Artificial marble capable of recycling and its preparation method

Abstract

The present application belongs to the field of building decoration materials, and discloses a recyclable artificial marble and a preparation method thereof. The artificial marble comprises the following raw materials in percentage by mass: 4-30% of an epoxy prepolymer, 2-20% of an imine curing agent, 0.05-1% of a catalyst, 50-90% of an inorganic filler, and 0-20% of an auxiliary agent. The artificial marble is obtained by hot-pressing and curing the above raw materials. The method uses a combination of the epoxy prepolymer, the imine curing agent and the catalyst as an adhesive, and uses the function of the dynamic covalent bond of the imine that can be recombined with the matrix resin through a dynamic reversible exchange reaction under certain conditions to achieve the recycling purpose of the artificial marble. The artificial marble has a simple preparation process, a low shrinkage rate in the curing process, excellent mechanical, heat-resistant and corrosion-resistant properties, and can shield ultraviolet rays. The edge and corner scraps and waste can be recycled and reused, thereby saving energy and protecting the environment.

Description

Technical Field

[0001] This invention relates to the field of building decoration materials, specifically a recyclable artificial marble and its preparation method. Background Technology

[0002] Artificial marble is made by imitating the surface texture of marble. It has similar texture characteristics to marble, and the patterns can be controlled and determined by the designer. It has good reproducibility, is resistant to pollution, has good processing performance, and can be made into complex shapes such as arcs and curved surfaces. It is easy to construct. Among them, polyester-type artificial marble produced with unsaturated polyester as adhesive is the most widely used. Acrylic (polymethyl methacrylate, etc.) and epoxy resin (Li Huilu, Shao Kangchen, Han Jiangling, et al. Research on epoxy resin artificial marble [J]. Thermosetting Resins, 2015, 30(01):49-51) and other polymer materials can also be used as adhesives to prepare artificial marble. However, the production scraps and artificial marble waste are not degradable and are usually discarded or buried as construction waste, which not only wastes resources but also pollutes the environment. Summary of the Invention

[0003] The purpose of this invention is to propose a recyclable artificial marble.

[0004] The objective of this invention is achieved through the following technical solution:

[0005] A recyclable artificial marble comprises, by weight percentage, the following raw materials: 4%–30% epoxy prepolymer, 2%–20% imide curing agent, 0.05%–1% catalyst, 50%–90% inorganic filler, and 0–20% additives, wherein the artificial marble is formed by hot pressing and curing of the above raw materials.

[0006] Preferably, the epoxy prepolymer is a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, or a glycidyl amine type epoxy resin; the imine curing agent is an aliphatic diamine containing a semi-aromatic imine bond or an alicyclic diamine containing a semi-aromatic imine bond; and the catalyst is a tertiary amine or an imidazole catalyst.

[0007] Preferably, the epoxy prepolymer is any one or more of the following: bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S glycidyl ether, resorcinol diglycidyl ether, phenolic glycidyl ether, diglycidyl phthalate, tetrahydrophthalic acid diglycidyl ether, hexahydrophthalic acid diglycidyl ether, 1,2-epoxycyclohexane-4,5-dicarboxylic acid diglycidyl ether, p-aminophenol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,2-propanediol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, and trimethylolpropane glycidyl ether.

[0008] Preferably, the imine curing agent comprises any one or more of the following structures:

[0009]

[0010] Preferably, the inorganic filler is one or a mixture of two or more of the following: marble particles, basalt particles, quartz particles, granite particles, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, titanium dioxide, and carbon black.

[0011] Preferably, the catalyst is one or a mixture of two or more of 2,4,6-tris(dimethylaminomethyl)phenol, triethylamine, triethanolamine, benzyl dimethylamine, o-hydroxybenzyl dimethylamine, 2-ethyl-4-methylimidazole, 1-benzyl-2-ethylimidazole, and 1-aminoethyl-2-methylimidazole.

[0012] Preferably, the additive is one or more of flame retardants, coupling agents, defoamers, pigments, and organic solvents. All of the above additives are commonly used commercially available products.

[0013] The method for preparing the artificial marble includes the following steps:

[0014] (1) Disperse the epoxy prepolymer with inorganic fillers and additives evenly to obtain mixture A;

[0015] (2) Add imine curing agent and catalyst to mixture A and mix thoroughly to obtain mixture B;

[0016] (3) Pour mixture B into a mold, vibrate to degas, heat press to solidify and shape, grind and polish to obtain artificial marble.

[0017] Preferably, the hot-press curing molding conditions are as follows: maintain a pressure of 10-40 MPa, heat to 30-120°C at a heating rate of 5-20°C / min, hold at that temperature for 0.5-10 hours, then heat to 120-180°C at a heating rate of 1-10°C / min and hold at that temperature for 0-3 hours, and finally cool and demold at a rate of 1-5°C / min.

[0018] Preferably, the process further includes the following steps: recycling and crushing the scraps and / or waste of the aforementioned artificial marble into granules to obtain recycled material; directly adding the recycled material to mixture A and / or B, stirring evenly, and then reusing it for the production of artificial marble. Before adding the recycled material, the proportions of each component in mixture B are independent of the recycled material content. The resin on the surface of the recycled material is integrated with the cured mixture B through imine dynamic covalent bonds, and the addition of the recycled material has virtually no impact on the performance of the artificial marble.

[0019] This invention uses a composition of epoxy prepolymer, imine curing agent, and catalyst as a binder. It leverages the ability of imine dynamic covalent bonds to recombine with the matrix resin under certain conditions through a dynamic and reversible exchange reaction to achieve the recycling of artificial marble. The mechanism of the dynamic exchange reaction of imine dynamic covalent bonds is as follows:

[0020]

[0021] in The semi-aromatic imine bond structure represents the recycled material. It represents the semi-aromatic imine bond structure of the matrix resin. Under certain conditions, a dynamic exchange reaction of imine bonds can occur at the interface between the recycled material and the matrix resin, making the two fuse together.

[0022] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0023] (1) The process of this invention is simple, the artificial marble prepared has a low shrinkage rate during the curing process, and has excellent mechanical, heat resistance and corrosion resistance properties, and can shield ultraviolet rays.

[0024] (2) The artificial marble scraps and waste prepared by this invention can be recycled and crushed into granules and then directly recycled and reused for the production of artificial marble. The addition of recycled materials has virtually no impact on the performance of artificial marble. Attached Figure Description

[0025] Figure 1 This is a diagram of the surface morphology of artificial marble.

[0026] Figure 2 This is a diagram of the internal structure of artificial marble. Detailed Implementation

[0027] The present invention will be further described below with reference to specific embodiments, but the content of the present invention is not limited to the following embodiments.

[0028] Example 1

[0029] 12 parts of bisphenol A glycidyl ether NPEL-128 (Nanya), 2 parts of flame retardant phenoxycyclophosphamide, 0.5 parts of coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.3 parts of defoamer BYK-1765 (BYK), 3 parts of pigment iron oxide, 50 parts of granite particles, and 25 parts of aluminum hydroxide were added to a mixing tank and mixed thoroughly. 7 parts of curing agent C and 0.2 parts of 2,4,6-tris(dimethylaminomethyl)phenol were added and rapidly stirred for 10 minutes to obtain a mixture. The mixture was poured into a mold, degassed by vibration, and heated to 60°C at a pressure of 20 MPa. The temperature was increased to 60°C at a rate of 5°C / min and held for 1 hour. The temperature was then increased to 120°C at a rate of 3°C / min and held for 2 hours. The mixture was cooled to room temperature at a rate of 2°C / min and demolded. The resulting product was then ground and polished to obtain artificial marble.

[0030] Example 2

[0031] The scrap material from Example 1 was crushed into particles smaller than 5mm to obtain recycled material A.

[0032] 30 parts of recycled material A, 8.4 parts of bisphenol A glycidyl ether NPEL-128 (Nanya), 1.4 parts of flame retardant phenoxycyclophosphonitrile, 0.35 parts of coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.21 parts of defoamer BYK-1765 (BYK), 2.1 parts of pigment iron oxide, 35 parts of granite particles, and 17.5 parts of aluminum hydroxide were added to a mixing tank and mixed thoroughly. 4.9 parts of curing agent C and 0.14 parts of 2,4,6-tris(dimethylaminomethyl)phenol were added and rapidly stirred for 10 minutes to obtain a mixture. The mixture was poured into a mold, degassed by vibration, and heated to 60°C at a pressure of 20 MPa. The temperature was increased to 60°C at a rate of 5°C / min and held for 1 hour. The temperature was then increased to 120°C at a rate of 3°C / min and held for 2 hours. The mixture was cooled to room temperature at a rate of 2°C / min and demolded. The product was then ground and polished to obtain artificial marble.

