m er 3 når A er N eller P, og m er 2 når A er S, og X er valgt fra halogenider og konjugat-baser av organiske syrer. Fortrinnsvis er A nitrogen og X valgt fra gruppen bestående av carboxylater, sulfonater phenyl or substituted phenyl, m is 3 when A is N or P, and m is 2 when A is S, and X is selected from halides and conjugate bases of organic acids. Preferably, A is nitrogen and X is selected from the group consisting of carboxylates, sulfonates
og fosfater. and phosphates.
Efter dannelsen av den grunnleggende polymerstruktur After the formation of the basic polymer structure
kan det kationiske utgangsmateriale bringes i kontakt med vanlige alkyleringsmidler, som et alkylhalogenid, alkylsul- ' fonat, alkyltoluensulfonat, trialkylfosfat eller aralkyl-halogenid. Alkyleringsmidler som har vist. seg å være spesielt tilfredsstillende, innbefatter methyltoluensulfonat, dimethylsulfat og benzylklorid. the cationic starting material can be contacted with common alkylating agents, such as an alkyl halide, alkyl sulfonate, alkyl toluene sulfonate, trialkyl phosphate or aralkyl halide. Alkylating agents that have shown found to be particularly satisfactory include methyl toluene sulphonate, dimethyl sulphate and benzyl chloride.
De fysikalske karakteristika til blokkopolymerene i blant-, dingen ifølge oppfinnelsen, innbefattende molekylvekten for blokkene og nærværet av de ioniske deler på én av blokkene, kan bekreftes ved hjelp av vanlige analysemetoder, innbefattende differensiell scanningkalorimetri, kjernemagnetisk resonnans, gasskromatografi og infrarød analyse. For eksempel kan blokkenes kjemiske sammensetning bestemmes ved hjelp av proton-kjernemagnetisk resonnans- eller infrarød analyse eller ved pyrolyse og gasskromatografianalyse. Blokkstørrelsene i kopolymerene kan bestemmes ved hjelp av kjernemagnetisk resonnans, glasstemperatur (Tg), opp-løselighet eller mi.celledannelse som målt ved kvasi-elastisk lysspredning. The physical characteristics of the block copolymers in the mixture according to the invention, including the molecular weight of the blocks and the presence of the ionic parts on one of the blocks, can be confirmed using common analytical methods, including differential scanning calorimetry, nuclear magnetic resonance, gas chromatography and infrared analysis. For example, the chemical composition of the blocks can be determined by means of proton nuclear magnetic resonance or infrared analysis or by pyrolysis and gas chromatography analysis. The block sizes in the copolymers can be determined by nuclear magnetic resonance, glass transition temperature (Tg), solubility or microcell formation as measured by quasi-elastic light scattering.
De erholdte blokkopolymerer oppviser utmerket oppførsel som dispergeringsmiddel. De kan derfor anvendes effektivt som pigmentdispergeringsmidler i malingoppskrifter og som oljetilsetninger. Pigmentdispersjoner omfatter typisk pigment, oppløsningsmiddel og dispergeringsmiddel og kan fremstilles for eksempel som beskrevet i US patent 3912677 (Baker et al.), herved inkorporert ved henvisning. Selv om lignende forbindelser er blitt anvendt slik tidligere, er de beskrevne kopolymerer effektive uten anvendelse av motioner, som ionisert kolofoniumsyre eller sulfonert aromatisk hydrocarbon som tidligere har vist seg å være nødvendige for tilfredsstillende dispergeringsmiddelopp-førsel. Dessuten gir den jevne blokkarakter i de beskrevne forbindelser forbedret og mer pålitelig dispergerings-middeloppførsel. The obtained block copolymers exhibit excellent behavior as a dispersant. They can therefore be used effectively as pigment dispersants in paint recipes and as oil additives. Pigment dispersions typically comprise pigment, solvent and dispersant and can be prepared, for example, as described in US patent 3912677 (Baker et al.), hereby incorporated by reference. Although similar compounds have been used as such in the past, the described copolymers are effective without the use of counterions, such as ionized rosin acid or sulfonated aromatic hydrocarbon, which have previously been shown to be necessary for satisfactory dispersant behavior. Moreover, the uniform block character in the described compounds provides improved and more reliable dispersant behavior.
