HU195526B - Process for producing compositions of two-component saturated and in given case reinforced unsaturated polyester resin base - Google Patents

Abstract

The present invention relates to a process for the preparation of two-component compositions based on unsaturated polyester resin and optionally reinforced. The process according to the invention is characterized by mixing 100 parts by weight of a mixture of 10 to 40 parts by weight of monomer and 90 to 60 parts by weight of unsaturated polyester resin from 0.05 to 0.5 parts by weight of aromatic tertiary amine and 1 to 4 parts by weight of 1% by weight of metal salt. system; and a mixture of 1-4 parts by weight of solid peroxide catalyst and 1-4 parts of softener or liquid carrier is impregnated with 0.2-1 parts by weight of monomer solvent solution, after the impregnation the solvent is removed and clcgylicz is added 10-20 parts by weight, up to 0.01 mm. particle size quartz flour is mixed with microgranules by stirring, and the resulting granules are mixed with 4001,000 parts by weight of solid filler, or 4001,000 parts by weight of solid filler and 5-20 parts by weight of reinforcing material, and optionally mixed with 0.1-0.5 parts by weight of the resulting composition. 10-5 mm silicon dioxide. -1-

Description

FIELD OF THE INVENTION The present invention relates to a process consisting of a two component tetrachloride and optionally reinforced, unsaturated polyester resin; for the preparation and crosslinking of based compositions,

The process of the present invention makes it possible to develop two-component polymer concrete materials for repair or moldings.

Thermoplastic resins, in particular polyester and epoxy resins, and solid filler systems, have been used to make various artificial concrete (polymer concrete) articles for a longer period of time and to repair cracked or defective concrete articles for a longer period of time. The essence of these known technologies is to blend a filler of a particular granular composition, usually a sand-gravel mixture, into a resin which has previously been provided with the necessary crosslinking chemicals, an accelerator, a catalyst, or a crosslinker.

Of course, the resin so blended must be used within a short time, since the irreversible reaction begins immediately.

Therefore, the resin can only be mixed with the catalyst immediately before processing. This has the disadvantage of having to perform measurement operations at the workplace, which in many cases is difficult or impracticable. The known processes for the commercial use of small amounts of resin filler systems are completely inadequate. There is such a demand everywhere, but especially in the construction industry, where only a small amount of material is needed at a time for different repairs.

A sunken staircase, a broken wall surface, can often be repaired with just a few 100g of resin-filler mixture, but for this purpose, for example. in the case of polyester resin, only tens of grams of catalyst would have to be weighed on site, mixed into the resin and then mixed with fillers throughout the system. This is practically impossible. The known procedures require the following operations to be performed before use.

Measure resin, measure filler, measure catalyst, add catalyst to resin, filler into resin.

This is an easy task in laboratories, it is cumbersome at work, on roofs, in buildings and therefore not very widespread, with the widespread use of filled resin systems.

Of course, there are so-called feeders that produce charged systems. polymer concrete machines, which continuously feed the materials, mix. However, these machines are extremely expensive, high capacity (30-100 kg / min), heavy and energy intensive. Their use is therefore not possible with small amounts of material for repairs.

It can be seen from the above that resin filler systems, well known for their polymer or artificial concrete, despite their excellent properties, are not sufficiently used and practically barely used for construction repairs, where small amounts of less than 2-3 kg of material are required per repair site.

A polymer polymer system is described in U.S. Patent No. 2,106,320. Federal Republic of Germany, No. 2,414,837. Federal Republic of Germany, No. 2,521,664. No. 2,994,951 to the Federal Republic of Germany; Federal Republic of Germany, No. 2,948,965 No. 3,004,329 of the Federal Republic of Germany; No. 75 121 315 of the Federal Republic of Germany; Japanese Patent No. 7,688,528. Japanese, No. 7,776,520; Japanese Patent No. 2,006,219. English, Romanian Publication No. 67,009. From the study of these, it can be seen that in the state of the art 2, there is no system that meets the objectives of the present invention.

German Patent Publication No. 3,226,602 discloses a system in which a plasticizer-pasteurized catalyst is mixed with a polyester resin.

