NO125634B - - Google Patents
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- NO125634B NO125634B NO104769A NO104769A NO125634B NO 125634 B NO125634 B NO 125634B NO 104769 A NO104769 A NO 104769A NO 104769 A NO104769 A NO 104769A NO 125634 B NO125634 B NO 125634B
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- Prior art keywords
- urea
- formaldehyde
- parts
- aqueous solution
- net
- Prior art date
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 70
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 47
- 239000004202 carbamide Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 16
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 239000012798 spherical particle Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 8
- 239000007859 condensation product Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical class [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SUHOOTKUPISOBE-UHFFFAOYSA-N O-phosphoethanolamine Chemical compound NCCOP(O)(O)=O SUHOOTKUPISOBE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- NTOLGSSKLPLTDW-UHFFFAOYSA-N hydrogen sulfate;phenylazanium Chemical compound OS(O)(=O)=O.NC1=CC=CC=C1 NTOLGSSKLPLTDW-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
Description
Fremgangsmåte til fremstilling av høydisperse, faste, tilnærmet kuleformede partikler av nettdannede urinstoff-formaldehyd-polykondensasjonsprodukter med Process for the production of highly dispersed, solid, approximately spherical particles of net-formed urea-formaldehyde polycondensation products with
midlere diameter mindre enn 1000 Å. mean diameter less than 1000 Å.
I britiske patenter nr. 1.0^3.^37 og 1.071.307 er det omtalt fremgangsmåter til fremstilling av "findelte, uoppløselige og usmeltbare faste stoffer med stor indre overflate" på basis av melamin og formaldehyd. Slike syntetiske, høydisperse faste stoffer egner seg til blua. forsterkning av natur- og syntesekautsjuk. I forhold til de vanligvis for dette formål anvendte høydisperse fyllstoffer på karbon- eller kiselsyrebasis utmerker de seg ved noen fordelaktige, i praktisk bruk verdifulle egenskaper som gode mekan-iske, egenskaper, små varige deformasjoner forbundet med lav tetthet og lys farge av gummi-vulkanisatene. Kautsjukblandinger og vulkani-sater.som inneholder denne nye type av høydisperse fyllstoffer er omtalt i britisk patent nr. 1.029-Ml. In British patents Nos. 1,0^3,^37 and 1,071,307, methods are described for the production of "finely divided, insoluble and infusible solids with a large internal surface" on the basis of melamine and formaldehyde. Such synthetic, highly dispersed solids are suitable for blua. reinforcement of natural and synthetic rubber. In relation to the highly dispersed carbon or silicic acid-based fillers usually used for this purpose, they are distinguished by some advantageous, in practical use valuable properties such as good mechanical properties, small permanent deformations associated with low density and light color of the rubber vulcanizates . Rubber compounds and vulcanizates containing this new type of highly dispersed fillers are described in British patent no. 1,029-Ml.
Kfr. kl. 39b<2>-ll/74 Cf. at 39b<2>-ll/74
Ifølge fransk patent nr. 898.915 er det kjent en fremgangsmåte hvor det bare fåes viskose forkondensasjonsprodukter av urinstoff eller tiourinstoff eller blandinger herav med acetataldehyd og formaldehyd, og først ved videreforarbeidingen som f.eks. impregneringsmiddel eller som tilsetning til pressmasser overføres i en høymolekylær tilstand. Ved overføring av slike forkondensater ved anvendelse av f.eks. varme og/eller trykk i høyere nettdannede faste kondensasjonsprodukter og knusing etter vanlige metoder fåes pulvere med helt irregulær partikkelstørrelse og -former. Det er umulig bare ved slik mekanisk knusing å fremstille partikler mindre enn 1000 Å. According to French patent no. 898,915, a method is known in which only viscous precondensation products of urea or thiourea or mixtures thereof with acetaldehyde and formaldehyde are obtained, and only during further processing such as e.g. impregnating agent or as an additive to pressing compounds is transferred in a high molecular state. When transferring such pre-condensates using e.g. heat and/or pressure in higher net formed solid condensation products and crushing according to usual methods, powders with completely irregular particle sizes and shapes are obtained. It is impossible to produce particles smaller than 1000 Å just by such mechanical crushing.
