CN112812369B - Polymer-coated composite hollow microsphere and preparation method and application thereof - Google Patents
Polymer-coated composite hollow microsphere and preparation method and application thereof Download PDFInfo
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- CN112812369B CN112812369B CN202011636887.5A CN202011636887A CN112812369B CN 112812369 B CN112812369 B CN 112812369B CN 202011636887 A CN202011636887 A CN 202011636887A CN 112812369 B CN112812369 B CN 112812369B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
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Abstract
The invention provides a polymer-coated composite hollow microsphere and a preparation method and application thereof. The polymer-coated composite hollow microsphere comprises the following components in parts by weight: inorganic hollow microspheres, a polymer coating layer and an auxiliary agent; the inorganic hollow microspheres are hollow glass microspheres; the polymer coating layer is obtained by drying a polymer dispersion liquid volatile solvent; the polymer dispersion liquid is selected from one or a mixture of more of polyurethane dispersion liquid, polyacrylate emulsion, silicone-acrylic emulsion and modified ethylene-vinyl acetate emulsion. According to the invention, the brittle inorganic hollow microspheres are wrapped by polyurethane dispersion liquid, polyacrylate emulsion, silicone-acrylic emulsion and modified ethylene-vinyl acetate emulsion, so that the crushing resistance of the obtained inorganic hollow microspheres is effectively improved, and the breakage of the inorganic hollow microspheres can be effectively inhibited in the plastic screw extrusion blending modification process.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polymer-coated composite hollow microsphere and a preparation method and application thereof.
Background
The hollow microsphere has low density, large effective area, heat insulation, sound absorption and light covering performance, can be used as a density lightening agent, a resin additive and the like, and is widely applied to industries and fields of papermaking, oil exploitation, building coatings, biomedicine and the like. However, the inorganic materials used for the inorganic hollow microspheres are brittle and have poor deformability, so that the inorganic hollow microspheres are very easy to break during dynamic use, such as adding to a resin as a filler or using as a drilling fluid, and the application is limited. In order to reduce the breakage of the inorganic hollow microspheres, the prior art adopts polymerization to coat the inorganic hollow microspheres. Chinese patent (CN 103665747A) adopts water-soluble phenolic resin to form uniform slurry in water, the slurry is mixed with hollow glass microspheres, and the phenolic resin/glass composite hollow microspheres are dried, but because the brittleness of the phenolic resin is high, the composite hollow microspheres prepared by the method have weak resin melt shearing resistance, and are easy to break in the process of screw blending extrusion when being added into thermoplastic plastics for modification processing.
Disclosure of Invention
The invention provides a polymer-coated composite hollow microsphere for overcoming the problem that the resin melt shearing resistance of the composite hollow microsphere in the prior art is weak.
The invention also aims to provide a preparation method of the polymer-coated composite hollow microspheres.
The invention also aims to provide application of the polymer-coated composite hollow microspheres.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polymer-coated composite hollow microsphere comprises the following components in parts by weight:
30-80 parts of inorganic hollow microspheres;
10-60 parts of a polymer wrapping layer;
0-10 parts of an auxiliary agent;
the inorganic hollow microspheres are hollow glass microspheres; the polymer coating layer is obtained by drying a polymer dispersion liquid volatile solvent; the polymer dispersion liquid is selected from one or a mixture of a plurality of polyurethane dispersion liquid, polyacrylate emulsion, silicone-acrylic emulsion and modified ethylene-vinyl acetate emulsion (VAE emulsion).
According to the invention, the brittle inorganic hollow microspheres are wrapped by polyurethane dispersion liquid, polyacrylate emulsion, silicone-acrylic emulsion and modified ethylene-vinyl acetate emulsion, so that the crushing resistance of the obtained inorganic hollow microspheres is effectively improved, and the breakage of the inorganic hollow microspheres can be effectively inhibited in the plastic screw extrusion blending modification process.
Preferably, the polymer-coated composite hollow microsphere comprises the following components in parts by weight:
40-60 parts of inorganic hollow microspheres;
38-55 parts of a polymer wrapping layer;
0-5 parts of an auxiliary agent.
Preferably, the polymer-coated composite hollow microsphere comprises the following components in parts by weight:
40-60 parts of inorganic hollow microspheres;
38-55 parts of a polymer wrapping layer;
2-5 parts of an auxiliary agent;
the polymer dispersion liquid is polyacrylate emulsion; the auxiliary agent is polyisocyanate and nano silicon dioxide solid hydrosol.
The mass ratio of the polyisocyanate to the nano-silica solid hydrosol is 1:3.
the average particle size of the inorganic hollow microspheres is 5-80 μm, preferably 40 μm.
The auxiliary agent is one or more of a curing agent, a filler, a defoaming agent, a dispersing agent and an anti-settling agent.
