DE1720511A1 - Copolymers containing hydroxyl groups - Google Patents

Description

.ji.r: ■ Jr-finduri} - · he meet i ", niahij ^ -elated, in solvents löalio-'Θ, hyriroy.yl _e ; rupOenl'altige j..iacli ^ ol.yr ;; erisate so ".vie whose "<'- j £':, 'h-ilX \ m ^. Jnr) b630nfJere concerns the Tirfj.ndunf. the I.isoL ~'; ol7r: erLr; f.rtiori of r.ionofi.- thyleni-soh. unsaturated dicarbon— / ^; ■■ ifvjij, irjH especially from luii: j.rsä.ure and 1 taconsätire in one: c>. ■: ·. ·: ii.i.:; ::? ion LöyungrjKiJ! - tel, in which these acids are poorly soluble j · '·.''> na _t

: ono "I; .v / le" ü Liioh un ^ enflt ti _t c, te DionrbonH Acids, in particular: · u.: -i r :. ^: l'iv <> ήη. i L: ioonr;? - i.ure,! '(inside nor'iii.'il prove nut ia ^ f.tjfijj. fs η; (; η / τ; η in. i. iciinolymo γ · .ι: ; β te, which by gaps''•"i-, i (jf! · <-' luniidn HH rderi, einvtirle ι \> l werrJen, B; ie;" - '■' Ι // eil fii ο nifii. ; jtr-.n Viriy l / i'onoüieron see ·; -uL in the

109827/1601

the polymerization are soluble in common solvents and in it quickly inischoolyrnerize, whereas the in! 'rage .1: imitative Dicarboxylic acids only have such a low solubility

in have that a larger proportion / susoenyion that may be present

is present and not available for the interpolymerization stands. For this reason, the polymerizate obtained as a product contains hardly any polymerized dicarboxylic acids, i.e. only a few percent to a maximum of about 10 Oe \ v.-f <, also when much larger proportions of the monomeric dicarboxylic acids were used.

Is there a dicarboxylic acid anhydride k.S. Calcium anhydride, the anhydride has a much greater solubility in organic solvents and can therefore be copolymerized will. However, the production of satisfactory hydroxyl derivatives of anhydride ·! ', Ischrjolymerisaten not easy. Even if you have a powerful process n used, contains the 1-isch polymer obtained as product only one hydroxyl group per anhydride group.

Of course, the mixed polymerisation does not need to be in solution perform, but have the copolymers that diu * ch Bulk polymerization or by polymerization in aqueous emulsion, generally a very high one Molecular weight and thus also a reduced solubility in solvents and a reduced reactivity

109827/1601

"keil, '.ve shall) she rait the products made in solution are not comparable.

ils . ', - i'Ot still other Iv-öglic >> ride to produce ay ^ ro ^ yl i.-isc'-'- polymers. Thus, R can, of I ο on car ton Saur s, 7 .. ¹ U. acrylic acid or "..ethacrylsäure in Γ cm: he t Fydroxylester as CUyäthylmethacryl3t, verv / forming, doc" is .ies ur.3tync. liCu, and r-an receives a (remembered network density than after veria'aren according to the invention. I can; iuo however, the method is etenialls expensive and the products have only limited compatibility with other ^{i'ilmbildenden% T} ar / .en, especially AcrylndsciiOclynerissten.

Thus, the invention concerns a rroblen., ·; ·:. £ riuf der ;, laughing area has long been considered difficult _c

According to the invention, the 1st ischpolymerisation is carried out in a solvent solution in the presence of dispersed, inonoätliyleniscli unsaturated dicarboxylic acid, which as the polymerisation proceeds by reaction with an I..0110- ·. epoxy under conditions that favor esterification, partly. is made soluble at elevated temperatures of at least about 93 ⁰ O and in the presence of an esterification analyzer.

