PL89128B1 - - Google Patents
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- Publication number
- PL89128B1 PL89128B1 PL16288173A PL16288173A PL89128B1 PL 89128 B1 PL89128 B1 PL 89128B1 PL 16288173 A PL16288173 A PL 16288173A PL 16288173 A PL16288173 A PL 16288173A PL 89128 B1 PL89128 B1 PL 89128B1
- Authority
- PL
- Poland
- Prior art keywords
- urea
- formaldehyde
- resin
- condensation
- surfactants
- Prior art date
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 7
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- MLQBTMWHIOYKKC-KTKRTIGZSA-N (z)-octadec-9-enoyl chloride Chemical compound CCCCCCCC\C=C/CCCCCCCC(Cl)=O MLQBTMWHIOYKKC-KTKRTIGZSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- UZXLOVYBQPDQCA-UHFFFAOYSA-N 2-butylnaphthalene-1-sulfonic acid;sodium Chemical compound [Na].C1=CC=CC2=C(S(O)(=O)=O)C(CCCC)=CC=C21 UZXLOVYBQPDQCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- 239000003607 modifier Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alkyl sulphonate Chemical compound 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Mold Materials And Core Materials (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
Przedmiotem wynalazku jest sposób wytwarzania spoiwa, na bazie zywicy mocznikowo-formaldehydowej, do sporzadzania mas formierskich i rdzeniowych zwlaszcza o zwiekszonej plynnosci.Znany sposób wytwarzania spoiw zywicznych mocznikowo-formaldehydowych o niskiej zawartosci wol¬ nego formaldehydu polega na trójetapowej kondensacji mocznika i formaldehydu przy ogólnym stosunku molowym mocznika do formaldehydu wynoszacym 1 :1,3 do 2,1. W pierwszym etapie kondensacje prowadzi sie w srodowisku zasadowym o wartosci pH 7,0-8,5, w temperaturze 10-96°C w czasie 20-60 minut. W drugim etapie, proces przebiega w srodowisku kwasnym przy pH 3,8—6,0, w trzecim etapie produkt, kondensuje sie dodatkowo z alkaliami po dodaniu srodków zywico-twórczych takich jak: mocznik, tiomocznik, cyjamamid i tym podobnych. Po zakonczeniu trzeciego etapu kondensacji, zywice zageszcza sie pod próznia w srodowisku alkalicznym lub zobojetnia do pH7. ' Otrzymane tym sposobem spoiwa charakteryzuja sie przyrostem lepkosci w czasie skladowania, co miedzy innymi powoduje ograniczenie ich zastosowania przy sporzadzaniu mas formierskich i rdzeniowych, zwlaszcza mas o zwiekszonej plynnosci.Wedlug wynalazku, sposób wytwarzania spoiwa, którym jest zywica mocznikowo-formaldehydowa o nis¬ kiej zawartosci wolnego formaldehydu, otrzymana na drodze trójetapowej kondensacji mocznika i formaldehydu przy ogólnym stosunku molowym mocznika do formaldehydu jak 1 : 1,2 do 2,5 polega na dodatkowym modyfikowaniu jej srodkami powierzchniowo-czynnymi.Reakcje w pierwszym etapie kondensacji przeprowadza sie w srodowisku alkalicznym, najkorzystniej przy pH 7,0—8,5 w temperaturze 10—96°C. W drugim etapie kondensacji pH masy reagujacej obniza sie do 3,0—6,0, proces prowadzi sie najkorzystniej w temperaturze wrzenia. Trzeci natomiast etap kondensacji prowadzi sie w podwyzszonej temperaturze w srodowisku alkalicznym, przy czym w celu obnizenia stosunku molowego reagentów dodaje sie srodki wiazace formaldehyd, najkorzystniej mocznik, tiomocznik, dwucyjanodwuamid, melamine lub quanidyne. Stwierdzono takze, ze równiez stabilne wlasnosci zywicy uzyskuje sie prowadzac trzeci etap kondensacji w srodowisku obojetnym lub slabo kwasnym.Do tak przygotowanej zywicy wprowadza sie w dowolnym etapie kondensacji srodki powierzchniowo- czynne, najkorzystniej: chlorek kwasu olejowego z N-metylotauryna^sulfonian alkilowy, addukty tlenku etylenu2 89128 i alkilofenolu lub ich mieszaniny. Srodki powierzchniowo-czynne moga byc wprowadzone równiez w postaci roztworów wodnych. Srodki powierzchniowo-czynne dodaje sie najkorzystniej w ilosci 0,1 do 10% wagowych w odniesieniu do zywicy.Spoiwo otrzymane sposobem wedlug wynalazku, charakteryzuje sie jednorodnoscia i stabilnoscia w czasie skladowania, oraz zawiera minimalne ilosci wolnego formaldehydu.Spoiwo wedlug wynalazku znajduje zastosowanie przede wszystkim przy sporzadzaniu mas formierskich lub rdzeniowych, zwlaszcza posiadajacych zwiekszona plynnosc, posiada znikomy stopien toksycznosci, a masy sporzadzane na bazie tego spoiwa charakteryzuja sie doskonala wybijalnoscia.Przyklady wytwarzania spoiwa sposobem wedlug wynalazku: Przyklad I. 172,5 czesci wagowych 40% formaliny doprowadza sie do pH 7,2 przy uzyciu 10% roztworu NaOH. Nastepnie