TW200401798A - Liquid duroplastics - Google Patents

Abstract

Reinforced liquid duroplastics are prepared by adding to the duroplastics a pyrogenically prepared silica which has been surface-modified with silanes containing methacrylic groups.

Description

200401798 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for strengthening liquid hard plastic, and related hard plastic. [Previous technology] Hard plastic refers to all plastics made from curable resins. According to D IN 7 7 2 4, when the decomposition temperature is reached, they are highly cross-linked, closed sieve highly polymerized materials. These materials are steel at a lower temperature and elastic at a temperature of 50 ° C or higher to the decomposition temperature. There are extremely restricted and flexible behaviors. Shear modulus does not fall at 102kp / cm2 at any temperature. Hard plastics are usually amorphous. Due to the cross-linking of hard plastic, they cannot perform any micro-Brownian motion. On the other hand, the Brownian motion of polymer molecules at the glass transition temperature (which is higher than 5 0 t) is 0. The term hard plastic is the same as the name hard body (dur 0 me Γ), which is better because it Formally more closely related to elastomers and plastics (sex plastics), when these two other types of plastics are named. Hard plastics are widely used as molding compositions, casting resins, resins, and lacquer resins. Hard plastics especially include diallyl phthalate resin (), epoxy-melamine-formaldehyde resin (MF), melamine-phenol-formaldehyde resin (MP), phenol-formaldehyde resin (PF Commercially important material group of unsaturated polyester resin (UP)

Eyes and shapes of the sub-permanently powerful thermoplastic resin sometimes connected to DAP (cyanocyanine) and DIN (2) (2) 200401798 7 7 2 8 5 P 1; 1 9 8 8 January 1 , Which is abbreviated in parentheses). It is known to use powdered silica as a filler for polymers. Usually ' is surrounded by a softer polymer in the form of a hard phase to provide a finer distribution of the modified material / many of the commercially available valuable mechanical properties. These include hardness, tensile strength, stress and other measurable properties. In principle, there must be a distinction between thermoplastics and crosslinkable polymers. Shi Xishi can be used as a material in this kind of materials. However, the amount and effect of addition may vary greatly depending on the polymer. It is also known as a thickener in liquid hard plastics. However, that is not the subject of the invention; instead, the thickening effect of sand and gravel should be as small as possible. This invention describes the use of silica modified with unsaturated organic groups in reactive polymers of low molecular weight, usually liquid. It is known that it is possible to achieve an advantageous combination of rheology and mechanical properties, that is, on the one hand, low viscosity and low flow limit in the uncrosslinked state, and, on the other hand, high hardness and high in the crosslinked state Modulus. It is known that the polymers used in polymers are treated with vinyl silanes or methacrylic silanes to obtain advantageous properties in the crosslinked products. This is done in the prior art during the mixing of the aggregate into the polymer. The disadvantage of that procedure is that the sequence of chemical reactions required for the desired bonding of the silane to the solid occurs in an uncontrollable environment, and its reproducibility needs to be improved. Furthermore, alcohols are formed as an unavoidable waste product; alcohols are often unwanted constituents of polymer materials that cause injuries and must be removed in complex operations. Silanes themselves and the cracked products formed by them are hazardous sources in terms of flammability and toxicity (3) 200401798 and often require additional safety measurements and investigations. It is therefore desirable to use a polymer which already contains the desired reactive gene and which does not release any undesired polymers or into the environment. [Summary of the Invention] The present invention provides a method for strengthening a liquid hard plastic. The method is characterized by preparing a mixture of uncrosslinked resin and silica prepared by pyrolysis that has been surface-modified with methacrylic group-containing silanes. .

The present invention also provides liquid hard plastics, which are characterized in that they contain fumed silicas which have been surface-modified with methacrylic group-containing silanes. In a particular entity of the invention, the silica prepared by pyrolysis can be modified structurally. According to the present invention, a particularly effective material is a kind of silica, which contains methyl propionate: ¾ acid-based groups and has been prepared by flame hydrolysis and its structure has been changed by mechanical post-treatment. Pyrolytic BET surface area that can be used in accordance with the present invention, particle size in meters to grams, nanometer 塡 filling density, gram / liter pH 値 carbon content ,. 4 DBP number, 0/0 can be prepared in the following way: The prepared silica is characterized by: 20 to 380 6 to 1 1 〇5 0 to 6 0 0 3 to 1 0 〇 1 to 1 5 < 200 first Intense in a suitable mixing device

