CN111908951B - Production process of high-temperature-resistant flame-retardant building composite stone - Google Patents
Production process of high-temperature-resistant flame-retardant building composite stone Download PDFInfo
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- CN111908951B CN111908951B CN202010820273.6A CN202010820273A CN111908951B CN 111908951 B CN111908951 B CN 111908951B CN 202010820273 A CN202010820273 A CN 202010820273A CN 111908951 B CN111908951 B CN 111908951B
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- 239000004575 stone Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 50
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 44
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 239000000440 bentonite Substances 0.000 claims abstract description 33
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 33
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 33
- BHIZVZJETFVJMJ-UHFFFAOYSA-N 2-hydroxypropyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(C)O BHIZVZJETFVJMJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940026235 propylene glycol monolaurate Drugs 0.000 claims abstract description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 28
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 20
- 239000004576 sand Substances 0.000 claims abstract description 20
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 20
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000003292 glue Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- UQPHVQVXLPRNCX-UHFFFAOYSA-N erythrulose Chemical compound OCC(O)C(=O)CO UQPHVQVXLPRNCX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001723 curing Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 claims description 8
- 229920002907 Guar gum Polymers 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000665 guar gum Substances 0.000 claims description 7
- 229960002154 guar gum Drugs 0.000 claims description 7
- 235000010417 guar gum Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002932 luster Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005034 decoration Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/70—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
- B28B19/0053—Machines or methods for applying the material to surfaces to form a permanent layer thereon to tiles, bricks or the like
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a production process of a high-temperature-resistant flame-retardant building composite stone, which comprises the following steps: s1, adding water into copper chloride powder for dissolution, adding a mixed solution A for reaction, adding 2-hydroxy terephthalic acid and erythrulose for reaction, taking out, centrifuging, discarding supernatant, and vacuum drying to obtain a modified material, wherein the modified material is mixed with the mixed solution B to obtain a modified solution; s2, bentonite, magnesium oxide and propylene glycol monolaurate are taken, ball milling is carried out, fine sand and N-aminoethylpiperazine are added after the bentonite, the magnesium oxide and the propylene glycol monolaurate are mixed with sodium silicate water glass and epoxy resin glue, and the mixture is uniformly mixed to obtain slurry; s3, grouting slurry on the surface of the stone base layer, drying and curing, coating the surface of the cured slurry with the modifying liquid, and drying to obtain the high-temperature-resistant flame-retardant building composite stone. The production method provided by the invention is easy for industrial production, and the produced building composite stone has good temperature resistance and flame retardance, high strength, rich surface texture, stable color and luster and good decorative effect.
Description
Technical Field
The invention relates to the technical field of building stones, in particular to a production process of a high-temperature-resistant flame-retardant building composite stone.
Background
With the development of society, the living standard of people is rapidly improved, and the requirements on living environment and living quality are also higher and higher. In the modern building decoration process, the composite stone has become one of the important auxiliary materials in the building decoration process for the reasons of beautiful appearance, high quality, excellent durability, good heat conductivity, easy processing and use and the like. More and more designers use composite stone as a primary decorative material in many public decorative processes, such as wall tiles, floor tiles, and the like. Because the public places are dense in personnel and large in people flow, the security work of the public places is particularly important, and the fire safety performance of the building materials is difficult to control in the process of fire statistics of a plurality of buildings. The stone itself has no combustibility, but because various combustible materials and adhesives are used in the preparation process of the composite stone, the substances are exposed to the air and then meet high temperature or mars, so that the composite food material has certain potential safety hazard. Based on certain potential safety hazards existing in the existing composite stone, the invention provides a production process of a high-temperature-resistant flame-retardant building composite stone.
Disclosure of Invention
The invention aims to solve the defects of potential safety hazard and unsatisfactory high temperature resistance and flame retardant performance of the existing composite stone, and provides a production process of the high temperature resistant flame retardant building composite stone.
