DE1081222B - Process for the production of polymerisation products based on unsaturated polyester resin compositions - Google Patents

Description

GERMAN

The preparation of polymerization products from monomeric polymerizable compounds and unsaturated polymerizable polyester resins are known. These polymerizable mixtures can optionally with the addition of fillers, fibers or fabrics, in particular made of glass, with the aid of radical-forming agents Catalysts processed into insoluble and infusible cast, pressed or laminated bodies will. The disadvantage here is that the surfaces exposed to the air are affected by the polymerisation-hindering Effect of atmospheric oxygen remain sticky and can be attacked by solvents.

It has therefore been proposed to use allyl alcohol etherified methylol compounds of urea and melamine to be used as a monomeric component which can be polymerized onto unsaturated polyester resins. Such Although polymerizable mixtures produce dry surfaces after curing, they have other disadvantages to have. Such is the surface of the polymerization products made from unsaturated polyester resins and dialyyl ether desdimethylolurea is not resistant to solvents and is also difficult to grind. In boiling The surface is strongly attacked by water. The products become cloudy and cracked and absorb a lot of water. Similar results are obtained if the corresponding ethers are used instead of methylolhariate allyl ethers used by methyl amines. Another disadvantage of the allyl ethers of methylolureas lies in their poor compatibility with the unsaturated polyester resins.

The subject of patent 1,067,210 is a process for the production of polymerization products on the basis of mixtures of unsaturated polyester resins and methylolureins which can be polymerized onto them and which are etherified with β, γ-aqueous saturated alcohols, with shaping. The etherified methylolureines used here are highly viscous or resinous condensation products of the methylolureines etherified with ^, ^ - unsaturated alcohols with themselves or with non-polymerizable compounds containing several hydroxyl and / or carboxyl groups, optionally in addition to conventional monomeric compounds for polymerizing.

It has now been found that instead of the highly viscous or resinous condensation products Methylolureine etherified with /S.y- unsaturated alcohols with non-polymerizable compounds containing several hydroxyl and / or carboxyl groups still soluble, from the etherified methylolureins or from these alone, optionally also together with non-polymerizable, several hydroxyl and / or carboxyl groups having compounds formed Condensates with polymerizable compounds containing several hydroxyl and / or carboxyl groups Method of manufacture

of polymerization products

on the basis of unsaturated

Polyester resin compounds

Addendum to patent 1,067,210

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Herbert Willersinn, Ludwigshafen / Rhine,

Dr. Hans Scheuermann,

Ludwigshafen / Rhein-Oggersheim,

and Dr. Alfred Woerner, Limburgerhof (Palatinate),

have been named as inventors

Polymix condensates obtained, optionally in addition to the usual monomeric compounds for polymerizing, can use.

The used monomeric ^ -unsaturated ethers of methylolurein contain the imidazolidone radical at least once in the molecule. They can be derived from glyoxalmonourein or glyoxyldiurein, where one or both hydrogen atoms linked to the glyoxal carbon atoms by aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic or heterocyclic radicals can be replaced. These primal ones contain at least one radical of an / S-unsaturated, bonded to nitrogen via an oxymethylene group Alcohol. Such radicals are preferably / 3-unsaturated Alkenyl or cycloalkenyl radicals, e.g. B. allyl, methallyl, crotyl, cyclohexenyl or cyclopentenyl radicals. If urines with several etherified methylol groups are used, the methylol groups can also be used be etherified with various unsaturated alcohols. You can also use methylol monoureins, their hydroxyl groups bonded to carbon atoms such as their methylol groups in the specified Are wise ethereal. The hydroxyl groups contained in the methylolureins can also partially through etherified saturated aliphatic or cycloaliphatic, heterocyclic or aromatic hydroxy compounds

009 508/436

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be. Particularly favorable connections of this kind are to be pursued. Connections can also be used

the tetraallyl ether of tetramethylolglyoxaldiurein, which have at least one carboxyl group and less Dialryl ether of tetramethylolglyoxaldiurein or contain at least one hydroxyl group in the molecule,

of Dimethylolglyoxaldirueins, the triallyl ethers of the tri- These monomers or too low molecular weight resinous

methylolglyoxaldiureins, the monobutyldialryl ether of the 5-like compounds condensed / ^ - unsaturated

Trimethylolglyoxaldiureins, also the diallyl ether of the ether, are now with polymerizable compounds

Dimethylol glyoxal monourein. with several hydroxyl and / or carboxyl groups in the