(4) (4) 200401798 Mix silica with water or dilute acid, and then mix the surface modifier; or apply a mixture of different surface modifiers by spraying. The ingredients are further mixed for 15 to 30 minutes, and then heat-treated at 100 to 400 ° C for 1 to 6 hours. In the preferred entity of the present invention, silica prepared by pyrolysis can be used as the silica. Pyrolyzed silica is prepared from volatile silicon compounds such as SiCl4, methyltrichlorosilicon or the like. They are known from U 11 ma η η s Ε η zyk 1 0 padiedertechnischen C hemie 4th edition, 21st volume, 46.4 pages (1 982). In a preferred entity of the present invention, it is possible to use Fumed silica with a BET surface area of 200 m2 / g. As for the surface modifying agent, a monomer substance such as methacryloxypropyltrialkoxysilane can be used, in which the alkoxy group means nailoxy, ethoxy and / or propoxy. An essential feature of the present invention is the linkage of the photopolymer to the reactive monomers and oligomers of the lacquer for photopolymerization. Surprisingly, it has been found that, using a special liquid resin system, even if light is not present, silica containing methacrylic groups that has been prepared by flame hydrolysis and whose structure has been changed by institutional post-treatment will be disproportionate. Rigid polymers, which are distinguished by advantageous properties. Examples of such resin systems are: • Unsaturated polyester resins of different compositions: A. Ethylene unsaturated polyester, -8-(5) (5) 200401798 B. Ethylene unsaturated monomer copolymerized with A, C. 5 to 30% by weight of fibrous reinforcing agent based on A + B, D. Optionally, powdery concrete, E. Optionally, 0.5 to 5% by weight of thickener based on A + B, F. Based on A + B, 0.5 to 5% by weight of organic peroxides, G. Aromatic amines, metal salts of organic acids, such as cobalt compounds, Η. Optionally, further customary additives. A. As for unsaturated polyesters, suitable are the general polycondensation products of the following: polyvalent, especially divalent carboxylic acids and their esterifiable derivatives, especially acid anhydrides, which are linked to the polybasic by way of esters, In particular, diols, and optionally additional unit alcohol and / or hydroxycarboxylic acid groups, at least some of which must have copolymerizable groups that are unsaturated in ethylene. As for the multi-element, especially di-valent, optionally unsaturated alcohols, suitable are general alkanediols and oxaalkanediols having acyclic or cyclic groups, such as ethylene glycol, 1,2-propanediol, 1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylene-1,3-propanediol, diethylene glycol, triethylene glycol Glycol, polyethylene glycol, dipropylene glycol, 1,2-cyclohexanediol, 2,2-bis (hydroxycyclohexyl) propane, trimethyl alcohol propane monoallyl ether, or 1,4-butanediol . It is also possible to use co-existing auxiliary amounts of mono-, tri-, or polyhydric alcohols, such as ethylenehexanol, fatty alcohols, benzyl alcohol, 1,2-bis (allyloxy) propanol- (3 ), Glycerol, pentaerythritol, or trimethylol propane. Polyol's, especially diols, are usually reacted stoichiometrically with polyvalents, especially dicarboxylic acids or their condensable derivatives. (6) (6) 200401798 Suitable carboxylic acids and their derivatives are binary, olefinically unsaturated, preferably mono-olefinically unsaturated carboxylic acids such as maleic acid, fumaric acid, chloromaleic acid ' Itaconic acid, methylene glutaric acid and mesaconic acid and their esters or, preferably, their anhydrides, in addition, may have other binary unsaturated and / or saturated and aromatic residual acids having a modification effect. Condensation into polyesters, for example, succinic acid, glutaric acid, methylglutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, dicarboxylic acid Hydrophthalic acid, Tetrahydrophthalic acid, Tetrachlorophthalic acid, 3,5-Pyridynyl, 1,2,3,6-tetrahydrophthalic acid, Pyridyl tetrachlorophthalic acid or Hexachloroprylidene