阅读说明：本技术 一种表面改性硅灰石及其制备方法和应用 (Surface modified wollastonite and preparation method and application thereof ) 是由 王光硕 彭鹤松 李海滨 陈超 袁铭伟 宋波 于 2020-07-22 设计创作，主要内容包括：本发明涉及硅灰石改性技术领域,尤其涉及一种表面改性硅灰石及其制备方法和应用。本发明提供的表面改性硅灰石,按重量份数计,包括硅灰石20～30份,碳化钨1～5份,聚乙二醇单硬脂酸酯7～12份,硫化铅锌矿浮选尾矿6～9份,增韧剂3～7份,润滑剂4～8份,破乳剂5～7份,橄榄油1～3份,艾蒿提取物4～10份,十二烷基磺酸钠1～5份,聚乙烯吡咯烷酮0.6～3份,3-(甲基丙烯酰氧)丙基三甲氧基硅烷2～6份,氨基磺酸10～19份,无水乙醇46～62份和水60～85份。本发明所述的表面改性硅灰石与ABS树脂复合后得到的产物的抗拉伸强度≥75MPa,抗冲击强度≥5.3KJ/m<Sup>2</Sup>,制品合格率≥98％。(The invention relates to the technical field of wollastonite modification, in particular to surface-modified wollastonite and a preparation method and application thereof. The surface modified wollastonite comprises, by weight, 20-30 parts of wollastonite, 1-5 parts of tungsten carbide, 7-12 parts of polyethylene glycol monostearate, 6-9 parts of lead-zinc sulfide ore flotation tailings, 3-7 parts of a toughening agent and 4-8 parts of a lubricant5-7 parts of demulsifier, 1-3 parts of olive oil, 4-10 parts of artemisia argyi extract, 1-5 parts of sodium dodecyl sulfate, 0.6-3 parts of polyvinylpyrrolidone, 2-6 parts of 3- (methacryloyloxy) propyl trimethoxy silane, 10-19 parts of sulfamic acid, 46-62 parts of absolute ethyl alcohol and 60-85 parts of water. The tensile strength of the product obtained by compounding the surface modified wollastonite and the ABS resin is more than or equal to 75MPa, and the impact strength is more than or equal to 5.3KJ/m 2 The product percent of pass is more than or equal to 98 percent.)

1. The surface modified wollastonite is characterized by comprising the following preparation raw materials in parts by weight:

2. the surface modified wollastonite of claim 1, which comprises the following raw materials in parts by weight:

3. the surface modified wollastonite of claim 1, which comprises the following raw materials in parts by weight:

4. the surface-modified wollastonite of claim 1, 2 or 3, wherein the toughening agent is an ethylene-1-octene copolymer, a polybutadiene or a styrene-butadiene copolymer.

5. The surface-modified wollastonite of claim 1, 2 or 3, wherein the lubricant comprises a polyethylene wax, a paraffin wax and a liquid paraffin wax;

the mass ratio of the polyethylene wax to the solid paraffin to the liquid paraffin is (0.8-1.2): (2.8-3.3): (3.6-4.5).

6. The surface modified wollastonite of claim 1, 2 or 3, wherein the demulsifying agent comprises calcium chloride and ethylene glycol butyl ether;

the mass ratio of the calcium chloride to the ethylene glycol monobutyl ether is (1.8-2.5): (4.5-5.3).

7. The surface-modified wollastonite of claim 1, 2 or 3, wherein the lead zinc sulfide flotation tailings comprise, in mass percent: 45-56% of silicon oxide, 10-17% of aluminum oxide, 14-20% of magnesium oxide, 3-8% of ferric oxide, 0.5-1.3% of calcium oxide and 5-11% of carbonate.

8. The method for preparing the surface modified wollastonite of any one of claims 1 to 7, comprising the steps of:

mixing wollastonite, tungsten carbide, polyethylene glycol monostearate, lead-zinc sulfide flotation tailings, a lubricant and a toughening agent for the first time to obtain a first mixture;

carrying out second mixing on 3- (methacryloyloxy) propyl trimethoxy silane, sodium dodecyl sulfate and part of water to obtain a first solution;

thirdly mixing polyvinylpyrrolidone, olive oil, a mugwort extract and ethanol to obtain a second solution;

fourthly, mixing sulfamic acid and the residual water to obtain a third solution;

and fourthly mixing the first mixture, the first solution, the second solution, the third solution and a demulsifier, and drying to obtain the surface modified wollastonite.

