NO140992B - WATER DISTRIBUTIONS OF REINFORCED NATURAL RESIN AND DISPENSER FOR USE IN PAPER Gluing - Google Patents
WATER DISTRIBUTIONS OF REINFORCED NATURAL RESIN AND DISPENSER FOR USE IN PAPER Gluing Download PDFInfo
- Publication number
- NO140992B NO140992B NO742757A NO742757A NO140992B NO 140992 B NO140992 B NO 140992B NO 742757 A NO742757 A NO 742757A NO 742757 A NO742757 A NO 742757A NO 140992 B NO140992 B NO 140992B
- Authority
- NO
- Norway
- Prior art keywords
- resin
- parts
- approx
- water
- reinforced
- Prior art date
Links
- 238000004026 adhesive bonding Methods 0.000 title claims description 20
- 239000000025 natural resin Substances 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 52
- 239000011347 resin Substances 0.000 claims description 194
- 229920005989 resin Polymers 0.000 claims description 194
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 56
- 229920000768 polyamine Polymers 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 34
- -1 poly(diallylamine) Polymers 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 239000000057 synthetic resin Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 51
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- 238000004519 manufacturing process Methods 0.000 description 19
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- 239000003960 organic solvent Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
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- 239000003054 catalyst Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 244000037364 Cinnamomum aromaticum Species 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 239000004743 Polypropylene Substances 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
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- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- JOXWSDNHLSQKCC-UHFFFAOYSA-N ethenesulfonamide Chemical compound NS(=O)(=O)C=C JOXWSDNHLSQKCC-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- HYSQEYLBJYFNMH-UHFFFAOYSA-N n'-(2-aminoethyl)-n'-methylethane-1,2-diamine Chemical compound NCCN(C)CCN HYSQEYLBJYFNMH-UHFFFAOYSA-N 0.000 description 2
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 2
- DPXZYPCARKJGQV-UHFFFAOYSA-N n'-[2-[2-aminoethyl(methyl)amino]ethyl]-n'-methylethane-1,2-diamine Chemical compound NCCN(C)CCN(C)CCN DPXZYPCARKJGQV-UHFFFAOYSA-N 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
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- 102000004169 proteins and genes Human genes 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- OIFAHDAXIUURLN-UHFFFAOYSA-N 2-(fluoromethyl)oxirane Chemical compound FCC1CO1 OIFAHDAXIUURLN-UHFFFAOYSA-N 0.000 description 1
- AGIBHMPYXXPGAX-UHFFFAOYSA-N 2-(iodomethyl)oxirane Chemical compound ICC1CO1 AGIBHMPYXXPGAX-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- GCZWLZBNDSJSQF-UHFFFAOYSA-N 2-isothiocyanatohexane Chemical compound CCCCC(C)N=C=S GCZWLZBNDSJSQF-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- RJFAYQIBOAGBLC-BYPYZUCNSA-N Selenium-L-methionine Chemical compound C[Se]CC[C@H](N)C(O)=O RJFAYQIBOAGBLC-BYPYZUCNSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- KDKJYYNXYAZPIK-UHFFFAOYSA-J aluminum potassium disulfate hydrate Chemical compound O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KDKJYYNXYAZPIK-UHFFFAOYSA-J 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 125000002704 decyl group Chemical group [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])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XPXMKIXDFWLRAA-UHFFFAOYSA-N hydrazinide Chemical compound [NH-]N XPXMKIXDFWLRAA-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 239000004297 potassium metabisulphite Substances 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 125000004079 stearyl 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])C([H])([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
- 238000003860 storage Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 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
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/62—Rosin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2393/00—Characterised by the use of natural resins; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Colloid Chemistry (AREA)
Description
Oppfinnelsen angår nye typer vandige dispersjoner av "forsterket" naturharpiks. Spesielt omhandler oppfinnelsen vandige dispersjoner som består i det vensentlige av finfordelte forsterkede naturharpikspartikler, et vannoppløselig kationisk dispergeringsmiddel for de finfordelte harpikspartikler, samt vann. Dispergeringsmidlet skal beskrives mer detaljert i det følgende. De nye typer forsterkede naturharpiksdispersjoner ifølge oppfinnelsen brukes til liming av papir. The invention relates to new types of aqueous dispersions of "reinforced" natural resin. In particular, the invention relates to aqueous dispersions which consist essentially of finely divided reinforced natural resin particles, a water-soluble cationic dispersant for the finely divided resin particles, and water. The dispersant will be described in more detail below. The new types of reinforced natural resin dispersions according to the invention are used for gluing paper.
Masseliming av papir med naturharpiks (i det følgende Mass gluing of paper with natural resin (in the following
bare kalt harpiks) diskuteres av Casey i "Pulp and Paper", simply called resin) is discussed by Casey in "Pulp and Paper",
annen utgave, bind II: Papermaking, kapittel XIII, side 1043-1066. second edition, volume II: Papermaking, chapter XIII, pages 1043-1066.
På side 1048 omtaler Casey lim av forsterket naturharpiks og sier at disse harpikslim fremstilles ved å omsette maleinsyreanhydrid eller andre dienolfile forbindelser med harpiks for økning av antall karboksylsyregrupper. Casey hevder også at et typisk forsterket harpikslim kan inneholde ca. 1-30% maleopimarsyreanhydrid. On page 1048, Casey mentions reinforced natural resin adhesives and says that these resin adhesives are prepared by reacting maleic anhydride or other dienolphilic compounds with resin to increase the number of carboxylic acid groups. Casey also claims that a typical reinforced resin adhesive can contain approx. 1-30% maleopimaric anhydride.
På side 1047 nevner Casey under overskriften "Free Rosin Size" (lim med fri harpiks) at de innbyrdes fordeler med lim inneholdende store mengder fri harpiks og med lite innhold av fri harpiks, har vært et stridsspørsmål i mange år, men at det nå i alminnelighet godtas at et lim med stort innhold av fri harpiks gir bedre liming og krever mindre lim. On page 1047 Casey mentions under the heading "Free Rosin Size" that the relative merits of adhesives containing large amounts of free rosin and those with a low content of free rosin have been a matter of contention for many years, but that now in it is generally accepted that an adhesive with a high content of free resin provides better bonding and requires less adhesive.
På side 1050 under overskriften "Protected Rosin Size" On page 1050 under the heading "Protected Rosin Size"
(lim med beskyttet harpiks) nevner Casey at ved å benytte et beskyttende kolloid kan man fremstille meget stabile limtyper inneholdende opptil 90% fri harpiks. På side 1051 omtaler Casey "Bewoid"-metoden for fremstilling av harpikslim med høyt innhold av fri harpiks, og hevder at "Bewoid"-limet slik det (glue with protected resin) Casey mentions that by using a protective colloid, very stable types of glue containing up to 90% free resin can be produced. On page 1051, Casey discusses the "Bewoid" method of making resin adhesives with a high free resin content, and claims that the "Bewoid" adhesive as it
fremstilles på vanlig måte, inneholder ca. 90% fri harpiks dispergert i en liten mengde harpikssåpe og stabilisert ved hjelp av ca. 2% kasein eller annet protein. Kaseinet brukes som beskyttelseskolloid for å hindre vekst av harpikspartikler, for slik å holde dem i fin fordeling. is produced in the usual way, contains approx. 90% free resin dispersed in a small amount of resin soap and stabilized using approx. 2% casein or other protein. The casein is used as a protective colloid to prevent the growth of resin particles, in order to keep them in a fine distribution.
På side 1051 og 1052 omtaler Casey "Prosize"-metoden On pages 1051 and 1052, Casey discusses the "Prosize" method
for fremstilling av et beskyttet lim med stort innhold av fri harpiks. Harpikspartiklene hindres fra å vokse til større aggre-gater ved å tilsette et overflateaktivt protein som soyabønne-protein. for the production of a protected adhesive with a high content of free resin. The resin particles are prevented from growing into larger aggregates by adding a surface-active protein such as soybean protein.
Tysk patent nr. 1.131.348 hevder at lim av fri harpiks German Patent No. 1,131,348 claims that glue of free resin
er dispersjoner av uforsåpede kunstharpikssyrer med en viss prosent naturharpikssåpe. Det nevnes også at dispersjonene fremstilles etter en spesiell metode, at de vanligvis brukes med et innhold av fri harpiks på 60-9 5%, og ved siden av harpiks inneholder emulgatorer og stabilisatorer som stearater, trietanol-amin, kasien og voks. are dispersions of unsaponified synthetic resin acids with a certain percentage of natural resin soap. It is also mentioned that the dispersions are produced according to a special method, that they are usually used with a free resin content of 60-95%, and next to resin contain emulsifiers and stabilizers such as stearates, triethanolamine, cassia and wax.
I henhold til tysk patent nr. 1.131.348 har forsterkede harpikser hittil ikke vært egnet for fremstilling av dispersjoner, siden de for det meste har for høyt smeltepunkt og har en tendens til krystallisering, eller under dispergering danner fine skorper som fører til sedimentering. Det tyske patent beskriver og hevder beskyttelse for et papirlim og en fremgangsmåte for fremstilling av et papirlim i form av en vandig dispersjon med høyt innhold av fri harpiks, ut fra forsterket harpiks, karakterisert ved at den forsterkede harpiks er blandet med fettsyrer, fettsyreblandinger og/eller naftensyrer, ved forhøyet temperatur, og at dispersjonen utføres på kjent måte. According to German Patent No. 1,131,348, reinforced resins have so far not been suitable for the production of dispersions, since they mostly have too high a melting point and tend to crystallize, or during dispersion form fine crusts leading to sedimentation. The German patent describes and claims protection for a paper glue and a method for producing a paper glue in the form of an aqueous dispersion with a high content of free resin, from reinforced resin, characterized in that the reinforced resin is mixed with fatty acids, fatty acid mixtures and/ or naphthenic acids, at an elevated temperature, and that the dispersion is carried out in a known manner.
US-patent nr. 3.565.755 beskriver en i det vesentlige homogen, stabil, vandig suspensjon av finfordelt harpiksbasert materiale. Harpiksmaterialet kan være forsterket i sin helhet, eller kan være en blanding inneholdende forsterket harpiks. En meget liten mengde av harpiksforbindelsen er forsåpet. og virker som dispergeringsmiddel for harpikspartiklene. Denne sammenset-ning som inneholder vesentlig harpiksmateriale, forsåpet harpiks og vann, brukes for liming av papir. Limtypen beskrevet i dette patent inneholder en stor mengde fri harpiks siden den bare inneholder en meget liten mengde forsåpet harpiks. Videre har blandingen god stabilitet (lang lagringslevetid) og krever ikke de stabilisatorer som hittil har vært tilsatt til stabile lim inneholdende store mengder fri harpiks som f.eks. kasien og soyabønneprotein. US Patent No. 3,565,755 describes a substantially homogeneous, stable, aqueous suspension of finely divided resin-based material. The resin material can be reinforced in its entirety, or can be a mixture containing reinforced resin. A very small amount of the resin compound is saponified. and acts as a dispersant for the resin particles. This composition, which contains essential resin material, saponified resin and water, is used for gluing paper. The type of adhesive described in this patent contains a large amount of free resin since it contains only a very small amount of saponified resin. Furthermore, the mixture has good stability (long storage life) and does not require the stabilizers that have so far been added to stable adhesives containing large amounts of free resin such as e.g. cassia and soybean protein.
Til slutt skal nevnes norsk patent nr. 127.6 76 som beskriver et materiale fremstilt med et naturharpikssåpedisperger-ingsmiddel hvortil det er satt en vannoppløselig kationisk aminopolyamid/epiklorhydrinharpiks. Denne sistnevnte harpiks tilsettes imidlertid ikke som dispergeringsmiddel, men for å oppnå god limingseffektivitet ved generelt nøytrale pH-verdier. Finally, mention should be made of Norwegian patent no. 127.6 76, which describes a material produced with a natural resin soap dispersant to which a water-soluble cationic aminopolyamide/epichlorohydrin resin has been added. However, this latter resin is not added as a dispersant, but to achieve good gluing efficiency at generally neutral pH values.
I henhold til oppfinnelsen tilveiebringes vandige dispersjoner av forsterket naturharpiks for liming av papir. De vandige dispersjoner i henhold til oppfinnelsen har god stabilitet og krever ikke tilsetning av harpikssåpe eller såpe av forsterket harpiks. I tillegg krever de vandige dispersjoner ifølge oppfinnelsen ikke bruk av stabilisatorer som hittil har vær anvendt for fremstilling av harpikslim med høyt innhold av fri harpiks. According to the invention, aqueous dispersions of reinforced natural resin are provided for gluing paper. The aqueous dispersions according to the invention have good stability and do not require the addition of resin soap or reinforced resin soap. In addition, the aqueous dispersions according to the invention do not require the use of stabilizers which have hitherto been used for the production of resin adhesives with a high content of free resin.
Oppfinnelsen angår således vandige dispersjoner av forsterket naturharpiks og dispergeringsmiddel til bruk ved liming av papir, og disse dispersjoner karakteriseres ved at de på vektbasis inneholder (A) fra 5-50% forsterket uforsåpet harpiks og (B) fra 0,5-10% vannoppløselig dispergeringsmiddel av kationisk syntetisk harpiks, hvor komponent (B) velges blant (1) en vann-oppløselig polyaminopolyamid/epiklorhydrinha.rpiks, (2) en vannopp-løselig alkylenpolyamin/epiklorhydrinharpiks eller (3) en vannopp-løselig poly(diallylamin)/epiklorhydrinharpiks. The invention thus concerns aqueous dispersions of reinforced natural resin and dispersing agent for use in gluing paper, and these dispersions are characterized by the fact that they contain, on a weight basis, (A) from 5-50% reinforced unsaponified resin and (B) from 0.5-10% water-soluble cationic synthetic resin dispersant, wherein component (B) is selected from (1) a water-soluble polyaminopolyamide/epichlorohydrin resin, (2) a water-soluble alkylene polyamine/epichlorohydrin resin, or (3) a water-soluble poly(diallylamine)/epichlorohydrin resin .
