DE1067210B - Process for the production of polymerization products based on unsaturated polyester resin compositions - Google Patents

Description

REGISTRATION DATE MAY 31, 1958

ANNOUNCEMENT THE REGISTRATION AND ISSUE OF THE ADSLE FONT.

October 15, 1959

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 Catalysts which form free radicals to insoluble and infusible cast, pressed or laminated bodies are processed. 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 that methylol compounds of urea and methylol alcohol which are etherified with allyl alcohol To use melamine as a monomeric component which can be polymerized to unsaturated polyester resins Such polymexisable mixtures give dry surfaces after hardening, but they do have other disadvantages So is the surface of the Polymerization products from unsaturated polyester resins and the diallyl ether of dimethylol shark not resistant to solvents and can be Also badly sanding The surface is severely attacked in boiling water. The products become cloudy and cracked and absorb a lot of water. Similar results are obtained if one takes in place of methylolurea allyl ethers the corresponding ethers of methylolmelamines are used Another The disadvantage of the allyl ethers of methylolureas is their poor compatibility with the unsaturated polyester resins

It has now been found that polymerization products based on mixtures of unsaturated Polyester resins and polymerisable thereon, etherified with ^, / - unsaturated alcohols Methylolureinen under shaping with excellent Properties are obtained when highly viscous or resinous condensation products are used as etherified methylolurems that with ^, / - unsaturated alcohols etherified methylolurein with themselves or with non-polymerizable compounds containing several hydroxyl and / or carboxyl groups, if appropriate used in addition to conventional monomeric compounds for polymerizing

The ^ -unsaturated ethers of methylolurein, which are assumed in the manufacture of the condensates used contain the imidazolidone radical at least once in the molecule you can derive from glyoxal monourem or glyoxaldiurein, wherein one or both of the glyoxyl carbon atoms linked hydrogen atoms by ahphatic, cycloaliphatic, aromatic, aliphatic aromatic or heterocyclic radicals replaced his method of preparation

of polymerization products

based on unsaturated

Polyester resin compounds

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhem

Dr Herbert Willersmn, Ludwigshafen / Rhem,

r> r Hans Scheuermann,

Ludwigshafen / Rhem-Oggersheim,

and Dr Alfred Woerner, Limburgerhof (Palatinate),

smd has been named as the inventor

These urines can contain at least one bound to nitrogen via an oxymethylene group Residue of a / J-unsaturated alcohol Such Residues are preferably,-unsaturated alkenyl or Cycloalkenyl, ζ Β allyl, methallyl, crotyl, cyclohexenyl or cyclopentenyl radicals Ureine with several etherified methylol groups are used, the methylol groups can also be used with different unsaturated alcohols be etherified Furthermore, one can also use methylolmonone pure, whose hydroxyl groups bonded to carbon atoms, how their methylol groups are etherified in the manner indicated contained hydroxyl groups can also partially by saturated aliphatic or cycloaliphatic, heterocyclic or aromatic hydroxy compounds be etherified. Particularly cheap Compounds of this type are the TetraaUylather des Tetramethylolglyoxaldiureins, the Diallylather des Tetramethylolglyoxaldiurein or dimethylolglyoxaldiurein, the Tr, iallylether des Tnmethylolglyoxaldmrein, the monobutyldiallyl ether of methylolglyoxaldiurein, also the diallyl ether of Dimethjylolglyoxalmonourems-

Suitable condensation products from ^ -unsaturated Ethern of Methylolureinen are ζ Β those, m which several Uremreste over methylene or

909 638/394

Methylenatherbrucken are linked to one another. They can be obtained by converting the uremes with formaldehyde and a /? - unsaturated alcohol under such conditions that, with elimination of water or alcohol, high molecular weight products are formed and condensation at a _pH value between about 1 and 4 in the presence of the alcohol and from about 5 to 20% water, based on alcohol, are carried out, it is also possible to first prepare the monomeric unsaturated ether of ^ Methylolureine and these then to polycondense at elevated temperature, preferably in the presence of acidic catalysts and 10 to 20% water. The most favorable reaction temperatures are between 40 and 180 ° C. All strong acids or their acidic salts can be used as condensation catalysts