Suitable low molecular weight homopolycondensation molecule condenses. These include, for example, maleic products from / S-unsaturated ethers of methyloleic acid, fumaric acid, itaconic acid, citraconic acid, aconiteins are, for example, those in which several urine residues are io acid, muconic acid or dimerized methacrylic acid, via methylene or methylene ether bridges branched unlinked. They can be obtained by the saturated polyesters of different degrees of condensation reaction of the urines with formaldehyde and one with terminal carboxyl and / or hydroxyl groups. S-unsaturated alcohol under such conditions. These unsaturated polyesters can be carried out in a conventional manner in which, with elimination of 15 by polycondensation of the abovementioned α-unge-water or alcohol, higher molecular weight products are preferred to desaturated dicarboxylic acids with polybasic ones. This can be achieved, for example, by wisely producing dihydric alcohols. Ge-etherification and condensation at a ρκ value suitable polyhydric alcohols are, for example: ethylene glycol, between about 1 and 4 in the presence of the alcohol and 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, butane from about S to 20% water, based on alcohol, through 2 ° diol-1,4, hexanediol-1,6, 2,2'-dimethylpropanediol-1,3, can be fed. But it is also possible to first produce the ten-2-diol-1,4, glycerol, trimethylolpropane, pentaerymonomers / 5-unsaturated ethers of methylolureine thrite, diethylene glycol, triethylene glycol, cyclohexane and then to produce these at increased tem- diol-1,4, Terephthalic alcohol or ethoxylated dihydroxy temperature, preferably in the presence of acidic cataly- phenylalkanes. In the unsaturated polyesters, a capacitors and 10 to 20% water can be used to polycondense. 35 Part of the α-unsaturated dicarboxylic acids are not replaced by the most favorable reaction temperatures between polymerizable dicarboxylic acids. As can geeig-40 and 180 ⁰ C. The condensation catalysts designated dicarboxylic acids are, for example, are suitable: Bernsteinalle strong acids or their acid salts using acid, glutaric acid, adipic acid, pimelic acid, Sebazinfinden. The condensation reaction must be acid, suberic, ct-methylglutaric acid, oxadibutter, so that products are formed that have a viscosity of 30 acid, sulfondibutyric acid, phthalic acid, isophthalic acid, about 100 to 200 DIN seconds in DIN cup No. 4 terephthalic acid, dihydrophthalic acid, Tetrahydrophthalic. Furthermore, the methylolureine or their acid, endomethylenetetrahydrophthalic acid, hexachloro-low molecular weight homopolycondensation products, in addition to endomethylenetetrahydrophthalic acid, tetrachlorophthalmit / ^ - unsaturated alcohols can be etherified with di- or polyacid, phenylenediacetic acid or the various cyclo-hydric dicarboxylic acids and higher hexadecarboxylic acids.

molecular compounds be condensed. The is contained in the polymerizable mixtures

it is possible to use the methylolureine simultaneously with / S-unsaturated polyester resins in the usual way,

saturated alcohols and with polyhydroxy compounds e.g. by polycondensation of the preceding

to implement, but it is more advantageous to first produce the components mentioned in the paragraph. Of the

^ -unsaturated ether of the methylolureine and con-40 degree of condensation of the unsaturated polyester is in the

This then condenses at an elevated temperature with generally adjusted so that its acid number is less than

the polyhydroxy compounds. Particularly suitable poly-50 and that the viscosity of the 60% solutions in

Hydroxy compounds that are used to produce the condensate styrene between about 50 and 300 DIN seconds (DIN

Methylolureine are bivalent cups no. 4, 20 ⁰ C).

Alcohols, because when they are used there is a risk of 45 In addition to unsaturated polyester resins and the

Gelation during the condensation reaction of small condensation products from / S-unsaturated ethers of

is than with trivalent or polyvalent hydroxy compounds. Methylolurinen can be used in the polymerizable mi-

But they can also be used. All known unsaturated poly-

include, for example, aliphatic, cycloaliphatic or aliphatic ester resins polymerizable monomeric compounds

Table-aromatic polyols such as ethylene glycol, propane 50 fertilize be included. Vinyl

1,2-diol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, compounds, e.g., vinyl aromatic compounds such as

1,6-hexanediol, glycerol, trimethylolpropane, pentaery styrene, alkylstyrenes, halostyrenes, divinylbenzenes or

thrite, diethylene glycol, triethylene glycol, dipropylene vinylnaphthalene, also vinylpyridine, N-vinylcarbazole,

glycol, 1,2-cyclohexanediol, terephthalic alcohol, or with vinyl ketones, such as vinyl methyl ketone, α-unsaturated Vi-

Polyhydric phenols reacted with ethylene oxide, such as ethonyl sulfones, e.g. methyl vinyl sulfone or divinyl sulfone,

xylated 4,4'-dihydroxydiphenylalkanes. Very good gel vinyl esters of saturated and unsaturated mono- and

