DE1720576A1 - Process for the production of waterless coating preparations - Google Patents

Description

PATENT LAWYERS β MUNICH 2, HIUBLESTRASSE 2O

Df.Barg Dipl.-Ing. Stapf, 8 MOnchen 2, HllblestraBe 20 Your reference Your letter Our reference l4 803 Date 5iAUQ · 197Q

P 17 20

iieue documents

On / a Itsakte-ilr. 14 iJ03

üsso liesearch and i'üncineerin ^ Company Elisabeth, xJev / Jersey / UoA

"Process for the division; of water-soluble Coating preparations "

jj.ie i.ri'infiun;. ;; uc.-trii'i't uln Verfauren for the production of waüijorlös Licnon iJberzu _t ;;; preparation by converting ίίοΗΌ- or copolymers !! conjugated dienes with 1,4-Kon i'ii.uration with Vei'bindun ^ en a u, [i-un ^ esaturated Dicär

New documents (Art 7 81 Ab «. 2 No. I Sau 3 de · Ämkmnasg 3. v. 4.9. K ..

x / na 109 8 27/1622

It is well known that relatively low molecular weight Polybutadienes, butadiene / styrene copolymers and many modified products from it for the formation of metals firmly adhering and these coatings are capable of protecting against corrosion. However, the well-known Coating compounds that are derived from butadiene are not water-soluble and can only be achieved with organic solvents be diluted. On the other hand, the water-soluble materials currently used as top coating materials correspond to the changes Resins such as the commercially available melamine, alkyd urea and acrylic resins do not always meet the requirements of the coating industry, such as with regard to low price, hydrolytic stability and good film properties.

Ss has now been found according to the present invention, daä you get new, valuable, water-soluble coating preparations by reacting homo- or copolymers conjugated dienes with 1,4-configuration with compounds an ot, β-unsaturated dicarboxylic acid can be obtained if homo- or copolymers of diolefins, their diolefin units have at least 50% 1,4 configurations and have a molecular weight of 500 to 10,000 are used and a compound a cx, ß-unsaturated dicarboxylic acid in such amounts

109827/1622 '- * -

ment

8η§ & ΐ§6η bound ehtnäit * üüt daä 8ί · Μΐΐ§η§ Addufc-fe iii §ifi iteiöniüm- öäär Aifcäii-

f tüirdfe according to the TdflifegeMeü tii-finding that ge # i§äö D§fiväi; fe d§s vöfö-feSiiend feirtähntfefi, pdlyäfereii iuid feö |> öiyiii§ren Aääük-fefeöiöis- i Öjööiy? ^l örmoi3riätiön & - and epoxydätions-Pröduki§j # iüä & §ilööliehe tibfefÄügöDiässeri result, which form frilnie of iietirbrfagena ^ n own business part;

Dei · Äusdtttbfc "terbindtihgen a oCjß-ttngesäitigien DicafbönSäürfe'S tie he Hief teffendei is * beaieht Resting on AEJM-tiiiggiä-t-preferential Di carbons on eh \ anhydrides,

Möhöeötf and Monoämide ^ e.g. * Maleic acid ^ ftuflar-Mäleinsäurfeähhyärlä, Mäleihsäureimid, lftaleih- and

The efficient rerWeMe-feeh homo- or copolymers * föü Di8igfitt§n siöd substances ^ which at least 5Ö ^ i

TB Ms 8 ^ ihrör SiSlefineinheiteri in M- ¥ erMüpli ίϋΒβη * ii fäii§ äef Ööpölymerisate a larger «olftren atl-fceil stn diolefins contain ÜÄÄ duröh eiü iÜiigiÄä # ii§g miitiefee MbieMläf-

ORIGINAL INSPECTED

weight in the range from 500 to 10,000, preferably from 1,000 to 4,000.

Typical examples of conjugated diolefins used for the preparation of the above-mentioned polymers and Oopolymers that can be used are! Butadiene and isoprene. Of the comonomers conjugated with the Diolefins can be copolymerized, be styrene, Called mesityl oxide, acrylonitrile and <x-01efine.

