DE2161909C3 - Process for the production of copolymers - Google Patents

Description

Quantities greater than 3.0 percent by weight such as very high polymerization temperatures.

Acrylic acid esters with 1 to 4 carbon atoms in the ester chain are understood to mean: acrylic acid methyl ester, Acrylic acid ethyl ester, acrylic acid n- and isopropyl ester, Acrylic acid n- and isobutyl ester, acrylic acid tert-butyl ester, preferably ethyl acrylate, n-propyl acrylate, n-butyl acrylate.

Examples of free radical initiators that have a half-life of 1 hour at 60 to 120 ° C. are named: 2,4-dichlorobenzene peroxide, tert.-butyl perpivalate, Isononyl peroxide, decanoyl peroxide, lauroyl peroxide, capryloyl peroxide, propionyl peroxide, sucv cinyl peroxide, diacetyl peroxide, benzoyl peroxide, tert-butyl peroctoate, p-chlorobenzoyl peroxide, tert-butyl perisobutyrate, Mono-tert-butylpermaleate, 3,5 5-trimethylcyclohexanoiiperketaKtert-butylperacetat.azodiisobutyronitril, Azodiisovaleronitrile, isopropyl percarbonate, cyclohexyl percarbonate; preferably be Cyclohexyl percarbonate, lauroyl peroxide, benzoyl peroxide and tert-butyl perpivalate are used.

The following alcohols, which are freely miscible with water, are used: methanol, ethanol, Isopropyl alcohol, tert-butyl alcohol, ethylene glycol, Ethyl glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; preferably one uses ethyl alcohol, isopropyl alcohol. Ethylene glycol and diethylene glycol.

The polymerization of said monomer mixture is preferably carried out so that one the free radical starter in the monomer mixture dissolves in the cold and the mixture under stirring and pure nitrogen in the solvent or solvent mixture introduced so that the desired polymerization temperature adjusts. The type of solvent cannot be used, but the ratio of Solvent to monomers can be varied within wide limits. 30 bis are particularly interesting 80% polymer solutions.

The polymer salt solutions converted with aqueous alkalis which are volatile at room temperature can Valuable, elastic films and foils can be processed, or they can be used for treatment or coating a wide variety of rigid or flexible supports can be used. By a thermal Aftertreatment at 50 to 200 ° C gives waterproof and extremely wet wipe-resistant products. The post-treatment time depends on the post-treatment temperature. Need high temperatures only very short times, low temperatures longer post-treatment times. The post-treatment temperature depends essentially on the temperature stability of the selected substrate.

So it is B. possible with the materials according to the invention sliding layers on photographic films to be applied with outstanding smoothness. Backing layers can also be used on photographic films be poured, which significantly improve the flatness of the films. You can use as a binder z. B. for Pesticides, pigments, leather covering paints are used and give the bound matter excellent adhesive strength and water resistance on a wide variety of materials, which practically does not change due to the effects of light and weather. As a binder Used for textiles, for example host fiber nonwovens, the result is cut-resistant nonwovens with good wash resistance.

When priming leather with the polymer solutions according to the invention, an excellent one is obtained Grain hardening without hardening the leather appreciably. They can also be saved as Coating agents for metals, wood, plastics, paper and other natural or synthetic Serving materials

The parts and percentages given in the examples are based on weight.

example 1

In a 40-1-stainless steel vessel with anchor stirrer 6030 parts of ethyl alcohol are introduced, the reaction chamber is purged of air by flushing with pure nitrogen and introduced with stirring at 100 ⁰ C within 2 hours following solution:

8,550 parts of acrylic acid bismuth ester,
6300 parts of methyl methacrylate,
3150 parts of acrylic acid and
360 parts of benzoyl peroxide.

The inside temperature rises to 130 to 135 ° C. After stirring briefly at 100 ⁰ C, the final yield is achieved close to 100%.

The polymer solution is drained off after cooling and with stirring with 25% ammonia switched to pH 8.5. A clear solution is obtained which is diluted to 30% with water. This shows a Ford cup viscosity of 6 mm / 25 C of Γ45 ".