109827/1601

The unsaturated dicarboxylic acid component is incorporated into the copolymer in lengths of 2 to 50, preferably in lengths of 5 to 30 ^ _1, based on the total weight of the polymerizable lionotneres.

All mono-ethylenically unsaturated dicarboxylic acids can be used, as these as a group have a very low solubility in organic polymerization solvents, with fumaric acid and itaconic acid being particularly poorly soluble are. The choice of the specific acid to be used depends partly from economic considerations, v / half ms η will mainly use the insoluble acid that is most readily available at the time.

The monoepoxide used is of secondary importance: one can use all lonoepoxides with an oxirane group (~ C -O-) use as the only functional group.

Suitable I.ionoepoxides are ethylene oxide, propylene oxide, butene-2-oxide, phenylglycidyl ether, isopropylglycidyl ether and ⁰ J tyroloxide. With the exception of ethylene oxide, it is stated in the literature that the hydroxyl groups that are formed by the reaction are mainly about rounder hydroxyl groups.

By reacting with the monooxide, all carboxyl groups that are used in the copolymer are preferably replaced ^; if l.ar .'line,

100627/1601 BADOWeiNAL

consumed, wa,: y but not absolutely necessary. Thus, at least 30 ^ι ; ά, preferably at least 90 ½ of the available carboxyl groups are converted into -)} _ y ester groups

vlbgleich the Liechpolymerisate according to the invention alone door for _"Jber2ii;: ast .3ir>; s, the j in an organic solvent -.- are elöct are useful, they are preferably susn.ihiiien iviit other film-forming resins with functional" runpen,? ,, V> . 'Jar bo.cylgruppen, Oxirangruppen, Ke thylolgrup-Tien or amine groups, are used, which can react with the oxy groups formed in the plastic polymers coming in V, e jrao-t.

Particularly preferred are those containing hydroxyl groups I.-ischpolymerisate according to the invention with amino resins or polyepoxy resins or cured with a combination of these two types of resin.

Particularly good results are obtained when the hydroxyl-containing copolymers according to the invention are combined with aluminum resins and polyepoxy resins. Zv / used square; 40 to 90 parts by weight of hydra / .yl group-containing copolymers to b to 40 parts by weight of minop-resin and 5 to 50 parts of polyepoxydhar / .e.

I) i.e products like 'Jeri' invention are particularly promotional

109827/1601

BATH ORIGINAL

as coating compounds that harden to give shiny, very hard and scratch-resistant coatings, despite their hardness are flexible and sufficiently impact-resistant. For this purpose, the I.ischpolymerisate according to the invention, the very cure largely and have good compatibility, in combination with aminoplast resins, especially heat-curable, Solvent-soluble condensation products of a triazine with excess formaldehyde are used will. Well known, the solubility in solvents is usually by etherification of the aminoplast resin with a G-, - Co-alcohol, preferably butanol, achieved.

All resin-like epoxies can be used to cure the L'isohpolymerisate according to the invention or for modification their curing with aminoplast resins can be used. Preferably the polyepoxide is a polyglycidyl ether organic polyhydroxyl compound, especially a dihydric phenol. A bis-phenol is particularly preferred, like the diglycidyl ethers of 2,2'-bis- (p-hydroxyphenylpropane) with an average molecular weight of about 360 to about 7000. La3 polyepoxide improves flexibility and the ability to adhere to a metal substrate, with only a slight reduction in the hardness of the baked films entry. The hardness is partly due to the high proportion of unsaturated vinyl monomers in the copolymer and to .., Part on the high compatibility with amino resins as well

109827/1601

can be attributed to the excellent curing, which is due to the "interaction between aminoplast resin and llischpolyme" risat is obtained.