9. The surface modified wollastonite in any one of claims 1 to 7 or the surface modified wollastonite prepared by the preparation method in claim 8 is applied to the fields of plastics, rubber, coatings and adhesives.

Technical Field

The invention relates to the technical field of wollastonite modification, in particular to surface-modified wollastonite and a preparation method and application thereof.

Background

The wollastonite is generally an aggregate of needle-like, radial and fibrous forms, has a white or off-white appearance, has a glass luster to a pearl luster, has a hardness of 4.5 to 5.0, and has a density of 2.78 to 2.91g/cm³The refractive index is 1.619-1.634, the melting point is 1455 ℃, and the pH of 10% 400-mesh wollastonite aqueous solution is about 10. Importantly, wollastonite also has a series of excellent physicochemical properties, such as low-temperature quick-firing performance: wollastonite can form a silicon-aluminum-calcium low-temperature eutectic body taking anorthite as a main crystal phase at 1020-1080 ℃, and the wollastonite can be used as a ceramic raw material to reduce the firing temperature and shorten the firing time, so that the wollastonite is an ideal low-temperature fast-firing ceramic raw material; electrical insulation: wollastonite has higher insulation resistance and low dielectric constant, and is a high-quality and high-frequency electromagnetic raw material; needle-like structure: needle-shaped wollastonite powder with the length-diameter ratio of 15-20 can be obtained through special processing, and is a rubber and plastic reinforced material with outstanding performance; optical properties: wollastonite has higher whiteness, brightness and refractive index, and can be used as rubber and paint filler to partially replace high-grade white pigments such as titanium dioxide, lithopone and the like. Therefore, wollastonite is a useful materialBecause wollastonite has the unique physical and chemical properties, wollastonite has wide application in the fields of plastics, rubber, coatings, adhesives and the like.

However, the surface of the existing natural wollastonite powder has hydrophilicity, so that the wollastonite powder is not well dispersed when being directly added into high polymer aggregate, when the wollastonite is mixed with organic polymer, the compatibility between the wollastonite and the organic polymer is extremely poor, and the wollastonite powder is not uniformly dispersed in the organic polymer, so that the viscosity of a mixed system is increased, the mixture is difficult to flow, the process forming performance is deteriorated, and the mechanical property of the composite material is reduced.

Disclosure of Invention

The invention aims to provide surface modified wollastonite and a preparation method and application thereof, wherein the surface modified wollastonite improves the compatibility with a matrix, wollastonite particles are uniformly distributed in the matrix, and the interface bonding strength of a composite material is improved, so that the mechanical property of the composite material is improved.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides surface modified wollastonite, which comprises the following preparation raw materials in parts by weight:

preferably, the preparation method comprises the following preparation raw materials in parts by weight:

preferably, the preparation method comprises the following preparation raw materials in parts by weight:

preferably, the toughening agent is an ethylene-1-octene copolymer, polybutadiene or styrene-butadiene copolymer.

Preferably, the lubricant includes polyethylene wax, paraffin wax and liquid paraffin wax;

the mass ratio of the polyethylene wax to the solid paraffin to the liquid paraffin is (0.8-1.2): (2.8-3.3): (3.6-4.5).

Preferably, the demulsifier comprises calcium chloride and butyl glycol ether;

the mass ratio of the calcium chloride to the ethylene glycol monobutyl ether is (1.8-2.5): (4.5-5.3).

Preferably, the lead-zinc sulfide flotation tailings comprise the following components in percentage by mass: 45-56% of silicon oxide, 10-17% of aluminum oxide, 14-20% of magnesium oxide, 3-8% of ferric oxide, 0.5-1.3% of calcium oxide and 5-11% of carbonate.

The invention also provides a preparation method of the surface modified wollastonite in the technical scheme, which comprises the following steps:

mixing wollastonite, tungsten carbide, polyethylene glycol monostearate, lead-zinc sulfide flotation tailings, a lubricant and a toughening agent for the first time to obtain a first mixture;

carrying out second mixing on 3- (methacryloyloxy) propyl trimethoxy silane, sodium dodecyl sulfate and part of water to obtain a first solution;

thirdly mixing polyvinylpyrrolidone, olive oil, a mugwort extract and ethanol to obtain a second solution;

fourthly, mixing sulfamic acid and the residual water to obtain a third solution;

and fourthly mixing the first mixture, the first solution, the second solution, the third solution and a demulsifier, and drying to obtain the surface modified wollastonite.

