DE1944756A1 - Process for the preparation of maleic, itaconic or aconitic anhydride homopolymers or the homopolymers of the free acids - Google Patents

Description

New York, N.Y., V.St.A.,

"Process for the production of maleic, itaeonic or aconitic anhydride homopolymers or the homopolymers of the free acids "

Priority: September 10, 1968, V.St.A., Wr. '. 758 669, 758 670 and 758 678

The invention relates to a method for the homopolymerization of Maleic, itaconic and aeonitic anhydride.

It is known that shark, itaconic and aconite anhydride can be homopolymerized. The homopolymers and their derivatives, such as the water-soluble salts, are all building blocks in detergents)! _{f used} as additives for other polymer systems, as textile auxiliaries and for the surface treatment of metals.

.fein of U.S. Patent 3,359,246 is a method of manufacture von Hoinopolymerieaten dee maleic anhydride and its derivatives described. As a polymerization initiator Acetyl peroxide used. Under these conditions one obtains a

J9U756

Homopolymer in yields up to £ 90. By So D. Hamann, Aust. J. Chem., 1967, VoIo 20, pages 605 to 609) the polymerization of Haieic acid anhydride under high bridge is described · ' In this publication it is reported that the homopolymer! on of sharkic anhydride is difficult to start, and that special polymerization methods are required in order to obtain satisfactory results pie same difficulties occur in the homopolymerization of itaconic and aconyl anhydride.

The use of acetyl peroxide as a polymerization initiator in the process according to the USA * patent 3 359 246 has significant Disadvantage. Acetyl peroxide is sensitive to impact and can detonate if handled improperly. Another disadvantage is that acetyl peroxide is currently only commercially available as a solution in dimethyl phthalate. The dimethyl phthalate makes this End product of the polymerization contaminated. To separate off the dimethyl phthalate, the polymer must be extracted with an organic solvent. When working on a small scale this does not offer any difficulties, but with a technical process this method is cumbersome

The use of high pressures to polymerize the anhydrides is not desirable in a technical process, since special expensive devices are required for this.

The object of the invention was to provide a simplified method for Homopolymerization of maleic, itaconic or aoonitic anhydride to create in which no dangerous polymerization initiators are used «This object is achieved by the invention

009819/1753 '

1344756

solved

The invention thus provides a process for the production of clay maleic, itaconic or aconitic anhydride homopolymers or the homopolymers of free acids with the aid of acyl peroxides as polymerization initiators / which is characterized in that the monomeric anhydride is heated to at least its melting point in the presence of the initiator heated _s whereby a compound of the general formula I or II is used as the initiator for maleic anhydride

I!

CH-C-OO-H

or ρ

CH-C-O-C-R

M dd

0 0

(I). (II)

for itaconic anhydride as initiator a compound of the general Formula III or IV

C-C-OO-C-H C-C-OO-H

0 -00 0 -R Il -0- η ^R l CH-C- -0 CH-C = C- η It 0 0

0 0 or 0 0

Il Il j _M ,,

CH ₂ -COGR ₁ CH ₂ -COOR

(III) (IV)

and for aconitic anhydride as initiator a compound of the general formula V, VI, or VII

009819/1763

19447 §6

O 0 ·> " 0 ti It st CH- C-OO-C-R -0-CR ₁ O 0 0 Ii It Il C-C -C-OC CH ₂

0
v? 0
It CH- = C-Q- = C-R ⁰ 0 I Il
CC -00- η
CR ₁ CH ₂ 0
It
-CO 0
Il
-CR

or

(V) (VI) (YII)

used in the R _g R ₁ and R ₀ are each aliphatic or cycloaliphatic radicals having 1 to 6 carbon atoms or phenyl-groups mean ,, which are unsubstituted or nitro- _p Cyan '= ·, methoxy or Ithoxygruppen j by halogen atoms, _p and optionally the anhydride homopolymer obtained saponified with water to form the homopolymer of the free acid »

In the process of the invention, the mixed maleic, itaconic, or aeonitic acyl peroxide initiator is extremely produced. Preferably the anhydride is first either in the presence or absence of a solvent, hydrogen peroxide is then melted in the melt registered The hydrogen peroxide reacts immediately and almost quantitatively with the anhydride to form the corresponding peracid ₀ This reaction proceeds using the example of the maleic anhydride follow dermassens

's °

CH-C-OO-H

CHC ^

i! > + H ₂ O> I.