All ethylenically unsaturated substances which are copolymerizable with the unsaturated dicarboxylic acid can be used, in particular styrene, vinyl toluene and other vinyl aromatics, such as £ \ -L.ethylstyrene, and other ^ I """^ a *" alkyl styrenes, ^w i ^e isopropenyl that Dialkylstyrole as dimethylstyrene, and the ^T ialogenstyrole as Lonochlorstyrol and Lethylmethacrylat. Since the copolymer containing hydroxyl groups contains the esterifying i .'-onoe-noxydß, which results in internal plasticization, large proportions of these iv-onomers, which act as hardeners, can be used. The mixed polymers preferably also contain up to 45% by weight of acrylic esters and kethacrylic esters with 2 or more carbon atoms in the esterifying alcohol. Preferred ionomers of this type are ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and butyl methacrylate.

If the ethylenically unsaturated material is a lonomer, it preferably does not contain any functional groups, which can react with the oxirane group. on the other hand can the polymeric unsaturated compounds contain acidic or basic groups, as these?, u are inert,

109827/1601

to disturb. Thus, ⁰ ^ 5 or install more unsaturated polyester resins having 0.005 to 0.40 LCoI ethylenically unsaturated component per 100 grams of polyester can, in particular polyester, in which the unsaturation is substantially limited to the side chains in the polyester backbone. These polyesters are obtained, for example, when using monoethylenically unsaturated monofunctional components, such as crotonic acid or allyl alcohol, in amounts of from about 0.03 to 0.3 CoI per 100 grams of polyester. The unsaturated polyester resin can contain residues of functional carboxyl or hydroxyl groups. Each of these functional groups can be present in slight excess over the other.

The polymerizates according to the invention are best prepared by one-stage solution copolymerization, the ionomers (except for the dicarboxylic acid and the monoepoxide) being dissolved in an organic solvent which is also a solvent for the isclvnolymerisat formed} the copolymerization carried out in the presence of a free radical polymerization catalyst, normally elevated temperatures are used to accelerate the reaction. The dicarboxylic acid is dispersed in the solvent, preferably in finely divided form. The dicarboxylic acid can YIC ¹ leicM by stirring with about one to four times Gewie 'Usmenge a liquid or a!''^ Ep in lussifkeitsgeniiac

109827/16 01 BAO ORIGINAL

suspend a distribution. The resulting suspension is • sufficiently liquid so that they perform when Reaktionste ^..: can be easily suspended -'5raxur.

Preferably, the monomers are dissolved in the organic solvent ;, which is added to the Henktionsgefg'.ß slowly (at best by continuous addition of arc) at a uniform speed, so that an accurate control of the lie ¹ Jrtion is possible and a more uniform - "he ischpolymeres "! old will. The continuous addition of the monomers makes it easier to regulate the temperature during the conversion: the strongly exothermic reaction that normally occurs.

Chain terminators, e.g. lercaptans, can be used 7 / srien, which their known './effect, the average l.olekulargev / iolrfc to degrade, exercise.

¹ Ub all free radical-forming polymerization / atalyr-iutoren can be used, whereby the selection is determined by the ge // Um-JCh se polymerization temperature. It is important that the substance forms free radicals under the correct conditions of the polymerization , so that the addition r> facilitate olymeci.'rvtion, v / lrd. The question that comes into question F.'ata.lyrjatori'l-ifjiie int Lekanri ';, r: o that a detailed discussion is not requiredLLch ir; i,} ( Jie ^f 'ei :: games explain suitable ones

3 \ iu-i refuel.

BATH ORIGINAL

109827/1601

The specific nature of the organic solvents used for the solution copolymerization or for the application of the copolymers or the mixtures containing these copolymers in dissolved form is not critical. Butanol or 2-butoxyethanol, preferably in a mixture with xylene, is a "preferred solvent system, but the invention is not limited to particular solvents, since many others are also suitable, such as toluene, methyl isobutyl ketone , acetone, butyl acetate and 2-Äthojcyäthanol the organic solvents preferably used sinci ketones, alcohols or aromatic hydrocarbons, the volatility which a normal boiling range of about 104 -. corresponding to 149 ⁰ O is chosen so that it is not necessary, in which Response to maintaining excessive pressure.

