DE1115022B - Process for the production of polymerizates branched or crosslinked via -N = CH bridges and cleavable by means of acids into the primary molecules - Google Patents
Process for the production of polymerizates branched or crosslinked via -N = CH bridges and cleavable by means of acids into the primary moleculesInfo
- Publication number
- DE1115022B DE1115022B DEI14159A DEI0014159A DE1115022B DE 1115022 B DE1115022 B DE 1115022B DE I14159 A DEI14159 A DE I14159A DE I0014159 A DEI0014159 A DE I0014159A DE 1115022 B DE1115022 B DE 1115022B
- Authority
- DE
- Germany
- Prior art keywords
- branched
- cleavable
- bridges
- acids
- polymerizates
- 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
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
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Es ist durch die grundlegende Arbeit von H. Staudinger, W. Heuer und E. Husemann (Berichte der Deutschen Chemischen Gesellschaft, 68, [1935], S. 1618) bekannt, daß Styrol bei der Copolymerisation mit Divinylbenzol unlöslich wird und nur noch begrenzt quellbare Produkte ergibt. Es wurde bereits früher versucht, durch Einbauen spaltbarer Gruppen in Polymere solche Produkte zu erhalten, die nachträglich wieder in lösliche primäre Moleküle übergeführt werden können. T. AIf rey jr. und M. Bertick (Journal of Polymer Science, 11 [1951], S. 61) versuchten dies durch Einführung von Disulfidbrücken in die Polymeren zu erreichen. Da die Sulfide aber nach R. M. Pierson, A. J. Costanza und A. H. Weinstein (J. Polymer Sei., 17 [1955], S. 221) bei der Polymerisation als Regler bzw. Überträger wirken, treten hierbei auch über nicht spaltbare Sulfidbrücken verzweigte und vernetzte Produkte auf.It is through the fundamental work of H. Staudinger, W. Heuer and E. Husemann (reports der Deutschen Chemischen Gesellschaft, 68, [1935], p. 1618) known that styrene in the copolymerization becomes insoluble with divinylbenzene and only results in products with limited swellability. It was already earlier attempts to obtain such products by incorporating cleavable groups into polymers that subsequently can be converted back into soluble primary molecules. T. AIf rey Jr. and M. Bertick (Journal of Polymer Science, 11 [1951], p. 61) attempted this by introducing disulfide bridges to achieve in the polymers. However, since the sulfides according to R. M. Pierson, A. J. Costanza and A. H. Weinstein (J. Polymer Sei., 17 [1955], p. 221) act as regulators or transmitters during the polymerization, Here, branched and crosslinked products also occur via non-cleavable sulfide bridges.
Es wurde nun gefunden, daß sich die Klasse der Divinyl-Schiffschen Basen mit Vinylmonomeren copolymerisieren läßt, ohne daß die Azomethinbindung an der Polymerisation teilnimmt, d. h. es entstehen hierbei je nach dem Gehalt an Divinyl-Schiffscher Base und je nach den Polymerisationsumsätzen über -N = CH-Gruppen verzweigte, noch lösliche bzw. vernetzte, nur noch quellbare Hochpolymere. Da die Azomethinbindung bekanntlich schon mit verdünnten Säuren leicht aufspaltbar ist, wobei die Ausgangskomponenten zurückgebildet werden, sind diese vernetzten bzw. verzweigten Hochpolymeren unter schonenden Bedingungen ohne jede Nebenreaktion quantitativ in die primären Moleküle spaltbar. Diese lassen sich durch Umsetzung mit bifunktionellen amino- bzw. carbonylgruppenhaltigen Verbindungen erneut in verzweigte bzw. vernetzte Produkte überführen.It has now been found that the class of divinyl Schiff bases copolymerize with vinyl monomers leaves without the azomethine bond participating in the polymerization, d. H. it arise here depending on the divinyl Schiff base content and depending on the polymerization conversions -N = CH groups branched, still soluble or crosslinked, only swellable high polymers. Since the As is known, azomethine bond can easily be split even with dilute acids, the starting components are regressed, these crosslinked or branched high polymers are under gentle Conditions quantitatively cleavable into the primary molecules without any side reaction. Let this by reaction with bifunctional amino or carbonyl group-containing compounds again in transfer branched or networked products.