I de nedenstående eksempler blir dispergeringsmiddel-kvaliteten målt ved sandmaling av en blanding av pigment, oppløsningsmiddel og dispergeringsmiddel og ved å bestemme hvilken andel av dispergeringsmiddel (om noen) som vil gi en jevn dispersjon, med et utseende lik flekket glass ved en optisk forstørrelse på 250 x. Til sammenligning har flokkulert pigment øer av farve avbrutt av områder av forholdsvis klart oppløsningsmiddel. Dispergeringsgraden bedømmes i henhold til en valgfri skala fra 1 til 4, som følger: 1 - deflokkulert dispersjon i hvilken pigmentpartikler er jevnt separert og i hvilken brownsk bevegelse av par-tiklene er tydelig. 2 - svakt flokkulert dispersjon i hvilken pigmentpartikler er separert, men immobile (intet tydelig tegn på In the following examples, the dispersant quality is measured by sandblasting a mixture of pigment, solvent and dispersant and by determining what proportion of dispersant (if any) will give a uniform dispersion, with an appearance similar to stained glass at an optical magnification of 250x. In comparison, flocculated pigment has islands of color interrupted by areas of relatively clear solvent. The degree of dispersion is judged according to an optional scale from 1 to 4, as follows: 1 - deflocculated dispersion in which pigment particles are evenly separated and in which Brownian motion of the particles is evident. 2 - weakly flocculated dispersion in which pigment particles are separated but immobile (no clear sign of
brownsk bevegelse). Brownian motion).
3 - flokkulerte dispersjoner i hvilke pigmentpartikler er løst aggregert med enkelte hulrom mellom aggregater. 4 - kraftig flokkulerte dispersjoner i hvilke pigmentpartikler er sterkt aggrregert med store hulrom mellom aggregater. 3 - flocculated dispersions in which pigment particles are loosely aggregated with individual voids between aggregates. 4 - strongly flocculated dispersions in which pigment particles are highly aggregated with large voids between aggregates.
Dispergeringsmidlene fremstilt i eksemplene ble bedømt sammen med en rekke forskjellige standardpigmenter og i oppløsningsmidler. De anvendte oppløsningsmidler var methylisobutylketon (MIBK eller M), toluen (T), xylener (X) og aceton (A). De følgende standardpigmenter ble anvendt for bedømmelsen: W505 - fthalocyaninblått, rødtonet (monastralblått) The dispersants prepared in the examples were evaluated with a variety of standard pigments and in solvents. The solvents used were methyl isobutyl ketone (MIBK or M), toluene (T), xylenes (X) and acetone (A). The following standard pigments were used for the assessment: W505 - phthalocyanine blue, red tinted (monastral blue)
W552 - fthalocyaninblått, flokkuleringsresistent grønn farvetone, toner W552 - phthalocyanine blue, flocculation resistant green tint, toner
W57 3 - tetraklor-CPC-blåttyfthalocyaninblå, toner, W57 3 - tetrachlor-CPC-blue thifthalocyanine blue, toner,
grønn farvenyanse, forbedret rheologi green color shade, improved rheology
W673 - tetraklorisoindolinon - irgazingult W673 - tetrachloroisoindolinone - irgazing yellow
W805 - monastralmagenta - magentaton er av kinakridontype W805 - monastral magenta - magenta tone is of the quinacridone type
W811 - monastralrødt - rød toner av kinakridontype W811 - monastral red - quinacridone-type red toner
W853 - organisk rød toner - kinakridontype gjennomsiktig monastralrødt BRT-233 W853 - organic red toner - quinacridone type transparent monastral red BRT-233
I alle eksempler i henhold til oppfinnelsen hadde blokkene av kopolymerene inneholdende de uthengende ioniske grupper en molekylvekt på fra 20 0 til 10000, og blokkkene uten de uthengende ioniske grupper hadde en molekylvekt på fra 500 til 100000. De spesifikke molekylvekter kan bestemmes av gjennomsnittsfagmannen ut fra de data som er fremsatt i de spesielle eksempler. I alle eksempler i henhold til oppfinnelsen var et gjennomsnitt på minst 2 uthengende ioniske grupper tilstede i hver blokk (a) av den fremstilte kopolymer. In all examples according to the invention, the blocks of the copolymers containing the protruding ionic groups had a molecular weight of from 200 to 10,000, and the blocks without the protruding ionic groups had a molecular weight of from 500 to 100,000. The specific molecular weights can be determined by the average person skilled in the art from the data presented in the particular examples. In all examples according to the invention, an average of at least 2 outgoing ionic groups were present in each block (a) of the copolymer produced.