Ved fremgangsmåten iTølge US-patent nr. 2.389-416 fåes heller ikke helt utherdede kondensasjonsprodukter. Alt etter anvendt molforhold av utgangsstoffene (urinstoff, formaldehyd og glycinderivat resp. sulfaminsyre) fåes enten enkle urinstoffderivater som er angitt formelmessig og utmerker seg ved spesielt smeltepunkt eller viskose og oppløselige forkondensasjonsprodukter som likeledes analogt med frem-garigsmåteproduktene ifølge ovennevnte franske patent er egnet som impregneringsmiddel resp. som tilsetning for pressmasser. Disse forkondensater overføres altså først ved videreforarbeidelsen resp. app-likasjon i den høyeremolekylære faste tilstand,og ved mekanisk knusing av disse faste kondensasjonsprpdukter kan det ikke fåes partikler av enhetlig form og størrelse mindre enn 1000 Å. With the method in Tølge US patent no. 2,389-416, completely cured condensation products are not obtained either. Depending on the molar ratio of the starting materials used (urea, formaldehyde and glycine derivative or sulfamic acid), either simple urea derivatives are obtained which are indicated by formula and are characterized by a special melting point or viscous and soluble precondensation products which are also suitable as an impregnating agent, analogously to the process products according to the above-mentioned French patent respectively as an additive for press materials. These pre-condensates are therefore only transferred during further processing or application in the higher molecular solid state, and by mechanical crushing of these solid condensation products, particles of a uniform shape and size smaller than 1000 Å cannot be obtained.
Mot en mer utbredt anvendelse i teknikken står fremstillingsomkostningene for disse nye høydisperse fyllstoffer i de omtalte britiske patenter, idet fremstillingsomkostningene ligger betraktelig over omkostningene for fremstilling av aktivsot eller kolloidal kiselsyre. Dette skyldes to grunner, nemlig for det før-ste er et av de for disse stoffer anvendte utgangsmaterialer, melamin, The production costs for these new highly dispersed fillers in the mentioned British patents stand against a more widespread use in the technique, as the production costs are considerably higher than the costs for the production of activated carbon or colloidal silicic acid. This is due to two reasons, namely, firstly, one of the starting materials used for these substances, melamine,
relativt dyrt, for det annet er det delvis nødvendig med høye for-tynninger og lange oppholdstider i reaksjonskarene eller kostbare av-vanningsmetoder som azeotropisk avdestillering av vann for å få disse stoffers spesielle strukturer. Avviker man fra disse tidligere om-stendelige fremgangsmåtebetingelser, får man sterkt agglomerert eller sågar sammensintrede produkter med en meget liten spesifikk overflate, hvis forsterkningsevne er meget liten i den elastomere. relatively expensive, secondly, high dilutions and long residence times in the reaction vessels or expensive dewatering methods such as azeotropic distillation of water are partly necessary to obtain the special structures of these substances. If you deviate from these previously circumstantial process conditions, you get highly agglomerated or even sintered products with a very small specific surface area, the reinforcing ability of which is very small in the elastomer.
I ovennevnte britiske patent nr. 1.029.441 omtales bl.a. også forsterkning av naturkautsjuk med et høydisperst nettdannet urinstoff-formaldehyd-kondensasjonsprodukt såvel som også dets fremstilling, som imidlertid bare lykkes med dårlig utbytte (4l# referert til anvendt urinstoff og formaldehyd). Videre kreves her ved fremstilling av høydisperse urinstoff-formaldehyd-kondensasjansproduktet store mengder av hjelpe-stoffer, som etanolamin-fosfat som ikke kan gjenvinnes, og den til slutt nødvendige azeotrope tørkning av dette gelerte poly-kondensasjonsprodukt er på grunn av dets store spesifikke overflate forbundet med store tap av azeotrop hjelpevæske. Forsøk til forbedring av utbyttet og til unngåelse av den azeotrope tørkning slo feil. In the above-mentioned British patent no. 1,029,441, among other things, also reinforcement of natural rubber with a highly dispersed network formed urea-formaldehyde condensation product as well as its production, which, however, only succeeds with poor yield (4l# referred to urea and formaldehyde used). Furthermore, in the production of the highly dispersed urea-formaldehyde condensation product, large quantities of auxiliaries, such as ethanolamine phosphate, which cannot be recovered, are required here, and the ultimately necessary azeotropic drying of this gelled poly-condensation product is connected due to its large specific surface area with large losses of azeotropic auxiliary liquid. Attempts to improve the yield and to avoid the azeotropic drying failed.