Den forsterkede harpiks kan drøyes om ønsket, ved hjelp av kjente drøyningsmidler som voks (særlig parafinvoks eller mikrokrystallinsk voks), hydrokarbonharpikser som f.eks. avledet av jordoljehydrokarboner og terpener o.l. Dette oppnås ved å blande den forsterkede harpiks med 10-100 vekt-% drøyningsmiddel, basert på vekten av forsterket harpiks. The reinforced resin can be drawn, if desired, using known drawing agents such as wax (especially paraffin wax or microcrystalline wax), hydrocarbon resins such as e.g. derived from petroleum hydrocarbons and terpenes etc. This is achieved by mixing the reinforced resin with 10-100% by weight of wetting agent, based on the weight of reinforced resin.
Man kan også bruke blandinger av forsterket harpiks og ren harpiks og blandinger av forsterket harpiks, harpiks og harpiksdrøyningsmiddel. Mixtures of reinforced resin and pure resin and mixtures of reinforced resin, resin and resin draining agent can also be used.
Blandinger av forsterket harpiks og harpiks vil inneholde 25-95% forsterket harpiks og 75-5% harpiks. Blandinger av forsterket harpiks, harpiks og harpiksdrøyningsmiddel kan inneholde 25-45% forsterket harpiks, 5-50% harpiks og 5-50% harpiksdrøy-ningsmiddel . Reinforced resin and resin mixtures will contain 25-95% reinforced resin and 75-5% resin. Mixtures of reinforced resin, resin and resin draining agent can contain 25-45% reinforced resin, 5-50% resin and 5-50% resin draining agent.
For fremstilling av vandige forsterkede harpiksdispersjo-ner i henhold til oppfinnelsen, blir den forsterkede harpiks (inklusive drøyningsmiddel eller ren harpiks, eller begge, hvis disse benyttes) først oppløst i et ikke-vannblandbart organisk oppløsningsmiddel som f.eks. benzen, xylen, kloroform eller 1,2-diklorpropan. Blandinger av to eller flere oppløsningsmidler kan brukes om ønsket. Det valgte oppløsningsmiddel skal heller ikke reagere med bestanddelene i dispersjonen. For the production of aqueous reinforced resin dispersions according to the invention, the reinforced resin (including draining agent or pure resin, or both, if these are used) is first dissolved in a non-water-miscible organic solvent such as e.g. benzene, xylene, chloroform or 1,2-dichloropropane. Mixtures of two or more solvents may be used if desired. The chosen solvent must also not react with the components of the dispersion.
Oppløsningen av organisk oppløsningsmiddel og forsterket harpiks blir derpå blandet med en vandig oppløsning av et kationisk harpiksdispergerende middel til en emulsjon som er i det vesentlige ustabil, og hvori oppløsningen av organisk oppløs-ningsmiddel/forsterket harpiks danner den dispergerte fase. Den i det vesentlige ustabile vandige emulsjon gjennomgår derpå behandling under ekstreme skjærkrefter under dannelse av en i det vesentlige stabil vandig emulsjon. Behandlingen under ekstreme skjærkrefter oppnås med fordel ved hjelp av en homogenisator. Ved å passere i det minste en gang gjennom homogenisatoren under et trykk på fra 70-560 kg/cm 2, vil den ustabile vannemulsjon gå over til en i det vesentlige stabil emulsjon. Derpå fjernes det organiske oppløsningsmiddel fra emulsjonen, og man får en i det vesentlige stabil vandig dispersjon av forsterket harpiks. The organic solvent and reinforced resin solution is then mixed with an aqueous solution of a cationic resin dispersant to form an emulsion which is substantially unstable, and in which the organic solvent/reinforced resin solution forms the dispersed phase. The substantially unstable aqueous emulsion then undergoes treatment under extreme shear forces to form a substantially stable aqueous emulsion. The treatment under extreme shear forces is advantageously achieved with the aid of a homogeniser. By passing at least once through the homogenizer under a pressure of from 70-560 kg/cm 2 , the unstable water emulsion will change to a substantially stable emulsion. The organic solvent is then removed from the emulsion, and a substantially stable aqueous dispersion of reinforced resin is obtained.
Den vandige forsterkede harpiksdispersjon ifølge oppfinnelsen kan fremstilles etter omvendingsmetoden som vist i eksempel 16. Oppløsningen av forsterket harpiks/organisk-oppløs-ningsmiddel blandes med en vandig oppløsning av kationeharpiks-dispergeringsmiddel i tilstrekkelig mengde til at det dannes en stabil vann-i-olje-emulsjon som derpå omvendes til en stabil olje-i-vann-emulsjon ved hurtig tilsetning av vann under kraftig omrøring. Det organiske oppløsningsmiddel blir derpå fjernet ved destillasjon under nedsatt trykk. The aqueous reinforced resin dispersion according to the invention can be prepared according to the inversion method as shown in example 16. The solution of reinforced resin/organic solvent is mixed with an aqueous solution of cationic resin dispersant in sufficient quantity to form a stable water-in-oil- emulsion which is then converted into a stable oil-in-water emulsion by rapid addition of water under vigorous stirring. The organic solvent is then removed by distillation under reduced pressure.
Den type (natur)-harpiks som brukes for fremstilling av de forsterkede harpikser i henhold til oppfinnelsen, kan være en hvilken som helst markedsført type naturhcirpiks som f.eks. treharpiks, naturgummiharpiks, talloljeharpiks eller blandinger av to eller flere av disse, i rå eller raffinert tilstand. Delvis eller fullhydrogenerte harpikser og polymeriserte harpikser, samt harpikser som er behandlet for å hindre krystallisasjon, f.eks. ved varmebehandling eller formaldehydomsetning, kan også brukes. The type of (natural) resin used for the production of the reinforced resins according to the invention can be any marketed type of natural resin such as e.g. wood resin, natural rubber resin, tall oil resin or mixtures of two or more of these, in the crude or refined state. Partially or fully hydrogenated resins and polymerized resins, as well as resins that have been treated to prevent crystallization, e.g. by heat treatment or formaldehyde conversion, can also be used.
Den forsterkede harpiks som brukes, er adduktreaksjons-produktet mellom harpiksen og en syreforbindelse som inneholder The reinforced resin used is the adduct reaction product between the resin and an acid compound containing
-^C=C-C=0-gruppen, og fremstilles ved å omsette harpiksen og -^C=C-C=0 group, and is produced by reacting the resin and
11 o syreforbindelsen ved forhøyet temperatur på ca. 150-210 C. 11 o the acid compound at an elevated temperature of approx. 150-210 C.
Den anvendte mengde syreforbindelse velges slik at man får en forsterket harpiks inneholdende fra 1-12 vekt-% addukt-syreforbindelse basert på vekten av forsterket harpiks. Frem-gangsmåter for fremstilling av forsterket harpiks beskrives i US-patent nr. 2.628.918 og 2.684.300. The amount of acid compound used is chosen so that a reinforced resin is obtained containing from 1-12% by weight of adduct acid compound based on the weight of reinforced resin. Methods for the production of reinforced resin are described in US Patent Nos. 2,628,918 and 2,684,300.
Eksempler på syreforbindelser inneholdende J^"C=C-C=0- Examples of acid compounds containing J^"C=C-C=0-
i gruppen og som kan brukes for fremstilling av forsterket harpiks, omfatter a-3-umettet organiske syrer og deres tilgjengelige anhydrider, spesielle eksempler er fumarsyre, maleinsyre, akrylsyre, maleinsyreanhydrid, itakonsyre, itakonsyreanhydrid, citra-konsyre og citrakonsyreanhydrid. Man kan bruke syreblandinger for fremstilling av den forsterkede harpiks, om ønsket. Videre kan man bruke blandinger av forskjellige forsterkede harpikser, om ønsket. Således kan f.eks. en blanding av et akrylsyreaddukt av harpiksen og fumarysreadduktet brukes for fremstilling av de nye dispersjoner ifølge oppfinnelsen. Også forsterkede harpikser som er i det vensetlige fullhydrogenerte etter adduktdannelsen, kan brukes. in the group and which can be used for the production of reinforced resin, include α-3-unsaturated organic acids and their available anhydrides, particular examples are fumaric acid, maleic acid, acrylic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride. Acid mixtures can be used for the production of the reinforced resin, if desired. Furthermore, mixtures of different reinforced resins can be used, if desired. Thus, e.g. a mixture of an acrylic acid adduct of the resin and the fumary red adduct is used for the production of the new dispersions according to the invention. Reinforced resins which are essentially fully hydrogenated after adduct formation can also be used.
Hvis harpiksen (dvs. den uforsterkede harpiks) brukes If the resin (ie the unreinforced resin) is used
i kombinasjon med forsterket harpiks, kan førstnevnte være en hvilken som helst type tilgjengelig (natur)-harpiks, som f.eks. treharpiks, gummiharpiks, talloljeharpiks eller blandinger av disse i rå eller eller raffinert form. Delvis eller fullstendig hydrogenerte harpikser og polymeriserte harpikser kan også brukes, det samme gjelder harpikser som er behandlet for å hindre krystallisasjon ved f.eks. varmebehandling eller formaldehydomsetning. in combination with reinforced resin, the former can be any type of available (natural) resin, such as e.g. wood resin, gum resin, tall oil resin or mixtures of these in crude or refined form. Partially or fully hydrogenated resins and polymerized resins can also be used, as can resins that have been treated to prevent crystallization by e.g. heat treatment or formaldehyde conversion.
De dispersjonsmidler som brukes for fremstilling av stabile vandige dispersjoner ifølge oppfinnelsen-, er kationiske polymerharpiksforbindelser som er vannoppløselige. The dispersants used for the production of stable aqueous dispersions according to the invention are cationic polymer resin compounds which are water-soluble.
Spesielt gunstige dispersjonsmidler er kationiske termo-herdende, vannoppløselige harpikser av aminopolyamid/epiklorhydrin, beskrevet i US-patent nr. 2.926.116 og 2.926.154. Disse harpikser er vannoppløselige pblymerreaksjonsprodukter av epiklorhydrin og aminopolyamid. Aminopolyamider fremstilles ved reaksjon mellom en dikarboksylsyre og et polyalkylenpolyamin i et molforhold polyalkylenpolyamin/dikarboksylsyre på fra 0,8:1 til 1,4:1. Particularly favorable dispersants are cationic thermosetting, water-soluble aminopolyamide/epichlorohydrin resins, described in US Patent Nos. 2,926,116 and 2,926,154. These resins are water-soluble polymer reaction products of epichlorohydrin and aminopolyamide. Aminopolyamides are produced by reaction between a dicarboxylic acid and a polyalkylene polyamine in a polyalkylene polyamine/dicarboxylic acid molar ratio of from 0.8:1 to 1.4:1.
Særlig gunstige dikarboksylsyrer er diglykolsyre og mett-ede alifatiske dikarboksylsyrer med fra 3-10 C-atomer, som f.eks. malonsyre, ravsyre, glutarsyre, adipinsyre, pimelinsyre, suberin-syre, azelainsyre og sebasinsyre. Particularly favorable dicarboxylic acids are diglycolic acid and saturated aliphatic dicarboxylic acids with from 3 to 10 C atoms, such as e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
Andre egnede dikarboksylsyrer er tereftalsyre, isoftalsyre, ftalsyre, maleinsyre, fumarsyre, itakonsyre, glutakonsyre, citra-konsyre og mesakonsyre. Other suitable dicarboxylic acids are terephthalic acid, isophthalic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, glutaconic acid, citraconic acid and mesaconic acid.
De tilgjengelige anhydrider av ovennevnte syrer kan brukes for fremstilling av vannoppløselige aminopolyamider, det samme gjelder estere av disse syrer. Blandinger av to eller flere dikarboksylsyrer, deres anhydrider og estere kan brukes for fremstilling av vannoppløselige aminopolyamider, om ønsket. The available anhydrides of the above-mentioned acids can be used for the production of water-soluble aminopolyamides, as can esters of these acids. Mixtures of two or more dicarboxylic acids, their anhydrides and esters can be used for the preparation of water-soluble aminopolyamides, if desired.
Det kan benyttes en rekke polyalkylenpolyaminer, inklusive polyetylenpolyaminer, polypropylenpolyaminer, polybutylenpolyaminer o.l. Polyalkylenpolyaminer kan foreligge som polyaminer hvor nitrogenatomene er bundet sammen ved hjelp av grupper med formelen ~cnH2n-/ ^vor n er et lite tall større enn 1, og antal-let slike grupper i molekylet utgjør fra 2 og opptil ca. 8. Nitrogenatomene kan være bundet til nabokarbonatomer i gruppen ~cnH2n~ eller til fjernere karbonatomer, men ikke til samme karbonatom. Polyaminer som dietylentriamin, trietylentetramin, tetraetylenpentamin og dipropylentriamin, som kan fremstilles i temmelig ren form, er egnet for fremstilling av vannoppløselige aminopolyamider. Andre polyalkylenpolyaminer som kan brukes, er metyl-bis-(3-aminopropyl)amin, metyl-bis-(2-aminoetyl)amin og 4,7-dimetyltrietylentetramin. Blandinger av polyalkylenpolyaminer kan også- brukes, om ønsket. A number of polyalkylene polyamines can be used, including polyethylene polyamines, polypropylene polyamines, polybutylene polyamines and the like. Polyalkylene polyamines can exist as polyamines where the nitrogen atoms are bound together by means of groups with the formula ~cnH2n-/ ^where n is a small number greater than 1, and the number of such groups in the molecule is from 2 and up to approx. 8. The nitrogen atoms can be bonded to neighboring carbon atoms in the group ~cnH2n~ or to more distant carbon atoms, but not to the same carbon atom. Polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and dipropylenetriamine, which can be produced in fairly pure form, are suitable for the production of water-soluble aminopolyamides. Other polyalkylene polyamines that can be used are methyl-bis-(3-aminopropyl)amine, methyl-bis-(2-aminoethyl)amine and 4,7-dimethyltriethylenetetramine. Mixtures of polyalkylene polyamines can also be used, if desired.