It is usually desirable to keep the temperature above the normal boiling point of the reaction mixture: this pressure is about 2.1-3 »5 atmospheres, as a result of which the reaction medium is kept in the liquid phase. The pressure can be with Can be adjusted with the help of carbon dioxide, nitrogen or other inert gases.

It is used, an esterification catalyst, preferably j is a tertiary amine, a quaternary ammonium salt or an alkali metal salt of ^r. The preferred catalysts are sodium benzoate, benzyltrimethylammonium chloride and ^ ri-n-propylamine. the

109827/1601 ^BAD o * ^{i6! NAL}

"The amount of the catalyst can be above 0.5% by weight, based on the weight of the dicarboxylic acid * The esterification should be carried out at" temperatures of 104-149 ° ^P '.

The hydroxyl group-containing copolymers according to the invention can impart en ¹ Ii genschaft by incorporation of additional reactive groups, which are arranged along the polymeric fat and self-curing the polymer T, are prepared. These additional reactive groups are, for example, alkylolaric groups such as ethylolacrylamide or etherified tetbylolamide groups and epoxy groups such as the allyl glycidyl ether group. Self-curing copolymers containing hydroxyl groups with 2 to 7 ° ß> acrylamide have excellent heat-curability.

The presence of an alkaline catalyst is necessary in the preparation of the acrylamide copolymers given above in a single-stage solution mixture depolymerization, especially if the acrylamide is also to be reacted with an aldehyde such as l'Ormaldehyde. The alkaline catalyst, in particular a tertiary amine or an ammonium sal quaternrires ζ, is used as an esterification catalyst for the reaction between the lÄonoepoxyd and the acid and as a catalyst for the reaction between the aldehyde and the amide.

109827/1601

The invention is explained by means of the following examples tert, in which all parts and percentages refer to the Relate weight, unless otherwise stated:

example 1

A non-gelled, solvent-soluble hydroxyl group-containing The mixed polymer was produced as follows:

Composition of the batch (parts by weight)

130 fumaric acid

180 butylene oxide

454 ethyl acrylate

270 Hnyltoluene

700 xylene

33O 2-ethoxyethanol acetate

10 benzyltrimethylammonium chloride (60 ^ solution in water)

6.6 di-tert-butyl peroxide
2.2 benzoyl peroxide

Manufacturing process

In a reaction vessel equipped with stirrer, Stickstoffeiiileitungsrobr, thermometer and reflux condenser, 330 parts of 2-.Stho, \ were yäthanolacetat, ay 320 parts of xylene and 10 parts of benzyltrimethylammonium chloride (60 $ solution in _Wnsoer); eji'llt. In this usefulness I; I30 parts of diluted juinic acid

^r "^ BAD OhIQlHAL

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riispersiert, whereupon the contents of the reaction vessel were heated ^{to about 121 0 O.} After the temperature of 121 ° ^{C. had been} reached, 180 parts of thitylene oxide were poured into the reaction vessel over a period of 10 limits. In a separate "container were 454 ^rn rush Xthylacrylat, 270 parts of vinyl toluene, j, '>' 'rush di-tert .- ^ utylperoxyd and 2.2 parts ⁿ T:; s ^ oylpero .- :. yd vorgemisoirtt This premix. . r-: XV3 '.onoiereu and catalysts was over a period of - where / vei hours in the reaction vessel, the "■ eriiperatur to about 121 - 127 ⁰ C.. This ^m emperafcur was noc ¹ :.; Maintained for four hours until the T ^T ; \. <r / yn: ilunc of the I.ionomer had ended.

