DE1037618B - Process for improving the properties of synthetic, polymeric drying oils - Google Patents

Description

Synthetic drying oils are made from butadiene alone or from mixtures that are made by various processes Containing butadiene and other starting materials which can be polymerized together with it, can be produced. To this end one has both the sodium polymerization, as well as the bulk polymerization in the presence of a diluent and a peroxide type catalyst served with varying degrees of success. In doing so, show However, various synthetic drying oils still have defects, e.g. too slow drying speed, poor adherence of the air dried coatings, poor wettability and consequently Difficult kneadability with pigments, too weak gloss and streakiness of the coated Coating layers. It was found that in general the sodium catalyzed polymers are cheapest are to be produced and have a high drying speed, however, these drying oils have one Particularly low wettability for pigments and coatings made from these oils resulted after application dull and very streaky films.

It has now been found that this overcomes the above deficiencies in synthetic drying oils can that one of the oils in the presence or absence of a solvent and a catalyst is sufficient brings it into contact with oxygen or air for a long time and at a sufficiently high temperature to give the oil a to incorporate a small amount of oxygen.

In practicing an embodiment of this invention, one oxidizes a liquid interpolymer a conjugated diolefin having a molecular weight of 5,000 to 10,000 and a viscosity from 0.3 to 22 poise at 50% non-volatile material content by using air or oxygen blows through a pipe or vertical container containing the interpolymer. The air or the Oxygen is in such a way sealed to the bottom of the container by a porous cartridge or distributor plate (Spreading plate) introduced that a maximum amount of oxygen is supplied to the copolymer. The temperature hold at 20 to 150 ° C and continue blowing for 1 hour to 4 days.

As copolymers of butadiene, such. B. with 0 to 40% styrene, styrenes with on the ring substituted alkyl groups, e.g. B. p-methylstyrene, dimethyl or diethyl styrene, acrylonitrile or methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl isobutyl ether, Methyl vinyl ketone and isopropenyl methyl ketone. These synthetic oils can advantageously be mass-polymerized produce, either in the presence of a hydrocarbon-soluble peroxide catalyst, z. B. benzoyl peroxide or cumene hydroperoxide, or of metallic sodium, if the monomers a diolefin or a mixture of a diolefin with methods of improvement

the properties of synthetic,

polymeric drying oils

Applicant:

Esso Research and Engineering Company, Elizabeth, N.J. (V. St. A.)

Representative: Dr. W. Beil, lawyer,
Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority:

V. St. v. America March 30, 1955

a styrene compound exist. Likewise, the emulsion polymerization technique can, under appropriate conditions, be useful for the preparation of the drying oils according to the present invention.
The polymers to be subjected to oxygen blowing have molecular weights up to 10,000 and viscosities up to 22 poise with a non-volatile content of 50% and are light yellow to colorless liquids.

The oxidation treatment according to the invention is best carried out in the presence of a solvent. Suitable solvents are e.g. B. Hydrocarbons with boiling points up to 200 ° C. A special one a suitable solvent is Varsol, an unprocessed mineral spirit with a specific gravity of 0.7839, a flash point of 40 ° C, a boiling range of 150 to 200 ° C and a Kauri-butanol value of 33 to 37.

To those for the oxidation reaction according to the invention

suitable catalysts include organic salts of metals, e.g. B. naphthenates, octoates and other hydrocarbon-soluble salts of cobalt, lead, iron and manganese. These catalysts is taken up in quantities of 0.001 to 0.1 ° / _0th Peroxides such as benzoyl peroxide and the like can also be added to shorten the induction time.

The reaction temperature and reaction time, the ratio of the reactants to each other, the degree of dilution, the presence or absence of solvents, etc. depend on such factors as that Degree of oxidation and texture desired

809 599/557

of the polymer used as the starting material. The invention is therefore not intended to apply to those mentioned above Conditions and examples may be limited as they are illustrative only.

The properties of the oxidized diolefin copolymer can vary greatly, depending on the extent of the oxidation carried out. The scope of the Oxidation in turn depends on various factors such as oxidation time, temperature, presence or absence of catalysts, type of solvent, etc. In general, a more thorough oxidation results Oxidized copolymers which are less soluble in paraffinic hydrocarbons. One can do the oxidation either drive only so far that the product is still soluble in paraffin hydrocarbons, what on it suggests that the oxidation has assumed only a minor extent; but one can also oxidize so far, that the product is insoluble in paraffinic solvents, but still in aromatic solvents is soluble. This means that the oxidation has reached a greater extent. The content of oxygen in the product varies between traces of up to 8% or more depending on the conditions used, e.g. B. between 0.05 and 8%.