Overraskende ble det imidlertid funnet at man kan fremstille høydisperse, nettdannede faste stoffer av urinstoff og formaldehyd som bl.a. egner seg som forsterkende fyllstoffer for elasto-: merer, som natur- eller syntesekautsjuk med gode utbytter, uten å Surprisingly, however, it was found that it is possible to produce highly dispersed, net-formed solids from urea and formaldehyde which, among other things, suitable as reinforcing fillers for elastomers, such as natural or synthetic rubber with good yields, without
måtte ta på kjøpet de ovennevnte fremgangsmåtetekniske vanskeligheter og økonomiske ulemper, når man geldanner et forkondensat av urinstoff og formaldehyd i nærvær av et beskyttelseskolloid ved hjelp av sulfaminsyre (amidosulfosyre, H2N-SO^H) eller et ammoniumhydrogensulfat. had to accept the above-mentioned process technical difficulties and economic disadvantages, when a pre-condensate of urea and formaldehyde is gelled in the presence of a protective colloid by means of sulfamic acid (amidosulfonic acid, H2N-SO^H) or an ammonium hydrogen sulfate.
Når man for fremstillingen av forkondensatet bringer mer enn 1 mol formaldehyd pr. mol urinstoff til reaksjon, får man etter tørking og knusing av gelen et produkt bestående av tilnærmet kuleformede partikler med midlere diameter under 1000 Å. When for the production of the precondensate, more than 1 mol of formaldehyde per moles of urea for reaction, after drying and crushing the gel, a product consisting of approximately spherical particles with an average diameter of less than 1000 Å is obtained.
Oppfinnelsen vedrører altså en fremgangsmåte til fremstilling av høydisperse, faste, tilnærmet kuleformede partikler av nettdannede urinstoff-formaldehyd-polykondensasjonsprodukter, eller av nettdannede modifiserte urinstoff-formaldehyd-polykondensasjonsprodukter, fortrinnsvis modifisert med melamin eller fenol, hvis midlere diameter er mindre enn 1000 Å, hvorved man knuser, tørker og desagglomererer polykondensasjonsproduktene som foreligger i gelform, idet fremgangsmåten er karakterisert ved at man anvender en vandig oppløsning av et forkondensat av urinstoff og formaldehyd eller et modifisert forkondensat av urinstoff og formaldehyd som i nærvær av et beskyttelseskolloid overføres i en nettdannet gel ved tilsetning av sulfamiÅsyre eller et vannoppløselig ammomiumhydrogensulfat med formel The invention thus relates to a method for the production of highly dispersed, solid, approximately spherical particles of net-formed urea-formaldehyde polycondensation products, or of net-formed modified urea-formaldehyde polycondensation products, preferably modified with melamine or phenol, whose average diameter is less than 1000 Å, whereby the polycondensation products which are in gel form are crushed, dried and deagglomerated, the method being characterized by using an aqueous solution of a pre-condensate of urea and formaldehyde or a modified pre-condensate of urea and formaldehyde which, in the presence of a protective colloid, is transferred into a net-formed gel by addition of sulfamic acid or a water-soluble ammonium hydrogen sulfate of formula
hvor R betyr et hydrogenatom eller en alkyl-, cykloalkyl-, hydroksy-alkyl-, aralkyl- eller arylrest, idet mengdeforholdet formaldehyd: urinstoff senest i geldannelsesøyeblikket er større enn 1. where R means a hydrogen atom or an alkyl, cycloalkyl, hydroxyalkyl, aralkyl or aryl residue, the amount ratio of formaldehyde: urea at the latest at the time of gel formation being greater than 1.
