CN115925321A - High-strength ecological stone slab and preparation method thereof - Google Patents
High-strength ecological stone slab and preparation method thereof Download PDFInfo
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- CN115925321A CN115925321A CN202310130901.1A CN202310130901A CN115925321A CN 115925321 A CN115925321 A CN 115925321A CN 202310130901 A CN202310130901 A CN 202310130901A CN 115925321 A CN115925321 A CN 115925321A
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Abstract
The invention relates to the technical field of stone slabs, in particular to a high-strength ecological stone slab and a preparation method thereof. The method comprises the following steps: s1: preparing coarse stone powder and fine stone powder; s2: preparing low polyether alcohol; s3: mixing low polyether alcohol, polytetrahydrofuran ether glycol, diisocyanate and an organic tin catalyst to obtain a polyurethane resin raw material; s4: mixing a polyurethane resin raw material with fine stone powder to obtain a raw material A; mixing novolac epoxy vinyl resin with coarse stone powder to obtain a raw material B; mixing the raw material A and the raw material B; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture; s5: pouring the mixture into a forming mold, standing at normal temperature for 24 hours, vacuumizing, performing vibration pressing and curing; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
Description
Technical Field
The invention relates to the technical field of stone slabs, in particular to a high-strength ecological stone slab and a preparation method thereof.
Background
The ecological stone slab is an ecological stone integrated slab which is formed by mixing natural stone crushed aggregates with materials such as resin and the like as a binder and performing vacuum-pumping pressing; because the self-weight is light, the natural stone is only one twentieth of the natural stone, the flatness is high, the aesthetic property is good, and the natural stone is widely used in the building and household industries as a decorative plate.
In the prior art, the traditional ecological stone plate has low density, so that the problems of deformation, shrinkage, low strength and the like of the plate exist. As the binder, an unsaturated resin, an epoxy resin, or the like is generally used. The unsaturated resin can be cured at normal temperature, but has the defects of low cohesiveness, poor permeability and large curing shrinkage; in comparison, the performance of the epoxy resin is superior to that of unsaturated resin in terms of cohesiveness and mechanical properties. However, the epoxy resin has large brittleness and small toughness due to the existence of benzene rings, so that cracks are easy to generate in the pressing process of the stone slab, and the mechanical strength of the ecological stone slab is reduced; meanwhile, the stone slab has low impact resistance due to high brittleness, and the application range is reduced. On the other hand, the epoxy resin is used as a bonding agent, and has poor fluidity and uneven mixing in the mixing process of the natural macadam due to large molecular weight, and bubbles are generated, so that the existing ecological stone slab has low strength and poor use effect.
In conclusion, the preparation of the high-strength ecological stone slab has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide a high-strength ecological stone slab and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a high-strength ecological stone slab comprises the following steps:
s1: crushing and grinding the natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use;
s2: preparation of the low polyether alcohol: s21: carrying out substitution reaction on eugenol and epoxy chloropropane to obtain epoxidized eugenol; s22: reacting epoxy eugenol with polyhydric alcohol to obtain low polyether alcohol;
s3: putting low polyether alcohol, polytetrahydrofuran ether glycol, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate into a mixing tank, and mixing for 30 to 60 minutes at the temperature of 60 to 70 ℃ and the rotating speed of 600 to 1000rpm under the nitrogen atmosphere to obtain a polyurethane resin raw material for later use;
s4: uniformly mixing a polyurethane resin raw material with fine stone powder to obtain a raw material A; uniformly mixing novolac epoxy vinyl resin with coarse stone powder to obtain a raw material B; uniformly mixing the raw material A and the raw material B; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture;
s5: pouring the mixture into a forming mold, standing at normal temperature for 24 hours, vacuumizing, performing vibration pressing and curing; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
Preferably, in step S1, the natural macadam comprises the following raw materials: 50 to 60 parts of marble, 20 to 30 parts of quartz stone, 10 to 12 parts of granite and 8 to 10 parts of rutile according to parts by weight.
Optimally, in the step S1, the coarse stone powder comprises 70 to 75 parts by weight of 10 to 50 meshes and 25 to 30 parts by weight of 50 to 100 meshes; the fine stone powder comprises the following particle size, by weight, 10-15 parts of 100-150 meshes, 55-65 parts of 150-200 meshes and 25-30 parts of 300-325 meshes.
Preferably, in step S2, the specific preparation process of the low polyether alcohol is as follows:
s21: sequentially adding eugenol, epoxy chloropropane and benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 to 3 hours at 118 to 122 ℃ in a nitrogen atmosphere; cooling to 50-60 ℃, dropwise adding a sodium hydroxide solution for 40-60 minutes, reacting for 3-5 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol;
s22: adding epoxy eugenol and sorbitol into a reaction bottle in sequence, stirring uniformly at 90-95 ℃ under the nitrogen atmosphere, adding triethylamine, heating to 135-140 ℃, reacting for 24-36 hours, and cooling to obtain the low polyether alcohol.