Tetrahydrophthalic acid, as well as mono-, tri-, and more carboxylic acids such as ethylhexanoic acid, fatty acids, methacrylic acid, acrylic acid, and propionic acid 1,2,4,5-benzoic acid. Maleic acid and its anhydride and fumaric acid are preferably used. Unsaturated polyesters which have been prepared using dicyclopentadiene can also be used to advantage. It is also possible to use mixtures of unsaturated polyesters, including those which have only limited solubility in monomer B and are easy to crystallize. Such easily crystallizable unsaturated polyesters may include, for example, fumaric acid, adipic acid, terephthalic acid, ethylene glycol, 1,4-monobutylene glycol, 1,6-monohexanediol, and neopentyl glycol. Unsaturated polyesters have a pH of 5 to 200, preferably 20 to 85, and an average molecular weight of about 800 to 600, preferably about 400 to 400. And selectable crystallizable unsaturated polyesters are usually prepared from their starting ingredients by continuous condensation or continuous discontinuous process melt condensation under azeotropic conditions. -10- (7) (7) 200401798 B. Suitable copolymerizable ethylene unsaturated monomer compounds are allyl and preferably vinyl compounds, such as ethylene, generally used in unsaturated polyester molding compositions. Alkylene compounds such as styrene, methylene styrene, p-chlorostyrene or vinyl toluene; esters of acrylic acid and methacrylic acid with alcohols having 1 to 18 carbon atoms, such as methyl methacrylate, butyl acrylate Esters, ethylhexyl acrylate, hydroxypropyl acrylate, dihydrodicyclopentadiene acrylate, butanediol diacrylate, and ammonium (meth) acrylate; allyl esters, such as diallyl phthalate, And vinyl esters such as vinyl ethylhexanoate, vinyl acetate, propylene vinyl ester, vinyl pivalate and others. Also suitable are mixtures of said ethylenically unsaturated monomers. Preferably, those suitable as component B are styrene, vinylbenzene and diallyl phthalate. The monomer B is usually contained in the polyester molding composition in an amount of 10 to 80% by weight, preferably 20 to 70% by weight based on the total weight of the components A and B. C. As a reinforcing fiber, there are suitable roving-shaped inorganic or organic fibers, or a flat structure such as mats, such as glass, carbon fiber, asbestos, cellulose, and synthetic organic fibers, such as polycarboxylate; Polycarbonate and polyamide. The reinforcing fiber dimension is used in an amount of 5 to 300% by weight, preferably 10 to 150% by weight, based on the component A + B. D. Suitable concrete materials are, for example, general fine powdered or granular inorganic materials such as chalk, kaolin, quartz powder, dolomite, heavy stone, metal powder, aluminum hydrate, cement, talc, diatomaceous earth, wood Dust, sawdust, pigments and the like. Based on A + B, they are used in the SMC molding composition in an amount of 0 to 200% by weight and in the BMC molding composition in an amount of 100 to 400% by weight. -11-(8) (8) 200401798 E · As a thickener, mention may be made of, for example, alkaline earth oxides or hydroxides such as oxide bromide, bromide hydroxide, mirrors and preferably magnesium oxide and its oxides or Mixture of hydroxides. They can also be partially replaced by zinc oxide. Polyisocyanates or metal alcoholates are also suitable in some cases. The weighting agent is added to the molding composition in an amount of 0.5 to 5% by weight based on A + B. F. As the polymerization initiator, a general organic peroxide that generates radicals at high temperature is used, and its amount is 0.05 to 5% by weight, preferably 0.1 to 3% by weight based on the total weight of A and B. / 〇. Suitable starters are, for example, phenylhydrazone peroxide, tert-butyl peroctoate, tert-butyl perbenzoate, dicumyl peroxide, ditert-butyl peroxide and peracetals such as trimethylcyclohexyl Monoperacetals and percarbonates. G. Further general additives are, for example, inhibitors such as hydroquinone, 2,6-dimethylhydroquinone, t-butylbenzocatechin, p-benzoquinone, chloroquinone, 