CH423246A - Process for the production of a synthetic resin and its use - Google Patents
Process for the production of a synthetic resin and its useInfo
- Publication number
 - CH423246A CH423246A CH418061A CH418061A CH423246A CH 423246 A CH423246 A CH 423246A CH 418061 A CH418061 A CH 418061A CH 418061 A CH418061 A CH 418061A CH 423246 A CH423246 A CH 423246A
 - Authority
 - CH
 - Switzerland
 - Prior art keywords
 - synthetic resin
 - styrene
 - added
 - tall oil
 - product
 - Prior art date
 
Links
- 229920003002 synthetic resin Polymers 0.000 title claims description 12
 - 239000000057 synthetic resin Substances 0.000 title claims description 12
 - 238000000034 method Methods 0.000 title claims description 11
 - 238000004519 manufacturing process Methods 0.000 title claims description 9
 - PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
 - LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
 - 239000003784 tall oil Substances 0.000 claims description 11
 - 239000002253 acid Substances 0.000 claims description 9
 - 239000003112 inhibitor Substances 0.000 claims description 6
 - BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 5
 - BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 5
 - RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
 - 238000000576 coating method Methods 0.000 claims description 5
 - WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
 - FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
 - DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical compound CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 claims description 3
 - LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
 - 150000008064 anhydrides Chemical class 0.000 claims description 2
 - JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
 - 230000001419 dependent effect Effects 0.000 claims 1
 - 239000000376 reactant Substances 0.000 claims 1
 - 239000002904 solvent Substances 0.000 claims 1
 - 239000000047 product Substances 0.000 description 9
 - QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
 - 239000000945 filler Substances 0.000 description 5
 - 239000003054 catalyst Substances 0.000 description 4
 - 238000006243 chemical reaction Methods 0.000 description 3
 - 239000011248 coating agent Substances 0.000 description 3
 - 239000000463 material Substances 0.000 description 3
 - 239000000203 mixture Substances 0.000 description 3
 - IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
 - CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
 - MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
 - VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
 - 239000007795 chemical reaction product Substances 0.000 description 2
 - 238000010438 heat treatment Methods 0.000 description 2
 - 238000006116 polymerization reaction Methods 0.000 description 2
 - 239000011541 reaction mixture Substances 0.000 description 2
 - 230000002269 spontaneous effect Effects 0.000 description 2
 - 150000003440 styrenes Chemical class 0.000 description 2
 - MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
 - -1 B. 25% Chemical compound 0.000 description 1
 - OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
 - 229910002092 carbon dioxide Inorganic materials 0.000 description 1
 - 239000001569 carbon dioxide Substances 0.000 description 1
 - 238000005266 casting Methods 0.000 description 1
 - 239000003795 chemical substances by application Substances 0.000 description 1
 - 238000005260 corrosion Methods 0.000 description 1
 - 230000007797 corrosion Effects 0.000 description 1
 - 230000000694 effects Effects 0.000 description 1
 - 235000013312 flour Nutrition 0.000 description 1
 - 239000007789 gas Substances 0.000 description 1
 - 239000003365 glass fiber Substances 0.000 description 1
 - NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
 - 239000011261 inert gas Substances 0.000 description 1
 - 239000012784 inorganic fiber Substances 0.000 description 1
 - VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
 - 239000011976 maleic acid Substances 0.000 description 1
 - 238000000465 moulding Methods 0.000 description 1
 - GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
 - 229910052757 nitrogen Inorganic materials 0.000 description 1
 - 238000010422 painting Methods 0.000 description 1
 - 150000002978 peroxides Chemical class 0.000 description 1
 - 239000000049 pigment Substances 0.000 description 1
 - 239000011435 rock Substances 0.000 description 1
 - 238000005507 spraying Methods 0.000 description 1
 - 238000003756 stirring Methods 0.000 description 1
 - 238000003860 storage Methods 0.000 description 1
 - 239000000126 substance Substances 0.000 description 1
 - 239000000725 suspension Substances 0.000 description 1
 - VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
 - 239000002023 wood Substances 0.000 description 1
 
Classifications
- 
        
- C—CHEMISTRY; METALLURGY
 - C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
 - C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
 - C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
 - C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
 
 - 
        
- 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
 - C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
 - C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
 - C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
 - C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
 
 - 
        
- 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
 - C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
 - C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
 - C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
 - C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
 - C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
 