Preferably, the mass ratio of the eugenol to the epichlorohydrin is 1 (2.6 to 2.8); the mass ratio of the epoxidized eugenol to the sorbitol is (8-9) to 3.
Preferably, in step S3, the polyurethane resin raw materials include the following materials: according to parts by weight, 25 to 30 parts of low polyether alcohol, 50 to 55 parts of polytetrahydrofuran ether glycol, 20 to 22 parts of 1, 6-hexamethylene diisocyanate and 0.8 to 1.2 parts of dibutyltin dilaurate.
Preferably, in step S4, the mixture comprises the following raw materials: according to parts by weight, 20 to 25 parts of polyurethane resin raw material, 250 to 275 parts of fine stone powder, 75 to 80 parts of novolac epoxy vinyl resin, 225 to 250 parts of coarse stone powder, 20 to 25 parts of curing agent and 1 to 2 parts of initiator; the initiator comprises a peroxide initiator and a photoinitiator in a mass ratio of 1.
Optimally, in the step S5, the vacuum degree of vacuumizing is 95 to 100KPa, the vibration frequency is 30 to 50Hz, the pressure of pressing is 5 to 6 tons, and the pressing time is 40 to 60 seconds; the curing process is that the curing is carried out under the ultraviolet illumination for 30 to 40 minutes at 80 to 100 ℃ for 1 to 2 hours and at 140 to 160 ℃ for 1 to 2 hours.
The ecological stone slab prepared by the preparation method of the high-strength ecological stone slab is more optimized.
In the technical scheme, natural crushed stone is ground into stone powder and is configured in multiple stages; the raw materials of epoxy resin and polyurethane resin are used as binders to form an interpenetrating network, so that the mechanical strength and the impact resistance of the ecological stone slab are synergistically increased.
In the specific scheme:
(1) In the scheme, marble is used as a main body, and quartz stone, granite and rutile are used as natural broken stone as an auxiliary body; the ecological stone slab is ground and sieved to be divided into coarse stone powder and fine stone powder with multi-stage particle sizes, so that the compactness of the mixture is improved, air bubbles are reduced, and the binding power between the stone powder and the binding agent is increased, thereby increasing the compactness and the mechanical strength of the ecological stone slab.
(2) In the embodiment, raw materials of novolac epoxy vinyl resin and polyurethane resin are used as the binder. On one hand, due to the introduction of single epoxy resin, the filling between coarse stone powder and fine stone powder is not compact, so that the mechanical strength of the ecological stone slab is not high, and the introduction of polyurethane increases the cohesiveness between polyurethane and stone powder, so that the filling is more compact, and the compressive strength of the stone slab is increased; on the other hand, an interpenetrating network of polyurethane and epoxy resin is formed after curing, and the formation of the interpenetrating polymer network is an effective toughening means, so that the brittleness of the epoxy resin is effectively improved, and the impact resistance of the ecological stone slab is improved.
On one hand, the polyurethane resin raw material is incompletely prepolymerized and has a small molecular weight, and can be well filled in gaps between coarse stone powder and fine stone powder, and the polyurethane resin raw material and macromolecular epoxy resin synergistically improve the compactness of resin filling. On the other hand, compared with the method of directly introducing polyurethane, the method has the advantages of better interpenetration property, less phase separation interfaces and reduced stress concentration, thereby improving the mechanical strength and the impact resistance.
The preparation method comprises the following steps of setting a mixing sequence, mixing a polyurethane resin raw material and epoxy resin with coarse stone and fine stone respectively to obtain a raw material A and a raw material B, mixing the raw material A and the raw material B, and finally introducing a curing agent and an initiator. The reason for this process setup is: firstly, the polyurethane resin raw material can well uniformly disperse fine stone powder in the raw material B, so that the mixing uniformity is improved; secondly, if the raw materials are directly mixed, the curing agent (amine) of the epoxy resin and the isocyanate in the polyurethane resin raw material have high reaction activity and can quickly react to generate phase separation after being directly mixed, so that the curing agent is introduced after the raw materials are mixed in the preamble and react for a period of time, the phase separation effect is effectively improved, the interpenetrating effect is increased, and the toughness is effectively enhanced.