2,6-dimethylquinone, Nitrobenzene, such as m-dinitrobenzene, thiodiphenylamine, or N-nitroso-N-cyclohexylhydroxylamine, and mixtures thereof. Based on the ingredients A + B, the inhibitor is usually contained in the molding composition in an amount of from 0.05 to 0.2% by weight, preferably from 0.1 to 0.1% by weight. As lubricants, for example, zinc stearate, magnesium and calcium, and polyalkylene ether waxes are considered. • Vinyl ester resin (this VE resin is also called phenyl acrylate resin, abbreviated as P Η A) is a reaction resin based on (extended) phenyl derivatives such as phenols, aromatic glycidyl ether smoke epoxidized varnish Its molecules have been esterified with (,) acrylic acid. So-called π vinyl ester resins have been considered for some years to be used in -12-200401798 〇) a wide range of resin applications' especially those requiring superior chemical resistance. The resin is chemically an epoxy resin reaction Products and epoxy unsaturated products of epoxy resins. Typical vinyl resins currently commercially available include EP 0 CRYL, sold by She 11 C hemica] Comany, DERKANE 411 (available from Dow Chemicals Company Household sales) and CO —REZYN VE — 8300 (sold by Itnerplastic Company). When using vinyl ester resins to prepare shaped products, especially glass fiber reinforced plastic (ERP) structures, the resin composition should be controlled Viscosity so that the composition is fluid and can be easily applied and has good wetting of materials and reinforcements, but it is not so fluid that it flows out from the vertical surface, causing areas of resin deficiency in the formed product. In many applications, for example, when molded products such as tubes, tanks, scrubbers, or ducts are prepared using vinyl ester resins, superior bodies and towers Characteristics are extremely important, if not necessary for the procedure, especially during forming and curing. In this application, the resin is typically dissolved in a vinyl monomer, such as styrene, after which it is shaped Curing to produce shaped products. If the physical and tower properties of the composition during the forming and curing steps will cause the composition to flow out or flow, for example, when the resin composition is applied to the vertical surface of the lining, The resin surface has a non-uniform thickness and has reduced mechanical strength. It has previously been suggested that the viscosity, bulk, and tower storage properties of vinyl ester resins be improved by adding certain thixotropic agents. It has been reported that cinnamonite is used in some ethylene Base resin resin composition is "very effective" thixotropy (see MU nsaturated Polyester Technology " edited by Paul F. Gruins, Gordon and Breach Science Publishers). -13-(10) (10) 200401798 Composition of the invention Substances may include comonomers to facilitate handling, curing, and provide the desired mechanical properties. Suitable compatible comonomers include reactive ethylene unsaturated comonomers such as Ethylene, chlorostyrene, vinyltoluene, methylstyrene, diallyl phthalate, triallyl cyanurate, acrylates, methacrylates, and divinylbenzene. Styrene is better compatible Adjuvants. This composition may also include non-reactive diluents such as acetone, in which the properties available only with neat resins are desired. The vinyl ester resin used in the present invention may be any known in the art And it can be prepared by the addition reaction between epoxy resin and ethylene unsaturated monocarboxylic acid. Methods for preparing suitable vinyl ester resins are disclosed in U.S. patent applications 3, 2 5 6 5 2 2 6; 3 5 3 1 7, 4 6 5; 3, 3 4 5, 4 0 1; 3, 3 7 3,22 1; 3,3 7 7,4 06; 3,43 2,47 8; 3,54 8,03 0; 3 5 5 6 4 5 0 7 4; 3,634,542 and 35637,518. In general, the reaction used to prepare the vinyl ester resin used in the present invention is straightforward. It can be catalyzed by suitable catalysts such as tertiary amines, phosphines, bases or tin salts. The reaction formula can be shown as follows: 〇 〇 〇 、