Avstanden mellom aminogrupper på aminopolyamidet kan The distance between amino groups on the aminopolyamide can
økes om ønsket. Dette kan oppnås ved å substituere et diamin som etylendiamin, propylendiamin, heksametylendiamin o.l. i stedet for en del av polyalkylenpolyaminet. For dette formål kan opptil ca. 80% av polyalkylenpolyaminet erstattes med en molekvivalent mengde diamin. Vanligvis vil en erstatning på can be increased if desired. This can be achieved by substituting a diamine such as ethylenediamine, propylenediamine, hexamethylenediamine and the like. instead of a portion of the polyalkylene polyamine. For this purpose, up to approx. 80% of the polyalkylene polyamine is replaced with a molar equivalent amount of diamine. Usually a replacement will on
ca. 50% eller mindre være tilstrekkelig. about. 50% or less will be sufficient.
Temperaturene ved omsetning mellom dikarboksylsyren og polyalkylenpolyaminet kan variere fra 110-250°C eller høyere, The temperatures during reaction between the dicarboxylic acid and the polyalkylene polyamine can vary from 110-250°C or higher,
ved atmosfæretrykk. For de fleste formål foretrekkes tempera- at atmospheric pressure. For most purposes, tempera-
turer mellom 160 og 210°C. Reaksjonstiden vil variere fra ca. \~ 2 timer, ved vanlig omsetning. Reaksjonstiden varierer i omvendt forhold med anvendt reaksjonstemperatur. trips between 160 and 210°C. The reaction time will vary from approx. \~ 2 hours, with normal turnover. The reaction time varies inversely with the reaction temperature used.
Ved utførelse av omsetningen foretrekkes det å bruke en tilstrekkelig mengde dikarboksylsyre til at denne kan reagere i det vesentlige fullstendig med de primære amingrupper i polyalkylenpolyaminet, men utilstrekkelig til å reagere med sekun-dære amingrupper og/eller tertiære amingrupper i noen vesentlig grad. Dette krever vanligvis et molforhold mellom polyalkylenpolyamin og dikarboksylsyrer på fra 0,9:1 til 1,2:1. Imidlertid kan man bruke molforhold på fra 0,8:1 til 1,4:1. Aminopolyamidet fremstilt som ovenfor beskrevet, omsettes med epiklorhydrin ved en temperatur på fra 45-100°C, fortrinnsvis mellom 45 og 70°C, inntil viskositeten for en 20%-ig oppløsning i vann ved 25°C har nådd over avlesningen C eller høyere på Gardner-Holdt-skalaen. Denne omsetning foretas med fordel i vandig oppløsning for å dempe reaksjonen. Innstilling av pH-verdien er vanligvis ikke nødvendig. Siden imidlertid denne vil synke under polymerisa-sjonsfasen, kan det være ønskelig i enkelte tilfelle å tilsette alkali som binder i det minste en del av den dannede syre. Når den ønskede viskositet er nådd, kan man tilsette vann for å regulere tørrstoffinnholdet til ønsket nivå, vanligvis fra 2-50%. When carrying out the reaction, it is preferred to use a sufficient amount of dicarboxylic acid so that it can react essentially completely with the primary amine groups in the polyalkylene polyamine, but insufficient to react with secondary amine groups and/or tertiary amine groups to any significant extent. This usually requires a molar ratio of polyalkylene polyamine to dicarboxylic acids of from 0.9:1 to 1.2:1. However, molar ratios of from 0.8:1 to 1.4:1 can be used. The aminopolyamide prepared as described above is reacted with epichlorohydrin at a temperature of from 45-100°C, preferably between 45 and 70°C, until the viscosity of a 20% solution in water at 25°C has reached above the reading C or higher on the Gardner-Holdt scale. This conversion is advantageously carried out in aqueous solution to dampen the reaction. Setting the pH value is usually not necessary. However, since this will decrease during the polymerization phase, it may be desirable in some cases to add alkali that binds at least part of the acid formed. When the desired viscosity is reached, water can be added to regulate the solids content to the desired level, usually from 2-50%.
Ved omsetningen mellom aminopolyamid og epiklorhydrin, kan man oppnå tilfredsstillende resultater ved å bruke fra 0,1 mol til 2 mol epiklorhydrin for hver sekundær eller tertiær aminogruppe på aminopolyamidet, fortrinnsvis 1-1,5 mol epiklorhydrin. In the reaction between aminopolyamide and epichlorohydrin, satisfactory results can be obtained by using from 0.1 mol to 2 mol epichlorohydrin for each secondary or tertiary amino group on the aminopolyamide, preferably 1-1.5 mol epichlorohydrin.
Et monofunksjonelt alkyleringsmiddel kan benyttes som tilleggsreaktant ved utførelse av ovenstående reaksjon, om ønsket. Et monofunksjonelt alkyleringsmiddel kan først omsettes med aminopolyamidet, fulgt av omsetning av aminopolyamidalkyler-ingsmiddel-reaksjonsproduktet med epiklorhydrin, eller alkyler-ingsmidlet kan omsettes med aminopolyamid/epiklorhydrinet. Således kan f.eks. epiklorhydrinet settes til en vandig oppløsning av aminopolyamidet ved en temperatur fra 45-55°C. Reaksjonsblandingen oppvarmes til en temperatur på mellom 50 og 100°C, fortrinnsvis 60-80°C, avhengig av den ønskede reaksjonshastighet. Etter et egnet tidsrom ved denne temperatur, fra 10-100 min, og fortrinnsvis inntil viskositeten for en ca. 25%-ig oppløsning av reaksjonsblandingen ved 25°C ligger på avlesningen A til B på Gardner-Holdt-skalaen, på dette tidspunkt vil mesteparten av epoksygruppene på epiklorhydrinet ha reagert med aminopolyamidets amingrupper, et monofunksjonelt alkyleringsmiddel tilsettes og reaksjonsblandingen oppvarmes, fortrinnsvis ved en temperatur på 60°C til 80°C, inntil viskositeten for en ca. 25%-ig oppløsning ved 25°C ligger på minst skalaavlesning A, fortrinnsvis minst avlesning B til C på Gardner-Holdt-skalaen. Forholdet mellom tørrstoffinnhold (konsentrasjon) og viskositet kan man finne ved direkte omsetning ved 25%-nivået fulgt av fortynning til 25% tørrstoff, eller omsetning ved lavere tørrstoffinnhold fulgt av en konsentrasjon ved mindre enn 40°C og under redusert trykk til 2 5% konsentrasjon. Lavere alkylestere av mineralsyrer som halo-genider, sulfater og fosfater, substituerte alkylhalogenider o.l., er egnede monofunksjonelle alkyleringsmidler. Illustrerende forbindelser som kan brukes, er dimetyl-, dietyl- og dipropylsulfat, metylklorid, metyljodid, etyljodid, metylbromid, propylbromid og mono-, di- eller trimetyl-, -etyl- og -propylfosfater. Visse aromatiske forbindelser som benzylklorid og metyl-p-toluensulfo-nat kan brukes. Man kan med fordel bruke fra 0,1-0,9 mol monofunksjonelt alkyleringsmiddel for hver aminogruppe. A monofunctional alkylating agent can be used as an additional reactant when carrying out the above reaction, if desired. A monofunctional alkylating agent may first be reacted with the aminopolyamide, followed by reaction of the aminopolyamide alkylating agent reaction product with epichlorohydrin, or the alkylating agent may be reacted with the aminopolyamide/epichlorohydrin. Thus, e.g. the epichlorohydrin is added to an aqueous solution of the aminopolyamide at a temperature of 45-55°C. The reaction mixture is heated to a temperature of between 50 and 100°C, preferably 60-80°C, depending on the desired reaction rate. After a suitable period of time at this temperature, from 10-100 min, and preferably until the viscosity of an approx. 25% solution of the reaction mixture at 25°C is on the reading A to B on the Gardner-Holdt scale, at this point most of the epoxy groups on the epichlorohydrin will have reacted with the amine groups of the aminopolyamide, a monofunctional alkylating agent is added and the reaction mixture is heated, preferably at a temperature of 60°C to 80°C, until the viscosity for an approx. 25% resolution at 25°C is at least scale reading A, preferably at least reading B to C on the Gardner-Holdt scale. The relationship between dry matter content (concentration) and viscosity can be found by direct reaction at the 25% level followed by dilution to 25% dry matter, or reaction at lower dry matter content followed by concentration at less than 40°C and under reduced pressure to 2 5% concentration. Lower alkyl esters of mineral acids such as halides, sulphates and phosphates, substituted alkyl halides and the like are suitable monofunctional alkylating agents. Illustrative compounds which may be used are dimethyl, diethyl and dipropyl sulfate, methyl chloride, methyl iodide, ethyl iodide, methyl bromide, propyl bromide and mono-, di- or trimethyl-, -ethyl- and -propyl phosphates. Certain aromatic compounds such as benzyl chloride and methyl p-toluenesulfonate can be used. One can advantageously use from 0.1-0.9 mol of monofunctional alkylating agent for each amino group.
I de følgende eksempler er alle mengdeforhold og pro-sentangivelser på vektbasis hvor intet annet er oppført. Limings-resultatene er nevnt i enkelte av eksemplene. Limingsresultåtene bestemmes på en "Hercules Sizing Tester". Limingsprøvene måler motstanden hos et limt papirark for gjennomtrengning av en prøve-oppløsning nr. 2 (en vandig oppløsning av 1,0% maursyre og 1,25% naftolgrønt B, vektbasis). Den nødvendige tid som medgår for at blekket skal redusere lysrefleksjonen enten 80 eller 85% In the following examples, all quantities and percentages are on a weight basis where nothing else is listed. The gluing results are mentioned in some of the examples. The gluing results are determined on a "Hercules Sizing Tester". The bonding tests measure the resistance of a bonded paper sheet to the penetration of a test solution No. 2 (an aqueous solution of 1.0% formic acid and 1.25% naphthol green B, weight basis). The time required for the ink to reduce the light reflection either 80 or 85%
(fremgår av eksemplene) av arkets opprinnelige refleksjonsverdi, brukes som mål på limingseffekten. (appears from the examples) of the sheet's original reflectance value, is used as a measure of the gluing effect.
Det følgende eksempel viser fremstilling av en aminopolyamid/epiklorhydrinharpiks som er særlig egnet som kationisk dispergeringsharpiks for bruk i henhold til oppfinnelsen. The following example shows the production of an aminopolyamide/epichlorohydrin resin which is particularly suitable as a cationic dispersion resin for use according to the invention.
Eksempel A Example A
Man fremstiller et aminopolyamid ved å tilsette 219,3 deler adipinsyre langsomt og under omrøring til 151,3 deler dietylentriamin i en kolbe forsynt med rører og vannkjølefelle. Reaksjonsblandingen omrøres og oppvarmes ved 170-180°C under nitrogenatmosfære til amiddannelsen er ferdig. Etter luftkjøling' til ca. 140°C tilsettes varmt vann under omrøing inntil man har en 50%-ig oppløsning av polyamidharpiks med en egenviskositet på 0,140 målt ved hjelp av en 2%-ig oppløsning i IN NH^Cl. Man fremstiller epiklorhydrinderivatet av aminopolyamid ved å tilsette ca. 110,25 deler vann til 50 deler av nevnte 50%-ige oppløsning og derpå tilsetter 14,0 deler (0,157 mol) epiklorhydrin. Reaksjonsblandingen oppvarmes ved 70°C under omrøring og tilbake-løpskjøler inntil Gardner-Holdt-viskositeten ligger på E til F på avlesningsskalaen. Reaksjonsblandingen fortynnes med vann til tørrstoffinnhold ca. 12,5%. An aminopolyamide is prepared by adding 219.3 parts of adipic acid slowly and with stirring to 151.3 parts of diethylenetriamine in a flask fitted with a stirrer and water cooling trap. The reaction mixture is stirred and heated at 170-180°C under a nitrogen atmosphere until the amide formation is complete. After air cooling' to approx. At 140°C, hot water is added while stirring until you have a 50% solution of polyamide resin with an intrinsic viscosity of 0.140 measured using a 2% solution in IN NH^Cl. The epichlorohydrin derivative is produced from aminopolyamide by adding approx. 110.25 parts of water to 50 parts of said 50% solution and then add 14.0 parts (0.157 mol) of epichlorohydrin. The reaction mixture is heated at 70°C with stirring and refluxed until the Gardner-Holdt viscosity is at E to F on the reading scale. The reaction mixture is diluted with water to a dry matter content of approx. 12.5%.