A production process of a high-temperature-resistant flame-retardant building composite stone comprises the following steps:
s1, taking copper chloride powder, adding a proper amount of water for dissolution, adding the copper chloride powder into 8-10 times of mixed solution A, stirring and mixing for 20-30 min at 60-70 ℃, adding 2-hydroxyterephthalic acid and erythrulose, continuously stirring and mixing for 3-4 h, transferring into a reaction kettle, heating to 120-130 ℃, preserving heat for 6-8 h, taking out, centrifuging, discarding supernatant, and carrying out vacuum drying at 50 ℃ for 3-4 h to obtain a modified material, wherein the modified material is prepared by the steps of: 5-6, adding the mixture into the mixed solution B, stirring and mixing for 1-2 h at 40-50 ℃, and cooling to room temperature to obtain a modified solution;
s2, taking bentonite, magnesium oxide and propylene glycol monolaurate, placing the bentonite, the magnesium oxide and the propylene glycol monolaurate into a ball mill, ball milling for 1-2 hours at 45-55 ℃, cooling to room temperature, transferring the mixture into a high-speed heating mixer, adding sodium silicate water glass and epoxy resin glue into the high-speed heating mixer, heating to 75-80 ℃, mixing for 30-35 min, cooling to 40-50 ℃, adding fine sand and N-aminoethylpiperazine, mixing uniformly, and cooling to room temperature to obtain slurry;
s3, pouring the slurry obtained in the step S2 on the surface of the stone base layer, drying and curing, coating the modified liquid prepared in the step S1 on the surface of the cured slurry, and drying to obtain the high-temperature-resistant flame-retardant building composite stone with the coating thickness of 120-130 mu m.
Preferably, in step S1, the mass of water added is determined by adding water 1 to 1.6 times the mass of copper chloride powder to copper chloride powder each time, placing the copper chloride powder in an ultrasonic instrument for ultrasonic dispersion for 5 minutes, and repeating the above operation if copper chloride powder which is visible to the naked eye exists, until copper chloride powder which is not visible to the naked eye exists at the end of ultrasonic treatment, and stopping adding water, wherein the total mass of added water is the added mass of water at the moment.
Preferably, in step S1, the mixed solution a is prepared from the following materials in a volume ratio of 30:104 to 107:2 to 2.6 of water, ethanol and acetonitrile.
Preferably, in step S1, the mixed solution B is prepared from the following materials in a volume ratio of 12 to 14: 5-8 of ethanol and dimethyl carbonate.
Preferably, the mass ratio of the copper chloride powder to the 2-hydroxyterephthalic acid to the erythrulose is 38-42: 2 to 4:0.9 to 1.4.
Preferably, in the step S2, the bentonite, the magnesium oxide, the propylene glycol monolaurate, the sodium silicate water glass, the epoxy resin glue, the fine sand and the N-aminoethylpiperazine are respectively 20-26 parts, 4-8 parts, 0.3-0.6 part, 2-5 parts, 1-3 parts, 36-46 parts and 0.12-0.15 part by weight.
Preferably, in the step S2, 23 parts, 6 parts, 0.5 part, 4 parts, 2 parts, 40 parts and 0.14 part of bentonite, magnesium oxide, propylene glycol monolaurate, sodium silicate water glass, epoxy resin glue, fine sand and N-aminoethylpiperazine are calculated according to parts by weight respectively.
Preferably, in the step S2, during ball milling, a material consisting of a mass ratio of 100: 2-7 of ethanol and guar hydroxypropyl trimethyl ammonium chloride, and the added mass of the ball milling auxiliary agent is 0.5-0.9% of the total mass in the ball mill.
Preferably, in step S3, the stone base layer is natural stone, the thickness is 2-6 mm, and the thickness of the slurry cured on the stone base layer is 3-4 mm.
