JPH0463891B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is a CIP application of U.S. Patent Application No. 182,560, filed August 29, 1980. The present invention relates to polymeric concrete compositions, ie, composite materials formed by polymerizing one or more monomers in the presence of inert inorganic particulate or particulate materials. The polymerized monomer acts as a binder in the resulting polymer concrete. The term “polymer concrete” is abbreviated to
"concrete)" is sometimes referred to by the abbreviation PC hereafter. U.S. Patent No. 3,575,785 by Mc Manimie et al., which was patented on April 21, 1971, is (a)
Discloses a method for coating building surfaces by applying a preformed resin coating composition consisting of an inorganic filler and (b) polyalkyl methacrylate that has been pretreated with an organosilane coupling agent. Zdanowski et al., U.S. Pat. No. 3,805,907, patented on April 16, 1967, uses a shaped but uncured heated asbestos cement composition containing methyl methacrylate as a major component and minor amounts of comonomers and Applying an aqueous dispersion coating containing a linear copolymer of an organic solvent (temporary plasticizer), heating the coating composite to remove the plasticizer, and curing the coating cement composite. A method of manufacturing a coated cement product comprising: Rubenstein, U.S. Pat. No. 3,150,032, issued on June 25, 1956, discloses a first plastic resin surface structure and a fibrous material composite and bonded with a core of porous material, and optionally Discloses a pre-stressed, pre-filled article having a core of porous material reinforced with a filler of silicate and decorative material and disposed in a second plastic resin surface structure. For example, the products constitute chairs and desks. A wide variety of resins useful in making the products are listed at columns 25-27 of the patent, for example, column 25, lines 18-22 and column 26, lines 39-42 contain active unsaturated resins. Unsaturated polyesters cross-linked with monomeric vulcanizing agents are disclosed. No. 2,414,089 to Bruson, patented on January 14, 1947, discloses the preparation of esters of hydroxydiclopentadiene and unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid. . The resulting esters are disclosed to be useful as vehicles for paints, varnishes and similar coating materials. Also the fourth
In columns 53-55, the patent reveals that the ester is useful as an impregnating agent for the sand core during molding. Emmons, Nyi, patented April 8, 1980, which is a continuation-in-part of U.S. Patent Application No. 687,856, patented March 19, 1976, and now abandoned. and Sperry, U.S. Pat. Co-pending Application No. 3055, filed in 1999, discloses the production of polymeric concrete using dicyclopentenyl acrylate or methacrylate as a binder for aggregates such as sand and crushed stone. These two monomers used separately or as a mixture are designated by the symbol
DCP(M)A, and individual monomers are specifically designated as DCP(M)A in applications and patents belonging to the above.
and DCPMA. The mentioned DCP(M)A is very useful to apply, i.e. the mentioned usefulness is known, but DCP(M)A has a specific characteristic, despite its low volatility. It spreads easily and has a persistent and unpleasant odor. Odors are particularly noticeable when applying PC indoors for construction or repair on industrial floors, or outdoors for construction or repair on interior yards, roads, bridge decks and the like.
Even when applying PC, it is severely disadvantageous. Moreover, the use of DCP(M)A tends to result in extremely hard coatings, which are necessary to prevent breakage when the product is subjected to severe impacts during use, which is common in the case of industrial floors and roads. requires a considerable amount of plasticizer. U.S. Pat. No. 4,097,677 to Emmons and Nair, issued June 27, 1978, describes polymeric concrete compositions in which dicyclopentenyloxyalkyl methacrylates and acrylates are described as binder components of inorganic powder or particulate materials. It is widely disclosed. (See columns 25-26). U.S. Pat. No. 4,145,503 to Emmons and Naai, issued March 20, 1979, describes soluble linear addition polymers of dicyclopentenyloxyalkyl methacrylate or acrylate as autoxidizing compositions, and dicyclopentenyloxyalkyl methacrylate or acrylate. Acrylate coating and/or impregnation compositions, drying oils or film-forming addition or condensation polymers, polyvalent metal salts or complex catalysts, and optionally volatile oxime stabilizers are disclosed. Emmons and Nye, U.S. Patent Application No. 21,660, filed March 19, 1979, which is assigned to the same assignee, is (b) dicyclopentenyloxyethyl acrylate or diclopentenyl consisting of an essentially anhydrous slurry of (a) inert inorganic particulate aggregate in oxyethyl methacrylate or mixtures thereof, the slurry consisting essentially of (c)
It contains an organic peroxide or hydroperoxide and/or (d) a polyvalent metal salt desiccant dissolved therein. Compared to DCP(M)A, dicyanopentenyloxyethyl acrylate and methacrylate have substantially lower volatility and are liquid reactive monomers with high flash points and virtually no odor; PC compositions containing can be applied by troweling and can be installed or repaired on indoor floors without emitting unpleasant odors in the workplace, or on roads even in hot climates. Or it can be installed or repaired on concrete pavements of expressways. Although dicyclopentenyloxyethyl methacrylate and acrylate have been found to be useful and advantageous over previously used methyl methacrylate and DCP(M)A in polymer concrete compositions, epoxy resins as binders compared to the PC product made using
There is a need to further improve the chemical resistance of polymeric concrete made using dicyclopentenyloxyethyl methacrylate as a binder.
