CN108249821B - Composition for improving artificial stone patterns and glossiness and application thereof - Google Patents
Composition for improving artificial stone patterns and glossiness and application thereof Download PDFInfo
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- CN108249821B CN108249821B CN201810074233.4A CN201810074233A CN108249821B CN 108249821 B CN108249821 B CN 108249821B CN 201810074233 A CN201810074233 A CN 201810074233A CN 108249821 B CN108249821 B CN 108249821B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses a composition for improving artificial stone patterns and glossiness, which comprises resin and Al (OH) in a mass ratio of 1:13Also comprises a medium-temperature curing agent with the dosage of 0.5 to 1.5 percent of the weight of the resin and fumed silica with the dosage of 0.5 to 1.5 percent of the weight of the resin. The invention also discloses application of the composition for improving the patterns and the glossiness of the artificial stone in the artificial stone, the artificial stone with the patterns diversified and a preparation method thereof. The composition is used for being dripped into artificial stone raw materials in the stirring, curing and forming process of the artificial stone, different patterns are formed in the cured artificial stone by utilizing the curing time difference and the curing temperature difference, the glossiness of the artificial stone is improved, and the diversified requirements of the artificial stone are met.
Description
Technical Field
The invention relates to the technical field of artificial stones, in particular to a composition for improving the patterns and the glossiness of the artificial stones and application thereof.
Background
In the building decoration industry, natural marble is popular and popular in the world, but has the disadvantages that the natural marble belongs to a mineral resource, the production area is not very large in the world, the yield is limited, the natural marble has excessive rigidity and insufficient strength, is extremely easy to break and destroy, and causes difficulties in transportation and daily maintenance. These reasons have greatly limited their use. Therefore, in order to meet the market demand and scientific development, people turn the research direction to utilize waste resources or other low-price raw materials to develop artificial boards with low cost and simple process, namely decorative materials with natural marble patterns, which are prepared by certain technological processes by certain adhesives, additives and coarse and fine aggregates.
Artificial marble (commonly known as artificial stone) with a firm surface has been successfully developed in the united states since the 60 s, and has incomparable superiority with natural marble and other materials in aspects of sanitation, style, processing, beauty (seamless splicing can be realized), and the like, so that the artificial marble has attracted market attention from the beginning. After more than thirty years of development and improvement, a series of products are formed. The resin can be classified into the following two groups according to the raw material resin used: an artificial stone using unsaturated resin (UPR) as bonding material (at present, most of the artificial stones in China are products of the type). The other type of artificial stone is an artificial stone using Acrylic modified resin (Acrylic) as a bonding material, and has the characteristics of ultraviolet light resistance, random bending and molding after being heated, and the like (mainly represented by Dupont Korea and Korea).
The artificial stone is prepared by taking unsaturated resin as a main bonding material and aluminum powder as a main filling material, and adopting a process of natural curing at room temperature and post-curing at 80 ℃ in the forming process. The method has the advantages of simple forming condition and less equipment investment, and the curing time is controlled by adjusting the dosage of the accelerator and the curing agent along with the difference of seasons and temperatures during production. However, the obtained artificial stone has single pattern, and the glossiness is difficult to meet the requirement of diversified use.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the composition for improving the patterns and the glossiness of the artificial stone, the composition is used for being dripped into the raw material of the artificial stone in the stirring, curing and forming process of the artificial stone, different patterns are formed in the cured artificial stone by utilizing the curing time difference and the curing temperature difference, the glossiness of the artificial stone is improved, and the diversified requirements of the artificial stone are met.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a composition for improving artificial stone patterns and glossiness comprises resin and Al (OH) in a mass ratio of 1:13Also comprises a medium-temperature curing agent with the dosage of 0.5 to 1.5 percent of the weight of the resin and fumed silica with the dosage of 0.5 to 1.5 percent of the weight of the resin.
As a further embodiment, the resin of the present invention is a UPR resin or a modified unsaturated resin.