The product obtained is ideally suited as a paint base. Depending on the type of pigment used and the final use can vary the pigment content in the various paints within move a very wide area, e.g. B. between 5 and 75%, based on the weight of the non-volatile, polymeric components of the base material from the drying oils. So the added amount is at Carbon black usually 6 to 10%, for titanium oxide 40 to 60% and for lead pigments even more. To manufacture the Base paste, concentrations of up to 300 parts pigment per 100 parts drying oil are by no means unusual. These mixtures can then be used with hydrocarbons boiling at about 80 to 200 ° C. as solvents be relocated; they can be solvents of the same type as those used for the oil synthesis described above serve as reaction diluents, or other solvents, e.g. B. xylene, white spirit, Benzines and white oils as well as aromatic mixtures of the benzene and xylene range.

In addition, the oxygen-treated, oily products that already have protective coatings in themselves fairly balanced properties can still be modified by using them with other drying oils such as linseed oil, wood oil, soybean oil or other unsaturated vegetable oils.

The invention will be further improved by the following examples, which are provided for illustrative purposes only become understandable.

example 1

A sample of a copolymer oil made from butadiene and styrene by sodium polymerization (70% butadiene, 30% styrene with 59% non-volatile components; viscosity] 1.2 poise with 50% non-volatile components) was placed in a measuring vessel, this in a 50 to 60 ° C warm water bath was standing. The oil contained 0.3% Pb, 0.03% Mn and 0.03% Co in the form of the naphthenates as catalysts. The oil was made from a glass frit for 4 hours with air and then for 4 hours with oxygen blown. The data below show that the drying rates and wetting properties butadiene-styrene copolymer oils for pigments are improved by blowing with air or oxygen will.

Catalysts
containing
Starting oil

Blown oil

0.63
0.37

ίο ¹ J Meaning of the digits: 9, 8 = when touched damp,
7 = sticks to the finger, 6 = firmly when touched,
5, 4 = degrees of stickiness, 3 = dust-free, 2, 1 = slightly sticky,
0 = tack free.

² ) Gardner test: cm ^{3 of} oil required to moisten 1 gTiO _a.

Example 2

A sample of a mixed polymer oil made from 80% butadiene and produced by sodium polymerization 20% styrene was as in Example 1 at 50 to 60 ° C

blown with oxygen. The oil had a viscosity of 2.0 poise at a 50% non-volatile content Ingredients and contained 0.3% Pb, 0.03% manganese, 0.03% Co (all as naphthenates). It was made with a Treated with a 40% non-volatile content.

The loss of solvent during the blowing was replaced by white spirit. The following data were found:

Bubble time Gardner Gardner
colour Wetting
ability ¹ ) viscosity No. Poise / 50%
not Starting oil more fleeting 0.63 IStd. Components 7th 0.55 1 2 hours. 0.85 6th 0.48 2 3 hours. 1.25 6th 0.48 3 4 hours 1.00 6th 0.46 4th 5 hours 1.25 5 0.47 5 1.25 6th 1.25

Gardner test method: cm ^{3 of} oil necessary for wetting 1 g

Nos. 1 and 6 of this table were diluted with white spirit to a content of 36% non-volatile constituents and used to produce paints according to the recipe 50 g TiO ₂ -RA, 208 g oil (36% non-volatile constituents). The following observations were made:

I. 80 g of oil no. 1 were _{triturated with 50 g of TiO 2} -RA to form a paste. The mixture was passed through a roller mill four times. The trituration was feathery and did not form a rolling lump. When the resulting base paste was diluted with the rest of the oil, the finished paint became lumpy, viscous, and difficult to filter. After filtering, it had a viscosity of 155 seconds (Ford open cup). A sample layer painted on a metal sheet did not have an even layer and covered poorly.

II. 42 g of No. 6 oil were _{mixed with 50 g of TiO 2} -RA and rubbed through the roller mill four times. A lump-free grinding resulted. The paint obtained had a smooth appearance after dilution with the rest of the oil. After filtering, its viscosity was 45 seconds (Ford open cup). A spread-on layer adhered evenly to the substrate and resulted in a smooth, hard coating.

The above data show that the interpolymer oil when treated with air or oxygen in accordance with the invention improved pigment wetting properties

owns and manufactures high quality Varnishes is suitable.