[0033] Example 3

[0034] The artificial marble (simulated waste) produced in Example 1 was crushed into particles smaller than 5 mm to obtain recycled material B.

[0035] 60 parts of recycled material B, 4.8 parts of bisphenol A glycidyl ether NPEL-128 (Nanya), 0.8 parts of flame retardant phenoxycyclophosphonitrile, 0.2 parts of coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.12 parts of defoamer BYK-1765 (BYK), 1.2 parts of pigment iron oxide, 20 parts of granite particles, and 10 parts of aluminum hydroxide were added to a mixing tank and mixed thoroughly. 2.8 parts of curing agent C and 0.08 parts of 2,4,6-tris(dimethylaminomethyl)phenol were added and rapidly stirred for 10 minutes to obtain a mixture. The mixture was poured into a mold, degassed by vibration, and heated to 60°C at a pressure of 20 MPa. The temperature was increased to 60°C at a rate of 5°C / min and held for 1 hour. The temperature was then increased to 120°C at a rate of 3°C / min and held for 2 hours. The mixture was cooled to room temperature at a rate of 2°C / min and demolded. The product was then ground and polished to obtain artificial marble.

[0036] Example 4

[0037] Nine parts of bisphenol A glycidyl ether NPEL-128 (Nanya), 0.6 parts of coupling agent γ-aminopropyltriethoxysilane, 0.3 parts of defoamer BYK-A500 (BYK), 10 parts of acetone, and 85 parts of aluminum hydroxide were added to a mixing tank and mixed thoroughly. Four parts of curing agent C, one part of curing agent J, and 0.1 parts of benzyl dimethylamine were added and rapidly stirred for 15 minutes to obtain a mixture. The mixture was poured into a mold, degassed by vibration, and heated to 50°C at a pressure of 25 MPa. The temperature was increased to 50°C at a rate of 5°C / min and held for 1 hour. The temperature was then increased to 160°C at a rate of 5°C / min and held for 1 hour. The mixture was cooled to room temperature at a rate of 5°C / min and demolded. Grinding and polishing were performed to obtain artificial marble. The surface morphology and internal structure are as follows: Figure 1 , 2 As shown.

[0038] Example 5

[0039] Five parts of phenolic glycidyl ether (DEN431), one part of neopentyl glycol diglycidyl ether, 0.2 parts of coupling agent γ-aminopropyltriethoxysilane, 0.25 parts of defoamer BYK-1765 (BYK), 15 parts of tetrahydrofuran, 10 parts of quartz granules, and 80 parts of calcium carbonate were added to a mixing tank and mixed thoroughly. 3.5 parts of curing agent E and 0.05 parts of 2-ethyl-4-methylimidazole were added and rapidly stirred for 20 minutes to obtain a mixture. The mixture was poured into a mold, degassed by vibration, and heated to 80°C at a pressure of 30 MPa. The temperature was maintained for 0.5 hours, then increased to 150°C at a rate of 3°C / minute and held for 1 hour. The mixture was then cooled to room temperature at a rate of 5°C / minute for demolding. Grinding and polishing were performed to obtain artificial marble.

[0040] Comparative Example 1

[0041] The difference between this comparative example and Example 1 is that 15.5 parts of NPEL-128 and 3.5 parts of isophorone diamine are used instead of 12 parts of NPEL-128 and 7 parts of curing agent C.

[0042] Comparative Example 2

[0043] The difference between this comparative example and Example 2 is that: scrap materials produced in Comparative Example 1 are used instead of scrap materials produced in Example 1 to prepare recycled materials; 10.9 parts of NPEL-128 and 2.4 parts of isophorone diamine are used instead of 8.4 parts of NPEL-128 and 4.9 parts of curing agent C.

[0044] Comparative Example 3

[0045] The difference between this comparative example and Example 3 is that the artificial marble produced in Comparative Example 1 was used instead of the artificial marble produced in Example 1 to prepare the recycled material; 6.2 parts of NPEL-128 and 1.4 parts of isophorone diamine were used instead of 4.8 parts of NPEL-128 and 2.8 parts of curing agent C.

[0046] Table 1. Comparison of the properties of artificial marble

[0047]

[0048] Note: The UV shielding effect of the sample was tested using a UV-Vis spectrophotometer. The sample thickness was approximately 0.5 mm, and the UV wavelength was 200–400 nm. The acid resistance was tested by immersion in a 10% citric acid solution, and the alkali resistance was tested by immersion in a 10% sodium carbonate solution for 7 days.

[0049] Table 1 shows that the artificial marble prepared by this invention has a low shrinkage rate during the curing process, excellent mechanical, heat-resistant, and corrosion-resistant properties, and can shield against ultraviolet rays. Artificial marble scraps and waste can be directly recycled and reused after being collected, crushed into granules, and used in the production of artificial marble. Furthermore, the addition of recycled materials has virtually no impact on the performance of the artificial marble.

[0050] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A recyclable artificial marble, characterized in that, The artificial marble comprises, by weight percentage, the following raw materials: 4% to 30% epoxy prepolymer, 2% to 20% imide curing agent, 0.05% to 1% catalyst, 50% to 90% inorganic filler and 0% to 20% additives, and is formed by hot pressing and curing of the above raw materials; The epoxy prepolymer is a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, or a glycidyl amine type epoxy resin; the imine curing agent is an aliphatic diamine containing a semi-aromatic imine bond or an alicyclic diamine containing a semi-aromatic imine bond; the catalyst is a tertiary amine or an imidazole catalyst. The imine curing agent comprises any one or more of the following structures: 。 2. The artificial marble according to claim 1, characterized in that, The epoxy prepolymer is any one or more of the following: bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S glycidyl ether, resorcinol diglycidyl ether, phenolic glycidyl ether, diglycidyl phthalate, tetrahydrophthalic acid diglycidyl ether, hexahydrophthalic acid diglycidyl ether, 1,2-epoxycyclohexane-4,5-dicarboxylic acid diglycidyl ether, p-aminophenol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,2-propanediol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, and trimethylolpropane glycidyl ether.

3. The artificial marble according to claim 1 or 2, characterized in that, The inorganic filler is one or a mixture of two or more of the following: marble particles, basalt particles, quartz particles, granite particles, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, titanium dioxide, and carbon black.

4. The artificial marble according to claim 1 or 2, characterized in that, The catalyst is one or a mixture of two or more of 2,4,6-tris(dimethylaminomethyl)phenol, triethylamine, triethanolamine, benzyl dimethylamine, o-hydroxybenzyl dimethylamine, 2-ethyl-4-methylimidazole, 1-benzyl-2-ethylimidazole, and 1-aminoethyl-2-methylimidazole.

5. The artificial marble according to claim 1 or 2, characterized in that, The additives are one or more of flame retardants, coupling agents, defoamers, pigments, and organic solvents.

6. The method for preparing artificial marble according to any one of claims 1 to 5, characterized in that, Includes the following steps: (1) Disperse the epoxy prepolymer with inorganic fillers and additives evenly to obtain mixture A; (2) Add imine curing agent and catalyst to mixture A and mix thoroughly to obtain mixture B; (3) Pour mixture B into a mold, vibrate to degas, heat press to solidify and shape, grind and polish to obtain artificial marble.

7. The preparation method according to claim 6, characterized in that, The conditions for hot-press curing molding are as follows: maintain a pressure of 10~40MPa, heat to 30~120℃ at a heating rate of 5~20℃ / min, hold at that temperature for 0.5~10 hours, then heat to 120~180℃ at a heating rate of 1~10℃ / min and hold at that temperature for 0~3 hours, and finally cool and demold at a rate of 1~5℃ / min.

8. The preparation method according to claim 6 or 7, characterized in that, It also includes the following steps: recycling and crushing the scraps and / or waste of the artificial marble according to any one of claims 1 to 5 into granules to obtain recycled material; adding the recycled material directly to mixture A and / or B, stirring evenly, and then using it again to produce artificial marble.

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