DE1570487A1 - Process for the preparation of non-gelling interpolymers - Google Patents

Description

concerning
Process for the preparation of non-gelling interpolymers.

The invention relates to a method of manufacture new interpolymer of an amide of an ethylenically unsaturated carboxylic acid, e.g. B. of acrylamide with other monomers that are thermosetting and thereby give hard, flexible and solvent-resistant coatings which have high gloss can have. These new copolymers or interpolymers (these terms are used here as synonyms) are particularly valuable for coating preparations in organic solvents, especially when mixed with in Solvent-soluble, thermosetting aminoplast resins, alone or in combination with oil-modified alkyd resins. The interpolymer can optionally by reaction with a Aldehyde can be alkylolated, but excellent properties were achieved without reaction with an aldehyde,

009809 / 169A

Etherified, alkylolated, acrylamide-based interpolymers have already been used as coating preparations in solutions in organic solvents. With the known Preparations was the alkylolation of the interpolymer for the cure was substantial and when the alkylolated interpolymer was made in the presence of acid it was extensive Terethering is essential for the storage stability of the preparation. Furthermore, the interpolymer was the only film-forming ingredient of the coating, it has usually not been possible to achieve a completely satisfactory combination of properties to achieve. Mixing with epoxy resins. was of some use, but the gloss of such deteriorated Resins with long-term use. Blending with amino resins or alkyd resins has also been of some use, however The poor tolerance resulted in many difficulties, such as pigment flocculation, color drift (color drift in the package) and loss of shine.

The interpolymer produced according to the invention is a non-gelling interpolymer made from:

(A) an amide of an ethylenically unsaturated carboxylic acid,

(B) at least one other polymerizable, ethylenically unsaturated material that is at least 20 wt .- ^ on the total weight of the unsaturated, polymerizable

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Materials "based, a mono-ethylenically unsaturated Ester component contains, wherein the terminal carbon chain of the ester is sufficiently long to, a to yield extensive internal softening and (C) an aliphatic, monoethylenically unsaturated, hydroxyl-containing monomer.

A proportion of an aliphatic, monoethylenically unsaturated carboxylic acid is preferably also included in the copolymer or interpolymer incorporated.

A rope of the amido hydrogen atoms in the interpolymer can go through the group

R.
- CHOIR ₁

be replaced, in which R is a hydrogen atom, a puryl radical or a saturated, aliphatic hydrocarbon radical with up to 10 carbon atoms and R ^ a hydrogen atom or an alkyl or alkoxyalkyl radical with up to 10 carbon atoms is. R is preferably a hydrogen atom and, if etherification is desired or permissible, results the etherifying alcohol an Ithergruppe, in the R .. a Is an alkyl radical of 3 Ms 8 carbon atoms.

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As will be seen in greater detail below, there is considerable variation in the nature and ratio of the Ethylenically unsaturated substances used, the aldehyde used as a modifier, the etherifying one The means and the extent of the etherification are permissible.

Acrylamide is the preferred unsaturated amide, but other acrylamide monomers such as methacrylamide can also be used and itaconic acid diamide. The use of amides of other unsaturated acids, such as maleic acid diamide, fumaric acid diamide, Sorbic acid amide and muconic acid diamide are less preferred. '■'. '

The acrylamide monomer is preferably used in Quantities from about 5 to about 45 percent by weight are particularly preferred from about 5 to about 30 percent by weight based on the total weight of the Mixed polymerization based, unsaturated material.

A second essential component is the aliphatic ^, unsaturated monomers containing hydroxyl groups. Preferred hydroxyl-containing monomers are 2-hydroxyethyl methacrylate and glycerol allyl ether, but these are only examples of this group, which also includes other hydroxyalkyl methacrylates and acrylates, such as 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and 2-hydroxyethyl acrylate, includes. ¥ other usable hydroxyl groups

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_ 5 -

containing monomers are ethylene glycol allyl ether and propylene glycol allyl ether , Butylene glycol allyl ether, diethylene glycol allyl ether, Irimethylolpropane allyl ether and 2-hydroxymethyl-5-. norbornene (the endoisomer or exoisomer, or mixtures thereof). Furthermore, allyl alcohol, methallyl alcohol, Grotyl alcohol and unsaturated fatty alcohols, which correspond to the fatty acids of drying oils, are used.