In the scheme, low polyether alcohol is introduced into the polyurethane resin raw material, so that the affinity with stone powder and the compatibility with epoxy resin are effectively improved, and the interpenetration of a polyurethane network and an epoxy resin network is enhanced, so that the mechanical property and the impact resistance of the ecological stone plate are effectively improved. The oligoether alcohol takes eugenol as a starting point, epoxy groups are grafted by utilizing the substitution reaction of phenolic hydroxyl and chlorine to obtain epoxidized eugenol, then the ring-opening reaction between the epoxy groups and sorbitol is utilized to obtain the oligoether alcohol containing eugenol branched chains, the similar benzene rings of the eugenol and the epoxy resin are utilized to increase the compatibility, and the unsaturated bond on the eugenol is utilized to increase the reaction compatibility with the unsaturated bond of the novolac epoxy vinyl resin and increase the interpenetration property. Thereby effectively increasing the crosslinking density and increasing the impact resistance. It should be noted that: the amount of the oligoether alcohol to be introduced and the amount of the polytetrahydrofuran ether glycol are limited because the oligoether alcohol is introduced to increase the interpenetration property, but contains rigid benzene rings, and when the amount of the oligoether alcohol to be introduced is too large, the toughness of the polytetrahydrofuran ether glycol chain segment is increased, so that the impact resistance is reduced.
In the scheme, two initiators are introduced, including a peroxide initiator and an ultraviolet initiator. Firstly, ultraviolet light is utilized to initiate crosslinking of unsaturated bonds, and although rutile is introduced to absorb light to increase photo-crosslinking in the scheme, a part of uncrosslinked part of the internal part of the crosslinking is still remained, so that a peroxide initiator is also introduced to initiate crosslinking of internal free radicals in the process of heating and curing. In the curing process, different photo-thermal curing modes and curing at different temperatures are used, and the curing stress is effectively buffered and the shrinkage rate is reduced by utilizing the different conditions of the reaction rate, the temperature and the like of each group, so that the generation of cracks in the compression molding process is inhibited, and the yield and the mechanical property of the ecological stone slab are increased.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples and comparative examples, the novolac epoxy vinyl ester resin has the model of FX-470, and the manufacturer is Shanghai Kayin chemical Co., ltd; the CAS number of the polytetrahydrofuran ether glycol is 25190-06-1, and the manufacturer is Jinan Yifengda chemical industry Co., ltd; the CAS number of eugenol is 97-53-0, the CAS number of epichlorohydrin is 106-89-8, the CAS number of benzyltriethylammonium chloride is 56-37-1, the CAS number of triethylamine is 121-44-8, and the CAS number of 1, 6-hexamethylene diisocyanate is 822-06-0; the curing agent is triethylene tetramine, and the CAS number is 112-24-3; are all commercially available. In addition, the following parts are taken as mass units, and 1 part is 100g.
Example 1: s1: crushing and grinding the natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use; wherein, the natural macadam comprises the following raw materials: 55 parts of marble, 25 parts of quartz, 10 parts of granite and 10 parts of rutile in parts by weight; the coarse stone powder comprises the following particle sizes, by weight, 70 parts of 25 meshes and 30 parts of 80 meshes; the fine stone powder comprises the following particle sizes, by weight, 15 parts of 120 meshes, 60 parts of 170 meshes and 25 parts of 325 meshes;
s2: preparation of the low polyether alcohol: s21: sequentially adding 10g of eugenol, 27g of epoxy chloropropane and 1.5g of benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 hours at 120 ℃ in a nitrogen atmosphere; cooling to 60 ℃, dropwise adding 3g of 20wt% sodium hydroxide solution for 45 minutes, reacting for 3 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol; s22: sequentially adding 42.5g of epoxidized eugenol and 15g of sorbitol into a reaction bottle, stirring uniformly at 90 ℃ in a nitrogen atmosphere, adding 3.6g of triethylamine, heating to 140 ℃, reacting for 30 hours, and cooling to obtain low polyether alcohol, wherein the low polyether alcohol can be subjected to an equal-proportion amplification experiment;
s3: placing low polyether alcohol, polytetrahydrofuran ether glycol, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate in a mixing tank, and mixing for 60 minutes at 65 ℃ and 1000rpm under the atmosphere of nitrogen to obtain a polyurethane resin raw material; wherein, the polyurethane resin raw materials comprise the following substances: 28 parts of low polyether alcohol, 52 parts of polytetrahydrofuran ether glycol, 20 parts of 1, 6-hexamethylene diisocyanate and 1 part of dibutyltin dilaurate;
s4: stirring and mixing a polyurethane resin raw material and fine stone powder for 30 minutes to obtain a raw material A; stirring and mixing the novolac epoxy vinyl resin and the coarse stone powder for 30 minutes to obtain a raw material B; stirring and mixing the raw materials A and B for 15 minutes; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture; wherein the mixture comprises the following raw materials: according to parts by weight, 22 parts of polyurethane resin raw material, 260 parts of fine stone powder, 78 parts of novolac epoxy vinyl resin, 240 parts of coarse stone powder, 23 parts of curing agent and 2 parts of initiator; the initiator comprises benzoyl peroxide and a photoinitiator 819 in a mass ratio of 1;
s5: pouring the mixture into a forming die, standing for 24 hours at normal temperature, vacuumizing until the vacuum degree is 100KPa, setting the vibration frequency to be 40Hz and the pressure to be 6 tons, and pressing for 50 seconds; vacuumizing, vibration pressing at wavelength of 365nm and 150 μ W/cm 2 Is irradiated for 30 minutes at an intensity of 100 ℃ for 2 hoursCuring at 150 ℃ for 1 hour; and opening the die, and grinding and polishing to obtain the ecological stone slab.
