DE1923380C - Process for making an alkyd resin - Google Patents

Description

[esses, like ζ. B. in steam cracking, steam or butadiene, and the more than 5 weight

rfia thermal cracking or sand cracking contains a percentage of indene or an "indene index"

light or heavy gasoline, kerosene, gas oil or more than 11%. The "Inden-Index" becomes

Elo oil for the production of ethylene, propylene, butane defined by the following formula:

“Indene Index” (weight percent) = weight of the indene and alkylindene in the material . _{1 (χ)>}

Weight of the polymerizable component in the material *)

♦) Total weight of unsaturated compounds including styrene, indene, their derivatives, monoelefins ^,! Diolefins and their derivatives.

To adjust the desired indene content of the aromatic one or more polyhydric alcohols in the fraction of a hydrocarbon oil, the presence of an alcoholysis catalyst, such as. B. If necessary, indene and alkylindene of the black lead [= lead (II) oxideJ or sodium peroxide, fraction added, lighter parts of the fraction 15 to by distilling the mixture to 180 to 270 ⁰ C and lighter parts, the of the fraction are distilled off in a time of 20 minutes to 2 hours, and the residue is heated with stirring, and esterified (2) the esterification product obtained is added to the aromatic fraction with the acid-modified aromatic. matic resin and a polybasic carboxylic acid

The aromatic hydrocarbon resin or its anhydride is produced by heating to 180 to

made by polymerizing the indene containing 270 ° C in a time of 30 minutes to 15 hours,

aromatic fraction at a temperature of During the esterification (2) one can use the acid-modi

-30 to +40 ⁰ C within 20 minutes to the aromatic resin and polybasic resin

15 hours in the presence of 0.05 to 5 weight carboxylic acid de: n transesterification product, which according to (1)

percent of a Friedel-Crafts catalyst, such as Alu- 35 is obtained, add at the same time, or you can

minium chloride and boron trifluoride, which deactivate the acid-modified aromatic resin first

of the catalyst with acid or alkali after the transesterification product (1) and then react

Termination of the reaction and separation of the non-esterifying with the polybasic carboxylic acid,

reacted material and lower polymers The preferred composition of the compo-

by evaporation or distillation. 30 nents is in the following range:

The hydrocarbon resin obtained has a

Softening point of over 140 ⁰ C, a low part by weight

Content of unsaturated components, a bromine number, acid-modified aromatic

from 5 to 40 and a pale color. Resin 1 to 50

The method according to the invention differs from polybasic carboxylic acid

of the known processes in that or their anhydride 2 to 60

an aromatic hydrocarbon resin with a polyhydric alcohol 2 to 30

high softening point and low fatty oil content 10 to 90

is used on unsaturated.

The aromatic hydrocarbon resin is then 40 fatty oils, which according to the inventive method

melted or used in a hydrocarbon solvent are linseed oil, tung oil,

solvent and this one unsaturated multi-castor oil, dehydrated castor oil and tall oil,

valued carboxylic acid, such as. B. Maleic acid, or These fatty oils can be used on their own or

an unsaturated polybasic carboxylic acid anhydride, two or more used together in mixture

such as B. maleic anhydride added. 45 become. Polyvalent ones suitable for transesterification

In general, 1 to 30 parts of alcohols are used are dihydric alcohols, such as ethylene-unsaturated polybasic carboxylic acid or its glycol, propylene glycol, trihydric alcohols such as anhydride per 100 parts of aromatic carbo-glycerol, trimethylolpropane and tetravalent alcoholic hydrogen resin. The mixture will hole up to 120, like pentaerythritol. These polyvalent Alko-250 ⁰ C for a time of 1 to 16 hours in 50 holes can also be used alone or in two or more absence or in the presence of 0.01 to mixed.

5 percent by weight of a catalyst, such as. B. Polybasic carboxylic acids and their anhydrides,

a peroxide, heated. which are used by the method according to the invention

Suitable unsaturated polybasic carboxylic acids are maleic acid, phthalic acid, citric acid or their anhydrides are maleic acid, citraconic acid, endomethylenetetrahydrophthalic acid, tetric acid, Endomethylenetetrahydrophthalic acid and dehydrophthalic acid and their anhydrides as well ren anhydrides. These unsaturated polybasic fumaric acid, isophthalic acid and terephthalic acid. Carboxylic acids and their anhydrides can be used alone paints and printing inks, which are made from the after or used in combination. the AI produced according to the invention according to the invention If the alkyd resin is made 60 kyd resins are made, stand out against Implementation of (A) one with one of the known alkyd resins saturated polybasic carboxylic acid modified

aromatic hydrocarbon resin, hereinafter (a) a high proportion of dryness, abbreviated as "acid-modified aromatic resin" (b) high hardness, referred to, (B) a polybasic carboxylic acid or 65 (c) good adhesion,

their anhydride, and (C) a transesterification product (d) high resistance to chemicals,

a polyhydric alcohol with a fatty oil. (c) high competitiveness and

This involves esterifying (1) one or more fatty oils with (f) good color properties.

