DE1031961B - Laminates made from fibrous glass materials - Google Patents

Description

Laminates of Fibrous Glass Materials The invention relates to refer to layered objects made up of a multitude of layers of fibrous There are glass material, which is made of an N-vinylpyrrolidone by means of a copolymer and a diallyl ester of a dibasic acid are linked to one another.

There are already various polymers and copolymers as Binder for glass fabric, glass fibers, glass mats, rovings, etc. proposed been.

Polymers of allyl esters of saturated and unsaturated dibasic Acids have been used in the manufacture of fiberglass sheet materials and with glass reinforced Used plastic objects. Mixtures of diallyl esters with one another mono- or polyfunctional monomeric vinyl compounds were copolymerized, supplied a large number of crosslinked copolymers, which as reinforcement or Binders for glass laminates have been proposed.

The main disadvantage of such polymers and copolymers is there when used as a coating agent that the resulting cured Polymer or mixed polymer only has a low level of adhesion to the glass fabric, which has fiberglass and glass mats, etc. When glass fabrics, mats or fibers impregnated with such polymers and copolymers and by curing are used to build up laminates, the laminates do not show optimal properties, e.g. B. in the flexural strength and the modulus of elasticity.

It is important that the resin adheres firmly to the glass fibers, etc. to achieve maximum physical properties of the laminate. Used to be this is achieved in part by the fact that the glass fibers, etc. z. B. with vinylsilanes have been preheated. The need to improve physical properties cannot be underestimated as this is a very important factor in the industry of fiberglass laminates.

It has now been found that when using well-defined copolymers preheating of an N-vinylpyrrolidone with a diallyl ester of a dibasic acid the fiberglass is not necessary, which makes it possible to use the fiberglass laminates to be produced directly with maximum physical properties. The N-vinyl pyrrolidone actually enters the final cured polymer and is an integrating one Part of the same. Try taking N-vinylpyrrolidone to a solution that already has one contains prepared prepolymer of a diallyl ester of a dibasic acid, admit are not very successful due to the loss of N-vinylpyrrolidone during evaporation of the solvent. This makes the production of coating layers, especially for a dry application, impractical.

It is known that diallyl phthalate first forms a partial polymer. As the polymerization proceeds, molecular crosslinking occurs and gel formation. It has been found that the best results are obtained when the N-vinyl pyrrolidone is incorporated prior to the formation of crosslinked products. It has also been found that the copolymers obtained when 5 to 20 percent by weight of an N-vinyl pyrrolidone and 80 to 95 percent by weight of one Diallyl ester of a dibasic acid are copolymerized, after the final Curing provides a resin that has an extraordinarily high level of adhesion to glass fabrics, fibers and mats etc. possesses, which is due to the greatly improved flexural strength and the modulus of elasticity is proven even after long immersion in water.

Experiments have shown that when using a copolymer of an N-vinylpyrrolidone with a diallyl ester of a dibasic acid, the flexural strength slightly over 35 ° / 0 in the dry and 100 ° / 0 when wet and the modulus of elasticity slightly above 50 0.1 in the dry and 100% in the wet state can be improved. The use of an N-vinylpyrrolidone in the specified percentage amounts and the achievement of the improved properties even after long immersion in water is surprising and was in no way to be expected because glass laminates obtained when more than 20% of an N-vinylpyrrolidone are used have a lower strength than glass laminates which as polymers of diallyl phthalate or others. Diallyl ester of dibasic Acids were produced.

The N-vinylpyrrolidones used to produce the copolymers with diallyl esters of dibasic acids have the following formula: In this formula, R stands for hydrogen or a methyl group and R for hydrogen, a methyl or ethyl group. The following compounds may be mentioned as examples of N-vinylpyrrolidones which can be used: N-vinyl-pyrrolidone- (2), N-vinyl-methyl-pyrrolidone- (2), N-vinyl-5-ethyl-pyrrolidone- (2), N- Vinyl-3,3-dimethyl-pyrrolidone- (2), N-vinyl-3-methyl-pyrrolidone- (2), N-vinyl-4-methyl-pyrrolidone- (2), N-vinyl-4-ethyl pyrrolidone- (2).