Homo- and copolymers of conjugated diolefins suitable for use in the process of the present invention Suitable invention include polybutadienes, polyisoprenes and copolymers of butadiene and isoprene with Styrene and mesityl oxide with a content of up to 30 mol # of styrene and / or meeityloxide, which are the above have the structure and molecular weights described. A preferred starting material is polybutadiene with 75 to $ 85 1,4 structure and average molecular weight within the range of 1,000 to 4,000.

To produce the new water-soluble coating preparations of the present invention, the homo- or copolymer with a sufficient amount of a ot ȧ-unsaturated dicarboxylic acid compound with formation

109827/1622 - 5 -

Adducts8 implemented «its ammonium salt largely Eat soluble in water. Depending on the condition and the molecular weights of the components are different amounts of dicarboxylic acid compound, depending on the desired degree of water solubility required *

80 it is, for example. when using maleic anhydride advantageous to aim for adducts with a content of 10 to 30 $ of chemically bound maleic anhydride, because such substances are salts with sufficiently high solubility in water or water-alcohol mixtures form.

When carrying out the reaction of the homo- or copolymers with the οι, β-unsaturated dicarboxylic acid compounds, e.g. with maleic anhydride, the components are heated together to a temperature that is high enough is to allow the adduct to form in a reasonable time.

In general, temperatures in the range from 150 to 240 ^° C. are suitable for this purpose. Although the reaction can be carried out in a high-boiling solvent, for example in decahydronaphthalene, it is preferred to work without a solvent.

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The reaction time depends on the temperature and the temperature Extent of the desired attachment. At temperatures within the range indicated above, useful products are made by heating the components for periods of 15 minutes to 5 hours, preferably for about 1 hour to 1 1/2 hours.

Various methods can be used to remove the unreacted dicarboxylic acid compound from the reaction mixture, such as extraction with water or heating under reduced pressure. A very convenient and effective method is based on keeping the reaction mixture at a pressure of 1 to 5 mm Hg. At a temperature of 150 ° to 250 ° C. in order to distill off the unreacted οι., Ss-unsaturated dicarboxylic acid compound. Under these conditions, adducts with <Ö _# 2 wt .- ^ maleic acid can be prepared in about 30 minutes to 1 hour. -isi &

The adducts thus formed can either be used as such or in the form of certain chemically modified ones Products for the manufacture of aqueous Hara solutions be used as coating preparations intended for a variety of coating purposes are suitable.

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According to the present invention, the above-mentioned Adducts converted into water-soluble salts without further chemical modification.

Furthermore, according to the present invention, the above-mentioned adducts before the salt formation by oxidation, Hydroxylation / pormoxylation or epoxidation modified will.

Furthermore, the unmodified adducts or their modified products according to the present invention can first with a compound containing amino or hydroxyl groups implemented and then brought into aqueous solution.

Both reactions, namely the salt formation as well as the optional implementation of the adducts or their modified ones Products with a compound containing amino or hydroxyl groups are carried out using methods which are independent of the particular nature of the material, i.e. the unmodified adduct or des by oxidation, hydroxylation / formoxylation or Epoxidation modified adduct. These two stages will therefore be described later.

109827/1622 -8-

Although the unmodified adducts coatingspreparations form, which are completely satisfactory for some purposes and, other uses require a modification of the properties of the underlying Resin such as solubility, viscosity, and film properties. It has been found according to the present invention that such a modification can be achieved by three types of reaction, namely by oxidation, Hydroxylation / formoxylation and epoxidation. In this way, the properties of the underlying Resin to be adapted to the special purposes.