As a further scheme, raw materials for preparing the modified unsaturated resin include maleic anhydride and phthalic acid as acid raw materials, and propylene glycol, diethylene glycol and trimethylolpropane as alcohol raw materials; wherein the ratio of alcohol to acid is 1: (1-1.2), the molar ratio of the total molar amount of propylene glycol and diethylene glycol to the trimethylol group is (0.75-0.95): 0.1; the catalyst also comprises styrene, alpha-methyl styrene and a polymerization inhibitor, wherein the dosage of the styrene is 30-33 percent of the total mass of the acid raw material and the alcohol raw material, the dosage of the alpha-methyl styrene is 2-6 percent of the total mass of the acid raw material and the alcohol raw material, and the polymerization inhibitor is 0.01-0.05 percent;
the modified unsaturated resin is prepared by the following method:
an esterification reaction step: introducing nitrogen into a reaction kettle, adding maleic anhydride and phthalic acid into the reaction kettle according to a ratio, mixing propylene glycol, diethylene glycol and trimethylolpropane, adding the mixture into the reaction kettle through a pipeline, heating the reaction kettle by adopting heat conduction oil with the temperature of 220-;
modification reaction steps: adding styrene and alpha-methyl styrene into a diluting kettle which is treated by nitrogen or vacuumization through a pipeline, and adding a polymerization inhibitor; when the temperature of the esterified substance is reduced to 140-150 ℃, slowly adding the esterified substance in the reaction kettle into the diluting kettle by using negative pressure, controlling the temperature of the diluting kettle to be below 85 ℃, and stirring the material in the diluting kettle until the temperature of the material is reduced to be below 48 ℃ to obtain a semi-finished product;
and (3) filtering: and filtering the semi-finished product to obtain a finished product.
As a further scheme, the medium-temperature curing agent is one of TBPO, 2-methylimidazole and 2-ethyl-4-methylimidazole.
Another object of the present invention is to provide a use of the composition for improving artificial stone patterns and gloss in the manufacture of artificial stones.
The invention also relates to the application of the composition in the preparation of artificial stone.
The third purpose of the invention is to provide an artificial stone with diversified patterns, which comprises the composition for improving the patterns and the glossiness of the artificial stone.
The artificial stone with diversified patterns is prepared from the raw materials of the composition and the artificial stone, wherein the mass ratio of the composition to the artificial stone is (0.2-0.8): 1; wherein the artificial stone raw material comprises the following components in percentage by mass
UPR resin: 30 to 50 percent,
Filling: 40 to 62 percent,
Curing agent: 0.1 to 0.5 percent of,
Accelerator (b): 0.05 to 0.1 percent
Color paste: 5 to 10 percent.
As a further proposal, the filler of the invention is Al (OH)3Or Al (OH)3With CaCO3One or more than two mixed fillers of MgO, short glass fiber and hollow microsphere.
As a further scheme, the curing agent is MEKP, and the accelerator is one of cobalt naphthenate solution, cobalt octoate solution and cobalt isooctanoate solution containing potassium ions.
The fourth purpose of the invention is to provide a preparation method of the artificial stone with various patterns, which is to drop the composition for improving the patterns and the glossiness of the artificial stone in the stirring, curing and forming process of the artificial stone so as to obtain the artificial stone with various patterns and high glossiness.
A method for preparing artificial stone comprises
The step of preparing the mixture: putting UPR resin, filler, curing agent and color paste into a vacuumized polymerization kettle according to a proportion, then adding an accelerant, stirring in vacuum, after the raw materials are uniformly stirred, dropwise adding the composition into the polymerization kettle in the stirring process, stopping stirring until the temperature of the reaction kettle does not rise any more, and removing bubbles to obtain a mixture;
casting and molding: slowly pouring the mixture into a mold cavity of a pretreated mold, scraping the mixture by using a scraper, naturally leveling the mixture, sending the mold with the cast mixture into a vacuum box, vacuumizing again, taking out the mold, and standing to obtain a molded artificial stone semi-finished product;
and (3) curing: demoulding the semi-finished artificial stone after standing, putting the semi-finished artificial stone on a shaping frame, and putting the semi-finished artificial stone into a drying room for curing to obtain artificial stone;
post-treatment: and cutting off the irregular parts on the upper and lower surfaces of the artificial stone, and then grinding and polishing to obtain the artificial stone.