Furthermore, the Methylolureine or their low molecular weight condensation products except with / ^ - unsaturated alcohols with di- or polyhydric Hydroxyl compounds are etherified and condensed to form high molecular weight compounds it is possible to use the methylolureine at the same time / J-unsaturated alcohols and with polyhydroxy compounds implement, but it is more advantageous to first use the ^ -unsaturated ethers of the methylolureines and then condenses them at an elevated temperature with the polyhydroxy compounds especially suitable polyhydroxy compounds which serve to produce the condensed methylolureine can are dihydric alcohols because at their Avoid using the risk of gelation during the Condensation reaction is less than with three- or polyvalent hydroxy compounds However, such compounds can also be used. Pay ζ Β for this aliphatic, cycloaliphatic or aliphatic aromatic Polyols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, Glycerine, methylolpropane, pentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, Cvclohexanediol-1,2, terephthalic alcohol or with Ethylene oxide converted polyvalent phenols, such as athoxylated 4,4'-dihydroxydiphenylalkanes Very good suitable polyhydroxy compounds are also linear or branched polyesters with terminal hydroxyl groups, which in the usual way, ζ B from bivalent Carboxylic acids and di- and polyhydric alcohols are made

Furthermore, with ^ -unsaturated alcohols etherified methylolurems or their low molecular weight Condensation products with compounds that have two or more carboxyl groups in the molecule contain, be polycondensed with elimination of part of the / ^ - unsaturated alcohol the urine residues via methylol ester bridges linked together The course of this reaction can easily be determined by determining the acid number of the reaction mixture Likewise, compounds can be used that contain at least one Contain carboxyl group and at least one hydroxyl group in the molecule

Suitable compounds with several carboxyl groups in the molecule are polyvalent aliphatic, cycloaliphatic or mixed aliphatic aliphatic carboxylic acids, such as succinic acid, glutaric acid, adipic acid, carballylic acid, the various phthalic acids, cyclohexanoic acid or branched resin-like polyesters with terminal carboxyl, hydroxyl or carboxyl and hydroxyl groups can be used.Depending on the type and amount of the compounds used with several carboxyl groups or hydroxyl groups in the molecule, the properties of the copolymerization products can be changed.The condensation products with several urine residues in the molecule can often be advantageous use in a mixture with one another or in a mixture with the monomeric β, γ- unsaturated ethers of the methylolureine The condensed unsaturated atoms or esters are, depending on their structure and degree of condensation, liquids or honey-like masses or resin-like, solid products that pull in the warmth. Protection on the division of the starting materials is not claimed at this point

Those contained in the polymerizable mixtures unsaturated polyester resins can be used in usual Way, ζ B by polycondensation of a-unsaturated α, / J-dicarboxylic acids with preferably divalent Saturated alcohols can be produced. Some of the unsaturated dicarboxylic acids can be produced by saturated alcohols polybasic carboxylic acids can be substituted. Suitable unsaturated dicarboxylic acids are ζ Β in question maleic acid, fumaric acid, itaconic acid, Citraconic acid, aconitic acid or their substitution products, ζ B Chloromaleinsaui e, or anhydrides of these acids which may also be used saturated polybasic carboxylic acids can be aliphatic, cycloaliphatic or mixed aliphatic aromatic Be carboxylic acids, ζ Β succinic acid, Glutaric acid, adipic acid, pimelic acid, sebacic acid, Cork acid, a-methylglutaric acid, oxadibutyric acid, Sulfondibutyric acid, phthalic acid, isophthalic acid, Terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, Endomethylene tetrahydrophthalic acid, hexachloroendomethylene tetrahydrophthalic acid, tetrachlorophthalic acid, Phenylenediacetic acid, the various cyclohexanedicarboxylic acids or anhydrides of these acids By using monohydric carboxylic acids or alcohols in the polycondensation the degree of condensation of the unsaturated polyester resins and thus the viscosity of their Solutions in the monomeric compounds to be set

The condensation level of the unsaturated polyesters is generally adjusted so that their acid number is less than 50 and that the viscosity of the 60% strength solutions in styrene is between about 50 and 300 Din-Sec (Din cup Ni 4, 20 ° C.)
In addition to the unsaturated polyester resins and the condensation products of / ^ - unsaturated ethers of methylolureins, all known monomeric compounds that can be polymerized onto unsaturated polyester resins can also be contained in the polymerizable mixtures. Particularly suitable are vinyl compounds, ζ B vinylaromatic compounds, such as styrene, alkylstyrenes, halostyrenes, divinylbenzenes or vinyl naphthalene, also vinyl pyridine, N-vinyl carbazole, vinyl ketones, such as vinyl methyl ketone, α-unsaturated vinyl sulfones, ζ Β methyl vinyl sulfone or divinyl sulfone, vinyl esters of saturated and unsaturated mono- and polycarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl acetate, vinyl propionate, or divinyl succinate Vinylpyrrolidone or N-vinylcaprolactam, as well as vinyl ethers of mono- and polyhydroxy compounds,

