NO171682B - REACTION BLENDS CONTAINING COPOLYMERS OF HYDROPHOBE ACRYLIC RESP. METACRYLIC ACID ESTERS AND HYDROPHILIC COMMONOMERS, PREPARING AND USING THEREOF - Google Patents
REACTION BLENDS CONTAINING COPOLYMERS OF HYDROPHOBE ACRYLIC RESP. METACRYLIC ACID ESTERS AND HYDROPHILIC COMMONOMERS, PREPARING AND USING THEREOF Download PDFInfo
- Publication number
- NO171682B NO171682B NO874319A NO874319A NO171682B NO 171682 B NO171682 B NO 171682B NO 874319 A NO874319 A NO 874319A NO 874319 A NO874319 A NO 874319A NO 171682 B NO171682 B NO 171682B
- Authority
- NO
- Norway
- Prior art keywords
- acid
- esterification
- alkylphenol
- residues
- residue
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims description 33
- 239000011541 reaction mixture Substances 0.000 title claims description 13
- 150000002735 metacrylic acids Chemical class 0.000 title 1
- 238000005886 esterification reaction Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 230000032050 esterification Effects 0.000 claims description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000007334 copolymerization reaction Methods 0.000 claims description 15
- 239000010779 crude oil Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 10
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 7
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical group CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000006266 etherification reaction Methods 0.000 claims description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229920001521 polyalkylene glycol ether Polymers 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 40
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 30
- 239000008096 xylene Substances 0.000 description 30
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 18
- 150000001298 alcohols Chemical class 0.000 description 16
- 150000004703 alkoxides Chemical class 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 methallyl alcohols Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000005956 quaternization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 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
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- XOUAQPDUNFWPEM-UHFFFAOYSA-N 2,3,4-tris(hydroxymethyl)phenol Chemical compound OCC1=CC=C(O)C(CO)=C1CO XOUAQPDUNFWPEM-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000036982 action potential Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KQJLZBJOEUYHIM-UHFFFAOYSA-N diethylaminomethyl prop-2-enoate Chemical compound CCN(CC)COC(=O)C=C KQJLZBJOEUYHIM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000012374 esterification agent Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C08F8/10—Acylation
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- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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Description
Oppfinnelsen vedrører reaksjonsblandinger som inneholder kopolymerer som er basert på hydrofobe akrylsyre- resp. metakrylsyre-estere, en fremgangsmåte for fremstilling av disse reaksjonsblandinger og anvendelse av disse som jordoljeemulsjonsspaltere for hurtig-awanning av råoljer. The invention relates to reaction mixtures containing copolymers which are based on hydrophobic acrylic acid or methacrylic acid esters, a method for the preparation of these reaction mixtures and their use as crude oil emulsion splitters for rapid dewatering of crude oils.
Etter en begynnelsesfase hvor det utvinnes praktisk talt ren råolje, fremkommer den største del av den produserte råolje som vann-i-olje-emulsjoner. After an initial phase where practically pure crude oil is extracted, the largest part of the produced crude oil appears as water-in-oil emulsions.
Vannet må fraskilles før transporten, eller konsentrasjonen av det må senkes til under et godtagbart nivå. Dette gjøres for det meste ved tilsetning av såkalte jordoljeemulsjonsspaltere, hvorved en oppvarming av råoljen letter og fremskynder opp-spaltingen. Sammensetningen av råoljen varierer sterkt med utvinningsstedet. For å oppnå optimale de-emulgeringsresultater anvendes det derfor rundt om i verden mange forskjellige jordoljeemulsjonsspaltere. Det er imidlertid en stor interesse for de-emulgatorer som ved forskjellige råoljeemulsjoner gir raskere oppspalting i vann i olje og også gode restvann- og restsalt-mengder. The water must be separated before transport, or its concentration must be lowered below an acceptable level. This is mostly done by adding so-called crude oil emulsion splitters, whereby heating the crude oil facilitates and accelerates the split-up. The composition of the crude oil varies greatly with the place of extraction. To achieve optimal de-emulsification results, many different crude oil emulsion splitters are therefore used around the world. There is, however, a great interest in de-emulsifiers which, in the case of various crude oil emulsions, provide faster splitting in water in oil and also good amounts of residual water and residual salt.
De hyppigst anvendte de-emulgatorer er etylenoksyd/propylenoksyd-blokkpolymerer, alkoksylerte alkylfenol-formaldehyd-harpikser, alkoksylerte polyaminer og spesielt tverrbindings-produkter av de ovenfor angitte grunnklasser med flerfunksjonene reagenser såsom diisocyanater, dikarboksylsyrer, bisglycidyletere, di- og trimetylolfenol. The most frequently used de-emulsifiers are ethylene oxide/propylene oxide block polymers, alkoxylated alkylphenol-formaldehyde resins, alkylated polyamines and especially cross-linking products of the above-mentioned basic classes with multifunctional reagents such as diisocyanates, dicarboxylic acids, bisglycidyl ethers, di- and trimethylolphenol.
Polymere jordoljeemulsjonsspaltere er også kjent (kanadisk patentskrift nr. 1.010.740 og DE-C1 33 38 923). Polymeric petroleum emulsion separators are also known (Canadian Patent No. 1,010,740 and DE-C1 33 38 923).
I henhold til dette kanadiske patentskrift blir det innført umettede radikalisk polymeriserbare funksjoner i alkoksylerte alkoholer og alkoksylerte alkylfenol-formaldehyd-harpikser ved foretring med umettede glycidylforbindelser (f.eks. glycidyl-akrylat), ved forestring med maleinsyreanhydrid eller fumarsyre eller ved omforestring med akrylestere eller metakrylestere, hvilke så blir polymeriserrt ved en påfølgende omsetning med andre monomerer i løsning. I DE-C1 33 38 923 er beskrevet produkter som oppnås ved kopolymerisering av polyoksyalkylen-etere av allyl- eller metallyl-alkoholer med vinylestere eller According to this Canadian patent, unsaturated radical polymerizable functions are introduced into alkylated alcohols and alkylphenol-formaldehyde resins by etherification with unsaturated glycidyl compounds (e.g. glycidyl acrylate), by esterification with maleic anhydride or fumaric acid or by transesterification with acrylic esters or methacrylic esters, which are then polymerized by a subsequent reaction with other monomers in solution. DE-C1 33 38 923 describes products obtained by copolymerization of polyoxyalkylene ethers of allyl or methallyl alcohols with vinyl esters or
akryl- eller metakrylsyreestere. acrylic or methacrylic acid esters.
Alle disse produkter fremviser virkningsspesifikke eller fremstillingsbetingende svakheter. Ved anvendelse av glycidylforbindelser for innføring av den umettede funksjon kommer det således ved polymeriseringen ofte til dannelse av gel-legemer og uhomogeniteter, ved anvendelse av allylalkohol, metallylalkohol og maleinsyre fås dårlige kopolymeriserings-betingelser og ved omforestringen med akrylsyreestere eller metakrylsyreestere fås det en vanskelig utvikling av den fullstendige og selektive forestring av den delvis flerfunksjonene alkoksylerte utgangsalkohol. All of these products exhibit performance-specific or manufacturing-related weaknesses. When using glycidyl compounds to introduce the unsaturated function, the polymerization often results in the formation of gel bodies and inhomogeneities, when using allyl alcohol, metallyl alcohol and maleic acid, poor copolymerization conditions are obtained and when the transesterification with acrylic acid esters or methacrylic acid esters results in a difficult development of the complete and selective esterification of the partially polyfunctional starting alcohol alcohol.
Videre vil det ved lagring av kopolymerene ofte opptre gelerings- og størkningsreaksjoner, spesielt ved anvendelse av flerfunksjonene utgangsalkoholeir ved alkyleringen. Produkter med høyt virkningspotensial og bredt anvendelsesspektrum kan imidlerid oppnås allerede ved anvendelse av alkoksylerte flerfunksjonene alkoholer. Furthermore, when the copolymers are stored, gelation and solidification reactions will often occur, especially when using the multifunctional starting alcohol during the alkylation. Products with high action potential and a broad spectrum of applications can, however, already be obtained by using alkylated polyfunctional alcohols.
Det er nå overraskende funnet at kopolymerer egnet som jordoljeemulsjonsspaltere dannet av hydrofobe akrylsyre- eller metakrylsyreestere, hvis alkoholkomponenter stammer fra en blanding av polyglykoler og polyglykoletere, med hydrofile etylenisk umettede komonomerer, blir lagringsstabile og får forhøyet effekt når i denne kopolymer (i) alle eller nesten alle frie OH-grupper er foretret, forestret eller overført i en uretangruppering, og/eller (ii) den ved forestringen som katalysator anvendte syre er nøytralisert ved amin-tilsetning. Det henvises forøvrig til krav 1. It has now surprisingly been found that copolymers suitable as petroleum emulsion breakers formed from hydrophobic acrylic acid or methacrylic acid esters, whose alcohol components derive from a mixture of polyglycols and polyglycol ethers, with hydrophilic ethylenically unsaturated comonomers, become storage stable and have an increased effect when in this copolymer (i) all or almost all free OH groups are etherified, esterified or transferred in a urethane grouping, and/or (ii) the acid used as a catalyst in the esterification is neutralized by amine addition. Incidentally, reference is made to requirement 1.