Also, compared to cheap epoxy resins, the use of dicyclopentenyloxyethyl methacrylate as a binder in PC has the drawback of being relatively expensive. The present invention uses acrylic binder monomers together with inert inorganic particulate or granular aggregate materials to create an essentially anhydrous polymeric concrete PC that can improve chemical resistance and lower cost. It is to provide. The term "essentially anhydrous" does not mean excluding small amounts of water, eg, up to 1% of the water in the inorganic particulate or granular aggregate material. The present invention provides (a) an inert inorganic fine particulate or granular aggregate material with a void portion smaller than 0.37; (b) (a) (wherein R is CH ₃ or H and R ¹ is () an alkylene group having from 2 to 6 carbon atoms and () having from 4 to 6 carbon atoms, each segment is selected from methacrylic acid or acrylic acid represented by , 25% to 75% by weight, based on the total amount of monomers, of at least one dicyclopentenyloxyalkyl ester of a β-unsaturated monocarboxylic acid, and (b) (In the formula, R ² is a straight chain or branched chain (C ₁ to C ₆ )
from 75% to 25% by weight, based on the total amount of monomers, of at least one hydroxyalkyl methacrylate represented by an alkyl group or a ( _C3 - _C6 ) cycloalkyl group; 10% to 35% by weight, based on component (a), of non-volatile binder monomers consisting of 100%); and (c) (a) ( _C3 to _C18 hydrocarbyl peroxide From about 0.1% by weight based on the total amount of monomers
3% by weight of an aromatic amine polymerization accelerator and about 0.1% to 5% by weight based on the total amount of monomers, or (b) a monomer of ( _C3 - _C18 ) hydrocarbyl hydroperoxide. from about 0.1% to 3% by weight based on the total amount of polyvalent metal salt or complex,
Approximately 0.0005% to 2% by weight based on the total amount of monomers
% by weight, or (c) a mixture of (a) and a polyvalent metal salt or complex from 0.0005% to 2% by weight, based on the total amount of monomers; or (d) (a) and (b). ); a polymerization catalyst selected from; Surprisingly and unexpectedly, using the mixture of hydroxyalkyl methacrylate and dicyclopentenyloxyalkyl methacrylate or dicyclopentenyloxyalkyl acrylate of the invention as the binder monomer system, Increasing the amount of hydrophilic monomer is not expected to improve the chemical resistance without the concomitant significant decrease in water resistance and wet strength, and improve the physical performance (tensile strength) of cured products made from PC. , bending stress, bending strain, bending modulus and shear bonding strength), and
It has been discovered that it provides an advantageous combination of properties including low volatility (high flash point). The dicyclopentenyloxyalkyl methacrylates and acrylate esters used in the present invention as one or more necessary components of the binder monomer defined by formula () above are known compounds. These ester-ether compounds and methods for their preparation are disclosed in the above-mentioned US Pat. No. 4,097,677. Preferably, this component of the binder monomer is at least one member selected from the group consisting of dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyisopropyl methacrylate, dicyclopentenyloxyisopropyl acrylate, and dicyclopentenyloxyneopentyl methacrylate. Become. Most preferred is dicyclopentenyloxyethyl methacrylate. Used in the present invention as another component of the two required components in the binder monomer and having the above formula ()
The hydroxylalkyl methacrylate ester defined by is a known ingredient. Preferably, this component consists of at least one of hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA). As mentioned above, the binder monomer is the
It consists of about 10% to 35% by weight, preferably about 12% to 20% by weight, particularly preferably about 15% by weight, based on the amount of aggregate material. The relative amounts of the dicyclopentenyloxyalkyl ester and hydroxyalkyl methacrylate components of the binder monomers range from about 25% by weight each based on the total amount of monomers.
It can be varied by 75% by weight, making the total amount 100%. The term non-volatile as applied to the binder monomer of the PC of the present invention means that the monomer or mixture thereof is about 50% of the binder monomer before complete curing or polymerization.
