DE943381C - Process for the preparation of terpene maleic anhydride resins - Google Patents
Process for the preparation of terpene maleic anhydride resinsInfo
- Publication number
- DE943381C DE943381C DEA20608A DEA0020608A DE943381C DE 943381 C DE943381 C DE 943381C DE A20608 A DEA20608 A DE A20608A DE A0020608 A DEA0020608 A DE A0020608A DE 943381 C DE943381 C DE 943381C
- Authority
- DE
- Germany
- Prior art keywords
- maleic anhydride
- reaction
- turpentine
- preparation
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 11
- 235000007586 terpenes Nutrition 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 title claims description 5
- 239000011347 resin Substances 0.000 title claims description 5
- -1 terpene maleic anhydride Chemical class 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001293 FEMA 3089 Substances 0.000 claims description 8
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000001739 pinus spp. Substances 0.000 claims description 6
- 229940036248 turpentine Drugs 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000003505 terpenes Chemical class 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 description 6
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 229930006722 beta-pinene Natural products 0.000 description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 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
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Description
Verfahren zur Herstellung von Terpen-Maleinsäureanhydrid-Harzen Es ist bekannt, daß man Säureharze erhalten kann, wenn man mono- oder bicyclische Terpene, wie a-Terpinen, a-Pinen, ß-Pinen, Limonen, in der Wärme mit Maleinsäureanhydrid umsetzt.Process for the preparation of terpene-maleic anhydride resins It is known that acid resins can be obtained if mono- or bicyclic terpenes, such as α-terpinene, α-pinene, β-pinene, limonene, are reacted with maleic anhydride under heat.
Gemäß diesen -bekannten Verfahren werden die Reaktionskomponenten zusammengegeben und dann zusammen erhitzt, bis die Temperatur der Reaktionsmischung auf etwa 2oo' C gestiegen ist, was im allgemeinen in etwa 5 Stunden der Fall ist. Die nicht in Reaktion getretenen Stoffe werden im Vakuum abdestilliert. Später hat man vorgeschlagen, das Maleinsäureanhydrid portionsweise zu dem siedenden Terpentin zu geben. Gegenstand der vorliegenden Erfindung ist ein verbessertes Verfahren zur Herstellung von Terpen-Maleinsäureanhydrid-Harzen, durch das in mehreren Beziehungen beträchtliche . Vorteile erzielt werden.According to these known processes, the reaction components are combined and then heated together until the temperature of the reaction mixture has risen to about 200 ° C. , which is generally the case in about 5 hours. The substances that have not reacted are distilled off in vacuo. It was later proposed to add the maleic anhydride in portions to the boiling turpentine. The present invention is an improved process for the preparation of terpene maleic anhydride resins, by which in several respects considerable . Benefits can be achieved.
Die Erfindung beruht auf der Erkenntnis, daß die Art, wie man die Reaktionskomponenten zusammenbringt, für die Reaktionsgeschwindigkeit wie -auch für die Farbe und andere -Eigenschaften des erhaltenen Endproduktes von wesentlicher Bedeutung ist., Dies gilt besonders bei der Verwendung von nichtkonjugierten, bicyclischen Terpenen, wie a-Pinen und fl-Pinen, was offenbar darauf zurückzuführen ist, daß diese Terpene mit geschmolzenem Maleinsäureanhydrid nicht mischbar sind. Wenn man z. B. Maleinsäureanhydrid und Terpentinöl, wie es bei der Zellstoffherstellung nach dem Sulfatprozeß gewonnen wird, das aüßer /\3-Caren beträchtliche Mengen von a-Pinen und ß-Pinen enthält, unter starkem Rühren- erhitzt, so geht die Reaktion nur langsam vonstatten, und es sind mindestens 5 Stunden erforderlich, bevor die Temperatur auf 2oo' gestiegen ist und die bei&n Komponenten vollstäridig miteinander reagiert haben, so daß nuf noch eine Phase vorhanden ist. Das auf diese Weise erhaltene Endprodukt ist dunkelgefärbt und opaleszent (Gardnerzahl > 18). Wenn die.Reaktion in Gegenwart von Katalysatoren durchg#f ührt wird, so steigt die Reaktionsgeschwindigkeit etwas, jedoch ohne daß das Endprodukt verbessert wird. Es. werden auch keine nennenswerten Verbesserungen erhalten, wenn man Maleinsäureanhydrid zu dem siedenden Terpentin gibt.The invention is based on the knowledge that the way in which the reaction components are brought together is of essential importance for the rate of reaction as well as for the color and other properties of the end product obtained. This is particularly true when using non-conjugated, bicyclic terpenes such as a-pinene and fl-pinene, which is apparently due to the fact that these terpenes are immiscible with molten maleic anhydride. If you z. B. maleic anhydride and turpentine oil, as it is obtained in the production of pulp after the sulphate process, which also contains considerable amounts of α-pinene and β-pinene, heated with vigorous stirring, the reaction proceeds only slowly, and at least 5 hours are required before the temperature has risen to 2oo 'and the components have reacted strongly with each other in the case of & n components, so that only one phase is still present. The end product obtained in this way is dark in color and opalescent (Gardner number > 18). If the reaction is carried out in the presence of catalysts, the reaction rate increases somewhat, but without the end product being improved. It. Also, no significant improvements are obtained when maleic anhydride is added to the boiling turpentine.