Man kan hvis ønsket i første rekke fremstille et forkondensat av urinstoff og mindre enn den totalt nødvendige mengde CH20 (f. eks. 1 mol CH20 pr. 1 mol uirinstoff) ,og først tilsette den resterende mengde formaldehyd ved den etterfølgende geldannelse. If desired, one can first of all prepare a pre-condensate of urea and less than the total required amount of CH20 (e.g. 1 mol CH20 per 1 mol of urea), and first add the remaining amount of formaldehyde during the subsequent gel formation.
Hensiktsmessig anvender man imidlertid allerede ved forkondensatets fremstilling mer enn 1 mol, og fortrinnsvis omtrent 1,5 mol formaldehyd pr. 1 mol urinstoff. Anvendelsen av mer enn 2 mol formaldehyd pr. 1 mol urinstoff er riktignok ikke uoperativt, imidlertid uøkonomisk. Appropriately, however, more than 1 mol, and preferably approximately 1.5 mol of formaldehyde per 1 mole of urea. The use of more than 2 mol of formaldehyde per 1 mol of urea is certainly not inoperable, but uneconomical.
Forkondensatet fremstiller man på hensiktsmessig måte The pre-condensate is prepared in an appropriate manner
i pH-området mellom 6 og 9 og i temperaturområdet mellom 40 og 100°C. Reaksjonstiden skal hensiktsmessig være så lang at den største del av formaldehydet (omtrent 90%) har anledning til å reagere med urin-stof f et, imidlertid ikke så lang at forkondensatets vanntoleranse blir så liten at dets homogene sammenblanding med syreoppløsningen ikke mer er mulig. Relativt høye temperaturer og relativt lave pH-verdier fører i kortere tid til den ønskede polykondensasjonsgrad. Hensiktmessig tilsettes beskyttelseskolloidet til forkondensatet ved et eller annet stadium av dets fremstilling; man kan imidlertid uten ulempe for seg tilberede en oppløsning av beskyttelseskolloidet og sette dette til den ferdige forkondensatoppløsning først før geldannelsen. Med beskyttelseskolloider forstås i denne forbindelse vann-oppløselige makromolekylære stoffer som sterkt øker vandige oppløs-ningers viskositet.- Typiske representanter for denne forbindelses-klasse er natriumsaltet av karboksymetylcellulose, metyl-, etyl- og 6-hydroksyetylcellulose, polyvinylalkohol, vannoppløselige polymere og copolymere av akryl- eller metakrylsyre. De konsentrasjoner hvori disse stoffer utfolder deres beste virkning, avhenger av deres kjem-iske struktur og av deres molekylvekt. De er vanligvis virksomme i mengder mellom 0,1 og 10%, fortrinnsvis mellom 0,5 og 5$, referert til vekten av urinstoff og formaldehyd. in the pH range between 6 and 9 and in the temperature range between 40 and 100°C. The reaction time should appropriately be so long that the largest part of the formaldehyde (approximately 90%) has the opportunity to react with urea, but not so long that the water tolerance of the precondensate becomes so small that its homogeneous mixing with the acid solution is no longer possible. Relatively high temperatures and relatively low pH values lead in a shorter time to the desired degree of polycondensation. Conveniently, the protective colloid is added to the precondensate at some stage of its preparation; however, one can prepare a solution of the protective colloid and add this to the finished pre-condensate solution only before the gel is formed. In this context, protective colloids are understood as water-soluble macromolecular substances that greatly increase the viscosity of aqueous solutions. - Typical representatives of this class of compounds are the sodium salt of carboxymethyl cellulose, methyl, ethyl and 6-hydroxyethyl cellulose, polyvinyl alcohol, water-soluble polymers and copolymers of acrylic or methacrylic acid. The concentrations in which these substances exert their best effect depend on their chemical structure and on their molecular weight. They are usually effective in amounts between 0.1 and 10%, preferably between 0.5 and 5%, referred to the weight of urea and formaldehyde.