The lündeifvenscaaften of the hyuroxyl group containing Lischpoly- meris'its were as follows:

> est3ho "i '-. i e (percent) 49.4

Viscosity (Gardner) T

Color (Gardner-HoldO 3-4

(non-volatile
Acids) 1.5

Zuio anmen rseb zurif, d en An. ^c iat ^{r /} , e a ( parts by weight) ΊΊ lJufcy

BATH 109827/1 601

225 vinyl toluene

200 'ethyl acrylate
350 xylene
200 2-butoxyethanol
80 isopropyl alcohol

5 Benzyltrimethylaimnoniumchlorid (60 ° /> ige solution in water)

2.5 di-tert-butyl peroxide
2.5 benzoyl peroxide

Manufacturing method

In a Reaktionsgef9.fi with stirrer, nitrogen inlet tube, 'thermometer and reflux condenser, 100 parts of xylene, 75 parts of fumaric acid, 200 ^rr' rush 2-butoxyethanol and 5 parts of benzyltrimethylammonium chloride (βθ $ solution in water) was charged. In a separate vessel, 99 parts of butylene oxide, 225 ^ rush vinyltoluene, 200 ¹ Téhé Xthylacrylat, 2.5 parts and 2.5 parts Benzo.ylperox.yd of di-tert-butyl peroxide.. premixed. This premix of luonomeren and catalysts was added over a period of 2 1/2 hours into the reaction vessel, while the temperature was maintained at about 129-135 ⁰ ^. This temperature was held for a further two hours, after which 150 parts of xylene and 80 parts of isopropyl alcohol were added to adjust the viscosity. ,. ,

The final properties of the copolymer were as follows 1

109827/1601

- Λ'- _

1 es'CGtofi'e (percent) 48.4 "Viscosity (Gardner). X - Y 'Color (Gardner-Holdt) Acid number (volatile

Acids) 5.1

Example 3

Composition of the batch (parts by weight)

330 2-butoxyethanol 320 xylene 12 & fumaric acid

8, & benzyltrimethylammonium chloride (bO ^ ige solution in water)

270 styrene oxide

270 vinyl toluene

454 methyl acrylate

4.4 di-tert-butyl peroxide

4.4 benzoyl peroxide

200 xylene

130 Iaopropyl alcohol

Manufacturing method

'In a herniometer Heaktionsgefäß with stirrer, Hückflußkühler, ^ai and Stickstoi'feinleitungsrolir were 320 parts of xylene, 33Ο ^rn parts 2-butoxyethanol, 128 parts of fumaric acid and 8.8 parts of benzyltrimethylammonium uO ^ follow solution in Y / ater)'

109827/1601

filled. The mixture was ^{heated to about 132 0} O, whereupon 270 parts of styrene oxide were added. The mixture was then held for one hour at about 132 ⁰ G, followed started with the addition of the mixture of Xthylacrylat, vinyltoluene and peroxide in the reaction vessel} the addition took r.wei hours. The mixture was kept at 132-138 ⁰ O until an acid number of 14-16 was reached.

The final properties of the copolymer are as follows:

Pesticides (percent) 49.4

Viscosity (Gardner) KL
Acid number 15.3

Color (Gardner-Holdt) 3-4

Example 4 Composition of the batch (parts by weight)

3OO 2-butoxyethanol

290 xylene

116 fumaric acid

8.0 Benzyltrimethylammonium chloride (60 $ solution in water)

116 propylene oxide

349 vinyl toluene

309 ethyl acrylate

4 di-tert-butyl peroxide

4 benzoyl peroxide

250 "" yloi ^, 09827/1601 1 "" UM ".

50 isopropyl alcohol

^yT ei'at elun g swei se

In an autoclave having leader, thermometer and nitrogen inlet tube were ~ 290 parts xylene, 300 parts 2-butoxy ^rn ~ "ithrmol, 11 ο" rush fumaric acid and 1 part of "ßensyltrimethylamr.oniumchlorid (60 f ^ solution in ./asser) filled .
ilaoh displacing the air with nitrogen, the Ge was miscu to about 110 ⁰ ^ heated ^/ whereupon 116 parts of propylene oxide "But a period of were added zvrel hours to obtain a Stickstoifdruck was maintained from about 1.4 atm. The mixture was approximately one Hour "kept at about 1.32 ⁰ O, • 70 over r.-ii b the addition of the mixture of ethyl acrylate," vinyl toluene and peroxide in the reaction vessel was started "the Zagbe was over a period of ^ four hours at about
127 to I32 ⁰ O continued, whereupon the mixture was kept at the low temperature until an acid number of
Ii-18 was obtained.

