DE1469925B2 - PROCESS FOR THE PRODUCTION OF PLASTICS REINFORCED BY GLASS FIBERS OR SYNTHETIC FIBERS FROM THE BASIS OF POLYACRYLIC OR POLYMETHACRYLIC ACID ESTERS OR UNSATURATED POLYESTER RESINS - Google Patents

Description

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amines in very fine distribution on the surface of the As a further advantage of the process according to the invention Fibers, fabrics, mats or strands. The so-called is the fact that the polymerization of traded fibers are very durable and almost any fiber runs out, so that a shrinking of the long shelf life. ■ synthetic resin is effected on the fiber. Since also

The peroxidic compounds which, in the case of the invention, uniformly digest the peroxide in the synthetic resin compound Process is used as catalysts, post-curing is made much easier, and it are known per se. Belonging to this group there is no risk of underhardening. The after ren all organic peroxides, such as. B. Benzoylper- this process produced structures show a oxide. They can be advantageous together with likewise very good bond between fiber and resin, whereby known hydroperoxides are used. io the weather resistance and the wet strength very strong . As reinforcing fibers, glass will preferably be improved. .;

fibers used. But there are also synthetic fibers, the production of fiber-reinforced plastics

• Such as polyamide fibers and polyester fibers, and natural- using heat curing is generally borrowed fibers as well as fabrics made from them, mats associated with the advantage of a long pot life, since or strands can be used with good success. Purpose- 15 the synthetic resin forming mass as a catalyst only In the process according to the invention it is moderately peroxide-containing. This method is disadvantageous furthermore, the synthetic resin-forming masses do not. but in a mixture with a further polishing and its precise regulation, great expenditure Substance and / or with another monomeric gene are necessary. This is increasingly the case polymerizable, organic compound to be used in the manufacture of large components. Turn back. The polymers include in particular the opposite is characterized by a process which is under polymeric esters of acrylic or methacrylic acid. You're applying the work hardening to be carried out can be present in the mixture in amounts up to 50%, due to the simplicity of its feasibility be. For the other monomeric compounds from. In the method according to the invention falls especially styrene, vinyl acetate, acrylonitrile, 25 also have a favorable weight that the quality of the her-vinyltoluene, Diallyl phthalate, allyl methacrylate and formed structures of those according to a hot hair general Crosslinkers such as ethylene glycol dimethacrylate; corresponds to the procedure shown. In the case of the pre-triallyl cyanurate, Divinylbenzene et al. The latter method also falls short of the pot life Substances can be used in amounts up to 40% and the "mono-" way. This is especially true when processing mer compounds used in amounts of up to 80% in large amounts are advantageous. Even if in the process of being invented. · '. :: according to the method, the initial hardness at any

The monomeric esters of acrylic or methacrylic should be somewhat lower in one place, so this is expediently in syrupy form without acid _; Importance because the well-distributed peroxide in the mixture z. B. as a mixture with the corresponding polymer. is able to bring about a significant post-cure. It is also often useful to feed the mono-35.

In addition, the process according to the invention can

turn around. A monomer-polymer is preferably also carried out, advantageously using pressure and / or a mixture of acrylic or methacrylic acid esters, in particular at elevated temperatures. In this case, special methyl methacrylate is used, which is to be noted as a remarkable advantage that up to about 30 to 40% polymethyl methacrylate contains 40 lower temperatures than otherwise with hot and can usually be maintained according to a process known per se (Belgian hardening, namely Patent 572,359 and French Patent specification, are not exceeded in a so-called "one-pot reaction";; generally temperatures from 100 ⁰ C 1,221,537). Preferably, this type of the preferably using a sulfur-containing; ; Curing takes place at temperatures of 50 to 70 ⁰ C, regulator, for example a mercaptan or its .45 while otherwise temperatures of 100 to about 150 ⁰ C derivatives, or in the presence of a radical form-; have been required. As a result, in particular a catalyst, such as azodiisobutyric acid dinitrile, which facilitates the production of thick-walled parts, has been produced. Furthermore, dyes and because there is no fear of blistering, since · fillers or flours of inorganic or organic nature are added in the process according to the invention, the boiling point; ■ : "', -.:., - ■■ ..": ■ .. ■■' ■■ '.' .50. of the mixtures present in the synthetic resin - As already stated, according to the invention, monomers are not achieved. In addition, according to this method, the amines are applied to the surface of the with a better bond between the synthetic resin and fibers, mats, Tissue or strands preserved in fine fiberglass. Applied as a result of the extraordinary division. In contrast to the previously short hardening time, a quick ejection of the recognized processes is possible, in which the peroxy- 5.5 'manufactured parts are possible.

