DE2302186A1 - POLYMERIZABLE MATERIALS - Google Patents

Description

"Polymerizable Materials"

The present invention relates to improvements
regarding porymerizable materials and their manufacture and use. In particular, the invention relates to substantially monomeric polymerizable materials which can be used as a component or as the sole component of a polymerizable composition or mass, such as, for example, 3. a surface coating compound, impregnating compound, lamination compound or adhesive compound or adhesive compound can be used.

Essentially monomeric polymerizable materials, which the acrylic or methacrylic part:

CHp - C (X) GO -

(wherein X is a hydrogen atom or a methyl group) are well known, examples of such
Materials have acrylic acid and methacrylic acid themselves,

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their esters, for example, methyl methacrylate or methyl metal acrylic acid ester, ethylene glycol dimetacrylate, trimethylolpropantriacrA ^ lat and hydroxyethyl acrylate and their unsubstituted. and N-substituted amides, such as rf.cryla.raid, Hetacrylamid, K-hydroxymethylacrylamide, rJ-butylmetacrylamide and N- (1,1-dimethyl-3-oxobutyl) acrylamide.

These materials can be polymerized or misclipolymerized using a free radical initiator (e.g. a peroxide) or by using an ionizing beam Ituig or exposed to ultraviolet light. However, some of the known acrylic or methacrylic monomers can be used in the form thin films by exposure to ultraviolet light or through Ionizing radiation can be readily and effectively polymerized alone, its use being due to factors such as volatility, viscosity and cost can be further restricted. The amides are also at room temperatures present in the solid state and have only limited solubility in many of the solvents, monomers and polymers or compatibility with these solvents, monomers and polymers, which in the formulation of Surface coatings, impregnating agents, laminating agents or Adhesives or adhesives are commonly used.

In order to overcome the disadvantages of these known acrylic monomers, it has been common practice to use the monomeric acrylic acid esters or methacrylic acid esters in conjunction with polymers (which may or may not be unsaturated). For example, the simple alkyl acrylates or alkyl acrylic acid esters or methacrylates or methacrylic acid esters polymerize sufficiently quickly, - ^ rerai they are exposed to an ultraviolet light or an ionization beam, unless they have a portion of the dissolved polymer, such a solution for use according to the conventional Process can then be too viscous. The triacrylates of trivalent Aiko-

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polymerize hole, etv / as faster, but they are weak Solvents, so that it is difficult to formulate products from them which have the necessary equilibrium or application properties or attachment characteristics, Have film properties and costs.

It has now been found that essentially monomeric porymerizable materials which are generally liquids at temperatures of 15-3O ° C and can be porymerized thermally or by exposure to ultraviolet light or aev high-energy radiation can be produced by in one or more stages (A) acrylamide or methacrylamide, (B) at least 1.5 Hol per mole of acrylamide or methacrylamide, of formaldehyde and (c) a hydroxyl group-containing component which has one or more hydroxyl group-containing compounds which have a have up to four primary or secondary hydroxyl groups per molecule, at least one of the hydroxyl group-containing compounds being a monoacrylate or monometacrylate of a diprimary diol, disecondary diol or a primary-secondary diol.

When calculating the proportions or ratios in which A, B and C are to be used, it is assumed that not more than two moles of formaldehyde can be reacted with every mole of acrylamide or methacrylamide. If more than two moles of formaldehyde are used, the excess beyond two boils is not taken into account when calculating the amount of C. The component G containing hydroxyl groups should therefore be used in an amount which is equivalent to that of formaldehyde when this is used in an amount of 1.5 to 2 parts per mole of acrylamide or methacrylamide, if more than 2 moles of formaldehyde per mole Acrylamide or methacrylamide are used, two equivalents of C should be completed. The monoacrylate or conometacrylate in the

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Component C containing hydroxyl groups should be used in an amount of 0.1 to k mol per mole of acrylamide or methacrylamide. can be used when the average number of hydroxyl groups per molecule of the hydroxyl group-containing component is greater than 1, where k is the number of moles of formaldehyde used per mole of acrylamide or methacrylamide, ignoring any excess over 2 moles.

Accordingly, the present invention creates a polymerizable material which is formed by the reaction of the following components: (A) acrylamide or methacrylamide, (B) 1.5 to 2 moles per mole of acrylamide or methacrylamide or methacrylamide of formaldehyde; and (C) an amount which is equivalent to formaldehyde, or a hydroxyl group-containing component, which is one or more hydroxyl-containing monomers having one to four primary or secondary hydroxyl groups per molecule, at least one of the hydroxyl group-containing monomers is a monoacrylate or monometacrylate of a diprimary diol, disecondary diol or a primary-secondary diol, the monoacrylate or methacrylate being used in an amount of 0.1 to K moles per mole of acrylamide or methacrylamide, if the average number of hydroxyl groups per molecule of hydroxyl groups containing component is 1, and in an amount of 0.95 to k moles per mole of acrylamide or metacrlyamide when the average number of hydroxyl groups per molecule of the hydroxyl group-containing component is greater than 1, where k is the number of gram molecules of formaldehyde that per Mol of acrylamide or metacrlyamide has been reacted. .

The monoacrylate or monometacrylate or the monoacrylic acid ester or monometacrylic acid ester is preferably used in one

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Amount from 0.95 to 1 hol per mole of acrylamide or methacrylamide is used regardless of the average number of I-hydroxyl groups per molecule of the hydroxyl group-containing Component.

It is generally preferred that 1.9 to 2 gram molecules of formaldehyde be reacted per mole of acrylamide or methacrylamide, since it has been found that amounts of formaldehyde below this range can (depending on the nature of the hydroxyl group-containing component) into a product that contains excessive amounts of deposited solids that require either filtration (with attendant losses and increased costs) or redissolution of the precipitate by diluting the composition or mass with a solvent containing vinyl or Viiiylidene groups, such as styrene or a Acrylate or methacrylate ester or an acrylic acid ester or a metacrylic acid ester ¹ . While it is possible to use such a solvent diluent in the compositions of the present invention, it is often preferred not to do so.