Geldannelsen tilveiebringes ved sammenblanding av forkondensatet med en oppløsning av amidosulfonsyre eller av eventuelt substituerte ammoniumhydrogensulfater ved temperaturen mellom værelse-temperatur og 100°C. Når syrestyrken og temperatur velgesoriktig, starter geldannelsen i løpete av få sekunder. Man må derfor sørge for intens korttids sammenblanding av forkondensat og syreoppløsning. En kontinuerlig sammenbinding av de to oppløsninger er hertil spesielt hensiktsmessig. Geldannelsen er svakt eksoterm - varmekapasiteten av reaksjonsblandinger rekker imidlertid godt til, også under adia-batiske betingelser å oppta reaksjonsvarme, som vanligvis forårsaker en temperaturøkning på 10-15°C. The gel formation is provided by mixing the pre-condensate with a solution of amidosulphonic acid or of optionally substituted ammonium hydrogen sulphates at a temperature between room temperature and 100°C. When the acid strength and temperature are chosen correctly, gel formation starts within a few seconds. One must therefore provide for intense short-term mixing of precondensate and acid solution. A continuous connection of the two solutions is particularly appropriate for this purpose. The gel formation is slightly exothermic - however, the heat capacity of reaction mixtures is sufficient, even under adiabatic conditions, to absorb reaction heat, which usually causes a temperature increase of 10-15°C.
Eksempler for eventuelt substituerte ammoniumhydrogensulfater med formel (I) er ved siden av NH, <9> . HSOj. <6>; CH^-NH^<®>. HSO^ C2H5NH3 . HSO^ HO-CH2CH2-NH3 . HSO^ ; Examples of optionally substituted ammonium hydrogen sulfates with formula (I) are next to NH, <9> . HSOj. <6>; CH^-NH^<®>. HSO^ C 2 H 5 NH 3 . HSO^ HO-CH2CH2-NH3 . HSO^ ;
Hvor aminkomponentens basisitet er for stor er det hensiktsmessig å tilsette noe overskytende svovelsyre til ammoniumsalt-oppløsningen. Where the basicity of the amine component is too great, it is appropriate to add some excess sulfuric acid to the ammonium salt solution.
På tross av dets høye vanninnhold er gelen formbestandig. Den er lett å knuse, eksempelvis ved hjelp av en ekstruder eller en skjæregranulator. Etter knusning kan gelen gjøres nøytral i vandig oppslemming. Den frafiltreres eller frasentrifugeres og eventuelt vaskes for å fjerne uorganisk salt. Etter tørking og avkjøling des-agglomerer man det faste, usmeltbare og uoppløselige polykondensa-sjonsprodukt ved hjelp av en slag- eller strålemølle. Despite its high water content, the gel is dimensionally stable. It is easy to crush, for example with the help of an extruder or a cutting granulator. After crushing, the gel can be made neutral in an aqueous slurry. It is filtered off or centrifuged off and possibly washed to remove inorganic salt. After drying and cooling, the solid, infusible and insoluble polycondensation product is desagglomerated using an impact or jet mill.
I polykondensasjonsjréaksjonen kan man - enten det er, i forkondensasjonsstadiet eller geldannelsesstadiet - foruten urinstoff dessuten la det delta andre forbindelser som er i stand til med formaldehyd å danne polykondensasjonsharpikser. Som slike kommer det i første rekke på tale aminoplastdannere som tiourinstoff, dicyandiamid, melamin, benzoguanamin og anilin; imidlertid egner også fenol og al-kylfenoler seg hertil. Med denne type av modifisering kan man for-andre strukturen og overflateaktiviteten av disse høydisperse, nettdannede polykondensasjonsprodukter og å tilpasse dem på denne måte til spesifikke anvendelsesformål. In the polycondensation reaction, one can - whether in the pre-condensation stage or the gel formation stage - in addition to urea, other compounds which are capable of forming polycondensation resins with formaldehyde can also be added. As such, aminoplast formers such as thiourea, dicyandiamide, melamine, benzoguanamine and aniline are primarily mentioned; however, phenol and alkylphenols are also suitable for this. With this type of modification, it is possible to change the structure and surface activity of these highly dispersed, net-formed polycondensation products and to adapt them in this way to specific application purposes.
I de følgende eksempler betyr deler vektdeler og pro-senter vektprosenter. In the following examples, parts means parts by weight and percent means percentages by weight.
