DE1793271A1 - Process for the preparation of cotelomers of styrene with half-esters of maleic acid - Google Patents

Description

Appendix I.
to the Pat-entanmoldunT Fw 5344

Process for the production of Cotelor.eren the styrene's nit Ilalbestorn of maleic acid.

The present invention concerns, inter alia, a process for the preparation of 3tyrene-oleic acid half-ester T3lo: ners with low molecular weights in the presence of alcohols as solvents. " ^:

The cotelorcerization of styrene with maleic anhydride is already known. Using initiators which produce free radicals, the reaction is carried out in solvents which are suitable as telogens, that is to say exert a chain-breaking effect and are incorporated into the telogen. Mainly aromatic hydrocarbons are used. ^r ie benzene, toluene, xylene and cumene are used. Eekonnllich häii'jt di> s M'il ';f.;-'. 7Lc-: i ^! : der Tatoneren stcr ". from the xlorktior.stenperatur ab. r '- ^; and.:rf :.'i int er ess ü have styrene-Ma 1 one acid hydrid ~ Tel one re nit one. Mononoren - Verhr. i 11 rii ·; ν αϊ 1: 1 and mean MoI- ■■ 'j: - ;: lcht (;? i'unl'ir 1000. '.'iese- - ^r> rO'! ukt-j firkn, possibly . nnch ΐϊπ - '. oLz'.!. t; j ··: · ^% t \\ iydri.r [\ ^r ■>. ·· 'pi' ~ -u: '\ t Λ i -.'. oho Jen zu flc: n ents; iro <- 'ion ^f : on Ur ¹ I ¹¹ JC ¹ SIt-Tr ₁ , !! (ivij!';';R; u! .Ι'Λϊ, ΜηΊιιτ; ruif dc ^ _1. Lr-ck ^ obiet. And r < ^v .itor-

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as an additive for self-gloss emulsions and hot-melt adhesives. For the preparation of these low molecular weight styrene-maleic anhydride telomers Reale tion temperatures of about 200 and, since the solvents used at lower temperatures boil, pressure vessels required.-Under these conditions of action unwanted discoloration of the products often occurs.

The copolymerization of styrene with half esters of maleic acid in bulk or in solvents such as aromatic hydrocarbons is already known. For example, in British patent 588,725 Ila'leinsäureha! Best, "- _: _ such as maleic acid monomethyl ester, copolymerized with styrene in solvents such as benzene or xylene or in an aqueous emulsion.

It has now been found that cotelomers made from styrene and half-x. ' . esters of maleic acid with molecular weights between 5CO and 2000,. ,, - can advantageously be produced if 40 to SO 11ο1 ^σ ₀ styrene and 60 to 20 Uol% of one or more half esters of, .. r maleic acid with aliphatic or cycloaliphatic primary or secondary Alcohols with 1 to 10 carbon atoms, the carbon chain can be interrupted by 1 to 4 oxygen atoms, in the presence of an aliphatic or cycloaliphatic primary or secondary alcohol with 1 to 10 carbon atoms, the carbon chain of which is interrupted by 1 to 4 oxygen atoms säin k; : \ nt \, "Whereby the molar ratio of alcohol to monomers is 5: 1 to 1: 5 and 0.05 to 10% by weight , based on the monomers, of an initiator which forms idioms is telomerized at 65 to ISO C. - /

The resulting products are completely colorless. For example, one with isobutanol as a solvent at boiling temperature ""^{; :} 'for the styrene monoisobutyl maleate telomer produced at 103 has an average molecular weight of 700. If, instead of isobutanol, one uses cumene, ie an aromatic hydrocarbon, eleven solvents, so: must mn η in Work autoclave at 170 °,

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to get an equally low molecular weight. The reinforced This shows that alcohols have a chain-breaking effect on aromatic hydrocarbons.

The yields are over 85 %, based on the monomers, in many cases they are quantitative. The telomeres formed remain dissolved in the alcohol; it only increases the viscosity of the reaction mixture. After the solvent has been removed by distillation, which is possible without difficulty with the low-boiling alcohols typically used, the telomers remaining as residue can be used further directly. The reaction products dissolve clearly in aqueous ammonia and thus do not contain any styrene homopolymers. .

The end groups of the Teloneren are characterized by the incorporation of the alcohols used as telogen, according to the Scheme

H - (- CH-CH ₀ -CH-CH.) R ² OH (R ¹ OH = R ² OH or R ² - R ¹ minus H)

C-H- COOR COOH H

6 ο

The Teloneren therefore contain "reactive hydroxyl groups, the at, higher temperatures, mainly at temperatures above their melting point and at reduced pressure, r.it the can convert existing carboxyl and ester groups, which is achieved by a considerable increase in the melting temperature and the molecular weight makes noticeable. In order to maintain the low molecular weights, the solvent is therefore preferably at distilled off at low temperatures. On the other hand, it can be done subsequently above the melting temperature, if necessary in a vacuum achieve partial crosslinking of the telomerans; for certain Applications, for example in the paint sector, can be used by Be an advantage.