The invention also provides application of the surface modified wollastonite in the technical scheme or the surface modified wollastonite prepared by the preparation method in the technical scheme in the fields of plastics, rubber, coatings and adhesives.

The invention provides surface modified wollastonite, which comprises the following preparation raw materials in parts by weight: 20-30 parts of wollastonite, 1-5 parts of tungsten carbide, 7-12 parts of polyethylene glycol monostearate, 6-9 parts of lead-zinc sulfide ore flotation tailings, 3-7 parts of a flexibilizer, 4-8 parts of a lubricant, 5-7 parts of a demulsifier, 1-3 parts of olive oil, 4-10 parts of a mugwort extract, 1-5 parts of sodium dodecyl sulfate, 0.6-3 parts of polyvinylpyrrolidone, 2-6 parts of 3- (methacryloyloxy) propyl trimethoxy silane, 10-19 parts of sulfamic acid, 46-62 parts of anhydrous ethanol and 60-85 parts of water. The added sulfamic acid and tungsten carbide can play a role in adsorbing formaldehyde in air, and the toughening agent increases the toughness of wollastonite, tungsten carbide, polyethylene glycol monostearate and lead-zinc sulfide ore flotation tailings, so that raw materials are prevented from being damaged; the polyethylene glycol monostearate can improve the hydrophobicity of the surface of the wollastonite, increase the compatibility of the wollastonite in the mixing with the organic polymer, ensure that the wollastonite is uniformly dispersed in the organic polymer, optimize the process forming performance and improve the mechanical property of the product; meanwhile, the olive oil and the artemisia argyi extract are added to play a role in bacteriostasis, and wollastonite has fresh smell, so that a user has better experience; by adding the lead-zinc sulfide ore flotation tailings, not only is waste utilization realized and the cost is saved, but also the modified wollastonite has synergistic effect with other raw materials, so that the strength of the modified wollastonite is improved; by adding sodium dodecyl sulfate, polyvinylpyrrolidone and 3- (methacryloyloxy) propyl trimethoxy silane and utilizing the emulsification effect, the bonding effect of wollastonite powder is further increased, and the compatibility of wollastonite and organic polymers is greatly improved when the wollastonite is mixed with the organic polymers. According to the description of the embodiment, the tensile strength of the product obtained by compounding the surface modified wollastonite and the ABS resin is more than or equal to 75MPa, and the impact strength is more than or equal to 5.3KJ/m²The product percent of pass is more than or equal to 98 percent.

Detailed Description

The invention provides surface modified wollastonite, which comprises the following preparation raw materials in parts by weight:

in the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.

The raw materials for preparing the surface modified wollastonite comprise 20-30 parts by weight of wollastonite, preferably 23-27 parts by weight of wollastonite and more preferably 26 parts by weight of wollastonite. In the invention, the particle size of the wollastonite is preferably 100 to 200 meshes, and more preferably 150 meshes. In a specific embodiment of the invention, the wollastonite is selected from silica-rich wollastonite ore rock in New Jiangxi; preferably, a long-cavity jaw crusher is adopted to crush the wollastonite ore rock rich in silicon newly in the west and the river before the wollastonite ore rock is used; the long chamber jaw crusher is of the type PEX-250 x 750.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 1-5 parts of tungsten carbide, preferably 2-4 parts, and more preferably 4 parts. In the present invention, the carbide preferably has a particle size of 200 to 325 mesh, more preferably 270 mesh.

In the invention, the tungsten carbide can adsorb formaldehyde in the air, and the compactness of the surface of wollastonite is improved, so that the mechanical property of a polymer matrix is improved.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 7-12 parts of polyethylene glycol monostearate, preferably 8-10 parts, and more preferably 8.5-9.5 parts.

In the invention, the polyethylene glycol stearate can improve the hydrophobicity of the surface of the wollastonite, so that the compatibility of the wollastonite and an organic polymer is increased, the wollastonite is uniformly dispersed in the organic polymer, the process forming performance is optimized, and the mechanical property of a product is improved.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 6-9 parts of lead-zinc sulfide flotation tailings, preferably 7-8 parts, and more preferably 7 parts. In the invention, the lead-zinc sulfide flotation tailings preferably comprise, by mass: 45-56% of silicon oxide, 10-17% of aluminum oxide, 14-20% of magnesium oxide, 3-8% of ferric oxide, 0.5-1.3% of calcium oxide and 5-11% of carbonate. In the invention, the granularity of the lead-zinc sulfide flotation tailings is preferably 200-300 meshes, and more preferably 250 meshes.