 - 
        
- 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
 - C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
 - C08G63/66—Polyesters containing oxygen in the form of ether groups
 - C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
 - C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
 
 
Landscapes
- Chemical & Material Sciences (AREA)
 - Chemical Kinetics & Catalysis (AREA)
 - Organic Chemistry (AREA)
 - Health & Medical Sciences (AREA)
 - Medicinal Chemistry (AREA)
 - Polymers & Plastics (AREA)
 - Oil, Petroleum & Natural Gas (AREA)
 - Life Sciences & Earth Sciences (AREA)
 - Engineering & Computer Science (AREA)
 - Materials Engineering (AREA)
 - Wood Science & Technology (AREA)
 - Macromonomer-Based Addition Polymer (AREA)
 - Paints Or Removers (AREA)
 - Polyesters Or Polycarbonates (AREA)
 - Compositions Of Macromolecular Compounds (AREA)
 
Description
  
  
 
  Verfahren zur Herstellung eines Kunstharzes und seine Verwendung
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Kunstharzes mittels   Tallöl,    welches Kunstharz zur Herstellung von Oberflächen überzügen, zum Schutze gegen Korrosion, Poröswerden oder gegen Angriff von Chemikalien und Feuchtigkeit auf allen Arten von Materialien, verwendet werden kann.
   Das Kunstharz kann auch mit verschiedenen Füllmitteln vermischt werden und zur Herstellung von geformten Körpern (Formstücken) dienen.
   Das Verfahren zur Herstellung genannten Kunstharzes ist erfindungsgemäss dadurch gekennzeichnet, dass man Tallöl mit einem Glykol und einer dibasischen Säure oder deren Anhydrid zur Reaktion bringt. Die Reaktion erfolgt vorteilhafterweise bei einer Temperatur von   180-2200C,    während einer genügenden Zeitspanne, um eine   gewünschte Kon-    sistenz und Säurezahl zu erhalten. Zu diesem Produkt kann dann ein Inhibitor, welcher eine spontane Polymerisation während der Lagerung verhindern soll, hinzugefügt werden.
   Dieses so erfindungsgemäss erhaltene Kunstharz kann als Überzug auf verschiedenartige Oberflächen oder zur Herstellung von geformten Körpern durch Giessen verwendet werden. Unmittelbar vor der Verwendung kann vorteilhafterweise eine bestimmte Menge Styrol, die von der gewünschten Viskosität abhängt, ein Beschleuniger und ein Katalysator zu oben genanntem, erfindungsgemäss erhaltenen Produkt hinzugefügt werden. Diesem Gemisch kann auch gewünschtenfalls vor der Anwendung ein Füllmittel beigemengt werden. Das auf diese Weise hergestellte Material ist zum Gebrauch bereit und kann als Überzug auf verschiedene Oberflächen angewendet oder in Formen gegossen werden. Das Härten geht spontan vor sich, und ein Erhitzen ist notwendig.
   Die Härtezeit wird durch die hinzugefügten Mengen des Katalysators und des Beschleunigers be  stimmt.    Ein hoher Gehalt derselben verkürzt die Härtezeit auf nur einige Minuten, z. B. 5-10 Minuten, während bei einem niedrigen Gehalt dieselbe bis zu 8 Stunden dauert. Der Härteprozess ist exothermisch.
   Die Herstellung des Kunstharzes wird vorteil  hafternveise    mit   25-60%      Tallöl,    welches einen Abietinsäuregehalt von   4-29%    aufweist, 10-30% Glykol und   1640%    einer dibasischen Säure, durchgeführt. Der prozentuale Gehalt der verschiedenen Komponenten bezieht sich auf das Gewicht des Pro  duktes,    inkl. der Inhibitorlösung. Nachdem die genannten Komponenten zur Reaktion gebracht wurden, sollte die Säurezahl des Reaktionsproduktes in der Regel 30-60 sein und kann,   falls    notwendig, durch Hinzugabe eines Gemisches einer dibasischen Säure, bevor die Reaktion fortgesetzt wird, korrigiert werden.
   Das Glykol kann geeigneterweise ein Di-Propylenglykol oder Äthylenglykol sein. Die dibasische Säure kann Maleinsäure sein; mit Vorteil wird auch   Phthalsäure-oder    Maleinsäureanhydrid verwendet.
  Ein Tallöl mit einem höheren   Ahietinsäuregehaft    verursacht eine schnellere Polymerisation, als ein Tallöl mit einem niedrigen Abietinsäuregehalt. Als Inhibitor wird vorteilhafterweise Hydrochinon, in einer Menge von   0,05-0,2    %, und zwar in Form einer Styrollösung, hinzugefügt. Die Menge dieses für die Lösung des Inhibitors verwendeten Styrols beträgt etwa   10-20 %    des Produktes.
   Zu dem auf diese Weise erzeugten Produkt, werden unmittelbar vor der Verwendung, weitere Styrolmengen in Abhängigkeit von der gewünschten Viskosität, hinzugegeben. Zum Formen und zum Oberflächenanstrich werden nicht mehr als   30 %    Styrol beigemengt, während zum Aufspritzen eines   Über-     zuges bis zu   50 %    Styrol, vorteilhafterweise unter   Beimischen    einer kleinen Menge der dibasischen Säure, z. B.   5 %,    vor der Fortsetzung der Reaktion, hinzugesetzt werden. Wird das erfindungsgemäss her  gestellte    Produkt, z. B. zur   Herstellung    eines Brettes verwendet, dann soll   40-50%    Styrol zu dem Pro dukt hinzugefügt werden.
   Im Falle, dass das gewünschte Endprodukt die Form einer verglasten Oberfläche aufweisen soll, muss eine kleine Menge an Styrol, z. B.   25 %,    anwesend sein; zu dem Produkt wird   ein Beschleuni    gungsmittel, vorteilhafterweise Kobaltnaphthenatoder Kobaltoctoat in Form einer 6 % igen Styrollösung, oder   Aliiminiumchlorid    als Suspension in Styrol, hinzugesetzt. Der Katalysator besteht aus einem Peroxyd, z. B. Wasserstoffperoxyd, gelöst in Äthyl-butylketon. Dieser wird in einer Menge von etwa   2%    hinzugesetzt.
   Beispiel
Es wird ein Kunstharz erzeugt aus:
Tallöl mit   22 %      Abietinsäure      40%   
Di-Propylenglykol   22 %   
Maleinsäure-anhydrid 26 %    88%   
Styrol + Hydrochinon   12%   
100%
Die drei zuerst genannten Komponenten werden in ein verschliessbares, mit einer Gaszuführung und einem Rührer versehenes, Gefäss gefüllt. Nach Durchleiten eines inerten Gases, wie   Kohlendioxyd    oder Stickstoff über dem Reaktionsgemisch, wurde mit dem Erhitzen auf   200-2200C    unter Rühren begonnen. Bei dieser Temperatur wurde das Reak  tionsgemisch    während etwa 4 Stunden gehalten, dann wurde es gekühlt und die Hydrochinonlösung hinzugefügt. Das so erzeugte Produkt kann gelagert werden.
   Vor der Hinzugabe von Styrol wird ein Beschleunigungsmittel und ein Katalysator wie oben   beschrie    ben hinzugesetzt. Danach wird zu dem Gemisch ein Füllmittel, welches jedes üblicherweise benützte Füllmittel sein kann, beigegeben. Falls ein gewisser Farbeffekt gewünscht wird, können auch Pigmente hinzugefügt werden. Als Beispiele für Füllmittel können Gesteinsmehl, Sägemehl, Holzspäne und organische oder anorganische   Fibermateriahen,    wie Glasfiber, genannt werden.   
  