Fremgangsmåten for fremstilling av reaksjonsblandingene i henhold til oppfinnelsen og anvendelsen av de nevnte reaksjonsblandinger er beskrevet henholdsvis i krav 6 og 8. The method for producing the reaction mixtures according to the invention and the use of the aforementioned reaction mixtures are described respectively in claims 6 and 8.
Blandingen av polyalkylenglykoler og polyalkylenglykoletere som anvendes til forestring består som regel av alkoksylater med The mixture of polyalkylene glycols and polyalkylene glycol ethers used for esterification usually consists of alkoxylates with
formelen the formula
hvor R<1> betyr en rest av en én- eller flerverdig alkohol eller alkylfenol eller en rest av et alkylfenol/formaldehyd- eller alkylfenol/acetaldehyd-kondensasjonsprodukt, AO er en etylen- where R<1> means a residue of a monohydric or polyhydric alcohol or alkylphenol or a residue of an alkylphenol/formaldehyde or alkylphenol/acetaldehyde condensation product, AO is an ethylene-
oksyd-, propylenoksyd- eller 1,2-butylenoksydrest eller blandinger av disse rester eller blokker av disse rester, og x betyr et tall fra 5 til 120. oxide, propylene oxide or 1,2-butylene oxide residue or mixtures of these residues or blocks of these residues, and x means a number from 5 to 120.
Gjenstand for oppfinnelsen er således spesielt reaksjonsblandinger av kopolymerer hvor The object of the invention is thus in particular reaction mixtures of copolymers where
A) akrylsyreester eller metakrylsyreester med alkoksylater med A) acrylic acid ester or methacrylic acid ester with alkoxylates with
formelen the formula
hvor R<1>, AO og x har de ovenfor angitte betydninger, er where R<1>, AO and x have the meanings given above, is
kopolymerisert med copolymerized with
B) hydrofile kopolymerer med formelen B) hydrophilic copolymers of the formula
hvor where
R<2> betyr hydrogen eller en rest -COOH, -COOC2H4OH, -COOC2 H4 N (C2 Hs ) 2 , -CONH2 , -CN, , -OCOCH3 , -CH2 OH, -NHCHO, -COOCH3 , -COOC2 H5 , eller R<2> means hydrogen or a residue -COOH, -COOC2H4OH, -COOC2 H4 N (C2 Hs ) 2 , -CONH2 , -CN, , -OCOCH3 , -CH2 OH, -NHCHO, -COOCH3 , -COOC2 H5 , or
R<3> betyr hydrogen eller -COOH, og R<3> means hydrogen or -COOH, and
RA betyr hydrogen eller -CH3, RA means hydrogen or -CH3,
under den forutsetning at minst én av gruppene R<2> eller R<3 >er en hydrofil gruppe, under the condition that at least one of the groups R<2> or R<3> is a hydrophilic group,
hvorved vektforholdet mellom A) og B) er på 3 00:1 til 1:50 whereby the weight ratio between A) and B) is 3 00:1 to 1:50
og hvorved and whereby
C) de frie OH-grupper er overført ved foretring, forestring eller uretandannelse til en ikke lenger reaktiv form, C) the free OH groups have been transferred by etherification, esterification or urethane formation to a no longer reactive form,
og/eller and or
at den ved fremstillingen av esteren ved A) og/eller forestringen ved C) som katalysator anvendte syre er nøytralisert med et tertiært amin. that the acid used as a catalyst in the preparation of the ester at A) and/or the esterification at C) is neutralized with a tertiary amine.
Omsetningen av de frie OH-grupper kan også foregå før polymeriseringen og endog delvis før fremstillingen av ester-komonomeren. The conversion of the free OH groups can also take place before the polymerization and even partially before the preparation of the ester comonomer.
Kopolymerene blir fremstilt på i og for seg kjent måte, f.eks. ved radikalisk kopolymerisering i løsning, emulsjon eller suspensj on. The copolymers are produced in a manner known per se, e.g. by radical copolymerization in solution, emulsion or suspension.
Forestringen av akrylsyren eller metakrylsyren foregår fortrinnsvis i nærvær av sure forestringskatalysatorer og under anvendelse av trekkmidler. The esterification of the acrylic acid or methacrylic acid preferably takes place in the presence of acidic esterification catalysts and using drawing agents.
Som sure forestringskatalysatorer kan det anvendes vanlige uorganiske eller organiske katalysatorer såsom svovelsyre, p-toluensulfonsyre, dodecylbenzensulfonsyre, saltsyre eller sure ionebyttere. Common inorganic or organic catalysts such as sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrochloric acid or acidic ion exchangers can be used as acid esterification catalysts.
Som trekkmiddel kan nevnes organiske løsningsmidler som vanligvis danner en azeotrop med vann, spesielt xylen eller toluen. Organic solvents which usually form an azeotrope with water, especially xylene or toluene, can be mentioned as drawing agents.
Til foretring av de frie OH-grupper kan det anvendes midler såsom eksempelvis metyljodid, dimetylsulfat eller benzylklorid. Agents such as, for example, methyl iodide, dimethyl sulfate or benzyl chloride can be used for etherification of the free OH groups.
Til forestring av de frie OH-grupper blir det fortrinnsvis anvendt karboksylsyreanhydrider såsom acetanhydrid, maleinsyreanhydrid eller ravsyreanhydrid. Carboxylic anhydrides such as acetic anhydride, maleic anhydride or succinic anhydride are preferably used for esterification of the free OH groups.
Overføringen av de frie OH-grupper til en uretangruppering, d.v.s. den foretrukne reaksjon etter kopolymeriseringen, foregår hensiktsmessig ved innvirkning av isocyanater på i og for seg kjent måte f.eks. med fenylisocyanat eller stearylisocyanat. The transfer of the free OH groups to a urethane grouping, i.e. the preferred reaction after the copolymerization conveniently takes place by the action of isocyanates in a manner known per se, e.g. with phenyl isocyanate or stearyl isocyanate.
Til nøytralisering av de som forestringskatalysator anvendte syrer anvender man aminer, fortrinnsvis tertiære aminer. I de enkelte tilfeller anvender man eksempelvis trietylamin, tributylamin, dimetyl-Cy-amin (y = C8-C18) eller trietanolamin. To neutralize the acids used as esterification catalyst, amines are used, preferably tertiary amines. In the individual cases, for example, triethylamine, tributylamine, dimethyl-Cy-amine (y = C8-C18) or triethanolamine are used.
Mer detaljert foregår eksempelvis fremstillingen av de nye polymerer som følger: In more detail, for example, the production of the new polymers takes place as follows:
Fremstilling av alkoksylater med formelen F^-O-tAOj-H Preparation of Alkoxylates with the formula F^-O-tAOj-H
a) Fremstilling av de alkoksylerte alkoholer a) Preparation of the alkoxylated alcohols
Fremstillingen av de alkoksylerte alkoholer foregår på The production of the alkoxylated alcohols takes place on
kjent måte ved omsetning av mono- eller flerfunksjonene alkoholer med et alkoksyd eller en blanding av flere alkoksyder eller blokkvis med flere alkoksyder ved hjelp av basiske katalysatorer ved temperaturer fra 80 til 160°C. Som alkoholer kan det f.eks. anvendes etanol, butanol, isopropanol, talgfett- known way by reacting the mono- or polyfunctional alcohols with an alkoxide or a mixture of several alkoxides or blockwise with several alkoxides using basic catalysts at temperatures from 80 to 160°C. As alcohols, it can e.g. ethanol, butanol, isopropanol, tallow fat are used
alkohol, stearylalkohol, alkylfenoler med den generelle formel alcohol, stearyl alcohol, alkylphenols of the general formula
hvor R f.eks. er C9H19, CH3, CH(CH3)2, C(CH3)3 eller C8H17, etylenglykol, propylenglykol, bisfenol A, glycerol, trimetylolpropan, pentaerytritt, sorbitt, polyglycerol eller de nedenfor beskrevne alkylfenol/formaldehyd- resp. acetaldehyd-kondensa-sj onsprodukter. where R e.g. is C9H19, CH3, CH(CH3)2, C(CH3)3 or C8H17, ethylene glycol, propylene glycol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol, sorbitol, polyglycerol or the alkylphenol/formaldehyde resp. described below. acetaldehyde condensation products.
Foretrukne alkoksyder er propylenoksyd og 1,2-butylenoksyd eller blandinger av slike hvor også etylenoksyd kan være til stede. Preferred alkoxides are propylene oxide and 1,2-butylene oxide or mixtures thereof where ethylene oxide may also be present.
Reaksjonsbetingelsene varierer etter art og mengde av de anvendte alkoksyder. Reaksjonstemperaturen ligger vanligvis mellom 80 og 160°C og mengden av basiske katalysatorer varierer mellom 0,25 og 5%, og her er kaliumhydroksyd og natriumhydroksyd foretrukket. Alt etter konsistensen av utgangsalkoholen resp. sluttproduktet kan det som fortynning tilsettes et inert løsningsmiddel, som ikke innvirker på omsetningen. Xylen er foretrukket. The reaction conditions vary according to the nature and quantity of the alkoxides used. The reaction temperature is usually between 80 and 160°C and the amount of basic catalysts varies between 0.25 and 5%, and here potassium hydroxide and sodium hydroxide are preferred. Depending on the consistency of the starting alcohol or an inert solvent can be added as a dilution to the end product, which does not affect the turnover. Xylene is preferred.
