DE1089551B - Process for the production of copolymers based on unsaturated fatty acids and olefinic compounds - Google Patents

Description

It is known that drying oils with various copolymerizable, olefinically unsaturated substances, especially those with conjugated double bonds containing hydrocarbons, can be implemented. Such hydrocarbons close acyclic conjugated dienes such as 1,3-butadiene, isoprene and piperylene, cycloaliphatic hydrocarbons with conjugated double bonds, such as cyclopentadiene, and compounds in which one olefinic double bond is conjugated with the double bonds in an aromatic ring, such as Styrene, α-methylstyrene, vinyl toluenes, vinyl naphthalenes and nuclear methyl-substituted and nuclear chlorine-substituted derivatives of these aromatic hydrocarbons. In addition to cyclopentadiene, dicyclopentadiene and addition compounds of cyclopentadiene can also be used with «, / ^ - unsaturated dicarboxylic acids and their derivatives, such as maleic anhydride, can be used. In addition to dicyclopentadiene, the diners of others can conjugated dienes can be used, e.g. B. Dipentene, which is a dimer of isoprene. By those reactions that involve copolymerization of the unsaturated glyceride with the unsaturated hydrocarbon od. The like. May include compositions of improved drying properties and compositions obtained the films of higher water resistance compared with the original drying ones oils can form.

It has now been found that a particularly valuable series of drying compositions is obtained in this way can be that certain condensation products of the type described in more detail below reacts with those olefinic compounds which are copolymerizable with drying oils, especially with hydrocarbons of the type specified above.

Condensation products of the required kind can be used according to methods such. B. in the German Auslegeschrift 1073 665 (patent application U 3621 IVc / 22h), namely by heating linoleic acid or mixtures of Fatty acids that contain a substantial proportion of linoleic acid and / or linolenic acid, such as Acids of linseed oil, cottonseed oil; Sunflower oil, safflower oil, soybean oil, tall oil, and peanut oil Temperatures from 220 to 330 ° C in the presence of a catalyst consisting of a non-oxidizing oxygen compound of boron, preferably boric oxide or boric acid, with removal of water (and of carbon dioxide) formed in the reaction until the condensation product is at least 60 percent by weight of unsaponifiable material having an average molecular weight of at least three times which contains acid.

Method of manufacture

of mixed polymers based on

of unsaturated fatty acids

and olefinic compounds

Applicant:
Unilever NV, Rotterdam (Netherlands)

Representative: Dr. E. Wiegand, Munich 15,

and Dipl.-Ing. W. Niemann, Hamburg 1, Ballmdamm 26,

Patent attorneys

Claimed priority:
Great Britain January 24, 1958

Johannes Donatus of Mikusch-Buchbexg,

Hamburg-Harburg,
and Maurice Robert Mills, Sevenoaks, Kent

(Great Britain),
have been named as inventors

Such condensation products contain unsaponifiable substances with a molecular weight of at least three times and less than six times, preferably less than four times Average molecular weight of the acids from which they are formed.

Some of the monocarboxylic acids used as starting material can be saturated or only one Contain double bonds, such as oleic acid, but in order to achieve the required properties, at least must be part of the acids of the formula R-CO-OH, in which the hydrocarbon radical R is two or contains more olefinic bonds in the molecule, including at least two bonds which form the group -C = C-C-C = C-. Examples Of such unsaturated acids are: linoleic acid, linolenic acid and the highly unsaturated acids that found in marine animal oils such as herring oil, whale oil, pilchard oil, sardine oil. Particularly suitable mixtures of fatty acids are those obtained from linseed oil, cottonseed oil, sunflower oil, peanut oil, safflower oil, Soybean oil, tall oil originate.

Alternatively or in addition to the use of the monocarboxylic acids themselves in the formation of the condensation products, their anhydrides can be used. As intermediates in the condensation are

009 608/352

unsubstituted aliphatic ketones could be identified in the course of the production of the condensation

den, and such ketones, e.g. ketones of the formula Product, e.g. by adding the

R-CO-R, in which R gradually adds the abovementioned meaning to the reaction mixture, in

processing, can in the reaction mixture which contains the condensation product in solution in a

are closed, from which the condensation 5 inert hydrophobic solvents under atmospheric

products are manufactured. spherical pressure is formed, whereby water and the

In general, it is advantageous that the solvents used are removed by distillation. Of the

dete fatty acid mixture an iodine number of no less proportion of copolymerizable unsaturated sub-

ais 100 and preferably between 100 and 150 that with the fatty acid condensation product

sits and that the condensation product obtained is copolymerized io, between about 1 and

an iodine number of not less than .120, e.g. B. between 40%, preferably between 10 and 35%, based

120 and 200 and in particular between 120 and based on the weight of the condensation product.