A! Peil of the hydroxyl-containing monomer can with be esterified to a drying oil or a fatty acid derived from such. Examples of this are in particular unsaturated substances such as dehydrated castor oil or the fatty acids derived from it.

To obtain a sufficient number of hydroxyl functions in the internal polymer for the curing mechanism to function effectively, the hydroxyl-containing monomer will normally be added in an amount of at least 2% by weight, preferably about 4% by weight, based on the total weight of the the copolymerization supplied, based ethylenically unsaturated monomers used Normally used no more than 25 wt -. ° / o and usually less than 15 parts by weight hydroxyl-fo monomer.

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Interpolymers, the copolymerized acrylamide and contain unsaturated hydroxyl-containing I-tonomer, result in cross-linked coatings during heat curing, that are au brittle. This brittleness is particularly evident and harmful if the interpolymer contains large proportions of styrene, yinyltoluene or I-ethyl methacrylate. Here "at result in products of little value.

It is therefore essential that the interpolymer at least about 20% by weight, preferably at least about 40% by weight, of one contains mono-ethylenically unsaturated ester, wherein the The end-hour carbon chain is so long that an extensive one inner softening is achieved. This will be best by using acrylic acid esters with allcanols that contain at least 2 carbon atoms and preferably with a proportion of acrylic acid ester in which the terminal carbon chain contains at least 6 carbon atoms. Ifen can also use methacrylic acid esters with 3 or more carbon atoms in the terminal carbon chain. Further you can maleic acid, fumaric acid or crotonic acid ester and -diester with alkanols, dig & at least 2 carbon atoms, preferably containing 2 to 20 carbon atoms, use e.g. B. dibutyl maleate and dxbutyl fumarate.

Appropriate are monomers such as styrene and vinyl toluene and / or methyl methacrylate, in the interpolymer

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present, the amount of which is normally below about 40 ^c ß>, • preferably below about 30 $ ".

Preferably, a smaller amount of an aliphatic, monoethylenically unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, Groton acid, 5 ¹ U mar acid, maleic acid or miileinic acid ethyiester, is also used, whereby the hardening is increased and so coatings of somewhat greater hardness and flexural strength are obtained. However, the presence of free carboxyl radicals in the interpolymer is not essential, since extremely hard, flexible and compatible polymers are obtained even in the absence of carboxyl functions.

The amount of aliphatic, monoethylenically unsaturated carboxylic acids is advantageously quite small, e.g. B. it is about 1 to about 15 wt .- ^, preferably about 2 to about 8 wt .-%.

For best results, use from about 2 to about 5% by weight of an acid such as acrylic or methacrylic acid.

The rest of the interpolymers can consist of a polymerizable, Ethylenically unsaturated material. Preferably

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ORiGiNAt INSPECTED

one uses monoethylenically unsaturated monomers, especially those which _{contain the group CH 2} = G ^. However, you can also use other Ä.thylenisch unsaturated material, e.g. B. an unsaturated polyester resin, as disclosed in the unpublished German patent application S 79 821 IVd / 39c.

One can use about $ 5 or more unsaturated polyester resin, containing about 0.005 to about 0.40 gmol of ethylenically unsaturated component ^.) per 100 g of polyester, use. In particular, polyesters are used in which the unsaturated groups are essentially in the side chains of the polyester molecule are located. Such is obtained z. B. by using a monoethylenically unsaturated, monofunctional Component, such as crotonic acid or allyl alcohol, in such an amount that about 0.03 to about 0.3 gmoles of unsaturated component 100 g of polyester are present.

Furthermore, other ethylenically unsaturated substances can be present, such as acrylonitrile, vinyl acetate, vinyl stearate, Butene-1, butene-2, unsaturated fatty acids, ζ. Β. Fatty acids from dehydrated castor oil, 1,3-butadiene and n-butyl vinyl ether.

The interpolymers are preferably prepared by a 1-stage solution copolymerization, in which case

0Q9809 / 169 *

Dissolve the monomers in an organic solvent, which is also a solvent for the interpolymer being formed and the interpolymerization is carried out in the presence of a polymerization catalyst which yields free radicals, wherein normally uses elevated temperatures to accelerate the reaction,

Usually one brings the amido hydrogen atoms of the unsaturated amide component, z. B. the acrylamide monomer, does not react in the interpolymer. However, an alkylolation can also be carried out by reaction with a monoaldehyde carry out. This can be done in a 1-stage solution copolymerization take place, as described in more detail in the unpublished German patent application S 78 864 IVd / 39 c is.