The sin characteristics of the Kischpolymerisa ts were as follows}

Solids ("percent) 49.8
"iuu-kv.uhl 17.8

Viscosity (Gardner) Y

Card index fGurrlrier-Holdt,) ? - 3

10 9 8 2 7/1601

Investigation; of the hydroxyl group-containing polymerizates in coatings

Because of the nature of the hydroxyl-containing polymerizate resins Modifications are necessary, uni heat-treatable TSmailles to inherit.

Are obtained with different combinations of hydroxyl-Krupp eniialt strength IQ schpolymerisäten with epoxy resins and methylolated or butylated Lelaminharzen enamels with a wide B _e reaching of physical and Viderstandseigenschaiten.

Vie can be seen from the following approaches that yield higher proportions of I.elaminharz enamels ärte with greater ^TJ and chemical "resistance, but they are ^f .veni. £ he pliable.

The introduction of a proportion of epoxy resin leads to greater flexibility and balanced overall properties. The wide range of physical and chemical properties of the hydroxyl-containing copolymer systems enables the preparation of numerous desired coating solutions.

Example ^

The hydroxyl lip-containing copolymers according to the invention can with other resinous substances, such as

10 9 8 2 7/1601 BAD OWGJNAL

butylated l'.'elairdn and epoxy resins, are mixed, here compatible mixtures are obtained which "bein: Er - ']" - its.en to films with excellent physical properties, such as hardness, scratch resistance, Ci lan :, adhesive strength and '-de ^ samkeit, harden. The mixes are also opposite Solvents, greases, tires and detergents chemiseV .. resistant.

It was hergestelltί an enamel of the aforementioned ^m YPS ir.it following composition

32 fo Non-volatile resin
28 fo ^T itandioxyd

Zusamtr.ensetzung the nonvolatile Harnes 70 <fo IMischpolymerisat according to Example 2

15 $ butylated I-elamine-lomaldehyde resin (Note 1)

13 / ^ epoxy resin

(Note 2)

The enamel was made by grinding in the titanium dioxide pigment prepared in the solution of the copolymer according to Example 2 in an organic solvent. For grinding a ball mill was used with xylene added as needed.

(Note i) s The epoxy resin was essentially the diglycidyl

10 9827/1601 bad original

ether of 2,2'-bis (p - HydroxyphenylT) ropan) with a molecular weight of about 1000, an EOOxydequivalent weight of about 500 (grams per Bpoxide equivalent weight) and a snow? point from 55 - 75 ⁰ G.

(Note; 2) t The butylated Kelamin-formaldehyde resin was a thermosetting, solvent-soluble T.elamin-formaldehyde condensate that was etherified with jutanol to make it soluble in the solvent? it was used in a solution with 55 wt .- ^ resin solids, 25 $ butanol and 2 ' ^Λ < ° h xylene in Torrn. The melamine-formaldehyde was prepared by reacting 5 _f 5 mol I'ormaldehyd with 1 Hol I-ielamin in the heat in the presence of excess butanol and a small amount of an acid catalyst.

About 0.075 ir.m strong wet films were deposited on chromatbehandel te steel plates and baked for 20 minutes at about 163 ⁰ ^. · There were obtained the following results »

Pencil hardness 3H

Gloss reading
{Photovolt 60 °) 89

Very good scratch resistance

Shock resistance, forward

(Impact forward) greater sis 3O cm kg

flexibility

(Curving around a thorn)

(Flexibility, mandrel bend) less than about 3 »2 mm adhesive strength of a

second coating

(Recoat adhesion) very good

109827/1601

BATH ORIGINAL

The stain resistance, hardness, flexibility, Detergent, salt and abrasion resistance were much better than conventional alkyd-amine coatings.