If desired, 2 moles of formaldehyde per mole of acrylamide or To implement metacrylamide, the reaction of the components can be carried out in practice by a minor Excess of Formaldelryd used beyond this amount is because, as mentioned above, only 2 moles of the formaldehyde are converted per mole of the amide. The use of a small one Excess formaldehyde, such as 2.1-2.2 moles of formaldehyde per mole of acrylamide or methacrylamide, tends to to accelerate implementation, with the cost of material losses generally being negligible.

As mentioned above, the hydroxyl group-containing component (c) a mixture of hydroxyl groups

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Compounds and are thus considered to have two components (C ¹ ), a monoacrylate or ilonometaaylate or a monoacrylic acid ester or monometacrylic acid ester of a diprimary diol, a disecondary diol or a primary-secondary diol, and (D) monomers containing one or more hydroxyl groups ( other than the said monoacrylate or monometacrylate or the said monoacrylic acid ester or monometacrylic acid ester) which contain one to four primary or secondary hydroxyl groups, where η is the average number of hydroxyl groups per molecule in component (D) and then those according to the invention. Materials derived from the reaction of components (A), (B), ic ¹ ) and (D) in the following ratio: A, 1 mole; B, Ic mol, c ¹ , χ mol; and D, (kx) / n moles; wherein k is 1.5-2, χ 0.5-1 when η is 1, and 0.95-1 when η is greater than 1. In a preferred embodiment according to the invention, η = 3, lc = 2 and χ = 1.

In the following description, general reference is made to the materials according to the invention and their preparation, in which the component (C) containing hydroxyl groups has two components _t namely the monoacrylate or monometacrylate or the monoacrylic acid ester and the monometacrylic acid ester (C ¹ ) and the other compound or other compounds (D) containing a hydroxyl group or some hydroxyl groups. It can be seen that the following discussion applies in general ^{to the compositions in which components (c) consist only of (C 1} ), the monoacrylate or monometacrylate or the monoacrylic acid ester or monometacrylic acid ester.

While not wishing to be limited by theoretical considerations, it is believed that the Implementation according to the invention, which for the formation of the polymerizable monomeric materials than in several

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Stages taking place v / he looks at the can. It is thus believed that in the first stage the amide reacts with the formaldehyde (in one or two substages) to give a dimethylolated amide or, if less than 2 moles of formaldehyde per mole of amide have been used, a mixture of monomethylolated and dimethylolated amides according to the reaction scheme:

2CH ₂ O

= CX. CO NH,

CH _n O

CH ₀ O

; H _o = CX. COII (CH ₀ OH),

= CX. COIJH. CH ₂ OH

In the second stage of the process, the dimethylolated Amide presumably etherified with the hydroxyl-containing components C and D. These etherifications One- or two-stage maturities can also be considered, as shown below:

CH ₀ = CX.CCUH (CH ₂ OH ^ + R.OH *> CH ₂ = CX.CO.N.CHgOH

H ₂ OR

nCH ₂ = CX. CO. K. CH ₂ OII
CH ₀ OR

+ R »(OH) η

- ^ PJ (O CH ₀ NiCO.CX = CH ₉ ) n

CH ₀ = CX.CO.NH.CH ₀ OH + ROH

CH ₀ -CX. CO.NH. CH ₀ OR

nCH _o - CX.CCInLCH ₂ OH + Ii '

Ιϊ (0 CH ₂ .NH.CO.CX = CH ₂ )

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23Q21S6

"Wherein Il the reads the acrj ^ lat- or lietaci ^ latlcomponente C and. R ¹ - the remainder of the other hydroxyl-containing compound D is.

From the above, it can be seen that the reaction product does not have a single compound and can actually be a mixture of all possible products which result from the free alternation of R and 'R * in the formulas overleaf, the proportions of R and IV can only be determined by the proportions of the starting materials C and D.

It is also evident that the process can be carried out in one stage (as is generally preferred for economic reasons) or in several stages. For example, some of the formaldehyde can be introduced as a preformed formaldehyde of the hydroxyl-containing compound D or as the N-methylolamide. It is also possible to form the intermediates ROCHpNH.CO.CX = CH ₂ or IV (OCII ₂ NH. CO.CX = CH ₂ ) and to react them with further formaldehyde or the components C ¹ or D.

The amount and nature of the ingredients that make up a Any particular material used in accordance with the invention will depend on the ultimate use of the material. In general, however, it can be said that products containing a large number of vinyl or vinylidene double bonds contained in the molecule that tend to cure faster and end products with a larger To give strength or rigidity than connections which have a smaller number of said double bonds contain. Similarly, compositions or There is a tendency for masses or materials with a relatively high content of long alkyl, alkenyl or alkoxy chains to be relatively soft and pliable, being as a result

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a high content of polar groups, e.g. through the use of of a polyalkylene glycol formed as the component C, the tendency arises, the resistance of the cured To lower the object against water. So it is clear that the purpose of a certain mass can be modified and selected by choosing the appropriate nature of the ingredients, in particular of the constituents ^! ") and (D), being the nature or quality of components (A) and (B) is specified. As mentioned above, component B is the formaldehyde in the form a paraformaldehyde is used, although, for example, an aqueous solution of foraaldeliyd can be used, although the use of this formaldehyde the elimination of the additional water by distillation would.

Examples of the component (C ¹⁾ "that is, the monoacrylate or Moiiometacrylats or the Monoacrylsäureesters or Monometacryl-Sclureesters containing hydroxyl groups include hydro xyäthylacrylat, Hydroxyäthylmet at acrylic, 2-Hydrox3 ^r propyl acrylate, 2-H \ 'droxyprop3'-lmetacrylat , 3-hydroxypropyl acrylate, S-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydro-; ybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl metacylate, 3-hydrox3 ^r butylacr3 ^r lat, 3-H> ^r dro3 ^ 1metacrylate, 3-Hydro} ry-2-meth3-propylacr3> aat, 3-H3>-droxy-2-methylprc> pyl-methacrylate, 2-hydrox3 ^ octyl acrylate, 2-hydroxyoct3 "methacrylate, 3-oxa -5-Hydro2iypent3'-Iacrylate and 3-Thia-5-hydroxypentylmetacr3 ^r lat. In general, the acrylates or acrylic acid esters are preferred over the oil acrylates or methacrylic acid esters, whereby it is often preferred to use compounds which contain primary efydroxy groups, instead of those which contain secondary hydroxyl groups, there are the former the latter actually react or be implemented faster than the latter.

