DE1246249B - Process for the preparation of polymers containing free hydroxyalkyl groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C08f

German class: 39 c - 25/01

1246 249
S95224rVd / 39c
January 28, 1965
August 3, 1967

There are already processes for the production of. free Hydroxyalkyl group-containing polymers by reacting those containing free carboxyl groups Polymers with alkylene oxides known.

For example, according to the British patent 771 569 a polymer containing free carboxyl groups at an elevated temperature in one anhydrous and inert medium and in the presence of an alkaline catalyst among such Conditions brought to reaction with an alkylene oxide that no polymerization of the latter eüv occurs. The alkaline catalysts are very alkaline reactive substances, namely alkali metals, alkali metal oxides, hydroxides, hydrides and -alkoxides, and weakly alkaline compounds such. B. tertiary amines mentioned. The very awake Catalysts with an alkaline reaction are preferred because they do not initiate the polymerization of alky-] enoxides catalyze. According to the information in British patent specification 771 569, however, catalyze the alkali metals and their strongly alkaline compounds such a polymerization, so that in their Use of unwanted graft polymers from the acidic polymers and the alkylene oxide are formed. The same disadvantage occurs with the methods of U.S. Patent 2,607,761, US Pat German Auslegeschrift F 12976 IVb / 39c and German Patent 926 725, in which carboxyl group-containing polymers with alkylene oxides in aqueous alkaline solutions, the ammonium, Contain sodium or potassium hydroxide.

A process has now been established for the preparation of polymers containing free hydroxyalkyl groups by reacting polymers containing free carboxyl groups with alkylene oxides in Found the presence of alkaline-acting alkali metal compounds as catalysts in which the above-mentioned disadvantages of the known processes are avoided when acting as alkaline Alkali metal compound an alkaline lithium compound is used.

It has been shown that alkaline lithium compounds, as strongly alkaline catalysts, do not lead to graft polymer formation, moreover _; make working in an inert solvent superfluous and not, like the weakly alkaline organic compounds preferred according to British patent specification 771569, adversely affect the properties of the end products.

A major advantage of the inventive method for producing free
Containing hydroxyalkyl groups
Polymers

Applicant:

Shell International Research

Maatschappij N.V., The Hague

Representative:

Dr. E. Jung, patent attorney,

Munich 23, Siegesstr. 26th

Named as inventor:

Willem Martin Mazee,
Amsterdam, Netherlands)

Claimed priority:

Netherlands 30 January 1964 (6 400 774)

Process compared to the procedure described for example * in British patent 771 569 also consists in the fact that the reaction time is significantly shorter. In British patent 771 569, a reaction time of 69 hours is mentioned for a reaction temperature of 130 ° C. the method of the invention at a temperature of 110 ⁰ C is already a reaction time of 20 hours at a lower by about 10Qf surface concentration of catalyst is sufficient.
With regard to the amount of catalyst required, the process according to the invention has advantages compared to the procedure of British patent 771 569. In the exemplary embodiment below, an amount of only 0.04 percent by weight of lithium hydroxide, based on the solution of the starting polymer, is used. This corresponds to an amount of 1 part by weight of lithium hydroxide per 106 parts by weight of methacrylic acid. In contrast, British patent 771 569 recommends the use of 1 to 10 parts by weight of catalyst per part by weight of the unsaturated carboxylic acid present in the starting polymer. This corresponds to a catalytic converter that is 100 to 100 times larger

709 619/705

3 4

amount than they are used in the embodiment according to and Sfearylmethäcrylat / by

Invention is used. a copolymer of methacrylic acid, lauryl meth-

Suitable lithium compounds are, for example, ethoxylated acrylate and stearyl methacrylate.

