DE1058261B - Process for the preparation of polymerization products from olefinically unsaturated compounds - Google Patents

Description

The present invention relates to a process for the polymerization of olefinically unsaturated compounds using peroxide compounds which are activated by organic nitrogen bases.

It has been proposed to use certain nitrogenous bases for activating peroxy compounds which serve as polymerization catalysts to thereby cause the polymerization reaction to start rapidly and in a specified manner Moment begins.

The main feature of the present invention is to provide a method for activating known peroxide compounds propose to enable them to have a sufficient level of catalytic activity in the Polymerization of olefinically unsaturated compounds at temperatures below the lowest limit of the Area in which they are normally active. By the present process, the peroxide compounds activated and enabled increased catalytic effects within the temperature range in which the peroxides are normally active.

According to the present invention, there is provided a method for producing a polymer by polymerizing proposed a polymerizable compound which is the non-aromatic group > C = C <contains, in the presence of an organic peroxy compound as a polymerization catalyst and one as an activator for these serving nitrogen-containing base, which is characterized in that the nitrogen-containing base is a Is tetrazene or an N-substituted heterocyclic secondary amine.

According to the method according to the present invention, vinyl chloride, vinyl esters, styrene, chlorostyrenes, Acrylate esters, allyl esters, crotonic acid esters and esters of malic and fumaric acid can be polymerized.

Examples of suitable tetracenes are tetramethyltetrazen-2, 1 ^ -Bis-cyclopentyltetrazene ^, N-N'-Azomorpholine, sym.-dimethyldiphenyl tetrazene. Such tetracenes and their preparation are for example in the book by Sidgwick, "Organic Chemistry of Nitrogen", 1937 (Oxford University Press), p. 465.

Examples of N-substituted, heterocyclic, secondary amines are N-ethylpiperidine, N-phenylpiperidine, N-methyl-1,2,5,6-tetrahydropyridine. Such amines also include N-alkylpyrrolidines, N-alkylhexamethyleneimines and the corresponding N-alkenyl compounds. Peroxide compounds include: Acid epoxyde, z. B. lauroyl peroxide and benzoyl peroxides; Alkyl peroxides, e.g. B. Di-tert.-butyl peroxide, peroxydicarbonates,

Method of manufacture

of polymerization products

from olefinically unsaturated compounds

Applicant:

Imperial Chemical Industries Limited, London

Representative: Dipl.-Ing. A. Bohr, Munich 5,

Dr.-Ing. H. Fincke, Berlin-Lichterfelde, Drakestr. 51, and Dipl.-Ing. H. Bohr, Munich 5, patent attorneys

Claimed Priority: Great Britain May 22, 1956 and May 10, 1957

John Carswell McGowan and Leslie Seed,

Northwidi (Great Britain) have been named as inventors

The reaction temperature is generally between -20 and + 60 ° C and depends on the choice of peroxide compound and the nitrogen base and the monomer to be polymerized.

The ratio of peroxide compound and nitrogen SS base is generally between 1:10 and 10: 1 mol; The range between 1: 1 and 4: 1 is particularly useful.

The amounts of the peroxide compound and the nitrogen base can each be up to about 5% of the weight of the monomer be. It has been found that concentrations of 1% give very satisfactory results achieve.

The following examples illustrate the present invention without restricting it.

example 1

50 ecm of stabilizer-free vinyl acetate are placed under a Treated nitrogen atmosphere with 0.5 ecm of lauroyl peroxide and 0.5 g of tetraethyl tetrazene-2. After 19 hours

"_ .. - -. at room temperature the vinyl acetate has become a

z. B. ^ Diisopropyl peroxydicarbonate and di-tert-butyl per- 50 solid mass polymerized. However, this does not take place

oxydicarbonate, as well as derivatives of these compounds; Perester, e.g. B. tert-butyl benzoate; Peracids, ζ. Β. Peracetic acid; Hydroperoxides, e.g. B. Cyclohsxanojiperoxide.

Polymerization takes place under the same conditions with only one component.