 
  Process for the production of a synthetic resin and its use
The present invention relates to a method for producing a synthetic resin by means of tall oil, which synthetic resin can be used for the production of surface coatings, for protection against corrosion, becoming porous or against attack by chemicals and moisture on all types of materials.
   The synthetic resin can also be mixed with various fillers and used to produce shaped bodies (molded pieces).
   The process for the production of said synthetic resin is characterized according to the invention in that tall oil is reacted with a glycol and a dibasic acid or its anhydride. The reaction is advantageously carried out at a temperature of 180-2200 ° C., for a period of time sufficient to obtain the desired consistency and acid number. An inhibitor, which is intended to prevent spontaneous polymerization during storage, can then be added to this product.
   This synthetic resin thus obtained according to the invention can be used as a coating on various surfaces or for the production of shaped bodies by casting. A certain amount of styrene, which depends on the desired viscosity, an accelerator and a catalyst can advantageously be added to the above-mentioned product obtained according to the invention immediately before use. If desired, a filler can also be added to this mixture before use. The material produced in this way is ready for use and can be applied as a coating to various surfaces or poured into molds. Hardening is spontaneous and heating is necessary.
   The hardening time is determined by the amounts of catalyst and accelerator added. A high content of the same shortens the curing time to only a few minutes, e.g. B. 5-10 minutes, while at a low level the same takes up to 8 hours. The hardening process is exothermic.
   The manufacture of the synthetic resin is advantageously carried out with 25-60% tall oil, which has an abietic acid content of 4-29%, 10-30% glycol and 1640% of a dibasic acid. The percentage of the various components relates to the weight of the product, including the inhibitor solution. After the components mentioned have been reacted, the acid number of the reaction product should generally be 30-60 and, if necessary, can be corrected by adding a mixture of a dibasic acid before the reaction is continued.
   The glycol may suitably be a di-propylene glycol or ethylene glycol. The dibasic acid can be maleic acid; Phthalic anhydride or maleic anhydride is also advantageously used.
  A tall oil with a higher abietic acid content causes faster polymerization than a tall oil with a low abietic acid content. Hydroquinone, in an amount of 0.05-0.2%, in the form of a styrene solution, is advantageously added as an inhibitor. The amount of this styrene used for the solution of the inhibitor is about 10-20% of the product.
   Immediately before use, further amounts of styrene are added to the product produced in this way, depending on the desired viscosity. No more than 30% styrene is added for molding and surface painting, while up to 50% styrene is added for spraying on a coating, advantageously with the addition of a small amount of the dibasic acid, e.g. B. 5%, may be added before continuing the reaction. If the product made according to the invention, z. B. used to make a board, then 40-50% styrene should be added to the product.
   In the event that the desired end product is to be in the form of a glazed surface, a small amount of styrene, e.g. B. 25%, be present; An accelerating agent, advantageously cobalt naphthenate or cobalt octoate in the form of a 6% strength styrene solution, or aluminum chloride as a suspension in styrene, is added to the product. The catalyst consists of a peroxide, e.g. B. hydrogen peroxide dissolved in ethyl butyl ketone. This is added in an amount of about 2%.
   example
A synthetic resin is made from:
Tall oil with 22% abietic acid 40%
Di-propylene glycol 22%
Maleic anhydride 26% 88%
Styrene + hydroquinone 12%
100%
The three components mentioned first are filled into a closable vessel equipped with a gas inlet and a stirrer. After an inert gas such as carbon dioxide or nitrogen had been passed through the reaction mixture, heating to 200-2200 ° C. was begun with stirring. The reaction mixture was held at this temperature for about 4 hours, then it was cooled and the hydroquinone solution was added. The product thus produced can be stored.
   Before the addition of styrene, an accelerator and a catalyst are added as described above. Then a filler, which can be any commonly used filler, is added to the mixture. If a certain color effect is desired, pigments can also be added. As examples of fillers, rock flour, sawdust, wood shavings and organic or inorganic fiber materials such as glass fiber can be mentioned.
 