ζ B isobutyl vinyl ether or butanediol-1,4-divinyl ether Acrylic compounds are also often well suited, ζ B esters, amides or nitriles of α-unsaturated Monocarboxylic acids, such as ethyl acrylate, methyl methacrylate, Glycol dimethacrylate, α-chloroacrylic acid ethyl ester, acrylonitrile, methacrylonitrile, Acrylamide or methacrylamide and allyl compounds, ζ B allyl esters of saturated or unsaturated Mono- or polycarboxylic acids or inorganic acids, such as diallyl phthalate, diallyl maleate, Tallyl cyanurate or tallyl phosphate, and allyl ethers of mono- or polyhydroxy compounds, such as glycol diallyl ethers or pentaerythene tetra allyl ethers As the used condensed / S-unsaturated Ethers of methyloluremes and also the unsaturated ones Polyester resins are mostly highly viscous oils or tough, sticky resins, it is often beneficial to if the monomers also used are polymerizable Compounds are thin so one can determine the viscosity of the polymerizable Adapt mixtures to practical requirements

Shall the polymerizable mixtures as paints are used, so it is also possible not to be polymerizable add volatile organic solvents, ζ B ethyl acetate, butyl acetate or toluene, to set the most favorable viscosity

The mixing ratio of those with / ^ - unsaturated Alcohols etherified high molecular weight methylolurein condensates to the other components in the polymerizable mixtures can be m wide are changed, but the mixtures suitably generally contain not less than 5, preferably more than 15 and generally not more than 70 percent by weight, based on the Total weight of the polymerizable mixture

The polymerizable mixtures can be used in a known manner Way, ζ B by exposure to light, especially ultraviolet light, or polymerization catalysts, such as peroxides, ζ Β methyl ethyl ketone peroxide or benzoyl peroxide, azo compounds, ζ B azo-bis-isobutyric acid nitrile, or other, radicals forming compounds or with the aid of redox systems. The polymerization catalysts are in the usual amounts, ζ B between about 0.5 and 3%, based on the polymerizable mixture, applied

Depending on the catalysts used, the polymerization can take place at room temperature or at higher temperature, ζ B at 60 to 150 ° C will

About non-stick and solvent-resistant coatings To obtain, it is advisable in most cases to add metal siccatives. Particularly suitable are ζ B the naphthenates of the metals iron, cobalt, nickel, manganese, chromium. Lead, zinc, cerium, Aluminum or calcium Instead of naphthenates, the corresponding resinates, octoates, can also be used or Lmoleates or other metal compounds soluble in the polymerizable mixtures are used Sometimes it is also beneficial to use mixtures of different siccatives.

It is useful to use the polymerizable mixtures to stabilize premature gait by adding the usual polymerization inhibitors to prevent Suitable compounds of this type are ζ B mono- or polyhydric phenols, ζ Β. Hydroquinone, resorcinol, pyrocatechm or 2,6-di-tert-butyl-p-cresol These phenols can partially aminophenols are also suitable, as are aromatic amines, ζ B phenylnaphthylamm, odei also quinones They are the polymerizable mixtures in amounts between about 0.01 and 0.1% added

The polymerizable mixtures can, if appropriate after the addition of fillers, as casting resins for the production of moldings, as embedding compounds or in connection with glass or textile fibers or woven fabrics therefrom can be used to produce laminates in this way car bodies, boat hulls and other components can be produced Here you are no longer forced to to protect the surfaces exposed to the air from the influence of atmospheric oxygen rather, hard and solvent-resistant surfaces are obtained without taking any precautionary measures Above all, however, the proposed ones are polymerizable Mixtures of excellent varnishes, with which pigmented and non-pigmented coatings Can be produced with excellent gloss, great hardness and good resistance to solvents They can also be used together with other varnish raw materials These paints have excellent filling power and flow well In addition, they can contain particularly large amounts of styrene or other liquid monomers without that the viscosity drops so much that the processing on coating machines or by spraying and dipping is made more difficult

Those responsible for carrying out the procedure in accordance with The condensates used in the invention and having several primordial residues in the molecule can be prepared as follows be

a) 100 parts of the tetraallyl ether of Tetramethylolglyoxaldmreins 0.1% p-toluenesulfonic acid is added and the mixture is heated at 140 ° C. for 272 hours condensed with stirring and passing nitrogen over it In the process, small amounts of allyl alcohol are split off. A highly viscous oil is also formed a viscosity of 290 Dm-sec at 20 ° C (Dm cup No. 4)

b) 100 parts of the tetraallyl ether of Tetramethylolglyoxaldiui become one with 0.3% p-toluenesulfonic acid added and condensed for 2 hours at 140 ° C with stirring and passing nitrogen over it A tough, sticky, stringy resin is obtained The viscosity of a 75% solution in styrene is 243 Din-Sec at 20 ° C, measured in a Dm cup No. 4