CH-C ^ * ^d CC-OH

«It

0 0

An acylating agent, usually a carboxylic acid anhydride, is then added to the peracid. The acylating agent reacts with the peracid to form a mixed maleic _P

0098 19/175 3

ο =. 5 = »

Itaconic or Aoonitsäureacylperoxids _o the example of the use of acetic anhydride as acylating and Peroxymaleinsäu 're the reaction proceeds folgendermassenj

+ 2CH ₃ C-OH

O + 2 0 JH_ 0 0 -0-C- -CH Il Il It Il 0 CH-C-OO-H ^ C-C -C-OO-C CH ₃ H ο CH-C-OH
H ^v c ~ c
19th = c =
Il 0 0 0 - * CH- I! - CH-

Other carboxylic acid anhydrides, the _s used as acylating agents are graining Z ₀ B ₀ propionic acid, hexanoic acid and Cyclohexancarbonsaureanhydrid. It is also possible to use asymmetrical, i.e. mixed, carboxylic acid anhydrides. Examples of these compounds are formic acid-acetic anhydride, benzoic acid-acetic anhydride, propionic acid-acetic anhydride and cyclohexanoarboxylic acid-acetic anhydrido

The carboxylic acid anhydrides which are suitable as acylating agents can either be unsubstituted or substituted by halogen atoms, nitro, cyano, methoxy or ethoxy groups. Examples of substituted carboxylic acid anhydrides are trifluoroacetic acid, triehloroacetic acid, chloroacetic acid, p-nitrobenzoic acid, methoxybenzoic acid, cyano anhydride, cyano anhydride. Furthermore, the phenyl groups in the acylating agents can be substituted by lower aliphatic groups with ΐ to 6 carbon atoms. An example of this is Aoylierungsmittel isopropylbenzoic-acetic anhydride _e

Ketene can also be used as acylating agent in such amounts that 1 or 2 moles of ketene 3β moles of a maiein or itaconic acid peracid and 1 to 3 moles per mole of an aconite

00931S / 1753

BADORLGiNAL

peracid are used «, When using Z ₀ B ₀ 1 mole of ketene per mole of permaleic acid, the monoethylated product is obtained, which is used as an initiator for the homopolymerization of maleic anhydride. This implementation proceeds as follows:

0 0

it η

CH-CK) O-H CH-C = OO-H

"+ CH ₉ = C = O *"

CH-C-OH ^ά CH-CO = C-CH,

It Il Il - ^

0 0 0

If 2 moles of ketene are used, a diacetylated product is obtained. This reaction takes place according to the following reaction equation ¹ . ^s

0 0 0

QC I »! I

CH-C-OO-H CH-C = OO-C-CH,

* + 2CH ₉ -C = O>

CH-C-OH <■,

M Il Il - *

0x0 0

B * 5i the implementation of the polymerization of maleic, itaeonic or aconitic anhydride, the anhydride is melted in the presence of corresponding mixed maleic, itaconic or aconitic acyl peroxide and the reaction is carried out at temperatures between 65 and 95 ⁰ C for maleic anhydride, at 70 to 100 ⁰ C for Itacon-

ti

Acid anhydride and carried out at 80 to HO ⁰ C for aconitic anhydride. Since the polymerization is exothermic, heat should be dissipated at least during the initial reaction in order to keep the temperature in the specified range. «The polymerization is usually complete within 4 to 6 hours,

The polymerization can be carried out in the presence or absence of a solvent be carried out «The solvent should be carried out with the

009818/1753 *

Peroxidinitiatorρ not the anhydride or the homopolymer react Examples of suitable solvents are benzene, Chlorobenzene ,, o-dichlorobenzene and alkyl acetates such as butyl acetate and isopropyl acetate "