Therefore, if one wishes to carry out an alkylolation, become, in the presence of an organic solvent, the aldehyde, an acrylamide and the others, ethylenic unsaturated substances with each other using heat and in the presence of a basic catalyst and a free radical polymerization catalyst brought to reaction, wherein the polymerization and Alkylolation take place simultaneously.

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- ίο -

The alkaline catalyst is for the 1-stage reaction essential under alkylolation, since in its absence unusable, insoluble, gelled substances are obtained.

To avoid gelling, use at least about 0.1 wt .-% alkaline catalyst, based on the weight of the Copolymerization supplied monomers based, essential. On the other hand, it is preferable to use a maximum of etsia 1.0 Weight .- $ alkaline catalyst, since the larger amounts Products obtained harden slowly and are less suitable.

Han can use any alkaline compound, preferred but those that contain nitrogen bases »amines and tertiary amines are particularly preferred. Inorganic, alkaline compounds, e.g. B. alkali hydroxides or alkaline earth hydroxides can be used, but these are less preferred as they add impurities to the resinous product bring in. Ammonia and quaternary ammonium compounds, such as tetramethylaminoniuiahydroxyde · Also, are quite suitable you can use amines such as ethylamine and butylamine. However, tertiary amines such as iriethylamine and fripropylamine are used and tributylamine, particularly preferred. The degree of etherification can be done by changing the amount of alkaline used. Catalyst can be changed and controlled

1694

In the presence of an alcohol and under continuous Water removal, e.g. B. with refluxing boiling connected with azeotropic distillation, etherification and some of the methylol groups in the alkylolated one take place at the same time Product can optionally be etherified.

The aldehyde optionally used as a modifier is expediently in an amount of about 0.2 to about 5 equivalents of aldehyde, preferably from about 1 to about 2 equivalents of aldehyde for each in making the acrylamide interpolymer used amido group used. Formaldehyde is preferred as the aldehyde, but others can be used Monoaldehydes, such as acetaldehyde, propionaldehyde, butyraldehyde and furfural or aldehyde-producing substances, such as araformaldehyde, hexamethylenetetramine or trioxyraethylene, also use.

The etherification of the Araid interpolymer modified by an aldehyde can be carried out, but is this is not essential. Preferably, lower alcohols with up to 10 carbon atoms are used for teretherification, especially butanol. You can get up to $ 100's in the interpolymer etherify any alkylol residues present, but prefer a partial etherification. The degree of teretherification becomes easy by the amount of the alkaline catalyst and the

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remote water controlled. ¥ ith a etherification of below 100 fo reached, the product is a mixture wherein the amido Wasserstoffatoae in some Iloleläiien of acrylamide interpolymers by the group -ROH and Amidowasserstoffatome in other molecules of the acrylamide interpolymers by the group -ROR ₁ are replaced, where R is a saturated aliphatic hydrocarbon _{radical derived from the aldehyde and R 1 is} the radical of the alcohol participating in the etherification.

Further aspects of the solution copolymerization, with or without alkylolation are the following:

Preferably the monomers are dissolved in the organic solvent and slowly and uniformly Speed, preferably by continuous addition, brought into the reaction vessel for a more precise Siwrung to allow reaction and a more uniform interpolymer to receive. The continuous addition of the monomer during the reaction also increases the temperature, more easily mastered, in spite of what normally occurs strongly exothermic reaction.

One can use chain terminators, such as mercaptans, which are known to average molecular weight humiliate.

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The choice of free radical polymerisation catalyst depends on the desired temperature of the polymerisation reaction away. The catalyst must be - merization conditions deliver free radicals, so the To catalyze addition polymerization.

You can therefore use copolymerization catalysts that generate free radicals even at low temperatures start delivering, e.g. B. at about 30 to about 50 ° G. Such Catalysts are, for example, acetylbenzoyl peroxide, peracetic acid, Hydroxybutyl peroxide, isopropyl percarbonate, cyclohexanone peroxide, Cyclohexyl peroxide, 2,4-dichlorobenzoyl peroxide and Oumol hydroperoxide.