The action temperatures are between 65 and ISO, in the most cases, between SO and 160. Preferably -sa-n works at

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Alcohols with 3 to 6 carbon atoms at the boiling point of the Alcohol under reflux, which corresponds to a temperature range of 100 to 160; possibly the reaction can also take place under Printing can be carried out. The!, Ionomer mixture drips or you pump together with the initiator, e.g. a peroxide, to the alcohol. In this way one avoids that the llaleic acid half-ester unnecessarily long comes into contact with excess alcohol and maleic acid diester, which is essential cotelomerizes more slowly, can continue to yaw.

While telomers containing anhydride groups only go through several hours of heating with an alcohol to temperatures above 150 ° in the presence of alkali salts of fatty acids in the Transferring half esters (cf. Brit. Patent 980 112), runs the conversion of monomeric maleic anhydride with alcohols to LIaleic acid half-esters from very easily, depending on the The reactivity of the alcohol is sufficient, equimolar amounts of alcohol and sharkic anhydride for one half to one hour to heat to 100. Since the maleic acid half esters, in contrast to the solid maleic anhydride, are liquid at itaurate temperature are, the output components can be handled without difficulty; heated storage vessels and supply pipes are superfluous.

For the esterification of the maleic anhydride, as well as a solvent that acts as a telogen, aliphatic and cycloaliphatic alcohols, the carbon chain of which can be interrupted by 1 to 4 oxygen atoms, with 1 to C atoms are possible v / ie ethanol, propanol, isopropanol, Butanol, isobutanol, isooctanol, glycol mono-alkyl ether, cyclopentanol, cyclohexanol. The solvent used can be an alcohol other than that used for the esterification of maleic anhydride; however, transesterification during the telomerization cannot be ruled out. In the case of alcohols with more than 10 carbon atoms, the boiling point becomes so high that complete removal from the reaction mixture is difficult.

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39soncl3r3 the ielor.ierisr.tion runs favorably when using Alcohols with 3 to 3 carbon atoms: ξ η s.b.

The amount of alcohol affects the yield and that middle. Molecular weight of the te loner is a ts. One works in generally nit a no 1 ar en ratio of alcohol to Monomers from 5: 1 to 1: 5, preferably 3: 1 to 1: 3.

The proportion of dea 3tyi-ol in the tightness of the monomers can be between 40 and 50%, preferably between 50 and 6%. The greater the proportion of styrene, the longer the required reaction times and ur .: the higher the MoI-gev / icht der Teloraeren, equiraolcive "close styrene and maleic acid semiesters" can be teloraerized particularly advantageously; the reaction is running in this 7all quickly and delivers pick-up weights that are less than 1000.

Cetylpero IAE azodiisobutyronitrile, Di:;;, di-tert-butylpero :: id, Lcuroylnaroxid and Cur.olh ^ 'droperozid id Amounts zv.- as initiators radicals are forming "onnectivity v ^r ie Dibenzoylpero?. is 0.05 and 10%, based on the monomers, essentially about 0, 5 and 5 %, preferably about 1 and 2%.

The styrene-maleic acid monester-Telor-eren also find v, ^r ie the styrene-Mp.l.eins-aurscinhydrid-Te-ionere-n use in the field of jackets as well as for self-gloss emulsions and hot-melt adhesives.

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Example 1:

6Gg of maleic anhydride (0.7 οΙ) and 52 g of isobutanol (0.7 mol; v / earth 30 minutes at 100 °
Inonoisobutyl ester takes place.

v / earth heated to 100 for 30 minutes, whereby Ur.iS2.tz to maleic acid

The half-ester thus obtained, which is liquid at low temperature, is set 68 g of styrene, 30 g of tert-butylbrenzcatecb.in and 3.5 g of dibenzoyl peroxide to, the Genisch can be added dropwise over the course of 1 hour to 100 ml of refluxing isobutanol and 1 hour post-react at boiling temperature. The solvent is at 100 i.V. distilled off. Zs v / earth 181 g of colorless Telor.erisat, that melts at 110-120, with an average molecular weight of 7C0 and an acid number of 133.

Example 2:

The procedure is as in Example 1, line mixture of 4.Z0 g of oleic acid monoisobutyl ester, which has been prepared from 272 g of maleic anhydride and 203 g of isobutanol, 272 g of styrene, 120 kg of tert-butylpyrocatechol and 14 g of dibenzoylpero;: id v / er da η added dropwise to 200 ml of isobutanol boiling under P.üclifluß. 755 g of colorless Telor.ieres are obtained with a "rweicIni-igsb range of" 110-120 °, e
number of IGo.