Hormalerweise already sufficient amounts of about 2 weight _o ~ $ j of the initiator based on the weight of the monomer? the reaction going to put ₀ It can, however, large quantities USAGE = det be "Larger quantities are desired ₉ about the polymerisation reaction rasoh to set in motion" The exact amount of Ini tiators depends on the acyl group from _B for the production of the peroxide is used

In practice, the method of the invention can _s be carried out so that one is present, the required amount of the monomer with or without a solvent in a reaction vessel, erhitsc on the reaction temperature and then hydrogen peroxide in such an amount is added _p that it reacts with a portion of the anhydride " The hydrogen peroxide is normally used in an amount of at least about 0.5% by weight _, based on the anhydride used. Of course, larger amounts of hydrogen peroxide can also be used. Usually the amount is not more than 2 weight _e ~ $ _o The hydrogen peroxide reacts with a stoichiometric amount of the anhydride to form the peracid "The resulting peracid acts seihst not as polymerization _o also does not react with the unreacted anhydride. At least the stoichiometric amount of an acylating agent required for reaction with the peracid and normally a small excess is then added to the reaction mixture

00 9819/1753

Acylating agent settles with the peracid to form the mixed maleic _? Itaeon "or aconitic acid acyl peroxide". The mixed peroxide obtained then starts the homopolymerization of the anhydride. In the polymerization of maleic anhydride, the product obtainable by the process of the invention can have a molecular weight of 500 to 50,000. Normally poly (maleic anhydride) a molecular weight of about 3000 to 70C0 »In the polymerization of itaconic or aconite anhydride according to the process of the invention, the product can have a molecular weight of 350 to 1,500,000»

The purification of the homopolymer is carried out in a simple manner by distilling the product under reduced pressure. ^{in order to separate} volatile compounds o As volatile compounds the acids come into question, which correspond to the acylating agents t which were used for the production of the mixed peroxides. The homopolymers produced in the process of the invention are solvents in water as well as organic, such as acetone »tetrahydrofuran _P l _r 2-dimethoxyethane ₉ Alky! Acetate _P * methyl ethyl ketone and dioxane easily soluble. When the anhydride honey polymers are dissolved in water, they are converted into the corresponding homopolymers of the free acids. Metal salts can be prepared from the polycarboxylic acids obtained using customary methods. A simple process for the preparation of these salts consists in ^{dissolving the anhydride homopolymer in water at about 100.degree.} C., the aqueous solution obtained with a base, e.g. _o Sodium hydroxide solution, neutralized to a p ^ value of 10.0 and the resulting solution heated for 3 to 4 hours «

009819/17 53 SAD ORIGINAL

Thereafter, the p _H ~ value is again adjusted to about 1O ₈ O 'is obtained, the alkali metal salt back bleibte as a solid after evaporation of the water

The examples illustrate the invention.

example 1 Experiment A - method of the invention

In a 1 liter three-necked flask _s equipped with a stirrer and a reflux condenser, 650 g of maleic anhydride are presented the flask is erwärmtj until the maleic anhydride melted in a water bath at 65 ° 0 "Thereafter, the stirrer in motion is set, and there are 7.0 g of 90 5% peroxide added dropwise over the course of 5 minutes The reaction mixture is ^{heated to 65 to 75 °} C. for a _{further 10 minutes p} then 100 g of acetic anhydride are added »Shortly thereafter, an exothermic polymerization reaction begins» The flask is cooled with cold water, to keep the temperature of the reaction mixture at 75 to 95 ° C. After about 2 hours of reaction, the reaction subsides and the cooling water is replaced by warm water in order to keep the temperature of the reaction mixture at 75 to 95 ° C. for a further 2 to 3 hours until the polymerization has ended. Then the flask is turned off evacuated, and most of the acetic acid formed as a by-product is distilled off. The distillation is stopped as soon as the reaction mixture is very viscous. The raw, viscous product is then dissolved in about 2 liters of hot water. This saponifies the maleic anhydride polymer to form poly (maleic acid). The water is distilled off from the mixture under reduced pressure. 693 g of crude poly (malelic acid) remain.

