DE1130165B - Process for the manufacture of fiber reinforced plastics from polyester resin compositions - Google Patents

Description

GERMAN

PATENT OFFICE

D 33505 IVd / 39b

REGISTRATION DAY: JUNE 9 , 1960

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL MAY 24, 1962

Shaped bodies, such as plates and the like, which are made from glass fiber reinforced synthetic resins, are already available known for a long time. Instead of glass fibers, synthetic fibers are also used for the same purposes Fibers used. To produce such moldings, fabrics, mats or the like are used. from, which are first treated with unsaturated polyester resins, optionally together with other polymerizable, organic compounds such as styrene, methyl methacrylate and the like, or impregnated with epoxy resins or coated. The hardening of these structures can be done with the help of catalysts accelerators, exposure to temperature, exposure to ultraviolet light take place. It is also possible to cure at room temperature, with certain Advantages, such as efficient production, is connected. On the other hand, this type of hardening is beneficial also significant difficulties with it. This is especially true in the continuous production of the Molded body the case and is due to the limited pot life of the with the catalyst and the Mixture of the monomeric, polymerizable and polymeric compounds mixed with accelerators. Another difficulty here is very often the poor adhesion of the synthetic resin to the Fibers on. In order to avoid this as far as possible, it is known to pretreat the fibers in some way. This is done by applying copper oxide to the fibers and then applying them Reduction to metallic copper and treatment with silanes or cationic adhesives in question.

It has also become known that a better bond between the glass fibers and the synthetic resin can thereby be achieved achieve that the polymerization was allowed to proceed from the glass surface. For this purpose were the peroxides were applied to the fiberglass while adding the accelerator to the resin. It were able to reduce the water absorption of the produced structure and the water resistance increase. The disadvantage of this process was an extension of the curing times, in addition, the risk of underhardening increased as a result of localization of the hardening close to the glass.

It has also been suggested in the manufacture of fiberglass or synthetic Fibers reinforced plastics based on polyacrylic or polymethacrylic acid esters to the Reinforcing fibers, fabrics, mats, strands and the like, first hydrochlorides or chlorides organic bases or inorganic hydrochloric acid salts,

Method of manufacture

of reinforced by fibers

Plastics made from polyester resin compounds

Applicant:
German gold and silver separator

formerly Roessler,
Frankfurt / M., Weißfrauenstr. 9

Dipl.-Chem. Dr. Erich Bäder, Hanau / M. ₃
has been named as the inventor

which contain a labile chlorine atom and optionally other components of the accelerator system to apply and then these fibers, mats and fabrics with the polyacrylic or polymethacrylic acid ester mass, which must contain a peroxide catalyst, to be handled and then cured.

It has now been found that the difficulties and disadvantages identified above in the production, but especially in the continuous production of fiber reinforced plastics Polyester resin compositions, the unsaturated polyester, organic peroxides as catalysts, hydrochlorides or chlorides of organic bases or inorganic salts of hydrochloric acid as accelerators and optionally further known accelerators and optionally monomeric, partially polymerizable, organic ones Containing compounds can be avoided by using the reinforcing fibers that are also in Form of fabrics, mats or strands can be present, first with the hydrochloride or chloride the organic base or the inorganic salt of hydrochloric acid and optionally with a further one Treated known accelerator and then the unsaturated polyester resin composition (A) optionally together applied with a polymeric substance (B) and then hardened. The polyester resin mass (A) must contain a peroxide catalyst in uniform distribution.

The accelerator with which the fiber is treated must at least consist of a hydrochloride or Chlorides of an organic base or an inorganic salt of hydrochloric acid consist. Besides that, you can on the fiber further known as accelerators

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Compounds, in particular copper compounds, contain polymethyl methacrylate and after a to be brought. This also includes conventional organic known processes in a so-called Sulfur compounds, such as a-aminosulfones, a-oxy "one-pot reaction", preferably using sulfones and mercaptans. Of these substances, a sulfur-containing regulator, for example one a-aminosulfones, which contain at least one aromatic 5 mercaptans or its derivatives, or in the presence of a residue contain, and mercaptans are preferably used. a radical-forming catalyst, such as azo