Lithium hydroxide and lithium salts of weak acids, if the reaction product is liquid, the how lithium salts of carbonic acid and organic 5 'reaction can be carried out without solvents,

weak acids, e.g. B. the lithium salt of free fall but a solvent is used,

Polymer containing carboxyl groups. It is not necessary that this is preferred in relation to the

However, lithium hydroxide is wisely used. The initial polymerisation or the alkylene oxide is inert,

Lithium compounds can also be used, as has already been pointed out above. That

Contain water. Further suitable lithium compound polymer with free carboxyl groups has in particular

applications are lithium carbonate and lithium acetate. It specializes in a non-polar solvent

however, other lithium compounds, tendency to form intramolecular hydrogen bonds, can also be used.

like lithium hydride and lithium alkoxides, as catalysts, whereby the viscosity of the solution is quite considerable.

are used. - ■ - - -hch increases. "

The reaction between the free carboxyl 15 The reaction with the alkylene oxide is therefore group-containing polymers and the alkylene oxyden, preferably in the presence of a polar substance, can already take place at room temperature, which bridges the formation of hydrogen but it is preferably carried out at elevated temperatures Temperature, prevented. For this purpose may be an alcohol, at temperatures between 95 and vorinsbesondere zugsweise- a low-boiling alcohol used 13O ⁰ C is performed. Factors that will turn 20 among others. For example, methanol, ethanol, products affect the length of the reaction time, the panoil (1) and propanol (2) are very suitable solution-applied reaction temperatures, the catalyst agents.

amount and concentration of free carboxyl but the reaction is preferably carried out in polymer containing presence groups. The most favorable unit carried out by methanol. Mixtures of conditions can ¹ in a simple 'way by 35 an alcohol and determine a liquid • hydrocarbon-preliminary experiments. For example, the reaction time required for a substance, preferably an aromatic hydrocarbon, at a temperature of substance, such as toluene, are also suitable solutions -95 ° C, a catalyst concentration of 0.04 equivalents. A valent lithium is very well suited for this purpose Equivalent of the free carboxy mixture of 70 percent by weight of toluene and polymer containing 30 groups and one percent by weight of methanol.

concentration of the free carboxyl group-containing, for example, a copolymer can be omitted

Polymer of 0.5 milliequivalents per gram of 2-Hydroxyäthylmethacrylat, Laurylmethacrylat and

Reaction mixture about 20 hours. Make the same stearyl methacrylate by using the

The reaction time of 20 hours is, however, even with a speaking copolymer of methacrylic acid in one

a temperature of 110 ⁰ C, a 35 Catalyst loadings concentration corresponding to 0.5 milliequivalents

concentration of 0.03 equivalents of lithium per equivalent acid groups per gram of solution in a mixture

valent of the poly containing free carboxyl groups from 70 percent by weight of toluene and 30 percent by weight

merisats and a concentrate of the free carboxyl percent of methanol and then at a temperature

groups containing polymer of 0.5 milli- temperature from 110 ⁰ C and with the addition of 0.03 to

equivalents per gram of the reaction mixture 40 0.04 equivalents lithium hydroxide per equivalent

sufficient. of the polymer containing free carboxyl groups

The amount of catalyst to be used depends on 1.5 to 2.0 times the stoichiometric amount

of the reaction temperature, the concentration of the ethylene oxide converts.

Starting polymer and the desired reac- ^> ie produced according to the invention, free hydroxy

tion time. It can easily be determined experimentally. 45 polymers containing alkyl groups are available as

In general, an amount of catalyst corresponding to lubricating oil additives is usable. In general

0.001 equivalents of lithium per equivalent of free can be added to the basic permitting agents, in particular

Polymer containing carboxyl groups is already a mineral lubricating oil, in smaller proportions

sufficient. It is generally not necessary to add from 0.1 to 10 percent by weight,

use more catalyst than 0.10 equivalents 50. .

the lithium compound per equivalent of the free car example

corresponds to the polymer containing boxyl groups. A copolymer of stearyl methacrylate, lauryl

The free carboxyl groups can be from both methacrylate and methacrylic acid, which are the ones in question

unsaturated monocarboxylic acids as well as unsaturated monomer units in a molar ratio of

saturated dicarboxylic acids. The invention contained 55 5: 5: 4 and a molecular weight of