Suitable polyhydroxy compounds are also linear or polybasic carboxylic acids, such as vinyl acetate, vinyl

branched polyester with terminal hydroxyl groups, propionate or succinic acid divinyl ester, N-vinyl

in the usual way, for. B. from divalent carbon lactams, such as N-vinylpyrrolidone or N-vinylcaprolactam,

acids and di- and polyhydric alcohols and vinyl ethers of mono- and polyhydroxy compounds

are posed. fertilize, e.g. isobutyl vinyl ether or butanediol-1,4-di-

Furthermore, the ^ -unsaturated alcohols can vinyl ethers. Acrylic compounds are also often well etherified Methylolureine or their low molecular weight are suitable, e.g. esters, amides or nitriles of a-unge homopolycondensation products with non-polymerized monocarboxylic acids, such as ethyl acrylate, barren compounds containing two or more carboxyl groups, methyl methacrylate, glycol dimethacrylate, oct-chlorine Molecule contain, be polycondensed. Among ethyl acrylate, acrylonitrile, methacrylonitrile, acrylic cleavage Part of the ^ -unsaturated alcohol are amide or methacrylamide, also AEyI compounds, the urine residues with one another via methyl ester bridges, e.g. allyl esters of saturated or unsaturated ones connected. The course of this reaction can be light or polybasic carboxylic acids or inorganic by determining the acid number of the reaction mixture 70 acids, such as diallyl phthalate, diallyl maleate, triallyl

5 6

Keep cyanurate or triallyl phosphate, as well as allyl ether from. Above all, however, are the proposed ones

Mono- or polyhydroxy compounds, such as glycol-polymerizable mixtures, excellent paints with

diallyl ether or pentaerythritol tetraallyl ether. As the pigmented and non-pigmented coatings

used condensed / 3-unsaturated ether of with excellent gloss, great hardness and good

Methylolurein and also the unsaturated polyester 5 solvent resistance can be produced. You can

resins mostly highly viscous oils or tough, sticky resins also used together with other paint raw materials

it is often beneficial if they are also used. These varnishes have excellent filling power

monomeric polymerizable compounds have a low viscosity and flow well. They can also be special

are. So one can adjust the viscosity of the polymerizable large amounts of styrene or other liquid monomers

Adapt mixtures to practical requirements. 10 included without the viscosity dropping so much that the

Should the polymerizable mixtures be processed as lacquers on lacquer casting machines or by spraying

are used, so it is also possible not to polymerize and make immersion difficult.

sable volatile organic solvents, e.g. ethyl- For the production of the starting materials for the here

acetate, butyl acetate or toluene, for which protection is desired, are listed below

to set the most favorable viscosity. 15 work regulations a) to c) are given.

The mixing ratio of the ^ -unsaturated a) A mixture of 87 parts of the tetraallyl ether Alcohols etherified methylolurein condensates to that of tetramethylolglyoxaldiurein and 13 parts of maleic acid Components in the polymerizable mixed acid, which contains 0.1% p-toluenesulfonic acid, is The gene can be varied over a wide range, but this takes 2 hours while stirring and passing nitrogen through It is expedient in general not to keep the mixtures condensed at 140.degree. One receives at room temperature less than 5 percent by weight of methylolurein condensate, tough resin that is "stringy when heated" with the preferably more than 15 and generally no more than 10 acid number.

than 70 percent by weight, based on the total weight b) A mixture of 46.0 parts of the tetraallyl ether

the polymerizable mixture. des Tetramethylolglyoxaldiurein and 54 parts of one

The polymerizable mixtures can be composed of 3 mol of maleic anhydride and polyester resin

in a known manner, e.g. by exposure to light, ins- 2.5 mol of propylene glycol with the acid number 133 becomes with

special ultraviolet light, or polymerization 0.1 _{% / 0} p-toluenesulfonic acid and 0.01% hydroquinone under

catalysts, such as peroxides, for example methyl ethyl ketone stirring and ^{condensed under nitrogen at 140 0} C, to

peroxide or benzoyl peroxide, azo compounds, e.g. B. the acid number of the reaction product has fallen to 42.

Azo-bis-isobutyric acid nitrile, or other radicals, form 30 A tough, stringy when exposed to heat is obtained

end compounds or with the help of redox systems resin.

are polymerized. The polymerization catalysts c) A mixture of 58.5 parts of the tetraallyl ether are in the usual amounts, for example between about 0.5 of the tetramethylolglyoxaldiurein and 41.5 parts of one and 3 ⁰ I ₀ , based on the polymerizable mixture, resinous reaction product of 2 mol Maleic acid applied. _ 35 anhydride and 1 mol of 2,2-dimethylpropanediol-1,3 with the

Depending on the catalysts used, the polyacid number can be 384 with stirring and under nitrogen

merization at room temperature or at higher temperatures at 140 to 150 ° C condenses until the acid number reaches 70

Temperature, e.g. at 60 to 150 ° C. has fallen. A solid at room temperature is obtained

To glue-free and solvent-resistant coatings tough resin.