Eksempel 1. Example 1.
6,3 deler av en høymolekylær natrium-karboksymetylcellulose oppløses i 315 deler vann, 450 deler 30#-ig vandig formalde-hydoppløsning tilsettes, med fortynnet natronlut innstilles pH = 7, og oppvarmes til 70°C. Man tilsetter 180 deler urinstoff og kondens-erer i 3 timer ved pH = 7 og 70°C. 6.3 parts of a high molecular weight sodium carboxymethyl cellulose are dissolved in 315 parts of water, 450 parts of 30% aqueous formaldehyde solution are added, with diluted caustic soda the pH is set to 7, and heated to 70°C. 180 parts of urea are added and condensed for 3 hours at pH = 7 and 70°C.
Det således dannede forkondensat avkjøles^ til 50°C og sammenblandes hurtig med en oppløsning av 9,7 deler sulfaminsyre i 300 deler vann, som likeledes var blitt oppvarmet til 50°C. Geldannelsen starter etter 12 sekunder, temperaturen øker til 60-65°C. Man hensetter gelen i 3 timer ved denne temperatur, knuser den i en skjæregranulator, oppslemmer den i 1-2 ganger vannmengden, frasentrifugerer, vasker og tørker den ved 80°C i luftstrøm. Etter avkjøling desagglo-merer man produktet ved maling i en stiftmølle. The precondensate thus formed is cooled to 50°C and quickly mixed with a solution of 9.7 parts of sulfamic acid in 300 parts of water, which had likewise been heated to 50°C. Gel formation starts after 12 seconds, the temperature increases to 60-65°C. The gel is left for 3 hours at this temperature, crushed in a cutting granulator, slurried in 1-2 times the amount of water, centrifuged, washed and dried at 80°C in a stream of air. After cooling, the product is deagglomerated by grinding in a pin mill.
Man får 230 deler av et hvitt pulver med en volumvekt (engelsk "bulk density") på ca.. 77 g/liter og med en spesifikk vekt på 1,46 g/crn^. Det elektronmikroskopiske bilde viser tilnærmet kuleformede enkeltpartikler med en midlere diameter på 400 Å. Den spesifikke overflate utgjør 72 m 2/g. You get 230 parts of a white powder with a bulk density of approx. 77 g/litre and a specific weight of 1.46 g/cmn^. The electron microscopic image shows approximately spherical single particles with a mean diameter of 400 Å. The specific surface area is 72 m 2 /g.
Eksempel 2. Example 2.
Man oppløser 11,5 deler polyvinylalkohol i 380 deler vann, oppvarmer til 70°C og tilsetter 465 deler 30%- ig vandig form-aldehydoppløsning, 162 deler urinstoff og 37,7 deler melamin, idet man holder mest mulig konstant pH = 7 og temperatur = 70°G. Man kon-denserer i 3 timer ved pH = 7 og 70°C. Man avkjøler til 50°C og sam-menblander forkondensatet hurtig med en oppløsning av 2,2 deler n-butylamin og 9,8 deler svovelsyre i 300 deler vann av 50°C. 11.5 parts of polyvinyl alcohol are dissolved in 380 parts of water, heated to 70°C and 465 parts of a 30% aqueous formaldehyde solution, 162 parts of urea and 37.7 parts of melamine are added, keeping the pH = 7 as constant as possible and temperature = 70°C. Condensation is carried out for 3 hours at pH = 7 and 70°C. It is cooled to 50°C and the precondensate is quickly mixed with a solution of 2.2 parts of n-butylamine and 9.8 parts of sulfuric acid in 300 parts of water at 50°C.
Produktet opparbeides etter 3 timer, således som er omtalt i eksempel 1. Utbytte: 218 deler, volumvekt: 218 g/liter, spesifikk overflate: 30 m<2>/g. The product is worked up after 3 hours, as described in example 1. Yield: 218 parts, volumetric weight: 218 g/litre, specific surface area: 30 m<2>/g.
