DE1024716B - Process for the production of polyester resins - Google Patents
Process for the production of polyester resinsInfo
- Publication number
- DE1024716B DE1024716B DER17639A DER0017639A DE1024716B DE 1024716 B DE1024716 B DE 1024716B DE R17639 A DER17639 A DE R17639A DE R0017639 A DER0017639 A DE R0017639A DE 1024716 B DE1024716 B DE 1024716B
- Authority
- DE
- Germany
- Prior art keywords
- methacrylic acid
- unsaturated
- polyester
- oligomeric
- acid compounds
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920001225 polyester resin Polymers 0.000 title claims description 4
- 239000004645 polyester resin Substances 0.000 title claims description 4
- 229920006305 unsaturated polyester Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000006384 oligomerization reaction Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- -1 ethylene carboxylic acids Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
Verfahren zur Herstellung von Polyesterharzen Ungesättigte Polyesterharze werden bekanntlich derart hergestellt, daß zunächst Polycarbonsäuren mit mehrwertigen Alkoholen, von denen wahlweise die Saure oder der Alkohol oder beide polymerisationsfähige Doppelbindungen enthalten müssen, kondensiert und die so erhaltenen ungesättigten Polyester « mit polymerisierbaren monomeren Verbindungen mischpolymerisiert werden.Process for the production of polyester resins Unsaturated polyester resins are known to be produced in such a way that initially polycarboxylic acids with polybasic Alcohols, of which either the acid or the alcohol or both are polymerizable Must contain double bonds, condensed and the unsaturated so obtained Polyester «are copolymerized with polymerizable monomeric compounds.
Als Polycarbonsäuren sind außer Maleinsäure, Adipinsäure, Phthalsäure, Tetrahydrophthalsäure auch bereits die bei der Dimerisierung bzw. Oligomerisierung von Methacrylsäureestem entstehenden Ester bzw. deren entsprechende Säuren zum Aufbau ungesättigter Polyester vorgeschlagen worden. Als polymerisierbares Monomere wird in der Technik bisher in erster Linie Styrol angewandt, jedoch können auch andere monomere Vinyl-und Acrylverbindungen benutzt werden.Other polycarboxylic acids are maleic acid, adipic acid, phthalic acid, Tetrahydrophthalic acid is also used during dimerization or oligomerization from methacrylic acid esters resulting esters or their corresponding acids for the structure unsaturated polyester has been proposed. As a polymerizable monomer is Styrene has hitherto primarily been used in technology, but others can also be used monomeric vinyl and acrylic compounds can be used.
Es wurde nun gefunden, daß als polymerisierbare Monomere mit besonderem Vorteil die bei der Dimerisierung bzw. Oligomerisierung von Methacrylsäureverbindungen entstehenden Produkte Anwendung finden können. Die genannten Monomeren haben gegenüber dem in der Technik bisher vornehmlich angewandten Styrol den Vorteil geringerer Flüchtigkeit, da ihr Siedepunkt bei Normaldruck über 200° liegt. Die auf die beschriebene Weise hergestellten Polyesterharze zeichnen sich durch Farblosigkeit, Klarheit und Glanz aus ; auch in gefülltem Zustand sind sie witterungsbeständig, insbesondere wenn als Füllstoff Glas oder Glasfasergewebe verwendet werden. It has now been found that as polymerizable monomers with particular Advantage in the dimerization or oligomerization of methacrylic acid compounds resulting products can be used. The monomers mentioned have opposite the advantage of styrene, which has hitherto mainly been used in technology, is less Volatility, as their boiling point at normal pressure is over 200 °. The on the described Wisely produced polyester resins are characterized by colorlessness, clarity and Shine off; Even when filled, they are weather-resistant, especially if glass or glass fiber fabric are used as filler.
Bei der Verwendung als Lackrohstoff ist neben dem hohen Siedepunkt auch die Unempfindlichkeit gegen Luftsauerstoff bei der Polymerisation bemerkenswert. When used as a paint raw material is next to the high boiling point the insensitivity to atmospheric oxygen during polymerization is also remarkable.