This means that it must have a vapor pressure/reactivity balance under ambient temperature conditions such that no more than % by weight is lost to evaporation. In general, the aggregate size ranges from about 100μ to about 2-mesh [US Wire Screen Standard (US
particulate or particulate material in the particle size range of wire screen standard). Generally a mixture of differently sized aggregates is used,
Mixtures are used when the aggregate material is one component of the aggregate, especially of large size at the upper end of the above range. Such large size aggregates minimize the void volume, especially the small size bones to have a void volume of less than 0.37, preferably less than 0.20, and suitably about 0.15 or less. This reduces the amount of liquid monomer required to mix with the material and thereby fill voids, thereby minimizing overall polymerization shrinkage and monomer component cost. The aggregate material used here can be any inert inorganic, i.e. organic and inorganic acids, salts and alkalis encountered in normal industrial installations, such as hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, acetic acid, formic acid, It may be resistant to sodium, potassium, calcium and magnesium salts, such as chlorides, sulfates, and alkali metal and alkaline earth metal hydroxides. Examples of suitable aggregates are sand, silica powder, quartz, karanite,
Includes crushed rocks or stones of feldspar, gneiss, basalt, porphyry and their pebbles. The sand that may be used may be of any quality within the above ranges or of any size, preferably sand of about 1 mm in diameter or less. "Ottawa" Sand and "Best" Sand or Part 2
Sorted sand of medium particle size, such as a mixture of seeds, may be used more advantageously. Otsutawa Sand is a spherical type of silica sand. The best sand is a type known as a ``spiky'' type. In both cases, microscopic particles have been removed. However, in general, the size of the sand sieve may vary within a fairly wide range. Instead of or in addition to sand, crushed colored glass marble, crushed glass, silica powder, diamond sand powder, crushed slag, and fine gravel can also be used. Small amounts of polyvalent metal salts or complexes can also be added to the mixture before molding, preferably together with organic hydroperoxides. The proportion of metal salts or complexes added to the composition before molding is based on the total weight of monomers.
It may be from 0.0005% to about 2% by weight, and the amount of hydroperoxide may range from 0.1% to 3% by weight. It is likewise possible to add an aromatic amine promoter, optionally a polyvalent metal salt or complex, to the mixture together with the organic peroxide before shaping. The proportion of organic peroxide to the composition may range from 0.1 to 3% by weight, and the aromatic amine promoter is in an effective amount, usually in the range of about 0.1 to 2% by weight. The polyvalent metal salt or complex and the hydroperoxide, or aromatic amine promoter and peroxide, are packaged in separate containers and transported separately to the operating site where the individual components are mixed and processed according to the invention. The composition is applied by pouring or troweling to apply or repair concrete floors or bases or pavements. Alternatively, the aromatic amine promoter and binder monomers and organic peroxide and aggregate materials, respectively, are added to the compositions of the invention for a short time prior to casting or molding the compositions. They may be mixed in packaging containers for storage and transportation prior to mixing. The composition can be modified by selecting colored aggregates or
Suitable amounts of pigments or dyes dissolved in binder monomers may be included in the aggregate or composition to provide color. The amount of such pigment or dye may vary from about 1% to 10% by weight of the composition. The polyvalent metal salt or complex used in the present invention can be any polyvalent metal-containing salt that catalyzes the oxidative curing of drying oils and, when added to oil-based varnishes and paints, accelerates their drying or curing. . These metal salts or complexes are also known in the art as "siccatives" or "driers". Such substances are polyvalent metal salts of higher fatty acids,
Examples include butyrate, pentanoate, hexanoate and salts of higher fatty acids or naphthenic acids having from 8 to 30 carbon atoms which have solubility in particular in the binder monomer. Generally, the most useful desiccant salts for the binder monomer compositions of the present invention are salts of naphthenic acids or ( _C8 - _C30 ) fatty acids. Examples of polyvalent metals are calcium, copper (),
Includes zinc (), manganese (), manganese (), lead (), cobalt (), iron (), vanadium () and zirconium (). These salts or complexes accelerate the action of organic hydroperoxides and promote oxidative curing in organic peroxide-amine catalysts. Other examples of acid components or anions of desiccant salts are resin acids (i.e., rosin acids), tall oil fatty acids, linseed oil fatty acids, 2-ethylhexanoic acid, lauric acid, palmitic acid, myristic acid, stearic acid, These are oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid, montanic acid and abietic acid.
Mixtures of desiccant salts may also be used. Preferred desiccant salts are salts of cobalt and manganese, such as cobalt octoate, cobalt naphthenate, cobalt acetylacetonate, and manganese octoate, manganese naphthenate, and manganese acetylacetonate. Aromatic amines may be used in small amounts with organic peroxides and generally enhance the action of the peroxides.