The oxidation of the adducts causes the introduction of carboxyl groups and other functional groups, i. of hydroxyl, carbonyl and epoxy groups. To carry out this type of modification, the adduct in dissolved in a suitable solvent and with air or oxygen at elevated temperature and in the presence treated with an oxidation catalyst. As a solvent, a hydrocarbon such as toluene and Xylene or a ketone such as methyl isobutyl ketone can be used. Generally a small amount will a common oxidation catalyst such as manganese naphthenate is added to the solution. The Oxyda-

109827/1622 - ⁹ "

tion is preferably BQI "into *! temperature" durqhgeführt from 90 to 150 ⁰ Q and for a period of 1.2 to 6 hours,

In this way, one can to the desired degree of oxidation by bubbling oxygen into a 25 "to 50 # solution of the resin in an aromatic hydrocarbon at a temperature of 110 to 12O ⁰ G for a period of 15 minutes, get to 4 hours. In these applied conditions, the concentration of oxidation catalyst can be approximately between 250 to 1,000 ppm.

Another mode of modification contemplated by the present invention is the introduction of Hydroxyl-formoxyl groups through reaction of the adducts with performic acid. Similar modifications can be made by reacting the adducts with other organic peracids be effected.

This type of modification, mentioned as hydroxylation / formoxylation, takes place when a Solution of the adduct, preferably in a chlorinated hydrocarbon such as chloroform or carbon tetrachloride, with performic acid at a temperature

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Bwiioben 45 and 80 ⁰ C, preceded "has jswieohen 50 and 53 ⁰ is treated Qt * The amount of formic acid applied mark of 0.1 bits per 2 moles of butadiene vary ie Addufct. AnateHe τοη performic acid can be used in the reaction in situ with hydrogen peroxide and formic acid, preferably in a molar ratio τοη approx Minutes up to 24 hours.

Finally, the adducts can age due to Bpoxydatlon Modified with the aid of a peracid or other suitable epoxidizing agent. To a To prevent cleavage of the Bpoxydringes, the reaction is preferably carried out at a temperature below carried out at 45 ° C. Suitable reaction times are within a range from 1 to 4 hours. Similar to hydroxylation / tormoxylation also works '' the epoxidation reaction will readily proceed in a chlorinated hydrocarbon solvent.

The preferred oxidizing agent is peracetic acid or a mixture of acetic acid with hydrogen per ~ oxide, preferably in a molar ratio of about 1 1 1.

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The modified products described above are made from their solutions by distilling off the solvent isolated under reduced pressure. In the presence of an aqueous phase, the organic product solution becomes separated first by decanting or otherwise. It is generally preferable wash the organic layer with water before removing the solvent.

Both the unmodified adducts and their modified products can by adding n-butanol or another alcohol stabilized at room temperature. The solutions thus obtained are long Time storable.

The application of the present coating preparations in aqueous solution is based on an oil softening of the acidic resins through salt formation. However, as mentioned earlier, salt formation can be a reaction precede the adducts or their modified products with a compound containing amino or hydroxyl groups »

The compounds containing amino and hydroxyl groups suitable for this possible reaction include amines,

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Amino alcohols and alcohols. Of the amines are ethylamine, Propylamine, butylamine, ethylenediamine, butylenediamine, Hexamethylenediamine and triethylenetetramine are mentioned, while ethanolamine, diethanolamine and trimethylolmethylamine are typical representatives of suitable amino alcohols. The list of alcohols that can be used includes n-butanol, n-hexanol, n-octanol, ethylene glycol, dihydroxypropionic acid etc.,

The reaction conditions depend on the nature of the reactants. Thus, in general, a temperature below 3O ⁰ C and a reaction time of 10 to 30 minutes to carry out the reaction dee adduct or its modified product with an amine sufficient. On the other hand, for the conversion of an adduct or its modified product into an ester by bringing it into contact with an alcohol, a temperature of 110 to 120 ^° C. and a reaction time of 30 to 60 minutes may be required.

In either case, the reaction is preferably carried out in a solvent such as toluene or xylene, though the use of a solvent is not absolutely necessary.

109827/1622 - 13 -

The molar ratio of the adduct or its modified product to the amine used in the reaction or alcohol can fluctuate within wide limits. In general, however, the proportions of the reactants will be chosen so that 0.5 to 1.5 moles of NH 2 or OH to 1 mole of anhydride in the adduct or the modified Adduct are included. Thus, one mole of anhydride can be in the adduct with one mole of butylamine or n-hexanol or react with 1/2 mole of ethanol arain or ethylene glycol.