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The hydroxyl group-containing compounds (D). preferably have melting points below about 25 ° C, but compounds with melting points above 25 ° C can be used in admixture with those having melting points below 25 ° C, provided that the whole mixture melts below about 25 ° C. Unless the melting point of the component (D) is below about 25 ⁰ C, thus the products exhibit airgemeinen the tendency of existing as Peststoffe or contain a solid in suspension, a dilution of the composition or mass with a solvent required is, the VinyΙο contains the vinylidene groups, or, if the solid is in suspension, it is necessary to remove the suspended solids by filtration. It should be noted, however, that both trimethylolpropane and pentaerythritol, which have melting points above 25 ° C., result in products which do not have the above deficiencies. A wide variety of hydroxyl group-containing compounds can be used as the component (D), and they can be suitably divided into five classes, namely monovalent compounds, divalent compounds, trivalent compounds, tetravalent compounds and mixtures of various compounds. The various classes and examples thereof are discussed below.

Monovalent connections

1a. Aliphatic monohydric primary or secondary alcohols of the general formula C _jn H _{2 1} OH in which m is from about 4 to 12. Alcohols with m = 2 or 3 can be used, but their volatility requires the use of special preparatory work which is bothersome and relatively costly. Typical examples of suitable aliphatic monohydric alcohols are n-butanol, isobutynol, n-pentanol,

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n-ethanol, 2-ethylhexanol, 3,5 »5-trimethylhexane-1-oil and n-decanol.

Tb. Cyclic alcohols such as cyclohexanol, the methylcyclohesanols, the dimethylcyclohexanoIe, benzyl alcohol and 2-phenylethanol.

1c. Aliphatic nonoxine-saturated primary and secondary monohydric alcohols of the general formula CH-, ₁ CH in which m '3 Ms is about 13, me for example allyl alcohol, methallyl alcohol, indec-10-en-1-oil and oleyl alcohol.

1d. Unsaturated fatty alcohols such as linoleyl alcohol and linoleyl alcohol.

1e. Hydroxyalkyl esters of saturated or unsaturated aliphatic monocarboxylic acids and hydroxyalkyl esters of the general type R ¹ OOC. R * ". COOR ³ where 00CR ² COO is the radical of an aliphatic or alycyclic

-1

Dicarboxylic acid, R is an alkyl or alkenyl group and Ii is a hydro: ^ alk3 ^r group, me ξ.3, ^ -hydroxybutypropionate, 2-hydroxyethyl oleate, 3-hydroxypropyl crotonate, n-butylhydroethyl maleate and n-amylhydroxyethyl tetrahydrophthalate.

£ 1. Monoailcyl- and Monoallcen ^ '- ether zsj / polyvalent alcohols, such as 3. 2-i \ thoxyethanol, 2-butoxyethanol, 2-allyloxypropan-1-ol, 3-0xs ~ pentan-1-oil and 3-oxa-heptan-i-ol.

1g. Dialq / 1 and Dialken ^^ läther trihydric alcohols and Trialkyl and trialkenyl ethers of tetravalent alcohols such as trimethylolpropane diallyl ether, pentaerythritol triallyl ether and pentaerythritol ether.

1h. The diesters of trihydric alcohols and the triesters

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four-word all; oho le with saturated or unsaturated aliphatic ororic acid, such as glycerol- dicrotonate, trimethylolpropanedicaprylate and pentaerythritol trioleate.

1i. , Alkyl and cycloalkyl esters of hydroxy acids such as e.g. a-Jithylliercylglycollat, - n-Butyllactat und Ciyclohe ^ lricinoleate.

Two valuable preludes

Aliphatic and acysyclic saturated and unsaturated dihydric primary or selamdary alcohols v / ie for example ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butaudioI, 2-butan-1, ^-1 I -dl oil and 2, 2-bis (4-Hydroxyc3 ^ clohe: iyl) -propane.

It should be noted here that many members of this class, containing more than about A carbon atoms, have melting points above about 25 ° C., but are used in admixture with other compounds, as described above, to obtain a mixture that melts below about 25 ° C.

2 B. Polyalkylene groups of the formula H (CCTI ₀ GIl) _m "GH

where P. 'is H or CH ₀ and m ¹ ' is at least 2 and preferably not more than 4, such as, for example, diethylene glycol, tri-ethylene glycol, dipropylene glycol and tripropylene glycol.

2c. 3-thia-pentane-1,5-diol.

2d. Monoesters of trihydric alcohols with saturated or unsaturated aliphatic carboxylic acids, such as, for example, 3. Glj'cei ^ lI -monocaproate, Glycer3 ^r l-1-monooleate, trimethylolpropaniiionocaprylate and tri.methylolätlianmoiiolinoleate.

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2e. Monoalkyl and Monoalkenjrlethei ¹ trihydric alcohols such as Glyceryl-1-allyl ether, Trimethylolpropanallyläthei ·, Trirnethyloläthanmonooleyläther, Glyceryl-1 -hexylather and 1-Metho;: \ biatan _2-f 3-diol.

2f. Di (hydroxyalkyl) esters of dicarboxylic acids me ζ. 3.

Di- (hydroxypropyl) -i taconate, di- (hydroxyethyl) -maleate and di- (Hydroxybut3 ^r l) -adipate. This class contains compounds of the structure:

C00 (CH ₂ -CHP ^ O) _a ii

_a i

T? ²

C00 (GH ₀ GIm ⁵ O) _K H

ο
where H "is the hydrocarbon portion of the carboxylic acid

/ ι c;

is, Ii ^r and K ^ H or GH "and (a. + b_) is approximately in the range of 4-20. Such compounds are expediently prepared by reacting the dicarboxylic acid with ethylene oxide and / or propylene oxide.