As a further scheme, the vacuum degree of the polymerization kettle is 0.09-0.095MPa, and the polymerization temperature is 55-80 ℃; in the curing step, curing is carried out in a drying room at 52-65 ℃ for 1-2 hours, and then the temperature is increased to 78-85 ℃ for curing for 1-2 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the composition for improving the patterns and the glossiness of the artificial stone is used for being dripped into the raw material of the artificial stone in the stirring, curing and forming process of the artificial stone, and different patterns are formed in the cured artificial stone by utilizing the curing time difference and the curing temperature difference, so that the glossiness of the artificial stone is improved, and the diversified requirements of the artificial stone are met;
2. according to the artificial stone, the composition is dropwise added in the preparation process, and the composition flows in the artificial stone mixture in the stirring process through the time difference and the temperature difference between the composition and the raw materials of the artificial stone, so that various patterns and decorative patterns can be formed according to different stirring speeds, and the artificial stone with different patterns and decorative patterns can be obtained.
Detailed Description
The invention will be further described with reference to specific embodiments:
in the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The composition for improving the artificial stone decorative patterns and the glossiness comprises resin and Al (OH) according to the mass ratio of 1:13Also comprises a medium-temperature curing agent with the dosage of 0.5 to 1.5 percent of the weight of the resin and fumed silica with the dosage of 0.5 to 1.5 percent of the weight of the resin. In this scheme, this composition is added at the in-process of rostone raw materials mixing polymerization, because with the temperature difference and the time difference of rostone raw materials mixing polymerization in-process, obtains the artificial stone of different patterns and decorative pattern through the unification of control stirring speed, satisfies the demand of rostone variety, reaches the purpose of improving the rostone performance simultaneously.
As a further scheme, the resin provided by the invention is UPR resin or modified unsaturated resin; the resin may be other unsaturated resins in the conventional raw materials for artificial stone, or may be the same resin as that used for artificial stone. The resin is chosen for good compatibility with the resin in the stone, taking into account its flowability in the composition.
In a specific embodiment of the present invention, it is preferable that the raw materials for preparing the modified unsaturated resin include maleic anhydride and phthalic acid as acid raw materials, and propylene glycol, diethylene glycol and trimethylolpropane as alcohol raw materials; wherein the ratio of alcohol to acid is 1: (1-1.2), the molar ratio of the total molar amount of propylene glycol and diethylene glycol to the trimethylol group is (0.75-0.95): 0.1; the catalyst also comprises styrene, alpha-methyl styrene and a polymerization inhibitor, wherein the dosage of the styrene is 30-33 percent of the total mass of the acid raw material and the alcohol raw material, the dosage of the alpha-methyl styrene is 2-6 percent of the total mass of the acid raw material and the alcohol raw material, and the polymerization inhibitor is 0.01-0.05 percent;
the modified unsaturated resin is prepared by the following method:
an esterification reaction step: introducing nitrogen into a reaction kettle, adding maleic anhydride and phthalic acid into the reaction kettle according to a ratio, mixing propylene glycol, diethylene glycol and trimethylolpropane, adding the mixture into the reaction kettle through a pipeline, heating the reaction kettle by adopting heat conduction oil with the temperature of 220-;
modification reaction steps: adding styrene and alpha-methyl styrene into a diluting kettle which is treated by nitrogen or vacuumization through a pipeline, and adding a polymerization inhibitor; when the temperature of the esterified substance is reduced to 140-150 ℃, slowly adding the esterified substance in the reaction kettle into the diluting kettle by using negative pressure, controlling the temperature of the diluting kettle to be below 85 ℃, and stirring the material in the diluting kettle until the temperature of the material is reduced to be below 48 ℃ to obtain a semi-finished product;
and (3) filtering: and filtering the semi-finished product to obtain a finished product.