c) A mixture of 66.0 parts of the tetraallyl ether of tetramethylolglyoxaldiurem and 34.0 parts of the diester of succinic acid and 2,2-dimethyl-1,3-propanediol with OH number 355, in Presence of 0.1 part of p-toluenesulfonic acid under Stir and pass nitrogen at 140 condensed up to 150 ° C. One obtains at room temperature tough, sticky resin After the condensation has ended, the reaction product is cooled 80 ° C and then mixed with 33 parts of styrene. The clear solution is highly viscous at room temperature

d) A mixture of 88 parts of the tetraallyl ether of tetramethylolglyoxaldiurem and 22 parts Succinic acid is under 2 hours at 140 ° C Stirring and condensing under nitrogen. At room temperature, a viscous, sticky, stringy one is obtained Resin with an acid number of 25

e) A mixture of 85 parts of the tetraallyl ether of tetramethylolglyoxaldiurem and 15 parts Adipic acid is kept at 140 to 150 ° C for 2 hours condensed

The parts mentioned in the examples are parts by weight

example 1

35 parts of the condensa obtained according to regulation a) tes are made with 39 parts of an unsaturated polyester resin made from maleic acid and propylene glycol The polymerizable mixture is mixed with 2% of a 40% cyclohexanone peroxide paste in dibutyl phthalate and 8% of a 5% cobalt naphthenate solution in styrene and applied in a layer about 400 μ thick on glass plates Coatings are dust-dry after a few hours and can be sanded well after 12 to 15 hours a good full strength

Example 2

A polymerizable mixture of 30.5% of the condensation product obtained according to procedure b), 37.0% of an unsaturated polyester resin made from maleic acid, 2,2-dimethyl-1,3-propanediol and diethyl glycol with an acid number of 17 and 32.5 «is produced. / »styrene ago This mixture has a viscosity of 80 Din-sec, measured in diameter cup No. 4 is 3% of a 40% Cyclohexanonperoxydpaste in dibutyl phthalate and lO ° / o of a 5Voigen Kobaltnaphthenatlosung added at 20 ⁰ C in styrene and applied to glass plates. The coatings obtained are dust-dry after about 2 to 3 hours and can be sanded after 12 hours

Example 3

100 parts of the condensate solution obtained in accordance with regulation c) are with a mixture of 50 parts of an unsaturated polyester resin made from maleic acid and propylene glycol with an acid number of 25 and 50 parts of styrene and stirred with 4 parts of a 40% cyclohexanone pexoxide paste in dibutyl phthalate and 16 parts of a 5% cobalt naphthenate solution in styrene are added Glass plates applied The course of the paint is very good. The coatings obtained are after a few Hours dust-dry and after 12 hours they are easy to grind even without the use of Sihkonol or similar means smooth and shiny.

Example 4

The product obtained according to regulation d) cools it is reduced to 80 ° C. and mixed with thorough stirring with so much styrene that the resulting mixture is about Contains 25% styrene. The solution obtained has at 20 ° C has a viscosity of 51 Dm-sec, measured in Din cup no 4

Of this, 60 parts with 40 parts of a mixture from 40% styrene and 60% of an unsaturated one Polyester resin from maleic acid and propylene glycol mixed. Add 3% cyclohexanone peroxide and 10% of a 5Voigen solution of cobalt naphthenate in styrene and carries the obtained Varnish on glass plates after just a few hours the coatings obtained are bone dry and Can be sanded after about 15 hours

Example 5

The obtained according to regulation e), at room temperature honey-like, viscous resin with the acid number 42 is made with 68 parts of styrene and 53.5 parts of a unsaturated polyester resin from maleic acid and propylene glycol with the acid number 25 mixed so obtained polymerizable mixture is with 3% of a 40% cyclohexanone peroxide paste in Dibutyl phthalate and with 10 Vo of a 5% cobalt naphthenate solution added in styrene and painted in a thin layer on glass plates Coatings are dust-dry after 2 to 3 hours and can be sanded after about 12 to 15 hours

Claims (1)

Claim Process for the manufacture of polymerization products based on mixtures of unsaturated polyester resins and polymerizable on them with / ^ - unsaturated alcohols etherified methyloluremes with shaping, characterized in that highly viscous or resinous condensation products are used as the etherified methylolureine that with ^, / - unsaturated alcohols etherified methylolureine with themselves or with non-polymerizable compounds containing several hydroxyl and / or carboxyl groups, optionally used in addition to conventional monomeric compounds for the polymerization will