Forholdet mellom alkohol og alkoksyd(er) kan variere sterkt, men det ligger hensiktsmessig i området fra 1:120 til 1:5. The ratio between alcohol and alkoxide(s) can vary greatly, but it is suitably in the range from 1:120 to 1:5.
b) Alkoksylerte alkylfenol/formaldehyd- resp.-acetaldehyd-kondensasj onsprodukter b) Alkoxylated alkylphenol/formaldehyde or acetaldehyde condensation products
De som alkoholer for alkoksylering anvendte alkylfenol/- formaldehyd- resp. acetaldehyd-harpikser kan fremstilles på kjent måte ved omsetning av aldehydet med alkylfenolen i forholdet 2:1 til 1:2, fortrinnsvis 1:1,05, med base- eller syre-katalyse, fortrinnsvis syrekatalyse, ved temperaturer fra 80 til 250"C ved hjelp av høytkokende løsningsmiddel for fullstendig azeotropisk fjerning av det dannede reaksjonsvann. Som alkylfenoler anvendes f.eks. nonylfenol, t-butylfenol eller oktylfenol, og som aldehyder anvendes fortrinnsvis formaldehyd og acetaldehyd. Som katalysator anvendes vanligvis en alkyl-sulfonsyre eller alkylbenzensulfonsyre, f.eks. dodecylbenzensulfonsyre i en mengde på 0,2 til 2%, fortrinnsvis 0,2 til 0,5%. Those who used alkylphenol/formaldehyde resp. Acetaldehyde resins can be prepared in a known manner by reacting the aldehyde with the alkylphenol in a ratio of 2:1 to 1:2, preferably 1:1.05, with base or acid catalysis, preferably acid catalysis, at temperatures from 80 to 250°C by means of a high-boiling solvent for complete azeotropic removal of the water of reaction formed. Nonylphenol, t-butylphenol or octylphenol are used as alkylphenols, for example, and formaldehyde and acetaldehyde are preferably used as aldehydes. An alkylsulphonic acid or alkylbenzenesulphonic acid is usually used as a catalyst, e.g. .eg dodecylbenzenesulfonic acid in an amount of 0.2 to 2%, preferably 0.2 to 0.5%.
Ved begynnelsen av omsetningen holdes temperaturen ved 90 til 120"C, inntil størstedelen av reaksjonsvannet er avdestillert. Deretter blir det, for å oppnå fullstendig omsetning, oppvarmet inntil kokepunktet for løsningsmidlet, og den gjenværende vannmengde blir fjernet azeotropisk. Gjennom-snittlig inneholder molekylet 4 til 12 aromatiske kjerner, fortrinnsvis 5 til 9. At the beginning of the reaction, the temperature is maintained at 90 to 120°C, until the majority of the reaction water is distilled off. Then, in order to achieve complete reaction, it is heated up to the boiling point of the solvent, and the remaining amount of water is removed azeotropically. On average, the molecule contains 4 to 12 aromatic cores, preferably 5 to 9.
De således oppnådde kondensasjonsprodukter blir alkoksylert som angitt under a). The condensation products thus obtained are alkylated as indicated under a).
c) Delvis omsetning av de frie OH-grupper i alkoksylatene fra a) og b) c) Partial reaction of the free OH groups in the alkoxylates from a) and b)
Etter avsluttet alkoksylering kan alkoksylatene fra trinnene a) eller b) delvis få endegruppene lukket, og det er foretrukket med en endegruppe-lukking på 20 til 90% av 0H-gruppene. Lukkingen av endestående hydroksylgrupper kan foregå ved syrekatalysert forestring med karboksylsyreanhydrider, fortrinnsvis eddiksyreanhydrid, ravsyreanhydrid og maleinsyreanhydrid, ved temperaturer fra 50 til 130"C, eller ved omsetning av alkoholatene med dimetylsulfat, benzylklorid og metyljodid, idet denne tilsetning av alkyleringsmiddel til natrium- eller kaliumalkoholater foregår ved temperaturer fra 40 til 80°C, og ved omsetning med isocyanater. After the carboxylation has been completed, the alkoxylates from steps a) or b) can partially have the end groups closed, and it is preferred to have an end group closure of 20 to 90% of the OH groups. The closing of terminal hydroxyl groups can take place by acid-catalyzed esterification with carboxylic acid anhydrides, preferably acetic anhydride, succinic anhydride and maleic anhydride, at temperatures from 50 to 130°C, or by reacting the alcoholates with dimethyl sulphate, benzyl chloride and methyl iodide, this being the addition of an alkylating agent to sodium or potassium alcoholates takes place at temperatures from 40 to 80°C, and by reaction with isocyanates.
A) Omsetning av alkoksylatene til umettede monomerer A) Conversion of the alkoxylates to unsaturated monomers
Siden de-emulgatorene for råoljeemulsjoner må være over-flateaktive midler, blir størrelsen på hydrofiliteten resp. hydrofobiteten innstilt med forholdet for polyetylenoksydblokk (hydrofil) til polypropylenblokk (hydrofob) til hydrofile komonomerer (f.eks. akrylsyre). Siden disse produkter må være løselige i råolje for at det skal oppnås maksimal virkning, er det viktig at den hydrofile polyakrylsyreandel i kopolymeren blir holdt oppløst i et aromatisk løsningsmiddel (f.eks. toluen, xylen eller aromatblanding) ved en stor hydrofob rest. Dette oppnås bare ved fullstendig og selektiv innføring av en radikalisk polymeriserbar funksjonalitet i den hydrofobe, alkoksylerte, eventuelt endegruppe-lukkede alkohol, og dennes anvendelse ved den etterfølgende radikaliske kopolymerisering med hydrofile komonomerer. Since the de-emulsifiers for crude oil emulsions must be surfactants, the magnitude of the hydrophilicity resp. the hydrophobicity set by the ratio of polyethylene oxide block (hydrophilic) to polypropylene block (hydrophobic) to hydrophilic comonomers (e.g. acrylic acid). Since these products must be soluble in crude oil for maximum effect, it is important that the hydrophilic polyacrylic acid portion of the copolymer is kept dissolved in an aromatic solvent (e.g. toluene, xylene or aromatic mixture) by a large hydrophobic residue. This is only achieved by the complete and selective introduction of a radically polymerisable functionality in the hydrophobic, alkylated, possibly end-group-closed alcohol, and its use in the subsequent radical copolymerization with hydrophilic comonomers.
For innføring av den umettede funksjonalitet i den alkoksylerte, eventuelt delvis endegruppe-lukkede alkohol, blir denne forestret i nærvær av sure katalysatorer (f.eks. p-toluensulfon-syre, svovelsyre eller dodecylbenzensulfonsyre) ved temperaturer fra 80 til 150°C med akrylsyre eller metakrylsyre, hvorved den nødvendige fullstendige fjerning av reaksjonsvannet gjennomføres med et azeotropt trekkmiddel, fortrinnsvis toluen eller xylen. To introduce the unsaturated functionality into the alkylated, possibly partially end-group-closed alcohol, this is esterified in the presence of acid catalysts (e.g. p-toluenesulfonic acid, sulfuric acid or dodecylbenzenesulfonic acid) at temperatures from 80 to 150°C with acrylic acid or methacrylic acid, whereby the necessary complete removal of the reaction water is carried out with an azeotropic drawing agent, preferably toluene or xylene.
For å forhindre polymerisering under forestringen, anbefales det å tilsette kjente stabilisatorer (fortrinnsvis hydrokinonmonometyleter). Forholdet mellom alkoksylert alkohol og akrylsyre resp. metakrylsyre kan variere mellom 1:1 og l:n, hvor n betyr funksjonaliteten (d.v.s. antall hydroksylgrupper) til utgangsalkoholen. Det foretrekkes et forhold på 1:1, da det ellers kan iakttas fremkomst av gelering under den etterfølgende polymerisering. Den fullstendige forestring av akrylsyren resp. metakrylsyren blir hensiktsmessig foretatt ved analytiske metoder (f.eks. syretall). Mengden av stabilisator varieres mellom 0,3 og 2 vekt%, fortrinnsvis 1 vekt%, basert på mengden av akrylsyre resp. metakrylsyre. Syrekatalysatoren tilsettes i mengder på 0,5 til 5 vekt%, fortrinnsvis 2 til 3 vekt%. Man oppnår like gode forestringsresultater ved anvendelse av akryl-syreanhydrid resp. metakrylsyreanhydrid og akrylsyreklorid resp. metakrylsyreklorid. Ved dette foregår utskillelsen av vann ved azeotrop destillasjon. To prevent polymerization during the esterification, it is recommended to add known stabilizers (preferably hydroquinone monomethyl ether). The ratio between alkoxylated alcohol and acrylic acid resp. Methacrylic acid can vary between 1:1 and 1:n, where n means the functionality (i.e. the number of hydroxyl groups) of the starting alcohol. A ratio of 1:1 is preferred, as gelation can otherwise be observed during the subsequent polymerization. The complete esterification of the acrylic acid or the methacrylic acid is appropriately determined by analytical methods (e.g. acid number). The amount of stabilizer is varied between 0.3 and 2% by weight, preferably 1% by weight, based on the amount of acrylic acid or methacrylic acid. The acid catalyst is added in amounts of 0.5 to 5% by weight, preferably 2 to 3% by weight. Equally good esterification results are obtained by using acrylic acid anhydride or methacrylic anhydride and acrylic acid chloride resp. methacrylic acid chloride. In this case, the separation of water takes place by azeotropic distillation.