175, has. The invention is explained below with reference to some

According to the examples explained in more detail for the products according to the invention, with all parts having the desired properties, the extent can denote fluctuating parts,
ken in what free. Acids or anhydrides in the ". -I ₁
Preparation of the initial fatty acid condensation egg

Product converted into unsaponifiable material The fatty acid condensation product used was

have been. Preferably, the percentage of according to the method of the above design

unsaponifiable material, which is from the acid or the 20 script 1 073 665 (patent application U3621IVc / 22h)

Anhydride derived, at least 60%, produced by distilled tall oil fatty acid

and it can advantageously be considerably higher, e.g. B. with 2% of their weight in boric acid for 36 hours

70 to 80% or even 80 to 95%. The acid number of 260 ° C under reduced pressure (initially 12 mm

condensation product used is preferably Hg, falling to 4 mm Hg) was cooked, wherein

lower than 10. 25 water and carbon dioxide released continuously

Details regarding the condensation ■ removed and the acids returned as reflux products and their manufacture are mentioned in the above. The tall oil fatty acid had the following characteristics Auslegeschrift 1 073 665 made. pay: ■

The copolymerizable, olefinically unsaturated acid number 189

Substance with the fatty acid condensation product 30 saponification number .. "'' 192

is to be implemented, preferably consists of an acyc death number * '137

ic or cycloaliphatic diene; Cyclopentadiene Unsaponifiables 4%
(used as such or in the form of a dimer)

proved to be particularly useful. With Cyclopen- The condensation product, which after distillation

In stages, the mixed polymerization takes place very quickly, 35 ^{of the} converted acid, washing out of the boron

no catalyst is necessary. Very useful acid with water, drying and clarifying through filtration

bare drying masses are also obtained as a result, had the following indicators:

been that as a copolymerizable unsaturated acid number .. 79

Substance was used in which a saponification number 3δ '

olefinic double bond with double bonds in 40 death number ... "'149

is conjugated to an aromatic ring, e.g. B. in viscosity (25 ° C) 75 poise

Styrene and vinyl toluene. With these aromatic, non-specific gravity (15.5 ° C) '.'. '. - 0.923
saturated, copolymerizable substances

the presence of a polymerization catalyst. This condensation product was heated to 230 ° C partaking and may be necessary. For this purpose 45 heated, and by heating d! Cyclopentadiene are made Free radical-generating polymerization catalysis fumes were allowed to pass through the product for 5 hours Sators, such as benzoyl peroxide and di-tert-butyl peroxide, passed through. During this time one occurred which are soluble in the monomers are very suitable. 12% weight increase, whereby the resulting

According to the method according to the invention, the mass can become very viscous.

A sample of the mass was obtained with 75% of its weight-drying properties without difficulty possess and are able to contain tes of titanium dioxide and a lot of naphthenate hardness To form coatings which (provided that dryer, equivalent to 0.5% lead and 0.03% Kodie Acid and saponification numbers of the bait used, processed into a paint, with so much solution condensation product low enough) a gasoline was added that the paint is spreadable Good resistance to water and alkalis 55 consistency received, the color gave one in 4 hours own. drying film that is very dry when dry

With cyclopentadiene, the reaction can simply be tough, but no brittleness after 24 hours

by being carried out that one possessed the condensation and good resistance to water and

showed product with the diene or with dicyclopentadiene on aqueous alkali.