Gemäß der vorliegenden Erfindung wird -das Terpentinöl zu dem erhiitzten, geschmolzenen Maleinsäureanhydrid gegeben. Der Zusatz kann entweder portionsweise oder kontinuierlich in einem dünnen Strom erfolgen. Die Temperatur des geschmolzenen Maleinsäurcanhydrids wird möglichst in die Nähe des Siedepunkts des zugesetzten Terpentins gebracht. Das Terpentinöl wird zweckmäßig vorer#itzt, bevor man es der Schmelze zugibt.According to the present invention, the oil of turpentine becomes the heated, given molten maleic anhydride. The addition can either be in portions or continuously in a thin stream. The temperature of the melted Maleic acid canhydride is as close as possible to the boiling point of the added Brought turpentine. The turpentine oil is expediently preheated before it is used Admits melt.
Unter diesen Bedingungen geht die Reaktion in weniger als 2 Stunden zu Ende, und zwar auch dann, wenn man nichtkonjugierte Terpene verwendet und in Abwesenheit von Katalysatoren arbeitet. Das Endprodukt hat eine auffallend hellere Farbe und ist heller als diejenigen Produkte, die man nach den obenerwähnten, bekannten - Verfahren erhält. Wenn man die Reaktion in Gegenwart eines Katalysators durchführt, den man entw - eder im voraus zu dem geschmolzenen Maleinsäureanhydrid gibt oder mit dem Terpei#tinöl zugibt oder auch getrennt einbringt, wird die Geschwindigkeit der Reaktion noch. mehr vergrößert und gleicherweise eine wahrnehmbare Verbesserung der Farbe. des Endproduktes er:zielt.. Als Beispiel für einen geeigneten Katalysator wird Phosphorsäure genannt. Die Menge.der Phosphorsäure kann in verhältnismäßig weiten Grenzen schwanken. Zum Beispiel können o,o25- bis o,250/ü Phosphorsäure (H.P04, 8511/eig), berechnet auf die Menge des Terpentinöls, zugesetzt werden. B e i s p i e 1 Terpentinöl und Maleinsäureanhydrid werden in äquivalenten Mengen bei gewöhnlicher Temperatur oder in vorerhitztem Zustand allmählich zusammengebracht, und zwar so, daß portionsweise das Terpentinöl zu dem geschmolzenen Maleinsäureanhydrid bei etwa i5o' C unter Erhitzen am Rückfluß gegeben wird. Die Reaktion ist exotherm und schreitet so schnell vor sich, daß alles Terpentinöl 'in weniger als -i Stunde zugegeben werden kann, ohne daß sich zwei Phasen im Reaktionsgefäß bilden. Nach dieser Zeit wird die Temperatur'auf etwa i8o' C gebracht und in weniger als i Stunde auf :2oo' C erhöht. Das so erhaltene Endprodukt ist rotgefärbt, klar und durchsichtig (Gardnerzahl 13-14).Under these conditions, the reaction is complete in less than 2 hours, even when using non-conjugated terpenes and working in the absence of catalysts. The final product has a strikingly lighter color and is brighter than those products which, after the above-mentioned known - gets process. If one carries out the reaction in the presence of a catalyst, which can entw - Eder are in advance to the molten maleic anhydride or added with the Terpei # tinöl or introduced separately, the rate of reaction will be. more magnified and at the same time a noticeable improvement in color. of the end product he: aims .. An example of a suitable catalyst is phosphoric acid. The amount of phosphoric acid can vary within relatively wide limits. For example, o, o25 to o, 250 / ü phosphoric acid (H.P04, 8511 / eig), calculated on the amount of turpentine oil, can be added. B ie EISP 1 turpentine oil and maleic anhydride are gradually brought together in equivalent amounts at ordinary temperature or in preheated state, and such that is added portionwise turpentine to the molten maleic anhydride at about i5o 'C under reflux. The reaction is exothermic and proceeds so quickly that all of the turpentine oil can be added in less than an hour without two phases being formed in the reaction vessel. After this time the Temperatur'auf is 'brought in C and less than i hour on 2oo' about i8o C increased. The end product obtained in this way is colored red, clear and translucent (Gardner number 13-14).
Wenn die-Reaktion in Gegenwart eines Katalysa:tors durchgeführt wirdi z. B. mit Phosphorsäure, kann die Reaktionszeit noch etwas verkürzt und die -Farbe des Endproduktes -verbessert werden (Gardnerzahl io-ii).When the reaction is carried out in the presence of a catalyst i z. B. with phosphoric acid, the reaction time can be shortened and the color of the end product can be improved (Gardner number io-ii).
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE943381X | 1953-07-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE943381C true DE943381C (en) | 1956-05-17 |
Family
ID=20396592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA20608A Expired DE943381C (en) | 1953-07-20 | 1954-06-27 | Process for the preparation of terpene maleic anhydride resins |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE943381C (en) |
-
1954
- 1954-06-27 DE DEA20608A patent/DE943381C/en not_active Expired
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