Vektforholdet for løsningsmiddel til summen av oksalkylert alkohol og umettet karboksylsyre kan variere mellom 30:70 og 70:30, og det er foretrukket med et forhold fra 50:50 til 30:70. The weight ratio of solvent to the sum of oxalkylated alcohol and unsaturated carboxylic acid can vary between 30:70 and 70:30, and it is preferred with a ratio of 50:50 to 30:70.
Etter forestring med akrylsyre resp. metakrylsyre kan frem-delses tilstedeværende hydroksylfunksjoner lukkes med karboksylsyreanhydrider og isocyanater. Foretrukket er ftalsyreanhydrid, eddiksyreanhydrid og maleinsyreanhydrid. Derved kan alle hydroksylgruppene lukkes ved tilsetning av ekvimolare mengder av anhydrider, alkyleringsmiddel eller isocyanater, eller det kan gjennomføres bare en del-lukking. Det er foretrukket med en omsetning av 70 til 100% av de tilstedeværende ende-stående hydroksylgrupper. Anhydridet eller isocyanater tilsettes løsningen av akryl- resp. metakrylsyreesteren, eventuelt i nærvær av en katalysator, og reaksjonen blir avsluttet alt etter After esterification with acrylic acid or Methacrylic acid can be closed with carboxylic acid anhydrides and isocyanates if the existing hydroxyl functions are closed. Phthalic anhydride, acetic anhydride and maleic anhydride are preferred. Thereby, all the hydroxyl groups can be closed by adding equimolar amounts of anhydrides, alkylating agents or isocyanates, or only partial closing can be carried out. It is preferred to have a conversion of 70 to 100% of the terminal hydroxyl groups present. The anhydride or isocyanates are added to the solution of acrylic or the methacrylic acid ester, optionally in the presence of a catalyst, and the reaction is terminated accordingly
reaktiviteten innen 0,5 til 5 timer ved 70 til 120°C. the reactivity within 0.5 to 5 hours at 70 to 120°C.
Etter avsluttet forestring kan den tilsatte katalytiske syre nøytraliseres ved tilsetning av ekvimolekylære mengder av aminer, f.eks. trietanolamin, trietylamin eller tributylamin. Det er imidlertid foretrukket med nøytralisering av syren etter gjennomført polymerisering og eventuelt kondensering. After esterification has been completed, the added catalytic acid can be neutralized by adding equimolecular amounts of amines, e.g. triethanolamine, triethylamine or tributylamine. However, it is preferred to neutralize the acid after completed polymerization and possibly condensation.
B) Kopolymerisering av alkoksylatester-monomerene fra A) med hydrofile komonomerer B) Copolymerization of the alkoxylate ester monomers from A) with hydrophilic comonomers
Fremstillingen av kopolymerene kan foregå ved løsnings-, emulsjons- eller fellings-polymerisering, og det er foretrukket med løsningspolymerisering i et upolart løsningsmiddel (såsom toluen eller xylen). Til løsningen av den forestrede, eventuelt endegruppe-lukkede, alkoksylerte alkohol, resp. en blanding av flere forskjellige eventuelt endegruppe-lukkede, alkoksylerte alkoholer fra A), tilsettes eller tildryppes komonomeren resp. en blanding av flere komonomerer, og omsetningen kan gjennom-føres med hjelp av kjente radikal-initiatorer ved temperaturer fra 60 til 140°C. Typiske komonomerer er: akrylsyre, metakrylsyre, maleinsyreanhydrid, hydroksyetylakrylat, N,N-dietylamino-metylakrylat, akrylamid, akrylnitril, vinylacetat, allylalkohol, vinylformamid, vinylimidazol, vinylpyrrolidon, fumarsyre, maleinsyre, N,N-dimetylakrylamid eller vinylmetyleter, hvorved akrylsyre, eventuelt i blanding med andre komonomerer i forholdet 10:1 til 1:1, er foretrukket. The preparation of the copolymers can take place by solution, emulsion or precipitation polymerization, and solution polymerization in a non-polar solvent (such as toluene or xylene) is preferred. For the solution of the esterified, possibly end-group-closed, alkylated alcohol, resp. a mixture of several different optionally end-group-closed, alkoxylated alcohols from A), is added or added dropwise to the comonomer resp. a mixture of several comonomers, and the reaction can be carried out with the help of known radical initiators at temperatures from 60 to 140°C. Typical comonomers are: acrylic acid, methacrylic acid, maleic anhydride, hydroxyethyl acrylate, N,N-diethylaminomethylacrylate, acrylamide, acrylonitrile, vinyl acetate, allyl alcohol, vinylformamide, vinylimidazole, vinylpyrrolidone, fumaric acid, maleic acid, N,N-dimethylacrylamide or vinyl methyl ether, whereby acrylic acid, optionally in a mixture with other comonomers in a ratio of 10:1 to 1:1, is preferred.
Som radikal-initiator anvendes som regel 2,2-azo-bis-iso-butyronitril (AIBN), dibenzoylperoksyd, t-butylperacetat eller 2,2-azo-bis-2,4-dimetylvaleronitril, og AIBN og dibenzoylperoksyd er foretrukket. Mengden av anvendt radikal-initiator er som regel mellom 0,1 og 2 vekt%, basert på det samlede monomerinnhold. For å oppnå en så lav restmonomer-konsentrasjon som mulig, anbefales det en reaksjonsvarighet på 5 ganger halve-ringstiden for initiatoren ved den valgte reaksjonstemperatur. Ved tildrypping av radikal-initiatoren, eventuelt i nærvær av kjente molekylvektsregulerende substanser, såsom merkaptaner eller aldehyder, eventuelt ved også samtidig tilsetning (en del) av komonomerene, kan den eksoterme kopolymerisering optimali-seres med hensyn til varmetoning, molekylvektsfordeling og restmonomer-innhold. Det er foretrukket med en engangs begynnelses-tilsetning av 0,1 til 0,8 vekt% AIBN for å løse esteren og komonomerene og med polymerisering ved 60 til 90°C i løpet av 2 til 5 timer og også kontinuerlig tildosering av AIBN til løsningen av ester og komonomerer (eventuelt etter begynnelses-tilsetning av AIBN til løsningen) i løpet av 0,5 til 3 timer ved temperaturer fra 60 til 90°C, eventuelt i nærvær av molekylvekts-regulerende forbindelser såsom merkaptaner og aldehyder i mengder på fra 0,05 til 1 vekt%, basert på komonomerene. Mulig, men ikke foretrukket, er også samtidig anvendelse av flere forestrede, eventuelt endegruppe-lukkede, alkoksylerte alkoholer og også tilsetning eller tildosering av flere komonomerer. Polymerisasjonskonsentrasjonen ligger mellom 20 og 70 vekt%, og foretrukket er 40 - 60 vekt%. For å oppnå meget virksomme produkter anbefales det mange ganger en for-polymerisering av den hydrofobe, eventuelt endegruppe-lukkede ester av alkoksylert alkohol og akrylsyre resp. metakrylsyre i løpet av 1 til 2 timer med den nevnte radikalinitiator og en påfølgende tilsetning eller kontinuerlig tildosering av komonomerene over 1/3 til 2/3 av reaksjonstiden, eventuelt med ytterligere radikalinitiator. As a rule, 2,2-azo-bis-iso-butyronitrile (AIBN), dibenzoyl peroxide, t-butyl peracetate or 2,2-azo-bis-2,4-dimethylvaleronitrile are used as radical initiators, and AIBN and dibenzoyl peroxide are preferred. The amount of radical initiator used is usually between 0.1 and 2% by weight, based on the overall monomer content. In order to achieve as low a residual monomer concentration as possible, a reaction duration of 5 times the half-life of the initiator at the selected reaction temperature is recommended. By adding the radical initiator drop by drop, possibly in the presence of known molecular weight regulating substances, such as mercaptans or aldehydes, possibly also by simultaneously adding (part of) the comonomers, the exothermic copolymerization can be optimized with regard to heat tinting, molecular weight distribution and residual monomer content. It is preferred with a one-time initial addition of 0.1 to 0.8 wt% AIBN to dissolve the ester and comonomers and with polymerization at 60 to 90°C during 2 to 5 hours and also continuous addition of AIBN to the solution of ester and comonomers (optionally after initial addition of AIBN to the solution) during 0.5 to 3 hours at temperatures from 60 to 90°C, optionally in the presence of molecular weight-regulating compounds such as mercaptans and aldehydes in amounts of from 0 .05 to 1% by weight, based on the comonomers. Possible, but not preferred, is also the simultaneous use of several esterified, possibly end-group-closed, alkylated alcohols and also the addition or dosing of several comonomers. The polymerization concentration is between 20 and 70% by weight, and 40 - 60% by weight is preferred. In order to obtain highly effective products, it is often recommended to pre-polymerize the hydrophobic, possibly end-group-closed ester of alkylated alcohol and acrylic acid or methacrylic acid over the course of 1 to 2 hours with the aforementioned radical initiator and a subsequent addition or continuous dosing of the comonomers over 1/3 to 2/3 of the reaction time, optionally with further radical initiator.