applied to the mat, it is' the quantities in which the peroxidic compounds

; In the present case, they are storable structures. fertilize and the amines are used are in themselves

On the other hand, the synthetic resin-forming mass is also known from other polymerisation processes.

'which only contains the peroxide catalyst, but in the present case it is advisable to use the

if storable, this mass can be: several 60 ^? peroxidic compounds in amounts from 0.5 to

Weeks at ~ room temperature and at a lower 3%, based on the synthetic resin-forming proportion, the

: Can be stored at temperatures for a few months .. Hydroperoxides in amounts up to 1.0% and the amines

When applying: this mass on. the fibers in amounts up to 1.0% based on the synthetic resin

the amines and the peroxidic catalyst-forming part come to be used. If you refer to the

gates in contact with one another, so that a very large amount of the tissue used must be the type

- Fast curing is made possible. This completely cure, _'of the product to be considered

: 'tung is with good success at room temperature and, as is well known, the fabric portion in the production

; also: feasible at a slightly elevated temperature. . of e.g. plates is 25 to 35%, while

80%

he can make up od in the production of pressed parts. Like. 60 to.

The inventive method is also particularly good for the continuous production of fiber-reinforced plastics are suitable, both the impregnation with the amine and the Application of the synthetic resin-forming masses can be carried out continuously. For example the fiber web with the help of pairs of rollers over or through a trough-like or tub-like, the amine solution or the container containing the synthetic resin forming mass are carried out or from above with the solution of the amine or the synthetic resin-forming mass from a tank with a spray device, which may have a mixing head, dripped, sprayed or sprinkled. On the same It is also possible to apply the mass in the form of a film. At the same time the to be produced Formations are continuously supplied with a slip sheet.

The table below shows the results of some of the tests that were carried out of the method according to the invention have been achieved. There are fiberglass mats (alkali-free glass silk mat with silane finish, 600 g / sqm) per 100 g of its weight with 120 ml of one Impregnated solution of 1.6 g of an N-dialkylolamine,

ίο dried and according to one specified in the table Storage time treated with various synthetic resin-forming compounds and cured. The synthetic resin Forming compositions contain 3 g benzoyl peroxide (50% in dibutyl phthalate) per 100 g. Only at Experiment no. 5 uses a non-finished glass fabric and 2.5 g of the specified amine. The polymerization times have been measured at room temperature.

Amine : - ■ * T J ~ | IT Il Ji 11 Resin forming masses Methyl methacrylate syrup,
made according to Belgian or French Methyl methacrylate,
containing 30% of dissolved Poly Unsaturated polyester resin, iltend Solution
middle Patent 572,359 1 221 537 commercial poly- merization J \) DlS OZ / o Poly-. sian patent Poly methyl methacrylate Time entuc merization No. Aging of the merization Aging of the Minutes Aging of the Time : impregnated Time impregnated 35 impregnated Minutes Diethylol mat Minutes mat mat 6th p-toluidine Methyl- Days 25th Days Days meth- 1 20th 8th 45 6th 1 Diisopropylene acrylate 21 5 p-toluidine Methyl- 25th meth- 1 30th 8th '·- 80 6th 2 Diisopropylene acrylate 21 20th 14th m-toluidine Methyl- 30th 40 meth- 1 45 to 50 8th 45 6th 3 Di-n-butylene acrylate 21 8th p-toluidine Methyl- 15th meth- 1 20th 8th - .. 6th 4th Diisopropylene acrylate 21 - p-toluidine Methanol 25th 8th 18th - -. 5 24 20th 35 20th 45

To compare the technical progress that can be achieved by the process according to the invention with the State of the art, as indicated in column 1, the following comparative tests were carried out:

• 1. Use of an untreated fiberglass mat, Adding the peroxide and the amine to the resin;

. 2. Use of a glass fiber mat pretreated with an amine by the process according to the invention, adding the peroxide to the resin;
"3. Using a glass fiber mat pretreated with a peroxide, adding the amine to the resin.