Example 2
As described in Example 1, a mixture of

10 800 parts of ethyl acrylate,
4,500 parts of methyl methacrylate,
2 700 parts of acrylic acid and
360 parts of benzoyl peroxide

polymerized and processed. A water-clear solution is obtained which is diluted to 30% with water and has a Ford cup viscosity of 6 mm / 25 ^: 'C of 55 ".

Example 3

As described in Example 1, 6030 parts of isopropyl alcohol and the following mixture are introduced added dropwise:

8100 parts of butyl acrylate,

6300 parts of methyl methacrylate,

3600 parts of acrylic acid and

180 parts of benzoyl peroxide.

After the polymerization and working up to a 30% strength aqueous solution, a Ford cup viscosity is obtained 6 mm / 25 ° C by 45 ".

Examples 4 to 10

In a three-necked flask equipped with a stirrer, reflux condenser and dropping funnel, 335 parts of ethyl alcohol were added submitted, heated to 78 ° C while stirring and rinsing with pure nitrogen and a solution follows.

added dropwise to the composition so that the reaction mixture boils vigorously under reflux:

650 parts of ethyl acrylate, 250 parts of methyl methacrylate, 100 parts of acrylic acid and
20 parts variable radical starter.

When a polymer yield of 100% is reached, the alcoholic polymer solution is with aqueous ammonia into a 30% aqueous alcoholic Solution with a pH of 8.5 transferred and the Ford cup viscosity 6 mm / 25 ° C.

Temperature comparative experiments 1 to 4 Examples 4 to in ° C for
Half-life IStd.

Comparative experiment 5

example

10

Used radical starter Be 147 in pieces 146 Cumene hydroperoxide 140 Di-tert-butyl peroxide 125 Tert-butyl hydroperoxide 94 Tert-butyl benzoate 94 p-clilobenzoyl peroxide 79 Benzoyl peroxide 77 Lauroyl peroxide 73 Tert-butyl perpivalate 62 2,4-dichlorobenzoyl hydroxide 60 Isopropyl percarbonate 46 Cyclohexyl percarbonal Acetylcyclohexanesulfonyl- peroxide % Polymer yield [»/] In ethanol i ^: order cup viscosity, i play 1 6 mm / 25 ° C

20th

20th

20th

20th

20th

20th

20th

20th

20th

20th

100 100 100 0.318 0.366 0.324 0.28 immeasurably high - * ■

100 0.22 18 '

100 0.19 14 '100 100 100 100 100 100 0.182 0.125 0.133 0.117 0.114 0.104 16 '6' 8 '2'45 "2'3O" immeasurable

high

11th

3350 parts of diethylene glycol are placed in a V4A kettle. The air oxygen is carefully enlfcrnl by evacuating and filling the reaction chamber three times with pure nitrogen. Then heats up the mixture is brought to 85 ° C. with stirring and the following solution is entered within 4 hours:

6500 parts of ethyl acrylate, 2500 parts of methyl methacrylate,

4 " 1000 parts acrylic acid and
275 parts of benzoyl peroxide.

The internal temperature rises to 120 ^° C. during this process. After reaching the final yield of almost 100%, the pH is adjusted to 8.5 with aqueous ammonia and the water is diluted to 30%. This solution shows a Ford cup viscosity 6mm / 25 ° C of 2Ί0 ".

Claims (2)