Compared with the prior art, the invention has the advantages that:
1. the production method of the composite stone provided by the invention is conventional in operation and easy for industrial production, and the produced composite stone has excellent high temperature resistance and flame retardant property, is nontoxic, odorless, non-radiative, safe and environment-friendly, has rich surface texture, stable color and luster and good decorative effect, effectively solves the problems of potential safety hazard and unsatisfactory high temperature resistance and flame retardant property of the existing composite stone, can be applied to the decoration of inner and outer walls of places such as large public buildings, villa hotels, advanced communities and garden landscapes, and has good social and economic benefits, and is worth popularizing.
2. The production method provided by the invention uses a common stone base layer as a first layer of the composite stone, the surface of the first layer of the composite stone is poured with slurry prepared from bentonite, magnesium oxide, propylene glycol monolaurate, sodium silicate water glass, epoxy resin glue, fine sand and N-aminoethylpiperazine, the second layer with high strength and high durability is obtained by drying and solidifying, the second layer of the composite stone and the first layer are firmly bonded, then the surface of the second layer of the composite stone is coated with a modified liquid with reasonable formula, and the third layer of the composite stone is obtained by drying, so that the composite stone compounded by three layers of materials is obtained.
3. The modified liquid used for the third layer of the composite stone is prepared by dissolving copper chloride powder in a reasonable proportion in a mixed solution A, then reacting with 2-hydroxy terephthalic acid and erythrulose in a reaction kettle to obtain a modified material which is easy to disperse, and uniformly dispersing the modified material in the mixed solution B so as to smoothly spread on the surface of the second layer of the composite stone, so that the modified material is easier to exert the effects of improving the high temperature resistance and the flame retardance of the composite stone.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
The invention provides a production process of a high-temperature-resistant flame-retardant building composite stone, which comprises the following steps:
s1, taking copper chloride powder, adding a proper amount of water for dissolution, adding 8 times of mixed solution A into the mixed solution A, stirring and mixing for 30min, adding 2-hydroxyterephthalic acid and erythrulose, continuously stirring and mixing for 4h, transferring into a reaction kettle, heating to 120 ℃, preserving heat for 8h, taking out, centrifuging, removing supernatant, and carrying out vacuum drying at 50 ℃ for 3h to obtain a modified material, wherein the modified material is prepared by the steps of: 5, adding the mixture into the mixed solution B in proportion, stirring and mixing for 2 hours at 50 ℃, and cooling to room temperature to obtain a modified solution;
the volume ratio of the mixed solution A is 30:104:2.6, mixing water, ethanol and acetonitrile; the volume ratio of the mixed solution B is 12:8, mixing ethanol and dimethyl carbonate;
s2, taking bentonite, magnesium oxide and propylene glycol monolaurate, placing the bentonite, the magnesium oxide and the propylene glycol monolaurate into a ball mill, ball-milling the bentonite and the propylene glycol monolaurate for 2 hours at 45 ℃, cooling the mixture to room temperature, transferring the mixture into a high-speed heating mixer, adding sodium silicate water glass and epoxy resin glue into the high-speed heating mixer, heating the mixture to 75 ℃, mixing the mixture for 35 minutes, cooling the mixture to 40 ℃, adding fine sand and N-aminoethylpiperazine, mixing the mixture to be uniform, and cooling the mixture to room temperature to obtain slurry;
bentonite, magnesium oxide, propylene glycol monolaurate, sodium silicate water glass, epoxy resin glue, fine sand and N-aminoethylpiperazine respectively account for 20 parts, 8 parts, 0.6 part, 2 parts, 3 parts, 36 parts and 0.15 part by weight;
during ball milling, adding a powder consisting of the following components in percentage by mass of 100:2, ethanol and guar gum hydroxypropyl trimethyl ammonium chloride, wherein the added mass of the ball milling auxiliary agent is 0.9% of the total mass of the ball mill;
s3, pouring the slurry obtained in the step S2 on the surface of the stone base layer, drying and curing, coating the modified liquid prepared in the step S1 on the surface of the cured slurry, wherein the thickness of the coating is 120 mu m, and drying to obtain the high-temperature-resistant flame-retardant building composite stone.
