DE881260C - Process for the production of copolymers from vinyl esters by copolymerization with vinyl crotonate - Google Patents

Process for the production of copolymers from vinyl esters by copolymerization with vinyl crotonate

Info

Publication number
DE881260C
DE881260C DEP5489D DEP0005489D DE881260C DE 881260 C DE881260 C DE 881260C DE P5489 D DEP5489 D DE P5489D DE P0005489 D DEP0005489 D DE P0005489D DE 881260 C DE881260 C DE 881260C
Authority
DE
Germany
Prior art keywords
vinyl
copolymers
crotonate
copolymerization
production
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
Application number
DEP5489D
Other languages
German (de)
Inventor
Wolfram Dr Haehnel
Willy O Dr Herrmann
Johann Dr Sixt
Rolf Dr Woehrl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HELLMUTH HOLZ DR
Original Assignee
HELLMUTH HOLZ DR
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by HELLMUTH HOLZ DR filed Critical HELLMUTH HOLZ DR
Priority to DEP5489D priority Critical patent/DE881260C/en
Application granted granted Critical
Publication of DE881260C publication Critical patent/DE881260C/en
Expired legal-status Critical Current

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
    • C08F214/00—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 halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • 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
    • C08F18/00—Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • 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
    • C08F18/00—Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/08—Vinyl acetate
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated

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)
  • Polymerisation Methods In General (AREA)

Description

Verfahren zur Herstellung von Mischpolymerisaten aus Vinylestern durch Mischpolymerisation mit Vinylcrotonat Im Patent ü74214 ist ein Verfahren geschützt, wertvolle Polymerisate aus organischen und anorganischen Estern des Vinylalkohols durch Polymerisation in Gegenwart von Vinylcrotönat herzustellen. Bei der weiteren Bearbeitung wurde nun gefunden, daß; aus Vinylestern und einem Zusatz von Vinylcrotoriat technisch besonders erwünschte und neuartige Produkte dadurch gewonnen werden können, da,U ein Gemisch beider Vinylester in Abwesenheit von Lösungsmitteln durch Perverbindungen in Gegenwart von Aldehyd bei Temperaturen unter dem Siedepunkt des monomeren Vinylesters polymerisiert wird. Als Perverbindung ist außer Benzoylsuperoxyd vor allem Acetpersäureester,wie er durch Oxydation von schwach cobaltlialtigem Acetaldehyd mit molekularem Sauerstoff bei etwa o° erhalten wird, sehr geeignet. Es werden bei einem Crotonatzusatz bis zu einigen Prozenten ])lasenfreie, glasklare, bei Zimmertemperatur zähe, gegen Stoß! und Schlag widerstandsfähige Produkte erhalten, die z. B. als organisches Glas Verwendung finden können. Beispiel 1 Eine Mischung von gi Gewichtsteilen Vinylacetat und 2 Teilen Vinylcrotonat wurde mit 5 Teilen 101/o Acetpersäureester enthaltendem Acetaldehyd versetzt und bei 5o bis 6o1 etwa 3 Tage polymerisiert. Die Mischung war schon nach einigen Stunden zu einer durchsichtigen Gallerte erstarrt. Allmählich erhärtete sie, worauf sie aus dem zylindrischen Glasgefälßi genommen wurde. An der Luft wurde die Masse nach kurzem Liegen so hart, daß sie mit dem Fingernagel nicht mehr eingedrückt werden konnte. Sie ist sehr zäh gegen Schlag und Stoß., überaus widerstandsfähig. Beim Erwärmen auf höhere Temperatur, z. B. 70°, wird das Produkt elastisch. Beispiel 2 Eine Mischung von 9i Gewichtsteilen Vinylacetat und 4. Teilen Vinylerotonat wurde mit 5 Teilen der obenei-wähnten Peresterlösung bei 5o bis 6o° polymerisiert. Es wurde ein ähnlich hartes, durchsichtiges Polymerisat erhalten.Process for the production of copolymers from vinyl esters by Mixed polymerisation with vinyl crotonate In patent ü74214 a process is protected, valuable polymers from organic and inorganic esters of vinyl alcohol by polymerization in the presence of vinyl crotonate. At the other Editing has now been found that; from vinyl esters and an addition of vinylcrotoriate Technically particularly desirable and novel products can be obtained in this way, da, U a mixture of the two vinyl esters in the absence of solvents by means of per compounds in the presence of aldehyde at temperatures below the boiling point of the monomeric vinyl ester is polymerized. In addition to benzoyl peroxide, the per-compound is above all acet peric acid ester, such as he by oxidation of weak cobalt-rich acetaldehyde with molecular oxygen obtained at about o ° is very suitable. If crotonate is added, up to to a few percent]) lase-free, crystal-clear, tough at room temperature, against impact! and impact resistant products obtained e.g. B. use as organic glass can find. Example 1 A mixture of gi parts by weight of vinyl acetate and 2 Parts of vinyl crotonate were mixed with 5 parts of acetaldehyde containing 101 / o acetic acid ester added and polymerized at 5o to 6o1 for about 3 days. The mixture after a few hours it had solidified into a transparent gelatinous gel. Gradually hardened it, whereupon it was removed from the cylindrical glass vessel. At the After lying there for a short time, the mass became so hard that it could not be touched with a fingernail could be pushed in more. It is very tough against impact and shock., Extremely resilient. When heated to a higher temperature, e.g. B. 70 °, the product becomes elastic. Example 2 A mixture of 91 parts by weight of vinyl acetate and 4th parts Vinylerotonat was with 5 parts of the above-mentioned perester solution at 5o to 6o ° polymerized. A similarly hard, transparent polymer was obtained.

