DE1420756A1 - Process for the polymerisation or copolymerisation of compounds containing at least one ethylene double bond - Google Patents

Description

Process, for polymerizing or interpolymerizing of compounds containing at least one ethylene double bond.

CO O

σο

co

The invention relates to a method for polymerizing or interpolymerizing compounds containing at least one ethylene double bond in the presence
an organic Borderivata of the general formula BRn (E = alkyl radical) as a catalyst, with new
catalytic systems based on an organic boron derivative are used, which are particularly active
and are able to use the Polymerisatlojj. and / or copolymerization of the compounds mentioned at low

! To bring about temperatures below atmospheric pressure »

BATHROOM 0RU3INAL
Documents (Art. 791 Para. 2 No. 1 and 3 of the amendment. % 4t 9.1967)

From Belgian patents 560 624, 562 433 and 562,701 it is known that compounds containing the group> C = C <^ can be obtained at low temperatures and under atmospheric pressure in the presence of organic boron compounds of the general formula BR ^, wherein R represents an alkyl group, can polymerize and / or co-polymerize. The ones after these Polymers and / or copolymers obtained from patents have improved mechanical properties and an increased degree of crystallinity

It has now been found that to a noticeable extent the activity of the catalysts is based on of boron trialkyl for the polymerisation and / or mixed polymerisation of an ethylenic double bond containing compounds can increase by adding suitable activators to these catalysts »

The inventive method for polymerizing improved or copolymerization of compounds containing at least one ethylene double bond in the presence an organic boron derivative of the general formula BRt (R = alkyl radical) as a catalyst is thereby characterized in that unsaturated compounds of the general formula

^R 2 ^R 4

wherein'R ₁ , R ₉ , R ^, R. mean hydrogen, an alkyl radical or a halogen, but at least one γοη

them is neither hydrogen nor an alkyl radical, 809806/0594 BAD

in the presence of a small amount of an organic Radical catalyst has been polymerized at low temperatures «

The radical catalysts are selected from the usual radical catalysts, such as the organic ones Peroxides or azodinitriles. One uses, for example the peroxides of benzoyl, lauroyl, 2-4-dichlorobenzoyl or the azodinitriles such as azodiisobutyronitrile. The amount of free-radical catalyst to be used can be 0.3 to 3 wt polymerizing monomers «

Among the vinyl to be polymerized according to the invention and acrylic monomers are for example:

Styrene and its ring-substituted derivatives, vinyl chloride, Vinylidene chloride, vinyl fluoride, vinylidene fluoride, the vinyl esters such as vinyl acetate, the vinyl ethers, those of acrylic acid and of their halogens substituted derivatives of methacrylic acid and of their derivatives substituted by halogens, the allyl halides and esters, acrylonitrile, Kethacrylic acid nitrile, vinyl pyridine, etc. "

The monomers of the corresponding general given ! Formulas can also be interchanged according to the previous

*? lying processes are copolymerized and one

** s. » In this way, it receives binary or tertiary mixed polyols meren according to the working conditions »

cd The length of the catalyst to be used varies from

0.1 to 3 G-ew.yi on the amount of the one or those used Ilononians, BAD 0FHGtNAt.

The polymerization can be carried out in the block or in the presence of an inert organic medium will. Since the trialkyl derivatives of boron are not particularly Are sensitive to the action of water, you can also use the polymerization in aqueous Environment according to known polymerisation processes like him Carry out emulsion or bead polymerization »Choose from the organic derivatives of boron preferably boron triethyl or normal boron tributyl.

The catalytic one used according to the invention System enables polymerization and / or interpolymerization of at least one ethylene double bond contained in the abovementioned compounds unusually low temperatures and with still perform considerable yields. The polymers and / or copolymers obtained by the process generally have an increased degree of crystallinity and improved mechanical properties over the polymers and co-polymers such as them are manufactured according to the previously usual processes »

In US Pat. No. 2,840,551 • Mentioned the possibility of polymerizing olefins in the presence of a catalytic system, which consists of a Boron trialkyl compound and a salt of an I \: e tails of groups IVa, Va and VIII of the leriodic system, For example, a metal azide consists “Obviously is this known method from the invention jars clearly different »

- - * ^Γ γ BAD OBtGINAL

809306/0594

In "Journal of Polymerseience" 1958, Vol. 28, pp. 227-29 is the activation of organic border derivatives Oxygen, hydrogen peroxide and metal oxides in the • Catalytic polymerization of vinyl monomers described. However, it could not be concluded from this that the activation of Bortriälkyl by radical catalysts like the organic peroxides or azp catalysts in the polymerization of vinyl and acrylic monomers would be favored.

Incidentally, the following comparative ^, tests carried out:

In ^: a flask provided with a stirrer, a heat-insulating cover and a nitrogen inlet, after purging the air by means of a stream of nitrogen, 140Og vinyl chloride and 100 g methanol were introduced while maintaining a temperature of -4O ⁰ G. 67 10 "^ moles of boron triethyl and 7.34 10" ^ moles of a peroxide were added. The temperature was kept at -40 ° C. and the yield of polyvinyl chloride formed was determined. The following table gives the yield of polymer and peroxide used : ·; - :. l

attempt Mrο type of peroxide ffebxldetes polymer
g / hour 43 1 tert-butyl hydroperoxide 44 41 '2 tert "butyl peracetate 37 3 Cumene hydroperoxide 0.7
BAD OFUGlNM, 4th te rt.Butylperlaura t 5 What is hydrogen peroxide a09806 / 059A

The attempt Mr. 5 clearly shows that the boron trialkyl-H _{2 O 2 system} did not cause the polymerisation of vinyl chloride at low temperature, in contrast to the claimed catalytic system of experiments 1-4

The invention will be described in more detail by reference further described on the following examples, which serve only for illustration and not for limitation » It is capable of many modifications which do not lead out of its area »

example 1

This example is given for comparison In a glass flask of 1 1 with three pipe inserts fitted ■ with a stirrer, a thermometric sheath and a nitrogen line is charged to expel the air by means of a Stickstoffstip mes to a temperature of -25 ⁰ C held 500 g vinyl chloride and 50 g normal hexane. 0.75 g of normal boron tributyl is added. The temperature is kept at -25 ° C. and after two hours of polymerization, 27 g of polyvinyl chloride are obtained.

Example 2

The procedure is as in Example 1, but 1 g of 2-4-dichlorobenzoyl peroxide is added to the reaction medium. Compartment two hours of polymerization at -25 ⁰ C wins to 36 g of polyvinyl chloride.

■ - ■ BAD ORlGlHM-

809806/0594

Example 3 -.

"The procedure is as in Example 1, but using the Reaktionsmilieia, 1 g Azodiisobutyrqnitril added""After two hours of polymerization at -25 ⁰ C wins to 42 g of polyvinyl chloride.

BATH ORIGINAL

809806 / 059A

Claims (1)

Claim Process for polymerizing or interpolymerizing of compounds containing at least one ethylene double bond in the presence of an organic boron derivative the general formula BIU (R = alkyl radical) as a catalyst, characterized in that unsaturated compounds of the general formula R ₂ R ₄ where R ₁ , Rp, R3 "R ^ are hydrogen, an alkyl radical or a halogen, but at least one of them is neither hydrogen nor an alkyl radical, can be polymerized at low temperatures in the presence of a small amount of an organic radical catalyst" 809806/0594 _{A q} ,., ". ^BATH N _b ue documents, *, > i -. - .. u, ι sau3, «, Ä ^ n ^, 4. ,. u ■>