In the step S1, the adding quality of water is determined by adding water which is 1.6 times of the quality of the copper chloride powder into the copper chloride powder each time, placing the copper chloride powder into an ultrasonic instrument for ultrasonic dispersion for 5min, repeating the operation until no macroscopic copper chloride powder exists at the end of ultrasonic treatment, and stopping adding water, wherein the total added water quality is the adding quality of water at the moment.
In the step S3, the stone base layer is natural stone, the thickness is 2mm, and the thickness of the solidified slurry on the stone base layer is 4mm.
Example 2
The invention provides a production process of a high-temperature-resistant flame-retardant building composite stone, which comprises the following steps:
s1, taking copper chloride powder, adding a proper amount of water for dissolution, adding the copper chloride powder into a mixed solution A which is 9 times of the mixed solution A, stirring and mixing for 30min, adding 2-hydroxyterephthalic acid and erythrulose, continuously stirring and mixing for 3h, transferring to a reaction kettle, heating to 1250 ℃, preserving heat for 7h, taking out, centrifuging, removing the supernatant, and carrying out vacuum drying at 50 ℃ for 4h to obtain a modified material, wherein the modified material is prepared by the steps of: 5, adding the mixture into the mixed solution B in proportion, stirring and mixing for 2 hours at 40 ℃, and cooling to room temperature to obtain a modified solution;
the volume ratio of the mixed solution A is 30:106:2.3, mixing water, ethanol and acetonitrile; the volume ratio of the mixed solution B is 13:6, mixing ethanol and dimethyl carbonate;
s2, taking bentonite, magnesium oxide and propylene glycol monolaurate, placing the bentonite, the magnesium oxide and the propylene glycol monolaurate into a ball mill, ball-milling the bentonite and the propylene glycol monolaurate for 2 hours at 50 ℃, cooling the mixture to room temperature, transferring the mixture into a high-speed heating mixer, adding sodium silicate water glass and epoxy resin glue into the high-speed heating mixer, heating the mixture to 80 ℃, mixing the mixture for 30 minutes, cooling the mixture to 45 ℃, adding fine sand and N-aminoethylpiperazine, mixing the mixture to be uniform, and cooling the mixture to room temperature to obtain slurry;
23 parts by weight of bentonite, 6 parts by weight of magnesium oxide, 0.5 part by weight of propylene glycol monolaurate, 4 parts by weight of sodium silicate water glass, 2 parts by weight of epoxy resin glue, 40 parts by weight of fine sand and 0.14 part by weight of N-aminoethylpiperazine;
during ball milling, adding a powder consisting of the following components in percentage by mass of 100:5, ethanol and guar gum hydroxypropyl trimethyl ammonium chloride, wherein the added mass of the ball milling auxiliary agent is 0.7% of the total mass of the ball mill;
s3, pouring the slurry obtained in the step S2 on the surface of the stone base layer, drying and curing, coating the modified liquid prepared in the step S1 on the surface of the cured slurry, wherein the thickness of the coating is 125 mu m, and drying to obtain the high-temperature-resistant flame-retardant building composite stone.
In the step S1, the adding quality of water is determined by adding water which is 1.3 times of the quality of the copper chloride powder into the copper chloride powder each time, placing the copper chloride powder into an ultrasonic instrument for ultrasonic dispersion for 5min, repeating the operation until no macroscopic copper chloride powder exists at the end of ultrasonic treatment, and stopping adding water, wherein the total added water quality is the adding quality of water at the moment.
In the step S3, the stone base layer is natural stone, the thickness is 4mm, and the thickness of the solidified slurry on the stone base layer is 3mm.