Eksempel 1 Example 1
En :r.eaksjonsbeholder ble fylt med 316 g tetrahydrofuran (THF), 0,5 ml xylener, 4,1 g 1 methoxy-l-trimethylsiloxy-2-methylpropen (11 initiator") og 0,100 ml 1 M tetrabutyl-ammonium-3-klorbenzoat i acetonitril ("katalysator"). For fremstilling av en blokk A som var fri for uthengende ioniske grupper, ble to charger påbegynt samtidig, dvs. at 91,2 g methylmethacrylat (MMA) ble tilsatt i løpet av 20 minutter og at 0,350 ml katalysator i 3 ml THF ble til- A reaction vessel was charged with 316 g of tetrahydrofuran (THF), 0.5 ml of xylenes, 4.1 g of 1 methoxy-1-trimethylsiloxy-2-methylpropene (11 initiator") and 0.100 ml of 1 M tetrabutyl-ammonium-3 -chlorobenzoate in acetonitrile ("catalyst"). To prepare a block A that was free of protruding ionic groups, two charges were started simultaneously, i.e., 91.2 g of methyl methacrylate (MMA) was added over 20 minutes and that 0.350 ml of catalyst in 3 ml of THF was added
satt i løpet av 2 timer. 2 0 minutter efter tilsetningen av MMA ble 98,9 g 2-N, N-dimethylaminoethylmethacrylat (DMEAMA) tilsatt i løpet av 10 minutter for fremstilling av en blokk inneholdende vedhengende ioniske grupper. 20 minutter efter tilsetningen av DMAEMA ble 9,9 g MMA tilsatt i løpet av 20 minutter. Én time efter den annen tilsetning av MMA set within 2 hours. 20 minutes after the addition of MMA, 98.9 g of 2-N,N-dimethylaminoethyl methacrylate (DMEAMA) was added over 10 minutes to produce a block containing pendant ionic groups. 20 minutes after the addition of DMAEMA, 9.9 g of MMA were added over the course of 20 minutes. One hour after the second addition of MMA
ble 5 ml methanol tilsatt. Harpiksen (251 g) ble tilsatt tilheptan J700 ml), det erholdte faststoff ble skilt fra væsken, og faststoffet ble vasket med 700 ml heptan og tørket. 5 ml of methanol was added. The resin (251 g) was added to heptane (700 ml), the resulting solid was separated from the liquid, and the solid was washed with 700 ml of heptane and dried.
For å kvaternere amingruppene i den erholdte blokk-kopolymer ble en porsjon (30,69 g) av kopolymeren oppløst i THF (50,5 g), og benzylklorid (3,0 g) ble tilsatt. Den erholdte oppløsning ble destillert under tilbakeløp i ca. 3 timer før 50,5 g isopropanol ble tilsatt. Destil-lasjonen under tilbakeløp ble fortsatt i 5 ytterligere timer. Den erholdte harpiks hadde et faststoffinnhold på 22% og To quaternize the amine groups in the resulting block copolymer, a portion (30.69 g) of the copolymer was dissolved in THF (50.5 g), and benzyl chloride (3.0 g) was added. The resulting solution was distilled under reflux for approx. 3 hours before 50.5 g of isopropanol was added. The distillation under reflux was continued for 5 additional hours. The resin obtained had a solids content of 22% and
et innhold av tertiært amin på 0,31 m M/g, og dette antydet en i det vesentlige fullstendig kvaternisering av amingruppene . a tertiary amine content of 0.31 m M/g, and this suggested essentially complete quaternization of the amine groups.
Kopolymeren ble bedømt som pigmentdispergeringsmiddel og ga en dispersjonsbedømmelse på 1 i MIBK (Ml) for standardpigmenter W505, W573, W673, W805 og W811. Kopolymeren ble også sammen med standardpigment W853 i MIBK» aceton og toluen bedømt til kvalitetsbetegnelsene henholdsvis M3, Al og T3. The copolymer was evaluated as a pigment dispersant and gave a dispersion rating of 1 in MIBK (Ml) for standard pigments W505, W573, W673, W805 and W811. The copolymer was also assessed together with standard pigment W853 in MIBK» acetone and toluene to the quality designations M3, Al and T3 respectively.