1 2 of acrylic acids and unsaturated, copolymerizable Pallet claims: free water-soluble carboxylic acids in the presence of radical formers at elevated temperatures, because-L Process for the production of mixed poly- characterized in that one iten from esters of aryl acids and unsaturated 5 40 to 70 percent by weight of an acrylic acid ester, copolymerizable, water-soluble carmh _{L to 4 c} . _{Atoms in the} alcohol component, Bonsauren in the presence of radical _{formers at 20 bjs} ^ percent by weight methacrylic acid Temperatures obtained, thus characterized by methyl ester and ζ eich η et that one ^ 10 to 20 weight percent acrylic acid 40 to 70 percent by weight of an acrylic acid ^lo . . . . . esters with 1 to 4 carbon atoms in the alcohol ¹ ^ ¹ J ⁰ . ^b '_ ^s } f 9'" ^a . ^{em AI} ^ ^oho1 ' ^dei " ^{mlt W} f ff / komnonente. is freely miscible, in the presence of 0.3 to 20 to «percent by weight of methacrylic acid - 3 percent by weight, based on the Mononvtht / iKtoinnH used mers, a monomer-soluble radical generator with Ste M Gewfchtsprozent acrylic acid ^{"of a} half-life of 1 hour at 60 to 120 ° C ^r copolymerized. at 70 to 140 ° C in an alcohol that is mixed with water. The limits given with regard to the used is unrestrictedly miscible, in the presence of 0.3 monomers, the polymerization temperature and des Up to 3 percent by weight, based on the radical initiators used, are critical and characteristic monomers, of a monomer-soluble radical- «> drawing for the procedure: bildners with a half-life of 1 hour. B. more than 70 percent by weight 60 to 120 ⁰ C copolymensiert. Acrylestem one, you get sticky films that through 2. The method according to claim 1, characterized at room temperature volatile aqueous alkalis, such as indicates that monomers and radical formers ammonia, methylamine, ethanolamine or ethyl continuously to the amine at polymerization temperature, preferably ammonia, is no longer clear temperature heated solvent can be given. aqueous-alcoholic solutions are to be transferred. If less than 40 percent by weight of acrylic ester is used in the monomer mixture, films are obtained low elasticity, and the polymers are not 30 more alcohol soluble. Compensating for the hardness of the polymers and the freedom from tackiness of the polymer films methacrylic acid methyl ester acts. However It is known that mixtures of acrylic acid esters or are obtained with a content of more than 40 Ge-methacrylic acid methyl ester and polymerizable weight percent methyl methacrylate in mono water soluble Carboxylic acids, such as acrylic, methacrylic, alcohol-insoluble products. The Acryl-Malein- or fumaric acid, in the presence of water-soluble acid mediates the solubility of the neutralized Licher initiators and, in the presence of mixtures, copolymers in aqueous or aqueous-alcoholic from water-miscible alcohols and water media. If it is used in amounts below 10% by weight polymerize and after the polymerization with zent, based on the monomer mixture, used, With aqueous alkalis or ammonia in clear poly- 4 °, no clear, aqueous or aqueous solutions are obtained to convict. The from these alcoholic polymer solutions and thus polymerized solutions The films obtained are partly water-bound, inadequate film formation. With higher redemptions, partly insoluble in water. They are used as adhesive set quantities as 20 percent by weight, based on the materials and for the treatment of textiles, leather or a mixture of monomers, acrylic acid gives the co-paper recommended (see DT-PS 8 62 956). 45 polymer is too hydrophilic. Will the The products obtainable according to lower polymerization temperature of 14O ⁰ C much about divorce steps from the known copolymers obtained highly branched and partially crosslinked by their different type of construction, another solution products which are insoluble and a transfer of the properties and their better of application-alcoholic Polymerisatgels with an aqueous-alcoholic properties. 50 no longer make the solution possible. One leads The object of the present invention wares, alcohol- make the polymerization at significantly lower temperatures soluble copolymers which once after than 70 ⁰ C, is obtained in poor PolyZusatz of aqueous alkalis addict than about merisatausbeute highly viscous solutions which are obtainable only with difficulty 30% aqueous -alcoholic solutions can be processed at t = 25 ° C and, when diluted accordingly, have a viscosity in the Ford beaker of <30 minutes after pouring and sitting with water or alcohol and which only result in very thin films after drying and short-term drying,
thermal aftertreatment at 50 to 200 ° C non-radical initiator with a half-life of 1 hour adhesive, waterproof and elastic films on the at <60 ° C and > 120 ° C, result in a wide variety of substrates or as binding polymer yields and viscous, poor Agent for pigments, opaque paints, plant protection 60 processable alcoholic polymer solutions. To medium and fleeces are suitable. offsetting these solutions with at room temperature The object was achieved in that lower temperature volatile aqueous alkalis are largest acrylic acid esters, Methacrylic acid methyl ester and acrylic partly heterogeneous mixtures obtained, their Fordbechersäure can no longer be measured in special quantity ranges using viscosity, i.e. special production methods were copolymerized 65 the products are practically not applicable. Lesser ones the. Amounts of peroxides than 0.3 percent by weight, the subject matter of the invention is thus a method based on the monomers used, have a similar effect for the production of copolymers from esters, such as low polymerization temperatures and large