I \ / \ W

C-C-C-R-C-C-C +2 / C-C = C

HO

/? I

C = CC-0 ^ CCCRCCC-0-CC = C OH OH where R is, for example, alkylene, cycloalkylene, alkylene, arylalkylene, oxyalkylene, oxyalkylene, or cycloalkylene Home base vinegar. β Suitable acids are acrylic acid, methacrylic acid; crotonic acid and cinnamic acid. Suitable epoxy resins are as follows: -14- (11) 200401798 Epoxide

Cycloaliphatic epoxide

D. A substantial number of different vinyl esters combining different characteristics can be prepared by combining different epoxy resins with various unsaturated acids. Many different products can of course be extended even further, depending on the choice of unsaturated monomers that can be combined and copolymerized with the vinyl ester resin. The vinyl ester resin which has hitherto reached the maximum usability and is therefore preferably used in the present invention is a bisphenol-A (BPA) -epoxy-based vinyl ester resin. These resins can be used with or without co-reactive monomers such as styrene. In addition to vinyl ester resins' thixotropic additives and, if desired, reactive or non-reactive diluents, The resin composition of the invention may also include catalyst-15- (12) (12) 200401798, inhibitors, additives, pigments and / or other known general additives. The composition of the present invention can be polymerized and crosslinked using a radical generation initiator known in the art. Polymerization of the resin is by a true addition reaction and typically does not form by-products. Suitable starters include peroxides, preferably organic peroxides such as phenylhydrazone peroxide or methyl ethyl ketone peroxide, and other sources of free radicals. For example, free radical-generating photoinitiators can also be used to initiate polymerization of the composition of the present invention. The initiator can be used with general accelerators or accelerators such as tertiary amines such as dimethyl or diethylaniline, and metal soaps such as caprylic acid- or cobalt naphthalate or manganese. Different forming methods can be used to shape the tree composition. Suitable methods include a manual lay-up method, a cold pressing method, a bag method, a mating mold method, a filament winding method, and a continuous molding method. • The acrylic resin may be a cold or heat cured synthetic resin, which may be obtained by homopolymerization of a (meth) acrylate (so-called pure-A), or by copolymerization with, for example, styrene or vinyl ester. Thermally-curable acrylic resins also contain functional groups (hydroxyl, methylol, carboxyl), through which they can perform cross-linking reactions. They can be cross-linked by themselves or (for example, by adding amine plastic or epoxy resin on the right) by external methods. And cross-linking. The solubility and mechanical properties of acrylic resins can be widely changed through the selection of monomers. The cured acrylic resin is usually a transparent product that is resistant to ultraviolet light and does not appear bleached. The cold-curing coating resin may have the following composition, for example: A) (meth) acrylic acid dilute acid ester 50 to 100% by weight (meth) acrylate 0 to 5% by weight (meth) acrylic acid 0 to 5% by weight -16- (13) (13) 200401798 c3 — C6 (meth) acrylate 0 to 97% by weight > C7 (meth) acrylate 0 to 50% by weight polyvalent (methyl ) Acrylate 3 to 10% by weight of comonomer 0 to 50% by weight of vinyl aromatic compound 0 to 30% by weight of vinyl ester 0 to 30% by weight. /. The composition of ingredient A is 100% by weight, B) per 1 part by weight of A, 0 to 2 parts by weight of (pre) polymer dissolved or swelled in A), based on B, (meth) acrylic acid The amount of ester or ethyl (meth) acrylate is greater than 5% by weight, C) per 100 parts by weight (A + B), 2 to 5 parts by weight of at least one stone and / or osmium, D)-a redox system At least one component of the redox must be kept separated until the polymerizable constituents of this system are polymerized. This redox system contains accelerators and peroxide catalysts or initiators in an amount sufficient to cool component A). Maturation, and E) -like additives. • The mixed resin can be a mixture of polyester resin and vinyl resin and / or acrylic resin to achieve a combination of properties, which is particularly advantageous from a commercial point of view. The resin is carefully mixed with the gravel and a curing agent and optionally an accelerator are added thereto. Depending on the curing agent, curing occurs at temperatures significantly below room temperature, in the room temperature region or in the temperature region significantly above room temperature. The upper temperature limit is usually determined by the material information of the resin such as the vapor pressure of the monomer. -17- (14) (14) 200401798 The liquid hard plastic according to the present