Es wurden 2,0-, 0,5-, 0,1-, 0,02- und 0,005%ige Lösungen von N,N'-Bis-(4-methacryloxy-benzyliden)-1,2-diaminoäthan in Styrol hergestellt und bei 60° C mit 0,75 Gewichtsprozent Azoisobutyronitril als Initiator polymerisiert. Zur Bestimmung des Gelpunktes wurden aus den etwa 150 ecm fassenden Ansätzen in Abständen von 10 Minuten 5-ccm-Proben entnommen, in Methanol ausgefällt und auf ihre Löslichkeit geprüft. Die Rückstände wurden bis zur völligen Umsetzung polymerisiert und zu Quellungsversuchen verwendet.There were 2.0, 0.5, 0.1, 0.02 and 0.005% solutions of N, N'-bis (4-methacryloxy-benzylidene) -1,2-diaminoethane made in styrene and at 60 ° C with 0.75 percent by weight azoisobutyronitrile as Initiator polymerizes. To determine the gel point, the approximately 150 ecm 5 ccm samples taken at intervals of 10 minutes, precipitated in methanol and applied to their Solubility checked. The residues were polymerized until they were completely converted and swelling tests were carried out used.
Verfahren zur HerstellungMethod of manufacture
von über —N==CH-Brücken verzweigtenbranched by —N == CH bridges
bzw. vernetzten und mittels Säurenor cross-linked and by means of acids
in die primären Moleküle spaltbarencleavable into the primary molecules
PolymerisatenPolymers
Anmelder:Applicant:
Dr. Elfriede Husemann,
Freiburg (Breisgau), Albertstr. 21Dr. Elfriede Husemann,
Freiburg (Breisgau), Albertstr. 21
Dr. Helmut Ringsdorf und Dr. Gerd Greber,Dr. Helmut Ringsdorf and Dr. Gerd Greber,
Freiburg (Breisgau),
sind als Erfinder genannt wordenFreiburg (Breisgau),
have been named as inventors
des Gelpunktes und des Quellungsgrades von dem Gehalt an Divinylverbindung sowie von der Polymerisationsdauer. the gel point and the degree of swelling, the divinyl compound content and the duration of the polymerization.
*) 1 = Die Proben waren nach dem Umfallen noch löslich.
**) q = Die Proben waren nach dem Umfallen nur noch teilweise löslich.*) 1 = The samples were still soluble after falling over.
**) q = The samples were only partially soluble after falling over.
Vernetzung von Polystyrol mit N,N'-Bis-(4-methacryloxybenzyliden) - 1,2-diaminoäthan. Abhängigkeit Es wurden 2,0-, 0,5-, 0,1-, 0,02- und 0,005%ige Lösungen von Terephthaldialdehyd-bis-(4-vinylanil) in Styrol hergestellt und bei 6O0C mit 0,75 Gewichtsprozent Azoisobutyronitril als Initiator polymerisiert. Zur Bestimmung des Gelpunktes wurden aus den etwa 150 ecm fassenden Ansätzen in Ab-Crosslinking of polystyrene with N, N'-bis (4-methacryloxybenzylidene) - 1,2-diaminoethane. Depending were 2.0-, 0.5-, 0.1-, 0.02 and 0.005% solutions of terephthaldialdehyde-bis- (4-vinylanil) in styrene and at 6O 0 C with 0.75 weight percent Polymerized azoisobutyronitrile as an initiator. To determine the gel point, the approx. 150 ecm batches were
109 708/443109 708/443
ständen von V2 Stunde 5-ccm-Proben entnommen, in Methanol ausgefällt und auf ihre Löslichkeit geprüft.5 cc samples were taken from V 2 hours, precipitated in methanol and tested for solubility.