  
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title | 
|---|---|---|---|
| SE943360A SE301206B (en) | 1960-04-08 | 1960-04-08 | 
Publications (1)
| Publication Number | Publication Date | 
|---|---|
| CH423246A true CH423246A (en) | 1966-10-31 | 
Family
ID=20276672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date | 
|---|---|---|---|
| CH418061A CH423246A (en) | 1960-04-08 | 1961-04-08 | Process for the production of a synthetic resin and its use | 
Country Status (5)
| Country | Link | 
|---|---|
| CH (1) | CH423246A (en) | 
| DE (1) | DE1250633B (en) | 
| DK (1) | DK103209C (en) | 
| GB (1) | GB906232A (en) | 
| SE (1) | SE301206B (en) | 
- 
        0
        
- DE DENDAT1250633D patent/DE1250633B/en active Pending
 
 - 
        1960
        
- 1960-04-08 SE SE943360A patent/SE301206B/xx unknown
 
 - 
        1961
        
- 1961-03-28 GB GB1126461A patent/GB906232A/en not_active Expired
 - 1961-04-08 CH CH418061A patent/CH423246A/en unknown
 - 1961-04-08 DK DK146361A patent/DK103209C/en active
 
 
Also Published As
| Publication number | Publication date | 
|---|---|
| GB906232A (en) | 1962-09-19 | 
| SE301206B (en) | 1968-05-27 | 
| DE1250633B (en) | 1967-09-21 | 
| DK103209C (en) | 1965-11-29 | 
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