DE1027401B - Process for the production of polymers or copolymers - Google Patents

Description

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OF THE GERMAN

PATEHTASITES

The polymerization of compounds of the general formula

R ₁

H ₈ C = CH-

.0-R-OCO-C = CH-R ₂

liei of the vinyl ether group as polymerization or otherwise reactive group is retained is not previously known and appeared in view of the Vinoxy group lability not feasible. With this view, the statements of Η are correct. Haas and M. Simon, Journal of Polymer Science, 1955, Vol. XVII, p. 424 that / S-vinoxyethyl methacrylate Although it can be polymerized in two stages in such a way that the vinyl ether group in the first stage cationic and the polymer obtained can be polymerized by free radicals in the second stage, but that an anionic polymerization of the methacrylic double bond with retention of the vinyl group does not is feasible.

Contrary to this view, compounds which correspond to the general formula mentioned can be polymerized anionically with retention of the vinyl ether group. In the formula mentioned, R is a divalent aliphatic radical containing at least 2 carbon atoms, optionally containing heteroatoms, R _{1 is} hydrogen or an alkyl radical and R _{2 is} hydrogen, an alkyl or an aryl radical. Certain substances, especially those with a free hydroxyl group, e.g. B. Glykolmonovinyläther, inhibit the progress of the anionic polymerization in liquid ammonia. Care must therefore be taken to ensure that they are absent. - Vinyl glycol methacrylate may be mentioned as a simple representative of the monomeric compound polymerizable in two stages in the context of the present process. Under the action of metallic potassium in liquid ammonia at -35 ° C, the monomer polymerizes to a white powder that is soluble in organic solvents. If the polymethacrylate obtained is dissolved in methyl methacrylate and benzoyl peroxide is added, strongly crosslinked, insoluble, possibly also non-swellable copolymers are obtained.

The soluble products obtained in the anionically excited polymerization stage can be as follows can be used: Those which represent a polymer and a polymerizable compound at the same time Products can be polymerized or copolymerized under the influence of free radical or cationic accelerators and converted into valuable end products. For further processing of the received Intermediate products are, for example, their copolymerization with unsaturated polyesters and other monomers to polyester resins.

Method of making
Polymers or copolymers

Applicant:

Röhm & Haas G. mb H.,
Darmstadt, Mainzer Str. 42

Herbert Schreiber, Darmstadt,
has been named as the inventor

The dense cross-linking of such products leads to hard, solvent-insoluble and non-swellable products Products that z. B. can be used as dental plastics. By dimensioning the Quantity ratio between buckets of the polymerizable Polymer containing vinyl ether groups on the one hand and a further copolymerizable polymer Compound on the other hand, products can be obtained, their degree of crosslinking and thus whose mechanical strength can be adjusted arbitrarily. The additional option of using the monomeric, compound corresponding to the formula mentioned with other anionically polymerizing monomers to copolymerize, opens up further possibilities for the production of new polymerization and reactive compounds.

It should be noted that the second polymerization step can be catalyzed not only radically, but also cationically - a possibility which may be advantageous in special cases.

The following examples by no means exhaust the options available. As inventive a procedure is generally asserted in which compounds of the specified formula type, i.e. the contain both a vinyl ether group and an optionally substituted acrylic group, in the first place Stage polymerized under the influence of anionic accelerators without changing the vinyl ether group and the products obtained, optionally by a free-radically or cationically initiated polymerization or mixed polymerisation can be converted into high-quality plastics.

Examples

1. In an apparatus which is sealed against humidity and which is equipped with a stirrer, thermometer, and a suction tube for ammonia,

709 958/443

Claims (2)

the 150 ecm condensed ammonia dried over caustic alkali. 0.5 g of metallic potassium is dissolved in the liquid ammonia. To the deep blue solution g / J-vinyloxy-ethylmethacrylate (Kp is allowed 40 m ₁₉ = 85 ° C |. ° = l 448 ₀ flow, by cooling keeping the temperature to -35 ° C. The blue solution -is. immediately discolored, and colorless or pale yellowish polymer precipitates. About 10 minutes are required for the feed and the polymerization. The catalyst is then inactivated by adding 5 ecm of water and the ammonia is evaporated. The polymer is dissolved in 100 ecm of acetone, precipitated by dilution with water, washed alkali-free with water and dried at room temperature in vacuo over calcium chloride.Drying can also take place at an elevated temperature of, for example, 70 ° C. without crosslinking occurring.Yield: 35 g ipsp / c = 0.011 "(in chloroform). The polymer is clearly soluble in acetone, benzene, chloroform or ethyl acetate. 20 g of the polymer produced in this way are dissolved in 100 g of methyl methacrylate, with 0.01 g Azodiisobutyronitrile is added, the mixture is polymerized for 16 hours at 60 and 6 hours at 100.degree. There arises a clear, hard, still thermoplastically deformable polymer, which swells only slightly in chloroform is. 2. A solution of 20 g /? - V (inyloxy-ethyl methacrylate 5 g of a 20% dispersion of sodium in paraffin oil are added to 100 g of anhydrous ether. The mixture remains under dry nitrogen for 1 day with occasional shaking. Then add 10 ecm of butanol and filter, after the gray color of the sodium has disappeared, the polymer from. This is dissolved in benzene, precipitated with methanol and dried in vacuo. Yield: 8 g j / sp / c = 0.015 (in chloroform). A mixture of 2 g of this polymer with 8 g Acrylonitrile is used with 0.01 g of benzoyl peroxide as a catalyst Polymerized for 8 hours at 60 ° C. A hard one which is insoluble in organic solvents is obtained Polvmerisat. 3. In the same way as in Example 1, a solution of 0.2 g of potassium in 150 ml of ammonia is added 5.9 g of o-Vmyloxy-butyl methacrylate flow. The monomer is sparingly soluble in ammonia. It gradually turns into a viscous mass. After the ammonia has evaporated, the polymer is dissolved in ether, filtered and precipitated with methanol and dried in vacuo. The polymer produced in this way is treated with 2.5 g of styrene with the addition of 0.25 g of benzoyl peroxide for 15 hours. polymerized at 60 ° C and 7 hours at 100 ° C. The copolymer is somewhat cloudy. It is less brittle as pure polystyrene and only slightly swellable in chloroform. 4. 5 g of an anionically polymerized according to Example 1 / J-vinyloxy-ethyl methacrylate are in Dissolved 10 ecm of styrene and poured it into a film. Put the film in an anhydrous atmosphere which contains gaseous boron fluoride. The film polymerizes into a hard, insoluble layer. Pa τέντα ν s ρ r ü ch ε ·. 1. A method for producing polymers or copolymers, characterized in that that monomeric compounds of the general formula H ₂ C = CH-OR-OCO-C = CH-R ₂ in which R is a divalent aliphatic radical containing at least two carbon atoms, optionally containing heteroatoms, R _{1 is} hydrogen or an alkyl radical, R _{2 is} hydrogen, an alkyl or aryl radical, is anionically polymerized and optionally further polymerized or copolymerized by radical or cationic means. 2. The method according to claim 1, characterized in that the first polymerization stage in liquid ammonia is carried out. © 709 95S / 443 3.58