Corresponding results were obtained with lauroyl peroxide and N-ethylpiperidine after 66 hours and with lauroyl

909 528/448

obtained peroxide and N-methyl-1,2,5,6-tetrahydropyridine, which set a rapid polymerization in motion on boiling and a thick brown one in an hour and 10 minutes Generated liquid. The latter experiment was repeated with only 0.025 g of N-methyl-1,2,5,6-tetrahydropyridine, taking the vinyl acetate to a solid mass in 6 hours polymerized.

If 1 ^ -Bis-cyclopentyltetrazene ^ as nitrogen base was used, the polymerization was complete in 2 hours 20 minutes, and with 1,4-bis (dihydroxycyclopentyl) tetrazene-2 it was complete in 24 hours, with the reaction mixture in both cases consisting of 50 g of vinyl acetate, 0.5 g of lauroyl peroxide and 0.5 g of the tetracenes at an initial temperature of about 18 ° C existed.

Example 2

50 ecm of purified vinyl acetate are treated with 0.5 g of benzoyl peroxide and 0.5 g of N-ethylpipidemic at 25 ° C. under nitrogen. After one hour the mixture is ao twice with 15 ° _o sodium carbonate, once with water, finally washed twice with 5 NH Cl and again with water. 1.0 g of hydroquinone is added and the vinyl acetate is removed by distillation with steam. The residue found was 12.0 g of polyvinyl acetate; after a reaction time of 6 hours, the yield was 16 g of polyvinyl acetate. If the experiment was repeated with benzoyl peroxide or N-ethylpiperidine alone, no polymer was formed.

Example 3

0.5 g of lauroyl peroxide and 0.5 g of sym.-dimethyldiphenyl tetrazene were added to 50 ecm of vinyl acetate. That Vinyl acetate polymerized to a solid within 90 minutes.

Example 4

When 0.5 g of t-butyl peroxydicarbonate to 50 ecm of vinyl acetate were added, polymerization to a solid occurred within 2 hours. With 0.5 g Dicyclopentyl tetrazene did not polymerize 50 ecm vinyl acetate in 48 hours. However, 50 ecm polymerized Vinyl acetate in 2 minutes with 0.5 g of t-butyl peroxydicarbonate and 0.5 g of dicyclopentyl tetrazene.

The following
manufactured:

Example 5
Mixtures were at

Room temperature

(a) 50 ecm styrene + 0.5 g lauroyl peroxide,
(b) 50 ecm styrene + 0.5 g lauroyl peroxide + 0.5 g dicyclopentyl tetrazene,

(c) 50 ecm styrene + 0.5 g lauroyl peroxide + 0.5 g sym.-dimethyldiphenyl tetrazene.

After 4 hours, the solutions were poured into 200 ecm of methanol and the precipitated polymer in Vacuum dried at 60 ° C and weighed; the yields were (a) nothing, (b) 3.2 g, (c) 3.2 g. The attempt was made repeated but the solutions were for 38 hours left before they were worked up; the yields were (a) 1.6 g, (b) 13.6 g, (c) 16.4 g.

Claims (4)

Patent CLAIM: 1. Process for the preparation of polymerization products from olefinically unsaturated compounds ao in the presence of an organic peroxy compound as Polymerization catalyst and a nitrogenous base as activator, characterized in that as nitrogenous base a tetrazene or an N-substituted heterocyclic secondary amine is used will. 2. The method according to claim 1, characterized in that the tetraethyl tetrazene-2 as tetrazene or 1,4-bis-cyclopenthyItetrazen-2 or sym.-dimethyldiphenyltetrazene is used. 3. The method according to claim 1, characterized in that the N-substituted heterocyclic, secondary amine is N-ethylpiperidine or N-methyl-1,2,5,6-tetrahydropiperidine is used. 4. The method according to claim 1 to 3, characterized in that that the molar weight ratio of organic peroxy compound to tetrazene or N-substituted, heterocyclic !, secondary amine between 1:10 and 10: 1, preferably 1: 1 and 4: 1, amounts to. Considered publications:
German Patent No. 863,414;
Swiss Patent No. 294 343;
interpreted documents of the Belgian patent No. 540292. © 909 528/44 «5.59