invention (which contains structurally modified acryl-containing silica) may be liquid, paste or solid. They can contain additional powdery or fibrous filler materials such as: quartz powder, glass fiber, pigments, flame retardants, metal oxides, metal powders, graphite, carbon black or solvent-based liquid additives, plasticizers, non- Reactive extender resins, such as hydrocarbon resins, resins imparting flexibility, phenol resins, resins, polymerization aids and adhesion promoters. Further additives can be: thickener, foaming agent, release agent, stabilizer to increase the use period. The silica used in accordance with the present invention containing methacrylic groups and which has been prepared by flame hydrolysis and whose structure has been changed by mechanical post-treatment makes the resin according to the present invention -18- (15) (15) 200401798 and The preparation made by him has many technical advantages. In contrast to known finely divided silicas, thixotropic behavior is extremely low. There are great benefits for applications and loss behavior of coatings and adhesive formulations. The propylene functional group firmly bonded to the solid surface reacts during the polymerization of the reactive resin to form a crosslinking site, which imparts a high degree of rigidity, strength and elasticity to the final product. In addition, the speed of the cross-linking reaction can be increased so that the coating is dust-dry more quickly and the laminate can be removed from the mold earlier. Similarly, the processing of the molding composition is improved, especially in In the case of highly charged systems, the reactivity of the silica according to the invention is uniformly and completely cured in a short time. When using silica containing methacrylic groups and prepared by flame hydrolysis, a particular advantage is that no free alcohol is formed in the formulation, such as when using liquid silanes according to the prior art. The alcohol released in situ by the hydrolysis reaction can cause many disadvantages during the further processing of the resin formulation, such as the acceleration or retardation of the crosslinking method. In addition, the ' silanization reaction requires a measurable time and / or use of catalyst and / or heat and a method of selectively removing formed alcohols and excess silanes. The use of the silica containing methacrylic acid groups and prepared by flame hydrolysis according to the present invention in liquid or paste resins has a beneficial effect on the deposition behavior of other materials (mainly those with larger particle sizes). , Even if the effect is not prominent. [Embodiment] -19- (16) (16) 200401798 Examples Comparative Examples] 100 parts by weight of unsaturated styrene-containing isophthalic acid polyester resin and 1 part by weight of 3% methyl ethyl A solution of ketone peroxide in dimethyl phthalate is mixed with the help of a dissolver. The viscosity is determined by means of an ammeter. (The viscosity data determined in this example and the following examples are extracted in Table 1). The liquid was then poured into a square steel mold lined with a separation foil and heated at 800 'for 15 minutes under a closed pressure of 100 bar. During that time, the composition was fully cured and formed into a transparent sheet. Comparative Example 2 100 parts by weight of resin from Comparative Example 1 were mixed with 15 parts by weight of silica by means of a dissolver, the silica was coated with trimethylmethanthine base and prepared by flame hydrolysis It has a specific surface area of 173 m 2 and a carbon content of 3.4% by weight measured by analysis and its structure has been changed by mechanical post-treatment. Viscosity is measured at 23 ° C by simple degassing in a low pressure cabinet. The resulting paste composition has significantly lower flow restrictions but is diffusible. A 1% by weight solution of M E kappa peroxide was added thereto, and heating was performed at 80 ° C for 15 minutes in a square mold. At that time, the formulation was fully cured and removed from the mold in the form of a translucent tablet. Comparative Example 3 (previous technique) As in Example 1, weight ° /. The 33% ΜΕΚ peroxide solution was added to 1,000 parts by weight of unsaturated styrene-containing ethyl bromide, ethyl bromide, and Greek resin-20- (17) 200401798; the mixture was shaped to Form flakes and mature. Comparative Example 4 (previous technique) As in Example 1, 0 parts by weight of unsaturated styrene-containing brominated vinyl ester resin was mixed with 15 parts by weight of silica, and the silica was coated with trimethylformyl Silicon-based and has been prepared by flame hydrolysis and has a specific surface area of 173 m 2 and its structure has been changed by mechanical post-treatment. This composition is easy to flow.