In the invention, the lead-zinc sulfide flotation tailings contain various metal elements, so that the waste utilization is realized, and the cost is saved; meanwhile, interfaces are formed between the raw materials and the surface of the wollastonite, and the interfaces are mutually restricted, mutually supplemented and mutually cooperated, so that the strength of the modified wollastonite can be improved.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 3 to 7 parts of a toughening agent, preferably 4 to 6 parts, and more preferably 5 parts. In the present invention, the toughening agent is preferably an ethylene-1-octene copolymer, polybutadiene, or styrene-butadiene copolymer.

In the invention, the toughening agent can improve the toughness of wollastonite, polyethylene glycol monostearate and lead-zinc sulfide flotation tailings, and prevent the raw materials from being damaged.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 4-8 parts of a lubricant, preferably 5-7 parts, and more preferably 6 parts. In the present invention, the lubricant preferably includes polyethylene wax, solidified paraffin and liquid paraffin; the mass ratio of the polyethylene wax to the solidified paraffin to the liquid paraffin is preferably (0.8-1.2): (2.8-3.3): (3.6-4.5), and more preferably 1:3: 4.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 5-7 parts of a demulsifier, preferably 5.5-6.5 parts, and more preferably 6 parts. In the present invention, the demulsifier preferably comprises calcium chloride and butyl glycol ether; the mass ratio of the calcium chloride to the ethylene glycol monobutyl ether is preferably (1.8-2.5): (4.5 to 5.3), more preferably 2: 5.

In the invention, the demulsifier has the function of destroying the structure of the emulsion, promoting the two-phase delamination and being beneficial to the purification of the modified wollastonite product in the later period.

The preparation raw materials of the surface modified wollastonite also comprise 1-3 parts by weight of olive oil, preferably 1.5-2.5 parts by weight, and more preferably 2 parts by weight based on the weight parts of the wollastonite.

The raw materials for preparing the surface modified wollastonite also comprise 4-10 parts of a mugwort extract, preferably 5-9 parts, and more preferably 6-8 parts by weight of the wollastonite. In the present invention, the mugwort extract is preferably a commercially available product.

In the invention, the olive oil and the artemisia argyi extract can play a role in bacteriostasis, so that the bacteriostasis effect of the modified wollastonite is improved, and the wollastonite has fresh smell.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 1-5 parts of sodium dodecyl sulfate, preferably 2-4 parts, and more preferably 3 parts.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 0.6 to 3 parts of polyvinylpyrrolidone, preferably 1 to 2.5 parts, and more preferably 1.5 to 2 parts.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 2-6 parts of 3- (methacryloyloxy) propyl trimethoxy silane, preferably 3-5 parts, and more preferably 4 parts.

In the invention, the sodium dodecyl sulfate, the polyvinylpyrrolidone and the 3- (methacryloyloxy) propyl trimethoxy silane play a role in emulsification, so that the bonding effect of wollastonite is further increased, and the compatibility of the wollastonite and an organic polymer is improved.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 10-19 parts of sulfamic acid, preferably 11-18 parts, and more preferably 12-16 parts.

In the invention, the sulfamic acid can adsorb formaldehyde in the air together with tungsten carbide, and simultaneously, the solubility of wollastonite is increased, and the binding capacity with organic polymers is improved.

Based on the weight parts of the wollastonite, the raw materials for preparing the surface modified wollastonite also comprise 46-62 parts of absolute ethyl alcohol, preferably 50-60 parts, and more preferably 54-56 parts.

The preparation raw materials of the surface modified wollastonite also comprise 60-85 parts of water, preferably 62-80 parts of water, and more preferably 65-75 parts of water based on the weight parts of the wollastonite. In the present invention, the water is preferably distilled water.

The invention also provides a preparation method of the surface modified wollastonite in the technical scheme, which comprises the following steps:

mixing wollastonite, tungsten carbide, polyethylene glycol monostearate, lead-zinc sulfide flotation tailings, a lubricant and a toughening agent for the first time to obtain a first mixture;

carrying out second mixing on 3- (methacryloyloxy) propyl trimethoxy silane, sodium dodecyl sulfate and part of water to obtain a first solution;

thirdly mixing polyvinylpyrrolidone, olive oil, a mugwort extract and ethanol to obtain a second solution;

fourthly, mixing sulfamic acid and the residual water to obtain a third solution;

and carrying out fifth mixing on the first mixture, the first solution, the second solution, the third solution and a demulsifier, and drying to obtain the surface modified wollastonite.

