DE1299119B - Process for the production of finely divided maleic anhydride copolymers - Google Patents

Description

It is known that copolymers of benzoyl peroxide or lauryl peroxide, perester, ketone-maleic anhydride can be used and vinyl ethers according to the peroxide or hydroperoxide, azo compounds, such as the principle of precipitation polymerization. Azodiisobutyric acid nitrile. One uses the Initia-Bei This process, the monomers are generally used in amounts of about 0.01 to organic liquids, in which the resulting 5 1 percent by weight, based on the monomers. Polymers are insoluble, e.g. B. in aliphatic or The polymerization is generally pressureless

aromatic hydrocarbons, polymerized. at temperatures between 40 and 120 ⁰ C, preferably

The polymers fall when the monomers are between 60 and 100 ^° C. It has a low concentration (below 20 ° / ₀ ) polymerizes to be advantageous at temperatures, as far as they polymerize vinyl ίο in addition to maleic anhydride, which at or below the boiling ether of alcohols with 1 to 3 carbon atoms poly-point each solvent used-Monomerized contain, in the form of fine particles. In the case of a mixture of mers.

the production of copolymers, the higher one particularly expediently works at the boiling point

Contain vinyl ether, and when polymerizing higher point, because this is the heat of polymerization or completely concentrated monomer solutions are difficult - 15 can be partially discharged via a cooler, due to the fact that the polymer is in the precipitant. The course of the polymerization can be advantageous Forms lumps that stick to the stirrer and that control if one part of the monomer or Adhere to the wall of the polymerization vessel. Here a monomer is placed in the reaction vessel and this disrupts the reaction process. In addition, the remaining portion or the comonomer portion is in the work-up of such polymers is difficult. 20 a part of the solvent dissolved to the extent

It has now been found that finely divided Malein can be run as the polymerization proceeds, acid anhydride copolymers by polymerizing Suitable high-molecular substances, in their counter-

the polymerization of the monomers was carried out using mixtures of maleic anhydride and a, j8-un-wart saturated ethers of alcohols, which is 1 to 8 carbon atoms, are z. B. polystyrene and copolymers of contained, in organic liquids, in which the 35 styrenes with methacrylic acid, acrylic acid and maleic monomers soluble and the copolymers are insoluble acid esters, polymers of acrylic acid esters ^ vinyls, those with maleic anhydride among the esters, vinyl ethers; Polyisobutylene, also soluble Polymerization conditions do not react with radi- cellulose derivatives, such as cellulose ethers or esters, eg. B. kaiischen polymerization initiators in especially pre-ethyl-, benzyl-, acetyl- or nitrocellulose, can produce part way, with the portrayed- 30 If you work in aromatic solvents, so th disadvantages do not occur if you use the poly- are all of the compounds mentioned, merization of the monomers in the presence of high- If you work in other solvents, so come Molecular substances that do not contain any unsaturated double only those of the high molecular weight compounds mentioned and which fertilize in the reaction in question, which are soluble in the reaction medium loosen medium, undertakes. 35 are e.g. B. when working with aliphatic carbon

As comonomers for the production of maleic hydrogens, polyvinyl acid esters with 4 and more acid anhydride copolymers are possible: vinyl carbon atoms in the alcohol radical or polyvinyl ether and ether of alcohols that contain 1 to 8 carbon atoms, polyisobutylene.

such as methyl, ethyl, n-propyl, isopropyl, η-butyl, the K values (according to Fikentscher) of the high

Isobutyl, tert-butyl, cyclohexyl, diisopropylcarbi- 40 molecular substances are expediently between 30 and nol or ethylhexyl vinyl ether; the unsaturated 100, preferably between 40 and 80. Ethers can also be heteroatoms, e.g. B. Oxygen. The monomers are advantageously polymerized in

contain, such as butanediol-1,4-monovinyl ether. Also the presence of 0.1 to 8 percent by weight, preferably Mixtures of the comonomers mentioned with wise in the presence of 0.5 to 5 percent by weight, Maleic anhydride are polymerized. 45 based on the monomers of high molecular weight

The advantage of the method is particularly in the connections. Larger amounts of the production of copolymers from maleic acid high molecular weight compounds such. B. 20 ° / ₀ and more, anhydride and vinyl ethers of alcohols with 3 to are used.