Example 2: s1: crushing and grinding natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use; wherein, the natural macadam comprises the following raw materials: 55 parts of marble, 25 parts of quartz, 10 parts of granite and 10 parts of rutile in parts by weight; the coarse stone powder comprises the following particle sizes of, by weight, 70 parts of 25 meshes and 30 parts of 80 meshes; the fine stone powder comprises the following grain sizes of 15 parts by weight of 120 meshes, 60 parts by weight of 170 meshes and 25 parts by weight of 325 meshes;
s2: preparation of the low polyether alcohol: s21: sequentially adding 10g of eugenol, 27g of epoxy chloropropane and 1.5g of benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 hours at 120 ℃ in a nitrogen atmosphere; cooling to 60 ℃, dropwise adding 3g of 20wt% sodium hydroxide solution for 45 minutes, reacting for 3 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol; s22: sequentially adding 40g of epoxidized eugenol and 15g of sorbitol into a reaction bottle, stirring uniformly at 90 ℃ in the nitrogen atmosphere, adding 3.5g of triethylamine, heating to 140 ℃, reacting for 30 hours, and cooling to obtain low polyether alcohol, wherein the low polyether alcohol can be subjected to an equal-proportion amplification experiment;
s3: placing low polyether alcohol, polytetrahydrofuran ether glycol, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate in a mixing tank, and mixing for 60 minutes at 65 ℃ and 1000rpm in a nitrogen atmosphere to obtain a polyurethane resin raw material; wherein, the polyurethane resin raw materials comprise the following substances: according to parts by weight, 25 parts of low polyether alcohol, 55 parts of polytetrahydrofuran ether glycol, 20 parts of 1, 6-hexamethylene diisocyanate and 1.2 parts of dibutyltin dilaurate;
s4: stirring and mixing a polyurethane resin raw material and fine stone powder for 30 minutes to obtain a raw material A; stirring and mixing the novolac epoxy vinyl resin and the coarse stone powder for 30 minutes to obtain a raw material B; stirring and mixing the raw material A and the raw material B for 15 minutes; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture; wherein the mixture comprises the following raw materials: according to parts by weight, 20 parts of polyurethane resin raw material, 250 parts of fine stone powder, 80 parts of novolac epoxy vinyl resin, 250 parts of coarse stone powder, 25 parts of curing agent and 2 parts of initiator; the initiator comprises benzoyl peroxide and a photoinitiator 819 in a mass ratio of 1;
s5: pouring the mixture into a forming die, standing for 24 hours at normal temperature, vacuumizing to 100KPa, setting the vibration frequency to be 40Hz and the pressure to be 6 tons, and pressing for 50 seconds; vacuumizing, vibrating and pressing at wavelength of 365nm and 150 μ W/cm 2 The intensity of the light source is irradiated for 30 minutes, and the light source is cured for 2 hours at 100 ℃ and 1 hour at 150 ℃; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
Example 3: s1: crushing and grinding the natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use; wherein, the natural macadam comprises the following raw materials: according to parts by weight, 55 parts of marble, 25 parts of quartz, 10 parts of granite and 10 parts of rutile; the coarse stone powder comprises the following particle sizes of, by weight, 70 parts of 25 meshes and 30 parts of 80 meshes; the fine stone powder comprises the following grain sizes of 15 parts by weight of 120 meshes, 60 parts by weight of 170 meshes and 25 parts by weight of 325 meshes;
s2: preparation of the low polyether alcohol: s21: sequentially adding 10g of eugenol, 27g of epoxy chloropropane and 1.5g of benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 hours at 120 ℃ in a nitrogen atmosphere; cooling to 60 ℃, dropwise adding 3g of 20wt% sodium hydroxide solution for 45 minutes, reacting for 3 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol; s22: sequentially adding 45g of epoxidized eugenol and 15g of sorbitol into a reaction bottle, stirring uniformly at 90 ℃ in a nitrogen atmosphere, adding 3.8g of triethylamine, heating to 140 ℃, reacting for 30 hours, and cooling to obtain low polyether alcohol, wherein the low polyether alcohol can be subjected to an equal-proportion amplification experiment;
s3: placing low polyether alcohol, polytetrahydrofuran ether glycol, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate in a mixing tank, and mixing for 60 minutes at 65 ℃ and 1000rpm under the atmosphere of nitrogen to obtain a polyurethane resin raw material; wherein, the polyurethane resin raw materials comprise the following substances: according to parts by weight, 30 parts of low polyether alcohol, 50 parts of polytetrahydrofuran ether glycol, 20 parts of 1, 6-hexamethylene diisocyanate and 1.2 parts of dibutyltin dilaurate;