Suitable catalysts that begin to deliver free radicals at slightly higher temperatures, for example at 60 ° G, are, for. B. t-butyl hydroperoxide, methyl amyl ketone peroxide, acetyl hydroperoxide, lauroyl peroxide, methyl cyclohexyl hydroperoxide, t-butyl permanent maleic acid, t-butyl perbenzoate, di-t-butyl diperphthalate, ΪΤ, ΙΤ ¹ -azodiisobutyronitrile and benzoyl peroxide.

Preference is given to using catalysts that are still at higher temperatures, around 100 ° C, free radicals too start delivering. Such are z. B. t-butyl perphthalic acid, p-Chlorobenzoyl peroxide, t-butyl peracetate, dibenzaldiperoxide and di-t-butyl peroxide,

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The type of in the solution copolymerization or as Solvent when applying the interpolation or such containing mixtures used solvent is not critical. Butanol, preferably in admixture with xylene, is a preferred solvent system, but the invention is not limited to certain solvents, as many others are available and can be used, such as toluene, methyl ethyl ketone, Methyl isobutyl ketone, acetone, butyl acetate, and also under the Tradename "Cellosolve" is known ethylene glycol monoethyl ether and the one under the trade name "Butyl-Cellosolve" known ethylene glycol monobutyl ether.

The interpolations that can be produced according to the invention can be used in particular in preparations for coatings which, when cured, produce very hard coatings that are resistant to spoilage, but are pliable and fairly impact-resistant despite their hardness. For this purpose, the interpolymers which can be prepared according to the invention, which cure strongly and have good compatibility, are used in combination with aminoplast resins, in particular thermosetting, solvent-soluble condensation products of a triazine with excess formaldehyde. As is known, solubility in solvents is usually achieved by etherification of the aminoplast resin with a C ₅ - Gg alcohol. preferably butanol. Many of the known Aerylamide interpolymers were compatible with at most 15 # of such condensation products, while those which can be prepared according to the invention are compatible

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Interpolate preferably about 20 % or more, Ms to about 70% of such condensation products, especially about 25 to 50%, based on the total weight of the interpolymer and the condensation product "ends.

The large group of thermosetting, solvent-soluble, aminoplast resins are well known; as an example, is called a typical, referred to as "triazine A", aminoplast resin as a solution of Benzoguanarain-iOrmaldehjrdharz 60 f * resin solids in a mixture of butanol and xylene in a ratio of 50: 50 is used wt .- $.

η The benzoguanamine-formaldehyde resin is a codensation product from 4 moles of formaldehyde with 1 mole of benzoguanamine, produced in Presence of excess butanol and an acidic one Catalyst ,. whereby a thermosetting resin is obtained which is esterified with butanol to achieve solubility in solvents. The solution of the benzoguanamine iOrmaldehyde resin has a Gardner-Holdt viscosity at 25 C of G-K.

If you want hard and flexible coatings and only a little less hardness is obtained, part of the Aisiiioplastharz.es is replaced by an oil-modified alkyd resin replaced. . .

The -öliBodified. Alkyd resin, and the aminoplast resin are GewShiiliph in a weight ratio of about 1: 4

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ORIGINAL IISISPECTID

to about 4: 1, preferably from about 1: 1.5 "to about 1.5: brought together and in a total amount of about 10 Ms about 70 wt .- $, preferably of about 20 Ms about 40 wt .- ^ on based on the total weight of the interpolymer, aminoplast resin and alkyd resin.

If alkyd resins were previously mixed with acrylamide interpolymers, the compatibility, in particular with oil-modified alkyd resins, was not satisfactory; that resulted in φ & aj? greater flexibility, but also a substantial deterioration in the hardness of the coating. This is in contrast to the results with the interpolymers which can be prepared according to the invention.

The term "oil-modified alkyd resin" is used herein in no broadest meaning used. Typical alkyd resins are well known and most of them are encompassed by the description below.

Alkyd resins ground through the intercondensation of a polyol, a polybasic acid and an unsaturated fatty acid manufactured. The alkyd resin chemistry is well known to those skilled in the art. The manufacture and physical properties of Alkyd resins have been described many times, e.g. See, for example, Henry Fleming Payne, "Organic Coating Technology", Vol. I, John Wiley and Sons, Inc., New York, 1954

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· ■ '■■ "- 17 -

Various polybasic acids can be used, e.g. B ₀ phthalic anhydride, isophthalic acid, succinic acid and 2,2,1-bicyclo-endo-ethylene-7-heptene-2,3-dlcarboxylic acid, phthalic anhydride is preferably used. Likewise, various types of polyols such as glycerol, trimethylolpropane, pentaerythritol, sorbitol and mannitol can be used, but glycerol and pentaerythritol are preferably used. The polyol can be a single compound or a mixture of several compounds and normally contains an average of about 2.5 to about 4> 5 hydroxyl groups per molecule, preferably about 3 hydroxyl groups per molecule.