Example 2 (according to the present invention)

15 parts by weight of silica is mixed with 1,000 parts by weight of unsaturated styrene-containing brominated vinyl resin. The silica contains methacrylic groups and has been prepared by flame hydrolysis and has a length of 160 m 2. The specific surface area per gram, the average particle size of 15 nanometers and the carbon content of 5%, and its structure has been changed by mechanical post-treatment. With no noticeable flow restrictions, this composition is extremely easy to pour. It was mixed with a 1% by weight solution of 33% MEK peroxide, degassed and shaped to form a sheet and cured as in Example 1. Comparative Example 5 (previous technique) A solution of 100 parts by weight of a PMMA resin in methyl methacrylate of a monomer was cured at room temperature and had the following composition: a) 20 to 95% by weight of monomer Ingredients, which consist of the following: a]) 60 to 100 parts by weight of (meth) propylene compound ;, a2) 0 to 40 parts by weight of polyfunctional (meth) acrylates 21-(18 200401798

Parts by weight of the cross-linking agent, b) 5 to 80c) 0.1 to 1% by weight of a polymer dissolved in component A), 5 parts by weight of a free radical generator, which already has a low Flow limited and mixed to mature at room temperature. ^ 5 Adhesive. ! Wt% of curing agent, pour out to form flakes and after hours, the sheet is fully cured. Comparative Example 6 with residual surface (according to the present invention): 1 S " s * / λ 7Γ / — IZΓ Miao stone mixed with 100 parts by weight of PMMA resin from Comparative Example 5 'The silica contains three Methylsilyl and has been prepared by flame hydrolysis of trimethylsilyl and has a specific surface area of 173 * 2 / g, 1 2 nm 2 (1 j: white & > puller size and 3 · 4% carbon content. Compared to Comparative Example 5, this has a significantly increased flow limit. It is mixed with 3% by weight of the curing agent to pour out to form a ratio and mature at room temperature. The surface has a slight residual stickiness Example 3 (according to the present invention) 100 parts by weight of the P Μ Μ Α resin from Comparative Example 5 is closely combined with 15 parts by weight of sand and gravel by means of an experimental dissolver, which contains methacrylic groups It has been prepared by flame hydrolysis and has a specific surface area of 60 m 2 / g. Compared to the resin without filling (Comparative Example 5), the flow restriction is only slightly increased. This mixture is then mixed with 3 parts by weight of a curing agent Mix, pour out to form flakes and ripen at room temperature. After 16 hours, this piece is fully ripened This surface is non-tacky. -22- (19) 200401798 Summary of test results Table 1: Intrinsic viscosity of uncured formulation, Pas, at 5 / s Rheological index 2.5 / 5 Upward flow limit, P as Comparative Example 1 1.34 1 0.2 Comparative Example 2 101.7 1.68 2 18 Example 1 12.9 1.42 7.6 Comparative Example 3 0.573 1 0.002 Comparative Example 4 95.7 1.77 258 Example 2 2.62 1.13 0.1 Comparative Example 5 8.24 1 40 Comparative Example 6 69 1.65 26 1 Example 3 23 1.26 65

Analysis of Table 1 Even at the selected high doses, silica containing methacrylic groups and prepared by flame hydrolysis gives a relatively small increase in viscosity and low flow restriction of the plastic resin composition. That property is extremely beneficial for further processing. -23-(20) 200401798 Table 2: Shaw D 1 〇s / 60 s Indentation Hardness Tensile Strength MP a Tensile Modulus M P a Flexural Modulus Comparative Example 1 7 8/76 87 47 2 3 6 7 1 3 8 5 3 PE Comparative Example 2 84/83 1 06 48 3 5 0 7 1 8 8 93 R82 00 Example 1 84/83 118 5 5 4 103 2 3 764 R7200 Comparative Example 3 86/85 73 70 42 18 23 764 VE Comparative Example 4 85/84 119 50 4960 252 1 3 R8200 Example 2 8 5/84 1 2 1 43 6 0 5 1 23 5 40 R7200 Comparative Example 5 82/80 10 1 n.m Comparative example 6 83/8 1 110 η. m. η. m. η. m. R82 00 Example 3 85/83 129 η. m. η. m. R7200 Analysis of cured raw materials " Raw kappa " Table 2: As expected, the two silicas increased the hardness and modulus in the crosslinked resin formulation. Although it has a lower BET surface area, silica modified with methacrylic groups is more distinguished due to its more substantial function. This is shown in Example 2 -24-(21) 200401798, which results in noticeable brittleness of the resin. . Those skilled in the art will understand the cost savings potential shown here and reduce the dosage or use of more flexible base resins. -25-

Claims (1)

200401798 ⑴ Pickup, patent application scope 1. A liquid hard plastic, characterized in that it contains silica prepared by pyrolysis which has been surface-modified with a silane containing methacrylic acid-based groups. 2. The liquid hard plastic according to item 1 of the patent application, wherein the silica prepared by pyrolysis has been structurally modified. < 3 · A method for strengthening hard plastics, which is characterized by preparing an uncrossed, unlinked resin and a silica prepared by pyrolysis which has been modified with a silane containing a methyl propionic acid group. Into a mixture. spring -26- 200401798 Lu, (a), the designated representative of the case is: Figure _ (b), the representative symbols of the representative diagram are briefly explained: 柒, if there is a chemical formula in this case, please reveal the best indication of the invention Chemical formula: