CN110357494B - Artificial stone and preparation method thereof - Google Patents

Abstract

The invention relates to an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight: 400 parts of filler 200-; the preparation of the artificial stone comprises the following steps: s1, stirring and mixing pure water and a filler to prepare a slurry; s2, adding the modified unsaturated polyester resin and the coupling agent into the slurry, and stirring and mixing; then adding the curing agent, the accelerator and the flame retardant and continuously stirring; finally, adding color master batches to mix the mixture to prepare a mixture; s3, pouring the mixture into a mold, and solidifying and molding the mixture; s4, demolding and drying: taking the condensate off the mold, and drying to obtain a preform; and S5, performing coarse grinding and fine grinding on the surface of the preformed product to obtain a finished product. The invention aims to improve the crack resistance of the artificial stone; the second purpose is to provide a preparation method of the artificial stone based on the first purpose.

Description

Artificial stone and preparation method thereof

Technical Field

The invention relates to the technical field of building materials, in particular to an artificial stone and a preparation method thereof.

Background

The artificial stone is made up by using unsaturated polyester resin as adhesive and non-natural mixture filler through a certain preparation process. The artificial stone is a novel composite material, has the advantage of comprehensive utilization of resources, has the function of being unappreciable in the aspect of environmental protection and energy conservation, is a famous green and environment-friendly product of building materials, and becomes a preferred facing material of modern buildings. The artificial stone is widely applied to the fields of commercial decoration, furniture, bathroom products, art processing and the like.

Unsaturated polyester resin is a kind of multifunctional thermosetting resin formed by dissolving unsaturated polybasic acid (or anhydride) and saturated polyalcohol in vinyl crosslinking monomer after polycondensation reaction, and has been widely used in the fields of building, chemical engineering, aviation and the like due to low price and excellent performance. However, most unsaturated polyester resins have highly crosslinked rigid benzene ring structures after being cured, and have the defects of small sliding range between molecular chains, low toughness, poor crack propagation resistance, easy combustion and the like. The artificial stone made by using unsaturated polyester resin as a binder often has the defect of easy cracking.

Disclosure of Invention

An object of the present invention is to provide an artificial stone having an effect of improving crack resistance of the artificial stone; the invention also aims to provide a preparation method of the artificial stone based on the first aim.

The technical purpose of the invention is realized by the following technical scheme: an artificial stone comprises the following components in parts by weight: 400 parts of filler 200, 80-100 parts of modified unsaturated polyester resin, 5-8 parts of color master batch, 2-4 parts of coupling agent, 2-4 parts of curing agent, 0.5-2 parts of accelerator and 1-3 parts of flame retardant; the modified unsaturated polyester is prepared from unsaturated polyester resin and epoxy resin according to a mass ratio of 1: (0.05-0.1) blending the resulting blend.

By adopting the technical scheme, the bisphenol A skeleton in the molecular structure of the epoxy resin provides toughness and heat resistance for the epoxy resin, and the hydroxyl provides reactivity and adhesiveness; because the unsaturated polyester resin and the epoxy resin have good compatibility, the unsaturated polyester resin and the epoxy resin are blended to improve the defects of low toughness and easy cracking of the cured product of the unsaturated polyester resin; and the good adhesiveness of the epoxy resin enables the epoxy resin to be tightly connected with surface groups of the unsaturated polyester resin, so that the stability of the blend is improved, and the adhesion effect between the modified unsaturated polyester resin and the filler is improved, so that the impact resistance of the finished stone product is improved, and the possibility of cracking of the finished stone product is reduced.

The invention is further configured to: the filler is prepared from the following components in a mass ratio of 1: (0.5-1) the recycled concrete powder and kaolin powder.