A typical example is the reaction product of

A "5 itaconic acid and propylene oxide, where R and Yr are CH ₃ , R

CH ₀ = C -CH ₀ and (a + b) are about 5. 2 j, 2 - -

2g. The dialkyl and dialkenyl ethers of tetravalent alcohols, such as pentaerythritol diallyl ether.

2h. The diesters of tetravalent alcohols with saturated or unsaturated aliphatic carboxylic acids such as erythritol di-2-ethylhexoate and pentaerythritol dilinoleate.

Trivalent connections

3ά · Aliphatic trivalent primary or secondary alcohols,

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such as glycerine, the butantrile, the hexantrile and trimethylolpropane.

3b. Monoesters of tetravalent alcohols with saturated or saturated aliphatic carboxylic acids. Most of these have melting points above about 25 ° C and are best used as mixtures as described above.

3c. Monoalkyl and monoallcenyl ethers of tetravalent alcohols. Most of them have melting points above about 25 ° C and are used as mixtures, as described above, best used.

Four-valued connections

4. Most of the commercially available tetravalent alcohols have melting points above about 25 ° C, with the exception of diglycerin, although notwithstanding its high Melting point pentaerythritol gives liquid products. In general, it is preferred to use these materials to be used in the form of mixtures.

Mixtures

Mixtures of the compounds containing hydroxyl groups can for economic reasons or should be used because it is desirable to use compounds which, when used alone, Solid material certificates have been obtained.

Typical mixtures used for economic reasons are the fatty alcohols obtained from the Mixed acids are produced that occur in natural oils and fat (e.g. the so-called palm kernel alcohols) the products of alcoholysis of soybean oil with

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Trimethylolpropane) 'and the mixture of partial esters, formed by the esterification of a polyhydric alcohol with less than the stüchimometric Equivalent of a carboxylic acid or a mixture of carboxylic acids.

Tj ^ i see compounds with melting points above about 25 ° C which tends to give solid products or products which are high in solids contained in suspension are n-tetradecanol, heopentyl glycol and glycdrin monopalmitate. These are in the form of mixtures, such as aesiuimolar Mixtures of n-tetradecanol with n-octanol, keopentyl glycol and diethylene glycol and glycerol monopalmitate with glycerol monolinoleate added, all of which these mixtures produce acceptable yields of liquid products result.

The reaction between components (α), (3), (c) and (d) can, as mentioned above, be carried out in one or more stages. If the components to be condensed contain vinyl or vinylidene unsaturation (ie in all cases with the exception of the stage of a multistage process which relates to the condensation of B with a non-vinyl or non-vinylidene component (D)), it is necessary to carry out the reaction in the presence of a free radical polymerization inhibitor, such as hydroquinone to prevent any significant amount from polymerizing during the condensation and to ensure that the product is essentially monomeric. As further precautionary measures to prevent premature polymerization and to prevent discoloration, the reaction is expediently carried out under an atmosphere of an inert gas, such as nitrogen.

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The materials can be easily produced by simply adding components (A), (3), (C) and (D) into the desired Amounts "in the presence of a free radical polymerization inhibitor at a temperature and such Pressure are heated together that the water of reaction is distilled freely from the mixture. Thus, the reaction can expediently at a temperature of about 1 30 C at atmospheric or slightly sub-atmospheric pressure.

An expedient process for the practical implementation of the method according to the invention is carried out as follows: using a reaction vessel fitted with a stirrer, thermometer and a Dean and Starks separator is provided.

A quantity of an inert solvent such as, for example, toluene, is introduced into the reaction vessel together with components (C ¹ ) and (D), whereupon the mixture is heated to about 30 ° C. and at this temperature component (A) is added. The temperature of the mixture is then increased to about 90 ^° C., component (b) being added in the form of paraformaldehyde. The temperature of the reaction mixture is then increased until the evolution of water begins, the reaction mixture being kept under reflux until no further water is collected in the Dean and Starks separator; this point is usually reached before the temperature of the reaction mixture exceeds 145 ° C. Reduced pressure is then applied to the flask and the inert solvent is distilled off, the material according to the invention remaining as distillation residue, which is then removed and cooled. If the remainder contains solids in suspension, this can either be removed by filtration or dissolved by adding a solvent that contains vinyl or vinylidene unsaturation.

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The inert solvent preferred for use in the methods described above is toluene, as it enables the reflux at a temperature which causes in the presence of a suitable inhibitor no premature polymerization, and therefore, since it is easily removed by vacuum distillation τιηά a generally is a satisfactory solvent for the real-life participants and the products. But it can also use other inert solvents, such as z.3. Xylene used v / earth. If the component (d) is not miscible with water, substantially, the result is an azeotrope with water which can be distilled at about 9O ° C to about 140 ⁰ C and in the amount used, the elimination of substantially all water of reaction at a Reaction temperature below 145 ° C allows, whereupon component (D). itself can be used as a reaction solvent. In general, in such a case, component (D) is used in excess and the excess is subsequently eliminated. An example of such a component (D) is n-butanol. *

As mentioned above, the polymerizable according to the invention Materials can be used as constituents of polymerizable compositions or masses, such as Varnishes, laminating agents, impregnating agents and adhesives, preferably being the only or main ones Form part of such masses. However, in order to give the masses the optimal application properties, the materials according to the invention can be achieved by adding monomers which have vinyl or vinylidene unsaturation contain, diluted or thickened by adding polymer materials (either saturated or unsaturated) a. known kind are dissolved in it. If it is desired to produce a colored product, the mass can be made with conventional Additives to obtain paints or printing inks are colored. The masses that the

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- 1

according to.Materialien can be thermal or by irradiation with ultraviolet light or by ionizing
Radiation to be cured. If the mass is thermal
is to be cured, it can contain a free radical initiator such as peroxide or the conditions of use can be provided so that the
Composition or mass with a free radial initiator before curing, for example by pretreatment
of the substrate in contact with the free radical initiator
comes. Shall the masses or compositions through
If ultraviolet light is to be heard, they must be e'ein
Contain ultraviolet sensitizer. If the compositions or masses are to be cured with ionizing radiation such as, for example, an electron beam, then there is no
Initiator or sensitizer required.