s4: stirring and mixing a polyurethane resin raw material and fine stone powder for 30 minutes to obtain a raw material A; stirring and mixing the novolac epoxy vinyl resin and the coarse stone powder for 30 minutes to obtain a raw material B; stirring and mixing the raw materials A and B for 15 minutes; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture; wherein the mixture comprises the following raw materials: according to parts by weight, 25 parts of polyurethane resin raw material, 275 parts of fine stone powder, 75 parts of novolac epoxy vinyl resin, 225 parts of coarse stone powder, 20 parts of curing agent and 2 parts of initiator; the initiator comprises benzoyl peroxide and a photoinitiator 819 in a mass ratio of 1;
s5: pouring the mixture into a forming die, standing for 24 hours at normal temperature, vacuumizing until the vacuum degree is 100KPa, setting the vibration frequency to be 40Hz and the pressure to be 6 tons, and pressing for 50 seconds; vacuumizing, vibrating and pressing at wavelength of 365nm and 150 μ W/cm 2 The intensity of the light source is irradiated for 30 minutes, and the light source is cured for 2 hours at 100 ℃ and 1 hour at 150 ℃; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
Comparative example 1: the polyurethane was introduced directly, the rest being the same as in example 1;
s1: crushing and grinding the natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use; wherein, the natural macadam comprises the following raw materials: 55 parts of marble, 25 parts of quartz, 10 parts of granite and 10 parts of rutile in parts by weight; the coarse stone powder comprises the following particle sizes of, by weight, 70 parts of 25 meshes and 30 parts of 80 meshes; the fine stone powder comprises the following grain sizes of 15 parts by weight of 120 meshes, 60 parts by weight of 170 meshes and 25 parts by weight of 325 meshes;
s2: preparation of the low polyether alcohol: s21: sequentially adding 10g of eugenol, 27g of epoxy chloropropane and 1.5g of benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 hours at 120 ℃ in a nitrogen atmosphere; cooling to 60 ℃, dropwise adding 3g of 20wt% sodium hydroxide solution for 45 minutes, reacting for 3 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol; s22: sequentially adding 42.5g of epoxidized eugenol and 15g of sorbitol into a reaction bottle, stirring uniformly at 90 ℃ in a nitrogen atmosphere, adding 3.6g of triethylamine, heating to 140 ℃, reacting for 30 hours, and cooling to obtain low polyether alcohol, wherein the low polyether alcohol can be subjected to an equal-proportion amplification experiment;
s3: dissolving oligoether and polytetrahydrofuran ether glycol in tetrahydrofuran to obtain a raw material solution; adding 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate into a reaction bottle, setting the temperature to 65 ℃, dropwise adding the raw material liquid for 1 hour, and reacting for 3 hours to obtain polyurethane; wherein the polyurethane comprises the following substances: 28 parts of low polyether alcohol, 52 parts of polytetrahydrofuran ether glycol, 20 parts of 1, 6-hexamethylene diisocyanate, 1 part of dibutyltin dilaurate and 120 parts of tetrahydrofuran in parts by weight;
s4: stirring and mixing polyurethane and fine stone powder for 30 minutes to obtain a raw material A; stirring and mixing the novolac epoxy vinyl resin and the coarse stone powder for 30 minutes to obtain a raw material B; stirring and mixing the raw materials A and B for 15 minutes; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture; wherein the mixture comprises the following raw materials: according to the weight parts, 22 parts of polyurethane, 260 parts of fine stone powder, 78 parts of novolac epoxy vinyl resin, 240 parts of coarse stone powder, 23 parts of curing agent and 2 parts of initiator; the initiator comprises benzoyl peroxide and a photoinitiator 819 in a mass ratio of 1;
s5: pouring the mixture into a forming die, standing for 24 hours at normal temperature, vacuumizing until the vacuum degree is 100KPa, setting the vibration frequency to be 40Hz and the pressure to be 6 tons, and pressing for 50 seconds; vacuumizing, vibration pressing at wavelength of 365nm and 150 μ W/cm 2 The intensity of the light source is irradiated for 30 minutes, and the light source is cured for 2 hours at 100 ℃ and 1 hour at 150 ℃; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
Comparative example 2: the raw materials were mixed directly, and the rest was the same as in example 1;
s1: crushing and grinding the natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use; wherein, the natural macadam comprises the following raw materials: 55 parts of marble, 25 parts of quartz, 10 parts of granite and 10 parts of rutile in parts by weight; the coarse stone powder comprises the following particle sizes of, by weight, 70 parts of 25 meshes and 30 parts of 80 meshes; the fine stone powder comprises the following grain sizes of 15 parts by weight of 120 meshes, 60 parts by weight of 170 meshes and 25 parts by weight of 325 meshes;