In U.S. Patent No. 4,273,689, the catalyst benzene peroxide paste is mixed with the filler. ^j γ

However, it is not possible to mix the catalyst with the filler or the resin to be crosslinked for complete homogeneity by known methods, which adversely affects the mechanical properties of the finished product.

It is an object of the present invention to provide a filled polyester resin based tendering system, such as polymer concrete, which consists of only two components, resin and filler, which means that it does not require a complicated measuring operation when used,

From a morphological point of view, the components can be used without measurement, the Emergency Blend is suitable for the production of individual polymer concrete products for vertical and horizontal formation of thin and thick layers, for concrete repair,

The crosslinked finished product is high strength, abrasion resistant, non-sticky. It is also applicable to the manufacture of polyester resin based systems, but may also be used with other synthetic resin initiator systems. These include, preferably, epoxy resins, phenol formaldehyde and furan resins.

The invention is based on the following insights;

With a suitable composition, a resin filler system can be formed in which the filler component includes all the curing agents as well as the morphological additives, so that only two components are to be mixed before use. The quartz cluster is preferably used as filler, but any other organic and inorganic filler may be used.

Further, it is recognized that the filler system can be provided with a composition and structure that does not necessarily require weight measurement when used. When the filler is added to the resin, the appropriate amount of crosslinker and other additives, together with the filler, is introduced into the resin with a relatively high degree of accuracy to achieve the viscosity required for use. Thus, for the first time, it is possible to work with polymeric concrete such as conventional materials such as gypsum, water.

When the polymeric concrete according to the invention is used primarily in the open air, the crosslinking must be carried out in such a way that it is suitable for the system to operate over a wide temperature range (+5 to -40 ° C), of course without changing the crosslinking amount and mixing ratio. According to the present invention, this can be achieved by a physical rtardation procedure.

According to the invention, a solid peroxide catalyst is used and a mixture of it with a plasticizer is impregnated with a portion of the monomer. The catalyst particles so coated and the very fine filler are further formed into a microgranule containing the catalyst inside the pellet.

The resulting microgranules are then mixed with additional filler or reinforcing material.

This system forms component B) of the composition of the invention. Component A) contains-21

195 526 glaze the remainder of the monomer, the resin and the accelerator.

Preferably, dinethylaniline or diethylaniline is used as the accelerator when using a benzoylproxide catalyst. In order to eliminate the oxygen sensitivity of the surface layers, a solution of cobalt naphthenate in xylene, which may contain 1/1000% of 3-nitroalizarin, is added to the resin. Thus, one of the components of the two-component system of the invention, i.e. the resin component, is prepared and stored in a suitable container, preferably in a metal container, for a long period of time of 3-10 months.

The assembly of the filler system according to the invention requires a particular solution. Here, the catalyst is contained in the filler material itself, in such a uniform distribution that any amount of filler material, wherever it is mixed with the resin in sufficient proportion, produces the desired crosslinking process. Such a system has not been possible so far. This is readily apparent as the catalyst content is 2-4% of the resin and only a fraction of the filler. It is almost impossible to introduce such a small amount into the filler system with proper uniformity. Therefore, according to the invention, the catalyst is converted into conglomerates with a small fraction of a filler system. The conglomerates are evenly distributed throughout the filler system and, with the aid of an additive, are attached to larger particles of the filler system.

The process uses a so-called binder or adhesive which is compatible with the polyester resin. Suitable for this purpose eg. styrene, polyvinyl acetate. The process of the present invention is primarily directed to the use of benzoyl peroxide catalyst systems.

In this case, the fine benzoyl peroxide-dicyclohexyl phthalate particles are glued with a fine filler particles, preferably one hundred millimeter quartz flour particles, using a mixture of ethyl alcohol and styrene.

Styrene polymerizes upon contact with the catalyst particles and low molecular weight polystyrene, as a coating, adheres the filler particles to the catalyst particles. In this way, the crosslinking particles are separated from each other, do not adhere under any circumstances and can be homogeneously distributed in the filler system.