In most cases it is advisable to obtain 40 The parts given in the examples are by weight

Add metal siccatives. Parts, for example, are particularly suitable.

the naphthenates of the metals iron, cobalt, nickel, Example 1
Manganese, chromium, lead, zinc, cerium, aluminum or calcium.

Instead of the naphthenates, the corresponding after the end of the condensation can be left according to

Resinates, Oetoate or Linoleate or other, reaction mixture obtained in the 45 procedure a) to 8O ⁰ C

polymerizable mixtures cool soluble metal compounds and mixed with so much styrene that the

fertilizing can be used. Sometimes it is also beneficial to mix 25% of these. The solution obtained

Use mixtures of different siccatives. has a viscosity of 107 DIN seconds at 20 ° C

It is advisable to use the polymerizable mixtures (DIN cup no. 4). 75 parts of this solution are with

by adding the usual polymerization inhibitors to 50 25 parts of a polymerizable mixture of 60%

stabilize to prevent premature gelation. an unsaturated polyester resin made from maleic acid and

Suitable compounds of this type are, for example, mono- or propylene glycol with an acid number of 25 and 40 ° / ₀ styrene

polyvalent phenols, e.g. hydroquinone, resorcinol, mixed. They are 2.5% of a 40 ° / ₀ solution of cyclohexanone

Pyrocatechol or 2,6-di-tert-butyl-p-cresol. This peroxydpaste in dibutyl phthalate and / _o 10% by weight of a 5 °

Phenols can be partially etherified. In addition, a solution of cobalt naphthenate in styrene is added and contributes to

Aminophenols suitable as well as aromatic amines, e.g. B. thin layer on glass plates. The received excess

Phenymaphthylamine, or quinones. You will feel the train is bone dry after a few hours and after

polymerizable mixtures sandable in amounts between about 12 to 15 hours.
° / ₀ was added 0.01 and 0.1.

The polymerizable mixtures can, given example A

if after the addition of fillers, as casting resins for the preparation of the reaction product obtained in accordance with regulation b)

position of moldings, as embedding materials or it is cooled to 80 ° C. and 33 parts of styrene are stirred in. the

in connection with glass or textile fibers or fabrics obtained solution is highly viscous and is well suited as

from this for the production of laminated bodies used paintable varnish. It can be diluted with styrene as required

will. In this way, bodies and boats can be made. Is added 3% of a 40 ° / ₀ solution of cyclohexanone

manufacture hulls and other components. Here, one is peroxydpaste in dibutyl phthalate and strength of 8 ° / ₀ of a 5 ° / ₀

no longer forced to and wear a solution of cobalt naphthenate in styrene to the surfaces exposed to the air

to protect against the influence of atmospheric oxygen. The mixture on glass plates. The coatings obtained

rather, without taking any precautionary measures, they are dust-dry after a few hours and after about

took on hard and solvent-resistant surfaces, 70 easy to sand and solvent-resistant for 12 to 24 hours.

Example 3

The reaction product obtained according to regulation c) is allowed to ^{cool to 80 °} C. and mixed with 33 parts of styrene. A highly viscous solution is obtained with a viscosity of 400 DIN seconds measured in a DIN-cup no. 4 at 20 ⁰ G. If we mix 80 parts of the resin solution in styrene with 10 parts of an unsaturated polyester resin from 2 moles of maleic anhydride, 1.1 mol of 2 , 2-dimethylpropanediol-1,3 and 1.1 mol of diethylene glycol with the acid number 17 and another 10 parts of styrene and mixed this polymerizable mixture with 2.5 ° / _{0 of} a 40 ° / ^ εη cyclohexanone peroxide paste in dibutyl phthalate and 8% of a 5% With a cobalt naphthenate solution in styrene, after application to glass plates, after about 2 hours, dust-dry coatings that can be sanded after about 12 hours are obtained.

Claims (1)

Claim: Process for the production of polymerization products on the basis of mixtures of un- ao saturated polyester resins and highly viscous or resin-like polycondensation products of the methylolureine etherified with / ?, γ-unsaturated alcohols in a modification of the process according to patent 1,067,210, characterized in that, instead of the highly viscous or resin-like condensation products, the condensation products with β, γ- unge saturated alcohols etherified Methylolureine with non-polymerizable more hydroxyl and / or carboxyl-containing compounds, soluble, from the etherified Methylolureinen or from thereof alone, optionally together with non-polymerisable, several hydroxyl and / or carboxyl compounds containing condensates formed with polymerizable, multiple hydroxyl and / or carboxyl group-containing compounds obtained polymixed condensates, optionally in addition to conventional monomeric compounds for the polymerization, can be used. ® 009 508/436 4.60