By adopting the technical scheme, the filler adopts the recycled concrete and the kaolin, and the recycled concrete has the following three effects: the recycled concrete contains cementing materials such as cement and the like, so that the recycled concrete has good viscosity, and the adhesion effect of the recycled concrete when being mixed with the modified unsaturated polyester resin is improved, so that the overall strength of a stone finished product is improved; the porosity of the recycled concrete is high, and the modified unsaturated polyester resin is easily filled in the pores of the recycled concrete, so that the connection tightness of the recycled concrete and the modified unsaturated polyester resin is improved; the recycling of waste concrete is realized, and the environment-friendly concept is met; the kaolin is used as a clay mineral and has good viscosity and a reinforcing effect, and the kaolin is added with the following two effects: the defect of insufficient strength of the recycled concrete is overcome, and the overall strength of the finished stone product is improved; the good viscosity of the kaolin improves the polymerization force between the filler and the modified unsaturated polyester resin, thereby further improving the overall strength of the finished stone product; therefore, the mixing and adding of the two components are beneficial to improving the crack resistance of the finished stone product.

The invention is further configured to: the components also comprise 2-4 parts of ramie fibers.

By adopting the technical scheme, the ramie fibers have good moisture absorption, air permeability and bacterial inhibition, and the ramie fibers have high strength, and the addition of a proper amount of the ramie fibers in the components is beneficial to improving the strength of the finished stone product, thereby improving the crack resistance of the finished stone product.

The invention is further configured to: the coupling agent is any one of KH560, KH1770 or KH 7180.

By adopting the technical scheme, the molecular structure of the coupling agent contains two groups with different chemical properties, one is an inorganophilic group which acts with the filler, the other is an organophilic group which acts with the resin, and the coupling agent improves the interface action between the inorganic substance and the organic substance, so that the performance of the composite material is improved, and the connection strength between the organic substance and the inorganic substance is enhanced; and organophilic groups in KH560, KH1770 and KH7180 are epoxy groups, and the epoxy groups react with hydroxyl groups in unsaturated polyester resin molecules, easily open the ring structures in the epoxy resin molecules and react with the hydroxyl groups on the epoxy resin molecular chains, so that one of the three groups is selected as a coupling agent.

The invention is further configured to: the curing agent is benzoyl peroxide.

By adopting the technical scheme, the peroxy groups on the benzoyl peroxide molecular chain respectively react with double bonds on unsaturated polyester resin and epoxy resin molecular chains, so that the modified unsaturated polyester resin is activated to promote the decomposition of the peroxy bonds to generate a large amount of free radicals, and chain polymerization reaction is carried out among the free radicals, thereby achieving the effect of curing the modified unsaturated polyester resin.

The invention is further configured to: the accelerant is N, N-dimethylaniline.

By adopting the technical scheme, although the benzoyl peroxide has a remarkable curing effect, the curing temperature is high, nitrogen atoms on N, N-dimethylaniline carry out nucleophilic attack on the benzoyl peroxide, so that peroxide bonds are non-uniformly cracked to generate ion pairs, and valence bonds are broken to form benzoyl free radicals.

The invention is further configured to: the flame retardant is a compound of red phosphorus and aluminum hydroxide or aluminum oxide.

By adopting the technical scheme, the red phosphorus and the aluminum hydroxide or the aluminum oxide are compounded for use, so that a composite phosphorus/aluminum flame-retardant system is formed in the components, and the flame-retardant effect of the stone finished product is improved.

The invention is further configured to: a preparation method of artificial stone comprises the following steps:

s1, preparing slurry: mixing pure water and filler according to the proportion of 1: (40-50) stirring and mixing for 3-5min, adding ramie fibers, and continuing stirring for 5-8min to obtain slurry;

s2, preparing a mixture: adding the modified unsaturated polyester resin and the coupling agent into the slurry, stirring and mixing, wherein the stirring temperature is 40-55 ℃, and the stirring time is 5-10 min; adding the curing agent, the accelerator and the flame retardant, and continuously stirring for 15-25 min; finally, adding color master batches to mix the mixture for 6-8min to prepare a mixture;

s3, curing and forming: pouring the mixture into a mould, standing for 0.5-2h, and solidifying and forming the mixture;

s4, demolding and drying: taking the condensate off the mold, and placing the condensate in an oven to dry water, wherein the oven temperature is 65-75 ℃, and the baking time is 4-8h, so as to prepare a preformed product;

s5, surface polishing: and (4) performing polishing treatment of two procedures of coarse grinding and fine grinding on the surface of the preformed product to obtain a finished product.