In a comparative experiment in which styrene leads diene through the heated condensation product, ■ instead of cyclopentadiene, no catalyst is necessary the first a color film that ^{required 6 1} A hours to dry erStufe a combination of the unsaturated substance and after 24 hours only about half that occurs with the condensation product, e.g. B. at tem- 65 hardness of the temperatures described in the previous paragraph within the range of 150 to 250 ⁰ C, possessed film,
while in the second stage, which occurs at higher tempe- R ■ · 1 9
temperatures, for example in the range from 250 to 300 ° C, ßeispiei.z
is carried out, a further reaction occurs, which was the condensation product used with which leads to an increase in viscosity. The reaction 70 those according to Example 1 is identical. It was at 208

up to 230 ° G with 10% of its weight in dicyclopentadiene Refluxed for 4½ hours, after which the distillation stopped. A sample of the reaction mixture at this stage was tested in the manner that a color film was prepared in the manner described in Example 1 -5. It was found that the drying time was shorter and the hardness of the film was greater than when using a similar sample of the initial condensation product was made instead of the reaction mixture. However, it was desired bring about a considerably greater improvement in both properties. This became through it achieved that the remainder of the reaction mixture for a further 4 hours at 280 to. 290 ° C heated.

Example 3

It became a condensation product of distilled tall oil fatty acids with a low resin content produced as in example 1. The product had an ao viscosity of about 40 poise at 25 ° C, an acid number of 7.5, a saponification number of 9 and one Iodine number of 163.5. 130 parts of the condensation product were heated in a closed vessel, that with a stirrer, a reflux condenser. and a dropping funnel for introducing the copolymerizable substance (vinyl toluene) and catalyst was provided.

2 parts of di-tert-butyl peroxide were added to 70 parts of vinyl toluene solved; the solution was allowed to run into the reaction vessel over the course of 2 hours while the stirrer worked. The reaction mixture was kept at 180 ° C for a further hour, after which the temperature was increased to 240 ° C, and heating at this temperature ceased Continued for 2 hours. While the stirrer was still operating, the reaction mixture was allowed to cool.

A sample of the mass thus obtained was diluted with an equal weight of mineral spirits.
- The diluted product had a viscosity of 1.3 poise at 20 ° C, and in the presence of 0.3 part of lead, 0.03 part of cobalt and 0.02 part of calcium in the form of naphthenates, it dried completely dry in 2 hours in 4 hours. The film hardness, measured with the Sward hardness swing, was 40 after 1 day and 80 after 10 days, compared to 18 and 53 for a condensation product that was not copolymerized, and 10 and 18 for linseed oil standing oil. The film showed pronounced water and alkali resistance, which was even better than that of an untreated condensation product.

Example 4

Fractionated cottonseed fatty acids with an iodine number of 130.4, an acid number of 205 and a saponification number 205.5 were in the presence of 2% boric acid under the conditions given in Example 1 with the Difference that the initial pressure was 16 mm Hg, converted into a condensation product, which as in Example 1 was purified and then had the iodine number 147, the acid number 7 and the saponification number 32.

The condensation product was copolymerized with styrene by adding a reaction mixture of the composition:

Condensation product 400 parts *

Styrene 80 parts

Benzoyl peroxide 0.5 parts

refluxed for 1½ hours, after which the non-volatile content had risen to 97%, giving a "styrene conversion of 82% indicated.

The product was a somewhat opalescent viscous oil that was completely soluble in mineral spirits. One Mineral spirits solution of viscosity of 2.5 poise containing 0.5% lead and 0.05% cobalt (based on the not volatile constituents), dried touch dry in 3 hours and was hard overnight.

Example 5

Using the same condensation product as in Example A , a copolymer was made from the following. Reagents made:

Condensation product .......... 200 parts

Styrene · 2OTeUe

Benzoyl peroxide 0.25 parts

The condensation product was refluxed at 180 ° C and the styrene and peroxide catalyst were slowly added over the course of one hour. The mixture was held at 180 ° C. for an additional 1.5 hours and yielded a clear product containing, non-volatile matter of. 97 _ä 5%, corresponding to a Styrolumwandlungvon 72%. When this product was poured onto glass, a perfectly clear film was obtained. The product was processed to a light green color with an equal weight of chrome green together with the required amount of mineral spirits and 0.5% lead and 0.05% cobalt (as KTaphthenate), calculated on the binder content. The film dried touch dry in .4 hours and hardened overnight. The film had good leveling and high gloss. ......

Example 6

A mixture of soybean fatty acids was obtained by breaking down. Soybean oil up to a crack height of 98% by means of the action of steam and water under high pressure (about 31 atmospheres) in one Autoclave manufactured.