In the invention, in order to ensure that a certain temperature difference and curing time difference are formed between the composition and the raw material of the artificial stone in the polymerization and curing processes and the use safety is ensured, a medium-temperature curing agent is adopted in the composition, and as a further scheme, the medium-temperature curing agent is one of TBPO, 2-methylimidazole and 2-ethyl-4-methylimidazole. In addition, in the present invention, fumed silica can improve the transparency, strength, toughness, and gloss of the artificial stone while improving the compactness of the artificial stone.
Another object of the present invention is to provide a use of the composition for improving artificial stone patterns and gloss in the manufacture of artificial stones.
The invention also relates to the application of the composition in the preparation of artificial stone.
The third purpose of the invention is to provide an artificial stone with diversified patterns, which comprises the composition for improving the patterns and the glossiness of the artificial stone.
The artificial stone with diversified patterns is prepared from the raw materials of the composition and the artificial stone, wherein the mass ratio of the composition to the artificial stone is (0.2-0.8): 1; wherein the artificial stone raw material comprises the following components in percentage by mass
UPR resin: 30 to 50 percent,
Filling: 40 to 62 percent,
Curing agent: 0.1 to 0.5 percent of,
Accelerator (b): 0.05 to 0.1 percent
Color paste: 5 to 10 percent.
In a specific embodiment, it is preferred that the filler of the present invention is Al (OH)3Or Al (OH)3With CaCO3One or more than two mixed fillers of MgO, short glass fiber and hollow microsphere. The filler contains Al (OH)3，Al(OH)3The powder with the granularity of 200-230 meshes is adopted, and the product prepared by using the aluminum hydroxide powder as the filler has good water resistance and pollution resistance, good flame retardant property and ideal specific gravity, and has the texture of jade. In addition, in the invention, the oil resistance and the stain resistance of the obtained artificial stone are influenced by the using amount and the granularity of the aluminum hydroxide, and when the using amount of the aluminum hydroxide is too low and the granularity is too coarse, the stain resistance and the oil resistance of the artificial stone are reduced.
As a further scheme, the curing agent of the present invention is MEKP (methyl ethyl ketone peroxide), and the accelerator is one of a cobalt naphthenate solution, a cobalt octoate solution and a cobalt isooctanoate solution containing potassium ions. In the invention, the accelerator contains potassium ions, and the potassium ions replace part of cobalt ions, so that the coloring effect of the cobalt ions is obviously reduced, and meanwhile, the addition of the potassium ions can shorten the UPR gel time and reduce the dosage of the accelerator. Preferably, the concentration ratio of potassium ions to cobalt ions in the promoter is (1.8-2): 1.
the fourth purpose of the invention is to provide a preparation method of the artificial stone with various patterns, which is to drop the composition for improving the patterns and the glossiness of the artificial stone in the stirring, curing and forming process of the artificial stone so as to obtain the artificial stone with various patterns and high glossiness.
A method for preparing artificial stone comprises
The step of preparing the mixture: putting UPR resin, filler, curing agent and color paste into a vacuumized polymerization kettle according to a proportion, then adding an accelerant, stirring in vacuum, after the raw materials are uniformly stirred, dropwise adding the composition into the polymerization kettle in the stirring process, stopping stirring until the temperature of the reaction kettle does not rise any more, and removing bubbles to obtain a mixture;
casting and molding: slowly pouring the mixture into a mold cavity of a pretreated mold, scraping the mixture by using a scraper, naturally leveling the mixture, sending the mold with the cast mixture into a vacuum box, vacuumizing again, taking out the mold, and standing to obtain a molded artificial stone semi-finished product;
and (3) curing: demoulding the semi-finished artificial stone after standing, putting the semi-finished artificial stone on a shaping frame, and putting the semi-finished artificial stone into a drying room for curing to obtain artificial stone;
post-treatment: and cutting off the irregular parts on the upper and lower surfaces of the artificial stone, and then grinding and polishing to obtain the artificial stone. In the scheme, the composition is added in the process of stirring the raw materials of the artificial stone, the composition flows in the mixed raw materials of the artificial stone to form a pattern in the stirring process due to the time difference existing in the mixing and polymerizing process of the raw materials of the artificial stone, and the pattern is likely to change again due to the fluidity of the composition and the difference between the curing temperatures of the curing agents in the curing process, so that the artificial stone with different patterns can be obtained. In addition, the composition contains aluminum hydroxide and fumed silica, so that the glossiness of the cured artificial stone can be effectively improved, and the performance of the artificial stone is improved.