For the preparation of the modified alkyd resins one can Use various unsaturated fatty acids, the fatty acids normally 'from a naturally occurring one vegetable or fish oil, such as linseed oil. Soybean oil, Tall oil, manhaden oil, lungol or castor oil.

Often, smaller amounts of additional ingredients are also used, such as maleic anhydride, dimerized or thickened fatty acids or saturated fatty acids are additionally used.

In general, the polybasic acid, the polyol and the fatty acid reacted with one another in such amounts that an about 5 to about 25 wt .- ^ iger excess of the Polyol is present. As an excess polyol you can use those

0098 0 9 / 16S4

Designate the amount of polyol which is present as an excess over the amount theoretically required for combination with the sum of the acidic groups in the fatty acid and the polybasic acid. Alkyd resins are appropriately referred to as short, oil-modified alkyd resins, medium-sized oil-modified alkyd hairs and long oil-modified alkyd resins, depending on the ratio of the fatty acid to the 2-base acid in the resin production. Long oil-modified alkyd resins are normally made by reacting about 3.1 to about 3.4 molar equivalents of polyol with about 2 molar equivalents of polycarboxylic acid and 1 molar equivalent of unsaturated fatty acid. To achieve a shorter "oil length", increasingly larger amounts of polycarboxylic acids and smaller amounts of unsaturated fatty acids are used. For example, short oil-modified alkyd resins can be produced by condensation of about 3.1 to about 3.4 molar equivalents of polyol with about 2.3 to about 2.5 molar equivalents of polycarboxylic acid and about 0.7 to about 0.5 molar equivalents of unsaturated fatty acid.

A vinyl monomer such as styrene or methyl methacrylate can be polymerized into the alkyd resin.

A typical, oil-modified, oil-modified thermosetting alkyd resin, hereinafter referred to as "oil-modified alkyd resin A", is represented by Heating a mixture of 34.1 parts by weight of dehydrated

Castor oil made with 11 parts of glycerine and 0.03 parts of lead oxide. The temperature is kept at 232 ° C. until 1 part of the product is soluble in 3 parts of methyl alcohol. After cooling to 193 ° C., 37.6 parts of phthalic anhydride, 3.1 parts of benzoic acid and 13.9 parts of glycerol are added, the mixture is heated to 216 ° and kept at this temperature until the Gardner-Holdt The viscosity at 25 ° G is about Z * - Zp and the product has an acid number of 3.0. .

The invention is explained in more detail with the aid of the following examples. In the description, examples and claims "parts" and "$" mean parts by weight and ^ by weight, if not, otherwise stated.

example 1

Using the weight ratios given in Table 1 below, a number of interpolymers were prepared manufactured. The interpolymers A, C, D, E and E ■ were prepared by solution copolymerization, as described below in relation to the preparation of the Interpoli ^ - inner A is described. Interpolymer B differs from Interpolymer Ά in that the acrylamide is mixed with formaldehyde was reacted so that there is essentially one amido hydrogen atom on each acrylamide radical in the copolymer Metliyloliert: was. Interpolymer B was like

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Interpolyraer Λ, with the difference that 0.15 $ triethylamine, based on the total amount of monomers, were used together with the peroxide catalysts, so that at the same time as the interpolymer is formed, the formaldehyde is mixed with it with methylolation of the acrylamide groups in reacted to the interpolymer.

Of the interpolymers listed in Table 1, interpolymer A contained acrylamide and glycerol allyl ethers as hydroxyl groups Interpolymer component and a small amount of methacrylic acid · Interpolymer B differed from that Interpolymer A only through the methylolation of the acrylamide groups. Interpolymer 0 differed from Interpolymer A in that the lack of methacrylic acid. Interpolymer D differed from Interpolymer A in the absence of acrylamide. Interpolymer E differed from the interpolymer A in that, instead of glycerol allyl ethers, an equivalent number Amount of 2-hydroxyethyl methacrylate containing hydroxyl groups was used. Interpolymer F differed from Interpolymer A in that glycerol allyl ethers had an approx equivalent amount of 2-hydroxymethyl-5-norbornene was replaced.