dodaje sie 60 czesci wagowych mocznika i otrzymana mieszanine podgrzewa sie w czasie okolo 20 minut do stanu wrzenia, po czym przy uzyciu 5% roztworu HCI obniza sie pH do 4,0 i proces kondensacji prowadzi sie do uzyskania tolerancji zywica-woda w stosunku 1 : 5,0. W nastepnej kolejnosci dodaje sie 10% roztwór NaOH do uzyskania pH 8,5 oraz 46,0 czesci wagowych mocznika. Otrzymany kondensat ogrzewa sie z kolei w czasie okolo 10 minut w temperaturze 60°C, ochladza sie i nastepnie dodaje 1,5 czesci wagowych produktu kondensacji chlorku kwasu olejowego z N-metylotauryna oraz 3,0 czesci wagowe sulfonianu alkilowego.Przyklad II. 165 czesci wagowych formaliny (40% objetosciowo) doprowadza sie do pH 8,5 przy uzyciu 10% roztworu NaOH. Nastepnie daje sie 60 czesci wagowych mocznika i otrzymana mieszanine podgrzewa sie w ciagu 15 minut do wrzenia. Po 10 minutach wrzacy roztwór zakwasza sie 3% roztworem kwasu solnego do pH 5,2 i proces kondensacji prowadzi sie do uzyskania tolerancji zywica-woda w stosunku 1 : 3,0.Nastepnie cfodaje sie 10% roztwór NaOH do uzyskania pH 6,7 oraz 23 czesci wagowe mocznika. Otrzymana zywice ogrzewa sie w czasie 20 minut w temperaturze 50°C, chlodzi do temperatury 30°C i dodaje mieszanine wodnego roztworu soli sodowej kwasu butylonaftalenosulfonowego z adduktem tlenku etylenu i alkilofenolu w stosunku 3 : 1 w ilosci 6 czesci wagowych w itosunku do zywicy.Przyklad zastosowania spoiwa wedlug wynalazku. 100 czesci wagowych piasku kwarcowego miesza sie z 1 czescia wagowa substancji hydrof ilowej w czasie 30 sekund do 1,5 minuty w zaleznosci od rodzaju urzadzen mieszajacych. Nastepnie dodaje sie 4,0 czesci wagowe spoiwa wedlug wynalazku i miesza sie w czasie od 1,0 do 2 minut. Na koncu dodaje sie kwasny katalizator wiazania i miesza sie ponownie przez 30 sekund. Z tak przygotowanej masy wykonuje sie rdzenie dla sreanich i ciezkich odlewów. PLThe subject of the invention is a method for the production of a binder based on urea-formaldehyde resin, for the preparation of molding and core sands, especially those with increased liquidity. a molar mole of urea to formaldehyde of 1: 1.3 to 2.1. In the first stage, condensations are carried out in a basic environment with a pH value of 7.0-8.5, at a temperature of 10-96 ° C for 20-60 minutes. In the second stage, the process takes place in an acidic environment at a pH of 3.8-6.0, in the third stage the product is additionally condensed with alkali after adding resin-forming agents such as urea, thiourea, cyamamide and the like. Upon completion of the third condensation step, the resins are concentrated under vacuum in an alkaline or neutralized environment to pH7. The binders obtained in this way are characterized by an increase in viscosity during storage, which, among other things, limits their use in the preparation of molding and core sands, especially sands with increased liquidity. According to the invention, the method of producing a binder, which is urea-formaldehyde resin with low the content of free formaldehyde obtained by the three-stage condensation of urea and formaldehyde with a general molar ratio of urea to formaldehyde of 1: 1.2 to 2.5 consists in additional modification of it with surfactants. The reactions in the first stage of condensation are carried out in an alkaline environment, most preferably at a pH of 7.0-8.5 and a temperature of 10-96 ° C. In the second stage of condensation, the pH of the reacting mass drops to 3.0-6.0, the process is most preferably carried out at the boiling point. The third condensation step, on the other hand, is carried out at elevated temperature in an alkaline environment, and formaldehyde binders, most preferably urea, thiourea, dicyandiamide, melamine or quanidines, are added to lower the molar ratio of the reactants. It has also been found that stable properties of the resin are also obtained by carrying out the third condensation stage in an inert or slightly acidic environment. To the prepared resin, surfactants are added at any condensation stage, most preferably: oleic acid chloride with N-methyl taurine, alkyl sulfonate, adducts ethylene oxide 89128 and alkylphenol or mixtures thereof. Surfactants can also be introduced in the form of aqueous solutions. The surfactants are most preferably added in an amount of 0.1 to 10% by weight, based on the resin. The binder according to the invention is homogeneous and stable during