By adopting the technical scheme, the ramie fibers are added into the filler and fully mixed, and the ramie fibers are filled in the pores of the recycled concrete and the kaolin, so that the compactness of the molecular structure of the filler is enhanced, and the strength of the filler is enhanced; adding the modified unsaturated polyester resin and a coupling agent into the slurry together, and improving the connection strength between the modified unsaturated polyester resin and the filler through the interface action of the coupling agent; and adding a curing agent, an accelerator and a flame retardant to carry out curing treatment on the mixture, and finally adding color master batches to carry out color matching, and carrying out the processes of curing, drying, polishing and the like to obtain a finished product.

In conclusion, the beneficial technical effects of the invention are as follows:

1. the good adhesiveness of the epoxy resin enables the epoxy resin to be tightly connected with surface groups of the unsaturated polyester resin, so that the stability of the blend is improved, and the adhesion effect between the modified unsaturated polyester resin and the filler is improved, so that the impact resistance of the finished stone product is improved, and the possibility of cracking of the finished stone product is reduced;

2. the recycled concrete contains cementing materials such as cement and the like, so that the recycled concrete has good viscosity, and the adhesion effect of the recycled concrete when being mixed with the modified unsaturated polyester resin is favorably improved, thereby improving the integral strength of the stone finished product; the porosity of the recycled concrete is high, and the modified unsaturated polyester resin is easily filled in the pores of the recycled concrete, so that the connection tightness of the recycled concrete and the modified unsaturated polyester resin is improved; (ii) a

3. Proper amount of ramie fiber is added in the components, which is beneficial to improving the strength of the finished stone product, thereby improving the crack resistance of the finished stone product.

Drawings

FIG. 1 is a flow chart of the production process of this example.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.

Embodiment 1 discloses an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	300
Unsaturated polyester resin-epoxy resin blend	90
		Color master batch	6.5
Ramie fiber	3
		KH560	3
Benzoyl peroxide	2.5
		N, N-dimethylaniline	1.25
Red phosphorus-aluminum hydroxide formulations	2

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the preparation method specifically comprises the following preparation steps:

s1, preparing slurry: mixing pure water and recycled concrete powder-kaolin powder according to the weight ratio of 1: stirring and mixing the components according to the mass ratio of 50, wherein the stirring time is 5min, adding the ramie fibers into the mixture, and continuously stirring the mixture for 6min to obtain slurry;

s2, preparing a mixture: adding the unsaturated polyester resin-epoxy resin blend and KH560 into the slurry, stirring and mixing, wherein the stirring temperature is 45 ℃, and the stirring time is 8 min; then adding benzoyl peroxide, N-dimethylaniline and the red phosphorus-aluminum hydroxide compound, and continuing stirring for 20 min; finally, adding color master batches to mix the mixture for 6min to prepare a mixture;

s3, curing and forming: pouring the mixture into a mould, standing for 1.5h, and solidifying and forming the mixture;

s4, demolding and drying: taking the condensate off the mold, and placing the condensate in an oven to dry water, wherein the oven temperature is 70 ℃, and the baking time is 6 hours, so as to prepare a preform;

s5, surface polishing: and (4) performing polishing treatment of two procedures of coarse grinding and fine grinding on the surface of the preformed product to obtain a finished product.

Embodiment 2 discloses an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	200
Unsaturated polyester resin-epoxy resin blend	100
		Color master batch	5
Ramie fiber	4
		KH560	2
Benzoyl peroxide	4
		N, N-dimethylaniline	0.5
Red phosphorus-aluminum hydroxide compound	1

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the specific preparation procedure was the same as in example 1.

Embodiment 3 discloses an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	400
Unsaturated polyester resin-epoxy resin blend	80
		Color master batch	8
Ramie fiber	4
		KH560	2
Benzoyl peroxide	2
		N, N-dimethylaniline	1
Red phosphorus-aluminum hydroxide compound	3

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the specific preparation procedure was the same as in example 1.

Embodiment 4 discloses an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	300
Unsaturated polyester resin-epoxy resin blend	90
		Color master batch	6.5
Ramie fiber	3
		KH560	3
Benzoyl peroxide	2.5
		N, N-dimethylaniline	1.25
Red phosphorus-aluminum hydroxide compound	2

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.5;

the specific preparation procedure was the same as in example 1.

Embodiment 5 discloses an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	300
Unsaturated polyester resin-epoxy resin blend	90
		Color master batch	6.5
Ramie fiber	3
		KH560	3
Benzoyl peroxide	2.5
		N, N-dimethylaniline	1.25
Red phosphorus-aluminum hydroxide compound	2

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 1;

the specific preparation procedure was the same as in example 1.

Embodiment 6 discloses an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	300
Unsaturated polyester resin-epoxy resin blend	90
		Color master batch	6.5
Ramie fiber	3
		KH560	3
Benzoyl peroxide	2.5
		N, N-dimethylaniline	1.25
Red phosphorus-aluminum hydroxide compound	2

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.05; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the specific preparation procedure was the same as in example 1.

Embodiment 7 discloses an artificial stone and a preparation method thereof, wherein the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	300
Unsaturated polyester resin-epoxy resin blend	90
		Color master batch	6.5
Ramie fiber	3
		KH560	3
Benzoyl peroxide	2.5
		N, N-dimethylaniline	1.25
Red phosphorus-aluminum hydroxide compound	2

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.1; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the specific preparation procedure was the same as in example 1.

Comparative example 1, an artificial stone and a method for preparing the same disclosed by the present invention, the artificial stone comprises the following components in parts by weight:

the mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the preparation method specifically comprises the following preparation steps:

s1, preparing slurry: mixing pure water and recycled concrete powder according to the proportion of 1: stirring and mixing the components according to the mass ratio of 50, wherein the stirring time is 5min, adding the ramie fibers into the mixture, and continuously stirring the mixture for 6min to obtain slurry;

S2-S5 were prepared as in example 1.

Comparative example 2, the artificial stone and the preparation method thereof disclosed by the invention comprise the following components in parts by weight:

components	Parts by weight
		Kaolin powder	300
Unsaturated polyester resin-epoxy resin blend	90
		Color master batch	6.5
Ramie fiber	3
		KH560	3
Benzoyl peroxide	2.5
		N, N-dimethylaniline	1.25
Red phosphorus-aluminum hydroxide compound	2

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the preparation method specifically comprises the following preparation steps:

s1, preparing slurry: mixing pure water and kaolin powder according to the weight ratio of 1: stirring and mixing the components according to the mass ratio of 50, wherein the stirring time is 5min, adding the ramie fibers into the mixture, and continuously stirring the mixture for 6min to obtain slurry;

S2-S5 were prepared as in example 1.

Comparative example 3, an artificial stone and a method for preparing the same disclosed by the present invention, the artificial stone comprises the following components in parts by weight:

the mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the preparation method specifically comprises the following preparation steps:

s1, preparing slurry: mixing pure water and recycled concrete powder-kaolin powder according to the weight ratio of 1: stirring and mixing the components according to the mass ratio of 50, wherein the stirring time is 5min, adding the ramie fibers into the mixture, and continuously stirring the mixture for 6min to obtain slurry;

s2, preparing a mixture: adding unsaturated polyester resin and KH560 into the slurry, stirring and mixing, wherein the stirring temperature is 45 ℃, and the stirring time is 8 min; then adding benzoyl peroxide, N-dimethylaniline and the red phosphorus-aluminum hydroxide compound, and continuing stirring for 20 min; finally, adding color master batches to mix the mixture for 6min to prepare a mixture;

S3-S5 were prepared as in example 1.

Comparative example 4, an artificial stone and a method for preparing the same disclosed by the present invention, the artificial stone comprises the following components in parts by weight:

components	Parts by weight
		Recycled concrete powder-Kaolin powder	300
Unsaturated polyester resin-epoxy resin blend	90
		Color master batch	6.5
Ramie fiber	0
		KH560	3
Benzoyl peroxide	2.5
		N, N-dimethylaniline	1.25
Red phosphorus-aluminum hydroxide compound	2

The mass ratio of the unsaturated polyester resin to the epoxy resin is 1: 0.08; the mass ratio of the recycled concrete powder to the kaolin powder is 1: 0.7;

the preparation method specifically comprises the following preparation steps:

s1, preparing slurry: mixing pure water and recycled concrete powder-kaolin powder according to the weight ratio of 1: stirring and mixing the components according to the mass ratio of 50, wherein the stirring time is 5min, and preparing slurry;

S2-S5 were prepared as in example 1.

The finished products prepared in examples 1 to 7 and comparative examples 1 to 4 were sampled, 20 parts of each example was sampled, and the samples were tested for impact resistance, and the test data are recorded in table 1;

breaking strength: the anti-bending strength of the sample is measured by adopting a DKZ-5000 electric anti-bending tester;

compressive strength: the compressive strength of the sample was measured by using a hydraulic type YE-30 pressure tester.

Data of each performance test of samples in examples 1 to 7 and comparative examples 1 to 4

As can be seen from the impact resistance test data of the samples of examples 1-3: the impact resistance of the finished product can be influenced but the influence is not large by changing the proportion of the components in a reasonable range;

according to the impact resistance test data of the samples of the example 1 and the examples 4 to 5, the following results can be obtained: the mass ratio between the recycled concrete and the kaolin is changed, so that a certain influence is generated on the impact resistance of a finished product, and the impact resistance of the finished product is slightly reduced due to excessive or too little addition of the kaolin;

according to the impact resistance test data of the samples of example 1 and examples 6 to 7, it can be seen that: the mass ratio of the unsaturated polyester resin to the epoxy resin is changed, so that the impact resistance of a finished product is influenced to a certain extent, and therefore, the addition amount of the epoxy resin needs to be controlled within a reasonable range;

according to the impact resistance test data of the samples of the example 1 and the comparative examples 1-2, the following results can be obtained: the impact resistance of the finished product is reduced by independently adding the kaolin or the recycled concrete, so that the blending of the kaolin and the recycled concrete has a beneficial effect of improving the impact resistance of the finished product;

according to the impact resistance test data of the samples of the example 1 and the comparative example 3, the following results can be obtained: compared with unsaturated polyester resin, the epoxy resin-unsaturated polyester resin blend has obvious beneficial effect on improving the shock resistance of the finished product;

according to the impact resistance test data of the samples of the example 1 and the comparative example 4, the following results can be obtained: the addition of the ramie fibers is beneficial to improving the shock resistance of the finished product.

The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.

Claims (5)

1. An artificial stone is prepared from the following components in parts by weight: 400 parts of filler 200, 80-100 parts of modified unsaturated polyester resin, 5-8 parts of color master batch, 2-4 parts of coupling agent, 2-4 parts of curing agent, 0.5-2 parts of accelerator, 2-4 parts of ramie fiber and 1-3 parts of flame retardant; the modified unsaturated polyester is prepared from unsaturated polyester resin and epoxy resin according to a mass ratio of 1: 0.08 blend formed by blending; the filler is prepared from the following components in a mass ratio of 1: (0.5-1) the recycled concrete powder and kaolin powder; the coupling agent is any one of KH560, KH1770 or KH 7180.

2. An artificial stone according to claim 1, characterized in that: the curing agent is benzoyl peroxide.

3. An artificial stone according to claim 1, characterized in that: the accelerant is N, N' -dimethylaniline.

4. An artificial stone according to claim 1, characterized in that: the flame retardant is a compound of red phosphorus and aluminum hydroxide or aluminum oxide.

5. The method for preparing an artificial stone according to any one of claims 1-4, comprising the following steps:

s1, preparing slurry: mixing pure water and filler according to the proportion of 1: (40-50) stirring and mixing for 3-5min, adding ramie fibers, and continuing stirring for 5-8min to obtain slurry;

s2, preparing a mixture: adding the modified unsaturated polyester resin and the coupling agent into the slurry, stirring and mixing, wherein the stirring temperature is 40-55 ℃, and the stirring time is 5-10 min; adding the curing agent, the accelerator and the flame retardant, and continuously stirring for 15-25 min; finally, adding color master batches to mix the mixture for 6-8min to prepare a mixture;

s3, curing and forming: pouring the mixture into a mould, standing for 0.5-2h, and solidifying and forming the mixture;

s4, demolding and drying: taking the condensate off the mold, and placing the condensate in an oven to dry water, wherein the oven temperature is 65-75 ℃, and the baking time is 4-8h, so as to prepare a preformed product;

s5, surface polishing: and (4) performing polishing treatment of two procedures of coarse grinding and fine grinding on the surface of the preformed product to obtain a finished product.

Images