The adhesive strength of a second coating (re-coat adhesion) was tested in an electric oven. It was! /. Inutes at about 153 ⁰ ^ baked about 20. One hour after the first bakeout, the panels were covered over a second quay. The enamel according to the present example, in which the copolymer containing hydroal groups from Example 2 was used, had excellent adhesive strength as a second coating.

The baked coatings produced according to the present example were extremely hard and glossy with excellent results "physical properties such as hardness, toughness, gloss, adhesive strength, flexibility and resistance to Discoloration with aging.

Example 6

An enamel was created, which is especially used as a cover for refrigerators, 7 / ash machines, tumble dryers and kitchen cupboards were made with the following compositionJ

32 fo non-volatile resin
28 f ' titanium dioxide

! 09827/1601 bathroom

~ 22 -

Composition of the non-volatile resin » ^J

65 i> copolymer according to example 4

15. $ epoxy resin (note 1, example 5)

20 ^ "butylated melamine-formaldehyde resin (Note 2, example 5)

Manufacturing process
135 titanium dioxide
68 Copolymer from Example 4

23 xylene

Milled in the ball mill, then adding "104 copolymer by B _e ispiel 4 59 epoxy resin of Anmerkμng 1

(50 ^ solution in 2-ethoxyethanol)

71 Butylated melamine-formaldehyde resin according to note

24 xylene
484 kg

There were thick films with a thickness of approximately 0.076 mm chromate steel plates coated and baked for 20 minutes at about 163 ⁰ G.

The following results were obtained »

Pencil hardness 3H - 4H

Glansswert

(Photovolt 60 °) 90

Very good scratch resistance

109827/1601.

'Shock resistance, forward flexibility

(Bend around a mandrel)

Resistance to toluene

bigger than et we. 35 cm kg

less than 3 »2 only.

excellent

Example 7

The present example explains the production of Kisch— polymers that are inherent, i.e. in the absence of additional reactive resins such as amino resins or epoxy resins, are thermosetting. The copolymer of the present example contained 6 wt .- ^ acrylamide and 13 Ge = v .- # Dihydroxyfurarate.

Production method 48O parts of xylene
28 ^ "butanol 80"

80 "

8th "

Fumaric acid propylene oxide

55

Benzyltrimethylammonium chloride (60 # solution in water)

Paraformaldehyde Pour into the autoclave equipped with a stirrer, thermometer and nitrogen inlet tube. Heat compartment displacing the air with nitrogen to about 116-121 ⁰ O, maintaining about 2.8 atmospheres nitrogen pressure.

552 parts of styrene, 412 ^fl ethylacrylate enforce 73 "Acrylamide-blend of monomers and catalysts over a period of up to 60 minutes at about 121 -.132 ⁰ C and pressure to about j, set 8 atmospheres to about 2.1.

_f 224 "butanol

«Xylene 109827/1601

2 parts of triethylamine

5.6 "di ~ tert-butyl peroxide

4.8 "cumene hydroperoxide

4 "azobisisobutyric acid nitrile

4.8 "eenzoyl peroxide

7 "tert" -dodecyl mercaptan

9 "cumene hydroperoxide Three parts each according to 1, 2 and

Add 3 hours. When the addition is complete, continue to heat until the L monomers are implemented and the desired acid is reached. The total "reaction time is 7 1/2 hours.

The sand properties of the copolymer were like

Solids (percent) 51.7
Viscosity (Gardner) 7,
Color (Gardner) 1-2

Acid number. 15 »1

An enamel for electric devices was produced, which was ground in a ball mill. The enamel would have following composition?