Example 3
The invention provides a production process of a high-temperature-resistant flame-retardant building composite stone, which comprises the following steps:
s1, taking copper chloride powder, adding a proper amount of water for dissolution, adding 10 times of the mixed solution A into the mixed solution A, stirring and mixing for 25min, adding 2-hydroxyterephthalic acid and erythrulose, continuously stirring and mixing for 3h, transferring into a reaction kettle, heating to 130 ℃, preserving heat for 7h, taking out, centrifuging, removing the supernatant, and carrying out vacuum drying at 50 ℃ for 4h to obtain a modified material, wherein the modified material is prepared by the steps of: 5, adding the mixture into the mixed solution B in proportion, stirring and mixing for 2 hours at 45 ℃, and cooling to room temperature to obtain a modified solution;
the volume ratio of the mixed solution A is 30:106:2.4, mixing water, ethanol and acetonitrile; the volume ratio of the mixed solution B is 13:7, mixing ethanol and dimethyl carbonate;
s2, taking bentonite, magnesium oxide and propylene glycol monolaurate, placing the bentonite, the magnesium oxide and the propylene glycol monolaurate into a ball mill, ball-milling the bentonite and the propylene glycol monolaurate for 2 hours at 50 ℃, cooling the mixture to room temperature, transferring the mixture into a high-speed heating mixer, adding sodium silicate water glass and epoxy resin glue into the high-speed heating mixer, heating the mixture to 75 ℃, mixing the mixture for 35 minutes, cooling the mixture to 40 ℃, adding fine sand and N-aminoethylpiperazine, mixing the mixture to be uniform, and cooling the mixture to room temperature to obtain slurry;
23 parts by weight of bentonite, 5 parts by weight of magnesium oxide, 0.5 part by weight of propylene glycol monolaurate, 3 parts by weight of sodium silicate water glass, 2 parts by weight of epoxy resin glue, 40 parts by weight of fine sand and 0.13 part by weight of N-aminoethylpiperazine;
during ball milling, adding a powder consisting of the following components in percentage by mass of 100:4, ethanol and guar gum hydroxypropyl trimethyl ammonium chloride are compounded to form a ball milling auxiliary agent, wherein the added mass of the ball milling auxiliary agent is 0.6 of the total mass in the ball mill;
s3, pouring the slurry obtained in the step S2 on the surface of the stone base layer, drying and curing, coating the modified liquid prepared in the step S1 on the surface of the cured slurry, wherein the thickness of the coating is 130 mu m, and drying to obtain the high-temperature-resistant flame-retardant building composite stone.
In the step S1, the adding quality of water is determined by adding water which is 1.3 times of the quality of the copper chloride powder into the copper chloride powder each time, placing the copper chloride powder into an ultrasonic instrument for ultrasonic dispersion for 5min, repeating the operation until no macroscopic copper chloride powder exists at the end of ultrasonic treatment, and stopping adding water, wherein the total added water quality is the adding quality of water at the moment.
In the step S3, the stone base layer is natural stone, the thickness is 3mm, and the thickness of the solidified slurry on the stone base layer is 3mm.
Example 4
The invention provides a production process of a high-temperature-resistant flame-retardant building composite stone, which comprises the following steps:
s1, taking copper chloride powder, adding a proper amount of water for dissolution, adding 10 times of the mixed solution A into the mixed solution A, stirring and mixing for 20min, adding 2-hydroxyterephthalic acid and erythrulose, continuously stirring and mixing for 3h, transferring into a reaction kettle, heating to 130 ℃, preserving heat for 6h, taking out, centrifuging, removing the supernatant, and carrying out vacuum drying at 50 ℃ for 4h to obtain a modified material, wherein the modified material is prepared by the steps of: 6, adding the mixture into the mixed solution B in proportion, stirring and mixing for 1h at 40 ℃, and cooling to room temperature to obtain a modified solution;
the volume ratio of the mixed solution A is 30:107:2, mixing water, ethanol and acetonitrile; the volume ratio of the mixed solution B is 14:5, mixing ethanol and dimethyl carbonate;