s2: preparation of the low polyether alcohol: s21: sequentially adding 10g of eugenol, 27g of epoxy chloropropane and 1.5g of benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 hours at 120 ℃ in a nitrogen atmosphere; cooling to 60 ℃, dropwise adding 3g of 20wt% sodium hydroxide solution for 45 minutes, reacting for 3 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol; s22: sequentially adding 42.5g of epoxidized eugenol and 15g of sorbitol into a reaction bottle, stirring uniformly at 90 ℃ in a nitrogen atmosphere, adding 3.6g of triethylamine, heating to 140 ℃, reacting for 30 hours, and cooling to obtain low polyether alcohol, wherein the low polyether alcohol can be subjected to an equal-proportion amplification experiment;
s3: placing low polyether alcohol, polytetrahydrofuran ether glycol, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate in a mixing tank, and mixing for 60 minutes at 65 ℃ and 1000rpm under the atmosphere of nitrogen to obtain a polyurethane resin raw material; wherein, the polyurethane resin raw materials comprise the following substances: 28 parts of low polyether alcohol, 52 parts of polytetrahydrofuran ether glycol, 20 parts of 1, 6-hexamethylene diisocyanate and 1 part of dibutyltin dilaurate;
s4: sequentially adding coarse stone powder, fine stone powder, polyurethane resin raw materials, novolac epoxy vinyl resin, a curing agent and an initiator into a mixing tank, and mixing and stirring for 30 minutes to obtain a mixture; wherein the mixture comprises the following raw materials: according to parts by weight, 22 parts of polyurethane resin raw material, 260 parts of fine stone powder, 78 parts of novolac epoxy vinyl resin, 240 parts of coarse stone powder, 23 parts of curing agent and 2 parts of initiator; the initiator comprises benzoyl peroxide and a photoinitiator 819 in a mass ratio of 1;
s5: pouring the mixture into a forming die, standing for 24 hours at normal temperature, vacuumizing until the vacuum degree is 100KPa, setting the vibration frequency to be 40Hz and the pressure to be 6 tons, and pressing for 50 seconds; vacuumizing, vibration pressing at wavelength of 365nm and 150 μ W/cm 2 The intensity of the light source is irradiated for 30 minutes, and the light source is cured for 2 hours at 100 ℃ and 1 hour at 150 ℃; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
Comparative example 3: low polyether alcohol is not introduced; otherwise, the same as example 1;
s1: crushing and grinding the natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use; wherein, the natural macadam comprises the following raw materials: according to parts by weight, 55 parts of marble, 25 parts of quartz, 10 parts of granite and 10 parts of rutile; the coarse stone powder comprises the following particle sizes of, by weight, 70 parts of 25 meshes and 30 parts of 80 meshes; the fine stone powder comprises the following grain sizes of 15 parts by weight of 120 meshes, 60 parts by weight of 170 meshes and 25 parts by weight of 325 meshes;
s2: placing low polyether alcohol, polytetrahydrofuran ether glycol, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate in a mixing tank, and mixing for 60 minutes at 65 ℃ and 1000rpm in a nitrogen atmosphere to obtain a polyurethane resin raw material; wherein, the polyurethane resin raw materials comprise the following substances: 80 parts of polytetrahydrofuran ether glycol, 20 parts of 1, 6-hexamethylene diisocyanate and 1 part of dibutyltin dilaurate in parts by weight;
s4: stirring and mixing a polyurethane resin raw material and fine stone powder for 30 minutes to obtain a raw material A; stirring and mixing the novolac epoxy vinyl resin and the coarse stone powder for 30 minutes to obtain a raw material B; stirring and mixing the raw materials A and B for 15 minutes; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture; wherein the mixture comprises the following raw materials: according to parts by weight, 22 parts of polyurethane resin raw material, 260 parts of fine stone powder, 78 parts of novolac epoxy vinyl resin, 240 parts of coarse stone powder, 23 parts of curing agent and 2 parts of initiator; the initiator comprises benzoyl peroxide and a photoinitiator 819 in a mass ratio of 1;
s5: pouring the mixture into a forming die, standing for 24 hours at normal temperature, vacuumizing until the vacuum degree is 100KPa, setting the vibration frequency to be 40Hz and the pressure to be 6 tons, and pressing for 50 seconds; vacuumizing, vibration pressing at wavelength of 365nm and 150 μ W/cm 2 The intensity of (2) is irradiated for 30 minutes, cured for 2 hours at 100 ℃, and cured for 1 hour at 150 ℃; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
Comparative example 4: the oligoether alcohol was introduced in an increased amount, otherwise the same as in example 1;
s1: crushing and grinding the natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use; wherein, the natural macadam comprises the following raw materials: 55 parts of marble, 25 parts of quartz, 10 parts of granite and 10 parts of rutile in parts by weight; the coarse stone powder comprises the following particle sizes of, by weight, 70 parts of 25 meshes and 30 parts of 80 meshes; the fine stone powder comprises the following grain sizes of 15 parts by weight of 120 meshes, 60 parts by weight of 170 meshes and 25 parts by weight of 325 meshes;