Comparative experiment 1

A laminate was made of three layers of glass mat, spun-split, with a silane finish, 450 g / m ² , size of the three layers: 10 x 20 cm each, total weight 27 g, and 80 g polyester casting resin, containing 30 to 32, between two release films made of polyterephthalate % Monostyrene, to which a further 10% monostyrene was previously added for dilution. 0.2% diisopropylene-p-toluidine and 1.0% benzoyl peroxide were added to the polyester casting resin for curing and mixed well. A thermocouple (iron-constantan) for temperature measurement was embedded in the middle layer of the glass mats and the temperature profile was measured with a millivoltmeter.

After 13 minutes from adding the

■ Amines and peroxides, a temperature maximum of +93 ⁰ C was reached. The laminate is hard after this time. Distributed over the plate, a large number of glass fiber bundles of straw-like white can be clearly seen, which greatly reduces the transparency.

The exact temperature profile is shown in the figure by the curve »Vers. 1 «reproduced.

g Comparative experiment 2

The procedure was as in Comparative Experiment 1, but the same amount of glass mat was previously used 27 ml of a solution of 0.6 g of diisopropylene-p-toluidine

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Treated in 100 ml of ethyl acetate and dry like experiment 1 spread over the plate, straw-like,

net. The 27 ml solution will be bundles of fiberglass visible from the glass mat. The transparency of the plate

completely absorbed, so that the glass mat is evenly significantly worse than in comparative experiment 2.

is damp. The polyester casting resin is 1.0%. The exact temperature profile is shown in the figure

Benzoyl peroxide added. 5 through curve »vers. 3 «reproduced.

After 21 minutes, calculated from complete penetration. The comparison tests show that a clear

soak the three layers of glass mat, a temperature-technical advance is given when the amine

Tower maximum of +59 ⁰ C reached. The laminate is applied to the fiberglass mat. The poly-

after this time hard and shows good transparency merization process is more balanced, creating a

without the straw-like protrusion of the fiberglass bundles, ίο better bond between fiberglass and resin

The exact temperature profile is shown in the picture. The shrinking of the resin from the fiber

through curve »vers. 2 «reproduced. does not enter, so that no white straw-like fiber

_v ι · i, ■ to bundle become visible. The balanced temperature

vergleicnsversucn i raturverlauf with a lower Temperaturmaxi-

The procedure was as in comparative experiment 2, 15 mum is particularly important for practice because the however, the same amount of glass mat is previously exposed to high temperature stresses 27 ml of a solution of 3 g of benzoyl peroxide in 100 ml are missing. Such tensions would lead to crack ethyl acetate treated and dried. Lead to the formation and warping of the finished parts. Polyester casting resin will be 0.2% diisopropylene-p-to- The appearance of straw-like fiber bundles would occur luidine added. 20 also reduces the resistance of the finished parts.

After 15 minutes, calculated from the total throughput, set as a result of its capillary action immersing intrigues of the three layers of glass mat, a temperature will penetrate turmaximum caused by moisture or chemicals from +89 ⁰ C achieved. The laminate is will. As a result, the bond between becomes hard after this time. It shows similarly to resin and fiber impaired.

1 sheet of drawings

Claims (1)