As a further scheme, the vacuum degree of the polymerization kettle is 0.09-0.095MPa, and the polymerization temperature is 55-80 ℃; in the curing step, curing is carried out in a drying room at 52-65 ℃ for 1-2 hours, and then the temperature is increased to 78-85 ℃ for curing for 1-2 hours.
Example 1
A modified unsaturated resin is prepared from maleic anhydride, phthalic acid, propylene glycol, diethylene glycol, trimethylolpropane, styrene, alpha-methyl styrene and polymerization inhibitor;
wherein the ratio of alcohol to acid is 1:1, the molar ratio of the total molar amount of propylene glycol and diethylene glycol to the trimethylol group is 0.75: 0.1; the dosage of the styrene accounts for 30 percent of the total mass of the acid raw material and the alcohol raw material, the dosage of the alpha-methyl styrene accounts for 2 percent of the total mass of the acid raw material and the alcohol raw material, and the polymerization inhibitor accounts for 0.01 percent;
the preparation method comprises the following steps:
an esterification reaction step: introducing nitrogen into a reaction kettle, vacuumizing, adding maleic anhydride and phthalic acid into the reaction kettle according to a ratio, mixing propylene glycol, diethylene glycol and trimethylolpropane, adding the mixture into the reaction kettle through a pipeline, heating the reaction kettle by adopting heat conduction oil at 220 ℃, starting a stirring paddle of the reaction kettle to perform stirring reaction on materials in the process of increasing the temperature in the reaction kettle, controlling the heating temperature, keeping the temperature for reaction for 1 hour when the temperature of the materials in the reaction kettle reaches 160 ℃, and stopping heating after the reaction is completed to obtain an esterified substance;
modification reaction steps: adding styrene and alpha-methyl styrene into a diluting kettle which is treated by nitrogen or vacuumization through a pipeline, and adding a polymerization inhibitor; when the temperature of the esterified substance is reduced to 140 ℃, slowly adding the esterified substance in the reaction kettle into the diluting kettle by negative pressure, controlling the temperature of the diluting kettle to be below 85 ℃, and stirring the material in the diluting kettle until the temperature of the material is reduced to be below 48 ℃ to obtain a semi-finished product;
and (3) filtering: and filtering the semi-finished product to obtain a finished product.
Example 2
A composition for improving artificial stone patterns and glossiness comprises a UPR resin and Al (OH) in a mass ratio of 1:13The UPR resin also comprises a medium-temperature curing agent TBPO with the amount of 0.5 percent of the weight of the UPR resin and fumed silica with the amount of 1.5 percent of the weight of the UPR resin.
Example 3
A composition for improving artificial stone patterns and glossiness comprises the modified unsaturated resin and Al (OH) in the mass ratio of 1:1 and described in example 13The modified unsaturated resin also comprises a medium-temperature curing agent TBPO with the dosage of 1.2 percent of the weight of the modified unsaturated resin and fumed silica with the dosage of 1.0 percent of the weight of the resin.
Example 4
A composition for improving artificial stone patterns and glossiness comprises a UPR resin and Al (OH) in a mass ratio of 1:13The UPR resin also comprises a medium-temperature curing agent TBPO with the dosage of 1.5 percent of the weight of the UPR resin and fumed silica with the dosage of 0.5 percent of the weight of the UPR resin.