For a better understanding of the invention, the following examples are given for the purpose of illustration. In the examples, the system used contained a multi-necked flask which was heated by an electric jacket and fitted with a stirrer, a nitrogen inlet, and a
Reaction gas immersed thermometer and a Dean and Starks separator was provided, which was connected to a water-cooled condenser. After the reaction was carried out, the Dean and Stark separator was replaced by a distillation device and a recipient that was equipped with a
Vacuum pump was in communication.

example 1

37 ml of toluene, 0.2 g of hydroquinone and 1 mole of n-butanol were placed in the reaction flask and heated to 80 ° C, whereupon one mole of hydroxyethyl acrylate or acrylic acid ester was added

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mirde. The temperature was again increased to 8O ⁰ C, wherein 1 mole of acrylamide was added. The temperature was then increased to 90 ° C., with 2.13 mol of formaldehyde in the form of Pa3? A £ ormaldehyde being added to the mixture. The mixture was then heated to reflux, the reaction water being removed by rapidly flowing toluene back over the separator. As soon as the temperature of the reaction mixture reached 140 C, the formation of water stopped. The process solvent (toluene) was then removed by vacuum distillation at a Boschickimgs temperature below 140G. The product remaining in the flask was cooled and then filtered. The filtrate was a composition or mass according to the invention in the form of a clear liquid with a viscosity of 0.3 stoles at 25 ° C.

Example 2

The procedure of Example 1 was repeated by 1 mol of 3,5 »5-trimethylhexanol-1 instead of the n-butanol was used. The product was a clear liquid with a viscosity of 0.6 Stok at 25 ° C.

Examples 3, 4 and 5

The procedure of Example 1 was repeated, the n-butanol by 1 mole of 3-oxy-heptanol-i, 1 mole of Oleyl alcohol and 1 mole of cyclohexanol was replaced. In each case the product was a clear, oily liquid.

Example 6

The procedure of Example 1 was repeated, wherein the n-butanol was replaced by n-decanol. The product was a clear oily liquid which separated some solid on standing.

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Example 7

The procedure of Example 1 was repeated, the hydroxyethyl acrylate or the ilydroxjö.thylacryläureestei ^{1 being} replaced by one mole of hydroxyethyl methacrylate or * Hydroxyäthylmet acrylic acid ester. The product was a clear oily liquid.

Example 3

In this example, component D is hydroxyethyl acetylate or Hydroxyätliylacryläureester and with component C identical.

37 ml of toluene, 0.2 g of hydroquinone and 2 mol of hydroxyethyl acrylate or hydroxyethyl acrylic acid ester were introduced into the reaction flask and ^{heated to 30 °} C., 1 mol of acrylamide being added at this temperature. The temperature was increased to 90 ° G , with 2.13 Hol of formaldehyde in the form of paraformaldehyde was added to the mixture. The temperature vivLTde for reflux increased, the üest of the procedure as in Example 1 was carried out. The product was a clear liquid with a viscosity of 1 stole at 25 ° C

Example 9

Example 8 was repeated, dev except that 1 Hol methacrylamide was used instead of Ac ^ lamids. The product was a clear oily liquid.

Example 10

The reaction flask was filled with 60 ml of toluene, 0.3 g of itydroquinone and 1 mole of ethylene glycol charged and heated to üO ° C, whereupon

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2 moles of hydroxyethyl acrylate or hydroxyethyl acrylic acid ester given me the. The mixture was heated again to CO ⁰ C, with 2 mol of acrylamide being added. The temperature was then increased to 90 ^° C., with 4.26 formaldehyde in the form of paraformaldehyde being added. The mixture was then heated to reflux, the procedure as in Example 1 being followed. Substantial amounts of solids were removed in the filtration step, however the filtrate was a clear, somewhat viscous liquid liquid.

Example 11

The reaction flask was charged with 75 ml of toluene, 0.45 g of hydroquinone and 1 pint of trimethylolpropane and ^{heated to 0} ° C., 3 poles of hydroxyethyl acrylate or hydroxyethyl acrylic acid ester being added. The temperature was increased again to i0 ^o C, with 3 mole of acrylamide were added. The temperature was then raised ax \ £ 90 ⁰ C, with 6.39 mol of formaldehyde was added in the form of paraformaldehyde, followed by the Whole-brought to an elevated temperature to reflux and the procedure as carried out in Example 1 to an end. The product was a clear liquid with a viscosity of 5 Stok at 25 ° C.

Example 12

The P.eaktionskolben was charged with 25 ml of toluene, 0.15 g of hydroquinone and 0.25 mol of pentaerythritol and heated to 80 ⁰ C, after which 1 mole of I-Iydroxyäthylacrylat or Hydroxyäthylacrylsäureester was added. After reheating to 80 ^° C., 1 mol of acrylamide was added. The mixture was then heated to 90 ° C., 2.13 Hols of formaldehyde were added in the form of paraformaldehyde, whereupon the whole was heated at an elevated temperature to achieve reflux τχ \ and the process as in Example 1 was carried out to the end. That

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Product was a clear liquid with a viscosity of 8.6 stoles at 25 ° C.

Example 13

a) Component D, a mixed ester containing an average of 2 primary hydroxyl groups per mole, was initially used follows prepared.

1 mole of trimethylolpropane was mixed with 1 mole of "acid 1093"

at 250 ° e under distillation conditions in a stream of nitrogen heated until the acid value of the mixture had dropped to less than 5 mgKOH / g. "Acid 1098" is a commercially available one Mixture of fatty acids with an average Chain length with about 9th carbon atoms, being mainly the acids with 3.9 and 10 carbon atom chain lengths are affected are. For 3s, the average molecular weight of the sample used was found to be 153 by alkali titration.

The misdiester obtained in this way probably had a medium one Molecular weight of 269 and a clearance of 2 primary Hydroxyl groups per mole.

b) The Kischester was used to produce one according to the invention Composition or mass used as follows.

The reaction flask was charged with 35 ml of toluene, 0.4 g of hydroquinone and 1 mol of the ester and heated to GO ⁰ C, wherein

2 moles of hydroxyethyl acrylate or hydroxyethyl acrylic acid ester were admitted. The mixture was reheated to 30 ° C with the addition of 2 moles of acrylamide. The mixture was then heated to 90 ° C., 4.2 mol of formaldehyde were added as paraformaldehyde and the whole was heated to reflux. The procedure was carried out according to Example 1 to the end. The product was a clear, somewhat viscous Cl.