s2, taking bentonite, magnesium oxide and propylene glycol monolaurate, placing the bentonite, the magnesium oxide and the propylene glycol monolaurate into a ball mill, ball-milling the bentonite and the propylene glycol monolaurate for 1h at 55 ℃, cooling the mixture to room temperature, transferring the mixture into a high-speed heating mixer, adding sodium silicate water glass and epoxy resin glue into the high-speed heating mixer, heating the mixture to 80 ℃, mixing the mixture for 30min, cooling the mixture to 50 ℃, adding fine sand and N-aminoethylpiperazine, mixing the mixture to be uniform, and cooling the mixture to room temperature to obtain slurry;
26 parts of bentonite, 4 parts of magnesium oxide, 0.3 part of propylene glycol monolaurate, 5 parts of sodium silicate water glass, 1 part of epoxy resin glue, 46 parts of fine sand and 0.12 part of N-aminoethylpiperazine in parts by weight;
during ball milling, adding a powder consisting of the following components in percentage by mass of 100:7, ethanol and guar gum hydroxypropyl trimethyl ammonium chloride are compounded to form a ball milling auxiliary agent, wherein the added mass of the ball milling auxiliary agent is 0.5% of the total mass in the ball mill;
s3, pouring the slurry obtained in the step S2 on the surface of the stone base layer, drying and curing, coating the modified liquid prepared in the step S1 on the surface of the cured slurry, wherein the thickness of the coating is 130 mu m, and drying to obtain the high-temperature-resistant flame-retardant building composite stone.
In the step S1, the adding quality of water is determined by adding water 1 time the quality of the copper chloride powder into the copper chloride powder each time, placing the copper chloride powder into an ultrasonic instrument for ultrasonic dispersion for 5 minutes, repeating the operation if the copper chloride powder which is visible to the naked eye exists, stopping adding water until the copper chloride powder which is visible to the naked eye does not exist at the end of ultrasonic treatment, and the total quality of the added water is the adding quality of the water at the moment.
In the step S3, the stone base layer is natural stone, the thickness is 6mm, and the thickness of the solidified slurry on the stone base layer is 3mm.
Comparative example 1
The production process of the building composite stone comprises the following steps:
s1, taking copper chloride powder, adding a proper amount of water for dissolution, adding 8 times of mixed solution A into the mixed solution A, stirring and mixing for 30min, adding 2-hydroxyterephthalic acid and erythrulose, continuously stirring and mixing for 4h, transferring into a reaction kettle, heating to 120 ℃, preserving heat for 8h, taking out, centrifuging, removing supernatant, and carrying out vacuum drying at 50 ℃ for 3h to obtain a modified material, wherein the modified material is prepared by the steps of: 5, adding the mixture into the mixed solution B in proportion, stirring and mixing for 2 hours at 50 ℃, and cooling to room temperature to obtain a modified solution;
the volume ratio of the mixed solution A is 30:104:2.6, mixing water, ethanol and acetonitrile; the volume ratio of the mixed solution B is 12:8, mixing ethanol and dimethyl carbonate;
s2, taking bentonite and magnesium oxide, placing the bentonite and the magnesium oxide in a ball mill, ball-milling for 2 hours at 45 ℃, cooling to room temperature, transferring the mixture into a high-speed heating mixer, adding sodium silicate water glass and epoxy resin glue into the high-speed heating mixer, heating to 75 ℃, mixing for 35 minutes, cooling to 40 ℃, adding fine sand, mixing uniformly, and cooling to room temperature to obtain slurry;
the bentonite, the magnesia, the sodium silicate water glass, the epoxy resin adhesive and the fine sand are respectively 20 parts, 8 parts, 2 parts, 3 parts and 36 parts by weight;
during ball milling, adding a powder consisting of the following components in percentage by mass of 100:2, ethanol and guar gum hydroxypropyl trimethyl ammonium chloride, wherein the added mass of the ball milling auxiliary agent is 0.9% of the total mass of the ball mill;
s3, pouring the slurry obtained in the step S2 on the surface of the stone base layer, drying and curing, coating the modified liquid prepared in the step S1 on the surface of the cured slurry, wherein the thickness of the coating is 120 mu m, and drying to obtain the high-temperature-resistant flame-retardant building composite stone.