K-verdien til de oppnådde polymerer er vanligvis på 15 til 60 (målt i l%ig xylenisk løsning). For å innvirke på molekylvekten kan det tilsettes vanlige kjedereguleringsmidler såsom aldehyder eller tioforbindelser (f.eks. tioetanol, tioglykol-syre). Også tverrbindende difunksjonelle komonomerer såsom metylenbisakrylamid kan anvendes for å forhøye molekylvekten. The K value of the polymers obtained is usually 15 to 60 (measured in 1% xylene solution). To influence the molecular weight, common chain regulators such as aldehydes or thio compounds (eg thioethanol, thioglycolic acid) can be added. Cross-linking difunctional comonomers such as methylene bisacrylamide can also be used to increase the molecular weight.
C) Endegruppe-lukking og/eller nøytralisering av de katalytiske syremengder etter avsluttet polymerisering C) End-group closure and/or neutralization of the catalytic acid quantities after completion of polymerization
For å forhøye effektiviteten og spesielt økningen av lagringsstabiliteten for kopolymerene foretas delvis indremolekylær forestring etter gjennomført polymerisering resp. en avsluttet lukking av fremdeles frie hydroksylfunksjoner ved hjelp av omsetning med anhydrider eller isocyanater og/eller nøytralisering av fremdeles tilstedeværende katalytiske syremengder med aminer for å unngå omforestringsreaksjoner, hvilke kan føre til geldannelse av produktene. In order to increase the efficiency and especially the increase in the storage stability of the copolymers, partial intramolecular esterification is carried out after completed polymerization or a completed closure of still free hydroxyl functions by means of reaction with anhydrides or isocyanates and/or neutralization of still present catalytic acid amounts with amines to avoid transesterification reactions, which can lead to gelation of the products.
En delvis indremolekylær kondensasjon oppnås ved oppvarming av polymerisasjonsløsningen fra B) til temperaturer fra 100 til 140°C i en tid på 1 til 5 timer. Det foretrekkes en 2-timers oppvarming av den xyleniske polymerisasjonsløsning fra B) fra 110 til 120°C. Ved videregående kondensasjon kan det fremkomme geldannelse. A partial intramolecular condensation is achieved by heating the polymerization solution from B) to temperatures from 100 to 140°C for a period of 1 to 5 hours. A 2-hour heating of the xylenic polymerization solution from B) from 110 to 120°C is preferred. In case of secondary condensation, gel formation may occur.
Omsetningen av de frie OH-grupper med anhydrider og isocyanater kan gjennomføres direkte etter polymeriseringen eller etter delvis indremolekylær kondensasjon, hvorved det også kan foregå en delvis lukking av de tilstedeværende hydroksylgrupper etter polymeriseringen og påfølgende kondensasjon med azeotrope trekkmidler under vannutpressing. Det er foretrukket med fullstendig endegruppe-lukking etter delvis indremolekylær kondensasjon ved 110 til 120°C og/eller lukking av 60 til 80% av de tilstedeværende hydroksylgrupper direkte etter polymerisering med påfølgende kondensasjon ved azeotrop utpressing av reaksjonsvannet ved hjelp av et trekkmiddel, fortrinnsvis xylen. The reaction of the free OH groups with anhydrides and isocyanates can be carried out directly after the polymerization or after partial intramolecular condensation, whereby a partial closure of the hydroxyl groups present after the polymerization and subsequent condensation with azeotropic drawing agents during water extraction can also take place. It is preferred with complete end-group closure after partial intramolecular condensation at 110 to 120°C and/or closure of 60 to 80% of the hydroxyl groups present directly after polymerization with subsequent condensation by azeotropic extrusion of the reaction water using a drawing agent, preferably xylene .
Endegruppe-lukkingen oppnås ved tilsetning eller tildosering av den ønskede mengde av anhydrid eller isocyanat til polymeriseringsoppløsning og oppvarming til 70 - 120"C i løpet av 0,5 -5 timer, eventuelt i nærvær av i og for seg kjente katalysatorer. Foretrukket som forestringsmiddel er eddiksyreanhydrid, ftalsyreanhydrid og ravsyreanhydrid. The end group closure is achieved by adding or dosing the desired amount of anhydride or isocyanate to the polymerization solution and heating to 70 - 120°C within 0.5 - 5 hours, possibly in the presence of catalysts known per se. Preferred as an esterification agent are acetic anhydride, phthalic anhydride and succinic anhydride.
Dersom endegruppe-lukkingen finner sted allerede ved trinnet med alkoksylatet eller den hydrofobe akrylsyre- eller metakrylsyreester, foretrekkes det å kondensere etter polymeriseringen ved hjelp av et azeotropt trekkmiddel. If the end group closure already takes place at the step with the alkoxylate or the hydrophobic acrylic acid or methacrylic acid ester, it is preferred to condense after the polymerization with the aid of an azeotropic drawing agent.
I tilegg til eller alternativt til endegruppe-lukkingen blir det fortsatt nøytralisering av enda tilstedeværende katalytiske syremengder fra forestringstrinnet med aminer. Nøytraliseringen blir fortrinnsvis gjennomført etter avsluttet polymerisering, hvorved videregående forestringsreaksjoner, som kan føre til geldannelse, blir forhindret. In addition to or alternatively to the end-group closure, there is continued neutralization of still present catalytic amounts of acid from the esterification step with amines. The neutralization is preferably carried out after completion of polymerization, whereby further esterification reactions, which can lead to gel formation, are prevented.
Nøytraliseringen av de ennå tilstedeværende spor av katalytisk syre fra forestringsreaksjonen foregår ved tilsetning av ekvimolekylære mengder av aminer, f.eks. trietanolamin, tributylamin eller trietylamin, til løsningen av de eventuelt endegruppe-lukkede polymerer og omsetning ved temperaturer fra 20 til 80°C i løpet av 2 timer. Den fullstendige nøytralisering kan gjennomføres ved hjelp av amintallet. The neutralization of the still present traces of catalytic acid from the esterification reaction takes place by adding equimolecular amounts of amines, e.g. triethanolamine, tributylamine or triethylamine, to the solution of the optionally end-group-closed polymers and reaction at temperatures from 20 to 80°C during 2 hours. The complete neutralization can be carried out using the amine number.
D) Modifisering av polymerene fra B) og C) (valgfritt) D) Modification of the polymers from B) and C) (optional)
For å øke effektiviteten og for å justere for den råolje som hver gang skal behandles, kan det eventuelt være fornuftig med en supplerende modifisering av de under B) og C) oppnådde kopolymerer. Alt etter de anvendte komonomerer ved kopolymeriseringen kan det gjøres følgende forandringer av produktet: 1) Sammenblanding med en alkoksylert alkohol eller en blanding av flere alkoksylerte alkoholer, f.eks. slike som beskrevet, oppnådd under b), eller med andre kopolymerer fra B) og C) i forholdet 10:90 til 90:10, og foretrukket 50:50 til 80:20. In order to increase the efficiency and to adjust for the crude oil to be treated each time, it may possibly make sense with a supplementary modification of the copolymers obtained under B) and C). Depending on the comonomers used during the copolymerization, the following changes can be made to the product: 1) Mixing with an alkylated alcohol or a mixture of several alkylated alcohols, e.g. such as described, obtained under b), or with other copolymers from B) and C) in the ratio 10:90 to 90:10, and preferably 50:50 to 80:20.
Bedre effektivitet kan dessuten også oppnås ved tilsetning av såkalte ko-tensider til kopolymerene i vektmengder fra 5 til 30 vekt%. Slike ko-tensider kan f.eks. være dodecylhydrogensulfat, alkylbenzensulfonat eller alkylnaftalen-sulfonat. 2) Det kan oppnås en molekylvektøkning ved supplerende tverrbinding med flerfunksjonene koblingsmidler, som reagerer med reaktive grupper på kopolymerene. Better efficiency can also be achieved by adding so-called co-surfactants to the copolymers in amounts from 5 to 30% by weight. Such co-surfactants can e.g. be dodecyl hydrogen sulfate, alkyl benzene sulfonate or alkyl naphthalene sulfonate. 2) An increase in molecular weight can be achieved by supplementary cross-linking with multifunctional coupling agents, which react with reactive groups on the copolymers.