Die als Monomere zu verwendenden Produkte werden z. B. nach dem deutschen Patent 903 932 derart hergestellt, daß die monomeren Ester, z. B. Methacrylsäuremethyl-,-äthyl-,-butyl-oder höhere Ester in Abwesenheit von Katalysatoren unter Druck auf eine Temperatur erhitzt werden, die über der kritischen Temperatur des Ausgangsmonomeren liegt. Dabei entstehen neben dem Dimeren auch die entsprechenden Trimeren, Tetrameren und weiteren niedrigmolekularen Polymerisationsprodukte-treffend auch als Oligomere bezeichnet-, deren Mengenverhältnis in weiten Grenzen variiert werden kann. Die gleichen Produkte lassen sich auch auf andere Weise herstellen, z. B. entstehen sie nach dem in der USA.-Patentschrift 2 232 785 beschriebenen Verfahren oder bei der thermischen Spaltung hochpolymerer Methacrylsäureester bzw. Methacrylsäure. The products to be used as monomers are z. B. after the German Patent 903,932 prepared such that the monomeric esters, e.g. B. Methacrylsäuremethyl -, - ethyl -, - butyl or higher esters heated to a temperature under pressure in the absence of catalysts which is above the critical temperature of the starting monomer. This creates in addition to the dimer, the corresponding trimers, tetramers and other low molecular weight Polymerization products - also appropriately referred to as oligomers - their quantitative ratio can be varied within wide limits. The same products can also be found on manufacture other ways, e.g. B. They are created according to the US patent specification 2,232,785 or in the thermal cleavage of high polymer Methacrylic acid ester or methacrylic acid.
Die genannten niedrigpolymeren Methacrylsäureverbindungen können-gegebenenfalls unter Mitverwendung anderer polymerisierbarer Verbindungen-entweder im Gemisch, wie es beispielsweise bei der Ausübung des Verfahrens gemäß dem deutschen Patent 903 932 anfällt, zur Anwendung kommen oder aus diesem Gemisch isoliert und als chemische Individuen verwendet werden. The low-polymer methacrylic acid compounds mentioned can-if appropriate with the use of other polymerizable compounds - either in a mixture, as is the case, for example, with the practice of the method according to the German patent 903 932 arises, come into use or from this Mixture isolated and used as a chemical Individuals are used.
Das Verfahren unterscheidet sich grundlegend von einer bekannten Arbeitsweise, nach der Alkydharze mit Polymerisaten oder Mischpolymerisaten der Ester von Athylencarbonsäuren modifiziert werden. In diesem Fall werden makromolekulare, d. h. aus ungesättigten, monomeren Verbindungen aufgebaute gesättigte Verbindungen, mit einem Molekulargewicht von 10 000 bis 50 000 den Alkydharzkomponenten während des Verkochungsprozesses zugesetzt. Im Gegensatz hierzu werden gemäß vorliegendem Verfahren ungesättigte Polyester mit ungesättigten, oligomeren, d. h. niedrigmolekularen, vornehmlich aus Dimeren, Trimeren und Tetrameren bestehenden Verbindung polymerisiert. The procedure is fundamentally different from a well-known one Method of operation, according to the alkyd resins with polymers or copolymers of the Esters of ethylene carboxylic acids are modified. In this case, macromolecular, d. H. Saturated compounds built up from unsaturated, monomeric compounds, with a molecular weight of 10,000 to 50,000 during the alkyd resin components added during the boiling process. In contrast, according to the present Process unsaturated polyesters with unsaturated, oligomeric, d. H. low molecular weight, polymerized compound consisting primarily of dimers, trimers and tetramers.