In summary, the present invention provides coating formulations based on acidic resins of the following types

1. Adducts, formed from homo- or copolymers of conjugated diolefins, their diolefin units have at least 509ε 1,4-configurations and a Molecular weight from 500 to 10,000 and a, ^, ß-unsaturated dicarboxylic acid compound in such Quantities applied that the end product is 10 to 30 $ the , y, ß-unsaturated dicarboxylic acid chemically bound which are substantially soluble in aqueous ammoniacal solutions;

109827/1622 -H-

2 »Oxidation products of 1?

3. hydroxylation / formocylation products of 1;

4. epoxidation products of 1;

5. Reaction products of 1, 2, 3 and 4 with a compound that has an amino and / or hydroxyl group contains.

The top coat preparations mentioned above can either be used alone or in the form of mixtures with conventional ones water-soluble resins such as melamine resins, urea resins or the like can be used. The composition of these mixtures can vary within wide limits, but in general the ratio will of conventional resins in such mixtures 50 wt .- ^, based on the total mixture, do not exceed.

With regard to the application of the new resins, water-soluble coating preparations are now made by reacting the Adduct with an alkaline substance with formation of a salt which is soluble in water or in mixtures of water with organic compounds containing hydroxyl groups. The salt formation takes place

109827/1622 - 15 -

- I O -

instantaneously and can be obtained by mixing the acidic adduct at room temperature with a large number of alkaline ones Compounds such as ammonia, sodium hydroxide and amines of sufficient basicity, such as triethylamine, can be achieved.

A particularly easy and advantageous method of solubilization by salt formation is based on treatment of the acidic adduct with gaseous or aqueous ammonia.

The solubility of the salt thus obtained depends, inter alia, on the nature and the amount of the in the resin chemically bound acid. Thus, the introduction of $ 30 maleic anhydride into a homopolymer results in viz e.g. in a high 1,4-polybutadiene, an adduct, its ammonium salt can already be dissolved in water alone, while it is clearer for production Solutions of the ammonium salts of high 1,4-polybutadiene adducts with only 10 to 15 # of chemically bound maleic anhydride Mixtures of water with a suitable co-solvent such as alcohols or esters required are.

The type of Oo-solvent, if such a

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- 16 -

may affect the properties of the coating formulations of the present invention. It has been found that particularly good films from aqueous solutions of malein-modified high 1,4-polybutadiene ammonium salts, which n-butoxyethanol, or n-butoxyethanol and 2-ethyl-n-hexanol, or contain n-butoxyethanol and n-octanol.

In the case of the ammonium salts, it is advantageous to use the p ™ of the aqueous solution to a value of 7 to 8. This can be done by mixing the basic acidic adduct with an appropriate ammonia solution or by adding the required amount of ammonia to a ammonium salt solution prepared beforehand.

The coating formulations of the present invention have many uses. They are particularly suitable for use as a primer Metal objects such as automobile bodies, metal containers, canisters, typewriters, and household items. You can apply to the object to be coated by any conventional method, e.g. Dipping, painting, spraying and electrical application.

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The application of the coating preparations by electrical means, especially galvanically, gives excellent results. In this technique, the resins can be used in the form of their dilute aqueous solutions of their ammonium salts. Suitable concentrations are 5 ° / t> for unpigmented and 10 $ for pigmented material.

Applying the new resin to the one to be coated The article is followed by a conventional hardening treatment such as drying or baking at 130 to 180 ° 0 of 30 minutes.

The present resins have excellent properties. Advantages over other comparable substances are their good electrodeposition properties and their high hydrolytic resistance.

Example 1 Preparation of high polybutadiene

181 ml of a 15 # solution of butyllithium catalyst in η-hexane was added to 3 liters of toluene under nitrogen protection. 1,200 ml of 1,3-butadiene were slowly added over the course of 2 hours with stirring, a temperature of 40 ^° C. being maintained.