The role of ethyl alcohol is to facilitate the wetting process and to reduce the surface tension of styrene. Thus, according to the invention, one of the small particle size fractions of the filler system and the catalyst are used to form conglomerates in which the organic peroxide catalyst is contained within the conglomerate. The particles thus formed are mixed with the total amount of filler.

According to the invention, a further step is taken to achieve perfect homogeneity.

The mixed catalyst granulate is distributed with a colloidal particle size additive in larger particles of the filler. For this purpose, 0.1 to 1% by weight of colloidal silicon oxide is added to the filler system. These small 10 micron colloidal disks exert an adhesive effect and bind the catalyst containing conglomerates to the larger particles. This ensures that the catalyst is evenly distributed throughout the filler system and does not disintegrate during movement or transport.

The process according to the invention has further advantages. Organic peroxide catalysts and crosslinking agents in general are moisture, oxygen and photosensitive. If the catalyst particles are encapsulated, they will be prevented from premature decomposition.

It is another object of the present invention that the two-component mixture can be used over a wide temperature range without changing the ratio. It is known that more or less catalysts may be added to the resin, depending on the ambient temperature and technological need, within certain limits. Of course there are minimum and maximum quantities of catalysts.

In polymeric concrete, outside workplaces should be given sufficient time to work, even at temperatures of 4 ° C. A small amount of catalyst is required. But you have to work with the same composition, maybe the next day at significantly lower temperatures.

We want to do this with the original two-component system without changing the ratio. The use of inhibitors does not work because, in cold environments, the induction period is shifted so much that it impedes the technology and causes other deleterious effects (evaporation of styrene).

By placing the catalyst as granules in the system as described above and placing it in a "shell" as described above which prevents immediate contact of the catalyst with the resin, the process of curing can be retarded. This is achieved by starting the catalyst through diffusion causing crosslinking. Thus, after mixing the two components, the catalyst does not come into contact with the resin after cross-linking, i.e. no curing occurs for a period of 5 to 10 minutes. By diffusion local polymerization foci are formed, but at this stage the entire system is still liquid because of a non-polymerized resin layer on the filler particles. Thus, the material can be spread and processed for a relatively long time. it is only as the polymerization progresses that the gelation begins to cross-section the entire resin when the inert material cannot be formed without damage. In this way, the filled polyester composition of the present invention can be processed for about twice as long as conventional resin systems.

According to the invention, it is expedient to provide a two-component polymer concrete system which is suitable for both repair and self-assembly.

In the conventional method of repair, the surface to be repaired is first moistened with a catalyst resin and then applied with a polymer concrete layer to ensure proper bonding.

When using the composition of the present invention, it is not necessary to formulate compositions with a higher resin content than usual. The resin: filler / filler ratio of 1: 5 to 1: 7 is formed by adding colloidal silicon oxide, which also serves to reduce the tendency to flow, to the resin component.

The retarded polymerization process by diffusion allows processing over a wide temperature range without changing the volume ratios. The retarded process also results in improved strength properties.

The composition of the invention for repair, 3

195 526 can be used on vertical and horizontal surfaces suitable for surface coating as well as for self-assembly. Thus, the process according to the invention is characterized in that a mixture of - 100 parts by weight - 10-40 parts by weight of monomer, preferably styrene, or methyl methacrylate and unsaturated polyester resin is mixed with 0.05-0.5 parts by weight of aromatic tertiary amine and 1-4 parts by weight. a mixture of 1-4 parts by weight of a solid peroxide catalyst, preferably benzoyl peroxide and 1-4 parts by weight of a plasticizer or liquid carrier, is impregnated with 0.2-1 parts by weight of monomer, preferably styrene or methyl solution of methacrylate, the solvent is removed on the impregnation pad and 1020 parts by weight of quartz flour up to 0.01 mm are added to the mixture to form microgranules with stirring, and the resulting granulate is mixed with 400-1000 parts by weight of solid or 400 parts. solid filler and 5 to 20 parts by weight of a reinforcing agent, and then 0.1 to 0.5 parts by weight of silica having a particle size of 10 to ⁵ mm is optionally added to the resulting composition.