The invention is explained in more detail below by means of examples.

Production of the aromatic hydrocarbon resins used according to the invention, of comparative hydrocarbon resins and "acid-modified" aromatic resins "

A cracked petroleum fraction having a boiling range from 140 to 220 ⁰ C, the gasoline Dampfkrackung has been recovered as a by-product of, contained 40.2 percent by weight of polymerizable components, and 6.2 percent by weight of indene, as determined by gas chromatography. The »Inden Index of this faction is 15.4%.

The fraction was polymerized at 10 ⁰ C for 7 hours using a boron trifluoride ethyl ether catalyst. After deactivating the catalyst with an aqueous sodium hydroxide solution and washing with water, the unreacted material and the lower polymers were separated by distillation. An aromatic hydrocarbon resin (I) was obtained in a yield of 27.9% by weight; Softening point 142 ° C (Japanese industrial standard JIS K 2531), Bromzahi 24 (ASTM D-1158), color 2 (Gardner scale, ASTM D-1544-58T, 2 g of the sample dissolved in 25 ml of benzene).

The fraction which boiled in a range from 160 to 225 ° C. had a content of polymerizable components of 43.2 percent by weight and an indene content of 8.0 percent by weight. "Inden Index" was 18.5%. An aromatic hydrocarbon resin (II) was prepared from the fraction in the same manner as described above. Yield of resin (II) 28.5 percent by weight, softening point 155 ° C., bromine number 19, color 1.
The fraction boiling in the range of 120 to 180 ⁰ C, had a content of polymerizable component of 40.0 weight percent and an indene content of 3.0 weight percent. "Indene index" was 7.5%. An aromatic hydrocarbon resin ίο (III) was prepared from this fraction in the same manner as described above. Yield of resin

(III) 25.0 percent by weight, softening point 98 ° C, Bromine number 25, color 1.

The fraction that ranges from 20 to 100 ^° C

is boiled, had a content of polymerizable components of 56.0 percent by weight, and the indene content was zero. The fraction contained 29.5 percent by weight conjugated diolefins. The hydrocarbon resin (IV) was prepared by polymerizing the fraction at 20 ^° C. for 2 hours in the presence of 0.8 percent by weight of catalyst (aluminum chloride). Yield of resin

(IV) 30.0 percent by weight, softening point 75 ° C, Bromine number 85, color 4.

a ₅ The resins (I), (II), (III) and (IV) were polymerized with maleic anhydride at 20O ⁰ C for 9 hours to give maleic anhydride-modified aromatic hydrocarbon resins A, B, C, D, E and F. The amounts of maleic anhydride used and the properties of the acid-modified resins obtained are shown in Table I below.

Table I.
Properties of Acid Modified Aromatic Resins

Acid modified
aromatic resin

KWSt-Harz *

Maleic anhydride

(added grams per 100 g of KWSt resin) Properties of the acid-modified aromatic resin

Softening point
⁰ C

color
(Gardner scale)

Bromine number

I.
I.

II

II

III

IV

6.5

4.5
5.5
10.0
5.5
5.5

153
148
168
167
115
90

17th
16
14th
10
23
80

* Hydrocarbon resin.
· ♦ Comparative resin.

_R ..... To the soybean oil and pentaerythritol was Example ι black lead in an amount of 0.15 percent by weight alkyd resin AI was added by using the catalyst and acid-modified aromatic resin A from Ta 55 long at 250 ° C for 70 minutes interesterified. Belle I, pentaerythritol, phthalic anhydride and soy-the acid-modified aromatic hydrocarbon bean oil were produced in the following ratio to the transesterification product: resin A and phthalic anhydride were added. The VerGewichts- esterification was carried out at 230 ⁰ C and beem'st parts by 4 hours. By dissolving the received

Acid modified aromatic resin A 22 ^6o alkyd resin in light mineral oils became a

Pentaerythritol 16 lacquer with a solids content of 50 ° / ₀ produced.