In the step S1, the adding quality of water is determined by adding water which is 1.6 times of the quality of the copper chloride powder into the copper chloride powder each time, placing the copper chloride powder into an ultrasonic instrument for ultrasonic dispersion for 5min, repeating the operation until no macroscopic copper chloride powder exists at the end of ultrasonic treatment, and stopping adding water, wherein the total added water quality is the adding quality of water at the moment.
In the step S3, the stone base layer is natural stone, the thickness is 2mm, and the thickness of the solidified slurry on the stone base layer is 4mm.
Comparative example 2
The production process of the building composite stone comprises the following steps:
s1, bentonite, magnesium oxide and propylene glycol monolaurate are taken, put into a ball mill for ball milling at 45 ℃ for 2 hours, cooled to room temperature, transferred into a high-speed heating mixer, added with sodium silicate water glass and epoxy resin glue, heated to 75 ℃, mixed for 35 minutes, cooled to 40 ℃, added with fine sand and N-aminoethylpiperazine, mixed to uniformity, cooled to room temperature, and finally obtained slurry;
bentonite, magnesium oxide, propylene glycol monolaurate, sodium silicate water glass, epoxy resin glue, fine sand and N-aminoethylpiperazine respectively account for 20 parts, 8 parts, 0.6 part, 2 parts, 3 parts, 36 parts and 0.15 part by weight;
during ball milling, adding a powder consisting of the following components in percentage by mass of 100:2, ethanol and guar gum hydroxypropyl trimethyl ammonium chloride, wherein the added mass of the ball milling auxiliary agent is 0.9% of the total mass of the ball mill;
s2, pouring the slurry obtained in the step S2 on the surface of the stone base layer, and drying and curing to obtain the building composite stone.
In the step S2, the stone base layer is natural stone, the thickness is 2mm, and the thickness of the solidified slurry on the stone base layer is 4mm.
1) Basic Performance test
The performance of the building composite stone materials produced in the above examples 1 to 4 was examined, and the results are shown in Table 1.
Table 1:
| example 1 | Example 2 | Example 3 | Example 4 | |
| Impact rating | 10J | 10J | 10J | 10J |
| Contact angle (°) | 112.4 | 114.7 | 115.4 | 110.6 |
| Water resistance | 4h impervious to water | 4h impervious to water | 4h impervious to water | 4h impervious to water |
| Weather resistance | By passing through | By passing through | By passing through | By passing through |
The weather resistance in table 1 means that no cracking, peeling, and bulging occurred after the weather resistance test by performing the artificial aging test for 1000 hours.
The experimental results in table 1 show that the impact resistance level of the building composite stone material produced in the embodiments 1-4 can reach 10J, the contact angle is larger than 110 degrees, the water resistance test is watertight for 4 hours, the weather resistance can also pass, and the experimental results show that the building composite stone material obtained by the production method provided by the invention has excellent comprehensive performance.
2) Intensity test
The strength test is performed on the building composite stone material produced in the example 1 and the comparative example 1, and the strength of the building composite stone material produced in the example 1 is improved by 12% compared with that of the building composite stone material produced in the comparative example 1, which shows that the addition of the propylene glycol monolaurate and the N-aminoethylpiperazine in the step S2 of the invention at a proper time can have an enhancement effect on the strength of the building composite stone material.
3) Heat resistance and flame retardance test
Flame retardant rating test and heat resistant temperature test were performed on example 1 and comparative example 2, and the results are shown in table 2.