As examples of diallyl esters of saturated or unsaturated dibasic Acids, which are copolymerized with the N-vinylpyrrolidones, its the Diallyl esters of the following unsaturated dibasic acids maleic acid, ethyl maleic acid, Citraconic acid, muconic acid, fumaric acid, aconitic acid, mesaconic acid, itaconic acid, monochloromaleic acid, Dichloromaleic acid, and of the following saturated dibasic acids adipic acid, Azelaic acid, phthalic acid, sebacic acid, dodecylsuccinic acid, succinic acid, Tetrachlorophthalic acid, hexahydrophthalic acid, 1, 4, 5, 6, 7, 7-hexachlorobicyclo- (2, 2, 1) -heptane-2, 3-dicarboxylic acid, called malic acid.

Although preferably the above saturated and unsaturated allyl esters can be used in the form of their diallyl esters, but the monoesters and Mixtures of mono- and diallyl esters are used, with similar being useful Results are achieved. The expression> allyl esters of dibasic acids., Like it is used herein, therefore, is intended to include both the mono- and diallyl esters and their Enclose mixtures. Similarly, the expression "N-vinylpyrrolidonex only for the compounds that are characterized by the above general formula, be understood.

The copolymers of the allyl ester and N-vinylpyrrolidone are produced by copolymerizing in bulk, in emulsion or in solution. The first stage consists in the copolymerization of the monomers to form an intermediate stage, at what time the prepolymer obtained in the appropriate organic Solvents such as benzene, dioxane, acetone, methyl ethyl ketone, dimethylformamide, pyrrolidone, Butyrolactone, tetrahydrofuran, ethyl acetate, ethylene dichloride, etc., and mixtures the same is still soluble. The solution of the prepolymer is then combined with the glass fibers etc. mixed, allowed to evaporate the solvent present and the preparation by additional heat and / or catalytic curing in the insoluble and transferred to the infusible state.

The in the process for the preparation of the premix polymers and Catalysts used for final cure are those commonly used Catalysts which include organic peroxides, peracids, hydroperoxides, etc. Connections of this type are e.g. B. benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, 1,1'-Hydroperoxydiglycol, Hexylproxyd, Methyläthylketonperoxid, tert-Butylperoxid, a, a-azodiisobutyronitrile, etc. In addition to the catalysts mentioned, Accelerators such as dimethylaniline, diethylaniline, doimethyl-p-toluidine, or any Another known equivalent catalyst to strengthen the hardening effect of the catalyst contained in the copolymer can be used. The amount of Accelerator can be 0.1 to 5 percent by weight of the allyl ester used.

By the expression "fiber-shaped glass materials" as used herein is used, glass fabrics of all weaves, glass fibers, glass mats, rovings, Glass strands, cut glass strands, etc. are understood.

The following examples illustrate the preparation of those of the invention Copolymers and the use as layering agents for layers of fibrous Glass materials and the results obtained with them. All parts are parts by weight.

Example 1 A. Preparation of the prepolymers a) 120 parts of diallyl phthalate, 180 parts of dioxane and 3 parts of tert-butyl perbenzoate were stirred and refluxed heated and heating continued for 21/2 hours. A small sample was taken poured onto glass and allowed to evaporate the dioxane from the film. The remaining one The residue was a viscous liquid. There were now 3 parts of tert-butyl perbenzoate added and refluxed for a further 4½ hours.

A sample left one after evaporation give way, some sticky film. Then 1.5 parts of tert-butyl perbenzoate were added and heated under reflux for a further three hours. One sample showed after evaporation a soft, non-sticky film.

The mass, a solution, was quickly cooled to room temperature ; it had a viscosity of less than A according to the Gardner-Holdt scale (cf. on this Handbook of Plastics by Simonds & Ellis, pp. 457, 458 [1943]).