32 $> non-volatile resin according to Example 7 28 i> titanium dioxide

Thick films with a thickness of about 0.07 -

109827/1601 bath

• Ruf chromate-treated '31; dial plates on painted and 15 --i ~ Grooves "at about 177 °" healed. 13s were the following results e rlial t s:

"Pencil hard

)O

"J fjoss strength, forward flexibility

X.71 ο IL e 31 · ϊ η d i fjl <"e i t

3 y

90

from ge: · -. ei chnet greater than 35 cm kg less than 3 »2 rcm excellent

As shown by the above results, this has hydroxyl groups: Vil ' _u i; e Polyijierisat excellent self-curing properties »

- Patent claims ~

109827/1601

Claims (5)

-, 26 ~ claims: 1. A process for the preparation of non-gelled, solvent-soluble, hydroxyl-containing copolymers of at least one ethylenically unsaturated I-onorr.eren and a monoethylenically unsaturated dicarboxylic acid, characterized in that an organic solvent, d? .3 the ethylenically unsaturated monomer in solution and contains the monoethylenically unsaturated dicarboxylic acid, which is poorly soluble in the solvent, in the form of discrete particles in amounts of 2 to 50 wt elevated temperatures under "conditions in which a catalyzed esterification reaction between the acid and a monoepoxide is favored, in the presence of a free radical forming polymerization catalyst and an organic conoepoxide containing an oxirane group as the only functional group, for conversion brings the organic Konoepoxyd in a. There is an amount sufficient to convert at least 30 % of the available carboxyl groups of the acid into hydroxyl ester groups. 109827/1601 2. The method according to claim 1, characterized in that rnnri d: the reaction in the presence of an esterification catalyst and. at "temperatures of at least 93 ⁰ ^,? .3" at 121 to 13i " ⁰ O. 3. The method according to claim 2 ", characterized in that a tertiary amine, a qua ternary it Arjrüoniuiüsal" or an alkali metal is used as the esterification catalyst? in I narrow of Tinoescens 0,:. Wt .- ^, based on crack dish of the dicarboxylic acid, used. 4. The method according to claim 1 to 3, characterized in that there is used as the monoethylenically unsaturated dicarboxylic acid Fumaric acid or itaconic acid or a mixture of these acids is used. 5. The method according to claim 4, characterized in that the mixed polymer 5 to 30% by weight of fumaric acid - is composed. j. Method according to claims 1 to 5, characterized in that that as Ilonoepoxide Kthylenoxyd, Propylenoxyd, 33uten-2-0-X.yd, Phenyl glycidyl ether, isopropyl glycidyl ether or Styrene oxide used. ItD 109827/1601 7. Veri their according to Ansi:>ruc.> 1 Ms 6, characterized in that the "iso polymer :: - u 20 Ms 4 '?.% Sue an acrylic or j-eths.crylester with at least two carbon atoms in the esterifying group and the rust of the hiscimolymeris? t & essentially -au3 an aromatic I i.onovinyl compound or ι ethylr ethacrylate "consists. ^^ 8. Procedure n :. c r -Anspruc'i ^ 1 "to 7, characterized jTekennzeichnet, daP the I ^ onoepoxyri used in steering '.vird sufficient Uni least ° -0 ^C, O of the \ ^r erfügoaren Carooxylgruppen in the Sy acid.? in "ydro_ \ ylestei-yruT: -pen ur.:3ivvandeln. 9, procedure ηεο> AnsOruch 1 "to 8, characterized in that that ir, ··! η as oiv. mix solvent a mixture of aromatic hydrocarbons and alcohols are used. a 10. The method according to claim 1 "to 9, characterized in that the organic solvent additionally a mono - ethylenically unsaturated amide, ζ. ¹ ?, an acrylamide, in! .. narrow from 2" to 7 wt.? ', "Based on the total weight of the polymerizable ilateriol, as well as an aldehyde such as formaldehyde, dissolved. 109827/1601 bad O-IS.N * L