For example, aniline, N,N-dimethylaniline, N,N-diethylaniline, toluidine,
N,N-dimethyl-p-toluidine, N,N-di(hydroxyethyl)toluidine and p-dimethylaminobenzaldehyde as binder monomers.
It may be added for this purpose in amounts of 0.1 to 2% by weight. Organic peroxides and hydroperoxides that may be used include peroxides and hydroperoxides derived from hydrocarbons containing about 3 to 18 carbon atoms so as to dissolve in the binder monomer. do. A suitable organic hydroperoxide is tert
-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone hydroperoxide and diisopropylbenzene hydroperoxide. Suitable peroxides include benzoyl peroxide, tert-butyl perbenzoate, 2,2-
bis-(tert-butylperoxy)-butane, bis-(1-hydroxy-cyclohexyl)-butane,
Includes bis-(1-hydroxy-cyclohexyl)-peroxide and tret-butylperoxyisopropyl carbonate. More preferred polymerization catalysts are mixtures of organic peroxides and aromatic amines. A particularly preferred polymerization catalyst is a mixture of benzoyl peroxide and N,N-dimethyl-p-toluidine. Any method may be used to form the composition by molding. For example, mixtures of binder monomers, aggregates, desiccants and peroxides may be used in the casting of concrete floors or pavements, or in the casting of cement using cement as wall or ceiling tiles or panels. It may also be poured into a mold. This purpose can also be achieved by adding a mixture of binder monomers to a is 1/
The proportions may be such that the composition can be troweled to be applied in a relatively thin layer of 16 to 1/2 inches. If additional viscosity is required in such compositions to facilitate troweling or other forming methods, thickeners or rheological control agents may be included. It may be formed at ambient temperature. In any case, the compositions according to the invention are completely free of volatile substances and can avoid shrinkage which is difficult to control when using other compositions containing volatile components. The PC compositions may be utilized to coat substrates such as metals, glasses, and plastics using conventional application techniques to provide surfaces with advantageous chemical resistance. The use of both an organic peroxide and an aromatic amine accelerator or an organic hydroperoxide and a polyvalent metal salt desiccant ensures curing of the formed PC to the solid state in a relatively short period of time, e.g. 5 to 30 minutes. work. However, additional drying time of up to 24 hours is required to overcome tackiness, as surface curing inhibits polymerization of binder monomers due to free radical action occurring at the air/surface interface. . This initial tackiness can be overcome more quickly by coating the exposed surfaces shortly after initial hardening of the composition with a free radical initiator contained in a suitable immiscible liquid that excludes air from the surface after application. Good too. The compositions are generally hard and tough after curing. When it is desired to make such compositions more flexible, a drying oil such as linseed oil or an acrylic polymer with a low second order transition temperature (Tg), e.g.
A small amount of poly(ethyl acrylate, poly(butyl acrylate), or poly(2-ethylhexyl acrylate)), or a mixture of a drying oil and a low Tg acrylic polymer, is added to the dicyclopentenyl alkyl (meth)acrylate-hydroxyalkyl methacrylate composition. may be added and may replace some of the binder monomers. Alternatively, the required monomers are of low volatility, reducing the stiffness of the final composition and making it more flexible. or auxiliary liquid monomers capable of imparting elasticity may be used with small amounts of acrylic and/or vinyl ester binder-forming materials. Mixtures of drying oils and auxiliary monomers may also be used. Such other acrylic ester monomers may be (C ₁₂ -
_C30 ) alkyl, or ( _C12 - _C30 ) alkenyl,
Acrylates, or methacrylates, including lauryl acrylate, myristyl acrylate, palmityl acrylate, oleyl acrylate, linoleyl acrylate, linolenyl acrylate, stearyl acrylate, as well as the necessary binder monomers to improve flexibility. Long-chain ( _C12 - _C30 ) fatty acid vinyl esters, along with the body
For example, vinyl laurate, vinyl oleate, vinyl stearate or di( _C4 - _C8 ) alkyl esters of maleic acid, fumaric acid or itaconic acid, such as dibutyl, dihexyl or dioctyl fumaric acid, maleic acid or itaconic acid. It can also be obtained by incorporating an ester. The required binder monomers can also be polyfunctional,