The application of the above substances can be diisobutyric acid dinitrile, which has been produced. according to known methods, such as soaking, spraying. In many cases it is also advantageous to use further

etc., and expediently subsequent dry monomeric, polymerizable organic compounds take place. The substances are preferably fertilized in the form ίο (C), such as styrene, vinyl acetate, acrylonitrile, a solution used. Vinyl toluene, diallyl phthalate, allyl methacrylate and all substances that are volatile and accelerate to common crosslinkers, such as ethylene glycol dimethacrylate, can be used as solvents. be able to solve, be used. Examples are triallyl cyanurate, divinylbenzene and the like to be added. Methyl methacrylate, methyl acetate, acetone, methanol As already stated, according to the invention

and water. 15 according to the method of the accelerator or accelerators

Of course, when applying the coating to the surface of the fibers, mats, fabrics, It is faster to ensure that the finishing of the strands and the like is applied in a fine distribution. in the Mat with sizing, finishing and finishing agents in contrast to the previously known process (Finish) as well as with binders if possible not removed because the peroxide has been applied to the mat will. This can primarily be done by a professional, if it is a storable structure. Other niche On the other hand, the choice of solvent used is also the synthetic resin, which only the peroxydschehen. This is how mats feel, for example, the catalyst and possibly one or more using methanol or water in part of the accelerator system, also have been impregnated, soft and loose, while storable, and indeed this mass can be several on the other hand when using, for example, 25 weeks at room temperature and at lower methyl methacrylate or methyl acetate can be stored at temperatures for a few months, solvent can detect a slight hardening. When applying these masses to the fibers

After this treatment, the substances in the accelerator components and the very come lie finer distribution on the surface of the fibers, Ge catalysts in contact with each other, so that a weave, mats and the like. The fibers 30 treated in this way harden very quickly. This curing are very durable and can be stored for almost any length of time. is with good success at room temperature and also As copper compounds, the various can be carried out at elevated temperature. As another most like salts and complexes of copper used. Organic copper causes are preferably mentioned that the polymerization of the Bonds used that go out like copper naphthenate in the fiber, so that a shrinking of the synthetic resin forming mass are easily soluble. It is made of resin on the fiber. Since also that are evenly distributed in small amounts, preferably in ppm peroxide, in the synthetic resin compound Amounts, based on the resin-forming mass, post-curing is made much easier, and it is used. . there is no risk of underhardening. The structures produced according to this process show a very good result contain, for example, the chlorinated water- good bond between fiber and resin, whereby chemical acid and its salts, especially organic, weather resistance and wet strength are very strong Bases, e.g. B. the tertiary amines. Furthermore, for can be improved.

The same purpose quartchloride and betaine or otherwise the method according to the invention can

Hydroxylamine derivatives can be used. 45 advantageous also when applying pressure and /

Glass or elevated temperatures are preferably used as reinforcing fibers, fibers used. But there are also synthetic fibers, which is to be noted as a notable advantage Polyamide fibers and polyester fibers and naturally that lower temperatures than usual Borrowed fibers as well as fabrics made from them, hot forming usual, can be adhered to mats, Strands and the like can be used with good success. 50 nen, and in general temperatures Polyester resin compositions are expediently not exceeded by 100.degree. Preferably finds in a mixture with a polymeric substance (B) in men- this type of curing at temperatures of 50 gen up to 50% and / or together with a mono to 70 ° C, while otherwise temperatures of 100 mer, polymerizable, organic compounds up to about 150 ° C have been required. Through this Formation (C) hi quantities of about 5% to 70% are used in particular for the production of thick-walled parts det. The polymeric substances (B) are particularly relieved because blistering is not an issue the polymers of the esters of acrylic or fear, since yes in the case of the ver methacrylic acid according to the invention; Polymethacrylic is preferably the boiling point of that present in the synthetic resin acid methyl ester used. These substances cannot be monomers. In addition, we will live here or used in a mixture with one another. 60 with a better bond between the synthetic resin Furthermore, the polyester resin composition can also contain the den and the glass fiber. As a result of the very last named polymeric substances corresponding neatly short curing time is a faster end of monomers be added; Likewise, it is often possible to reproach the manufactured parts, Partially, the polymeric substance (B) in only partially polymerized The constituents of the invention

to use in a state of the art. Preference is given to using catalysts or accelerators Monomer-polymer mixtures of the acrylic acid ester systems are known. Even the quantities in and methacrylic acid esters, in particular of methyl- which these are advantageously used methacrylate, which has already been described several times up to about 50 to 60%. It recommends

but the peroxides, based on 100 g of the synthetic resin, are in an amount of 0.5 to 2.0%, the hydroperoxides up to 1.0%, the organic sulfur compounds up to 0.5%, the copper compounds in Quantities from 10 to 3000 / and the hydrochlorides or chlorides of organic bases or the inorganic bases hydrochloric acid salts should be used in amounts of 0.01 to 0.5%. If you relate the quantities to what is used Fabric, the type of product to be manufactured must be taken into account, as is well known the proportion of fabric in the production of, for example, panels is 25 to 35%, while it is in the Production of pressed parts or the like. Can make up 60 to 80%.