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T a la e 1 1 e 1

Components A. - B. 0 composition
polymer, (wt
DE 47 of the Inter-
.-Parts monomer
F. • Ethyl acrylate 47 47 47 47 24 47 Styrene 24 40 follow formaldehyde
solution in n-butanol 24- 24 24 12th 24 2-ethyl-hexyl-
acrylate 12th 12 ' 12th 12th 3 12th Egg s-methaeryl-
acid 3 3 3 9 3 Acrylamide 9 9 9 9 Grlycerin allyl
ether LPv VJI VJl Ul 10 2-hydoxyethyl
methacrylate 2-hydroxymethyl
5-north> ornen 10 20th

Properties of the finished interpolymer

Solids, fo 5I Viscosity (Gardner-Holdt) Z Color (Gardner-

Holdt) 2-3

50.1 50.6 53.0 50.3

2-3

Y Z

1-2

49.4

W-X

2-3

As an example of the preparation of the interpolymers A-F, the preparation of the interpolymer A ■ described:

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approach

Xylene 546 g

n-butanol 90 g

Allyl glycerol ether. 50 g

Acrylamide 90 g

2-ethoxyethanol 135 g

n-butanol 45 g

2-ethylhexyl acrylate 120 g

Ethyl acrylate 470 g

Styrene 240 g

Ice methacrylic acid 30 g

Di-tert-butyl peroxide 10 g

n-dodecyl nercaptan 6 g

Cumene hydroperoxide 5 g

Polymerization process

546 g xylene, 90 g butanol and 50 g glycerine allyl ether were placed in a reaction vessel with a stirrer, condenser, thermometer and nitrogen inlet tube.

The batch was heated to 124 "to 129.5 ° 0. 90 g of acrylamide were then dissolved in 135 g of 2-ethoxyethanol and 45 g of n-butanol. All other monomers and catalysts were added to this monomer mixture. The mixture of monomers and catalysts was added in the course of 2.5 hours at a temperature of 124 to 129.5 ° C. The mixture was kept at this temperature until the end of the reaction (5-6 hours) and then the reaction vessel

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Reaction product of such an amount of butanol added -EE- that there was obtained a $ 51> solids containing ib'sung.

The resins AF of the example were used in a synthetic resin paint containing 28% titanium dioxide and 32 % non-volatile resin. The pigmented resin solutions were placed in a ball mill to a ^M ahlgrad of 7 1/2 FS milled.

The synthetic resin paints were applied as a coating (drawdown) 0.076 mm thick on bare steel plates and these Oven cured for 20 minutes at 163 ° C.

The results obtained are shown in Tables 2 and 3:

Table 2

Interpolymer Solids 70 fo Triazine Resin A 15 $

oil-modified alkyd resin A 15 $>

Modified interpolymers

A B C D E

Gloss value

(Ehotovolt, 60 °) 92 91 89 90 92 90 Pencil hardness 2H-3H 2Η-3Ή 2HH 3H 3H Bending test (3 »2 best-best-best-best-best-best ~ best-existing mandrel) den den den den den

Impact resistance
, (Top; cm / kg
Impact (Forward),
Inch / pound

112 0 140 112 6 94 112 140 1 12th 20th 25th 20th 20th 25th 20th 0 098 9/1

Modified interpolymers

Consistency very much
good against spoilage

(DoIu olbe stood very much
age good

very very

good Good

very very

good Good

very very very

well well well

bad very very

good Good

Table 3

Interpolymer solids
iDriazine Resin A. B. 70 pounds
$ 30> C. 84
15th D. E. P. 112
20th 56
10 92 90 very
Well 91 92 90 ■ out
drawing
net out
draws A. 3H-4H Modified interpolymers 3H out
drawing
net 2H 4H 3H-4H out
drawing
net out
draws G-lanzwert
(Hiotovolt, 60 °) 94 best-best-
the the be stan-be stan-be stan
the the the Pencil hardness 3H-4H 112
20th 84
15th Bending test
(6.35 mm thorn) passed
the out
drawing
net mas
sig Impact resistant
speed (top)
cm / kg
Inches / pounds 84
15th out
drawing
net mas
sig Resistance ge
to doom out
drawing
net Toluene resistant
speed out
drawing
net