8 carbon atoms given. According to the method according to the invention

The polymers obtained in the form of a finely divided suspension are suitable as solvents for the monomers or precipitants for the polymers obtained in the precipitant. The particle size of, in particular, aliphatic hydrocarbons, such as polymers is highly dependent on type and amount of pentane, hexane, heptane or petroleum fractions of high molecular compound, the concentration of a boiling range of about 50 to 140 ⁰ C, cycloaliphatic monomers in the mixture and the driving . Phatic hydrocarbons, such as cyclohexane or suspension, are of low viscosity, so that the reaction mixture, methylcyclohexane, aromatic hydrocarbons, is easily stirred and the heat of polymerization such as benzene, toluene, ethylbenzene, xylene or cumene. can be easily discharged. According to the method, ethers such as diethyl ether are also suitable. It is impossible to use highly concentrated monomer solutions which are solvents which polymerize with the maleic acid so that a good space-time anhydride reacts, e.g. B. Alcohols. 60 loot is given. The work-up of the monomer solutions obtained can be carried out up to about polymer dispersions according to the known percent by weight of monomers, based on the drive. For example, the poly solution may contain; In general, one works with merisate suspension directly in an evaporator with 20 to 50% strength solutions. to be dried. The polymer can also be used. The polymerization initiators which can be used for this purpose are first of all to separate the bulk of the solvent from the usual under the polymerization conditions by filtration or centrifugation and to remove the compounds which decompose on free radicals. Then dry them. The polymers can, since they are compounds, for. B. organic peroxides, such as finely divided, slightly heterogeneous

3 4

Reaction to derivatives such as esters or hemiamides

ammonium salts. ^p

From the suspensions, the copolymers and one dissolve 0.8 parts of polyvinyl acetate (K value = 60)

Their derivatives can be prepared by adding water, and 9.8 parts of maleic anhydride in 60 parts of benzene soap and then distilling off the solution 5 and heated to 78 to 80 ° C. For this purpose, a

can also be obtained by means of directly aqueous solutions. Mixture of 14.2 parts of di-i-propylcarbinol vinyl

The mixed polyethers produced by this process, 0.2 parts of polyvinyl acetate (K value = 60),

merisates are suitable e.g. B. as adhesives, protective colloids, 10 parts of benzene and 0.1 part of azodiisobutyric acid

Dispersants and textile auxiliaries. nitrile to the same extent as the polymerization

The parts and percentages mentioned in the examples progresses. A finely divided suspension is obtained,

are parts by weight or percentages by weight. which, as indicated in Examples 1 to 4, are listed

_,. . , “Is working. example 1

Example 6

In a stirred kettle, 29.4 parts of maleic anhydride and 1.8 parts of polystyrene (K value = 55) are added in 15 to a solution of 9.8 parts of maleic an-40 Parts of benzene dissolved and the solution to 75 ° C erhydride and 0.4 parts of polyvinyl isobutyl ether (K value heats. A = 60) in 70 parts of toluene is then added within 1 to 2 hours at 90.degree Mixture of 30 parts of vinyl isobutyl ether, 0.2 parts of a solution of 0.4 parts of polyvinyl iso-benzoyl peroxide for 1 hour and 5 parts of benzene flow in. Anbutyl ether (K value = 60), 0.2 parts of benzoyl peroxide Finally, polymerization is carried out at 80 ° C. for 1 hour, ao and 12.6 parts of cyclohexyl vinyl ether in 10 parts A finely divided polymer suspension is obtained. The toluene. After the polymerisation is complete, the polymerizate is dried in a paddle dryer. falling finely divided suspension of the copolymer

If the monomers are polymerized in their absence as worked up in the examples given above, of polystyrene, but otherwise under the same conditions,

the maleic anhydride copolymer is thus obtained in Example 7 in the form of coarse lumps.

. 1 -j mixtures of 20 parts vinyl isobutyl ether,

Example 2 19.6 parts of maleic anhydride, 0.8 parts of a

19.6 parts of maleic copolymer composed of 80 parts of styrene and 20 parts are placed in a stirred kettle Acid anhydride and 0.8 part polyacrylic acid butyl 30 acrylic acid butyl ester (K value = 58), 0.2 part azo

ester (K value = 33) dissolved in 50 parts of toluene and diisobutyronitrile and 53 parts of benzene

heated to 100 ° C. This is added within 1 hour with stirring in vacuo for a duration of

17.2 parts of vinyl n-propyl ether and a solution of 1 hour to the reac-

0.2 parts of lauroyl peroxide in 5 parts of toluene. Man heated tion temperatures. It is at the boiling point

the suspension obtained then keeps polymerized, the boiling temperature by Va-

1 hour at 100 to HO ⁰ C. The polymer is reduced from riation of the pressure in each case. The on-

the suspension filtered off and dried. emerging heat of polymerization is transferred via the back