The solution thus obtained was mixed with 4 times the volume of methanol. A white precipitate was formed which was filtered and washed with methanol became. This was then dried in vacuo at room temperature and delivered a white, free flowing powder that was soluble in dioxane. b) 108 parts of monomer Diallyl phthalate, 12 parts of N-vinylpyrrolidone- (2), 180 parts of dioxane and 3 parts of tert-butyl perbenzoate were heated with stirring and reflux. After 2 1/2 hours of heating, how described under a), a sample is taken, which evaporates a viscous liquid left behind. 3 parts of tert-butyl perbenzoate were then added and a further 4 parts Heated under reflux for hours. After evaporation, a sample provided a soft, very little sticky film.

Then 1.5 parts of tert-butyl perbenzoate were added and three more Heated to reflux for hours. After evaporation, one sample produced a medium viscous, not sticky film. The solution was quickly cooled to room temperature. she had a viscosity less than A on the Gardner-Holdt scale.

The solution of the prepolymer produced in this way was 4 times as high Volume of methanol mixed and the precipitated solid resin filtered, washed and, as described under a), dried. The dry, free flowing, white powder was analyzed for nitrogen and showed a nitrogen content of 1.25%. This analysis corresponded to a copolymer of 90% diallyl phthalate and 10% N-vinyl-pyrrolidone- (2). c) 101 parts of monomeric diallyl phthalate, 19 parts of N-vinylpyrrolidone (2), 3 parts of tert-butyl perbenzoate and 180 parts of dioxane became slow with stirring Heated to reflux. The heating was continued for 21/4 hours and a sample was taken. After the solvent had evaporated, this left behind a viscous liquid.

Then 3 parts of tert-butyl perbenzoate were added and a further 33/4 Heated at reflux for hours. A sample did not provide one after evaporation sticky, tough film. The reaction mixture was quickly cooled to room temperature. It had a viscosity of A on the Gardner-Holdt scale.

A solution of the prepolymer produced in this way was 4 times as high Volume of methanol mixed and, as described under a), the dry, solid, free flowing white polymer powder produced. The polymer had a nitrogen content of 1.98%, which is a copolymer of 84.2 diallyl phthalate and 15.8% N-vinyl-pyrrolidone- (2). d) 85 parts of diallyl phthalate, 35 parts of N-vinyl pyrrolidone (2), 180 parts of dioxane and 3 Teilel of tert-butyl perbenzoate were stirred and Heated to reflux and continued heating for 21/4 hours. A sample taken was allowed to evaporate; the residue was a viscous liquid. The mixture was heated for a further 21/2 hours, during which the viscosity increased visibly. One sample provided a medium-hard, non-sticky film after evaporation. The mass was quickly cooled to room temperature. It had viscosity of D according to the Gardner-Holdt scale.

To this solution, 6 times the volume of methanol was gradually added and then with 1 part water thinned, whereupon a soft, resinous material precipitated, which coagulated at the bottom of the vessel. The liquid above was decanted and the resin dried at room temperature. The chemical analysis gave 3.42% nitrogen (theoretically 3.64%), which is a copolymer of 70.9% diallyl phthalate and 29.1% N-vinylpyrrolidone- (2) corresponded. e) 120 parts Diallyl hexachloroendomethylene tetrahydrophthalate, 180 parts of dioxane and 3 parts of tert-butyl perbenzoate were heated with stirring and reflux and heating continued for 4 hours. A sample was taken and allowed to evaporate as described under a). The residue was soft and almost no longer sticky. There were now 3 parts of tert-butyl perbenzoate added and refluxed for a further 4 hours.

A sample evaporated as described above left a medium-soft, not sticky film. The mass was cooled to room temperature. You owned a viscosity less than A on the Gardner-Holdt scale.

This solution was mixed with 5 times the volume of methanol. A white precipitate formed, which was washed as described under a) and dried. The dried powder was white and free flowing. f) 110 Parts of diallylhexachlorendomethylene tetrahydrophthalate, 10 parts of N-vinyl-pyrrolidone- (2), 180 parts of dioxane and 3 parts of tert-butyl perbenzoate were stirred and Reheated walnut. After 31/2 hours, a sample was taken as described under a). The residue was soft and not sticky. Then 3 parts of tert-butyl perbenzoate were added added and refluxed for a further 4 hours. The one that was finally removed Sample was evaporated as under a) and left a firm, non-sticky appearance Movie. The solution was cooled to room temperature. It had viscosity less than A on the Gardner-Holdt scale.