In the following examples the usage
various hydroxyl group-containing monomers for the production of methylated acrylamide interpolymers are shown:

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Example 2

There were interpolymers of those in Table 4 in parts by weight specified compositions made:

■ Table 4

Composition of the interpolymer Components A. Interpolytner C. (Parts by weight of monomer) Trimethylolpropane monoallyl ether 66 B. - 2-Hydro: xyethyl methacrylate - - - 2-hydroxymethyl-5-nor'bornen - 100 100 Ethyl acrylate 470 - 470 ' Styrene 240 470 240 2-ethylhexyl acrylate 120 240 120 Ice methacrylic acid 30th 120 30th Acrylamide 90 - 30 90 90

40 follow three? Ormaldehydlösung in n-

Butanol 190 190 190

The preparation of the interpolymers is shown using the preparation of interpolymer A of this example:

A reaction vessel with stirrer, condenser, thermometer, nitrogen inlet tube and a Dean-Stark water trap was with 545 g of xylene, 90 g of n-butanol and 66 g of trimethylolpropane monoallyl ether "Beschiokt. This approach was derived from 124 heated to 129.5 ° C. Then 90 g of acrylamide were dissolved in 135 g of 2-ethoxyethanol and 45 g of n-butanol. This one

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6 g of n-dodecyl mercaptan, 10 g of di-butyl peroxide and 5 g of gumol hydroperoxide were added to the monomer mixture. This mixture of monomers and catalysts was added to the reactor at 124 to 129.5 G over the course of 2.5 hours and this temperature was maintained for 5 to 6 hours until the reaction had ended. The reactor contents were cooled to 116 ° C. and 195 g of a 40% solution of formaldehyde in butanol were added. The contents of the reactor were then heated to refluxing for a further hour, 25 ml of water being distilled off, which were collected in the Dean-Stark water trap. That '.
cooled and filtered.

were caught. The product was then reduced to 82 g

The interpolymer resins A, B and G were in a synthetic resin varnish 28 ° / o of titanium dioxide and 32 ^r ß> containing non-volatile resin. The pigmented resin solutions were ball milled to a freeness of 7 1/2 IT. S. wed.

The synthetic resin varnish was applied as a coating 0.0 - 6 mm thick applied to bare steel plates and oven-hardened at 163 ° G for 20 minutes.

Testing of the interpolymers in this example gave the values listed in Tables 5 and 6:

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Table 5

Interpolation solids
Triazine resin A 70 ok
30 io B. 0 93 90 Modified InterOolymers 3H 2II-3H Glanzvrert (Hiotovoit, 60 °) Ά passed passed Pencil hardness 92 112 84 Bending test (6.35 mm mandrel) 3H 20th 15th Impact resistance (front),
cm / lcg passed
the out
draws out
draws Inches / pounds 112 out
draws out
draws Resistance to spoilage 20th Toluene resistance out
draws out
draws

lab rush 6

Interpolymer solids 70 $ triazine resin A 15 ° / °

Oil-modified alkyd resin A 15

Modified interpolymers

A. B. 0 90 92 92 2H 2H-3H 2H-3H passed passed
the passed 140
25th 140
25th HO
25th out
draws very much applies ■

Gla.nzvrert (Ehotovolt, 60 °) pencil hardness
Bending test (3.2 mm mandrel)

Impact strength (top), cm / kg

Inch / pound

Resistance to spoilage

Toluene resistance

excellent-excellent-excellent net net

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Example 3

A typical unsaturated ester for use in the present invention was prepared as follows:

A reaction basket with a thermometer, heating mantle, nitrogen inlet tube and stirrer was dehydrated with 400 g of glycerol monoallyl ether and 800 g of fatty acids Castor oil loaded,

) The mixture was heated to 204 ° C. and held at this temperature until the acid number was less than 2. The resulting ester contained unsaturated allyl groups and had the following properties:

Solids, fo 100

Acid number 1.9

The preparations of Examples 1 and 2 can be modified by removing a portion of the unsaturated ester Example 3 is also used, whereby products with increased flexural strength are obtained.

From the stated test results it can be seen that the Interpolymers that can be prepared according to the invention largely cure and extremely hard, solvent-resistant coatings result, which despite their hardness have good flexural strength and impact strength.