. -I? Flux cooler discharged. The finely divided poly

Example 3 merisate differ in their K value depending on

To a solution of 20 parts of vinyl n-butyl ether 40 of the set polymerization temperature, and 1 part of a copolymer of 80% styrene and
20% butyl acrylate (K value = 58) in 50 parts
a gasoline fraction with a boiling point of 60 to 140 ° C
19.6 parts of molten maleic acid 45 are melted at a temperature of 80 ° C. with vigorous stirring
anhydride and 0.2 parts of azodiisobutyronitrile in
1 part of dissolved benzene was added within 90 minutes.
A finely divided suspension of the copolymer is obtained. According to the procedure as described in Example 7

If polymerization is carried out in the absence of the copolymer, copolymers are in each case at 80.degree

Sats made from styrene and butyl acrylate, that's how it falls. Vinyl ether was the approach

Maleic anhydride copolymer in the form of coarse each added within different periods of time

Lump on. puts. As the table shows, the K value of the

To obtain 14 finely divided polymers by modifying

55 the feed time of the monomeric vinyl ether within

In 40 parts of benzene, 0.8 parts of polyvinyl will vary relatively wide limits, methyl ether (K value = 47) and 19.6 parts of maleic

temperature K value 50 ° C 92 60 ° C 91 70 ° C 80 80 ° C 70 Example 8

acid anhydride dissolved. At 78 ° C., the vinyl ether is added at this time

Solution within 1 hour 20 parts of vinyl isobutyl ether

K value

70 55 45 31

and a solution of 0.15 parts Azodiisobutter- 6o _Gesamtme added n e _g at the beginning

saurenitnl in 5 parts of benzene. After an hour and 30 minutes

Polymerization is allowed to take place at about room temperature for 1 hour .

cool down and lead to the formation of a hemiamide - 2 hours

the necessary amount of ammonia gas.

After filtering off and drying, a colored 65 B e i s ρ i e 19 is obtained

loose powdery hemiamide ammonium salt of

Copolymer, which dissolved in water a clear 100 parts of a mixture of maleic anhydride

Solution results. and vinyl isobutyl ether in equimolar proportions,

2 parts of a mixed polymer of 70 parts of styrene and 30 parts of butyl acrylate (K value = 55) and 0.1 part of azodiisobutyronitrile are dissolved in so much benzene in a stirred vessel with a reflux condenser that the monomer content in the solution (vinyl isobutyl ether + maleic anhydride) is 20, 30, 40 and 50 ° / ₀ . The four approaches are polymerized at 80 ⁰ C. Very finely divided suspensions of the copolymer in benzene are obtained. The table shows the dependence of the K value of the polymers on the monomer concentration.

Monomeric

concentration

in O

20th
30th
40
50

K value of the vinyl isobutyl ether-maleic anhydride copolymer

15th

57
72
80
82

Example 10

sation is finished. A finely divided suspension of the vinyl ether-maleic anhydride copolymer is obtained.

Example 12

A mixture of 9.8 parts of maleic anhydride, parts of isobutyl vinyl ether, 0.4 part of a copolymer of 70 parts of styrene and 30 parts of butyl acrylate (K value = 55), 0.02 parts of azodiisobutyronitrile and 40 parts of diisopropyl ether is about 1 hour at 60 to 63 ⁰ C polymerized. A finely divided suspension is obtained which can be dried to give a loose, colorless powder.

If the monomers are polymerized in the absence of the copolymer of styrene and butyl acrylate, the copolymer is obtained in the form of coarse lumps that block the stirrer.

In a stirred vessel 9.8 parts of maleic anhydride, 10 parts of vinyl isobutyl ether, 0.6 part of benzyl, 0.1 part of azodiisobutyronitrile and 37 parts of benzene is heated with stirring at 8O ⁰ C. The polymerization has ended after 1 hour. A very finely divided suspension of the copolymer is obtained.

Example 11

In a stirred tank, 9.8 parts of maleic anhydride, 10 parts of vinyl isobutyl ether, 0.2 parts of ethyl cellulose, 0.02 parts of azodiisobutyronitrile and 24.5 parts of benzene are ^{heated to 8O 0} C until the polymer

Claims (1)

Claim: Process for the production of finely divided maleic anhydride copolymers by polymerizing of mixtures of maleic anhydride and vinyl ethers of alcohols from 1 to Contains 8 carbon atoms in organic liquids, in which the monomers are soluble and the copolymers are insoluble and those with maleic anhydride under the polymerization conditions do not react, with radical polymerization initiators, thereby marked e t that the polymerization of the monomers in the presence of high molecular weight substances, the do not contain any unsaturated double bonds and which dissolve in the reaction medium.