Eksempler 2- 4 og Sammenligningseksempel A Examples 2-4 and Comparative example A
I sammenligningseksempel A ble en ABA blokkopolymer fremstilt med tertiære uthengende ioniske grupper festet til B-segmentet. Blokkopolymerens generelle sammensetning var MMA/BMA/DMAEMA/MMA/BMA med forventede polymerisasjons-grader på 20/20//8//20/20. I Eksemplene 2-4 ble denne blokkopolymer kvaternisert med tre forskjellige kvaterniser-ingsmidler under dannelse av et materiale for en blanding i henhold til den foreliggende oppfinnelse. In Comparative Example A, an ABA block copolymer was prepared with tertiary protruding ionic groups attached to the B segment. The general composition of the block copolymer was MMA/BMA/DMAEMA/MMA/BMA with expected degrees of polymerization of 20/20//8//20/20. In Examples 2-4, this block copolymer was quaternized with three different quaternizing agents to form a material for a mixture according to the present invention.
I Sammenligningseksempel A ble en reaksjonsbeholder fylt med 1361 g THF, 21,5 g initiator og 1,2 ml katalysator. En påmatning av 581,5 g 41,3 vekt% MMA i butylmethacrylat ble tilsatt i løpet av 20 minutter, mens et isbad ble anvendt for å holde reaksjonstemperaturen mellom 20 og 35°C. Samtidig ble en påmatning i løpet av 150 minutter av 2,4 ml katalysator i 2,6 ml THF påbegynt. 45 minutter efter slutten av den første monomerpåmatning ble en påmatning i løpet av 20 minutter av 173,3 g 2-N,N-dimethylaminoethylmethacrylat In Comparative Example A, a reaction vessel was filled with 1361 g of THF, 21.5 g of initiator and 1.2 ml of catalyst. A charge of 581.5 g of 41.3 wt% MMA in butyl methacrylate was added over 20 minutes, while an ice bath was used to maintain the reaction temperature between 20 and 35°C. At the same time, a feeding of 2.4 ml of catalyst in 2.6 ml of THF was started during 150 minutes. 45 minutes after the end of the first monomer feed, a feed of 173.3 g of 2-N,N-dimethylaminoethyl methacrylate was added during 20 minutes
foretatt. 40 minutter efter slutten av den annen monomerpåmatning ble en påmatning av 505,1 g 41,3 vekt% MMA i BMA foretatt i løpet av 20 minutter. Isavkjøling ble igjen anvendt. Efter ca. 16 timer ble 40 ml methanol tilsatt. undertaken. 40 minutes after the end of the second monomer feed, a feed of 505.1 g 41.3% by weight MMA in BMA was carried out during 20 minutes. Ice cooling was again used. After approx. After 16 hours, 40 ml of methanol was added.
Den erholdte blokkopolymer med tertiære uthengende ioniske grupper ble bedømt som et pigmentdispergeringsmiddel, og resultatene er oppsummert i Tabell I. The obtained block copolymer with tertiary protruding ionic groups was evaluated as a pigment dispersant, and the results are summarized in Table I.
I Eksempel 2 ble en reaksjonsblanding av 513,2 g av blokkopolymeren ifølge Sammenligningseksempel A, 126,6 g ethanol og 25,0 g jodmethan kokt under tilbakeløp i 3 timer. Den erholdte blokkopolymer, med kvaterniserte uthengende ioniske grupper, ble bedømt som pigmentdispergeringsmiddel, og resultatene er oppsummert i Tabell I. In Example 2, a reaction mixture of 513.2 g of the block copolymer according to Comparative Example A, 126.6 g of ethanol and 25.0 g of iodomethane was refluxed for 3 hours. The resulting block copolymer, with quaternized protruding ionic groups, was evaluated as a pigment dispersant, and the results are summarized in Table I.
I Eksempel 3 ble en reaksjonsblanding av 500,2 g av blokkopolymeren ifølge Sammenligningseksempel A, 125 g ethanol og 30,3 g benzylbromid kokt under tilbakeløp i 16 timer. Den erholdte blokkopolymer, med kvaterniserte uthengende ioniske grupper, ble bedømt som tidligere, og resultatene er oppsummert i Tabell 1. In Example 3, a reaction mixture of 500.2 g of the block copolymer according to Comparative Example A, 125 g of ethanol and 30.3 g of benzyl bromide was refluxed for 16 hours. The obtained block copolymer, with quaternized protruding ionic groups, was evaluated as before, and the results are summarized in Table 1.