Example 5
The artificial stone with diversified patterns is prepared from the raw materials of the composition and the artificial stone, wherein the mass ratio of the composition to the artificial stone raw materials in the embodiment 2 is 0.2: 1; wherein the artificial stone raw material comprises the following components in percentage by mass
UPR resin: 50 percent of,
Al (OH) having a particle size of 2203：40％、
MEKP：0.1％、
Accelerator (b): 0.1 percent,
Color paste: 9.8 percent;
the promoter is a cobalt naphthenate solution containing potassium ions, wherein the concentration ratio of the potassium ions to the cobalt ions is 1.8: 1;
the preparation method comprises
The step of preparing the mixture: putting UPR resin, filler, curing agent and color paste into a vacuumized polymerization kettle according to a proportion, wherein the vacuum degree is 0.09MPa, then adding an accelerator, stirring in vacuum, after the raw materials are uniformly stirred, dropwise adding the composition into the polymerization kettle in the stirring process, wherein the polymerization temperature is 65 ℃, stopping stirring until the temperature of the reaction kettle is not increased any more, and removing bubbles to obtain a mixture;
casting and molding: slowly pouring the mixture into a mold cavity of a pretreated mold, scraping the mixture by using a scraper, naturally leveling the mixture, sending the mold with the cast mixture into a vacuum box, vacuumizing again, taking out the mold, and standing to obtain a molded artificial stone semi-finished product;
and (3) curing: demoulding the semi-finished artificial stone after standing, putting the semi-finished artificial stone on a shaping frame, putting the semi-finished artificial stone into a drying room for curing, curing for 2 hours at 52 ℃ in the drying room, and then heating to 78 ℃ for curing for 2 hours to obtain artificial stone;
post-treatment: and cutting off the irregular parts on the upper and lower surfaces of the artificial stone, and then grinding and polishing to obtain the artificial stone.
Example 6
The artificial stone with diversified patterns is prepared from the raw materials of the composition and the artificial stone, wherein the mass ratio of the composition to the artificial stone raw materials in the embodiment 3 is 0.5: 1; wherein the artificial stone raw material comprises the following components in percentage by mass
UPR resin: 40 percent of,
Al (OH) with a particle size of 2303：50％、
MEKP：0.5％、
Accelerator (b): 0.1 percent,
Color paste: 9.4 percent;
the promoter is a cobalt iso-octoate solution containing potassium ions, wherein the concentration ratio of the potassium ions to the cobalt ions is 2: 1;
the preparation method comprises
The step of preparing the mixture: putting UPR resin, filler, curing agent and color paste into a vacuumized polymerization kettle according to a ratio, wherein the vacuum degree is 0.092MPa, then adding an accelerator, stirring in vacuum, after the raw materials are uniformly stirred, dropwise adding the composition into the polymerization kettle in the stirring process, wherein the polymerization temperature is 75 ℃, stopping stirring until the temperature of the reaction kettle is not increased any more, and removing bubbles to obtain a mixture;
casting and molding: slowly pouring the mixture into a mold cavity of a pretreated mold, scraping the mixture by using a scraper, naturally leveling the mixture, sending the mold with the cast mixture into a vacuum box, vacuumizing again, taking out the mold, and standing to obtain a molded artificial stone semi-finished product;
and (3) curing: demoulding the semi-finished artificial stone after standing, putting the semi-finished artificial stone on a shaping frame, putting the semi-finished artificial stone into a drying room for curing, curing for 1.5 hours at 60 ℃ in the drying room, and then heating to 80 ℃ for curing for 1.5 hours to obtain artificial stone;
post-treatment: and cutting off the irregular parts on the upper and lower surfaces of the artificial stone, and then grinding and polishing to obtain the artificial stone.