That is, polyethylenically unsaturated monomers, such as polyol (meth)acrylates and polyalkylene polyol (meth)acrylates, such as ethylene glycol diacrylate or dimethacrylate, trimethylolpropane triacrylate or trimethacrylate, triethylene glycol (meth)acrylate, ) May be used with small amounts of acrylates, etc. All of these monomeric materials have low volatility, polymerize under the action of peroxides and metal salt desiccants, have excellent toughness,
Forms products that are resistant to water, organic solvents, acids and alkalis. The amount of these auxiliary monomers, if used, should be approximately
It may range from 0.5 to 25% by weight, but preferably does not exceed about 20% by weight of such component. The PC of the present invention is particularly useful for coating (and especially repairing) acid, alkali and salt resistant and organic solvent resistant industrial floors, basement floors, pavements, roads, bridges and ship decks or floors. In all such constructions, the cured product is resistant to water, organic solvents such as gasoline and highly corrosive substances such as acids, salts and alkalis. The PC of the present invention may also be used as a coating for various substrates such as metal and plastic sheets. In addition to the pigments and dyes mentioned above, other well-known auxiliaries can be contained, such as antioxidants, antiozidants, inhibitors, stabilizers and flow control agents. In the following examples illustrating some embodiments of the invention, parts and percentages are parts and percentages by weight and temperatures are in degrees Celsius, unless indicated otherwise. Mesh sizes shown for the aggregate materials used are based on standard US wire screen. The following abbreviations are used to indicate the relevant compounds. DCPOEME = dicyclopentenyloxyethyl methacrylate DCPOiPMA = dicyclopentenyloxyisopropyl methacrylate DCPOiPA = dicyclopentenyloxyisopropyl acrylate DCPONMA = dicyclopentenyloxyneopentyl methacrylate HEMA = hydroxyethyl methacrylate HPMA = hydroxypropyl methacrylate Polymer concrete composition of the present invention The following tests are used to evaluate the physical properties of hardened polymer concrete products made from concrete. Compressive force ASTM C-109-73 Tensile strength ASTM C-190-72 Flexural strength ASTM C-348-72 Shear bond adhesion “Test Methods for the Evaluation of Cement Modifiers”
Evaluation of Cement Modifiers” Rohm and Haas
Haas Company, Philadelphia, Pennsylvania, 19105, Technical Bulletin 83 D2, 4
Page (April 1977) Flashpoint Set a Flash Closed
Katupu Method (Set a Flash
Closed Cup Method）ASTM D−32−
78 Commercial quality hydroxyethyl methacrylate and hydroxypropyl methacrylate monomers were used, and as is known in the art, such commercial quality monomers generally yield about 90% and 92% of the desired ester product, respectively. It is to be understood that the remaining amount to 100% is high-boiling methacrylate compounds, methacrylic acid, dimethacrylate compounds and the corresponding alkylene oxides. Example 1 HEMA and EPMA at flash point of DCPOEMA
Effects of 2-hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA) are physically blended with DCPOEMA in different weight ratios. The flash point of each formulation is standard set-a-flash. Measured using the Standard Setaflash closed cup test method. The results are summarized in Table 1 below. [Table] The results shown in the table show that using HPMA or HEMA lowers the flash point of DCPOEMA. Even at levels of hydroxyalkyl methacrylates >50%, the flash point is still low, and large-scale shipping is difficult for transportation and combination use table corders.
Combustible Codes) and is >200〓, which indicates the range that does not require a red label. Example 2 Containing various amounts of hydroxyalkyl methacrylate ester as comonomer
Evaluation of PC Composition Based on DCPOEMA Hydroxypropyl methacrylate (HPMA), a typical hydroxyalkyl methacrylate ester used as a comonomer of the binder monomer in the PC composition of the present invention, was mixed with DCPOEMA in a different weight ratio. The resulting formulation is mixed with other ingredients to produce a PC composition according to the following representative PC formulation. During the formulation, the aggregate material is chosen on the basis of allowing the use of a minimum amount of acrylic monomer, which also exhibits good processability (trowelability). Initiators include the use of cobalt naphthenate/cumene hydroperoxide, which is a source of free radicals at room temperature. Other initiators such as benzoyl peroxide and amine promoters (e.g., dimethyl p-toluidine, or p-dimethylaminobenzaldehyde) and polyvalent metal salts or complexes (e.g., cobalt naphthenate) are used herein as starters. agents can be easily replaced. The evaluation results of the physical (mechanical) properties of the resulting polymerized (cured) PC products are summarized in the table following the formulations shown below. Formula of Acrylic PC Composition Dry Mixture Material Part No. 2 Sand (Pettinos) 41.07 No. 45 Sand (Petinos) 41.07 Silica Frauer 120 17.35 Fe ₃ O ₄ [Pfizer] 0.05 TiO ₂ (DuPont R −960 ^R ) 0.46 Add to 100 g of dry mixture Premix ¹ Binder monomer 17.78 Cumene hydroperoxide (73%) 0.36 Cobalt naphthenate 0.095 (Active metal 6%) (6 drops) 1 Premix just before use Manufacture. The cumene hydroperoxide is thoroughly mixed with the acrylate monomer prior to addition of the cobalt naphthenate. [Table] [Table] The data in the table shows that using HPMA does not result in drastic changes in compressive or tensile strength. Some increase in flexibility is seen when the amount of HPMA is 50% or higher. However, the most important result is that HPMA100%
The use of DCPOEMA/
50% in concentration of HPMA when using HPMA formulations
even if the adhesive strength is acceptable (and indeed remarkable). The wet adhesion of HPMA is so poor that it does not seem obvious that an amount of 50% is acceptable with DCPOEMA, and a favorable result is not expected or foreseeable. Example 2a Polymeric Concrete Composition Based on Combined Initiator and DCPOEMA The PC composition of Example 2 was formulated as an initiator containing cobalt naphthenate, N,N-dimethylaminobenzaldehyde and benzoyl peroxide. It was evaluated as a drug. Prescription Dry Mixture Materials for Acrylic PC Composition No. 2 Sand (Petainos) 41.08 No. 45 Sand (Petainos) 41.08 Silica Frauer 120 17.34 Fe ₃ O ₄ (Phizer) 0.05 TiO ₂ (DuPont R-960 ^R ) 0.45 Peroxide Benzoyl (powder) 0.71 [Cadox ^R (Cadox) BFF-50 ^R , activity amount 50
%, Noury Chemical
Corporation)] Cobalt neodecanoate (active amount 11.2%) 0.2 Add to 100 g of dry mixture. Premix ¹ Binder Monomer ² 17.78 p-dimethylaminobenzaldehyde 0.72 1 N,N dimethylbenzaldehyde is thoroughly mixed with the acrylate monomer before adding to the dry mixture. 2 DCPOEMA:HPMA=50:50 This formulation results in a PC composition having the properties shown in Table A below. Table A Properties of the Acrylic PC Composition of Example 2A Properties Measured Pot Life 0.66 hour cure rate (majority) 2 hour cure rate (surface) 2-4 hour compressive strength 6000 psi Tensile strength 1198 psi Flexural strength (5 days at 23°C) ) Stress 3839psi Strain 0.0018 (n/in) Modulus 2.110 ⁶ Shear Bond Adhesion (5 days at 23°C) 926psi (5 days at 23°C + 5 days immersed in water) 630psi Chemical resistance 20% acetic acid No change (NE) Gasoline NE 50% ethanol Very slightly surface softened Xylene NE 50% Sodium hydroxide NE Water NE Toluene NE Hydrochloric acid (37%) NE Ammonium hydroxide (28%) NE Example 3 Wet adhesion on acrylic polymer concrete HPMA is a comonomer with DCPOEMA for
Comparison of HPMA and HEMA Using the formulation shown in Example 2, a series of polymeric concrete compositions containing varying amounts of HPMA and HEMA, along with DCPOEMA, are prepared. Measure shear adhesion under both wet and dry conditions. [Table] Surprisingly and unexpectedly, the results in Table
When HPMA is copolymerized with DCPOEMA,
It is shown that it is possible to obtain a product without a significant decrease in wet adhesion strength up to a level of HPMA of 75%. When immersed in water, HPMA
Since 90% of the samples will be spongy, the maximum amount of HPMA that can be blended with DCPOEMA to retain wet strength is 75-90%. Similarly the maximum amount of HEMA with DCPOEMA is 50-75%. Example 4 Chemical Resistance of Acrylic Polymer Concrete An important performance requirement in industrial flooring applications using polymer concrete is resistance to attack by acids, bases and various solvents. Samples of various acrylic polymer concrete compositions are cast using the formulation set forth in Example 2. Samples were kept at room temperature for 7 days [23℃, RH50%
(RH = relative humidity)] Harden. They are then immersed in 50 c.c. of the test liquid. After 14 days, qualitatively judge the degree of attack by the test liquid according to the following criteria. Good - most of the sample and surface remain hard (no change). Fairly good - most of it remains hard (no change)
However, the surface is hardened. Poor - Softened in large areas and surfaces. The results are summarized in the table below. [Table] [Table] The results in Table 4 show that hydroxyethyl methacrylate (HEMA) can be added to DCPOEMA in amounts ranging from 50% to less than 75% without reducing water resistance. However, hydroxypropyl methacrylate (HPMA) is 75%
However, it exhibits good water resistance to the extent of less than 90%. Depending on the intended special commercial application,