Et annet egnet dispergeringsmiddel i henhold til oppfinnelsen er vannoppløselige alkylenpolyamin/epiklorhydrinharpikser som er vannoppløselige polymerreaksjonsprodukter mellom epiklorhydrin og et alkylenpolyamin. Another suitable dispersant according to the invention is water-soluble alkylene polyamine/epichlorohydrin resins which are water-soluble polymer reaction products between epichlorohydrin and an alkylene polyamine.
Alkylenpolyaminer som kan omsettes med epiklorhydrin har formelen H„N(C H_ NH) H hvor n er et tall fra 2-8 og x et tall Alkylene polyamines that can be reacted with epichlorohydrin have the formula H„N(C H_ NH) H where n is a number from 2-8 and x a number
z n zn x 3 z n z n x 3
fra 1 og oppover, fortrinnsvis 1-6. Eksempler på slike alkylenpolyaminer er alkylendiaminer som etylendiamin, 1,2-propylendiamin, 1,3-propylendiamin, tetrametylendiamin og heksametylendiamin. Polyalkylenpolyaminer som polyetylenpolyaminer, polypropylenpolyaminer, polybutylenpolyaminer o.l., er eksempler på anvendelige alkylenpolyaminer. Spesielle eksempler på polyalkylenpolyaminer er dietylentriamin, trietylentetramin, tetraetylenpentamin og dipropylentriamin.. Andre brukbare polyalkylenpolyaminer er metyl-bis(3-aminopropyl)amin, metyl-bis(2-aminoetyl)-amin og 4,7-dimetyltrietylentetramin. Blandinger av alkylenpolyaminer kan også brukes om ønsket. from 1 and up, preferably 1-6. Examples of such alkylene polyamines are alkylene diamines such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, tetramethylenediamine and hexamethylenediamine. Polyalkylene polyamines such as polyethylene polyamines, polypropylene polyamines, polybutylene polyamines and the like are examples of usable alkylene polyamines. Particular examples of polyalkylene polyamines are diethylene triamine, triethylene tetramine, tetraethylene pentamine and dipropylene triamine. Other useful polyalkylene polyamines are methyl-bis(3-aminopropyl)amine, methyl-bis(2-aminoethyl)-amine and 4,7-dimethyltriethylenetetramine. Mixtures of alkylene polyamines can also be used if desired.
De relative mengdeforhold mellom alkylenpolyamin og epiklorhydrin kan varieres avhengig av det spesielle alkylenpolyamin som brukes. Generelt er det en fordel at molforholdet mellom epiklorhydrin og alkylenpolyamid ligger over 1:1 og under 2:1. Ved fremstilling av vannoppløselige harpikser av epiklorhydring og tetraetylenpentamin har man fått gode resultater ved molforhold fra 1,4:1 til 1,94:1. Reaksjonstemperaturen er fortrinnsvis mellom 40 og 60°C. The relative proportions of alkylene polyamine and epichlorohydrin can be varied depending on the particular alkylene polyamine used. In general, it is an advantage that the molar ratio between epichlorohydrin and alkylene polyamide is above 1:1 and below 2:1. In the production of water-soluble resins from epichlorohydration and tetraethylenepentamine, good results have been obtained at molar ratios from 1.4:1 to 1.94:1. The reaction temperature is preferably between 40 and 60°C.
Det følgende eksempel illustrerer fremstilling av et dispergeringsmiddel av ovenstående type: The following example illustrates the preparation of a dispersant of the above type:
Eksempel B Example B
Til en blanding av 29,2 deler trietylentetramin og 70 deler vann settes 44,4 deler epiklorhydrin i løpet av 12 min under periodevis kjøling. Etter at epiklorhydrinet er tilsatt, oppvarmes reaksjonsblandingen til 75°C og holdes på en temperatur mellom ca. 70 og 77°C i 33 min, da har Gardner-Holdt-viskositeten nådd ca. I. Den resulterende massen fortynnes med 592 deler vann til en vandig oppløsning som har et tørrstoffinnhold på ca. 11,7% og en pH-verdi på ca. 6,3. To a mixture of 29.2 parts of triethylenetetramine and 70 parts of water, 44.4 parts of epichlorohydrin are added over the course of 12 minutes under periodic cooling. After the epichlorohydrin has been added, the reaction mixture is heated to 75°C and maintained at a temperature between approx. 70 and 77°C for 33 min, then the Gardner-Holdt viscosity has reached approx. I. The resulting mass is diluted with 592 parts of water to an aqueous solution which has a solids content of approx. 11.7% and a pH value of approx. 6.3.
Et annet egnet dispergeringsmiddel i henhold til oppfinnelsen er en poly(diallylamin)-epihalogenhydrinharpiks. Harpikser av denne type kan fremstilles som beskrevet i US-patent nr. 3.700. 623, som det vises til som referanse. Another suitable dispersant according to the invention is a poly(diallylamine)-epihalohydrin resin. Resins of this type can be produced as described in US patent no. 3,700. 623, which is incorporated by reference.
Et poly(diallylamin)-epihalogenhydrinharpiks er harpiks-reaksjonsproduktet mellom (A) en lineær polymer med enheter av formelen A poly(diallylamine) epihalohydrin resin is the resin reaction product between (A) a linear polymer with units of the formula
hvor R betegner hydrogen eller lavalkyl og R' betegner hydrogen, alkyl eller substituert alkyl-, og (B) et epihalogenhydrin. where R denotes hydrogen or lower alkyl and R' denotes hydrogen, alkyl or substituted alkyl-, and (B) an epihalohydrin.
I ovenstående formel kan gruppene R være like eller forskjellige og er som nevnt hydrogen eller lavalkyl. Alkyl-gruppene inneholder fra 1-6 C-atomer og er fortrinnsvis metyl, etyl, isopropyl eller n-butyl. R<1> i formelen representerer hydrogen, alkyl eller substituert alkyl. R'-alkylgruppene inneholder fra 1-18 C-atomer (fortrinnsvis 1-6 C-atomer) som f.eks. metyl, etyl, propyl, isopropyl, butyl, tert.-butyl, heksyl, oktyl, decyl, dodecyl, tetradecyl og oktadecyl. R' kan også være en substituert alkylgruppe. Egnede substituenter omfatter generelt alle grupper som ikke vil delta i polymerisasjonen med en vinyldobbeltbinding. Typisk kan slike substituenter være karboksylat, cyan, eter, amino (primær, sekundær eller tertiær), amid, hydrazin og hydroksyl. In the above formula, the groups R can be the same or different and are, as mentioned, hydrogen or lower alkyl. The alkyl groups contain from 1-6 C atoms and are preferably methyl, ethyl, isopropyl or n-butyl. R<1> in the formula represents hydrogen, alkyl or substituted alkyl. The R'-alkyl groups contain from 1-18 C-atoms (preferably 1-6 C-atoms) such as e.g. methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and octadecyl. R' can also be a substituted alkyl group. Suitable substituents generally include all groups which will not participate in the polymerization with a vinyl double bond. Typically, such substituents can be carboxylate, cyan, ether, amino (primary, secondary or tertiary), amide, hydrazine and hydroxyl.
Polymerenheter i henhold til ovenstående formel kan fremstilles ved å polymerisere hydrohalogenidsaltet av et diallylamin (II) Polymer units according to the above formula can be prepared by polymerizing the hydrohalide salt of a diallylamine (II)
hvor R og R' har betydning som ovenfor angitt, enten alene eller som en blanding med andre kopolymeriserbare forbindelser, i nærvær av en fri radikalkatalysator, fulgt av saltnøytralisering for å frigjøre polymerbasen. where R and R' have the meaning as above, either alone or as a mixture with other copolymerizable compounds, in the presence of a free radical catalyst, followed by salt neutralization to release the polymer base.
Spesielle hydrogenhalogenidsalter av diallylaminer som kan polymeriseres til polymerenheter i henhold til oppfinnelsen, er diallylaminhydroklorid, N-metyldiallylaminhydroklorid, N-metyldiallylaminhydrobromid, 2,2'-dimetyl-N-metyldiallylaminhydroklorid, N-etyldiallylaminhydrobromid, N-isopropyldiallylamin-hydroklorid, N-n-butyldiallylaminhydrobromid, N-tert,-butyldi-allylaminhydroklorid, N-n-heksyldiallylaminhydroklorid, N-okta-decyldiallylaminhydroklorid, N-acetamidodiallylaminhydroklorid, N-cyanometyldiallylaminhydroklorid, N-3-propionamidodiallylamin-hydrobromid, N-karboetoksymetyldiallylaminhydroklorid, N-3-met-oksyetyldiallylaminhydrobromid, N-3-aminoetyldiallylaminhydro-klorid, N-hydroksyetyldiallylaminhydrobromid og N-acetohydrazid-substituert diallylaminhydroklorid. Special hydrogen halide salts of diallylamines that can be polymerized into polymer units according to the invention are diallylamine hydrochloride, N-methyldiallylamine hydrochloride, N-methyldiallylamine hydrobromide, 2,2'-dimethyl-N-methyldiallylamine hydrobromide, N-ethyldiallylamine hydrobromide, N-isopropyldiallylamine hydrochloride, N-n-butyldiallylamine hydrobromide, N-tert,-butyldiallylamine hydrochloride, N-n-hexyldiallylamine hydrochloride, N-octadecyldiallylamine hydrochloride, N-acetamidodiallylamine hydrochloride, N-cyanomethyldiallylamine hydrochloride, N-3-propionamidodiallylamine hydrobromide, N-carboethoxymethyldiallylamine hydrochloride, N-3-methoxyethyldiallylamine hydrobromide, N-3 -aminoethyldiallylamine hydrochloride, N-hydroxyethyldiallylamine hydrobromide and N-acetohydrazide-substituted diallylamine hydrochloride.
Diallylaminer og N-alkyldiallylaminer som brukes for fremstilling av polymerene i henhold til oppfinnelsen, kan fremstilles ved omsetning av ammoniakk eller et primært amin med et allylhalogenid idet man som katalysator, benytter en forbindelse som vil ionisere halogenidet som f.eks. natriumjodid, sinkjodid, ammoniumjodid, kobber(II)bromid, jern(III)klorid, jern(III)bromid, sinkklorid, kvikksølv(II)jodid, kvikksølv(II)nitrat, kvikksølv(II)-bromid, kvikksølv(Il)klorid og blandinger av to eller flere av disse. Således kan f.eks. N-metyldiallylamin fremstilles ved å omsette 2 mol allylhalogenid som f.eks. allylklorid med 1 mol metylamin i nærvær av en ioniserende katalysator blant en av de ovennevnte. Diallylamines and N-alkyldiallylamines which are used for the production of the polymers according to the invention can be produced by reacting ammonia or a primary amine with an allyl halide, using as a catalyst a compound which will ionize the halide such as e.g. sodium iodide, zinc iodide, ammonium iodide, copper (II) bromide, iron (III) chloride, iron (III) bromide, zinc chloride, mercury (II) iodide, mercury (II) nitrate, mercury (II) bromide, mercury (Il) chloride and mixtures of two or more of these. Thus, e.g. N-methyldiallylamine is produced by reacting 2 mol of allyl halide, e.g. allyl chloride with 1 mole of methylamine in the presence of an ionizing catalyst from one of the above.
Ved fremstilling av homopolymerer og kopolymerer av denne type, kan reaksjonen startes av et katalytisk redokssystem. I et redokssystem aktiveres katalysatoren ved hjelp av et reduksjons-middel som danner frie radikaler, uten bruk av varme. Reduk-sjonsmidlene som oftest brukes, er natriummetabisulfitt og kaliummetabisulfitt. Andre reduksjonsmidler er vannoppløselige tiosulfater og bisulfitter, hydrogensulfitter og reduserende salter som metallsulfater som foreligger i mer enn en valenstil-stand, f.eks. av kobolt, jern, mangan og kobber. Et spesielt eksempel på et slikt sulfat er jern(II)sulfat. Bruk av et redoks-initiatorssystem har flere fordeler, den viktigste er at man opp-når en effektiv polymerisering ved lav temperatur. Vanlige peroksydkatalysatorer som tert.-butylhydrogenperoksyd, kalium-peroksyd og ammoniumpersulfat anvendt sammen med ovenstående reduksjonsmidler eller metallaktivatorer, kan brukes. When producing homopolymers and copolymers of this type, the reaction can be started by a catalytic redox system. In a redox system, the catalyst is activated by means of a reducing agent that forms free radicals, without the use of heat. The reducing agents most often used are sodium metabisulphite and potassium metabisulphite. Other reducing agents are water-soluble thiosulphates and bisulphites, hydrogen sulphites and reducing salts such as metal sulphates which exist in more than one valence state, e.g. of cobalt, iron, manganese and copper. A special example of such a sulfate is iron(II) sulfate. Using a redox initiator system has several advantages, the most important of which is that an efficient polymerization is achieved at a low temperature. Common peroxide catalysts such as tert-butyl hydrogen peroxide, potassium peroxide and ammonium persulfate used together with the above reducing agents or metal activators can be used.
