DE1745954A1 - Process for the preparation of ethanolimide derivatives from styrene-maleic anhydride cotelomerizates - Google Patents

Description

17,595

FARBWERKE HOECHST AG. ι # * w ν ^ · »

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Frankfurt (M) -Hoechst

Appendix I.

January 25, 1968

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to the patent application Fw

5G22

Ancestors for the production of ethanolide derivatives from Styr O ₁ I -maleinic acid enn hyd r l d ~ CoteloraerIsa fen

It is well known that when ethanolanine is added, too Styrene- ^ alcinsnureanhydrld-Cotelomerisaten crosslinked products. The crosslinking is caused by the anhydride groups very easily both with the amino and with the hydroxyl group of the ethano larain under amide or React ester formation.

It is also known that uncrosslinked products with the help of a Two-step process can be produced. In this case, the anhydride groups are first treated with an alcohol, e.g. Amyl alcohol, converted to the half ester, and then the amine salt is made from the Haibeat ex * by adding Xthanolamine educated. iXtrch heating becomes dim with elimination of water Hal best ei'-amide and from it the ethanolimide derivative with elimination of alcohol educated.

ORIGINAL 109838/1328

The invention is a process for the production of ftthanolimide derivatives of styrene-maloic anhydride-OoteJo-Bterisatea by converting styrene-IIaleic anhydride coteloaerisates alt xthanolamine, which is characterized in that the reaction is carried out by heating a mixture of styrene-malelic anhydride-Coteloaerisaten old mean molecular weights between 650 and 16CX) and the equiaolar to 10-fold molar Amount, hexogenic on the anhydride group of the styrene-maleic anhydride-CotelO products, and Xthanolamine is carried out at temperatures from ISO to 250 ° C.

The process according to the invention enables production uncrosslinked thanolinide derivatives of styrene methyl anhydride * Copolyaeren In one step and in good yield. Included A networked, similar product is next formed, This, however, occurs when the body is heated to the lower molecular weight Äthanollmidderivat passes over.

Xthanolamine is used in an equiaolar to 10-fold molar amount used, besogen on the anhydride groups of the styrene-malelic acid anhydride-Coteloaerisate. The use of ethanolamine in an uborso of 1.5 is preferred to 5 moles per anhydride group.

01 · Styrene-Kalelnsäureanhydrld-CotolomeriBate dissolve in excess of ethanolamine at room temperature. If equivalent amounts of ethanol or a slight excess are used, a gelatinous mass is formed which, however, dissolves or melts with increasing temperature. After "11 ·· Copolymer 1" has dissolved, it is heated to 150 to 250 ° C, preferably 170 to 300 ° C. In the process, Xthanolamine is distilled over "ehts * lgw" and the WaMMr upper which is split off during the formation of the XmId. The taeserabspaltung can by Druckrermlnderung or dureh Zueata entrainers _y sB cumene or beeolileualgt will. "

BATH ORIGINAL

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A! Κ styrene-maleic anhydride cotelomers are low molecular weight cote ion elements with average molecular weights (number average) from 500 to 2600, preferably from 650 to 1600, used. The molar ratio of styrene to maleic anhydride in the Coteloaerlsaten is 0.8: 1 to 20: _1, preferably 1: 1 to .3 t 1.

The initial cotelcrnr.lsate can also be entered indirectly after the Manufacture, as e.g. in the Belgian patent specification 664,698 is described, reacted with ethanolamine. After the telomerization has ended, the ethanolamine is added the R «action temperature is pumped in. After dismantling dee Telögens and heating to 170 to 180 ° C that remains Ethanolimide derives from the telomerism.

Under Telogeaen "earth" here who all aromatic hydrocarbons, away. Xylene or cumene understood.

The xthanolimldderlv «te obtained in accordance with the invention are la Acetone, chloroform, methylene blear id and methanol perfectly soluble, which indicates that networking has taken place mat.