Example 3

A sample of a copolymer oil made from 80% butadiene and 20% styrene was used together with dryers

placed in a tube and diluted with Varsol to a non-volatile content of 50%, whereupon oxygen was blown through the solution from a corundum filter cartridge. Then the products of oxidation examined. Details about the experiments and the analysis data can be seen from Table I.

Table I.

Oxidation ¹ ) of a copolymer oil made from 80% butadiene and 20% styrene
(50% non-volatile components in Varsol)

attempt Catalysts ² ) ° C Time,
hours Vo
Acids V.
Ester Analysis d
Vo
Hydroxyl he produki
%
Carbonyl -e »)
Vo
Peroxide 0 /
/ 0
oxygen
all in all A. 0.2 Mn; 0.2 Co 25th 20th 0.76 0.43 0.012 B. 0.04Mn; 0.04Co 100 6.25 0.43 5.84 4.6 0.08 2.2 C. 0.04Mn; 0.04Co 100 4th 0.54 2.0 5.4 0.07 5.8 D. 0.04Mn; 0.04Co 100 3.2 0.11 8.3 2.16 2.6 0.05

¹ J By blowing with oxygen.

² ) Added as metal naphthenates; ° / o metal based on oil solids.

³ ) Percentage based on oil solids.

This example shows that when treated by the method of this invention, reactive groups {OH, etc.) can be introduced into the oil molecule.

Example 4

A sample of a copolymer oil of 80% butadiene and 20% styrene was with Varsol except for one

Content of 50% non-volatile components diluted and at 130 ° C in the presence of 0.75% cumene hydroperoxide and 1 to 2% sodium carbonate blown with oxygen. Films were made of the product thus obtained Poured onto tin-plated metal sheets and heated to 165 ° C for 30 minutes. The values found are as follows:

Gardner viscosity, poises / 50 ° / "non-volatile Components

Strength of
Films, mm

Sward hardness

Blind test (oil not blown)

1 hour

2 hours

4 hours

1.3 3.2

27

18th

2.0

1.8
1.5
2.0

6th
14th
14th
21

This example shows that one follows from the invention. A comparison of the inventive,

treated oils receives films that are much harder than the 50 blown copolymers with a blown, made from untreated oils. high polymer butadiene:

Experimental
No. oil Viscosity ¹ ) solvent concentration
of the polymer
in the solution gas temperature 1
2 Polybutadienes 1.0
1.0 Solvesso ² )
Solvesso ² ) 35%
35% O ₂
O ₂ 104 ° C
104 ° C Mixed polymer made from butadiene-styrene
(80/20)

Experimental
No. Blowing time Oxygen content
of the blown oil Acidity Color according to
Gardner Apply a coat of paint
48 hours ³ ) 1
2 3V ₂ hours
3 _^3/4 hrs 11.3
11.0 15.1
10.4 8 to 9
6th sticky
non-sticky

') In Varsol (single distilled solvent gasoline) with a non-volatile content of 50%.

² ) Mixture of predominantly aromatic hydrocarbons z. B. from methylbenzene, ethylbenzene and trimethylbenzene.

³ ) Measure of the drying speed in the air.

Claims (6)

Patent claims: 1. A process for improving the properties of synthetic, polymeric drying oils based on polybutadiene by blowing with oxygen, characterized in that copolymers of butadiene with ethylenically unsaturated monomers, in particular aromatic vinyl compounds such as styrene, after dissolving in a hydrocarbon, at 20 up to 150 ° C for so long with oxygen or air that they have absorbed ^{at least a small amount of oxygen, such as 0.05 0} J _0. 2. The method according to claim 1, characterized in that there is a solvent between Dissolving gasoline boiling at 150 and 200 ° C is used. 3. The method according to claim 1 and 2, characterized in that the drying oils with the Oxygen can be contacted for 1 to 4 days, preferably 1 to 4 hours. 4. The method according to claim 1, characterized in that the oxygen is smaller after addition Allowed amounts of organic salts of cobalt, manganese, lead and / or iron to act. 5. The method according to claim 5, characterized in that one is in the presence of a cobalt salt is working. 6. The method according to claim 1 to 6, characterized in that a liquid polymeric oil is used which is made from 60 to 99% of a conjugated C ₄ - to Cg diolefin hydrocarbon and 1 to 40 ° / _{0 of} an aromatic vinyl hydrocarbon, and is brought into contact with oxygen for so long that it takes up 0.05 to 8% of it. Considered publications:
German Patent No. 889 199;
Panzenhagen, The painter's practice, 1953, p. 47;
French patent specification No. 885 886. ® 809 599/557 8.