Som tidligere nevnt kan lineære polymerer av diallylaminer som omsettes med et epihalogenhydrin, inneholde forskjellige enheter med formel (I) og/eller enheter av en eller flere andre kopolymeriserbare monomerer. Typisk vil komonomeren være en annen diallylamin, en monoetylenisk umettet forbindelse som inneholder en enkelt vinyl- eller vinylidengruppe, eller svoveldioksyd, og foreligge i. en mengde på fra 0-95 mol-% av polymeren. Således er de aktuelle diallylaminpolymerer lineære polymerer hvorav 5-100% av de repeterende enheter har formelen (I) og fra 0 til 95% av de repterende enheter er monomerenheter avledet fra (1) en vinylidenmonomer og/eller (2) soveldioksyd. Fore-trukne komonomerer er akrylsyre, metakrylsyre, metyl- og andre alkylakrylater og -metakrylater, akrylamid, metakrylamid, akrylnitril, metakrylnitril, vinylacetat, vinyletere As previously mentioned, linear polymers of diallylamines which are reacted with an epihalohydrin can contain various units of formula (I) and/or units of one or more other copolymerizable monomers. Typically, the comonomer will be another diallylamine, a monoethylenically unsaturated compound containing a single vinyl or vinylidene group, or sulfur dioxide, and be present in an amount of from 0-95 mol% of the polymer. Thus, the relevant diallylamine polymers are linear polymers of which 5-100% of the repeating units have the formula (I) and from 0 to 95% of the repeating units are monomer units derived from (1) a vinylidene monomer and/or (2) soln dioxide. Preferred comonomers are acrylic acid, methacrylic acid, methyl and other alkyl acrylates and methacrylates, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers
som alkylvinyletere, vinylketoner som metylvinylketon og etylvi-nylketon, vinylsulfonamid, svoveldioksyd eller et annet diallylamin som omfattes av formel (II) ovenfor. such as alkyl vinyl ethers, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, vinyl sulfonamide, sulfur dioxide or another diallylamine which is covered by formula (II) above.
Spesielle kopolymerer som kan omsettes med et epihalogenhydrin omfatter kopolymerer av N-metyldiallylamin og svoveldioksyd, kopolymerer av N-metyldiallylamin og diallylamin, kopolymerer av diallylamin og akrylamid, kopolymerer av diallylamin og akrylsyre, kopolymerer av N-metyldiallylamin og metylak-rylat, kopolymerer av diallylamin og akrylnitril, kopolymerer av N-metyldiallylamin og vinylacetat, kopolymerer av diallylamin og metylvinyleter, kopolymerer av N-metyldiallylamin og vinylsulfonamid, kopolymerer av N-metyldiallylamin og metylvinylketon, terpolymerer av diallylamin, svoveldioksyd og akrylamid, samt terpolymerer av N-metyldiallylamin, akrylsyre og akrylamid. Particular copolymers which can be reacted with an epihalohydrin include copolymers of N-methyldiallylamine and sulfur dioxide, copolymers of N-methyldiallylamine and diallylamine, copolymers of diallylamine and acrylamide, copolymers of diallylamine and acrylic acid, copolymers of N-methyldiallylamine and methyl acrylate, copolymers of diallylamine and acrylonitrile, copolymers of N-methyldiallylamine and vinyl acetate, copolymers of diallylamine and methyl vinyl ether, copolymers of N-methyldiallylamine and vinyl sulfonamide, copolymers of N-methyldiallylamine and methyl vinyl ketone, terpolymers of diallylamine, sulfur dioxide and acrylamide, as well as terpolymers of N-methyldiallylamine, acrylic acid and acrylamide.
Epihalogenhydrinet som omsettes med diallylaminpolymeren, kan være et hvilket som helst epihalogenhydrin, dvs. epiklorhydrin, epibromhydrin, epifluorhydrin eller epijodhydrin, men fortrinnsvis epiklorhydrin. Generelt tilsettes epihalogenhydrinet i en mengde på mellom 0,5 og 1,5 mol, fortrinnsvis 1-1,5 mol/mol sekundær pluss tertiær amin som finnes i polymeren. The epihalohydrin reacted with the diallylamine polymer may be any epihalohydrin, ie epichlorohydrin, epibromohydrin, epifluorohydrin or epiiodohydrin, but preferably epichlorohydrin. In general, the epihalohydrin is added in an amount of between 0.5 and 1.5 mol, preferably 1-1.5 mol/mol of secondary plus tertiary amine present in the polymer.
Poly(diallylamin)-epihalogenhydrinharpiksen kan fremstilles ved å omsette en homopolymer eller kopolymer av et diallylamin som nevnt ovenfor, med et epihalogenhydrin ved en temperatur på fra 30-80°C, fortrinnsvis 40-60°C, inntil viskositeten som måles for en 20-30%-ig oppløsning ved 25°C har nådd skalaavelsningen A til E, fortrinnsvis C til D, på Gardner-Holdt-skalaen. Reaksjonen utføres med fordel i en vandig oppløsning for å dempe reaksjonen, og ved en pH-verdi på fra ca. 7-9,5. The poly(diallylamine)-epihalohydrin resin can be prepared by reacting a homopolymer or copolymer of a diallylamine as mentioned above, with an epihalohydrin at a temperature of from 30-80°C, preferably 40-60°C, until the viscosity measured for a 20 -30% resolution at 25°C has reached scale breeding A to E, preferably C to D, on the Gardner-Holdt scale. The reaction is advantageously carried out in an aqueous solution to dampen the reaction, and at a pH value of from approx. 7-9.5.
Når den ønskede virkositet er nådd, tilsettes tilstrekkelig vann til å regulere faststoffinnholdet i harpiksoppløs-ningen til ca. 15% eller mindre, og produktet avkjøles til romtemperatur (ca. 2 5°C). When the desired strength has been reached, sufficient water is added to regulate the solids content in the resin solution to approx. 15% or less, and the product is cooled to room temperature (approx. 25°C).
Poly(diallylamin)-epihalogenhydrin-harpiksen kan stabili-seres mot geldannelse ved å tilsette til den vandige oppløsning tilstrekkelig vannoppløselig syre (f.eks. saltsyre eller svovelsyre) slik at pH-verdien holdes på ca. 2. The poly(diallylamine)-epihalohydrin resin can be stabilized against gel formation by adding to the aqueous solution sufficient water-soluble acid (e.g. hydrochloric acid or sulfuric acid) so that the pH value is kept at approx. 2.
Følgende eksempel illustrerer fremstilling av poly(diallylamin) -epiklorhydrinharpiks . The following example illustrates the preparation of poly(diallylamine)-epichlorohydrin resin.
Eksempel C Example C
En oppløsning av 69,1 deler metyldiallylamin og 197 deler 20° Be saltsyre i 11,7 deler ionefritt vann gjennombobles med nitrogen for å fjerne luften og behandles derpå med 0,55 deler t-butylhydroperoksyd og en oppløsning av 0,0036 deler jern (II)-sulfat i 0,5 deler vann. Den resulterende oppløsning polymeriseres ved 60-69°C i 24 timer og gir da en polymeroppløsning som inneholder 52,1% faststoff med RSV (redusert spesifikk viskositet) lik 0,22. 122 deler av ovennevnte oppløsning innstilles til en pH-verdi av 8,5 ved å tilsette 95 deler 3,8%-ig natriumhydroksyd og fortynnes med 211 deler vann samt 60 deler epiklorhydrin. Blandingen oppvarmes ved 45-55°C i 1,35 timer inntil Gardner-Holdt-viskositeten av en prøve avkjølt ved 25°C nådde B+. Den dannede oppløsningen surgjøres med 25 deler 20° Be saltsyre og oppvarmes til 60°C inntil pH-verdien blir konstant lik 2,0. Den fremstilte harpiksoppløsning har et faststoffinnhold på 20,3% og en Brookfieldviskositet = 77 cp. (målt på "Brookfield Model LVF Viscometer", spindel nr. 1 ved 60 omdr./min, med beskyttelse). A solution of 69.1 parts of methyldiallylamine and 197 parts of 20° Be hydrochloric acid in 11.7 parts of deionized water is bubbled with nitrogen to remove the air and then treated with 0.55 parts of t-butyl hydroperoxide and a solution of 0.0036 parts of iron ( II)-sulphate in 0.5 parts water. The resulting solution is polymerized at 60-69°C for 24 hours and then gives a polymer solution containing 52.1% solids with RSV (reduced specific viscosity) equal to 0.22. 122 parts of the above solution are adjusted to a pH value of 8.5 by adding 95 parts of 3.8% sodium hydroxide and diluted with 211 parts of water and 60 parts of epichlorohydrin. The mixture is heated at 45-55°C for 1.35 hours until the Gardner-Holdt viscosity of a sample cooled at 25°C reaches B+. The resulting solution is acidified with 25 parts of 20° Be hydrochloric acid and heated to 60°C until the pH value becomes constantly equal to 2.0. The resin solution produced has a solids content of 20.3% and a Brookfield viscosity = 77 cp. (measured on "Brookfield Model LVF Viscometer", spindle #1 at 60 rpm, with guard).
Eksempel D Example D
Dette eksempel illustrerer fremstilling av fumarsyreforsterket harpiks. Fumarsyre, 6,5 deler, omsettes til et addukt med formaldehydbehandlet talloljeharpiks, 9 3,5 deler, ved ca. 205°C. Fumarsyren oppløses i den smeltede tallojeharpiks og reagerer med denne til en fumarsyreforsterket talloljeharpiks. Etter at i det vesentlige all fumarsyren er reagert med talloljeharpiksen, avkjøles den forsterkede harpiks til romtemperatur (ca. 23°C). Den forsterkede harpiks inneholder ca. 6,5% fumarsyre, hvorav praktisk alt foreligger i bundet eller adduktdannet form. This example illustrates the preparation of fumaric acid reinforced resin. Fumaric acid, 6.5 parts, is converted to an adduct with formaldehyde-treated tall oil resin, 9 3.5 parts, at approx. 205°C. The fumaric acid dissolves in the melted tall oil resin and reacts with this to form a fumaric acid-reinforced tall oil resin. After essentially all of the fumaric acid has reacted with the tall oil resin, the reinforced resin is cooled to room temperature (approx. 23°C). The reinforced resin contains approx. 6.5% fumaric acid, practically all of which is present in bound or adducted form.
Eksempel 1 Example 1
En oppløsning fremstilt ved å oppløse 300 deler forsterket harpiks fremstilt i henhold til eks. D i 300 deler benzen. Denne oppløsning blandes grundig med 400 deler (50 deler faststoff) aminopolyamid/epiklorhydrinharpiksoppløsning fremstilt som i eks. A, fortynnet med 350 deler vann, hvilket gir en forblanding som homogeniseres to ganger ved 140 kg/cm 2. Det dannede produkt er en stabil olje-i-vann-emulsjon. Nesten all benzen fjernes fra. emulsjonen ved avdestillering under redusert trykk med badtemperatur ca. 40°C. Faststoffinnholdet i dispersjonen er ca. 35%. Av tørrstoffinnholdet er ca. 30% forsterket harpiks og ca. 5% er epiklorhydrin-aminopolyamid/epiklorhydrinharpiks. Dispersjonen er stabil i ca. 6 måneder. A solution prepared by dissolving 300 parts of reinforced resin prepared according to ex. D in 300 parts benzene. This solution is thoroughly mixed with 400 parts (50 parts solid) aminopolyamide/epichlorohydrin resin solution prepared as in ex. A, diluted with 350 parts water, which gives a premix that is homogenized twice at 140 kg/cm 2. The product formed is a stable oil-in-water emulsion. Almost all benzene is removed from. the emulsion by distillation under reduced pressure with bath temperature approx. 40°C. The solids content in the dispersion is approx. 35%. Of the dry matter content, approx. 30% reinforced resin and approx. 5% is epichlorohydrin-aminopolyamide/epichlorohydrin resin. The dispersion is stable for approx. 6 months.
Eksempel 2 Example 2
Man gjentar eks. 1 med 200 deler forsterket harpiks fremstilt som i eks. D oppløst i 200 deler benzen med 150 deler aminopolyamid/epiklorhydrinharpiks (18,8 deler tørrstoff) blandet med 550 deler vann. Faststoffinnholdet i den vandige dispersjon er ca. 24%. Av dette faststoffinnhold er ca. 22% forsterket harpiks og ca. 2% aminopolyamid/epiklorhydrinharpiks. Dispersjonen har god stabilitet. One repeats e.g. 1 with 200 parts of reinforced resin prepared as in ex. D dissolved in 200 parts benzene with 150 parts aminopolyamide/epichlorohydrin resin (18.8 parts solids) mixed with 550 parts water. The solids content in the aqueous dispersion is approx. 24%. Of this solids content, approx. 22% reinforced resin and approx. 2% aminopolyamide/epichlorohydrin resin. The dispersion has good stability.
Eksempel 3 Example 3
Man gjentar eks. 1 med 750 deler aminopolyamid/epiklor-hydrinharpiks (93,8 deler tørrstoff) med 750 deler vann. Faststoffinnholdet i vanndispersjonen er ca. 22%. Av dette er ca. 17% forsterket harpiks og 5% aminopolyamid/epiklorhydrinharpiks. Dispersjonen har god stabilitet. One repeats e.g. 1 with 750 parts aminopolyamide/epichlorohydrin resin (93.8 parts solids) with 750 parts water. The solids content in the water dispersion is approx. 22%. Of this, approx. 17% reinforced resin and 5% aminopolyamide/epichlorohydrin resin. The dispersion has good stability.
Eksempel 4 Example 4
Man gjentar eks. 1 med 500 deler aminoamid/epiklorhydrin-harpiks (62,5 deler faststoff) med 250 deler vann. Faststoffinnholdet i vanndispersjonen er ca. 35%. Av dette er ca. 29% forsterket harpiks og 6% aminopolyamid/epiklorhydrinharpiks. Dispersjonen har god stabilitet. One repeats e.g. 1 with 500 parts aminoamide/epichlorohydrin resin (62.5 parts solids) with 250 parts water. The solids content in the water dispersion is approx. 35%. Of this, approx. 29% reinforced resin and 6% aminopolyamide/epichlorohydrin resin. The dispersion has good stability.