Example 7
An artificial stone with diversified patterns is prepared from the raw materials of the artificial stone, wherein the raw materials of the artificial stone comprise the composition and the raw materials of the artificial stone, and the mass ratio of the composition to the raw materials of the artificial stone in the embodiment 4 is 0.8: 1; wherein the artificial stone raw material comprises the following components in percentage by mass
UPR resin: 30 percent of,
Al (OH) having a particle size of 2003：62％、
MEKP：0.1％、
Accelerator (b): 0.05 percent,
Color paste: 7.85 percent;
the promoter is cobalt octoate solution containing potassium ions, wherein the concentration ratio of the potassium ions to the cobalt ions is 2: 1;
the preparation method comprises
The step of preparing the mixture: putting UPR resin, filler, curing agent and color paste into a vacuumized polymerization kettle according to a ratio, wherein the vacuum degree is 0.093MPa, then adding an accelerator, stirring in vacuum, after the raw materials are uniformly stirred, dropwise adding the composition into the polymerization kettle in the stirring process, wherein the polymerization temperature is 80 ℃, stopping stirring until the temperature of the reaction kettle is not increased any more, and removing bubbles to obtain a mixture;
casting and molding: slowly pouring the mixture into a mold cavity of a pretreated mold, scraping the mixture by using a scraper, naturally leveling the mixture, sending the mold with the cast mixture into a vacuum box, vacuumizing again, taking out the mold, and standing to obtain a molded artificial stone semi-finished product;
and (3) curing: demoulding the semi-finished artificial stone after standing, putting the semi-finished artificial stone on a shaping frame, putting the semi-finished artificial stone into a drying room for curing, curing for 1 hour at 65 ℃ in the drying room, and then heating to 85 ℃ for curing for 1 hour to obtain artificial stone;
post-treatment: and cutting off the irregular parts on the upper and lower surfaces of the artificial stone, and then grinding and polishing to obtain the artificial stone.
Comparative example 1
The artificial stone raw material formulation and preparation method of example 6 were followed, but in this comparative example 1, the composition according to the present invention was not added.
Performance testing
1. Surface topography glossing detection
The surface morphology of the artificial stone of examples 5 to 7 and comparative example 1 was observed under an optical microscope, and the gloss of the artificial stone was measured using a gloss meter, and the results are shown in table 1.
TABLE 1
2. Mechanical Property test
The mechanical properties of the artificial stones obtained in examples 5 to 7 and comparative example 1 were measured according to the methods in GB/T2567-. The test results are shown in Table 2.
TABLE 2
| Item | Example 5 | Example 6 | Example 7 | Comparative example 1 |
| Flexural Strength (MPa) | 57.14 | 59.01 | 58.37 | 51.89 |
| Compressive strength (Strength Limit MPa) | 91.71 | 93.56 | 92.84 | 81.62 |
3. Corrosion resistance test
The corrosion media are respectively 10% sodium hydroxide solution, 20% sulfuric acid solution and toluene, the test sample is immersed in the test medium for 30 days under the experimental conditions according to B/T3857-. See table 3 for results.
TABLE 3
| Item | Example 5 | Example 6 | Example 7 | Comparative example 1 |
| Flexural Strength/MPa (toluene reagent) | 29.15 | 37.12 | 29.46 | 26.37 |
| Flexural Strength/MPa (20% H)2SO4) | 31.59 | 41.48 | 34.25 | 27.16 |
| Flexural Strength/MPa (10% NaOH) | 29.97 | 39.75 | 32.59 | 26.58 |
Various other modifications and changes may occur to those skilled in the art, such as those described above, and other embodiments, and it is intended that all such modifications and changes fall within the scope of the appended claims.