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Example 1 <

Us is an example of the use of 1.5 hol formaldehyde per mole of acrylamide with: Hydro: -: yäthylacrylat bsw. H3 ^ cu? O3yäth3 ^r lacryl £; raireester as the zv / ei components G ¹ and D.

The ileation flask was sprayed with 20 ml of toluene, 0.17 g of hydroquinone and 1.5 pounds of hydroxyethyl acrylate or Hydrojcyäthylacrylsllureesterbielet and heated to GO C, wherein 1 mol of acrylamide was added. The mixture was heated to 90 ° C., 1.5 Hol of formaldehyde being added as paraformaldehyde and the geese then being heated to a higher temperature for reflux.3. The procedure was carried out as in Example 1 to end. The product was a clear somewhat viscous or viscous liquid.

Example 15

The procedure of Example 10 was repeated, wherein the ethylene glycol replaced by 1 mole of 3-thia-pentane-1,5-diol became. After the product was filtered to be free of deposited solids, it was a viscous one Cl.

Example 16

The procedure of Example 10 was repeated, wherein the ethylene glycol was replaced by a mixture of 1/3 mol of ethylene glycol, 1/3 mol of diethylene glycol and 1 / = mol of 1,3-propanediol Much solid has settled again, although the amount was significantly smaller than that in Example 10. To Upon filtration, the product was a thick or viscous oil.

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Example 17

The procedure of Example 8 was repeated by the hydroxyethyl acrylate or the hydroxyethyl acid ester by 2 moles of 4-hydroxybutyl acrylate or hydroxybutyl acrylic acid ester was replaced. The product was a clear oily liquid.

Example 18 The use of the two-step process.

The reaction flask was charged with 60 ml of toluene, 0.2 g of hydroquinone and 1 mol of hydroxyethyl acrylate or hydroxyethyl acrylic acid ester and ^{heated to 80 °} C., 1 mol of acrylamide being added. The mixture was heated to 90 ° C., 1.1 mol of formaldehyde being added as paraformaldehyde. The whole was then heated to reflux and at a higher temperature. held at reflux until no more water was distilled into the separator. The amount collected was about 1 mol. The mixture was then ^{cooled to 100 °} C., a further 1.1 mol of formaldehyde being added as paraformaldehyde together with butanol 1 mol plus 0.5 molar excess. The whole was heated again to a higher temperature for reflux, with 1 mole of water still being removed via the separator, the evolution of water having ceased and the temperature of the reaction mixture being 142.degree. The process solvent with the toluene and excess butanol was then removed by vacuum distillation, keeping the reaction mixture below 140 ° C. The product was filtered to obtain a clear oily liquid yield.

Hardening attempts

The above products have been used for curing purposes under various Conditions checked. Films of various thicknesses

309843/0758

were conventionally applied with a bar coater on various substrates such as glass, Tinplate, chipboard, aluminum and ABS plastic, wood Paper applied.

Electron beam curing was tested by passing the coated substrate through an atmosphere containing no more than 1 % oxygen at a rate of 100 linear feet per minute below the solid of an electron gun operating with 5 mA beam current at 125 keV , the impact material at a speed of 90 m.rad / sec. was treated. Passage through the beam under these conditions resulted in the coating at a dose of 4.7 m.rad. recorded.

Films, which varied in their thickness from about 5 microns to 40 microns and were applied to glass, tinplate, aluminum, ABS and chipboard and the unchanged products of BeispMe 1,2,3,5,7,3,9,10, 11, 12, 14, 15, 16, 17, 13 were all cured after one pass. Films from about 10 microns to about 40 microns thick containing the products of Examples 4 and 13 and the filtered suspension of Example 6 took two passes through the jet to achieve curing.

The curing in ultraviolet light was tested by applying films of the products with 5 percent by weight of a Ultraviolet sensitizer to the radiation from a Philips HTQ high pressure mercury lamp were exposed, which was provided with 'an elliptical reflector behind it. The ear was 3 inches long and calculated at 200 watts per linear inch. The distance from the lamp to the film was 1 inch. Different exposure times could be arranged with the help of a shutter, but doing so was difficult ■ was, exposure times that were less than 1 second,

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difficult to measure, although some films are obvious cured in less than 1 second. The sensitizer used was "Trigonal 14" (registered Trademark), which is believed to be a benzoin derivative. It was dissolved in the product before application to the support.

The products of Examples 1, 2, 6 (tilting suspension) 7, o, 9, 10, 11, 12, 13, 15 »16, 18 were tested in this way in the form of films with a thickness of 10-12 microns which applied to glass, tinplate, aluminum and ABS plastic. All products were after exposure fully cured in one second. The products of Examples 11 and 12 were less exposed to light cured than 1 second, but not the minimum time required with the method of the test used could be precisely determined.

A film 20 microns thick from a 5% solution of Trigonal 14 in the product of Example 11 on a glass plate when exposed to bright sunshine in the Cured in 40 minutes.

Example 19

A wood-filling mass was made by dispersing 32 sewing parts of micronized talc in a solution 5 parts of Trigonal 14 in 63 parts of the product of Example 11 were prepared. This mass was made using chipboard a ductor with a film thickness of 50 microns. The film was cured and, after exposure to the ultraviolet lamp, could be loaded or unloaded in the course of 5 seconds. be sent.

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- 71 -

20th

A printer ink carrier was made by dissolving 38 parts by weight of Santolite MHP (a commercially available toluene sulphonamide resin - Santolite is a registered trademark) in a mixture of the product of Example 3, 26 parts Arochlor 5460 (a polychlorinated polyphenyl - arochlor is a registered trademark) 17 parts and triethanolamine 1 part. Trigonal 14, 5 parts, was in the Color carrier dissolved, the whole then with 13 parts was colored by benzide yellow to obtain a printing ink. The paint was made using plastic printing paper printed on a pressure press. The imprints, their thickness was approximately 2 microns were cured by exposure to the ultraviolet lamp for 1 second. An otherwise similar color in which the product of Example 3 has been replaced by an inert solvent \? ar, could not cure under these conditions will.