Eksempel 5 Example 5
Man gjentar eks. 1 med bare 150 deler benzen for oppløs-ning av den forsterkede harpiks og bare 250 deler vann til fortynning av aminopolyamid/epiklorhydrinharpiksen. Man får da et samlet tørrstoffinnhold i den vandige dispersjon på ca. 37,5%. Tørrstoffinnholdet fordeler seg med 32% på forsterket harpiks One repeats e.g. 1 with only 150 parts benzene for dissolving the reinforced resin and only 250 parts water for diluting the aminopolyamide/epichlorohydrin resin. This results in a total solids content in the aqueous dispersion of approx. 37.5%. The solids content is distributed by 32% on reinforced resin
og 5,5% på aminopolyamid/epiklorhydrinharpiksen. Dispersjonen har god stabilitet. and 5.5% on the aminopolyamide/epichlorohydrin resin. The dispersion has good stability.
Eksempel 6 Example 6
Man gjentar eks. 1 med 600 deler benzen for oppløsning One repeats e.g. 1 with 600 parts of benzene for dissolution
av den forsterkede harpiks. Det samlede faststoffinnhold i vanndispersjonen er ca. 35%. Av dette er 30% forsterket harpiks og 5% aminopolyamid/epiklorhydrinharpiks. Dispersjonen har god stabilitet. of the reinforced resin. The total solids content in the water dispersion is approx. 35%. Of this, 30% is reinforced resin and 5% aminopolyamide/epichlorohydrin resin. The dispersion has good stability.
Eksempel E Example E
Dette eksempel illustrerer fremstilling av fumarsyreforsterket harpiks. 14 deler fumarsyre settes ved ca. 205°C til 86 deler formaldehydbehandlet talloljeharpiks. Fumarsyren opp-løses i den smeltede talloljeharpiks og reagerer med denne til fumarsyreforsterket talloljeharpiks. Etter at all fumarsyren har reagert med talloljeharpiksen, avkjøles den forsterkede harpiks til romtemperatur (ca. 23°C). Den forsterkede harpiks inneholder 14% fumarsyre hvorav nesten alt finnes i bundet form. This example illustrates the preparation of fumaric acid reinforced resin. 14 parts of fumaric acid are placed at approx. 205°C to 86 parts formaldehyde treated tall oil resin. The fumaric acid dissolves in the melted tall oil resin and reacts with this to form fumaric acid-reinforced tall oil resin. After all the fumaric acid has reacted with the tall oil resin, the reinforced resin is cooled to room temperature (about 23°C). The reinforced resin contains 14% fumaric acid, almost all of which is found in bound form.
Eksempel 7 Example 7
Man fremstiller en oppløsning av 128,5 deler forsterket harpiks i henhold til eks. E, 21,5 deler formaldehydbehandlet talloljeharpiks og 150 deler kopolymer av vinyltoluen og oc-metylstyren, med molvekt ca. 1400 og ring- og kulemykningspunkt på ca. 120°C, og et syretall på under 1, i 300 deler benzen. Denne oppløsning blandes grundig med 400 deler (50 deler faststoff) aminopolyamid/epiklorhydrinoppløsning fremstilt i henhold til eks. A, fortynnet med 350 deler vann til en forblanding som homogeniseres to ganger ved 210 kg/cm 2. Produktet er en stabil olje-i-vann-emulsjon hvorfra nesten all benzen avdestilleres under nedsatt trykk med badtemperatur 40°C. Faststoffinnholdet i dispersjonen er ca. 33%. Av faststoffinnholdet er ca. 14,2% vinyltoluen-a-metylstyrenkopolymer, ca. 4,8% er aminopolyamid/epiklor-hydrinharpiks og ca. 1,9% er bundet fumarsyre. A solution of 128.5 parts reinforced resin is prepared according to e.g. E, 21.5 parts formaldehyde-treated tall oil resin and 150 parts copolymer of vinyltoluene and o-methylstyrene, with a molecular weight of approx. 1400 and ring and ball softening point of approx. 120°C, and an acid number of less than 1, in 300 parts of benzene. This solution is thoroughly mixed with 400 parts (50 parts solid) aminopolyamide/epichlorohydrin solution prepared according to ex. A, diluted with 350 parts water to a premix that is homogenized twice at 210 kg/cm 2. The product is a stable oil-in-water emulsion from which almost all the benzene is distilled off under reduced pressure with a bath temperature of 40°C. The solids content in the dispersion is approx. 33%. Of the solids content, approx. 14.2% vinyltoluene-α-methylstyrene copolymer, approx. 4.8% is aminopolyamide/epichlorhydrin resin and approx. 1.9% is bound fumaric acid.
Eksempel 8 Example 8
Man gjentar eks. 7 med 134 deler formaldehydbehandlet talloljeharpiks og 37,5 deler vinyltoluen-a-metylstyrenkopolymer. Faststoffinnholdet i dispersjonen er ca. 34%. Av faststoffinnholdet er ca. 3,6% kopolymer, ca. 4,8% aminopolyamid/epiklor-hydrinharpiks og ca. 1,9% bundet fumarsyre. Dispersjonen har god stabilitet. One repeats e.g. 7 with 134 parts formaldehyde-treated tall oil resin and 37.5 parts vinyltoluene-α-methylstyrene copolymer. The solids content in the dispersion is approx. 34%. Of the solids content, approx. 3.6% copolymer, approx. 4.8% aminopolyamide/epichlorohydrin resin and approx. 1.9% bound fumaric acid. The dispersion has good stability.
Eksempel 9 Example 9
Man fremstiller en oppløsning av 128,5 deler forsterket harpiks i henhold til eks. E, 21,5 deler formaldehydbehandlet talloljeharpiks og 150 deler fullraffinert peirafinvoks (smeltepunkt ca. 6 3°C) i 300 deler benzen ved blanding og oppvarming ved ca. 60°C for oppløsning av parafinvoksen. Denne oppløsning blandes grundig med 400 deler (50 deler faststoff) aminpolyamid/ epiklorhydrinharpiksoppløsning fremstilt som i eks. A, fortynnet med 350 deler vann. Før man blander de to oppløsningene, oppvarmes den fortynnede aminopolyamid/epiklorhydrinharpiks til ca. 60°C. Den varme forblanding homogeniseres to ganger ved 280 kg/cm^ i en homogenisator som er forvarmet til ca. 60°C. Produktet er en stabil olje-i-vann-emulsjon hvorfra nesten all benzen av-destilleres under redusert trykk med badtemperatur 40-50°C. Det samlede faststoffinnhold i vanndispersjonen er ca. 31% hvorav 13,8% er voks, 4,4% er aminopolyamid/epiklorhydrinharpiks og ca. 1,8% er bundet fumarsyre. Dispersjonen har god stabilitet. A solution of 128.5 parts reinforced resin is prepared according to e.g. E, 21.5 parts formaldehyde-treated tall oil resin and 150 parts fully refined paraffin wax (melting point approx. 6 3°C) in 300 parts benzene by mixing and heating at approx. 60°C for dissolving the paraffin wax. This solution is thoroughly mixed with 400 parts (50 parts solid) amine polyamide/epichlorohydrin resin solution prepared as in ex. A, diluted with 350 parts water. Before mixing the two solutions, the diluted aminopolyamide/epichlorohydrin resin is heated to approx. 60°C. The warm premix is homogenized twice at 280 kg/cm^ in a homogenizer that is preheated to approx. 60°C. The product is a stable oil-in-water emulsion from which almost all benzene is distilled off under reduced pressure with a bath temperature of 40-50°C. The total solids content in the water dispersion is approx. 31% of which 13.8% is wax, 4.4% is aminopolyamide/epichlorohydrin resin and approx. 1.8% is bound fumaric acid. The dispersion has good stability.
Eksempel 10 Example 10
Man gjentar eks. 9 med 14,5 deler formaldehydbehandlet talloljeharpiks og 30 deler fullraffinert parafinvoks. Det samlede faststoffinnhold i vanndispersjonen er ca. 36% som fordeler seg på 3,1% voks, 5,3% aminopolyamid/epiklorhydrinharpiks og 2% bundet fumarsyre. Dispersjonen har god stabilitet. One repeats e.g. 9 with 14.5 parts formaldehyde-treated tall oil resin and 30 parts fully refined paraffin wax. The total solids content in the water dispersion is approx. 36% which is divided into 3.1% wax, 5.3% aminopolyamide/epichlorohydrin resin and 2% bound fumaric acid. The dispersion has good stability.
Eksempel F Example F
En reaksjonsbeholder forsynt med dampstrålevakuumsystem fylles med 704 deler vann og 476 deler epiklorhydrin. Dampstråle-vakuumsystemet settes på for å drive ut gasser gjennom en kjøler og hindre den fra å slippe ut gjennom det åpne fyllingshull. 420 deler "Amin 248" tilsettes under omrøring i løpet av 35 min mens temperaturen tillates å stige til 70°C. Man tilfører kjølevann for å begrense temperaturstigningen til 70°C. Etter avsluttet tilsetning av aminet, har blandingen en pH-verdi lik 7,8 og en viskositet lik A på Gardner-Holdt-skalaen. 6 deler 20% NaOH tilsettes for å påskynde reaksjonen. Etter to timer og 40 min ved ca. 70°C, har viskositeten nådd avlesningen U+, og harpiks-oppløsningen fortynnes med 640 deler vann som nedsetter viskositeten til ca. C-. Ialt 44 deler 20% NaOH tilsettes i fire separate porsjoner i løpet av 1-3/4 time for å påskynde reaksjonen. En viskositet på S nås etter 3 timer og 35 min, og reaksjonen stanses ved fortynning med 26 deler konsentrert svovelsyre i 1345 deler vann. Dette gir en vandig oppløsning med faststoffinnhold lik 23,3%, viskositet lik D og en pH-verdi lik 4,4. Mer H2SO4 og vann tilsettes slik at oppløsningen for en pH-verdi lik 4 og faststoffinnhold lik 22,5%. Harpiksoppløsningen filtreres" gjennom filter-patroner med mikroporestørrelser 100 y, hvilket gir ialt 3336 deler produkt. "Amin 24 8" er en markedsført flytende blanding av langkjedede alifatiske polyaminer. Minst 75% av "Amin 248" består av bis-(heksametylen)triamin og høyere homologer. Resten består av lavmolekylære aminer, nitriler og laktamer. A reaction vessel equipped with a steam jet vacuum system is filled with 704 parts water and 476 parts epichlorohydrin. The steam jet vacuum system is applied to expel gases through a cooler and prevent them from escaping through the open filler hole. 420 parts of "Amin 248" are added with stirring over 35 min while the temperature is allowed to rise to 70°C. Cooling water is added to limit the temperature rise to 70°C. After completion of the addition of the amine, the mixture has a pH value equal to 7.8 and a viscosity equal to A on the Gardner-Holdt scale. 6 parts of 20% NaOH are added to speed up the reaction. After two hours and 40 minutes at approx. 70°C, the viscosity has reached the reading U+, and the resin solution is diluted with 640 parts of water which reduces the viscosity to approx. C-. A total of 44 parts of 20% NaOH is added in four separate portions over 1-3/4 hours to speed up the reaction. A viscosity of S is reached after 3 hours and 35 minutes, and the reaction is stopped by dilution with 26 parts of concentrated sulfuric acid in 1345 parts of water. This gives an aqueous solution with a solids content equal to 23.3%, viscosity equal to D and a pH value equal to 4.4. More H2SO4 and water are added so that the solution has a pH value equal to 4 and solids content equal to 22.5%. The resin solution is filtered" through filter cartridges with micropore sizes 100 y, giving a total of 3336 parts of product. "Amin 24 8" is a marketed liquid mixture of long-chain aliphatic polyamines. At least 75% of "Amin 248" consists of bis-(hexamethylene)triamine and higher homologues.The remainder consists of low molecular weight amines, nitriles and lactams.
Eksempel 11 Example 11
En oppløsning fremstilles ved å oppløse 300 deler forsterket harpiks i henhold til eks. D i 300 deler benzen. Denne oppløsningen blandes grundig med 217,4 deler (50 deler faststoff) epiklorhydrin/polyaminreaksjonsprodukt fremstilt som i eks. F, og fortynnes med 533 deler vann, hvilket gir en forblanding som homogeniseres to ganger ved 140 kg/cm 2 trykk. Man får et produkt som er en stabil olje-i-vann-emulsjon hvorfra nesten all benzen avdestilleres under nedsatt trykk ved 40°C. Disper-sjonens faststoffinnhold er ca. 35%, som fordeler seg på 30% forsterket harpiks og 5% på epiklorhydrin/polyaminreaksjonsprodukt. Dispersjonen har god stabilitet. A solution is prepared by dissolving 300 parts of reinforced resin according to e.g. D in 300 parts benzene. This solution is thoroughly mixed with 217.4 parts (50 parts solid) epichlorohydrin/polyamine reaction product prepared as in ex. F, and diluted with 533 parts of water, which gives a premix that is homogenized twice at 140 kg/cm 2 pressure. You get a product that is a stable oil-in-water emulsion from which almost all the benzene is distilled off under reduced pressure at 40°C. The solids content of the dispersion is approx. 35%, which is divided into 30% reinforced resin and 5% epichlorohydrin/polyamine reaction product. The dispersion has good stability.