The acid mixture with the iodine number 135, the acid number 195 and the saponification number 200 was 2% Boric acid under the conditions given in Example 1 heated, with the difference that the initial pressure was 16 mm Hg. That after cleaning The condensation product resulting from Example 1 had an iodine number of 150, an acid number of 9.6 and a saponification number 36.

A copolymer was made from the following reagents:

Condensation product 340 parts

Vinyl toluene 160 parts

Benzoyl peroxide 1.6 parts

The condensation product was refluxed at 190 ° C, and vinyl toluene and peroxide catalyst were added over 2½ hours. The temperature was then at 190 ° C. for a further 1 hour held. The non-volatile content had increased to 92% indicating a vinyl toluene conversion represented by 75%. The product solidified to a plastic mass on cooling and was in Mineral spirits completely soluble. After dilution with mineral spirits, the naphthenate dryer, equivalent containing 0.5% lead and 0.05% cobalt, the resulting paint dried to touch dry 75 minutes and hard in 5 hours.

Claims (1)

7 8 Example 7 was a catalyst consisting of a non-oxidizing oxygen compound, a mixture of safflower oil fatty acids was obtained by obtaining safflower oil with water and steam in and releasing carbon dioxide and water in a high pressure autoclave at a pressure of 31 atmospheres is, with at least part of the split. This mixture had the iodine number 147, the 5 acid has the formula R-CO-OH, in which R acid number 197 and the saponification number 199, which means a hydrocarbon residue that was condensation in the presence of 2% boric acid chain containing at least 9 carbon atoms the manner described in Example 4 carried out. which has a plurality of double bonds The condensation product had after cleaning as including at least two the group in Example 1, the iodine number 172, the acid number 6.5, the io-C = CCC = C- forming double bonds, saponification number 35 and the viscosity of 150 poise contains, and where at least 60 percent by weight of the condensation product of unsaponifiable A copolymer was prepared from the following material with an average molecular weight reaction mixture: at least three times that of the condensation product 300 parts of 1S monocarboxylic acid consist of vinyltoluene 180 parts 2 · method according to Claim 1, characterized in a-methylstyrene ................. 20 parts that the monocarboxylic acid consists of a benzoyl peroxide ............ .... 2 parts is a mixture of fatty acids that contains a substantial amount of linoleic acid and / or linolenic acid by refluxing for 11Za hours. at during this time the temperature rose from 180 to 3. Process according to Claim 1 or 2, as a result of which 200 ° C. rose. The mixture was then cooled, characterized in that the iodine number of the monocarbon and resulted in a soft thermoplastic mass with acid between 100 and 150, a content of non-volatile material of 95%, 4. The method according to any one of claims 1 to 3, which a Represented monomer conversion of 75%. 25 characterized in that the condensation The product was dissolved in xylene and gave a product with an aromatic Monovinylverbin- clear solution, the 0.5% lead and 0.03% cobalt is copolymerized in manure. Form of naphthenates were added. The resulting 5. The method according to claim 4, characterized in that the paint dried dust-dry in 30 minutes shows that the compound was made of styrene or a and was tack-free in 2 hours. After air drying at 30 vinyltoluene is made. Room temperature for 24 hours, the 6th method according to claim 4 and 5, characterized film a scratch test of 1500 g load under loading characterized in that the condensation product use a 1-mm ball point. A film applied to an aluminum plate with α-methylstyrene was co-polymerized and dried for 30 minutes at 130 ° C in an oven, characterized in that the condensation-flexible coating, the Withstood a scratch test of 2500 g of product with cyclopentadiene or dicyclopentadiene exposure. is copolymerized. 8. The method according to any one of claims 1 to 7, claims: characterized in that the mixed polymer 1. Process for the production of mixed polymerisation in the presence of a polymerisation mers based on unsaturated fatty acids and a catalyst. olefinic compounds, characterized in that that one with drying oils mixed poly- Considered publications: merisable olefinic connection with a German color magazine, 5th year, 1951, Copolymerized condensation product, the 45 p. 37, in particular p. 40/41; by heating an unsaturated, non-conjugated plastic review, styrenated oils and alkyds aliphatic monocarboxylic acid in Gegenharze, 4th year, 1957, pp. 289 to 293, 348 to 351. Q; 009 608/352 9.60