Example 21

A clear wood varnish was obtained by dissolving 1.5 parts by weight of benzene peroxide in 93.5 parts of the product of the example 11 manufactured. The varnish was applied to smooth paranapine sheets with a film thickness of 20 microns. The coated panels were heated using a 2 kW infrared lamp placed 4 inches above the coated one Surface was arranged. The curing took place so rapidly that the film became brittle and numerous Defects or blisters appeared. It took 30 seconds to cure in the form of a satisfactory film, when the distance between the lamp and the film was increased by about 18 inches.

309848/0758

In a further series of tests relating to Examples to 23, the curing in ultraviolet light was tested by Films made from products with 5 percent by weight of Trigonal Ή exposed to radiation from a Haiiovia high pressure silver lamp that was calculated at 200 watts per linear inch and was 12 inches long and behind it with an elliptical reflector was provided.

The distance from the lamp to the film was 3 1/2 inches. Samples were placed under the lamp on a continuous conveyor at a speed of 200 Fu3 / min. guided. The change in the exposure time required to cure the film was achieved by moving the panel back.

Example 22

100 g of the suspension according to Example 6 were mixed with 50 g of a mixture of styrene and acrylic acid in a weight ratio of 1: 1 to obtain a clear solution, to which 5 percent by weight of Trigonal 14 were added. A film made from this varnish, which had been cured by the method described above, gave a hard film after an exposure of about 3/4 seconds.

A further 100 g of this suspension were mixed with 50 g of a mixture from styrene and hydroxyethyl acrylate or hydroxyethyl acrylic acid ester mixed with a weight ratio of 1: 1. The film made from this varnish was cured, whereby a hard film was obtained after exposure for about 1/2 second.

Example 23

The procedure of Example 1 was followed using

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the subsequent respondents repeated

Toluene 37 ml

Hydroquinone 0.2 gr

Hydroxyethyl acrylate 1 mole

Trimethylolpropane diallyl ether 0.3 mol

Methacrylamide 1 mole

Formaldehyde as paraformaldehyde 1 .3 mol

The product was a liquid that deposited some solids on standing. Filtration revealed a clear liquid to which 5 percent by weight of Trigonal 14 has been added. A film made from this varnish was cured under the ultraviolet lamp to form a flexible film in about 1/2 second.

Example 24
(Preparation of a component C)

c) 980 gr.Cardura E (the glycidyl ester of a sjmthetic Branch chain fatty acid - "Cardura" is a registered trademark) were heated to 135 ° C in a stream of nitrogen, 5 g of benzyldimethylamine (catalyst) and 2.8 g of hydroquinone (polymerization inhibitor) were added. Acrylic acid (32.8 g) was then added, at such a rate or introduced in such an amount that the temperature was kept at 135 ° C. Implementation continued, until the acid value of the mixture had dropped to 22 mg KOH / g. The product was a clear amber liquid with a viscosity of 1.95 Stok at 25 ° C.

b) 13 ml toluene, 26 ml of n-butanol and 0.1 g of hydroquinone were placed in a Jieaktionskolben and heated to 80 ⁰ C and a solution of a Hydroxyäquivalents

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Hydroxymonomer from (a) in 1 mol of n-butanol was added. The temperature was increased again to 30 ^° C., 1 mol of methacrylamide being added, whereupon the temperature was increased to 90 ° C. and 1.83 mol of formaldehyde in the form of paraformaldehyde was added to the mixture. The mixture was then heated to reflux, the water of reaction being removed by rapid reflux of toluene over the separator. The heating was stopped when a feed temperature of 140 ° C was reached. The process solvent (toluene and unreacted n-butanol) was then removed by vacuum distillation at a feed temperature below 140 ° C. The product remaining in the flask was cooled with 5 weight percent Trigonal 14 added to the product. A thin film of this solution was cured in the form of a flexible film under the ultraviolet lamp in about 1/4 seconds.

Example 25

37 ml of toluene, 0.2 g of hydroquinone, 1 mol of hydroxyethyl acrylate, 0.5 mol of n-butyl lactate and 0.25 mol of dipropylene glycol were placed in a reaction flask and heated to 80.degree. One mole of acrylamide was added, the temperature being increased to 90 ^° C. and 2.1 moles of formaldehyde in the form of paraformaldehyde being added to the mixture. The mixture was then heated to reflux, the water of reaction being removed by rapid reflux of toluene over the separator. Once the temperature of the reaction mixture reached 140oC, ■ listened to the water formation or deposition. The process solvent (toluene) was then removed by vacuum distillation at a feed temperature below 140 ° C. The product remaining in the flask was cooled and then filtered through a nylon gauze.

5 percent by weight of Trigonal 14 was added to the filtrate. A film made from this varnish was exposed under the ultraviolet

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lampe sum A hard film can be obtained in about i / 2o seconds hardened.

Example 26

The procedure of Example 25 was followed using the following. Materials repeated

Toluene 30 ml

Hydroquinone 0.1 g

Hydroxyethyl acrylate 1 mole

* Hydroxypropyl itaconate> 1 hydroxy equivalent

Acrylamide · 1 hol

Formaldehyde as paraformaldehyde 2.1 moles

- (a commercially available xm-pure material with a HydroxyI value of 410 mg ICOil / g).

The product was a clear liquid that was 5 percent by weight of Trigonal 14 were added. A film of the varnish became hard under the ultraviolet lamp Film cured in about 1/6 seconds.

Example 27 Manufacture of component D

a) A mixed portion of the ester of pentaerythritol was made from

Xylene 25 ml Pentaerythritol ' 1 mole Caprylic acid 1 mole Crotonic acid
manufactured. 1 mole

309848 / 07S8

The reactants were introduced into a reaction vessel which is provided with an agitator, a thermometer, a heating element and a Dean-Stark distillation system, whereupon they were heated to 225 ° C. The water of reaction was removed azeotropically. The reaction was continued at 225 ° C until an acid value of -3 mg KOH / g was achieved.