storage, and contains minimal amounts of free formaldehyde. in the preparation of molding or core sands, especially those with increased fluidity, it has a negligible degree of toxicity, and the sands made on the basis of this binder are characterized by excellent knock-out properties. Examples of binder preparation according to the invention: Example I. 172.5 parts by weight of 40% formalin is brought to pH 7.2 with 10% NaOH solution. Then 60 parts by weight of urea are added and the mixture is heated to boiling for about 20 minutes, then the pH is lowered to 4.0 with a 5% HCl solution and the condensation process is carried out to a resin-water tolerance of 1 : 5.0. Next, 10% NaOH solution is added until the pH is 8.5 and 46.0 parts by weight of urea. The resulting condensate is then heated for about 10 minutes at 60 ° C, cooled and then added 1.5 parts by weight of the condensation product of oleic acid chloride with N-methyl taurine and 3.0 parts by weight of an alkyl sulphonate. Example II. 165 parts by weight of formalin (40% by volume) is adjusted to pH 8.5 with 10% NaOH solution. Then 60 parts by weight of urea are added and the mixture obtained is heated to boiling for 15 minutes. After 10 minutes, the boiling solution is acidified with a 3% hydrochloric acid solution to a pH of 5.2 and the condensation process is carried out to a resin-water tolerance in a ratio of 1: 3.0. Then 10% NaOH solution is added to a pH of 6.7 and 23 parts by weight of urea. The resulting resin is heated for 20 minutes at 50 ° C, cooled to 30 ° C and a 3: 1 mixture of an aqueous solution of sodium butylnaphthalenesulfonic acid with an adduct of ethylene oxide and alkylphenol in an amount of 6 parts by weight relative to the resin is added. Example of the use of a binder according to the invention. 100 parts by weight of quartz sand is mixed with 1 part by weight of a hydrophilic substance for 30 seconds to 1.5 minutes, depending on the type of mixing equipment. Then 4.0 parts by weight of the binder according to the invention are added and mixed for 1.0 to 2 minutes. Finally, the acid binding catalyst is added and mixed again for 30 seconds. Cores for steel and heavy castings are made of such prepared mass. PL
Claims (4)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL16288173A PL89128B1 (en) | 1973-05-28 | 1973-05-28 | |
| DE2400908A DE2400908A1 (en) | 1973-05-28 | 1974-01-09 | Urea-formaldehyde foundry mould binder - has improved flowability, homogeneity and less free HCHO |
| ES425769A ES425769A1 (en) | 1973-05-28 | 1974-04-29 | Procedure for the manufacture of an agglutinant. (Machine-translation by Google Translate, not legally binding) |
| DD17873974A DD112086A5 (en) | 1973-05-28 | 1974-05-24 | |
| AT434374A AT348259B (en) | 1973-05-28 | 1974-05-27 | PROCESS FOR MANUFACTURING A UREA FORMALDEHYDE BINDING AGENT WITH LOW FREE FORMALDEHYDE CONTENT |
| IT2321474A IT1012844B (en) | 1973-05-28 | 1974-05-27 | PROCEDURE FOR THE PRODUCTION OF A BINDER BY GROUND FROM RIA FUND |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL16288173A PL89128B1 (en) | 1973-05-28 | 1973-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL89128B1 true PL89128B1 (en) | 1976-10-30 |
Family
ID=19962791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL16288173A PL89128B1 (en) | 1973-05-28 | 1973-05-28 |
Country Status (6)
| Country | Link |
|---|---|
| AT (1) | AT348259B (en) |
| DD (1) | DD112086A5 (en) |
| DE (1) | DE2400908A1 (en) |
| ES (1) | ES425769A1 (en) |
| IT (1) | IT1012844B (en) |
| PL (1) | PL89128B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK2474373T3 (en) | 2008-08-29 | 2014-03-10 | Basf Se | A method of stabilizing subterranean formations with the curable urea-formaldehyde resin |
-
1973
- 1973-05-28 PL PL16288173A patent/PL89128B1/pl unknown
-
1974
- 1974-01-09 DE DE2400908A patent/DE2400908A1/en active Pending
- 1974-04-29 ES ES425769A patent/ES425769A1/en not_active Expired
- 1974-05-24 DD DD17873974A patent/DD112086A5/xx unknown
- 1974-05-27 AT AT434374A patent/AT348259B/en not_active IP Right Cessation
- 1974-05-27 IT IT2321474A patent/IT1012844B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| ES425769A1 (en) | 1976-06-16 |
| IT1012844B (en) | 1977-03-10 |
| DD112086A5 (en) | 1975-03-20 |
| ATA434374A (en) | 1978-06-15 |
| DE2400908A1 (en) | 1974-12-05 |
| AT348259B (en) | 1979-02-12 |
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