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Except for a very good compatibility with amino resins and oil-modified alkyl resins, to which already has been pointed out, the interpolymers that can be prepared according to the invention also have excellent compatibility with epoxy resins, z. B. polyglycidyl ethers of bivalent phenols, in particular Bisphenols, furthermore with urea-orraaldehyde resins and phenol-ormaldehyde condensation products on.

Patent claims

0098 09/169 k

Claims (1)

^ y \ sohwiiqehsthassb * BHJS.V.PECHMANN Γ \ 1 κΟίτοηχ »;; ^ J p 70 4 87 ATXWT II 30 1A-3O 802 Claims 1 Λ Process for the production of non-gelling interpolymers cBy Hischpolyraerisierung at least one amide one Ethylenically unsaturated carboxylic acid with other polymerizable ■ Ethylenically unsaturated material, characterized in that at least 20 wt # - $, on the Total weight of the unsaturated, polymerizable material "based, at least one monoethylenically unsaturated ester with a terminal carbon chain of such a length that a comprehensive internal calibration is achieved and at least one aliphatic, mono-ethylenically unsaturated, hydroxyl-containing Monomer is also used in the copolymerization. 2. The method according to claim 1, characterized in that that an acrylamide is used as the amide of an ethylenically unsaturated carboxylic acid. 3. The method according to claim 1 or 2, characterized in that the amide of an äthylenieoh unsaturated carboxylic acid in an amount of about 5 to about 45% by weight, preferably from about 5 to about 30% by weight the total weight of the unsaturated polymerizable material related, used. 009809/1694 157048 / 4. The method according to claim. 1 to 3, characterized in that a monomer component with a CHp = OCi group, preferably styrene, vinyltoluene or methyl methacrylate, ends with " 5c method according to claim 4 »characterized 5 that the monomer component in one Amount of less than 30 wt .- ^, based on the total weight of the unsaturated polymerizable material is used. 6. The method according to claim 1 to 5s, characterized in that about 1 to about 15 wt «, -? ^ Preferably about 2 to about 8 wt _e -? £, based on the total weight of the unsaturated polymerizable material ^ of a mono-ethylenically unsaturated carboxylic acid , preferably acrylic acid or methacrylic acid, also used » 7. The method according to claim 1 to 6, characterized in that the unsaturated ester component an acrylic acid ester of an alcohol with at least 2 carbon atoms, preferably a Gp ■ = · OpQ-Alkanol used « 8 _{β The} method according to claim 1 to T _9, characterized ₉ that the aliphatic ₉ monoethylenically unsaturated hydroxyl-containing monomer in an amount of about 2 to about 25 wt «-» ^ _9, preferably from about 4 to about 15 % w / w based on the total weight of the unsaturated polymerizable material is used. 9. The method according to claim 1 to 8, characterized in that the aliphatic, monoethylene unsaturated, hydroxyl-containing monomer 2-hydroxyethyl methacrylate or glycerol allyl ether is used. 10. The method according to claim 1 to 9> characterized in that as a proportion of the aliphatic, mono-ethylenically unsaturated, hydroxyl-containing monomers such as those used with a drying oil or a fatty acid derived from such is esterified. 11. The method according to claim 1 to 10, characterized in that g e k e η η, that one amido hydrogen atoms through the group R.
-GHOR ₁ replaced, in which R is a hydrogen atom, a puryl radical or a saturated, aliphatic hydrocarbon radical with up to to 10 carbon atoms and R ^ is a hydrogen atom or a Al] cyl or alkoxyalkyl radical with up to 10 carbon atoms is. 009809/1694 1570-87 .12. Process according to Claims 2 to 11, characterized in that the amido groups are treated with formaldehyde to react. 13. Thermosetting resin preparation containing a solution of an interpolymer in an organic solvent, characterized in that - «em the interpolymer da, s product of a process according to claims 1 to 12 14. Resin preparation according to claim 13 »characterized in that also in the organic solvent an aminoplast resin, preferably a thermosetting condensation product of a triazine with excess formaldehyde, is solved ο 15 · Resin preparation according to claim 14 »characterized in that the aminoplast resin in an amount of at least about 20% by weight based on the total weight of the interpolymer and aminoplast resin. 16. Resin preparation according to claim 14 or 15 »thereby characterized in that in the organic solvent an oil-modified alkyd resin is also dissolved. 80 9/1694 ORIGINAL INSPECTED