Eksempel 3- Example 3-
1286 deler av en 1%- ig oppløsning av natriumkarboksy-metylcellulose i vann, 900 deler 30%- ig vandig formaldehydoppløsning og 324 deler urinstoff kondenseres i 3 timer ved pH = 7 og 70°C. 1286 parts of a 1% solution of sodium carboxymethylcellulose in water, 900 parts of a 30% aqueous formaldehyde solution and 324 parts of urea are condensed for 3 hours at pH = 7 and 70°C.
a) En halvdel av dette forkondensat sammenblandes hurtig med en oppløsning av 28,2 deler fenol og 9,7 deler sulfaminsyre i a) One half of this precondensate is quickly mixed with a solution of 28.2 parts phenol and 9.7 parts sulfamic acid in
300 deler vann ved 70°C Og geleres. Etter opparbeidelse ifølge det som er angitt i eksempel 1 får man 236 deler av et hvitt pulver med en volumvekt på 54 g/liter og en spesifikk overflate på 40 m 2/g. Den midlere partikkelstørrelse utgjør ca. 450 Å. 300 parts water at 70°C and gelled. After processing according to what is indicated in example 1, 236 parts of a white powder with a volume weight of 54 g/litre and a specific surface area of 40 m 2 /g are obtained. The average particle size is approx. 450 Å.
b) Forkondensatets annen halvdel geldannes med en oppløs-ning av 60,6 deler anilinhydrogensulfat i 270 deler vann. Etter opparbeidelse ifølge det som er angitt i eksempel 1 får man 243 deler av et blasst rosafarget pulver med en volumvekt på 50 g/liter og en spesifikk overflate på 22,3 m 2/g. Den midlere partikkelstørrelse utgjør ca. 700 Å.. b) The other half of the precondensate is gelled with a solution of 60.6 parts of aniline hydrogen sulphate in 270 parts of water. After processing according to what is indicated in example 1, 243 parts of a pale pink powder with a volume weight of 50 g/liter and a specific surface area of 22.3 m 2 /g are obtained. The average particle size is approx. 700 Å..
Eksempel 4. Example 4.
90 deler urinstoff og 150 deler 30%-ig vandig formalde-hydoppløsning kondenseres i 3 timer ved 50°C og pH 7,0. Dette forkondensat blir under omrøring ved 70°C inndryppet i en oppløsning av 2,7 deler polyvinylalkohol, 7,28 deler sulfaminsyre og av 2,5 deler formaldehyd i 480 deler vann. 90 parts of urea and 150 parts of 30% aqueous formaldehyde solution are condensed for 3 hours at 50°C and pH 7.0. This precondensate is dripped into a solution of 2.7 parts polyvinyl alcohol, 7.28 parts sulfamic acid and 2.5 parts formaldehyde in 480 parts water while stirring at 70°C.
Man lar det etterreagere i 6 timer ved 70°C under om-røring, avkjøler, innstiller til pH = 7,5, filtrerer og vasker. Etter tørkning og desagglomering som i eksempel 1 får man 101 deler av et hvitt pulver med en volumvekt på 217 g/liter og en spesiefikk overflate på 302 m 2/g. Det elektronmikroskopiske bilde viser en så sterk partikkelagglomering at bestemmelsen av dem midlere partikkeldiameter ikke mer er mulig. It is left to react for 6 hours at 70°C with stirring, cooled, adjusted to pH = 7.5, filtered and washed. After drying and deagglomeration as in example 1, 101 parts of a white powder are obtained with a bulk weight of 217 g/litre and a specific surface area of 302 m 2 /g. The electron microscopic image shows such a strong particle agglomeration that the determination of their average particle diameter is no longer possible.
Anvendelseseksempel. Application example.
I en Werner-Pfleiderer-blander fremstilleB en blanding av deler In a Werner-Pfleiderer mixer, a mixture of parts is prepared
+ beskyttet merkebetegnelse for mykningsmiddelolje fra Sun Oil Co. + protected brand name for plasticizer oil from Sun Oil Co.
(naftenisk petrolfraksjon med et flammepunkt på l65°C, som inneholder (naphthenic petrol fraction with a flash point of 165°C, which contains
19% aromatiske C-atomer, 4052 nafteniske C-atomer og Hl% parafiniske C-atomer). 19% aromatic C atoms, 4052 naphthenic C atoms and Hl% paraffinic C atoms).