00 ** 11 / 1TIL '

• ■ "- 10 .-

The yield is 90% of theory, based on _{0 maleic anhydride used}

Experiment B - lassun method Weff ff of the acyl anhydride The procedure of Experiment A is, however, repeated _s are 100 g of acetic anhydride not added Hach 6 hours of heating to 75 to 95 C is no polymerization "receive about 95% of the maleic anhydride used are unchanged recovered

This example shows that permaleic acid _9, which is formed by the reaction of hydrogen peroxide with part of the maleic anhydride, cannot initiate the polymerization of the maleic anhydride »

Example 2

The procedure of Example I ₉ Experiment A is repeated but 150 g of propionic anhydride are used instead of 100 g of acetic anhydride "The yield of poly (maleic acid) is 87 # of theory,

Example 3

The procedure of Example 1, Run A is repeated, except that 150 g of benzoic anhydride in place of the acetic anhydride used was 100 g Due yield of poly (maleic acid) is 72 $ of theory

Example 4

The procedure of Example 1, Experiment A ₁ is repeated, but 150 g of cyclohexanoarboxylic anhydride are used instead of 100 g of acetic anhydride. The yield of poly (maleic acid).

009118/1753

1944 758

is $ 74 of theory,

Example 5

The procedure of Example I ₉ Experiment A _p is repeated except that 150 g of trichloroacetic anhydride in place of the acetic anhydride used was 100 g The yield of poly ~ (maleic acid) is 92 i> theory "

Example 6

Bas procedure of Example I ₅ Experiment A ₉ is repeated except that 100 g of trifluoroacetic anhydride are used instead of 100 g of acetic anhydride used in this experiment, the temperature of the reaction mixture during the ersteh is ^"15 minutes after addition of the trifluoroacetic anhydride at 60 to 65 ° C held The anhydride, boiling at 42 ° C., boils under reflux. As soon as all of the trifluoroacetic anhydride has reacted, no more condensate is formed in the reflux condenser ₀ The reaction mixture is then heated to 75 to 95 ° C. After 6 hours of reaction, the yield of poly «(Maleic acid) 91 " h of theory _o

Example 7

Experiment A - method of the invention using ketene In a 1 liter faseenden three-necked flask _t equipped with a stirrer and a reflux condenser, 650 g of maleic anhydride are presented The flask is heated in a hot water bath until the temperature of the maleic anhydride is about 65 ⁰ C and the connection is completely melted. Then, the stirrer in motion is set, and there are added dropwise 7.0 g of 90% hydrogen peroxide "The reaction mixture is heated an additional 10 minutes at 65 to 75 C» and subsequently

00 98 19/1753

BATH ORIGINAL.

- '12 -

16 g of gaseous ketene introduced. The ketone is produced by pyrolysis of acetone according to the _{method described in J 0} Org "Chern" 5 _f page 122 (1940). 01 mol / min »initiated during 38 minutes ,, nitrogen is _t methane from the flask rinse au, which is a by-product of the acetone =" pyrolysis arises ₀ the reaction mixture is 5 hours at 75 to 95 C heated then passed through the reaction mixture the product isolated according to Example 1 "680 g of crude poly (maleic acid) are obtained. The yield is 88" 4 # of theory. "

Experiment B - Method of the invention using ketenes The procedure of Experiment A is repeated, but 8.0 g of ketene are used instead of 16 g. _c

Experiment C - method F ortlassung of ketene The procedure of Experiment A is repeated except that no ketene is introduced There is no polymer on ₀ Approximately 95 1 ° of the maleic anhydride used are unchanged recovered capable in situ generated permaleic the polymerization of the anhydride! cannot be started "

Example 8

Several mixed carboxylic acid anhydrides are prepared by reacting the corresponding carboxylic acids with ketene according to the method of R ₀ E. Dünbar and PC ₀ Garven, Journal of American Chemical Society, Vol. 77 (1955), page 4 161, * The mixed carboxylic acid-acetic anhydrides are used instead of acetic acid

009819/1753

bad original

Die used according to the procedure of Example 1, Experiment A Results are shown in Table I;

Table I.