Tabelle 2 ; ■ ;Table 2; ■;
Vernetzung von Polystyrol mit Terephthaldialdehyd-bis-(4-vinylanil). Abhängigkeit des Gelpunktes und des Quellungsgrades von dem Gehalt an Divinylverbindung sowie von der Polymerisationsdauer.Crosslinking of polystyrene with terephthalaldehyde bis (4-vinylanil). Dependence of the gel point and the degree of swelling on the divinyl compound content as well as the duration of the polymerization.
*) vergleiche Tabelle 1.
**) vergleiche Tabelle 1.*) compare table 1.
**) compare table 1.
2,72 mg eines Copolymerisates aus Styrol und 2,6 Gewichtsprozent (0,0021 Molprozent) Terephthaldialdehyd-bis-(4-vinylanil)
wurden 3 Tage in Toluol gequollen. Es handelte sich um ein Substanzpolymerisat, das bei 600C ohne Initiator bis zu völligem Umsatz
polymerisiert worden war. Dem Azomethingehalt dieses begrenzt quellbaren Gels von 11,5 mg entsprechend
wurde dem Quellungsmittel die äquivalente Menge von 20 mg Ameisensäure zugesetzt.
Nach 3 Stunden bildete das Reaktionsprodukt eine homogene, filtrierbare Lösung.
In einem weiteren quantitativen Spaltungsversuch2.72 mg of a copolymer of styrene and 2.6 percent by weight (0.0021 mol percent) of terephthalaldehyde bis (4-vinylanil) were swollen in toluene for 3 days. It was a bulk polymer which had been polymerized to complete conversion at 60 ° C. without initiator. Corresponding to the azomethine content of this gel with limited swellability of 11.5 mg, the equivalent amount of 20 mg of formic acid was added to the swelling agent. After 3 hours the reaction product formed a homogeneous, filterable solution.
In another quantitative attempt at splitting
ίο ließ man 3,36 g eines Copolymerisates aus Styrol mit 0,1 Gewichtsprozent Terephthaldialdehyd-bis-(4-vinylanil) in Toluol quellen und 1 ecm einer O3O5°/oigen Lösung von Ameisensäure in Benzol zutropfen. Dem berechneten Azomethingehalt von 0,54 mg entsprechend genügte die Menge von 0,5 mg Ameisensäure, um das Copolymerisat nach 48stündigem Stehen bei Zimmertemperatur aufzulösen.ίο were allowed to swell 3.36 g of a copolymer of styrene with 0.1 percent by weight of terephthalaldehyde bis (4-vinylanil) in toluene and 1 ecm of an O 3 O5% solution of formic acid in benzene was added dropwise. Corresponding to the calculated azomethine content of 0.54 mg, the amount of 0.5 mg of formic acid was sufficient to dissolve the copolymer after standing for 48 hours at room temperature.
Claims (1)
20 PATENT CLAIM:
20th
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEI14159A DE1115022B (en) | 1957-12-23 | 1957-12-23 | Process for the production of polymerizates branched or crosslinked via -N = CH bridges and cleavable by means of acids into the primary molecules |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEI14159A DE1115022B (en) | 1957-12-23 | 1957-12-23 | Process for the production of polymerizates branched or crosslinked via -N = CH bridges and cleavable by means of acids into the primary molecules |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1115022B true DE1115022B (en) | 1961-10-12 |
Family
ID=7185610
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEI14159A Pending DE1115022B (en) | 1957-12-23 | 1957-12-23 | Process for the production of polymerizates branched or crosslinked via -N = CH bridges and cleavable by means of acids into the primary molecules |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1115022B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3408339A (en) * | 1963-11-20 | 1968-10-29 | Monsanto Co | Polymeric scavenging systems |
-
1957
- 1957-12-23 DE DEI14159A patent/DE1115022B/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3408339A (en) * | 1963-11-20 | 1968-10-29 | Monsanto Co | Polymeric scavenging systems |
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