++ beskyttet merkebetegnelse for antioksydant fra ICI (substituert fenol). ++ protected brand name for antioxidant from ICI (substituted phenol).
Claims (3)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH416968A CH522007A (en) | 1968-03-21 | 1968-03-21 | Process for the production of highly dispersed solids consisting of urea-formaldehyde polycondensation products |
Publications (1)
Publication Number | Publication Date |
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NO125634B true NO125634B (en) | 1972-10-09 |
Family
ID=4271086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO104769A NO125634B (en) | 1968-03-21 | 1969-03-13 |
Country Status (9)
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AT (1) | AT292305B (en) |
BE (1) | BE730186A (en) |
CH (1) | CH522007A (en) |
DE (1) | DE1907914C3 (en) |
FR (1) | FR2004360A1 (en) |
GB (1) | GB1239143A (en) |
NL (1) | NL149823B (en) |
NO (1) | NO125634B (en) |
SE (1) | SE360088B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3931063A (en) * | 1973-07-30 | 1976-01-06 | Ciba-Geigy Ag | Process for the manufacture of porous solids consisting of crosslinked urea-formaldehyde polycondensation products |
CH599260A5 (en) * | 1974-06-07 | 1978-05-31 | Ciba Geigy Ag | |
US4454254A (en) * | 1982-12-01 | 1984-06-12 | Basf Wyandotte Corporation | Aminoplast resins, dispersions, and low flammability cellular and non-cellular polyurethane products prepared therefrom |
GB2172894B (en) * | 1985-03-29 | 1989-05-10 | Muirhead Data Communications L | Melamine/formaldehyde and urea/formaldehyde resinous materials |
US4960856A (en) * | 1988-11-28 | 1990-10-02 | Georgia-Pacific Corporation | Urea-formaldehyde compositions and method of manufacture |
US5110898A (en) * | 1988-11-28 | 1992-05-05 | Georgia-Pacific Corporation | Method for manufacturing amino-aldehyde compositions |
DE19518942C2 (en) * | 1995-05-23 | 1998-12-10 | Fraunhofer Ges Forschung | Process for the production of metallized polymer particles and polymer material produced by the process and their use |
DE19713189A1 (en) | 1997-03-27 | 1998-10-01 | Kimberly Clark Gmbh | Personal hygiene product applied to the human skin |
DE102007038824A1 (en) | 2007-08-16 | 2009-02-19 | Basf Coatings Ag | Use of bismuth subnitrate in electrodeposition paints |
DE102008016220A1 (en) | 2008-03-27 | 2009-10-01 | Basf Coatings Ag | Electrocoating paints containing polymethyleneurea |
-
1968
- 1968-03-21 CH CH416968A patent/CH522007A/en not_active IP Right Cessation
-
1969
- 1969-02-17 DE DE19691907914 patent/DE1907914C3/en not_active Expired
- 1969-03-04 FR FR6905861A patent/FR2004360A1/fr not_active Withdrawn
- 1969-03-13 NO NO104769A patent/NO125634B/no unknown
- 1969-03-18 GB GB1429469A patent/GB1239143A/en not_active Expired
- 1969-03-20 BE BE730186A patent/BE730186A/xx unknown
- 1969-03-20 NL NL6904317A patent/NL149823B/en unknown
- 1969-03-20 AT AT277369A patent/AT292305B/en not_active IP Right Cessation
- 1969-03-20 SE SE389169A patent/SE360088B/xx unknown
Also Published As
Publication number | Publication date |
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FR2004360A1 (en) | 1969-11-21 |
CH522007A (en) | 1972-04-30 |
DE1907914B2 (en) | 1974-02-14 |
NL6904317A (en) | 1969-09-23 |
AT292305B (en) | 1971-08-25 |
DE1907914A1 (en) | 1969-10-16 |
DE1907914C3 (en) | 1974-10-10 |
GB1239143A (en) | 1971-07-14 |
BE730186A (en) | 1969-09-22 |
NL149823B (en) | 1976-06-15 |
SE360088B (en) | 1973-09-17 |
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