Approximately 50% HPMA provides an advantageous balance of resistance to a variety of chemical agents, but obviously depending on the particular agent for which resistance is desired,
The amount of comonomer can be varied to be higher or lower. Example 5 Acrylic Polymer Concrete Containing Analogs of DCPOEMA as Binding Agents Some analogs of DCPOEMA were used in PC compositions and compared with products made from DCPOEMA to determine the physical properties of PC products made from the analogs. Evaluate properties. PC compositions were prepared as follows and the table below summarizes the physical properties of these PC products. Composition of acrylic PC composition Material weight No. 2 Sand (Petainos) 35 No. 45 Sand (Petainos) 35 Silica Frauer 120 15 Binder monomer 15 Cumene Hydroperoxide (73%) 0.3 Cobalt naphthenate 0.09 Results in the table shows that both -oxyneopentyl and -oxyisopropyl methacrylate analogs of DCPOEMA have good adhesion. Moreover, oxyisopropyl acrylate analogs have been shown to be acceptable binder monomers for making polymeric concrete. [Table] Example 6 Chemical resistance of acrylic polymer concrete/
Solvent Resistance The formulation shown in Example 5 is used to prepare a series of polymeric concrete compositions containing various acrylic binder monomer compositions. Samples of each acrylic polymer concrete composition were cast and cured for 7 days at room temperature (23°C, RH 50%), and the test liquid
Soak in 50ml (cc). The degree of attack by the test liquid is determined qualitatively after two weeks. Select toluene and aqueous ammonia from among typical chemicals and solvents. The results are summarized in the table below. [Table] [Table] The results shown in the table show that polymer concretes based on 100% DCPOEMA and its analogues have poor toluene resistance. Concrete based on 100% HPMA has poor ammonia resistance.
Polymer concretes using blends of HPMA with DCPOEMA and its analogs have a good balance of chemical resistance. Toluene resistance is substantially improved without sacrificing any reduction in ammonia resistance. Example 7 Evaluation of a two-component PC composition based on a blend of DCPOEMA and HPMA The PC composition, which is a blend of DCPOEMA and HPMA as binder monomers in a 1:1 weight ratio, has the following two-component formulation: obtained by. The initiators in this example were benzoyl peroxide and N,N-dimethyl-
Including using p-toluidine. This particular combination of organic peroxide and amine accelerator provides a short pot life for the ingredients (approximately 3 minutes) and relatively rapid curing of most of the PC (approximately 3-5 minutes). However, pot life and cure rate may be varied by selecting equal amounts, but slower reactive initiator components to provide suitable processing and handling times. This two-component PC composition containing an organic peroxide/amine promoter initiator is similar to a typical PC containing an organic hydroperoxide/metal salt or complex initiator (exemplified in Example 2 above).
has special benefits compared to the composition, and this benefit is
The PC composition components are simply provided in a two-component package;
Although stored and shipped, using the composition of Example 2 is to include more than just a two-component package. Polymerization (curing) of this example
The evaluation results of the mechanical properties of PC products are summarized in the table according to the recipe shown below. Prescription materials for two-component acrylic PC compositions Composition 1 No. 2 Sand (Petainos) 41.08 No. 45 Sand (Petainos) 41.08 Silica Frauer 120 17.34 Fe ₃ O ₄ (Phizer) 0.05 TiO (DuPont R-960) 0.45 Peroxide Benzoyl (active amount 50%) 0.71 Composition added to the above 100.71g 2DCPOEMA:HPMA (blending weight ratio 1:1) 17.78 N,N-dimethyl-p-toluidine 0.36 Benzoyl peroxide/N,N-dimethyl-p - Measured mechanical properties of acrylic polymer concrete product ¹ based on a two-component formulation containing toluidine initiator Compressive strength (psi) >6000 Tensile strength (psi) 1342 Flexural strength (psi) 3208 Flexural strain (psi) 0.0015 Flexural Modulus 2.2・10 ⁶ Shear Bond Adhesion (psi) 931 1 Samples were equilibrated for 7 days at 23°C prior to testing. The data in the table shows that using a two-component PC composition containing an organic peroxide/amine promoted initiator:
A comparable compound containing an organic hydroperoxide/metal salt or complex initiator as exemplified in Example 2 above
It is shown to provide a product with advantageous mechanical properties equivalent to those obtained with PC compositions.