The product was a white, non-homogeneous suspension.

b) The procedure of Example 25 was followed using of the following materials repeatedly

; , - toluene 37 ml

Hydroquinone '0.2 σ

Hydroxyethyl acrylate 1 mole

From '(a) above, he ropes 1 hydroxy equivalent

Acrylamide 1 mole

Formaldehyde as paraformaldehyde 2.1 moles

The product was a clear liquid that was 5 percent by weight of Trigonal 14 were added. A film made from this varnish was placed under the ultraviolet lamp in the form of a hard film cured in about 1/4 seconds.

Example 28 Manufacture of component D

a.) A mixed part ester of pentaerythritol was made from

linseed oil 1 Mole Pentaerythritol o1 1 Mole Lead acetate G, 25 g manufactured.

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The linseed oil was introduced into an reaction vessel that was filled with a stirrer, a thermometer, a heater and with Nitrogen atmosphere was provided, wherein it was heated to 100 C. The pentaerythritol and lead acetate were added, whereupon the temperature was increased to 240.degree. This temperature was maintained until a mixture with a weight ratio of 3: 1 of an industrial methylated spirit and the reaction mixture is clear Solution at room temperature.

b) The procedure of Example 25 was followed using of the following materials repeated:

Toluene 37 ml

Hydroquinone 0.2 g

Hydroxyethyl acrylate 1 mole

Alcoholysis product v. Ex. 29 1 Hydroxy! Equivalent Acrylamide 1 mole

Formaldehyde as paraformaldehyde 2.1 moles

The product was a liquid in which some solid was deposited upon standing. The filtration gave a clear liquid to which 5 percent by weight of Trigonal 14 was added. A film made from this varnish was cured under the ultraviolet lamp in the form of a flexible film in about 1/1 3 seconds.

Patent claims

309848/0758

Claims (1)

P ate ή ta η s ρ r ii che 1. Polymerizable material, characterized in that it is prepared by reacting (A) acrylamide or methacrylamide, (B) 1.5-2 moles and preferably 1.9-2 moles per mole of acrylamide or methacrylamide of a formaldehyde and (c) an amount, -v Which is equivalent to the formaldehyde of a hydroxyl-containing component which has one or more hydroxyl-containing compounds which contain 1-4 primary or secondary hydroxyl groups per molecule, at least one of the hydroxyl-containing compounds being a monoacrylate or monometacrylate or monoacrylic acid ester or monometacrylic acid ester of a diprimary , .Disecondary or primary-secondary diol and the monoacrylate or monometacrylate or the monoacrylic acid ester or monometacrylic acid ester is used in an amount of 0.1 to k mol and preferably 0.95 to 1 mol per mole of acrylamide or methacrylamide, if the average number of hydroxyl groups is each Molecule of the hydroxyl group-containing component 1 and in an amount of 0.95 to k Mol and preferably 0.95 to 1 mol per mole of acrylamide or methacrylamide, if the average number of hydroxyl groups per molecule of the component containing hydroxyl groups is greater than 1 and where k_ is the number of molecules of the converted formaldehyde per mole of acrylamide or methacrylamide. 2. Polymeri si erable material according to claim 1, characterized in that the hydroxyl-containing component (c) has a mixture of hydroxyl-containing compounds which have two components, namely (C ^1- ) a monoacrylate or monometacrylate or a monoacrylic acid - 309848/0758 ~ j J ester or a Konometacrylsäureester a diprimary disecondary Odei ¹ pidmär-secondary diol, and (d) one or more hydroxyl-containing compounds (other than said monoacrylate or monomethacrylate) which contain primary an average of 3 or secondary hydroxyl groups per molecule, wherein the material from the reaction of components (A), (B), (C ¹ ) and (D) in a molar ratio of 1: 2: 2: 1/3 is derived. 3. Polymerizable material according to claim 1 or 2, characterized characterized that component (c) is a monoacrylate or /. a monoacrylic acid ester on v / eist, the primary Contains hydroxyl groups. 4. Polymerizable material according to one of the preceding Claims, characterized in that the hydroxyl groups containing compound (other than the monoacrylate or i-Toiiometacrylat) has a melting point Lint below 25 ° C. 5. Polymerizable material according to one of claims 1-3, characterized in that the component containing hydroxyl groups (other than the monoacrylate or monometacrylate) Trimethylolpropaii or Pentae ^ thritoi is. process for the production of a polymerizable material according to claim 1, characterized in that (A) acrylamide or let acryl amide, (B) at least 1.5 moles - per mole of acrylamide or methacrylamide - from formaldehyde and (C) a hydroxyl group containing component with one or more hydroxyl group-containing compounds, the 1-4 primary or contain secondary hydroxyl groups per molecule, are implemented in one or more stages, with at least one of the compounds containing hydroxyl groups is a monoacrylate or monometacrylate of a diprimary, 309848/0758 is disecondary or dipriinary — secondary diol and the component containing hydroxyl groups is used in an amount which is equivalent to formaldehyde up to 2 moles of formaldehyde, while the monoacrylate or mono · methacrylate is used in an amount from 0.1 to k_ moles per mole of methacrylamide, is used when the average number of hydroxyl groups per molecule of the component containing hydroxyl groups is one and in an amount of 0.95 to k moles per mole of acrylamide or methacrylamide, when the average number of Hydroxyl groups per T-Io 1 eic "Jl dei: HydrüX3 ^r lgiuppe.-a-containing component is greater than 1, and where k_ is the number of converted formaldehyde molecules per mole of acrylamide or methacrylamide. 7. The method according to claim 6, characterized in that components (A), (D) and (c) are heated in the desired amounts in the presence of a free radial polymerization inhibitor at such a temperature and pressure that the Meaktionswasser is distilled off free from the mixture, preferably at a temperature of about 130 ⁰ G, and preferably in the presence of an inert solvent such as toluene. G. Po ryineri erable material, characterized in that d.a3 it is produced by a method according to claim 6 or 7. 9. Polymer! Sable composition or mass, characterized in that that they are a polymerized material according to one of claims 1-0 or 1 < together with one or more saturated or unsaturated solvents / Has diluents or thickeners. the patent attorney 309848/0758