Proper method is preferred for the um- 1 000 000, has been described in the below-

conversion of copolymers from monobasic manner by reaction with ethylene oxide in a

unsaturated aliphatic carboxylic acids applied. Copolymer of stearyl methacrylate, lauryl meth-

The process is particularly suitable for producing acrylate and converted 2-hydroxyethyl methacrylate:

of copolymers with free hydroxyalkyl groups 60 425 parts by weight of the copolymer were in

from copolymers of methacrylic acid. Very much a mixture of 70 percent by weight toluene and

Suitable starting materials for this are copolymers! - 30 percent by weight of dissolved methanol. The finished one

sate of methacrylic acid and methacrylic acid esters, solution contained 42.5 parts by weight of the copolymer

in particular of esters of methacrylic acid and sats per 100 parts by weight of the solution. The acidity

aliphatic alcohols with 6 to 30 carbon- 65 the solution was 0.525 milliequivalents per gram,

atoms. For example, the method according to 0.7 parts by weight are added to this solution

of the invention for the production of copolymers LiOH · H ₂ O added, which corresponds to an amount of 0.4 Ge

from 2-hydroxyethyl methacrylate, lauryl methacrylate parts by weight of anhydrous lithium hydroxide

spoke. Subsequently, the temperature was raised to HO ⁰ C, and 34.6 parts by weight of ethylene oxide, corresponding to a 50 ° / ₀ by weight excess in the solution with stirring, dissolved. The pressure above the solution was then 5 atmospheres absolute. The solution was kept at a temperature of HO ⁰ C for 20 hours with continued stirring. The acid content of the reaction mixture had dropped to zero after just 15 and _{2 hours.} After the mixture had cooled, a vacuum distillation was carried out until a bottom temperature of 100 ^° C. had been reached.

The acid value of the 2-hydroxyethyl methacrylate units thus obtained containing copolymer was 0 and the yield was 448 parts by weight.

The reaction product had a lithium content of 0.026 percent by weight. An analysis could no polyoxyethylene groups are found in the copolymer.

Comparative experiment

For comparison purposes, the reaction was carried out using 0.15 percent by weight of triethylamine repeated as a catalyst, while the other reaction conditions remained unchanged. The copolymer was obtained in the same yield and was otherwise identical to that according to the invention obtained except that it contained 0.037 weight percent nitrogen.

To demonstrate different properties, both reaction products were therefore related to tested for their effect as lubricating oil additives. A paraffinic lubricating oil distillate served as the lubricating oil base. The additives were dissolved in this oil at a concentration of 1.5 percent by weight. 0.75 percent by weight of a commercially available phenolic solution was added to this solution Antioxidant, namely 4,4'-methylene-bis- (2,6-di-tert-butylphenol) and 1.0 weight percent triphenyl phosphate added. The oil solutions were used as a lubricant in an Austin A-55 engine, which was allowed to run for 5 hours at an oil temperature of 120 ° C. and then shut down for 1 hour. After a total of 30 hours, i.e. H. five cycles of running and standing still, the piston became fouled rated, with a rating number of 10 means a completely clean flask.

The oil containing the polymer prepared according to the invention gave a piston rating of 7.0, while the oil with the additive prepared using triethylamine as a catalyst only achieved a rating of 2.1.

Claims (2)

Patent claims: 1. Process for the preparation of polymers containing free hydroxyalkyl groups by Reaction of polymers containing free carboxyl groups with alkylene oxides in the presence of alkaline alkali metal compounds as catalysts, characterized that the alkaline-acting alkali metal compound is an alkaline-acting one LitMum connection is used. 2. The method according to claim 1, characterized in that the alkaline lithium compound the lithium salt of the polymer containing free carboxyl groups is used will. Considered publications:
German Patent No. 926 725;
German Auslegeschrift F 12976 IVb / 39c, (published on 9/27/956);
British Patent No. 771,569;
U.S. Patent No. 2,607,761. 709 619/705 7.67 © Bundesdruckerei Berlin