Claims (1)

[Scope of Claims] 1 (a) Inert inorganic fine particulate or granular aggregate material, (b) (a) Formula (wherein R is CH ₃ or H and R ¹ is () an alkylene group having from 2 to 6 carbon atoms and () having from 4 to 6 carbon atoms, each segment is selected from methacrylic acid or acrylic acid represented by , 25% to 75% by weight, based on the total amount of monomers, of at least one dicyclopentenyloxyalkyl ester of a β-unsaturated monocarboxylic acid, and (b) (In the formula, R ² is a straight chain or branched chain (C ₁ to C ₆ )
from 75% to 25% by weight, based on the total amount of monomers, of at least one hydroxyalkyl methacrylate represented by an alkyl group or a ( _C3 - _C6 ) cycloalkyl group; 10% to 35% by weight, based on the amount of aggregate material, of a non-volatile binder monomer consisting of a total amount of 10%, and (c) (a) ( _C3 to _C18 ) From 0.1% by weight of hydrocarbyl peroxide based on the total amount of monomers
3% by weight and aromatic amine polymerization accelerator, 0.1% to 5% by weight based on the total amount of monomers,
or (b) 0.1% to 3% by weight, based on the total amount of monomers, of a ( _C3 - _C18 ) hydrocarbyl hydroperoxide and 0.0005% by weight, based on the total amount of monomers, of a polyvalent metal salt or complex. % to 2% by weight, or (c) a mixture of (a) and a polyvalent metal salt or complex, based on the total amount of monomers, from 0.0005% to 2% by weight, or (d) (a) and ( b) an acrylic polymer concrete composition consisting of an essentially anhydrous slurry of a polymerization catalyst selected from; 2. The composition according to claim 1, wherein the dicyclopentenyloxyalkyl ester is selected from dicyclopentenyl ethyl methacrylate, dicyclopentenyloxyisopropyl methacrylate, dicyclopentenyloxyisopropyl acrylate, and dicyclopentenyloxyoxyneopentyl methacrylate. . 3. The composition according to claim 1, wherein the dicyclopentenyloxyalkyl ester is dicyclopentenyloxyethyl methacrylate. 4. The composition of claim 1, wherein the hydroxyalkyl methacrylate is selected from hydroxyethyl methacrylate and hydroxypropyl methacrylate. 5. The composition of claim 1, wherein the aggregate material is from 100 microns to 2 meshes as measured on the standard American wire screen scale. 6 (a) Inert inorganic particulate or granular aggregate materials having particle sizes ranging from 100 microns to 2 meshes as measured on the standard U.S. wire screen scale; (b) (a) dicyclopentenyloxyethyl; 25% to 75% by weight, based on the total monomer amount, of at least one of methacrylate, dicyclopentenyloxyisopropyl methacrylate, dicyclopentenyloxyisopropyl acrylate, or dicyclopentenyloxyneopentyl methacrylate, and (b) hydroxy 75% by weight based on the total amount of monomers of at least one of ethyl methacrylate or hydroxypropyl methacrylate
~25% by weight, from 12% to 20% by weight of non-volatile binder monomers, and (c) (a) aniline, N,N-dimethylaniline together with ( _C3 - _C18 ) hydrocarbyl peroxide. , N,N-diethylaniline, toluidine, N,N-dimethyl p-toluidine, N,
an aromatic amine selected from N-di(hydroxyethyl)toluidine or N,N-dimethylaminobenzaldehyde; or (b) a ( _C8 - _C30 ) fatty acid or naphthenic acid together with a ( _C13 - _C18 ) hydrocarbyl hydroperoxide. A composition according to claim 1, comprising a polymerization catalyst selected from polyvalent metal salts of. 7 (b) A non-volatile binder monomer consisting of (a) dicyclopentenyloxyethyl methacrylate and (b) at least one of hydroxyethyl methacrylate and hydroxypropyl methacrylate, and (c) (a) cumene hydroperoxide. (b) benzoyl peroxide and N,N-dimethyl-p
7. The composition of claim 6, comprising: a polymerization catalyst selected from the group consisting of: -toluidine; or (c) a mixture of benzoyl peroxide, N,N-dimethylaminobenzaldehyde and cobalt naphthenate. 8 (a) Inert inorganic particulate or granular aggregate material; (b) (a) 50% by weight based on the total amount of monomers of dicyclopentenyloxyethyl methacrylate; (b) monomers of hydroxypropyl methacrylate (3) a polymerization catalyst consisting of cumene hydroperoxide and cobalt naphthenate; and (c) a polymerization catalyst consisting of cumene hydroperoxide and cobalt naphthenate. Compositions as described in Section. (b) 50% by weight, based on the total amount of monomers, of (a) dicyclopentenyloxyethyl methacrylate; and (b) hydroxypropyl methacrylate. (c) benzoyl peroxide and N,N-dimethyl-
7. The composition according to claim 6, comprising a polymerization catalyst comprising p-toluidine.