The inventive method is also particularly good for the continuous production of fiber-reinforced plastics suitable, namely can both the impregnation with the accelerator and the application of the synthetic resin are continuous be performed. For example, the fiber web can with the help of pairs of rollers over or be carried out through a trough-like or tub-like container and at the same time from above with the solution of the accelerator or with the synthetic resin from a tank of 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.

example 1

The table below shows the results of some tests that were achieved when the process according to the invention was carried out. There were alkali-free glass silk mats per 100 g of their weight with 120 ml of a solution of 0.3 g of the hydrochloride or chloride of an organic base or the hydrochloric acid, inorganic salt soaked, dried and after a storage time of 5 to 6 days with a mixture of an unsaturated Polyester resin and monostyrene treated. This mixture contained 1.6 ml of tert in 100 g. Butyl perbenzoate (50% in dimethyl phthalate), 0.2 g bis (tolylsulfonmethyl) amine paste (50% in dibutyl phthalate) and 0.1 ml copper naphthenate, dissolved in methyl methacrylate (100 γ Cu ⁺ + / ml).

accelerator Solution
middle Polymeri sation time No. Dimethylamine-H Cl methyl at room
tempe-
advises u τ metha Minutes 1. crylate 20th Dimethylamine-H Cl Methanol Dibutylamine HCl methyl 2. metha 15th 3. crylate 10 Dibutylamine HCl Methanol Triethylamine-HCl Methanol 4th Tolylethyldibutyl- Ethyl acetate 10 5. amine-HCl 10 6th Triethylamine oxide Methanol 10 HCl 7th 10

No. 6th accelerator Solution
middle Polymeri sation time at space
tempe 8th. NH ₂ OH-Cl Methanol rature 9. Betaine hydrochloride Methanol Minutes O 10. Tetraethylammonium Ethyl acetate 10 chloride 25th 11. Phenylethyldibutyl Ethyl acetate 10 ethylene ammonium IO chloride 10 12th Triethylammonium Methanol ethyl acetate chloride 10 13th Phenylethyldibutyl Methanol 15th ammonium- acetic acid- 8th ethyl ester chloride 20th

Example 2

A cotton fabric is 75 g per 110 ml of its weight with a solution of 0.25 g Phenyläthyldibutylaminhydrochlorid and 0.25 ml of a copper solution (1000 γ ⁺ Cu + as naphthenate per ml) in monomeric methyl methacrylate, dried, and after storage for 24 hours treated with an unsaturated polyester resin. 1.5 g of a 50% lauroyl peroxide paste (in dioctyl adipate), 0.25 ml of methyl ethyl ketone peroxide solution (40% in dimethyl phthalate) and 0.22 g of bis (tolylsulfonmethyl) amine paste ( 50% in dibutyl phthalate). A laminate consisting of four layers of the treated cotton fabric with the polyester described is cured in 120 minutes at room temperature.

Example 3

The procedure is as in example 2. Instead of the cotton fabric, however, a tricot fabric is made Polyaminocaprolactam used. A laminate of four layers of the treated fabric with the described polyester is cured in 70 minutes at room temperature.

Claims (7)

PATENT CLAIMS: 1. A process for producing fiber reinforced plastics from polyester resin compositions which contain unsaturated polyesters, organic peroxides as catalysts, hydrochlorides or chlorides of organic bases or inorganic salts of hydrochloric acid as accelerators and optionally other known accelerators and optionally monomeric, polymerizable organic compounds, thereby characterized in that the reinforcing fibers, also in the form of fabrics, mats or strands, are first treated with the hydrochloride or chloride of the organic base or the inorganic salt of hydrochloric acid and optionally with another known accelerator and then the polyester resin composition (A) optionally together applied with a polymeric substance (B) and then hardened. 2. The method according to claim 1, characterized in that the curing in space 7 8 temperature or at least at temperatures 4. The method according to claims 1 to 3, da- below 100 ° C. characterized in that one is called polymeric 3. Process according to Claims 1 and 2, substance (B) polyacrylic or polymethacrylic acid esters characterized in that the hydrochloride is used individually or in a mixture, optionally in an rid of an organic base the hydrochloride of a 5 essence of the corresponding monomers, Amine used. turns. © 209 601/462 5.62