Eksempel 12 Example 12
Man lager en oppløsning ved å oppløse 128,5 deler forsterket harpiks i henhold til eks. E, 141,5 deler talloljeharpiks og 30 deler fullraffinert parafinvoks i 300 deler benzen, ved blanding og varming til 60°C, for oppløsning av parafinvoksen. Denne oppløsning blandes grundig med 217,4 deler (50 g faststoff) epiklorhydrin / polyaminreaksjonsprodukt fremstilt som i eks. F, og fortynnes med 533 deler vann. Før man blander de to oppløs-ningene, oppvarmes det fortynnede epiklorhydrin/polyaminreaksjonsprodukt til ca. 60°C. Den varme forblanding homogeniseres to ganger ved 140 kg/cm 2 i en homogenisator som forvarmes til ca. 60°C. Produktet er en stabil olje-i-vann-emulsjon hvorfra praktisk talt all benzen avdestilleres under atmosfæretrykk, hvorved produkttemperaturen øker fra ca. 75-100°C. Faststoffinnholdet i den dannede dispersjon er ca. 36,0% som fordeler seg på 3,1% parafinvoks, 5,2% epiklorhydrin/polyaminreaksjonsprodukt og 2% bundet fumarsyre. Dispersjonen har god stabilitet. A solution is made by dissolving 128.5 parts of reinforced resin according to e.g. E, 141.5 parts tall oil resin and 30 parts fully refined paraffin wax in 300 parts benzene, by mixing and heating to 60°C, to dissolve the paraffin wax. This solution is thoroughly mixed with 217.4 parts (50 g solid) epichlorohydrin / polyamine reaction product prepared as in ex. F, and dilute with 533 parts of water. Before mixing the two solutions, the diluted epichlorohydrin/polyamine reaction product is heated to approx. 60°C. The warm premix is homogenized twice at 140 kg/cm 2 in a homogenizer that is preheated to approx. 60°C. The product is a stable oil-in-water emulsion from which practically all benzene is distilled off under atmospheric pressure, whereby the product temperature increases from approx. 75-100°C. The solids content of the resulting dispersion is approx. 36.0% which is divided into 3.1% paraffin wax, 5.2% epichlorohydrin/polyamine reaction product and 2% bound fumaric acid. The dispersion has good stability.
Eksempel G Example G
Til en oppløsning av 26,2 deler iminobis(propylamin), også kalt bis(3-aminopropyl)amin, i 82 deler vann, settes 55,6 deler epiklorhydrin i en porsjon. Blandingen holdes mellom 4 3 To a solution of 26.2 parts of iminobis(propylamine), also called bis(3-aminopropyl)amine, in 82 parts of water, add 55.6 parts of epichlorohydrin in one portion. The mixture is kept between 4 3
og 58°C ved ytre kjøling i ca. 0,7 timer, inntil den eksoterme del av reaksjonen er over. Blandingen oppvarmes derpå til ca. 70°C i 0,8 timer, hvorved blandingens viskositet øker til Gardner-Holdt-viskositet på over J. Blandingen fortynnes med 364 deler vann og innstilles til en pH-verdi av 4,5 med svovelsyre. Har-piksoppløsningen som dannes, inneholder 16,5% faststoff og har en Brookfield-viskositet på 10 centipoise (spindel nr. 1, 60 omdr./min). and 58°C with external cooling for approx. 0.7 hours, until the exothermic part of the reaction is over. The mixture is then heated to approx. 70°C for 0.8 hours, whereby the viscosity of the mixture increases to a Gardner-Holdt viscosity of over J. The mixture is diluted with 364 parts of water and adjusted to a pH value of 4.5 with sulfuric acid. The resulting resin solution contains 16.5% solids and has a Brookfield viscosity of 10 centipoise (spindle #1, 60 rpm).
Eksempel 13 Example 13
Man gjentar eks. 1 med 301 deler (50 deler faststoff) epiklorhydrin/polyaminreaksjonsprodukt fremstilt som i eks. G, med 300 deler vann som vannfase. Forblandingen homogeniseres to ganger ved 210 kg/cm 2. Det totale faststoffinnhold i dispersjonen er ca. 39%. Av dette er 5,6% epiklorhydrin/polyamin-reaks jonsprodukt og ca. 33% forsterket harpiks. Dispersjonen har god stabilitet. One repeats e.g. 1 with 301 parts (50 parts solid) epichlorohydrin/polyamine reaction product prepared as in ex. G, with 300 parts of water as the aqueous phase. The premix is homogenized twice at 210 kg/cm 2. The total solids content in the dispersion is approx. 39%. Of this, 5.6% is epichlorohydrin/polyamine reaction product and approx. 33% reinforced resin. The dispersion has good stability.
Eksempel H Example H
74 deler epiklorhydrin settes til en oppløsning av 37,8 deler tetraetylenpentamin i 112 deler vann, i løpet av 15 min. Temperaturen stiger til ca. 55°C. Blandingen oppvarmes utvendig og holdes på ca. 60°C i \ time, deretter på 70°C i 3 timer, da har Gardner-Holdt-viskositeten nådd avlesning B. Den resulterende harpiksoppløsning avkjøles til romtemperatur (25°C) og modnes i 11 dager, hvoretter harpiksoppløsningens viskositet på Gardner-Holdt-skalaen har nådd Z. Harpiksoppløsningen fortynnes derpå med 524 deler vann. Oppløsningen inneholder ca. 15,3% ikke-flyktige faste stoffer og har en Brookfield-viskositet lik 23 centipoise (viskosimeter "Modell LVF", spindel nr. 1, 60 omdr./min, 25°). 74 parts of epichlorohydrin are added to a solution of 37.8 parts of tetraethylenepentamine in 112 parts of water, over the course of 15 minutes. The temperature rises to approx. 55°C. The mixture is heated externally and kept at approx. 60°C for \ hour, then at 70°C for 3 hours, then the Gardner-Holdt viscosity has reached reading B. The resulting resin solution is cooled to room temperature (25°C) and matured for 11 days, after which the viscosity of the resin solution on the Gardner- The Holdt scale has reached Z. The resin solution is then diluted with 524 parts water. The solution contains approx. 15.3% non-volatile solids and has a Brookfield viscosity of 23 centipoise ("Model LVF" viscometer, spindle #1, 60 rpm, 25°).
Eksempel 14 Example 14
Eksempel 13 gjentas med 327 deler (50 deler faststoff) epiklorhydrin/polyaminreaksjonsprodukt fremstilt som i eks. H Example 13 is repeated with 327 parts (50 parts solid) epichlorohydrin/polyamine reaction product prepared as in ex. H
og 327 deler vann som vannfase. Produktets totale faststoffinnhold er ca. 37%. Av denne er 5,4% epiklorhydrin/polyaminreaksjonsprodukt og ca. 32% er forsterket harpiks. and 327 share water as the aqueous phase. The product's total solids content is approx. 37%. Of this, 5.4% is epichlorohydrin/polyamine reaction product and approx. 32% is reinforced resin.
Eksempel J Example J
Til 250 deler metyldiallylamin settes langsomt 230 deler 37%-ig saltsyre i ca. 240 deler ionefritt vann. Blandingen avkjøles for å hindre fordamping av forbindelser. Blandingens pH-verdi innstilles på 3,1 ved å tilsette 19 deler metyldiallylamin. Etter at oksygenet i reaksjonsbeholderen er fortrengt med nitrogen, tilsettes 2,2 deler t-butylhydrogenperoksyd. Dette følges av 0,0014 deler jern(II)sulfatheptahydrat i 1,1 deler ionefritt vann. Etter at reaksjonsblandingen er oppvarmet til 60°C, foregår en svak eksoterm reaksjon som bringer reaksjord-temperaturen kortvarig opptil ca. 66-70°C. I resten av den 24 timers reaksjonstiden holdes temperaturen på ca. 60°C. Etter avkjøling til 25-30°C, er produktets faststoffinnhold ca. 48,4% og RSV lik 0,21 cp. Til 220 deler ovennevnte polymeroppløsning settes tilstrekkelig (ca. 160 deler) natriumhydroksydoppløsning (10 deler natriumhydroksyd i 376 deler vann) til at pH-verdien blir ca. 8,5. Den nøytraliserte polymeroppløsning fortynnes med 366 deler ionefritt vann og oppvarmes til ca. 40°C. Til den varme oppløsning settes 106 deler epiklorhydrin, og reaksjonsblandingen varmes videre for å omsette epiklorhydrinet ved ca. 50-55°C. Man fortsetter omsetningen til reaksjonsblandingen har en Gardner-viskositet på ca. B+ (1,7 timer). På dette tidspunkt stanses reaksjonen ved hurtig tilsetning av ca. 35 deler 37%-ig saltsyre, slik at man får en endelig pH-verdi på ca. 2. Man får 859 deler produkt som inneholder ca. 20,7% totalt faststoff. Man gjennom-fører en serie forsøk som ovenfor beskrevet, til man har ialt 7395 deler produkt med ca. 20,4% totalt faststoff. To 250 parts of methyldiallylamine, slowly add 230 parts of 37% hydrochloric acid for approx. 240 parts deionized water. The mixture is cooled to prevent evaporation of compounds. The pH value of the mixture is adjusted to 3.1 by adding 19 parts of methyldiallylamine. After the oxygen in the reaction vessel has been displaced with nitrogen, 2.2 parts of t-butyl hydrogen peroxide are added. This is followed by 0.0014 parts iron (II) sulfate heptahydrate in 1.1 parts deionized water. After the reaction mixture has been heated to 60°C, a weak exothermic reaction takes place which briefly brings the reaction soil temperature up to approx. 66-70°C. During the rest of the 24-hour reaction time, the temperature is kept at approx. 60°C. After cooling to 25-30°C, the product's solids content is approx. 48.4% and RSV equal to 0.21 cp. To 220 parts of the above-mentioned polymer solution, add sufficient (approx. 160 parts) sodium hydroxide solution (10 parts sodium hydroxide in 376 parts water) so that the pH value becomes approx. 8.5. The neutralized polymer solution is diluted with 366 parts deionized water and heated to approx. 40°C. 106 parts of epichlorohydrin are added to the hot solution, and the reaction mixture is further heated to react the epichlorohydrin at approx. 50-55°C. The reaction is continued until the reaction mixture has a Gardner viscosity of approx. B+ (1.7 hours). At this point, the reaction is stopped by the rapid addition of approx. 35 parts 37% hydrochloric acid, so that you get a final pH value of approx. 2. You get 859 parts of product containing approx. 20.7% total solids. You carry out a series of tests as described above, until you have a total of 7,395 parts of product with approx. 20.4% total solids.
Eksempel 15 Example 15
Man gjentar eks. 13 med 245 deler (50 deler faststoff) epiklorhydrinmodifisert tertiær aminpolymer fremstilt som i eks. J, fortynnet med 505 deler vann som vannfase. Det totale faststoff innhold i den fremstilte stabile vannsuspensjon er ca. 33%. Av dette er 4,7% tert.-aminpolymer og 28% forsterket harpiks. One repeats e.g. 13 with 245 parts (50 parts solid) epichlorohydrin modified tertiary amine polymer prepared as in ex. J, diluted with 505 parts of water as the aqueous phase. The total solids content in the produced stable water suspension is approx. 33%. Of this, 4.7% is tert.-amine polymer and 28% reinforced resin.
Eksempel 16 Example 16
Man fremstiller en oppløsning ved å oppløse 300 deler forsterket harpiks fremstilt som i eks. D i 200 deler benzen i egnet beholder forsynt med kraftig røreverk i form av en luft-drevet propellrører. Til den grundig omrørte oppløsning settes 400 deler (50 deler faststoff) aminopolyamid/epiklorhydrin-harpiks fremstilt som i eks. A. Dette gir em stabil vann-i-olje-emulsjon som omvendes ved hurtig tilsetning av 350 deler kaldt vann (20°C) under kraftig og stadig omrøring. Etter avsluttet vanntilsetning, fortsetter man å omrøre i 23 min for å sikre fullstendig omvendig til den stabile olje-i-vann-emulsjon, hvorfra praktisk talt all benzen derpå avdampes ved destillasjon under redusert trykk, ved en badtemperatur av ca. 4 0°C. Det totale faststoffinnhold i den stabile vannsuspensjon er ca. 34%. Av dette er 4,8% aminopolyamid/epiklorhydrinharpiks og ca. 29% forsterket harpiks. A solution is prepared by dissolving 300 parts of reinforced resin prepared as in ex. D in 200 parts of benzene in a suitable container provided with a powerful stirrer in the form of an air-driven propeller stirrer. To the thoroughly stirred solution is added 400 parts (50 parts solid) aminopolyamide/epichlorohydrin resin prepared as in ex. A. This gives a stable water-in-oil emulsion which is reversed by the rapid addition of 350 parts of cold water (20°C) under vigorous and constant stirring. After completion of the water addition, stirring is continued for 23 min to ensure complete conversion to the stable oil-in-water emulsion, from which practically all the benzene thereon is evaporated by distillation under reduced pressure, at a bath temperature of approx. 40°C. The total solids content in the stable water suspension is approx. 34%. Of this, 4.8% is aminopolyamide/epichlorohydrin resin and approx. 29% reinforced resin.