Table 2:
the experimental results of table 2 show that the flame retardant grade of the building composite stone produced in the example 1 is A1, which shows that the building composite stone is nonflammable and does not generate open fire, and the flame retardant effect is far better than that of B2 of the comparative example 2; and the heat-resistant temperature is also greatly improved compared with comparative example 2. Experimental results show that the coating of the modifying liquid in the production process of the invention has obvious improvement on the flame retardant property and the temperature resistance of the building composite material.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The production process of the high-temperature-resistant flame-retardant building composite stone is characterized by comprising the following steps of:
s1, taking copper chloride powder, adding a proper amount of water for dissolution, then adding the copper chloride powder into a mixed solution A which is 8-10 times of the mixed solution A, stirring and mixing for 20-30 min, wherein the mixed solution A comprises the following components in percentage by volume: 104 to 107: 2-2.6, adding 2-hydroxy terephthalic acid and erythrulose, continuously stirring and mixing for 3-4 hours, transferring into a reaction kettle, heating to 120-130 ℃, preserving heat for 6-8 hours, taking out, centrifuging, discarding supernatant, and vacuum drying at 50 ℃ for 3-4 hours to obtain a modified material, wherein the modified material is prepared by the steps of: 5-6, and adding the mixture into a mixed solution B, wherein the mixed solution B comprises the following components in percentage by volume: 5-8 of ethanol and dimethyl carbonate, stirring and mixing for 1-2 h at 40-50 ℃, and cooling to room temperature to obtain a modified liquid;
s2, taking bentonite, magnesium oxide and propylene glycol monolaurate, placing the bentonite, the magnesium oxide and the propylene glycol monolaurate into a ball mill, ball milling for 1-2 hours at 45-55 ℃, and adding the bentonite and the propylene glycol monolaurate into the ball mill according to the mass ratio of 100: 2-7 of ethanol and guar gum hydroxypropyl trimethyl ammonium chloride, wherein the added mass of the ball milling auxiliary agent is 0.5-0.9% of the total mass in the ball mill, cooling to room temperature, transferring into a high-speed heating mixer, adding sodium silicate water glass and epoxy resin glue into the high-speed heating mixer, heating to 75-80 ℃, mixing for 30-35 min, cooling to 40-50 ℃, adding fine sand and N-aminoethylpiperazine, mixing uniformly, and cooling to room temperature to obtain slurry;
s3, pouring the slurry obtained in the step S2 on the surface of the stone base layer, drying and curing, coating the modified liquid prepared in the step S1 on the surface of the cured slurry, and drying to obtain the high-temperature-resistant flame-retardant building composite stone with the coating thickness of 120-130 mu m.
2. The process for producing the high-temperature-resistant flame-retardant building composite stone according to claim 1, wherein in the step S1, the adding quality of water is determined by adding water which is 1-1.6 times of the quality of copper chloride powder into the copper chloride powder each time, placing the copper chloride powder into an ultrasonic instrument for ultrasonic dispersion for 5min, repeating the operation until no macroscopic copper chloride powder exists when the ultrasonic operation is finished, and stopping adding water, wherein the total quality of the added water is the adding quality of the water.
3. The production process of the high-temperature-resistant flame-retardant building composite stone material according to claim 1, wherein the mass ratio of the copper chloride powder to the 2-hydroxyterephthalic acid to the erythrulose is 38-42: 2 to 4:0.9 to 1.4.
4. The production process of the high-temperature-resistant flame-retardant building composite stone according to claim 1, wherein in the step S2, the bentonite, the magnesium oxide, the propylene glycol monolaurate, the sodium silicate water glass, the epoxy resin glue, the fine sand and the N-aminoethylpiperazine are respectively 20-26 parts, 4-8 parts, 0.3-0.6 part, 2-5 parts, 1-3 parts, 36-46 parts and 0.12-0.15 part by weight.
5. The process for producing the high-temperature-resistant flame-retardant building composite stone according to claim 1, wherein in the step S2, 23 parts, 6 parts, 0.5 part, 4 parts, 2 parts, 40 parts and 0.14 part of bentonite, magnesium oxide, propylene glycol monolaurate, sodium silicate water glass, epoxy resin glue, fine sand and N-aminoethylpiperazine are respectively calculated according to parts by weight.
6. The process for producing the high-temperature-resistant flame-retardant building composite stone according to claim 1, wherein in the step S3, the stone base layer is natural stone, the thickness is 2-6 mm, and the thickness of the slurry solidified on the stone base layer is 3-4 mm.
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