Phthalic anhydride 25

Soybean Oil 38 Example2

The oil content is 39 ° / ₀ when the säuremodi- 65 alkyd resin was BI by using the

fized aromatic resin is included, and acid modified. aromatic resin B from Ta-

50% if the acid modifi / .icrtc aromatic resin belle I, pentaerythritol, phthalic anhydride and linseed oil

is excluded. manufactured in the following ratio:

7 8

Weight varnish was prepared by dissolving the obtained

^All alkyd resin in light mineral oils. The paint

Acid-modified aromatic resin B 22 had a solids content of 50 ° / _0th

Pentaerythritol 16

Phthalic anhydride 25 5. .

Linseed oil 38 B e. s ρ. e 1 4

The oil content and the method of preparation were the same as described in Example 1.

Example 3

Alkyd Resin C-I was made using the acid-modified aromatic resin C from Table I, pentaerythritol, phthalic anhydride and linseed oil manufactured in the following ratio:

Parts by weight _ao

Acid modified aromatic resin C 22

Pentaerythritol 11

Phthalic anhydride 18

Linseed oil 49

The oil content is 50% if the acid modified aromatic resin is included, and 64% when the acid-modified aromatic resin is excluded.

The transesterification was carried out at 25O ⁰ C after 70 minutes in the same manner as described in Example 1 were carried out. The acid-modified aromatic resin C and phthalic anhydride were added to the transesterification and the esterification was completed at 23O ⁰ C after 6 hours. An alkyd resin DI was prepared using the acid-modified aromatic resin D from Table I, pentaerythritol, phthalic anhydride and safflower oil in the following proportions:

Parts by weight

Acid modified aromatic resin D 22

Pentaerythritol 16

Phthalic anhydride 25

Safflower Oil 38

Comparative example 1

Alkyd Resins A-2, B-2, C-2, and D-2 were made from a polybasic carboxylic acid, a polyhydric alcohol and a fatty oil without Use of the acid-modified aromatic resin according to this invention. These alkyd resins A-2, B-2, C-2 and D-2 were each made under the same conditions as in the corresponding examples 1, 2, 3 and 4 described, prepared using the following ratios for the components so that the alkyd resins produced have the same oil content as those made using the acid modified aromatic resins obtained alkyd resins A-I, B-I, C-I and D-I possessed.

Alkyd resin Components Weight
share Corresponding
modified alkyd resins
according to the invention
appropriate procedures A-2
B-2 Pentaerythritol
Phthalic anhydride
Soybean oil
Pentaerythritol
Phthalic anhydride
linseed oil 78
143
202
78
143
202
78
143
360
78
143
202 AI
BI C-2 Pentaerythritol
Phthalic anhydride
linseed oil C-I D-2 Pentaerythritol
Phthalic anhydride
Safflower oil D-I

Comparative example 2

Modified alkyd resins E-I and F-I were made using the acid-modified comparison resins E and F from Table I, pentaerythritol, Phthalic anhydride and linseed oil in the same ratio as in Example 3 in the preparation of Alkyd resin C-I described prepared. They were made by dissolving them in light mineral oils Paints made with a solids content of 50%.

Paint tests on the alkyd resins and comparative resins produced according to the invention

Paint tests were carried out with paints obtained by dissolving the modified alkyd resins A-I, B-I, C-I ur D-I, the unmodified alkyd resins A-2, B-2, C and D-2 and the modified alkyd resins E and F-I made in light mineral oil was carried out. Each paint contained 0.5 percent by weight Lead as lead naphthenate and 0.05 percent by weight of cobalt naphthenate as a drying agent.

The results of these tests are shown in Table Π.

Table II Results of the paint test

10

AI II
BI

! 1Il
CI

IV
Tue

V Λ-2

1. Drying time (Japanese Industrial Standard JIS K5400), minutes

2. Adhesion-free time, minutes (')

3. Drying time, hours (*)

4. Pen hardness test (Japanese industry standard JIS K5651) ( ³ )

5. Spiral grinding test («) (»)

6. Cross hatch test (·) (')

7. Tape test (")

8. Water resistance test, 18 hours (Japanese industrial standard JIS K5400)

9. Alkali resistance test, 3 hours (Japanese industrial standard JIS K 5400) ....

10. Short-term weather test

25th

40

H 6 6 0/100

useful

low

bladder

useful 15th

30th

3H

10

10

0/100

useful useful optional

20th

35 2

3 H.

10

10

0/100

useful useful useful

8th 8th 0/100

brew · ι bar usable usable

40 60 10

3B

4 4 40/100

Bladder peels off usable

Table II (continued)