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The solvent was removed by vacuum distillation removed and there remained a yield of 729 g of a polymer * with the following properties:

Average Number average molecular weight 2,700 to 3,000 Peroxide content (ppm) 1 to 30 Iodine number 350 to 400 Microstructure

1.2 QmGi 15th

ice 1.4 C-C * 17

trans 1.4 C "C * 68

If films are dried from 0.0254 mm thickness of the above polybutadiene for 30 minutes at 170 ⁰ C, 180 ⁰ C or 190 ⁰ C, no satisfactory cure is obtained ·

Example 2 Preparation of a Maleinized Polybutadiene

80 g of a polybutadiene prepared according to Example 1 and 20 g of technically pure maleic anhydrides were heated under Stickstoffschute and efficient stirring for one hour at 200 ⁰ O. Unreacted maleic anhydride was removed by distillation under reduced pressure

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removed at 20O ⁰ G and obtained a maleinized polymer with an acid number of 170 to 190 mg KOH / g. This acid number corresponds to the incorporation of around 169ε maleic anhydride.

At s.p i e 1 3

Manufacture of an amide ammonium salt of maleinized polybutadiene

Maleinized polybutadiene prepared according to Example 2 was made by reacting with aqueous ammonium hydroxide solution Solubilized in water to a p ™ of 7 to 8 at room temperature. Other water soluble Resins can be obtained by:

1 · Reaction of maleinized polymers with monoethanolamine oder'diethanolamine;

2. Reaction of maleinized polymer with alkylamine, e.g., ethylamine;

3. Esterification of maleinized polybutadiene with up to

to 1 mole ratio of alcohol, for example n-butanol or n-octanol-hexanol n at 110 ° C and 30 minutes, and then forming dee ammonium salt by reacting at room temperature with a solution of ammonium hydroxide up to a p _H 7-8

109827/1622 ~ ^

ft fj, β ρ j, β ι 4

Hydroxylation / Formoxylation iron maleinieierten Polybutadiene

50 g of maleinized polybutadiene, prepared according to Example 2, were dissolved in 250 g of chloroform and 28 ml 90% formic acid was added to this solution became 12.6 g of 50 # rigem in the course of 15 minutes Hydrogen peroxide was added dropwise. The reaction mixture was 1 1/2 hours at a temperature of 50 ° C - 1 ° β touched. The organic layer was separated and the solvent was removed under reduced pressure and the hydroxylated / formoxylated maleinized was obtained Polymers with a hydroxyl number of 175 to 225 mg KOH / g, the Aald ammonium salt of the hydroxylated Polymers were obtained by adding an aqueous ammonium hydroxide solution at room temperature to a p »of 7 to 8 produced · The degree of hydroxylation can of course by regulating the amount of formic acid added during the reaction, as well as the temperature and the tent can be varied.

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Example 5

Manufacture of oxidized maleinized polybutadiene

50 g of maleinized polybutadiene in a 25 ^ -igen Toluene solution were made using a manganese naphthenate catalyst (250 to 1,000 ppm) with oxygen at a transfer rate of 10 ml / g per minute at 110 to 115 ° G over 3 hours oxidized. The toluene was removed by distillation under reduced pressure and 5 g of n-butoxyethanol was added added to stabilize the resin. The amide ammonium salt of the oxidized polymer was made by adding an aqueous ammonium hydroxide solution at room temperature up to a p ^ of 7 to 8.

Example 6

Manufacture of epoxidized maleinized polybutadiene

15 g of 38% peracetic acid were added dropwise to a solution of 56 g of maleinized polybutadiene according to Example 2 in 280 g of chloroform. The Heaktionsmischung was stirred at 4O ⁰ G 1 1/2 hours. The organic layer was separated, washed with water and the solvent under reduced

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Pressure removed, leaving epoxidized maleated polymer stayed behind. 5 g of n-butoxyethanol were added to stabilize the resin. The amide ammonium salt of the epoxidized maleinized polybutadiene by adding ammonium hydroxide solution at room temperature up to a ρ «of 7 to 8.