s2: preparation of the low polyether alcohol: s21: sequentially adding 10g of eugenol, 27g of epoxy chloropropane and 1.5g of benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 hours at 120 ℃ in a nitrogen atmosphere; cooling to 60 ℃, dropwise adding 3g of 20wt% sodium hydroxide solution for 45 minutes, reacting for 3 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol; s22: sequentially adding 42.5g of epoxidized eugenol and 15g of sorbitol into a reaction bottle, stirring uniformly at 90 ℃ in a nitrogen atmosphere, adding 3.6g of triethylamine, heating to 140 ℃, reacting for 30 hours, and cooling to obtain low polyether alcohol, wherein the low polyether alcohol can be subjected to an equal-proportion amplification experiment;
s3: placing low polyether alcohol, polytetrahydrofuran ether glycol, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate in a mixing tank, and mixing for 60 minutes at 65 ℃ and 1000rpm in a nitrogen atmosphere to obtain a polyurethane resin raw material; wherein, the polyurethane resin raw materials comprise the following substances: 40 parts of low polyether alcohol, 40 parts of polytetrahydrofuran ether glycol, 20 parts of 1, 6-hexamethylene diisocyanate and 1 part of dibutyltin dilaurate;
s4: stirring and mixing a polyurethane resin raw material and fine stone powder for 30 minutes to obtain a raw material A; stirring and mixing the novolac epoxy vinyl resin and the coarse stone powder for 30 minutes to obtain a raw material B; stirring and mixing the raw materials A and B for 15 minutes; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture; wherein the mixture comprises the following raw materials: according to parts by weight, 22 parts of polyurethane resin raw material, 260 parts of fine stone powder, 78 parts of novolac epoxy vinyl resin, 240 parts of coarse stone powder, 23 parts of curing agent and 2 parts of initiator; the initiator comprises benzoyl peroxide and a photoinitiator 819 in a mass ratio of 1;
s5: pouring the mixture into a forming die, standing for 24 hours at normal temperature, vacuumizing until the vacuum degree is 100KPa, setting the vibration frequency to be 40Hz and the pressure to be 6 tons, and pressing for 50 seconds; vacuumizing, vibrating and pressing at 365nm wavelength150μW/cm 2 The intensity of the light source is irradiated for 30 minutes, and the light source is cured for 2 hours at 100 ℃ and 1 hour at 150 ℃; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
And (3) sample testing: the ecological stone slabs prepared in the examples and the comparative examples are sampled, samples of 150mm multiplied by 100mm multiplied by 12mm are taken, and a strength tester is used for testing the strength at the speed of 1 mm/min; the impact test was also carried out on a specimen of 150mm X100 mm X12 mm, with a steel ball weighing 50kg, at a notch depth of 2 mm. The data obtained are shown below:
the data in the table above show that: the ecological stone slab prepared by the scheme has excellent mechanical property, and the impact toughness of the stone slab is effectively improved while the high tensile strength is kept.
Comparing the data of comparative examples 1 to 4 with example 1, it can be found that: in comparative example 1, the introduction of polyurethane directly resulted in a more phase separation interface due to reduced dispersibility and reduced network interpenetration, resulting in reduced performance; in comparative example 2, since the materials were directly mixed, phase delamination occurred and performance was reduced, in comparative example 3, since oligoether was not introduced, interpenetration of the polyurethane network and the epoxy resin network was reduced, and performance was reduced; in comparative example 4, the toughness was lowered due to the increase in the amount of oligoether alcohol used, so that the impact resistance was lowered.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a high-strength ecological stone slab is characterized by comprising the following steps: the method comprises the following steps:
s1: crushing and grinding natural broken stone to obtain stone powder, and screening to obtain coarse stone powder and fine stone powder for later use;
s2: preparation of the low polyether alcohol: s21: carrying out substitution reaction on eugenol and epoxy chloropropane to obtain epoxidized eugenol; s22: reacting epoxy eugenol with polyhydric alcohol to obtain low polyether alcohol;
s3: putting low polyether alcohol, polytetrahydrofuran ether glycol, diisocyanate and an organic tin catalyst into a mixing tank, and mixing for 30 to 60 minutes at the temperature of 60 to 70 ℃ and the rotation speed of 600 to 1000rpm under the nitrogen atmosphere to obtain a polyurethane resin raw material;
s4: uniformly mixing a polyurethane resin raw material with fine stone powder to obtain a raw material A; uniformly mixing novolac epoxy vinyl resin with coarse stone powder to obtain a raw material B; uniformly mixing the raw material A and the raw material B; adding a curing agent and an initiator, and uniformly mixing to obtain a mixture;
s5: pouring the mixture into a forming mold, standing at normal temperature for 24 hours, vacuumizing, performing vibration pressing and curing; and opening the mold, and grinding and polishing to obtain the ecological stone slab.