Mixed anhydride
Acylating agents Lot,
G Poly- (malein-
acid). G Yield, Benzoic Acetic Anhydride 150 620 80.5 Formic acid ^ acetic anhydride 100 605 78.7 Triehloroacetic acid-acetic acid-
anhydride 150 696 9O _f 4 m-chlorobenzoic acid acetic acid
anhydride 150 676 87.8 Cyelohexanecarboxylic acid acetic acid 150 610 79.2

anhydride

Example 9 Experiment A - method of the invention

25 g of itaconic anhydride are placed in a 100 ml three-necked flask equipped with a stirrer and a reflux condenser. The flask is heated in a water bath to 70 to 80 C until all of the itaconic anhydride has melted 10 drops of 90 # hydrogen peroxide are added within 5 minutes. The reaction mixture is heated to 75 to 80 ° C. for a further 30 minutes and then 5 ml of acetic anhydride are added. Shortly thereafter, an exothermic polymerization reaction begins. The flask is cooled with cold water to keep the temperature of the Reaktionsgemischeβ at 95 bie HO ⁰ C. After about 25 minutes of reaction the Polymeriaationereaktion subsides, the flask is set in an Heieewasserbad to maintain the temperature of the Reaktionegemieohes at about 100 ^O C. After a further hour, the polymerization is complete, Bas Reaktioasgemisqh

008810/1713

■ · - 14 -

' the'

dissolved in hot water ₉ and under reduced pressure / as

lifting the product formed acetic acid and / distilled water "is obtained 28 g of poly {~ itaeonsäure) as light yellow solids from The" yield is 96 ^ 6 $> of theory '

Experiment B - procedure with continued flow of acetic anhydride The procedure according to experiment A is repeated, but no acetic anhydride is added. After a 6-hour reaction at 95 ° C., no polymerization is obtained. About 95 # of the itaconic anhydride used is recovered unchanged

This experiment shows that the polymerization of itaconic anhydride by itacqnpersäure, produced by reaction of the hydrogen peroxide with a part of the itaconic anhydride _{8 is} not started,

Example 10

The process of Example 9 ₉ Experiment A is repeated, but instead of acetic anhydride, equivalent amounts of the acid anhydrides listed in Table II are used. The yield P of poly (itaoonic acid) is also given in this table

Table H.

Acid anhydride. Yield of poly (itaconic acid). Yes

Propionic anhydride. 94.3

Benzoic anhydride 91.0

Cyclohexanecarboxylic anhydride 92.0

Triohloroacetic anhydride 97.0

Trifluoresic acid aihydride 97.0

11 / m3

ßAD ORIGINAL

= 15 «-

Example 11

Experiment A - ° procedures OF INVENTION dung using ketene A 100-ml Dreihalskolbenjs equipped with a Eührwerk and a reflux condenser * is charged with 70 g Xtaconsäureanhydrid and heated in a water bath at about 75 ⁰ C, is melted until all itaconic " Thereafter, the stirrer is set in motion ^ and there are dripped l "0 g 90 # = hydrogen peroxide the reaction mixture is kept for another 10 minutes at 75 ° C _p and thereto are 2 ₉ 5 g of gaseous ketene introduced the ketene is reacted with through a glass tube an inner diameter of 6 mm at a rate of O ₈ Ol mol / minute for 6 minutes introduced the reaction mixture is stirred for a further 5 minutes, then nitrogen was introduced to displace the by-product in the production of ketene by "pyrolysis of acetone methane the reaction mixture is heated for 3 hours at 75 to 100 ⁰ C. the product of example 1, Versu ch A ₁ isolated yield 78 g of crude poly-citaconic acidjo yield 96 % of theory _c

Attempt B

Experiment A is repeated, but 1.3 g of ketene are used instead of 2.5 g used. The polymerization proceeds smoothly, and poly (itaconic acid) or the like is obtained in 94% yield