Vt Vi i Viii ix X B-2 C-2 O-2 EGG F-I 20th 40 40 40 45 50 50 60 55 55 7th 10 10 8th 10 2 B 2 B 3 B H B. 4th 4th 4th 6th 4th 4th 4th 4th 6th 4th 60/100 80/100 40/100 20/100 60/100 bladder bladder bladder useful bladder peels off peels off peels off bladder bladder useful low useful useful low acceptance acceptance of of Shine Shine

1. Drying time (Japanese industrial standard JlS K5400), minutes

2. Adhesion-free time, minutes ( ¹ yr

3. Drying time, hours ( ² )

4. Pen hardness test (Japanese industrial standard JIS K 5651) ( ³ )

5. Spiral joint test ( ⁴ ) ( ^s )

6. Cross hatch test (·) (')

7. Tape test («)

8. Water resistance test, 18 hours (Japanese industrial standard JIS K 5400) ....

9. Alkali resistance test, 3 hours (Japanese industrial standard JIS K 5400) ....

10. Short-term weather test

C) The point in time from which the surface of the paint film is no longer tacky. C) Time for the paint film to dry out completely. C) Notch hardness test. C) Test for the adhesion of the paint film to the substrate with a spiral-shaped grinding wheel feed. C) Test for the adhesion of the paint film to the substrate in the case of scratch hatching with two intersecting sequences of parallel scratches

linicn.

C), C) The value 10 indicates the best adhesion and 0 no adhesion. C) An adhesive tape was pressed onto the paint, in which perpendicular grooves were cut, and

deducted. The adhesiveness was evaluated by the number of fields peeled off from 100 fields with the adhesive tape

became. The smaller the number of fields peeled off, the greater the adhesion. C), C). C) The paint film had a dry film thickness of 27 microns for each test.

As can be seen from Table II, the paints produced by the process according to the invention have from the modified alkyd resins A-I, B-I, C-I ur.d D-I significantly faster drying times than comparatively the lacquers made from the conventional alkyd resins A-2, B-2, C-2 and D-2.

Likewise, the hardness of the paint film of the paints, those made from the modified alkyd resins made by the process of the present invention become higher, and the adhesion of the paint film is better than that of the paint films made from Lacquers are made of conventional alkyd resins,

11 12

like the results of the pencil hardness test, the spiral compared with the varnish from the modified one

the grinding test, the crosshatching test and the adhesive alkyd resin C-I, which is made in the same way but under

tape tests show. Use a faction that has a sufficient

Furthermore, paints for varnishes are made from the amount of indene (8 percent by weight)

5 was produced by the method according to the invention. · modified alkyd resins are characterized by

that they have a higher resistance compared to chemical comparative example 3 calories, such as B. vlkali.

The varnish from the modified alkyd resin E-I, A modified alkyd resin was produced

using a petroleum fraction, the 3 ge io using the same components, exclusive

contains weight percent indene, whose borrowed pentaerythritol, in the same ratio as in

Indene content below the lower limit of Example 2 for obtaining the modified alkyd

According to the invention * petroleum fraction is described resin B-I, but the linseed oil

dries worse and has a lower adhesion - subject to acidolysis instead of alcoholysis,

15 Acidolysis was achieved by heating the linseed oil,

ficated alkyd resin C-I, with those of the acid-modified aromatic resin B and

Same method of manufacture, but carried out using one of phthalic anhydride. It showed

Fraction that contains 8.0 percent by weight indene, that the acidolysis did not start before the temperature

was applied, temperature had exceeded 300 ° C. This created

Finally, the varnish from the modified 10 is a significant loss of phthalic anhydride Alkyd Resin F-I, which is made using a petroleum sublimation, and the Modified Alkyd Resin

fraction was produced, which had a large proportion a dark color above 15 on the Gardner scale,

of dienes and contains no indene, worse in the. From this comparative example, it can be seen that the

Drying, weather resistance, water resistance and acidolysis for the production of modified alkyd Alkali resistance properties and in adhesion, »5 resins is not recommended.