I Eksempel 4 ble en reaksjonsblanding av 200,2 g av blokkopolymeren ifølge Sammenligningsegsempel A, 50,0 g isopropanol og 11,5 g methyl-p-toluensulfonat kokt under tilbakeløp i 16 timer. Den erholdte blokkopolymer, In Example 4, a reaction mixture of 200.2 g of the block copolymer according to Comparative Example A, 50.0 g of isopropanol and 11.5 g of methyl p-toluenesulfonate was refluxed for 16 hours. The obtained block copolymer,
med kvaterniserte uthengende ioniske grupper, ble bedømt som tidligere, og resultatene er oppsummert i Tabell 1. with quaternized protruding ionic groups, was assessed as before, and the results are summarized in Table 1.
Eksempel 5 Example 5
En AB-blokkopolymer ble fremstilt med den generelle sammensetning EHMA//DEAEMA 42//12. En reaksjonsbeholder ble fylt med 205 g toluen, 1,94 g initiator og 0,111 ml katalysator. Samtidig ble en 1 times påmatning av 0,222 ml katalysator i 5_irl toluen og en 2 0 minutters påmatning av 92,3 g 2-ethylhexylmethacrylat påbegynt. Efter 40 minutter ble 0,111 ml katalysator tilsatt. Efter ytterligere 3 timer ble 0,111 ml katalysator tilsatt, og en ti minutters påmatning av 20,92 g 2-N,N-dimethylaminoethylmethacrylat ble foretatt. Efter ytterligere 16 timer ble 5 ml methanol tilsatt. En porsjon (150 g) av den erholdte harpiks ble fortynnet med 37,61 g ethanol, 9,16 g benzylbromid ble tilsatt og den erholdte blanding ble kokt med tilbakeløp i 18 timer. An AB block copolymer was prepared with the general composition EHMA//DEAEMA 42//12. A reaction vessel was filled with 205 g of toluene, 1.94 g of initiator and 0.111 ml of catalyst. At the same time, a 1-hour feeding of 0.222 ml of catalyst in 5-irl toluene and a 20-minute feeding of 92.3 g of 2-ethylhexyl methacrylate were started. After 40 minutes, 0.111 ml of catalyst was added. After a further 3 hours, 0.111 ml of catalyst was added, and a ten minute feed of 20.92 g of 2-N,N-dimethylaminoethyl methacrylate was carried out. After a further 16 hours, 5 ml of methanol was added. A portion (150 g) of the resulting resin was diluted with 37.61 g of ethanol, 9.16 g of benzyl bromide was added and the resulting mixture was refluxed for 18 hours.
Kopolymeren ble vurdert som dispergeringsmiddel for standardpigmenter og viste seg å gi en The copolymer was evaluated as a dispersant for standard pigments and was found to give a
bedømmelse på X4 for pigment W505 og bedømmelser på XI for pigmenter W573, W805, W811 og W853. rating of X4 for pigment W505 and ratings of XI for pigments W573, W805, W811 and W853.
Eksempel 6- 7 og Sammenligningseksempler B- H Example 6-7 and Comparative examples B-H
I Eksemplene 6-7 og Sammenligningseksemplene B-H ble sammenligninger foretatt mellom blokk- og vilkårlige kopolymerer med lignende sammensetning og med varierende grad av kvaternisering av de uthengende ioniske deler på hver. In Examples 6-7 and Comparative Examples B-H, comparisons were made between block and random copolymers of similar composition and with varying degrees of quaternization of the exposed ionic moieties on each.
Ved fremstillingen av den vilkårlige kopolymer ble en reaksjonsbeholder fylt med 127,2 g toluen, 2,26 g initiator, 7 4,5 g BMA, 52,6 g MMA, 2 9,7 g 2-N,N-diethylaminoethylmethacrylat og 0,03 0 ml katalysator. Avkjøling ble anvendt for å holde reaksjonstemperaturen under 40°C. Efter 4 timers reaksjon ble 5 ml methanol tilsatt. In the preparation of the arbitrary copolymer, a reaction vessel was filled with 127.2 g of toluene, 2.26 g of initiator, 7 4.5 g of BMA, 52.6 g of MMA, 2 9.7 g of 2-N,N-diethylaminoethyl methacrylate and 0 .03 0 ml of catalyst. Cooling was used to keep the reaction temperature below 40°C. After 4 hours of reaction, 5 ml of methanol was added.