The mean molecular weights of the styrene-maleic acid amide «Cotelam * ren are about the molecular weight of the built-in ethanolamine higher than that of the original Cotefeaerisate. The middle ones Molecular weights of the prostacts dissolved in acetone were determined by isothermal de-distillation. The anhydride absorptions are missing in the IB spectrum at 5.4 mm4 5.63 / rev; the absorption occurs instead bande des MaIeInImAe * is 6.9 / U on. The analytically determined Sticket off salary eatsprays ta general the “rightful”. Values. .

- 4 - Pv 5622

The obtained Athanollaid derivatives are suitable for the condensation of old polycarboxylic acids to paint raw materials and for Conversion of old polyisocyanates to polyurethane! Ackon and Show fabrics. They also act as accelerators in the Hardening of epoxy resins.

Example 1 :

In an a I 1 round bottom flask with a stirrer, air cooler, dropping funnel and Theraoeeter has been given 100 g of styrene-ualeic anhydride-cofceloaerlsate (Molar ratio 1: 1, molecular weight 650, lialein anhydride equivalent 231) and 27 g of uhanolaain submitted. When heated, a gelatinous form is formed Mass that is dissolved at 150 ° C. Then at an internal temperature of 170 to 180 ° C and a pressure of 10 torr, the excess Xtaanolaain is distilled off.

Yield: 110 g

Nitrogen: calc. 6.1; g «f. 5.7 percent

Old molecular weight: 85O

Example 2:

Apparatus based on the method used in Example 1, but it is 100 g StTrol eelic acid anhydride coteloaerisate (molar ratio 1: 1, molecular weight 1540, maleic anhydride equivalent 234) and 100 g xthanol aln used.

Yield: 118 g

Nitrogen: calc. 5.9; found 5, θ percent

old teller weight: 2100

Example 3: Apparatus and procedures as in Example 1. However, they are

100 g styrene-maleic anhydride coteloaerisate (molar ratio 2: 1, molecular weight 1540, maleic anhydride equivalents 288) and 23 g of Xthanolaala were used.

Auebeuie: 112 g

Nitrogen: calc. 4.85; found 4.6 percent

alttiere Molar weight: 1800

109838/1328

-S- Fw 5622

Example 4:

300 ml of p-xylene are placed in a 2 liter steel autoclave equipped with a stirrer, thermometer, manometer and connections for the monomer and catalyst feed lines at room temperature. At an internal temperature of 250 C, the monomer solution, heated to 45 ° C, consisting of 100 g of styrene, 95 g of maleic anhydride and 200 ml of p-xylene, and a Xitaang of 6 g of di-tert-butyiperoxide in 100 ml of p-xylene is pumped in began. The pumping in of the monomer solution takes 4.5 minutes and that of the activator solution takes 5 minutes. Ks is nachgeheist further 5 minutes, then cooled to 170 ⁰ C, and then 140 g Xthanolamin within 10 Minuten'zugepumpt. The mixture is heated for 2 hours at 170 to ISO ⁰ C. and then distilling the p-xylene and excess Xthanolamin at 180 ⁰ C from.

Yield: 810 g

Sticketofl-: calc. 0.1; found 5.6 percent

medium · «molecular weight t 760

101838/1328 - ^

Claims (1)

"J Process aar the preparation of Kthanollmid-Derlvaten of styrene-IUlela * aUreaaJay <lrld ~ Coteloaerieaten duroh Uaeetcuag by StyjK> l- drld-Cotelomriaaten old Xthanolaala, characterized: that Umeetstfag daft duroh Brwftmea a «« Oeaiseaee of styrene-lanlelnelureanbydrld-CoteloeerlKaten old Middle Molgewlohten swlechen 650 and 1600 and the ftqulaolaren to 1Ofach molar amount _r besogen the Anaydrld-Oruppen dee StyrolnMalelnsMureaahydrld-CoteloBwrlaatea, and Xthanolanin is conducted at temperatures vo "150 to 250 ⁰ C. BATH ORIGINAL