Example 3:

Analogously to Example 1, 123 g of r-maleic acid nono-n-butyl ester, which has been prepared from 70 g of maleic anhydride and 53 g of n-butanol, 70 g of styrene, 30 mg of tert-butyl catechol and 3.5 g of dibenzoyl percide are carried out Then add 50 nl of refluxing ^1. N-Buto.nol teloir.erisiert. 174 g of colorless reaction product, which melts at 87-38, with a molecular weight of tieron are obtained

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of 7SO and an acid number of 200. - ' Beisoisi 4:'

According to Example 1, 113 g of mono-n-propylmaleinr.t, that is made from 70 g of maleic anhydride and 43 g of n-propanol received, together with 70 g of styrene, 30 mg of tert-butylpyrocatechol and 3.5 g of dibenzoyl peroxide to 150 sil under Dropped reflux boiling n-propanol. 152 g are obtained colorless Telor.eres that clicks at 35 - 100, with a:?, average molecular weight of 670 and an acid number of 210.

Example 5: "

Analogously to Example 1, a mixture of 133 g of mono-isooctyl maleate, which has been prepared from 70 g of maleic anhydride and 23 g of isooctanol, 70 g of styrene, 30 rig of tert-butyltfenzcatechol and 3.5 g of di-tert-butylperoxy is allowed to 150 ml of Isooctpncl at .150 °. 243 g of reaction product are obtained, which is already about half a half at room temperature, with a nitrated MoI weight of 3 SO and an acid cell. "-i 133,

Example 6:

As described in Example 1, a mixture of 124 g of maleic acid r.iono-r.ietho: -: yäthy! Ester, the γλ: ξ 70 g of maleic anhydride and 54 g of Giyltolnonor.ethyläther has been obtained, 70 g of styrene, Add 50 mg of tert-butylpyrocatechol and 3.5 g of dibenso: - ¹ ! - peroxide to 250 ml of refluxing glycol non-ethyl ether. 173 g of Telo'rieres, which melts at 135-144, with an average molecular weight of 1370 and an acid number of 247 are obtained.

Example 7:

Analogously to Example 1, 250 ml are refluxed Glykolnonoäthyläth-: r 134 g maleic acid monoethoxyethyl ester,

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which one consists of 70 g of ilaleic anhydride and 64 g of glycol monoethyl ether produced, 70 g styrene, 30 ng tert-butylpyrocatechol 'and 3.5 g of bibenzoyl peroxide were added dropwise. Man receives ISO g Teloneres with a softening range of 120 * ■ 130 °, an average molecular weight of 1200 and one Acid number of 221.

Example S:

250 ml .Cyclohexanol are heated to boiling under reflux. As in Example 1, a mixture of 142 g of maleic acid flfe monocyclohexyl ester formed by heating 70 g of maleic anhydride and 72 g of cyclohexanol to 100 ° for one hour. is, 70 g of styrene, 30 ng of tert-butylpyrocatechol and 3.5 g of di-tert-butyl peroxide were added dropwise. 217 g of colorless telomer, which melts at 37-110, with an average molecular weight of SSO and an acid number of 163 are obtained.

Example 9:

A solution of 316 g of monoisobutyl ester (1.8 mol), which has been prepared by heating 130 g of maleic anhydride and 133 g of isobutanol for 30 minutes, is added to 200 ml of refluxing isobutanol within 1 hour mg tert-3ut5 ^r lbrenzcatechin and 14 g of dibenzoyl peroxide in 360 g of styrene (3.5 moles) was added. The mixture is then stirred for 4 1/2 hours at reflux temperature. After the solvent has been distilled off at 1GO ° IV, 675 g of colorless telomerizate, which melts at 154-165, with an average molecular weight of £ 00 and an acid number of 142, remain.

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Claims (1)

- 9 - Fw 5844 patent claims 1. A process for the preparation of cotelomers from styrene and half-esters of '. Oleic acid with Ilänev / ichten zv / ischen 5CO and 2000, characterized in that 40 to 80 Ι, ΙοΓ ^ styrene and QO to 20'lol'o one or more half esters of maleic acid having aliphatic or cycloaliphatic primary or secondary alcohols having 1 to 10 carbon atoms, the carbon chain of which can be interrupted by 1 to 4 oxygen atoms, in the presence of an aliphatic or cycloaliphatic primary or secondary alcohol having 1 to 10 carbon atoms -Atones, the carbon chain of which can be interrupted by oxygen futures, although the molar ratio of alcohol to ionomers is 5: 1 to 1; 5, and 0.05 to IC Gsv, '.; i, based on the' Zonor.eren, a Hadikp.le forming. Initiators at 35 to 130 telor.ierized τ / earth " 2, method according to claim 1, characterized in that nan the liquid genic of styrene, half-ester of malsic acid and Initiator to alcohol can be dripped or /. pumps. 109827/1503 QAD ORIGINAL it St ί 1 ■ ',.'