2. The method for preparing the high-strength ecological stone slab as claimed in claim 1, wherein the method comprises the following steps: in the step S1, the natural macadam comprises the following raw materials: 50 to 60 parts of marble, 20 to 30 parts of quartz stone, 10 to 12 parts of granite and 8 to 10 parts of rutile according to parts by weight.
3. The method for preparing the high-strength ecological stone slab as claimed in claim 2, wherein the method comprises the following steps: in the step S1, the coarse stone powder comprises 70 to 75 parts by weight of 10 to 50 meshes and 25 to 30 parts by weight of 50 to 100 meshes; the fine stone powder comprises the following particle size, by weight, 10-15 parts of 100-150 meshes, 55-65 parts of 150-200 meshes and 25-30 parts of 300-325 meshes.
4. The method for preparing the high-strength ecological stone slab as claimed in claim 1, wherein the method comprises the following steps: in step S2, the specific preparation process of the low polyether alcohol is:
s21: sequentially adding eugenol, epoxy chloropropane and benzyltriethylammonium chloride into a reaction bottle, and refluxing for 2 to 3 hours at 118 to 122 ℃ in a nitrogen atmosphere; cooling to 50 to 60 ℃, dropwise adding a sodium hydroxide solution for 40 to 60 minutes, reacting for 3 to 5 hours under the condition of heat preservation, and extracting an organic phase to obtain epoxidized eugenol;
s22: adding epoxy eugenol and sorbitol into a reaction bottle in sequence, stirring uniformly at 90-95 ℃ under the nitrogen atmosphere, adding triethylamine, heating to 135-140 ℃, reacting for 24-36 hours, and cooling to obtain the low polyether alcohol.
5. The method for preparing the high-strength ecological stone slab as claimed in claim 4, wherein the method comprises the following steps: the mass ratio of the eugenol to the epichlorohydrin is 1 (2.6 to 2.8); the mass ratio of the epoxidized eugenol to the sorbitol is (8-9) to 3.
6. The method for preparing the high-strength ecological stone slab as claimed in claim 1, wherein the method comprises the following steps: in step S3, the polyurethane resin raw materials include the following: according to parts by weight, 25 to 30 parts of low polyether alcohol, 50 to 55 parts of polytetrahydrofuran ether glycol, 20 to 22 parts of diisocyanate and 0.8 to 1.2 parts of organic tin catalyst.
7. The method for preparing the high-strength ecological stone slab as claimed in claim 1, wherein the method comprises the following steps: in step S4, the mixture includes the following raw materials: according to parts by weight, 20 to 25 parts of polyurethane resin raw material, 250 to 275 parts of fine stone powder, 75 to 80 parts of novolac epoxy vinyl resin, 225 to 250 parts of coarse stone powder, 20 to 25 parts of curing agent and 1 to 2 parts of initiator; the initiator comprises a peroxide initiator and a photoinitiator in a mass ratio of 1.
8. The method for preparing the high-strength ecological stone slab as claimed in claim 1, wherein the method comprises the following steps: in the step S5, the vacuum degree of vacuumizing is 95 to 100KPa, the vibration frequency is 30 to 50Hz, the pressing pressure is 5 to 6 tons, and the pressing time is 40 to 60 seconds; the curing process is carried out under ultraviolet illumination for 30 to 40 minutes, at 80 to 100 ℃ for 1 to 2 hours, and at 140 to 160 ℃ for 1 to 2 hours.
9. The ecological stone slab prepared by the preparation method of the high-strength ecological stone slab according to any one of claims 1 to 8.
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| CN104478295A (en) * | 2014-12-15 | 2015-04-01 | 田忠和 | Compressive and fireproof artificial quartz stone sheet and preparation method thereof |
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| CN106348660A (en) * | 2016-08-31 | 2017-01-25 | 甘肃金润玉石业有限公司 | Machining method of waste residues of marbles |
| CN106700461A (en) * | 2015-08-20 | 2017-05-24 | 福家汇(北京)电子商务有限公司 | Antibacterial and mildew-proof artificial marble material |
| CN107572891A (en) * | 2017-08-29 | 2018-01-12 | 无为县鑫品石业有限公司 | One kind synthesis toughness marble and its manufacture method |
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| CN1709817A (en) * | 2005-05-31 | 2005-12-21 | 周卫 | Artificial granite, marble mechanical fitting and its preparing method |
| CN104478295A (en) * | 2014-12-15 | 2015-04-01 | 田忠和 | Compressive and fireproof artificial quartz stone sheet and preparation method thereof |
| CN106700461A (en) * | 2015-08-20 | 2017-05-24 | 福家汇(北京)电子商务有限公司 | Antibacterial and mildew-proof artificial marble material |
| CN105176034A (en) * | 2015-10-09 | 2015-12-23 | 上海艳紫化工科技有限公司 | Marble-imitated decorative line and preparation method thereof |
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