Ved dette blir tverrbindingen (avhengig av type tverrbind ingsmiddel) gjennomført med 0,1 til 10 vekt%, fortrinnsvis 1-4 vekt%, av flerfunksjonene komponenter ved temperaturer fra 80 til 140°C. Som flerfunksjonene tverrbindingsmidler blir det, alt etter anvendte komonomerer, anvendt bisglycidyleter (foretrukket bisglycidyleter av bisfenol A), flerfunksjonene alkoholer (f.eks. sorbitol, etylenglykol), diisocyanater (f.eks. toluendiisocyanat) og sammenlignbare forbindelser, som blir omsatt med reaktive steder på In this way, the cross-linking (depending on the type of cross-linking agent) is carried out with 0.1 to 10% by weight, preferably 1-4% by weight, of the multifunctional components at temperatures from 80 to 140°C. As multifunctional cross-linking agents, depending on the comonomers used, bisglycidyl ethers (preferably bisglycidyl ethers of bisphenol A), multifunctional alcohols (e.g. sorbitol, ethylene glycol), diisocyanates (e.g. toluene diisocyanate) and comparable compounds are used, which are reacted with reactive places on
kopolymerene. the copolymers.
3) Etter-alkoksylering med et alkoksyd, en blanding av flere alkoksyder eller blokkvis med forskjellige alkoksyder. Dermed blir kopolymerene fra B) og C) med basiske katalysatorer (natriumhydroksyd og kaliumhydroksyd er foretrukket) i mengder fra 0,5 til 5 vekt% ved temperaturer fra 100 til 150°C omsatt med alkoksydet (alkoksydene). Som alkoksyd anvendes fortrinnsvis etylenoksyd, propylenoksyd eller 1,2-butylenoksyd, hvorved forholdet mellom kopolymer 3) Post-alkylation with an alkoxide, a mixture of several alkoxides or blockwise with different alkoxides. Thus, the copolymers from B) and C) are reacted with basic catalysts (sodium hydroxide and potassium hydroxide are preferred) in amounts from 0.5 to 5% by weight at temperatures from 100 to 150°C with the alkoxide(s). Ethylene oxide, propylene oxide or 1,2-butylene oxide are preferably used as alkoxide, whereby the ratio between copolymer
og alkoksyd varierer mellom 5:95 og 95:5. and alkoxide varies between 5:95 and 95:5.
4) Kvaternisering av N-holdige kopolymerer med kjente kvaterniseringsmidler, såsom dimetylsulfat eller metyljodid ved temperaturer fra 50 til 120°C. Derved kan det foretas en fullstendig eller bare delvis kvaternisering av de tilstedeværende aminfunksjoner. 4) Quaternization of N-containing copolymers with known quaternization agents, such as dimethyl sulfate or methyl iodide at temperatures from 50 to 120°C. Thereby, a complete or only partial quaternization of the amine functions present can be carried out.
Det er ingen begrensning til noen spesiell anvendelse av en modifikasjon på kopolymeren fra C). Det kan derimot gjennom-føres valgfrie forandringer i henhold til 1) til 4) etter hver-andre . There is no limitation to any particular application of a modification to the copolymer from C). On the other hand, optional changes can be made in accordance with 1) to 4) one after the other.
Eksempel Example
a) Fremstilling av de alkoksylerte alkoholer (alkoksylater) a) Preparation of the alkoxylated alcohols (alkoxylates)
I en autoklav blir det under nitrogenatmosfære innført 31 g 31 g are introduced into an autoclave under a nitrogen atmosphere
trimetylolpropan og 0,3 g kaliumhydroksyd og blandingen blir ved 130 til 140"C og 6 bar omsatt med 800 g propylenoksyd innen 10 timer. Deretter blir det i et annet trinn ved 120 til 130"C tilsatt ytterligere 101 g etylenoksyd. Mot slutten av omsetningen holder man temperaturen i 1 time ved 140°C for om mulig å oppnå fullstendig omsetning. Molekylvekten beregnes fra det målte OH-tall til 3820. Dette er eks. a5 i den etterfølgende tabell. For å forenkle gis det avkall på utførende beskrivelse av de ytterligere eksempler. Reaksjonsbetingelsene er imidlertid i stor grad i samsvar med dem som er angitt i ovenstående eksempel. Ved omsetningen med blandingsoksyder blir det hver gang anvendte alkoksyd blandet til en forblanding og blir derpå tildosert. trimethylolpropane and 0.3 g of potassium hydroxide and the mixture is reacted at 130 to 140°C and 6 bar with 800 g of propylene oxide within 10 hours. Then, in another step at 120 to 130°C, a further 101 g of ethylene oxide is added. Towards the end of the reaction, the temperature is kept for 1 hour at 140°C in order to achieve complete reaction if possible. The molecular weight is calculated from the measured OH number to 3820. This is e.g. a5 in the following table. To simplify, detailed description of the further examples is waived. However, the reaction conditions are largely consistent with those indicated in the above example. In the reaction with mixed oxides, the alkoxide used each time is mixed into a premix and is then dosed.
b) Fremstilling av alkylfenol/formaldehyd- resp. acetaldehyd-harpikser b) Production of alkylphenol/formaldehyde resp. acetaldehyde resins
Til 440 g nonylfenol blir det satt 119 g xylen og ved 40°C blir det tildosert 60 g para-formaldehyd. Deretter tilsetter man ved 35°C, 1,5 g dodecylbenzensulfonsyre, hvoretter det begynner en eksoterm kondensasjon. Ved avkjøling holder man reaksjonstemperaturen i 3 timer ved 65-70°C. Deretter blir materialet oppvarmet i 2 timer ved 90°C. For å gjøre omsetningen fullstendig, oppvarmer man i 4 timer ved fra 95 til 100°C, hvorved materialet destilleres under tilbakeløp. Deretter blir reaksjonsvannet avdestillert og for fullstendig awanning blir vann fjernet azeotropisk med xylen i 6 timer. Etter avkjøling erholder man nonylfenol/formaldehyd-harpiksen som middelsviskøs 75 til 80%ig løsning i xylen. Dette er eks. bl i den etterfølgende tabell. 119 g of xylene is added to 440 g of nonylphenol and at 40°C 60 g of para-formaldehyde is added. Then, at 35°C, 1.5 g of dodecylbenzenesulfonic acid is added, after which an exothermic condensation begins. During cooling, the reaction temperature is maintained for 3 hours at 65-70°C. The material is then heated for 2 hours at 90°C. In order to make the reaction complete, it is heated for 4 hours at from 95 to 100°C, whereby the material is distilled under reflux. The reaction water is then distilled off and, for complete dewatering, water is removed azeotropically with xylene for 6 hours. After cooling, the nonylphenol/formaldehyde resin is obtained as a medium viscosity 75 to 80% solution in xylene. This is e.g. bl in the following table.
c) Endegruppe-lukking av alkoksylatene fra a) og b) c) End group closure of the alkoxylates from a) and b)
200 g av alkoksylatet fra eks. a 15 blir blandet med 8 g av 200 g of the alkoxylate from e.g. a 15 is mixed with 8 g of
50%ig natriumhydroksydløsning og alkoholatet blir fremstilt under forminsket trykk ved 100-170"C. 50% sodium hydroxide solution and the alcoholate are prepared under reduced pressure at 100-170°C.
Deretter tildrypper man ved 50-55"C, 12,6 g dimetylsulfat-løsning og tar etter avsluttet tilsetning prøve på fritt dimetylsulfat. Man lar det eventuelt etter-reagere ved 60-70°C, inntil testen på fritt dimetylsulfat viser negativt resultat. Dette er eks. c 1. Then, at 50-55°C, 12.6 g of dimethylsulphate solution is added drop by drop and after the addition is complete, a sample is taken for free dimethylsulphate. If necessary, it is left to react at 60-70°C, until the test for free dimethylsulphate shows a negative result. This is, for example, c 1.
A) Fremstilling av de alkoksylerte estermonomerer A) Preparation of the alkoxylated ester monomers
1) 122 g av produktet fra eks. a 5 blir blandet med 2,4 g akrylsyre, 24 mg hydrokinonmonometyleter, 2,5 g para-toluen sulfonsyre og 55 g xylen under nitrogenatmosfære. Ved oppvarming til 150°C fjerner man i løpet av 3 timer 0,6 ml vann. For å regulere den fullstendige forestring benytter man syretallet (d.v.s. mengden av ennå fri akrylsyre) i .løsningen. Dette må være nedsatt fra den teoretiske utgangsverdi på 20 til minst 6 for å fremvise en til-strekkelig forestring. Man oppnår akrylsyreesteren som en 70%ig klar løsning i xylen. Dette er eks. A3 i den etter-følgende tabell. 1) 122 g of the product from ex. a 5 is mixed with 2.4 g of acrylic acid, 24 mg of hydroquinone monomethyl ether, 2.5 g of para-toluene sulfonic acid and 55 g of xylene under a nitrogen atmosphere. When heated to 150°C, 0.6 ml of water is removed within 3 hours. To regulate the complete esterification, the acid number (i.e. the amount of still free acrylic acid) in the solution is used. This must be reduced from the theoretical starting value of 20 to at least 6 in order to demonstrate sufficient esterification. The acrylic acid ester is obtained as a 70% clear solution in xylene. This is e.g. A3 in the following table.