Example 7

Production of a paint that can be galvanically applied

150 parts by weight of the amide ammonium salt from Example 3, 40 parts by weight of n-butoxyethanol, 10 parts by weight of 2-ethyl-n-hexanol and 80 parts by weight of micronized Oxide red are ground together in a ball mill or a pulp roll mill, the p "being replaced by aqueous Ammonia is adjusted to 7 to 7.5. The resulting mixture becomes a solution with deionized water diluted, which contains 10 to 15 wt .- ^ of solids.

Example 8

The properties of films made from resins of the present invention are shown in the following tables}

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a b e 1 1 e

Film properties of the Amide-AmmoniumBalze e of maleic modified

high polybutadiene

Test series no.

Bialein modified (1,4) polybutadiene

Numerical average Molecular weight

Micros structure 1.2 *
ice 1, trans 1,

Acid number (mg.KOH / g)

57O / 89D ^ <k 57O / 89C—

«■ -

77 2700

15 17 68

137

170.5

Film formation

(D

Drying

Scheme (Min./ ⁰ G) 30/170 30 / I70 30/180 30/190 30/170 30/180 3/190

Film thickness (mil.) - 0.1

solvent

Film properties

Direct impact (in.Ib.) Reverse impact (in.Ib.) Ericksen (mm)

Flexibility (Durehm.in.) Hardness (pen) Hardening

1.0 1.0 1.0 1.0 1.0 1.0 -butoxyethanol / water

7-8

1.0

80

60 8.8

1/8 H

160

160 6.0

1/8 3B

HO

HO 7.0 100

2.0

3/16 1 3/16 1/8 HB 5H
perfect

HO HO 30th 150 HO <5 ^ 9.0 9.0 3.0 1/8 1/8 3/8 B. HB 5H

Spinning Resin (I.C.I. Spinner) on Bonderit 97T.

-

109827/1622

Film properties of the amide ammonium salt of the hydroxylated / formoxylated maleinmodifi ed high 1 _y 4-polybutadiene

Measurement series no. ^ 57O / 88B -> <487 / 91— ->

Male-modified (1.4-) polybutadiene

Numerous through
cut molecule
larweight ^ - 2700 ♦
^^ 2700 —-> Micro structure 1.2 * ^ 15th > i 15 > ice 1.4 *. <: 17 - y trans 1.4 * ^ 68 - > ^ 68 .—-> Acid number (mg KOH / g) ^ - 192 - ^ 4 · __— 192 _—> Hydroxylation

(Mole): BD (mole) ^ 1: 5 V ^ 1 ^{: 2} , 5>

(Mol): acid (mol) ^ 1: 3 - ^ ^ 1 «3 · ->

_22nd

Polymer (g): solu- _vv

solvent (g) i, ^{1: 5} ^ 4 ^{1: 5} 7

Hydroxylation _xv

temperature ΓΟ <£ .— 45-50> ^ 45-50>

Hydroxylation time

IStd.) T ¹

(2)

30/160 30/165 30/170 30/160 30/165 30/170 Film thickness (mil.) ± 0.1 1 »0 1.0 1.0 1.0 1.0 1.0

Solvent ^ butoxyethanol / water ^

P ₁₁ ^ k 7-8 >

Film properties
Direct impact (in.Ib.) 160-90 Reverse impact (in.Ib.) 160 45 Ericksen (mm) 8 7.5

Flexibility (Durchm.in.-) ^1/8 Hardness (pencil) HB 2H

Hardening reached (1) <objection-> softened (1) < objection-?

free free

(1) Film softened but not removed when rubbed with acetone. ^ 2 'Spinning Resin (I.C.I. Spinner) on Bonderite 97T.

109827/1622 ~ ²⁵

55 100 45 78 VJI 30th VJl 5 VJI 9.0 6.0 9.0 7/16 1/8 7/16 1/8 3H H 2H 3H

Table III

Film properties of the amide ammonium salt of oxidized maleic modified high 1,4-butadiene

Measurement series no.