The following examples illustrate the process of the invention.

Example 1

An adhesive solution was prepared from 4 g of ethyl alcohol and 2 g of styrene. This solution is applied to a solid initiator (catalyst) particle (Φ 0.1 mm) consisting of 10 g of dicyclohexyl phthalate and 10 g of benzoyl peroxide. After evaporation of the ethyl alcohol, 80 g of quartz flour (grain φ 0.01 min) was added to the mixture, which was uniform! They are distributed on the surface of the initiator particles. The quartz flour particles are glued to the initiator by the polystyrene prepolymer formed by the latter. The initiator particles prepared in this way are mixed with 3000 g of quartz sand gravel with a grain size of 0-5 mm. To this was added 1.5 g of colloidal silica with stirring. (Component B)

A homogeneous mixture of 350 g of unsaturated polyester resin, 150 g of styrene, 0.5 g of dinethylaniline and 10 g of xylene cobalt naphthenate is then prepared. (Component A)

When used, the resin-containing component "A" is added with stirring to component "B" prepared as above. The artificial concrete mix thus made is suitable for filling a repair space of 1800 cm ³ .

Depending on the external surface temperature, the mixture will solidify within 1-3 hours and may be used after another 24 hours.

Mixed concrete objects, eg. cracked steps, repair or fasten base bolts, anchor bolts in holes fixed in concrete.

Example 2

Component B, prepared according to Example 1, is prepared except that 750 g of quartz flour with a particle diameter of 0.01 mm is added instead of 3000 g of quartz sand gravel 4. During processing, this "B" component is mixed with the "A" component of Example 1. Then the mixture thus prepared is poured into the cavity of electric motors, transformers. The crosslinking is accelerated by heating to 80 ° C and is completed in 60 minutes.

Example 3

Kompon Component B of Example 1 was prepared, but instead of 3000 g of quartz sand gravel, 100 g of polyethylene powder was added to 106 g of solid catalyst mixture, followed by addition of 10 g of colloidal silica.

When used, 500 g of Component A according to Example I are mixed with Compound 3 prepared as above. The mixture thus prepared fills the voids between the rigid polyurethane foam boards, thereby providing a flexible connection between the polyurethane elements.

Example 4

All were carried out as in Example 1, but with 50 g of 5 mm long glass fiber 10 mm in diameter, component B of Example 1 was mixed. To Component B prepared in this manner is added Component A to Example 1. Λ The resulting composition is used to make a high strength Ion object.

Example 5

Ατ. The procedure is as in Example 1, but the components are thousands of times! proportion.

Smaller portions of the composition obtained after mixing components A and B are used for repair work, after 4 hours at + 5 ° C and after 30 minutes at + 40 ° C, the product cures and solidifies.

Example 6

Component B prepared according to Example 1 was prepared. but instead of 3,000 g of quartz sand gravel, 200 g of slurry polyvinyl chloride powder is added and 10 g of colloidal silica is added instead of 1.5 g of colloidal silicon dioxide.

When used, 500 g of Component A of Example 1 is mixed with Compound B prepared as described above.

The mixture thus prepared fills the voids between the rigid polyurethane foam boards, thereby providing a flexible connection between the polyurethane elements. ·

Example 7

A solution was prepared from 4 g of ethyl alcohol and 2 g of styrene. This solution is applied to a solid initiator particle of 0.01 mm in diameter consisting of 10 g of water and 20 g of benzoyl peroride. Evaporation of ethyl alcohol

After 195 526 100 g of quartz flour (particle diameter 0.01 mm) was added to the mixture, which was uniformly distributed over the surface of the initiator particles.

The quartz flour particles are bonded to the initiator by the polystyrene oligomer formed in situ. The resulting mixture 5 is mixed with 10,000 g of quartz sand gravel of 0-5 mm.

5 g of colloidal silica are then added with constant stirring. (Component B)

Then, to a mixture of 600 g of saturated polyester resin, 200 g of methyl inctaacrylate and 200 g of filters are added 5 g of dictylyl allyl and 40 g of cobalt naphthcnate in xylene, the latter having a cobalt content of 1% by weight. (Component A)

When used, Component A is added with continuous mixing of Component B prepared as described above.