2) 609,4 g av produktet fra eks. A15 blir blandet med 7,9 g akrylsyre, 79 mg hydrokinonmonometyleter, 7,6 g para-toluensulfonsyre og 268 g xylen under nitrogenatmosfære. Ved oppvarming til 150 °C fjerner man 1,9 ml vann i løpet av 3 timer. Syretallet faller etter 3 timer til en verdi på 2) 609.4 g of the product from ex. A15 is mixed with 7.9 g of acrylic acid, 79 mg of hydroquinone monomethyl ether, 7.6 g of para-toluenesulfonic acid and 268 g of xylene under a nitrogen atmosphere. When heated to 150 °C, 1.9 ml of water is removed within 3 hours. The acid value drops after 3 hours to a value of
4,0. Etter avsluttet forestring med akrylsyre avkjøler man, tilsetter 14,3 g eddiksyreanhydrid og oppvarmer til 100°C i 2 timer. Dette er eks. A14 i den etterfølgende tabell. 4.0. After esterification with acrylic acid has been completed, it is cooled, 14.3 g of acetic anhydride are added and heated to 100°C for 2 hours. This is e.g. A14 in the following table.
Fremgangsmåtene i de ytterligere eksempler er like. Eventuelt anvendes det lengre eller også kortere reaksjonstider for å oppnå en fullstendig forestring og endegruppe-lukking. The procedures in the further examples are similar. Optionally, longer or shorter reaction times are used to achieve complete esterification and end-group closure.
B) Kopolymerisering av den hydrofobe umettede B) Copolymerization of the hydrophobic unsaturated
ester fra A) med komonomerer ester from A) with comonomers
Eksempel Example
Til 587 g av løsningen av den under A3 fremstilte forestrede alkohol tilsettes under nitrogenatmosfære 72 g akrylsyre, 284 mg 2,2'-azo-bisisobutyronitril og 307 g xylen, og blandingen blir rørt i 3 timer ved 80"C. Deretter blir det oppvarmet i 2 timer ved 110°C. Den oppnådde kopolymer har en A-verdi på 28,3 (målt som l%ig xylenisk løsning). Dette er eksempel Bl i den etterfølgende tabell. To 587 g of the solution of the esterified alcohol prepared under A3, 72 g of acrylic acid, 284 mg of 2,2'-azo-bisisobutyronitrile and 307 g of xylene are added under a nitrogen atmosphere, and the mixture is stirred for 3 hours at 80°C. It is then heated for 2 hours at 110° C. The obtained copolymer has an A value of 28.3 (measured as 1% xylene solution). This is example B1 in the following table.
Eksempel 2 Example 2
764 g av løsningen av den under Al fremstilte forestrede alkohol blir tilsatt 212 mg 2,2'-azo-bisisobutyronitril og røres under nitrogenatmosfære i 2 timer ved 90°C. Deretter tilsetter man 72 g akrylsyre og 72 g xylen og rører i ytterligere 15 timer ved 100°C. Dette er eksempel B2 i den etterfølgende tabell. 764 g of the solution of the esterified alcohol prepared under Al are added to 212 mg of 2,2'-azo-bisisobutyronitrile and stirred under a nitrogen atmosphere for 2 hours at 90°C. 72 g of acrylic acid and 72 g of xylene are then added and stirred for a further 15 hours at 100°C. This is example B2 in the following table.
Eksempel 3 Example 3
Til 707 g av løsningen av den under A5 fremstilt forestrede alkohol blir det under nitrogenatmosfære tilsatt 10 g akrylsyre, 156 mg 2,2'-azo-bisisobutyronitril og 293 g xylen, og løsningen blir oppvarmet til 80°C. Man tildrypper deretter i løpet av 10 timer en løsning av 62 g akrylsyre i 62 g xylen. Etter avsluttet tilsetning etter-rører man i ytterligere 5 timer ved 120°C. Dette er eksempel B3 i den etterfølgende tabell. To 707 g of the solution of the esterified alcohol prepared under A5, 10 g of acrylic acid, 156 mg of 2,2'-azo-bisisobutyronitrile and 293 g of xylene are added under a nitrogen atmosphere, and the solution is heated to 80°C. A solution of 62 g of acrylic acid in 62 g of xylene is then added drop by drop over the course of 10 hours. After the addition has been completed, the mixture is stirred for a further 5 hours at 120°C. This is example B3 in the following table.
Eksempel 4 Example 4
Til 893 g av løsningen av den under A15 fremstilte forestrede alkohol blir det under nitrogenatmosfære tilsatt 95,8 g akrylsyre, 0,94 g n-butyraldehyd og 350 g xylen og løsningen blir oppvarmet under omrøring til 90°C. I løpet av 3 timer blir det tildryppet en løsning av 486 mg 2,2'-azo-bisisobutyronitril i 103 g xylen. Etter avsluttet tilsetning lar man det etter-reagere i ytterligere 2 timer. Dette er eksempel B16 i den etterfølgende tabell. To 893 g of the solution of the esterified alcohol prepared under A15, 95.8 g of acrylic acid, 0.94 g of n-butyraldehyde and 350 g of xylene are added under a nitrogen atmosphere and the solution is heated with stirring to 90°C. Over the course of 3 hours, a solution of 486 mg of 2,2'-azo-bisisobutyronitrile in 103 g of xylene is added dropwise. After the addition has been completed, it is left to react for a further 2 hours. This is example B16 in the following table.
Eksempel 5 Example 5
Til 893 g av løsningen av den under A14 fremstilte forestrede og delvis endegruppe-lukkede alkohol blir det under nitrogenatmosfære tilsatt 95,8 g akrylsyre, 436 mg 2,2'-azo-bisisobutyronitril og 453 g xylen. Man oppvarmer i 3 timer ved 80°C og fjerner deretter i 3 timer under tilbakeløp azeotropt vann. Produktet fås som en 50%ig løsning i xylen, har en K-verdi på 21,2 (målt som l%ig xylenisk løsning) og har et OH-tall på mindre enn 1. Dette er eksempel B17 i den etterfølgende tabell. 95.8 g of acrylic acid, 436 mg of 2,2'-azo-bisisobutyronitrile and 453 g of xylene are added under a nitrogen atmosphere to 893 g of the solution of the esterified and partially end-group-closed alcohol prepared under A14. It is heated for 3 hours at 80°C and then azeotropic water is removed for 3 hours under reflux. The product is available as a 50% solution in xylene, has a K value of 21.2 (measured as a 1% xylene solution) and has an OH number of less than 1. This is example B17 in the following table.
De etterfølgende produkter blir syntetisert analogt med eksemplet ovenfor. Ved kopolymeriseringen, hvor det anvendes to forskjellige estere fra A), benytter man begge komponentene ved begynnelsen av polymeriseringen, og går frem analogt med eksemplene 1 til 3. Ved kopolymerisering med to forskjellige komonomerer, tilsetter man begge før begynnelsen på omsetningen (analogt med eks. 1) eller tildrypper komonomerblandingen sakte under omsetningen (analogt med eks. 3). The subsequent products are synthesized analogously to the example above. In the copolymerization, where two different esters from A are used), both components are used at the beginning of the polymerization, and proceed analogously to examples 1 to 3. In the copolymerization with two different comonomers, both are added before the beginning of the reaction (analogous to ex . 1) or drips the comonomer mixture slowly during the reaction (analogous to ex. 3).
C) Endegruppe-lukking og nøytralisering av de katalytiske syremengder etter avsluttet C) End-group closure and neutralization of the catalytic amounts of acid after termination
polymerisering polymerization
I det etterfølgende eksempel, i hvilket 70% av de tilstedeværende OH-grupper blir lukket med eddiksyreanhydrid, gjennomføres en supplerende ytterligere forestring av resten av OH-gruppene ved azeotropisk forestring og en nøytralisering av p-toluensulfonsyren med tributylamin, og dette skal bare gi eksempler på mulighetene som endegruppe-lukkingen og nøytrali-seringen gir. Jo høyere antall det er av frie OH-grupper etter endegruppe-lukkingen, desto sterkere stiger K-verdien til polymeren ved den etterfølgende azeotrope forestring. In the following example, in which 70% of the OH groups present are closed with acetic anhydride, a supplementary further esterification of the rest of the OH groups is carried out by azeotropic esterification and a neutralization of the p-toluenesulfonic acid with tributylamine, and this should only give examples on the possibilities that end-group closure and neutralization provide. The higher the number of free OH groups after the end group closure, the stronger the K value of the polymer rises in the subsequent azeotropic esterification.