2705

Claims (1)

1 2 line film very brittle. In addition, after the Claim: Method of U.S. Patent 2,952,646 das Addition product of the unsaturated polyolefinic Process for the production of an alkyd resin petroleum resin and the polybasic carboxylic acid with by reacting a polybasic carboxylic acid 5 a fatty oil by acidolysis first to or its anhydride with a transesterification an acidic product, which is then reacted with a product of one or more fatty oils with a polyhydric alcohol is esterified, v / whether there is one or more polyhydric alcohols, d a- the acidolysis reaction, an undesirable color characterized by that one forms, which is, however, unavoidable.
The reaction also uses a polymer which, in the first stage, describes a process for the production of an alkylene resin, table fraction of a hydrocarbon oil with the addition of a boiling range of 140 to 280 ⁰ C as the polybasic acid component which comes from the product of an unsaturated polybasic carbon in the cracking process of petroleum, the acid of which contains a polydiene resin. The A & Mions indene content of more than 5 percent by weight Hegt 15 product is obtained by polymerizing one or the an "indene index", which contains as the fraction, the olefins and diolefin derivatives of the proportions by weight of indene and alkyl-cracked petroleum, and polymerisation with an indene to the proportions by weight of the polymerised polybasic carboxylic acid. The paint film, which is obtained from this alkyd resin multiplied by 100 solid components, is also above 11 percent by weight, in 20 it has poor weather resistance properties because the presence of a Friedel-Crafts catalyst leads to the alkyd resin. Resin has a high proportion of unsaturated aromatic hydrocarbon resin, the polydiene resin derivatives from the diolefin containing a degree of softening of over 140 ⁰ C, and contains material. The film is also brittle because further polymerization of the resin with one or only the addition product of a polydiene resin and several polybasic unsaturated carboxylic acids as the acid; i or their anhydrides are used as the polybasic acid component. Next is. furthermore, it is inevitable that the cost of the alkyd resin is high because it is caused by the so-called "Fatty acid process" is produced in which the additive 30 tion process of the polydiene resin and the polybasic carboxylic acid and the esterification with a Fatty acid and polyhydric alcohol It is known that lacquers, enamels and printing run off in a timely manner. Paints Made from Conventional Alkyd Resins These drawbacks can be overcome by finding the drawbacks of slow addition drying in the preparation of the alkyd resin, a soft and tacky paint film product of an aromatic hydrocarbon resin and have a low resistance made by polymerizing an indene containing water and chemicals such as alkali and hydrocarbon oils with one or more acids. unsaturated polybasic carboxylic acids or their To overcome these disadvantages, for. B. 40 anhydrides used as part of the polybasic carbon-alkyd resins with resins or phenolic resins for acid component of an alkyd resin. The invention relates to a method for producing the resistance to chemicals of an alkyd resin by converting a multi-chemical modified. Such modifications are alcohols basic carboxylic acid anhydride having ODTR however, other disadvantages, since they 45 a transesterification call the darkening of one or more fat of the resulting modified alkyd resin hervor- oils with one or more polyhydric, reduce the weather resistance properties. The method is characterized by causing paint film brittleness. that a polymer is used in the reaction. The USA. Patent 2,915,488 describes a method which, in the first stage, by polymerizing a process for obtaining an alkyd resin which forms a hard coating, aromatic fraction of a hydrocarbon oil, in which a part of those with a boiling range from 140 to 280 ⁰ C, which is replaced from fatty acids by benzoic acid. the cracking process of crude oil, whose US Pat. No. 2,952,646 relates to an indene content of more than 5 percent by weight, or to the production of an alkyd resin, which has an "indene index", which is the ratio of the polybasic acid component is an addition 55 weight fractions of indene and alkyl indene to the product of an unsaturated polybasic carbon weight fractions of the polymerizable components acid to a higher unsaturated polyolefin multiplied by 100, over 11 percent by weight petroleum resin, which is made up of the tarry soil residues has been obtained in the presence of a Friedel-Craft its cracked petroleum distillate, turned catalyst to an aromatic hydrocarbon. The unsaturated petroleum resin used here, which has a degree of softening of over 14O ⁰ C resin, has an iodine number of 90 to 225, preferably has and further polymerization of the resin with a 150 to 200. The use of this addition or more polybasic unsaturated carbon product The resulting alkyd resin gives acidic paint films or the anhydrides of which have been produced. with the disadvantage of the low weather resistance as a starting product for the production of the aroma property. Furthermore, if only the addition table hydrocarbon resin is used, an aroma product of polyolclinic petroleum resins and a table fraction of a hydrocarbon oil with an unsaturated polybasic carboxylic acid as a higher boiling range from 140 to 280 " ¹ Z, which are used as a by-product of the basic acid component, the an - a thermal or catalytic cracking pro-