Maleic modified (1,4) -Po Iy butadiene

570/90

Numerical through 2700 cut molecular weight 15th Micro structure 17th $ 1.2 68 to $ 1.4 192 trans $ 1.4 Acid number (mg KOH / g) Manganese naphthenai oxidation 500 catalyst 10 Catalyst (ppm) 110-115 Oxygen (ml / min / g) 3 Oxidation temperature (° 0) Oxidation time (hours) Film education «^

Drying schedule (min./°0) 30/170 film thickness (mil) ± 0.1 solvent

1.0

30/180
1.0

30/190 1.0

Butoxyethanol / water

- - - f ο -

Filmeigensc ha ften Direct impact (in.Ib.) Reverse impact (in.Ib.) Ericksen (mm) Flexibility (Durchra.in.) Hardness (pencil) Cure

160 160 50 160 160 10 > 9.0 > 9.0 2.0 1/8 1/8 11/32 3B B. H perfect

Spinning resin (I.CI. Spinner) on Bonderit 97T

1 09827/1622

Pilme-inherent dea amide ammonium salt of epoxidized talein-modified high 1.4-polybutadiene

Sea row no.

Maleic modified (M-polybutadiene

Numerical transit

son molecular weight

liikroBstuktur 1.2 *

cie 1.4 *

trans 1.4 * acid number (mg KOH / g)

Epoxidation

Peracetic acid (mol): BD (mol) polymer (g): solvent (g) epoxidation temperature ( ⁰ O) epoxidation time (hours) 570 / 10OA

Drying scheme (min / ° 0) Pilm thickness (mil) - 0.1 solvent 2700

15th

17th

68

192

4.0: 1.0

1: 5 40 ⁰ C 1 1/2

30/170 30/180 1.0 1.0 butoxyethanol / toluene / water ^ 7-8 - ^

Pilmelgensohhaften Direct impact (in.Ib.) Reverse impact (in.Ib.) Sricksen (mm)? Lexibility (diameter in. Hardness (pin) hardening

80

20th

5.0

8/32

40 10 5.4 11/32 2H perfect

Spinning Resin (I.C.I. Spinner) on Bonderit 97T.

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Claims (9)

Claims 1. A process for the production of water-soluble coating preparations by reacting homo- or copolymers of conjugated dienes with 1,4-configuration with compounds of a <X, ß-unsaturated dicarboxylic acid, characterized in that homo- or copolymers of diolefins whose diolefin units are at least 50 Have $ 1,4 configurations and have a molecular weight of 500 to 10,000, and a compound of an oC, ß-unsaturated dicarboxylic acid is used in such amounts that the end product 10 to 30? 6 of the, ß-unsaturated dicarboxylic acid chemically bonded contains, and the adduct obtained is converted into an ammonium or alkali salt. 2. The method according to claim 1, characterized in that that one as ot, ß-unsaturated dicarboxylic acid compound Maleic anhydride is used. 3. The method according to claim 1, characterized in that the diolefin polymer is polybutadiene with 75 to $ 85 1.4 configuration and average molecular weight used from 1,000 to 4,000. New Vn'aföffäj § / fg ² ^ ^{1 Sate3des} * "* ™" ■ ' ⁴ " ⁹ · ^r _ ₂ 8 - 4. The method according to one or more of the claims 1 to 3 »characterized in that the reaction is carried out in the presence of a solvent at a temperature of 150 to 240 ⁰ O. 5. The method according einem'oder more of claims 1 to 4, characterized in that one DAFL the adduct-treated before salt formation with air or oxygen at a temperature of 90 to 150 ⁰ C in the presence of customary oxidation catalysts. 6. The method according to one or more of the claims 1 to 4, characterized in that the reaction product is subjected to a hydroxylation / formoxylation reaction or performic acid at a temperature of 45 to 80 ⁰ O before sali formation. 7. Method according to one or more of the claims " 1 to 4, characterized in that the reaction product is epoxidized ^{at a temperature below 45 0 O with a peroxy acid before the salt formation.} 8. The method according to claim 7, characterized in that that 3? eressigaaure is used as peroxy acid 109827/1622 9. The method according to one or more of the claims 1 to 8, characterized in that the reaction product before the salt formation with an amino or Reacts hydroxyl group-bearing compound. 10982 7/1622