Beispiel 3 Eine Mischung von 9i Gewichtsteilen Vinylacetat und 2 Teilen Vinylcrotonat wurde mit o,5 Teilen Benzoylsuperoxyd bei gleichzeitigem Zusatz von 4. Teilen Acetaldehyd bei 5o bis 6o° polymerisiert. Nach 5 Tagen war das glasklare Produkt ziemlich hart und härtete bei kurzem Liegen an der Luft ähnlich Wie bei obigem Beispiel nach. Auch dieses Produkt war sehr zäh.Example 3 A mixture of 91 parts by weight of vinyl acetate and 2 parts Vinyl crotonate was with 0.5 parts of benzoyl peroxide with the simultaneous addition of 4. Part of acetaldehyde polymerized at 5o to 6o °. After 5 days it was crystal clear Product quite hard and hardened when left in the air for a short time, similar to that of according to the example above. This product was also very tough.

Ohne Acetaldehyd konnten ähnlich homogene, klare und gleichzeitig auch harte Produkte nicht erhalten werden.Without acetaldehyde could be similarly homogeneous, clear and at the same time even hard products are not obtained.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von Mischpolymerisaten aus Vinylestern durch Mischpolymerisation mit Vinylcrotonat gemäß, Patent 874 2I4., dadurch gekennzeichnet, daß die Poiymerisation in Abwesenheit von Lösungsmitteln mit Perverbindungen in Gegenwart von Aldehyden durchgeführt und dabei eine Temperatur eingehalten wird, die entsprechend unter dem Siedepunkt des monomeren Vinylersters liegt. PATENT CLAIM: Process for the production of copolymers from vinyl esters by copolymerization with vinyl crotonate according to patent 874 2I4., Characterized in that the polymerization is carried out in the absence of solvents with per compounds in the presence of aldehydes and a temperature is maintained which is correspondingly below the boiling point of the monomeric vinyl sters.
DEP5489D 1940-01-05 1943-05-29 Process for the production of copolymers from vinyl esters by copolymerization with vinyl crotonate Expired DE881260C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEP5489D DE881260C (en) 1940-01-05 1943-05-29 Process for the production of copolymers from vinyl esters by copolymerization with vinyl crotonate

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE226694X 1940-01-05
DE233502X 1940-01-05
CH226694T 1941-01-03
DEP5489D DE881260C (en) 1940-01-05 1943-05-29 Process for the production of copolymers from vinyl esters by copolymerization with vinyl crotonate

Publications (1)

Publication Number Publication Date
DE881260C true DE881260C (en) 1953-06-29

Family

ID=61628528

Family Applications (2)

Application Number Title Priority Date Filing Date
DEP3643D Expired DE874214C (en) 1940-01-05 1940-01-06 Process for influencing Polymerisationsvorgaengen and the properties of the resulting polymers
DEP5489D Expired DE881260C (en) 1940-01-05 1943-05-29 Process for the production of copolymers from vinyl esters by copolymerization with vinyl crotonate

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DEP3643D Expired DE874214C (en) 1940-01-05 1940-01-06 Process for influencing Polymerisationsvorgaengen and the properties of the resulting polymers

Country Status (4)

Country Link
BE (2) BE440208A (en)
CH (4) CH233502A (en)
DE (2) DE874214C (en)
FR (2) FR881719A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005809A (en) * 1957-09-05 1961-10-24 Air Reduction Vinyl alcohol-crotonic acid copolymers

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB496276A (en) * 1937-05-27 1938-11-28 Ig Farbenindustrie Ag Manufacture of artificial substances resembling rubber

Also Published As

Publication number Publication date
CH226694A (en) 1943-04-30
FR53726E (en) 1946-07-29
CH233501A (en) 1944-07-31
FR881719A (en) 1943-05-06
DE874214C (en) 1953-04-20
CH295895A (en) 1954-01-15
BE455982A (en) 1944-06-30
CH233502A (en) 1944-07-31
BE440208A (en) 1941-02-28

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