Example 12

Ee become several mixed carboxylic acid anhydrides by reaction of the corresponding carboxylic acids produced with ketene. These mixed carboxylic anhydrides are used instead of acetic acid in the method according to Example 9 »Experiment A, used. The results are summarized in Table III:

0 0 9 819/1753

1944758

III

Mixed anhydride acylic agent

Amount, poly- (itacon ~ base acid), g booty,

Benzoic Acetic Anhydride IfS , 0 26th »2 90 Formic acid ^ acetic acid anhydride 4th , 0 22nd 76 Triehloroacetic acid ^ acetic anhydride 8th .0 27 "O 93 m ^ Ohlorbensoic Acid ^ acetic anhydride 8th • o 25th 86 Cyclohexanecarboxylic acid 'acetic acid ajx-
hydride 7th , 0 25th 88 Example 13 Experiment A - method of the invention

In a 3.00 ml three-necked flask “equipped with a stirrer and a reflux condenser _? 25 g Aoonit anhydride referred The flask is heated in a water bath at 80 to 85 ⁰ G is melted until the aconitic anhydride. Then the stirrer is set in motion "and 5 drops of 90 S ^ hydrogen peroxide" instilled within 5 minutes, the Reafctionsgemiseh is he = warms another 20 Hinuten to 80 to 85 ⁰ C * and then with 3 ml of acetic anhydride versetztο Shortly thereafter an exothermic polymerization reaction begins »The flask is cooled with cold water» to keep the temperature of the reaction mixture at 90 to HO ⁰ C «> After about 25 minutes of reaction, the polymerization reaction sounds atao The flask is placed in a hot water bath to maintain the temperature keeping the reaction mixture for an additional 3 to 4 hours at about 100 ⁰ C, until the fully Polymerisationereaktion is "finally presented is achieved, the reaction mixture in hot water, and the acetic acid formed as a byproduct and the water is distilled off under reduced pressure. By adding water . 0 0 9 8 18/1753

the polymer is saponified to give poly (aconitic acid) * 28 g of a light yellow solid are obtained «. The yield is 96 i "of Theorieο

Experiment B ^ Procedure omitting the acetic anhydride Experiment A is repeated without adding acetic anhydride. After 6 hours of reaction at 95 ° = C is obtained no polymerization "About 90 i> of the Aconitsäureanhydrids used are unveränueri; recovered ,, This example shows that peroxyaconitic acid, which is formed by the reaction of hydrogen peroxide with part of the aconitic anhydride, does not initiate the polymerization of the aconitic anhydride.

Example 14

Example 13, experiment A, is repeated in place of acetic anhydride however, equivalent amounts of the acid anhydrides given in Table IV are used. The yield of poly (aconitic acid) is also indicated,

table IV

Acid anhydride yield of poly (aeonic acid) c #

Propionic anhydride 91

Benzoic anhydride 87

Cyclohexanecarboxylic anhydride 88

Triehloroacetic anhydride 94

Trifluoroacetic anhydride 95

009919/1753

Example 15 .

V beseech A - method of the invention using ketene A stud 100-ml Dreihai equipped with a stirrer and a reflux condenser, is charged with 75 g of aconitic anhydride and heated in a water bath at about 80 ⁰ C, is melted until the aconitic " The stirrer is then started and 1.0 g of 90% hydrogen peroxide are added. The reaction mixture is heated to 80 to 85 ° C for a further 10 minutes, and then 3 to 7 g of gaseous ketene are added at one flow rate The reaction mixture is introduced for a further 5 minutes, then flushed with nitrogen and ^{heated to 80 to 10O 0} O for 4 hours g of crude poly (aconitic) obtained »the yield is 92.5 fi theory _o

Attempt B

Experiment A is repeated, but 2.0 g of ketene are used instead of 3.7 g. The polymerization proceeds smoothly and poly (aconitic acid) _{0 is obtained in a yield of 86,56}

Example 16

There are several mixed carboxylic acid anhydrides by reaction the corresponding carboxylic acid mixed with ketene Carboxylic acid anhydrides are used instead of Acetic acid as acylating agent according to example 13 »experiment A, used »The results are compiled in Table V}.