Claims (8)
1. The composition for improving the decorative patterns and the glossiness of the artificial stone is characterized by comprising resin and Al (OH) in a mass ratio of 1:13The curing agent also comprises a medium-temperature curing agent with the dosage of 0.5 to 1.5 percent of the weight of the resin and fumed silica with the dosage of 0.5 to 1.5 percent of the weight of the resin;
the resin is modified unsaturated resin, raw materials for preparing the modified unsaturated resin comprise maleic anhydride and phthalic acid which are used as acid raw materials, and propylene glycol, diethylene glycol and trimethylolpropane which are used as alcohol raw materials; wherein the ratio of alcohol to acid is 1: (1-1.2), the molar ratio of the total molar amount of propylene glycol and diethylene glycol to trimethylolpropane is (0.75-0.95): 0.1; the catalyst also comprises styrene, alpha-methyl styrene and a polymerization inhibitor, wherein the dosage of the styrene is 30-33 percent of the total mass of the acid raw material and the alcohol raw material, the dosage of the alpha-methyl styrene is 2-6 percent of the total mass of the acid raw material and the alcohol raw material, and the polymerization inhibitor is 0.01-0.05 percent;
the modified unsaturated resin is prepared by the following method:
an esterification reaction step: introducing nitrogen into a reaction kettle, adding maleic anhydride and phthalic acid into the reaction kettle according to a ratio, mixing propylene glycol, diethylene glycol and trimethylolpropane, adding the mixture into the reaction kettle through a pipeline, heating the reaction kettle by adopting heat conduction oil with the temperature of 220-;
modification reaction steps: adding styrene and alpha-methyl styrene into a diluting kettle which is treated by nitrogen or vacuumization through a pipeline, and adding a polymerization inhibitor; when the temperature of the esterified substance is reduced to 140-150 ℃, slowly adding the esterified substance in the reaction kettle into the diluting kettle by using negative pressure, controlling the temperature of the diluting kettle to be below 85 ℃, and stirring the material in the diluting kettle until the temperature of the material is reduced to be below 48 ℃ to obtain a semi-finished product;
and (3) filtering: and filtering the semi-finished product to obtain a finished product.
2. The composition of claim 1, wherein the medium-temperature curing agent is one of TBPO, 2-methylimidazole and 2-ethyl-4-methylimidazole.
3. Use of the composition of claim 1 for the preparation of synthetic stone.
4. An artificial stone with diversified patterns, wherein the raw material for preparing the artificial stone comprises the composition of claim 1 and an artificial stone raw material, wherein the mass ratio of the composition of claim 1 to the artificial stone raw material is (0.2-0.8): 1; wherein the artificial stone raw material comprises the following components in percentage by mass
UPR resin: 30 to 50 percent,
Filling: 40 to 62 percent,
Curing agent: 0.1 to 0.5 percent of,
Accelerator (b): 0.05 to 0.1 percent
Color paste: 5 to 10 percent.
5. Artificial stone as in claim 4, characterized in that the filler is Al (OH)3Or Al (OH)3With CaCO3One or more than two mixed fillers of MgO, short glass fiber and hollow microsphere.
6. The artificial stone of claim 4, wherein the curing agent is MEKP and the accelerator is one of a cobalt naphthenate solution, a cobalt octoate solution, and a cobalt iso-octoate solution containing potassium ions.
7. A process for the preparation of an artificial stone according to any one of claims 4 to 6, comprising
The step of preparing the mixture: putting UPR resin, filler, curing agent and color paste into a vacuumized polymerization kettle according to a proportion, then adding an accelerant, stirring in vacuum, after the raw materials are uniformly stirred, dropwise adding the composition of claim 1 into the polymerization kettle in the stirring process, stopping stirring until the temperature of the reaction kettle does not rise any more, and removing bubbles to obtain a mixture;
casting and molding: slowly pouring the mixture into a mold cavity of a pretreated mold, scraping the mixture by using a scraper, naturally leveling the mixture, sending the mold with the cast mixture into a vacuum box, vacuumizing again, taking out the mold, and standing to obtain a molded artificial stone semi-finished product;
and (3) curing: demoulding the semi-finished artificial stone after standing, putting the semi-finished artificial stone on a shaping frame, and putting the semi-finished artificial stone into a drying room for curing to obtain artificial stone;
post-treatment: and cutting off the irregular parts on the upper and lower surfaces of the artificial stone, and then grinding and polishing to obtain the artificial stone.
8. A method for producing an artificial stone according to claim 7, wherein the degree of vacuum of the polymerizer is 0.09 to 0.095MPa, and the polymerization temperature is 55 to 80 ℃; in the curing step, curing is carried out in a drying room at 52-65 ℃ for 1-2 hours, and then the temperature is increased to 78-85 ℃ for curing for 1-2 hours.
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