The ready-mixed concrete mix is suitable for filling 5,000 cm ^{3 of} repair space. The mixture is ready to use within 30 minutes. 20

Depending on the external surface temperature, the material will solidify within one to three hours and may be used as intended after another 24 hours.

Example 8 ²⁵

Component B of Example 7 was prepared, but instead of 10,000 g of quartz sand-caviar, 8,000 g of 0-3 mm dried dolomite was used.

A homogeneous mix was then made from 700 g of polyester resin, 300 g of styrene, 3 g of dinretilanyl and 1 g of cobalt naphthenate in xylene (cobalt content 1% by weight). When used, mix with component A the component B prepared as described above. The resulting artificial stone mixture with a volume of 4500 cm ³ should be used within 35 hours.

The mixture solidifies after 3 hours and can be used as intended after 24 hours.

Example 9

In all of the procedures of Example 8, marble meal of the same grain size was used instead of dolomite.

Comparative Example 10

The components described in Example 1 are formulated, but for comparison, the catalyst is not coated with a styrene monomer. Component B is thus prepared by homogenizing the paste consisting of 10 g of benzoyl peroxide and 10 g of dicyclohexyl phthalate with the filler. The filler used is a mixture of 3001.5 g of quartz sand gravel (i.e., quartz sand is used instead of 1.5 g colloidal silica). 55

Component A contains 350g of unsaturated polyester resin,

It contains 152 g of styrene, 0.5 g of dimethylaniline and 10 g of a solution of cobalt naphthenate in xylene.

Components "A" and "B" are mixed and molded therefrom, which is cured for a period of time as described in Example 1.

Components A and B prepared as described in Example 1 are similarly prepared as specimens.

The bending and compression values of the specimens produced according to the invention and produced from the control body position are measured.

The results are as follows:

Flexural strength. Compressive strength, N / mm ² N / mm ²

control Example 1 control Example 1 Test piece 1 26.2 27.8 65 112 2nd test specimen 19.4 27.4 84 106 3rd test specimen 22.3 26.2 93 108 Test piece 4 21.5 28.5 67 111 Test piece 5 243 27.2 82 104 Test piece 6 19.7 26.3 89 111 Average 22.2 27.2 80 109.16

The test results show that, due to the substantially more homogeneous structure, the test results of the specimens obtained from the composition of the present invention are less scattering and show higher values.

Claims (5)

PATENT CLAIMS !. Process for the preparation of two-component filled and optionally reinforced crosslinkable polyester resin based compositions, unsaturated polyester resin, monomer, initiator. a mixture of accelerator, filler, and reinforcing material, wherein 100 parts by weight of a mixture comprising from 10 to 40 parts by weight of monomer and 90 to 60 parts by weight of unsaturated polyester resin are mixed in an amount of 0.05 to 0.5 parts by weight. with an accelerator system consisting of aromatic tertiary amine and 1 to 4 parts by weight of a metal salt; as well as A mixture of -1 to 4 parts by weight of solid peroxide catalyst and 1 to 4 parts by weight of a softener or liquid carrier solution is impregnated with 0.2 to 1 part by weight of monomer solvent, after which the solvent is removed and 10 to 20 parts by weight are not added. quartz flour, - mixing to form microgranules, the granulate thus obtained is admixed with 400-1000 parts by weight of solid filler or 400-1000 parts by weight of solid filler and 5-20 parts by weight of a reinforcing agent, and optionally further mixed with 0.1- 0.5 parts of 10 mesh silica ^-s. The process according to claim 1, wherein the monomer is styrene or methyl methacrylate. Process according to claim 1 or 2, characterized in that the accelerating metal salt is cobalt naphthenate, 4. Process according to any one of claims 1 to 3, characterized in that the filler is a mixture of quartz flour and sand, dolomite, marble powder, PVC powder. 5. A process according to any one of claims 1 to 4, wherein the reinforcing material is glass fiber.