Eksempel 17 Example 17
For å bestemme limingseffekten av den vandige dispersjon i henhold til eks. 1, fremstilles håndark idet man benytter dispersjonen som eneste limingsmiddel. For fremstilling av håndarkene benyttes en 50:50-blanding av Rayonier-bleket nåle-trekraftmasse og Weyerhaeuser-bleket løvtre-kraftmasse som sus-penderes i standard hardt vann og males til 500° Freeness (Canadien standard) i en "Noble and Wood"-mølle. En 2 liters porsjon av oppslemmingen fortynnet til 2,5% tørrstoff på vektbasis, behandles med tilstrekkelig alun til at man får en pH-verdi lik ca. 4,5. Oppslemmingen blir så fortynnet til en kon-sistens på 0,27% i blandeboksen med surt alunvann. To determine the gluing effect of the aqueous dispersion according to e.g. 1, hand sheets are produced using the dispersion as the only adhesive. For the production of the hand sheets, a 50:50 mixture of Rayonier bleached softwood pulp and Weyerhaeuser bleached hardwood pulp is used which is suspended in standard hard water and ground to 500° Freeness (Canadian standard) in a "Noble and Wood" -mill. A 2 liter portion of the slurry diluted to 2.5% dry matter by weight is treated with sufficient alum to obtain a pH value equal to approx. 4.5. The slurry is then diluted to a consistency of 0.27% in the mixing box with acidic alum water.
Fortynningsvannet fremstilles ved å redusere pH-verdien The dilution water is produced by reducing the pH value
i vann av moderat hardhet til 5,0 med svovelsyre, og så å tilsette tilstrekkelig alun til 5 ppm oppløselig aluminium. 1 liters porsjoner av masseoppslemming fra blandeboksen behandles med tilstrekkelig limblanding ifølge eks. 1 til å gi 0,4% lim basert på massens tørrvekt. Porsjonene fortynnes med syrealunfortynnings-vann til utløpskassekonsistens på 0,025% for fremstilling av håndark med kvadratmetervekt 60 g/m 2, i en "Noble and Wood"-arkformer. Man benytter lukket vannsystem. De formede arkene våtpresses til 33% tørrstoff og tørkes ved 115°C på damptrommeltørker. Alle håndarkene lagres minst 7 dager ved 22°C og 50% relativ fuktighet og gjennomgår prøver i disse omgivelser med hensyn på limingseffekten, etter en "Hercules"-limingsprøve. Med forsøksoppløsning nr. 2 er den medgåtte tid til 80% refleksjon ca. 139 sekunder. in water of moderate hardness to 5.0 with sulfuric acid, and then adding sufficient alum to 5 ppm soluble aluminum. 1 liter portions of pulp slurry from the mixing box are treated with sufficient adhesive mixture according to e.g. 1 to give 0.4% glue based on the dry weight of the mass. The portions are diluted with acid alum dilution water to a headbox consistency of 0.025% for the production of hand sheets with a square meter weight of 60 g/m 2 , in a "Noble and Wood" sheet former. A closed water system is used. The shaped sheets are wet-pressed to 33% dry matter and dried at 115°C on a steam drum dryer. All hand sheets are stored for at least 7 days at 22°C and 50% relative humidity and undergo tests in these environments with regard to the gluing effect, following a "Hercules" gluing test. With trial resolution no. 2, the elapsed time to 80% reflection is approx. 139 seconds.
Eksempel 18 Example 18
For å finne limingseffekten av en vandig dispersjon i henhold til eks. 1 ved en pH-verdi av 6,5, gjentok man håndform-ingen av ark som beskrevet i eks. 17, med bare 0,4% alun og systemets pH-verdi innstilt til 6,5 ved behov. Resultatene av "Hercules"-limingsprøve i dette tilfelle er 82 sekunder. To find the gluing effect of an aqueous dispersion according to e.g. 1 at a pH value of 6.5, the hand-forming of sheets as described in ex. 17, with only 0.4% alum and the system's pH adjusted to 6.5 if necessary. The results of the "Hercules" bonding test in this case are 82 seconds.
Eksempel 19 Example 19
For å finne limingseffekten av den vandige suspensjon fremstilt ifølge eks. 2, 3, 4, 5, 13, 14 og 15 utførte man overflatelimingsforsøk med bleket kraftpapir (6 g/m 2) ved en pH-verdi av 6,5 med 0,5% tilsatt alun. Arkene behandles i en liten horisontal laboratorielimpresse ved å tilsette prøver av vandige suspensjoner fortynnet til ca. 0,54% til limpressens nyp og føre håndppapirark gjennom oppløsningen før de avpresses av limpressens valser. Under disse forhold er arkopptaket av lim-presseoppløsning ca. 70% av arkvekten, hvilket gir ca. 0,38% lim opptatt av arket. De limte arkene tørkes ca. 18 sek. på labora-torietrommeltørker som holdt en overflatetemperatur på 93°C. Arkene lagres i 4 dager og gjennomgår forsøk med prøveoppløsning nr. 2 ifølge "Hercules"-limprøve inntil 85% refleksjon. Resultatene er som følger: To find the gluing effect of the aqueous suspension prepared according to e.g. 2, 3, 4, 5, 13, 14 and 15 surface bonding tests were carried out with bleached kraft paper (6 g/m 2 ) at a pH value of 6.5 with 0.5% added alum. The sheets are processed in a small horizontal laboratory glue press by adding samples of aqueous suspensions diluted to approx. 0.54% to the nip of the glue press and pass hand paper sheets through the solution before they are squeezed out by the rollers of the glue press. Under these conditions, the sheet uptake of glue press solution is approx. 70% of the sheet weight, which gives approx. 0.38% glue absorbed by the sheet. The glued sheets are dried approx. 18 sec. on a laboratory tumble dryer which maintained a surface temperature of 93°C. The sheets are stored for 4 days and undergo tests with test solution No. 2 according to the "Hercules" glue test up to 85% reflection. The results are as follows:
Eksempel 20 Example 20
For å bestemme limingseffekten av vandige suspensjoner ifølge eks. 7, 8, 9, 10, 11 og 12, utførte man limingsforsøk som i eks. 19, bortsett fra at limoppløsningene bare holdt ca. 0,45% faststoff, hvilket ga ca. 0,32% lim i arket. To determine the gluing effect of aqueous suspensions according to e.g. 7, 8, 9, 10, 11 and 12, gluing tests were carried out as in ex. 19, except that the glue solutions only lasted approx. 0.45% solids, which gave approx. 0.32% glue in the sheet.
Eksempel 21 Example 21
Ved en annen demonstrasjon av limingseffekten av vandige In another demonstration of the gluing effect of aqueous
suspensjoner fremstilt i eks. 1, ble ca. 0,4% faststoff i denne suspensjon og ca. 0,4% alun påført i ca. 4,5% "Penfordgummi 280" suspensions prepared in ex. 1, was approx. 0.4% solids in this suspension and approx. 0.4% alum applied for approx. 4.5% "Penford rubber 280"
(etoksylert maisstivelse) på overflaten av 60 g/m 2 bleket kraftpapir ved en pH-verdi av ca. 7,5. I dette tilfelle fikk man med forsøksoppløsning nr. 2 en tid på 252 sekunder inntil 80% refleksjon ved "Hercules"-limingsprøve. (ethoxylated corn starch) on the surface of 60 g/m 2 bleached kraft paper at a pH value of approx. 7.5. In this case, a time of 252 seconds up to 80% reflection was obtained with experimental solution no. 2 in the "Hercules" gluing test.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38613573A | 1973-08-06 | 1973-08-06 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO742757L NO742757L (en) | 1975-03-03 |
| NO140992B true NO140992B (en) | 1979-09-10 |
| NO140992C NO140992C (en) | 1979-12-19 |
Family
ID=23524317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO742757A NO140992C (en) | 1973-08-06 | 1974-07-30 | WATER DISTRIBUTIONS OF REINFORCED NATURAL RESIN AND DISPENSER FOR USE IN PAPER Gluing |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5834509B2 (en) |
| AT (1) | AT337525B (en) |
| BE (1) | BE818311A (en) |
| BR (1) | BR7406444D0 (en) |
| CA (1) | CA1045735A (en) |
| CH (1) | CH606265A5 (en) |
| DE (1) | DE2435614B2 (en) |
| DK (1) | DK155219C (en) |
| ES (1) | ES428964A1 (en) |
| FI (1) | FI62126C (en) |
| FR (1) | FR2240251B1 (en) |
| GB (1) | GB1439116A (en) |
| IT (1) | IT1017901B (en) |
| NL (1) | NL7408707A (en) |
| NO (1) | NO140992C (en) |
| SE (1) | SE414951B (en) |
| ZA (1) | ZA745014B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5025346U (en) * | 1973-06-29 | 1975-03-24 | ||
| JPS5025347U (en) * | 1973-06-29 | 1975-03-24 | ||
| JPS5025348U (en) * | 1973-06-29 | 1975-03-24 | ||
| AU504229B2 (en) | 1975-11-17 | 1979-10-04 | A.C. Hatrick Chemicals Pty. Ltd. | Aqueous disperse of fortified rosin |
| NZ183271A (en) * | 1976-03-08 | 1979-01-11 | Hercules Inc | Sized paper and paper board;sizing composition |
| SE415679B (en) * | 1976-07-21 | 1980-10-20 | Kenogard Ab | PROCEDURE FOR PREPARING A MAIN STABLE WATER DISPERSION OF COLOPHONIUM MATERIAL IN THE PRESENT OF A COTTON EMULDER |
| JPS53115549A (en) * | 1978-01-18 | 1978-10-09 | Sharp Corp | Moisture exchanging element |
| JPS53115550A (en) * | 1978-01-18 | 1978-10-09 | Sharp Corp | Moisture exchanging element |
| US4263182A (en) * | 1979-09-06 | 1981-04-21 | Hercules Incorporated | Stable dispersions of fortified rosin |
| JPS57111355A (en) * | 1980-12-27 | 1982-07-10 | Harima Kasei Kogyo Kk | Preparation of aqueous reinforced rosin dispersion for paper making |
| JPS63191805U (en) * | 1987-05-27 | 1988-12-09 | ||
| GB9610955D0 (en) * | 1996-05-24 | 1996-07-31 | Hercules Inc | Sizing composition |
| JP6180917B2 (en) * | 2013-12-19 | 2017-08-16 | ハリマ化成株式会社 | Dispersant for sizing agent, sizing agent composition and paper |
| JP6525397B2 (en) * | 2015-09-28 | 2019-06-05 | 荒川化学工業株式会社 | Rosin-based emulsion sizing agent and paper obtained using the sizing agent |
| JP6942754B2 (en) | 2019-06-11 | 2021-09-29 | 株式会社ミツバ | Electric oil pump for clutch engagement of automobile transmission, electric oil pump for clutch engagement of automobile transmission Control method, electric oil pump for clutch engagement vehicle of vehicle and automobile transmission |
| JP7287218B2 (en) | 2019-09-26 | 2023-06-06 | ニデックパワートレインシステムズ株式会社 | electric oil pump controller, electric oil pump |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL268563A (en) * | 1960-08-31 | |||
| US3565755A (en) * | 1969-03-27 | 1971-02-23 | Hercules Inc | Rosin size and paper containing said size |
-
1974
- 1974-06-24 CA CA203,190A patent/CA1045735A/en not_active Expired
- 1974-06-27 NL NL7408707A patent/NL7408707A/en not_active Application Discontinuation
- 1974-07-11 JP JP49079713A patent/JPS5834509B2/en not_active Expired
- 1974-07-24 DE DE19742435614 patent/DE2435614B2/en not_active Ceased
- 1974-07-30 NO NO742757A patent/NO140992C/en unknown
- 1974-07-30 DK DK407274A patent/DK155219C/en not_active IP Right Cessation
- 1974-07-31 FR FR7427208A patent/FR2240251B1/fr not_active Expired
- 1974-07-31 BE BE147131A patent/BE818311A/en not_active IP Right Cessation
- 1974-08-01 GB GB3408774A patent/GB1439116A/en not_active Expired
- 1974-08-01 SE SE7409938A patent/SE414951B/en unknown
- 1974-08-02 FI FI2323/74A patent/FI62126C/en active
- 1974-08-05 ES ES428964A patent/ES428964A1/en not_active Expired
- 1974-08-05 AT AT638174A patent/AT337525B/en not_active IP Right Cessation
- 1974-08-05 CH CH1069274A patent/CH606265A5/xx not_active IP Right Cessation
- 1974-08-05 IT IT25980/74A patent/IT1017901B/en active
- 1974-08-06 ZA ZA00745014A patent/ZA745014B/en unknown
- 1974-08-06 BR BR6444/74A patent/BR7406444D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5036703A (en) | 1975-04-07 |
| JPS5834509B2 (en) | 1983-07-27 |
| FI232374A (en) | 1975-02-07 |
| DE2435614A1 (en) | 1975-02-27 |
| SE7409938L (en) | 1975-02-07 |
| AT337525B (en) | 1977-07-11 |
| NO742757L (en) | 1975-03-03 |
| DK407274A (en) | 1975-04-01 |
| FI62126B (en) | 1982-07-30 |
| AU7196674A (en) | 1976-02-05 |
| ES428964A1 (en) | 1976-11-16 |
| DK155219B (en) | 1989-03-06 |
| ATA638174A (en) | 1976-10-15 |
| FI62126C (en) | 1982-11-10 |
| GB1439116A (en) | 1976-06-09 |
| IT1017901B (en) | 1977-08-10 |
| BE818311A (en) | 1974-11-18 |
| FR2240251B1 (en) | 1979-09-21 |
| SE414951B (en) | 1980-08-25 |
| BR7406444D0 (en) | 1975-05-27 |
| DE2435614B2 (en) | 1977-12-08 |
| DK155219C (en) | 1989-07-24 |
| NL7408707A (en) | 1975-02-10 |
| CA1045735A (en) | 1979-01-02 |
| ZA745014B (en) | 1975-08-27 |
| CH606265A5 (en) | 1978-10-31 |
| FR2240251A1 (en) | 1975-03-07 |
| NO140992C (en) | 1979-12-19 |
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