1 2 Patent claim · polyacrylic or polymethacrylic acid esters to the 'Reinforcing fibers, fabrics, mats or Process for the production of strands with glass fibers first a compound, which is a labile chlorine or synthetic fibers reinforced, hardened atom contains, and possibly other components th and deformed plastics on the base 5 of the accelerator system and then location of polyacrylic or polymethacrylic acid esters; these fibers, mats and fabrics with the synthetic resin or unsaturated polyesters using forming masses containing a peroxidic catalyst of organic peroxides as hardeners and N-Di- must contain, treat and then ausualkylolaminen as an accelerator, thereby hardening. indicates that the said io There has now been a process for the production of with Accelerators on the glass fibers, synthetic glass fibers or synthetic fibers reinforced, from- or natural fibers, optionally in _.: hardened and deformed plastics apf the Can be equipped in the usual way, applies the basis of polyacrylic or polymethacrylic acid and then with the organic peroxides esters or unsaturated polyesters using offset synthetic resin-forming masses offset 15 of organic peroxides as hardeners and N-di- and found under shaping with space or tempera-alkylolamines as accelerators, which doors up to 100 ⁰ C cures. > is characterized in that one of the mentioned : Accelerator on the fiberglass, synthetic or natural fibers that may be finished 20 can, and then with the organic ones Resin-forming peroxides Shaped bodies, such as plates, which are made of glass fiber reinforced masses and shaped at Raumten Synthetic resins have been produced for a long time at temperatures or temperatures of up to 100 ° C known. Instead of glass fibers one has to harden. the same purposes are already used by synthetic fibers turns. The difficulties and disadvantages set out above are involved in the production of such shaped bodies of fabrics or mats, which are initially used in production, but especially in continuous unsaturated polyester resins, possibly together with the production of glass fibers or synthetic Plastics reinforced with other polymerizable, organic fibers are avoided. Compounds such as styrene, methyl methacrylate, or 30 The synthetic resin-forming mass can be made from either impregnated or coated with epoxy resins. A monomeric ester of acrylic or methacrylic These structures can be hardened with the aid of catalic acid, preferably methyl methacrylate, or analyzers. with the help of accelerators, consist of an unsaturated polyester resin. she due to the influence of temperature, due to irradiation with but in both cases at least one peroxidic ultraviolet light. It is also possible to see the catalyst in the most evenly distributed carry out the curing at room temperature ^r, lung included. which is with certain advantages, such as efficient production, examples of the invention on the glass bonded. However, this type of hardening also causes considerable difficulties for fibers, synthetic or natural fibers on the other hand. Bringing N-dialkylolamines are diethylol-p-toluidine This is particularly the case with the continuous production 40 and diisopropylol-p-toluidine. The N-dialkylolamine development of the shaped bodies is the case and can be used individually or in a mixture, the limited pot life, the mixture from FIG. ^{1 mixed with the catalyst and, if appropriate, together with Verdem accelerator.} Bonds that contain a labile chlorine atom are applied to the monomeric, polymerizable and polymeric mats. The Oxydationsunemp-connection. Another difficulty here is the very sensitivity of the used. Amine is a self-often the poor adhesion of the synthetic resin to the understandable requirement. Applying the fibers to. In order to avoid this as far as possible, N-dialkylolamine can, according to per se known methods, advance the glass fibers in some way, such as soaking, spraying, etc., and treat them more appropriately. For this, the application of wise subsequent drying, take place. You will use copper oxide on the fibers and the subsequent 50 preferably in the form of a solution. All substances that are volatile and contain silanes or cationic adhesives in which the amines can dissolve can be used as a reduction to metallic copper and the hand-held solvents. • Question. _ ..- ......... examples are methyl methacrylate, methyl acetate, ace- It is also known to better combine clay, methanol and water. In this way, glass fibers can be achieved with the synthetic resin, 55 Of course, when applying the N-Didass one the polymerization of the glass surface alkylolamine, make sure that the finish is allowed to run out. For this purpose, the peroxides of the mat were applied to the glass fiber with sizing, finishing and finishing, while the agents (finish) and binders were not added to the resin as quickly as possible. This enabled it to be removed. This can primarily be reduced by a professional selection of the solution used that reduces the water absorption of the produced structure and the water resistance can be increased. by means of happening. For example, the disadvantage of this method was a requirement that mats, which were made using methanol or the hardening times, and the water that had been impregnated grew soft and loose, risk of underhardening as a result of localization while on the other hand the Use of hardening close to glass. 63 For example, methyl methacrylate or methyl acetate It has also already been proposed that a slight hardening can be established as a solvent in the manufacture of glass fibers or synthetic fibers.
Fibers-reinforced plastics based on After this treatment, the N-dialkylene