This solution was mixed with 6 times the volume of methanol. It A white precipitate formed which was filtered and washed several times with methanol and then dried in vacuo at room temperature.

It became a dry, free-flowing, white powder of the copolymer obtained from diallylhexachloroendomethylene tetrahydrophthalate and N-vinyl-pyrrolidone- (2). This showed a nitrogen content of 1.04%, which is a copolymer of 91.7 ° / 0 diallyl hexachloroendomethylene tetrahydrophthalate and 8.3 ° / 0 N-vinylpyrrolidone (2) corresponded.

B. Production of the laminated bodies Six different 40 ° / Oige Solutions of the prepolymers prepared according to a) to f), to which in each case 0.8% tert-Butyl perbenzoate had been added, which was about 2 percent by weight of the prepolymer corresponded, these diluted with dioxane and these solutions for uniform coating used by six different glass mats. The glass mats were covered in such a way that that they contained 21/2 times their weight in 40% prepolymer solution. The six coated mats were allowed to air dry overnight, whereby the smell of dioxane disappeared.

The next morning, the glass mats were processed in a suitable metal press by curing for 13 minutes at 150 ° C. and a pressure of about 2.8 atm into layers about 6 mm thick. The laminates obtained were very uniform and, on physical examination, gave the values given in the table below: % Flexural strength Prepolymer content of module kg / cm2 ratio kg / cm2 obtained according to the specification N-Vinylpyrro-1 ASTM D 790-49 T resin to glass ASTM D 790-49 T idon- (2) a) ................ 0 dry ............ 1 750 dry ............... 60 600 50:50 wet ............... 730 wet ............... 29 300 b) ................ 10.0 dry .............. 2 410 dry ........... ... 19 600 50:50 wet ............... 1 400 wet ................ 62 700 c) ................. 15.8 dry ................ 1,490 dry ........ ..... 60 100 50:50 wet ............... 1 330 wet .................. 53 100 d) ................. 29, 1 dry 905 dry 38 200 50: 50 naB 190 naB 12 700 e) ................. 0 dry ................... 1 975 dry ....... ......... 73 500 50:50 wet ............... 1 545 wet ................... 65 800 f) ................. 8, 3 dry ........... 2 525 dry 98 000 50: 50 naB 2 O50 naB 79 800 Example 2 a) Example 1 b) was repeated with the exception that the N-vinyl-pyrrolidone- (2) by an equivalent amount of N-vinyl-4-methyl-pyrrolidone- (2) and the diallyl phthalate by an equivalent amount of diallyl maleate have been replaced. The solution was cooled to room temperature. It had a viscosity less than A on the Gardner-Holdt scale. b) Example 1 c) was repeated with the exception that the N-vinyl-pyrroldione- (2) by an equivalent amount of N-vinyl-3, 3-dimethyl-pyrrolidone- (2) and the diallyl phthalate by an equivalent amount of one same mixture of diallylsebacate and monoallyl fumarate was replaced. The solution was cooled to room temperature. It had a viscosity less than A on the Gardner-Holdt scale. c) Example 1 d) was repeated with the exception that the diallyl phthalate was replaced by an equivalent amount of diallyladipate and the N-vinyl-pyrrolidone- (2) was replaced by an equivalent amount of N-vinyl-5-methyl-pyrrolidone- (2) became. The solution was cooled to room temperature. It had a viscosity less than A on the Gardner-Holdt scale.

The prepolymers obtained according to the above instructions a) to c) were as described in Example 1, treated and for covering glass mats used. Those obtained from physical examinations of the laminated bodies Results are the same as in the table above.

It should be noted that by the term allyl ester a dibasic Acid also mixtures of mono- and diallyl esters and mixtures of one or more Diallyl esters of saturated or unsaturated dibasic acids are understood.

Claims (1)

P A T E N T A N S P R Ü C H: Laminate consisting of layers fibrous glass materials, which by means of a copolymer from 5 to 20 Percentage by weight of an optionally alkyl-substituted N-vinyl-pyrrolidone- (2) and 80 to 95 percent by weight of an allyl ester of a dibasic acid are.