Wollastonite, tungsten carbide, polyethylene glycol monostearate, lead-zinc sulfide flotation tailings, a lubricant and a toughening agent are subjected to first mixing to obtain a first mixture. In the present invention, the first mixing preferably includes: mixing and grinding wollastonite, tungsten carbide, polyethylene glycol monostearate and lead zinc sulfide flotation tailings, adding a lubricant and a toughening agent, and continuously grinding. In the present invention, the time of the milling and mixing is preferably 1 h; the present invention does not have any particular limitation on the rate of the mixed grinding, and may be carried out at a rate well known to those skilled in the art. In the invention, the particle size of the material obtained after mixing and grinding is preferably 1000-3000 meshes, and more preferably 2000 meshes. In the present invention, the time for continuing the grinding is preferably 1 h; the rate of the continuous grinding is not particularly limited in the present invention, and may be a rate well known to those skilled in the art.

In the invention, the step-by-step grinding is adopted to increase the contact area between the lubricant and the toughening agent and wollastonite, tungsten carbide, polyethylene glycol monostearate and lead zinc sulfide flotation tailings, so that the toughening effect can be further improved.

The preparation method of the surface modified wollastonite also comprises the step of mixing 3- (methacryloyloxy) propyl trimethoxy silane, sodium dodecyl sulfate and part of water for the second time to obtain a first solution. The order of the second mixing is not particularly limited in the present invention, and the mixing may be performed in an order known to those skilled in the art. The amount of the water to be used in the present invention is not particularly limited, and the 3- (methacryloyloxy) propyltrimethoxysilane and the sodium dodecylsulfate can be dissolved in the amounts known to those skilled in the art. In the present invention, the second mixing is preferably performed under stirring; the stirring is not particularly limited in the present invention, and may be carried out by a procedure well known to those skilled in the art.

The preparation method of the surface modified wollastonite further comprises the step of carrying out third mixing on polyvinylpyrrolidone, olive oil, a mugwort extract and ethanol to obtain a second solution. In the present invention, the third mixing preferably includes: mixing polyvinylpyrrolidone and ethanol, and sequentially adding oleum Olivarum and folium Artemisiae Argyi extract. In the present invention, the third mixing is preferably performed under stirring conditions, and the stirring rate is not particularly limited in the present invention, and may be performed at a rate well known to those skilled in the art. In the present invention, the stirring time is preferably 5 min.

The preparation method of the surface modified wollastonite further comprises the step of mixing sulfamic acid and the rest water for the fourth time to obtain a third solution. In the invention, the mass ratio of the residual water to the partial water is preferably (1.54-2.2): 2. in the present invention, the fourth mixing is preferably performed under stirring; the stirring is not particularly limited in the present invention, and may be carried out by a procedure well known to those skilled in the art.

The preparation method of the surface modified wollastonite further comprises the steps of carrying out fifth mixing on the first mixture, the first solution, the second solution, the third solution and a demulsifier, and drying to obtain the modified wollastonite. In the present invention, the fifth mixing is preferably performed by mixing the first mixture and the first solution under stirring for 1 hour, then sequentially adding the second solution, the third solution and the demulsifier, and continuing to stir for 2 hours. The stirring is not particularly limited in the present invention, and may be carried out by a procedure well known to those skilled in the art. In the present invention, the drying method is preferably freeze-drying, and the freeze-drying method is not particularly limited, and may be performed under conditions well known to those skilled in the art.

The invention also provides application of the surface modified wollastonite in the technical scheme or the surface modified wollastonite prepared by the preparation method in the technical scheme in the fields of plastics, rubber, coatings and adhesives. The invention is not limited in any way to the manner of application described, and can be applied in a manner known to those skilled in the art.

The surface modified wollastonite and its preparation and use are described in detail in the following examples, which should not be construed as limiting the scope of the present invention.

Note: the wollastonite used in examples 1 to 4 was a wollastonite ore containing silicon and having a particle size of 200 mesh in the west and the river after being crushed by a long-chamber jaw crusher of PEX-250 × 750.