Eksempel 1 Example 1
Til 893 g av løsningen av den under Al5 fremstilte forestrede alkohol blir under nitrogenatmosfære tilsatt 95,8 g akrylsyre, 453 mg 2,2'-azo-bisisobutyronitril og 460 g xylen og det blir polymerisert i 3 timer ved 80°C. K-verdien til den oppnådde kopolymer ligger ved 13,2 (målt som l%ig xylenisk løsning). Man lar løsningen avkjøle, tilsetter 14,3 g eddiksyreanhydrid og oppvarmer i 3 timer ved 100"C. Deretter oppvarmer man i 3 timer ved fra 140 til 145°C og fjerner azeotropt vann. Etter avkjøling til 40°C tilsetter man 7,7 g tributylamin og etter-rører i 2 timer. Produktet fås som middels viskøs 50%ig løsning i xylen. K-verdien er på 23,8 (målt som l%ig xylenisk løsning). OH-tallet er mindre enn 1. Dette er eks. Cl i den etterfølgende tabell. 95.8 g of acrylic acid, 453 mg of 2,2'-azo-bisisobutyronitrile and 460 g of xylene are added under a nitrogen atmosphere to 893 g of the solution of the esterified alcohol produced under Al5 and polymerized for 3 hours at 80°C. The K value of the obtained copolymer is 13.2 (measured as a 1% xylene solution). The solution is allowed to cool, 14.3 g of acetic anhydride is added and heated for 3 hours at 100°C. The mixture is then heated for 3 hours at from 140 to 145°C and azeotropic water is removed. After cooling to 40°C, 7.7 g of tributylamine and after stirring for 2 hours. The product is available as a medium viscous 50% solution in xylene. The K value is 23.8 (measured as a 1% xylene solution). The OH number is less than 1. This is eg Cl in the following table.
D) Modifisering av de under B) og C) fremstilte kopolymerer D) Modification of the copolymers produced under B) and C).
Det etterfølgende eksempel skal bare eksemplvis gjøre det tydelig hvilke modifikasjoner som kan gjennomføres med polymerene fra B) og C). The following example should only make it clear by way of example which modifications can be carried out with the polymers from B) and C).
a) Sammenblanding med alkoksylerte alkoholer og/eller ko-tensider 1. 966 g av løsningen av den under Bl fremstilte kopolymer blir blandet sammen med 61 g av den under al4 alkoksylerte alkohol og 61 g xylen. 2. 768 g av løsningen av den under B9 fremstilte kopolymer blir blandet med 128 g dodecylhydrogensulfat a) Mixing with alkoxylated alcohols and/or co-surfactants 1. 966 g of the solution of the copolymer prepared under B1 are mixed together with 61 g of the alcohol alkylated under al4 and 61 g of xylene. 2. 768 g of the solution of the copolymer prepared under B9 is mixed with 128 g of dodecyl hydrogen sulfate
og 1613 g metanol. and 1613 g of methanol.
b) Delvis forestring av den under C) fremstilte blanding b) Partial esterification of the mixture prepared under C).
50 g av løsningen av produktet fra B14 blir blandet med 50 g of the solution of the product from B14 is mixed with
6,5 g av den under al3 og 6,5 g av den under al4 fremstilte alkoksylerte alkohol, og i tillegg tilsatt enda 52 g xylen. Ved koking under tilbakeløp fjerner man 0,8 ml vann i løpet 6.5 g of the alkoxylated alcohol produced under al3 and 6.5 g of that produced under al4, and in addition another 52 g of xylene added. When boiling under reflux, 0.8 ml of water is removed in the course
av 4 timer. of 4 hours.
c) Supplerende tverrbinding av kopolymerene fra B) c) Supplementary cross-linking of the copolymers from B)
50 g av løsningen av produktet fra B10 blir tilsatt 1 g 50 g of the solution of the product from B10 is added 1 g
bisglycidyleter av bisfenol A (epikote) og det blir oppvarmet ved 100°C i 8 timer. Den seigviskøse løsning bisglycidyl ether of bisphenol A (epicote) and it is heated at 100°C for 8 hours. The viscous solution
blir fortynnet ved tilsetning av 35 g xylen. is diluted by adding 35 g of xylene.
d) Supplerende alkoksylering av de under B) og C) fremstilte kopolymerer med etylenoksyd og/eller propylenoksyd d) Supplementary alkoxylation of the copolymers produced under B) and C) with ethylene oxide and/or propylene oxide
og eller butylenoksyd and or butylene oxide
100 g av løsningen av den under B7 fremstilte kopolymer blir tilsatt 1 g kaliumhydroksyd og omsatt med 50 g propylenoksyd i en autoklav ved 6 bar og ved 130-140°C. Etter avsluttet omsetning blir det porsjonsvis tildosert enda 290 g etylenoksyd ved 120-130°C. Mot slutten av omsetningen forhøyer man temperaturen i 2 timer til 150°C. 10 g of the solution of the copolymer prepared under B7 is added to 1 g of potassium hydroxide and reacted with 50 g of propylene oxide in an autoclave at 6 bar and at 130-140°C. After completion of the reaction, another 290 g of ethylene oxide is dosed in portions at 120-130°C. Towards the end of the reaction, the temperature is raised for 2 hours to 150°C.
Claims (8)
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DE19863635489 DE3635489A1 (en) | 1986-10-18 | 1986-10-18 | COPOLYMERISATE MADE OF HYDROPHOBIC ACRYLIC ACID OR METHACRYLIC ACID ESTERS AND HYDROPHILIC COMONOMERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PETROLEUM EMULSION SPLITTER |
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CA (1) | CA1309552C (en) |
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DE4104610A1 (en) * | 1991-02-15 | 1992-08-20 | Basf Ag | ACTION PRODUCTS OF ALKOXYLATES AND VINYLIC MONOMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE AS DEMULGATORS FOR CRUDEOULULULULULAR POWERS |
DE4326772A1 (en) * | 1993-08-10 | 1995-02-16 | Basf Ag | Reaction products from olefinically unsaturated carboxylic acids and polyetherols and their use as demulsifiers for crude oil emulsions |
CN1101238C (en) * | 1998-01-21 | 2003-02-12 | 辽河石油勘探局勘察设计研究院 | Crude de-emulsifier and its preparing process |
PL374428A1 (en) | 2002-06-11 | 2005-10-17 | Basf Aktiengesellschaft | (meth)acrylic esters of polyalkoxylated trimethylolpropane |
JP2005532430A (en) * | 2002-06-11 | 2005-10-27 | ビーエーエスエフ アクチェンゲゼルシャフト | (Meth) acrylic esters of polyalkoxylated trimethylolpropane |
KR20060024401A (en) | 2003-06-06 | 2006-03-16 | 바스프 악티엔게젤샤프트 | (meth)acrylic ester for alkylenylene glycol and the use thereof |
DE102005006030A1 (en) | 2005-02-09 | 2006-08-10 | Basf Ag | Hyperbranched polymers as demulsifiers for cracking crude oil emulsions |
US9296957B2 (en) | 2007-10-08 | 2016-03-29 | Basf Se | Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions |
DE102008037973A1 (en) | 2008-08-16 | 2010-02-18 | Clariant International Limited | Dry pigment preparations with anionic additives |
DE102008038071A1 (en) | 2008-08-16 | 2010-02-18 | Clariant International Limited | Anionic water- and solvent-soluble additives |
CA2747990A1 (en) | 2008-12-29 | 2010-07-08 | Basf Se | Hyperbranched polyesters and polycarbonates as demulsifiers for splitting crude oil emulsions |
DE102009019177A1 (en) * | 2009-04-28 | 2010-11-11 | Clariant International Ltd. | Use of biodegradable alkoxylated (meth) acrylate copolymers as crude oil emulsion breakers |
DE102009019179A1 (en) * | 2009-04-28 | 2010-11-11 | Clariant International Ltd. | Alkoxylated (meth) acrylate polymers and their use as crude oil emulsion breakers |
DE102009040495B4 (en) | 2009-09-08 | 2014-02-13 | Clariant International Ltd. | Alkoxylated thiacalixarenes and their use as crude oil emulsion breakers |
US20170189832A1 (en) | 2014-05-28 | 2017-07-06 | Basf Se | Coated mesh and its use for oil-water separation |
US20170203235A1 (en) | 2014-05-28 | 2017-07-20 | Basf Se | Mesh comprising a surface of hydrated aluminum oxides and their use for oil-water separation |
CN105968369A (en) * | 2016-05-26 | 2016-09-28 | 句容宁武高新技术发展有限公司 | Synthetic method for low-temperature efficient demulsifier |
WO2018108700A1 (en) | 2016-12-16 | 2018-06-21 | Basf Se | Coated meshes and their use, especially for oil-water separation |
US11518948B1 (en) | 2021-08-23 | 2022-12-06 | Saudi Arabian Oil Company | Methods for breaking emulsions |
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CA1010740A (en) * | 1973-02-09 | 1977-05-24 | Billy R. Moreland | Polyhydric substituted polyethylene backbone emulsion breaker |
US4141854A (en) * | 1977-05-31 | 1979-02-27 | Nalco Chemical Company | Emulsion breaking |
US4230844A (en) * | 1978-09-28 | 1980-10-28 | E. I. Du Pont De Nemours And Company | Processes for the preparation of polymeric thickeners and uses thereof |
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-
1986
- 1986-10-18 DE DE19863635489 patent/DE3635489A1/en not_active Withdrawn
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1987
- 1987-10-16 DE DE8787115126T patent/DE3783313D1/en not_active Expired - Lifetime
- 1987-10-16 EP EP87115126A patent/EP0264841B1/en not_active Expired - Lifetime
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CA1309552C (en) | 1992-10-27 |
EP0264841B1 (en) | 1992-12-30 |
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