Beispiel l Es wird ein ungesättigter Polyester aus 2 Mol Itakonsäure, 1 Mol Äthylenglykol und 1 Mol Propandiol-1,2 durch Kondensation bei 190° innerhalb von 7 Stunden hergestellt. Die erhaltene hochviskose, schwachgelb gefärbte Masse wird nach Abkühlung auf 100'mit einem gemäß dem deutschen Patent 903 932 aus Methacrylsäuremethylester hergestellten Dimeren (Kp. 12 118°) verdünnt. Die 65 0,/o Anteile an ungesättigtem Polyester enthaltende Lösung ist hochviskos, klar, schwachgelb gefärbt und kann, gegebenenfalls nach weiterer Verdünnung mit dimerem Methacrylsäuremethylester, der Polymerisation unterworfen werden. Example 1 An unsaturated polyester is made from 2 moles of itaconic acid, 1 mole of ethylene glycol and 1 mole of 1,2-propanediol by condensation at 190 ° within made of 7 hours. The highly viscous, pale yellow mass obtained is after cooling to 100 'with a methacrylic acid methyl ester according to German Patent 903 932 produced dimers (b.p. 12 118 °) diluted. The 65 0, / o fractions of unsaturated Solution containing polyester is highly viscous, clear, pale yellow in color and can, optionally after further dilution with dimeric methyl methacrylate, the Be subjected to polymerization.
Beispiel 2 Ein nach Beispiel I gewonnener ungesättigter Polyester aus den Komponenten Itakonsäure, Äthylenglykol und Propandiol-1, 2 wird mit dem gemäß dem deutschen Patent 903 932 aus Methacrylsäuremethylester gewonnenen Oligomerisierungsgemisch, aus dem nicht umgesetzter Methacrylsäuremethylester vorher abgetrennt wurde und das neben höhermolekularen Anteilen 79 0/, dimeren Methacrylsäuremethylester enthält, auf 70 °/0, bezogen auf ungesättigten Polyester, verdünnt. Die Weiterverarbeitung kann nach den für ungesättigte Polyesterharze gültigen Vorschriften erfolgen. Example 2 An unsaturated polyester obtained according to Example I. from the components itaconic acid, ethylene glycol and propanediol-1, 2 is with that according to the German patent 903 932 from methacrylic acid methyl ester obtained oligomerization mixture, from the unreacted methyl methacrylate was previously separated and that in addition to higher molecular weight fractions 79 0 /, dimeric methacrylic acid methyl ester contains, diluted to 70%, based on unsaturated polyester. The further processing can be carried out in accordance with the regulations applicable to unsaturated polyester resins.
Beispiel 3 Ein Polyester, hergestellt nach der im Beispiel 1 angegebenen Vorschrift, wird nach Abkühlen auf 70° mit einer Mischung aus 50 Teilen gemäß Beispiel 1 hergestelltem dimerem Methacrylsäuremethylester, 25 Teilen monomerem Methacrylsäuremethylester und 25 Teilen Styrol verdünnt. Eine auf 50 verdünnte, ungesättigte Polyesterlösung ist mittelviskos, klar, schwach gelblich. Example 3 A polyester prepared according to that given in Example 1 Regulation is after cooling to 70 ° with a mixture of 50 parts according to the example 1 produced dimeric methacrylic acid methyl ester, 25 parts of monomeric methacrylic acid methyl ester and 25 parts of styrene diluted. An unsaturated polyester solution diluted to 50 is of medium viscosity, clear, slightly yellowish.
Beispiel 4 Ein durch Alkoholyse hergestellter ungesättigter Polyester aus 4 Mol des nach dem deutschen Patent 903 932 gewonnenen dimeren Methacrylsäuremethylesters, 2 Mol Phthalsäuredimethylester und 6 Mol Propandiol-1,3 wird mit dem im Beispiel 2 angegebenen Oligomerisierungsgemisch, das bei der Behandlung von Methacrylsäuremethylester gemäß dem deutschen Patent 903 932 entsteht, auf 60 °/0 an ungesättigtem Polyester verdünnt. Example 4 An unsaturated polyester produced by alcoholysis from 4 mol of the dimeric methacrylic acid methyl ester obtained according to German Patent 903 932, 2 moles of dimethyl phthalate and 6 moles of 1,3-propanediol is the same as in the example 2 indicated oligomerization mixture, which in the treatment of methacrylic acid methyl ester according to the German patent 903 932 arises, to 60 ° / 0 of unsaturated polyester diluted.
Die hochviskose Lösung kann wie üblich polymerisiert werden.The highly viscous solution can be polymerized as usual.