004 $ IfV 176 3

at the

table V Mixed anhydride acylic
funds Lot, Poly ~ (aconite-
acid), g yield Benzoic Acetic Anhydride 4.0 26.0 90 Formic Acetic Anhydride 3 _? 0 2I ₁ O 73 Trichloroacetic acid eesigsäureaiiL'-
hydride 6,, O 27 ρ 0 94

m-chlorobenzoic acid acetic acid an- 6 _f 0 24 _f 0 84 cyclohexanecartionic acid eRSigB acid- 6 _ε Ο 23 _s O 80

anhydride

009819/1753

SAD ORiQ) NAL

1S44756

- 20 -

? attsi; .aa S ₁ H ₁₁₁ r; Ji ₁₁ c ft fe

1 »Yerfanren for the production of HaIeIu ^ ₈ Itaeon oiler Ä © © nit · = 6äureanhyd.riä-Hoiaopolyiflerisaten or the homopolymeriöaten of the free acids with the help of τ © η aeylper @ xiae as Bolymerisationsin = initiators _p da dure Ii g © te. e η ή ζ ei ö η η e t-? that there is an anhydride on at least its own size in the presence of the initiator, whereby a compound of the general or II

© Φ O

ir # #

I 1

M If ^X WJ *

For itacoic acid anhydride as an initiator I would like to find out about my formula II or

mi)

«Ad for Aconitsätireanhyäriä as initiator a connection of general formula Y, YI or YIl

00981Ö / 1753

Claims (1)

0
Il 0
Il CH -C-O- C. 0 r
ti 0
It C = C-OO- σ 0 CH ₂ ~ c ~ o - -R -R ₁ 0
Il CR ₂ (V) (VI) (VII) used in which R _p, R, and R ₂ each mean aliphatic or cycloaliphatic radicals with 1 to 6 carbon atoms or phenyl groups »which are unsubstituted or substituted by halogen atoms, nitro», cyano, methoxy or ethoxy groups ₈ and optionally the one obtained Anhydride homopolymer saponified with water to form the homopolymer of the free acid 2 ο Method according to claim 1, characterized in that maleic anhydride is used at temperatures from 65 to 95 C in the presence of at least about 2 wt .- # des Initiator polymerizes " 3o method according to claim 1 or 2, characterized in that maleic anhydride is ^{melted at a temperature of at least about 65 0} C, the melt is mixed with about 0.5 to 2 wt _o - # hydrogen peroxide, then keto or an acyl anhydride, which the mixed anhydride to be produced corresponds to the general formula I or II, feeds in and the reaction mixture is heated to temperatures of 65 to 75 ^{° C.} 4o method according to claim 1, characterized * because itaconic acid aahydride is used at temperatures 0OÖ81S / 17S3 6AD ORIGJHAL polymerized from 70 to 10O ⁰ C in the presence of at least 2 Gewo = # of the initiator 5ο method according to claim 1 or 4 »characterized in that itaconic anhydride is melted at a temperature of at least about 70 ⁰ C, the melt with about 0 ₉ 5 to 2 wt _o - # hydrogen peroxide is added ₉ then ketflta or an acyl anhydride _s that of the to be produced Compound of the general formula III or IV corresponds, feeds and the reaction mixture is ^{heated to temperatures of 75 to 100 0} C ~ 6o procedure according to; Claim 1, characterized in that aconitic anhydride is polymerized ^{at temperatures from 80 to 10 0} C in the presence of at least 2 genes? .. -1 »of _{the initiator β} 7o method according to claim 1 or 6 _f thereby marked ζ ei without; that aconitic C melts "the melt at about 0.5 to 2 wt _o at a temperature of at least about 80 ⁰ - # added hydrogen peroxide; subsequently ketone or an acyl anhydride corresponding to the produced compound of the general formula V, VI or VII, and feeds dae Reaktionsgemisph to temperatures of 80 to HO heated ⁰ C ₀ 0 901 / 17.8 3