Ved fremstillingen av den blokkede kopolymer ble en reaksjonsbeholder fylt med 130,3 g toluen, 0,5 ml xylener, 2,27 g initiator, 76,4 g BMA og 54,0 g MMA og 0,030 ml katalysator. Avkjøling ble anvendt for å holde reaksjonstemperaturen under 40°C. Efter 70 minutters reaksjon ble samtidige påmatninger av 29,4 g DEAEMA i løpet av 10 minutter og 0,2 0 ml katalysator i 5 ml toluen i løpet av 20 minutter påbegynt. Efter en ytterligere reaksjonstime ble 5 ml methanol tilsatt. In the preparation of the blocked copolymer, a reaction vessel was filled with 130.3 g of toluene, 0.5 ml of xylenes, 2.27 g of initiator, 76.4 g of BMA and 54.0 g of MMA and 0.030 ml of catalyst. Cooling was used to keep the reaction temperature below 40°C. After 70 minutes of reaction, simultaneous feeds of 29.4 g of DEAEMA over 10 minutes and 0.20 ml of catalyst in 5 ml of toluene over 20 minutes were started. After a further reaction hour, 5 ml of methanol was added.
De erholdte kopolymerer som har tertiære uthengende ioniske grupper og som er representative for sammenligningseksemplene B og C ble bedømt som dispergeringsmidler for standardpigment W552, og begge oppviste kvalitetstall på The obtained copolymers having tertiary leaving ionic groups and which are representative of comparative examples B and C were evaluated as dispersants for standard pigment W552, and both showed quality numbers of
A3, M4 og T4. A3, M4 and T4.
I Sammenligningseksemplene D-H og i Eksemplene 6 og 7 ble blokkopolymerene i henhold til Sammenligningseksemplene B og C begge fortynnet ved kombinasjon av 65 g harpiks og 19,5 g isopropanol. En 20 g porsjon av den erholdte harpiks ble kvaternisert under anvendelse av methyl-p-toluensulfonat idet 25 mol%, 50 mol%, 75 mol% eller 95 mol% methyl-p-toluensulfonat, basert på amininnholdet, ble anvendt. De erholdte oppløsninger ble holdt ved romtemperatur i 10 døgn. De erholdte kvaterniserte kopolymerer ble bedømt som pigmentdispergeringsmidler, og resultatene er oppsummert nedenfor. In Comparative Examples D-H and in Examples 6 and 7, the block copolymers according to Comparative Examples B and C were both diluted by combining 65 g of resin and 19.5 g of isopropanol. A 20 g portion of the resin obtained was quaternized using methyl p-toluenesulfonate, using 25 mol%, 50 mol%, 75 mol% or 95 mol% methyl p-toluenesulfonate, based on the amine content. The solutions obtained were kept at room temperature for 10 days. The quaternized copolymers obtained were evaluated as pigment dispersants, and the results are summarized below.
Claims (12)
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NO880738A NO169132C (en) | 1988-02-19 | 1988-02-19 | MIXTURE INCLUDING PIGMENT, ORGANIC FLUID AND A BLOCK POLYMER |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO880738A NO169132C (en) | 1988-02-19 | 1988-02-19 | MIXTURE INCLUDING PIGMENT, ORGANIC FLUID AND A BLOCK POLYMER |
Publications (4)
Publication Number | Publication Date |
---|---|
NO880738D0 NO880738D0 (en) | 1988-02-19 |
NO880738L NO880738L (en) | 1989-08-21 |
NO169132B true NO169132B (en) | 1992-02-03 |
NO169132C NO169132C (en) | 1992-05-13 |
Family
ID=19890679
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO880738A NO169132C (en) | 1988-02-19 | 1988-02-19 | MIXTURE INCLUDING PIGMENT, ORGANIC FLUID AND A BLOCK POLYMER |
Country Status (1)
Country | Link |
---|---|
NO (1) | NO169132C (en) |
-
1988
- 1988-02-19 NO NO880738A patent/NO169132C/en unknown
Also Published As
Publication number | Publication date |
---|---|
NO169132C (en) | 1992-05-13 |
NO880738L (en) | 1989-08-21 |
NO880738D0 (en) | 1988-02-19 |
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