Beispiel 5 Ein nach der USA.-Patentschrift 2 232 785, Beispiel 1, hergestelltes Oligomerisierungsgemisch wird als ungesättigte Dicarbonsäurekomponente benutzt. 2 Mol dieses Oligomerisierungsgemisches, 1 Mol Bernsteinsäuredimethylester werden mit 4 Mol Butandiol-1, 4 durch Alkoholyse umgesetzt. Die Kondensationstemperatur wird innerhalb von 8 Stunden bis auf 200° gesteigert und das dabei entstandene Methanol kontinuierlich abgezogen. Der so erhaltene ungesättigte Polyester wird mit einer Mischung aus 50 Gewichtsteilen dimeren Methacrylsäuremethylester und 50 Gewichtsteilen Styrol auf 70°lO verdünnt. Example 5 A US Pat. No. 2,232,785, Example 1, The oligomerization mixture produced is used as the unsaturated dicarboxylic acid component used. 2 moles of this oligomerization mixture, 1 mole of dimethyl succinate are reacted with 4 moles of 1,4-butanediol by alcoholysis. The condensation temperature is increased to 200 ° within 8 hours and the resulting methanol continuously withdrawn. The unsaturated polyester thus obtained is with a Mixture of 50 parts by weight of dimeric methyl methacrylate and 50 parts by weight Styrene diluted to 70 ° 10.
Man erhält eine gelbliche hochviskose Lösung, die den üblichen Polymerisationsbedingungen unterworfen werden kann.A yellowish, highly viscous solution is obtained which has the usual polymerization conditions can be subjected.
Beispiel 6 Ein aus l Mol Maleinsäuredimethylester und 1 Mol Äthylenglykol in Gegenwart von Blei (II)-oxyd hergestellter Polyester wird mit dem nach dem deutschen Patent 903 932 gewonnenen dimeren Methacrylsäuremethylester auf 65% verdünnt. Das Dimere enthält 0,01 °íO Hydrochinonmonomethvläther als Stabilisator. Example 6 One made from 1 mole of dimethyl maleate and 1 mole of ethylene glycol Polyester produced in the presence of lead (II) oxide is mixed with the German Patent 903,932 obtained dimeric methacrylic acid methyl ester diluted to 65%. That Dimer contains 0.01% hydroquinone monomethyl ether as a stabilizer.
Die Weiterverarbeitung erfolgt in der für Polyester üblichen Weise.Further processing takes place in the manner customary for polyester.
Beispiel 7 3 Mol eines nach dem deutschen Patent 903 932 hergestellten dimeren Methacrylsäuremethvlesters und 0, 8 Mol Phthalsäuredimethylester werden mit 2 Mol Propandiol-1,2 durch Alkoholyse in Gegenwart von l Gewichtsteil Zinkacetat (bezogen auf den Ansatz) umgeestert. Der erhaltene ungesättigte Polyester liegt im überschüssigen dimeren Methacrylsäuremethylester gelöst vor und kann direkt ohne weitere Verdünnung der Polymerisation unterworfen werden. Example 7 3 moles of one prepared according to German Patent 903,932 dimeric methacrylic acid methyl ester and 0.8 mol of phthalic acid dimethyl ester with 2 moles of 1,2-propanediol by alcoholysis in the presence of 1 part by weight of zinc acetate (based on the approach) interesterified. The unsaturated polyester obtained lies dissolved in the excess dimeric methyl methacrylate and can be used directly without be subjected to further dilution of the polymerization.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER17639A DE1024716B (en) | 1955-10-24 | 1955-10-24 | Process for the production of polyester resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER17639A DE1024716B (en) | 1955-10-24 | 1955-10-24 | Process for the production of polyester resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1024716B true DE1024716B (en) | 1958-02-20 |
Family
ID=7400029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER17639A Pending DE1024716B (en) | 1955-10-24 | 1955-10-24 | Process for the production of polyester resins |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1024716B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1295745B (en) * | 1959-08-10 | 1969-05-22 | Cincinnati Milling Machine Co | Production of hardening layers on copper foils through polymerization |
-
1955
- 1955-10-24 DE DER17639A patent/DE1024716B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1295745B (en) * | 1959-08-10 | 1969-05-22 | Cincinnati Milling Machine Co | Production of hardening layers on copper foils through polymerization |
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