DE918233C - Process for the production of plastics containing acrylic acid nitrile and esters of the acrylic acid series - Google Patents

Description

Issued on the basis of the First Oberleilungsgesetz of July 8, 1949

(WiGBl. P. 175)

FEDERAL REPUBLIC OF GERMANY

ISSUED SEPTEMBER 23, 1954

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 39c GROUP 25oi

R 2043 IVc j 3gc

Dr. phil. Walter Bauer, Darmstadt and

Dr. phil. Klaus Tessmar, Darmstadt

have been named as inventors

Röhm & Haas G.m.b.H., Darmstadt

Process for the production of acrylonitrile and esters of the acrylic acid series containing plastics

Addendum to patent 900 752

Patented in the territory of the Federal Republic of Germany on March 17, 1943 The period from May 8, 1945 up to and including May 7, 1950 is not counted towards the patent term

(Ges. V. July 15, 51)

The main patent started on March 17, 1943

Patent application published February 18, 1954

Patent issued August 12, 1954

The subject of the patent 900 752 is a process for the production of plastics of high hardness and Strength by polymerizing mixtures based on 40 to 80 percent by weight of acrylonitrile, acrylic acid amide or compounds of the general formula

CH ₂ = C-CONHR

in amounts up to 15 percent by weight and 60 to 20% of methacrylic acid esters of lower alcohols. In this formula, R can be alkyl, aryl or aralkyl, _furthermore _CONHR or —CH ₂ NHCOR.

It has now been found that copolymers having excellent mechanical properties with high acrylonitrile content can also be produced by replacing the acrylic acid amide or of the listed derivatives of this compound derivatives of methacrylic acid amide of the general formula

20 CH ₃

CH ₂ = C-CONHR

in amounts up to 15 percent by weight, based on the Total amount of substances to be polymerized, given

if necessary in the presence of non-polymerizable or other polymerizable substances into which copolymers are polymerized. Substances may be mentioned in particular in which R is alkyl, aryl or aralkyl, also CONHR, such as methacrylic urea, or CH ₂ N HC OR, such as methylenedimethacrylic acid amide.

A particular advantage can be found in the common Achieve use of several of the claimed substances such as in example io. A mixture according to the example io can be polymerized much faster, has more uniform properties and is completely free of haze.

Examples

Methacrylic acid additive Dibenzoyl Tensile, impact bending. cmkg / cm ² ° C methyl ester:
Acrylic acid nitr peroxide Heat resistance 50 95 = 30: 70 parts 0.1 part methylene dimethacrylic J. hurry kg / cm ² I. 99.9 acid amide 0.04 1000 50 100 0.5 parts methylene dimethacrylic 2 99-5 acid amide 0.04 I050 55 100 1.0 part methylene dimethacrylic 3 99.0 acid amide 0.04 1000 45 105 3.0 parts methylene dimethacrylic 4th 97.0 acid amide 0.04 1000 50 94 5.0 parts of N-methyl methacrylic 5 95.0 acid amide O ₁ I 960 50 95 15.0 parts of N-methyl methacrylic 6th 85.0 acid amide 0.1 1000 70 95 5, o parts of N-phenyl methacrylic 7th 95, o acid amide 0.04 950 50 95 5.0 parts N-butyl methacrylic 8th 95, o acid amide 0.04 950 45 102 8.5 parts methacrylic urea 55 98 9 9 *> 5 5.0 parts methacrylic acid amide + 0.04 UOO IO 94.7 0.3 parts of methylene dimethacrylic 0.04 1040 acid amide

The N-substituted substances can be z. B. off Prepare methacrylic acid chloride and the corresponding amides or amines.

That according to Examples 1, 2, 3, 4 and 10 to be used Methylenedimethacrylic acid amide can be prepared as follows:

1. 85 g of methacrylic acid amide with a melting point of iio ° (uncorr.) Are dissolved in a mixture of 38 ecm of 40% formaldehyde solution and 40 ecm of water and 20 ecm of conc. Hydrochloric acid added. The solution warms up slightly. After 2 days of standing 82 g Methylendimethacrylsäureamid crystallize a melting point of 161-162 ⁰ (uncorr.).

2. 200 g of acetone cyanohydrin and sulfuric acid, heated to 125 °, with a molar ratio of 1: 1.4 are gradually mixed with 34 cm of 40% formaldehyde solution and 10 g of water. The solution is kept at a temperature below 40 ^{0 by cooling.} It slowly crystallizes. After cooling to room temperature, 300 g of water are added, the precipitate is filtered off with suction and washed with water.

The 70 ⁰ dried crude product weighs 51 g. Melting point 151 to 155 ⁰ . It is recrystallized from 100 ecm of methanol. When the boiling hot solution cools, 42 g of methylenedimethacrylic acid amide with a ^{melting point of 161 to 162 0 (uncorr,) crystallize.}

Claims (1)

Claim: Process for the production of acrylonitrile-containing plastics of high hardness and strength Main patent 900 752, characterized in that instead of acrylic acid amide or its derivatives the derivatives of methacrylic acid amide of the general formula CH ₃ CH ₂ = C-CONHR can be used in which R is alkyl, aryl, aralkyl, CONHR, CH ₂ NHCOR. © 9548 9.54