The preparation method of the polymer-coated composite hollow microsphere comprises the following steps:
s1, sequentially adding pure water, inorganic hollow microspheres and an auxiliary agent into the polymer dispersion liquid to disperse and uniformly mix all the components to obtain the composite dispersion liquid.
S2, carrying out spray drying on the composite dispersion liquid obtained in the step S1, wherein the temperature of an air inlet of the spray drying is 120-300 ℃, and the temperature of an air outlet of the spray drying is 30-120 ℃; thus obtaining the polymer-wrapped composite hollow microsphere.
Preferably, the temperature of the air inlet of the spray drying is 140-200 ℃, and the temperature of the air outlet is 40-60 ℃.
The solid content of the polymer dispersion liquid in the preparation method is 10-60 wt%.
The polymer-coated composite hollow microsphere prepared by the invention has high resin melt shearing resistance, and is not easy to break in the screw blending extrusion process, so the invention also protects the application of the polymer-coated composite hollow microsphere in preparing a resin additive. Meanwhile, the application of the polymer-coated composite hollow microspheres in the preparation of drilling fluid is also protected.
The invention also protects a plastic product which comprises the polymer-coated composite hollow microsphere.
Further, the plastic product comprises the following components in parts by weight: 69 to-89 parts of thermoplastic plastic, 10 to 30 parts of polymer-coated composite hollow microspheres, 0.5 to 0.9 part of antioxidant and 0.1 to 0.5 part of processing aid.
The thermoplastic plastic is one or more of ABS resin, PP resin or PS resin.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the brittle inorganic hollow microspheres are wrapped by the specific polymer dispersion liquid, so that the crushing resistance of the obtained inorganic hollow microspheres is effectively improved, and the damage of the inorganic hollow microspheres can be effectively inhibited in the plastic screw extrusion blending modification process.
Detailed Description
The present invention will be further described with reference to the following embodiments. The starting materials in the examples and comparative examples are either commercially available or can be prepared by known methods. In the present specification, "part" and "%" represent "part by weight" and "% by mass", respectively, unless otherwise specified.
The manufacturers and designations of the raw materials used in the following examples and comparative examples are as follows:
1. hollow glass microspheres: the density was 0.38g/cm 3 Average particle size of 40 μm, compressive strength of 5500psi, VS5500, 3M;
2. polymer dispersion liquid:
polyurethane dispersion liquid: PU-608, 35% of solid content, guangzhou Zhi;
polyacrylate emulsion: w-3230, solids content 45%, badfish corporation;
silicone-acrylic emulsion: RS-996AD, 48% solids content, badifu corporation;
modified ethylene Vinyl Acetate (VAE) emulsion: CW40-705, solid content of 55 percent, sichuan vitamin;
phenolic resin: the water-soluble phenolic resin PF005 contains 55% of solid content and is prepared from Shandong North China sea;
3. auxiliary agent:
curing agent aziridine, RX-90, solid content is more than 99 percent, dongguan cooperative chemical engineering;
curing agent polyisocyanate, XP 2655, NCO content 21%, bayer;
nano silicon dioxide solid hydrosol, JN-25, solid content 25%, qingdao Yindao.
4. Antioxidant:
amine antioxidants 445, naugard 445, dimifant;
hindered phenol antioxidants 1010, IRGANOX 1010, basff;
phosphate antioxidants 168, IRGANOX 168, BASF;
5. processing aid:
oleic acid amide: ARMOSLIP CP, PMC Biogenix;
an organosilicone lubricant: MB50-002, dow;
zinc stearate lubricant: ZINC STEARATE (BS-2818), ZHONGSHANHONGTAI.
Examples and comparative examples
The contents (in parts by weight) of the respective components in the polymer-coated composite hollow microspheres of examples and comparative examples are shown in table 1.
The preparation method comprises the following steps:
s1, at normal temperature, adding pure water, hollow glass microspheres and an auxiliary agent (if any) into a polymer dispersion liquid with a solid content of 10-60 wt% while stirring, continuously stirring for 1min, and uniformly dispersing the hollow microspheres in the liquid by continuous stirring to obtain the composite dispersion liquid.
S2, conveying the composite dispersion liquid into a spray dryer through a peristaltic pump under the condition of keeping stirring (the flow rate is 100 ml/min), coating small droplets of the polymer dispersion liquid on the inorganic hollow microspheres formed through atomization, volatilizing and drying a solvent in the small droplets, forming a continuous and compact polymer coating layer on the surfaces of the inorganic hollow microspheres to obtain the polymer-coated composite hollow microspheres, and collecting the polymer-coated composite hollow microspheres through a cyclone collector.
TABLE 1
Performance testing
The polymer-coated composite hollow microspheres prepared in the above examples and comparative examples and the inorganic hollow microspheres (used as a control) without coating treatment were mixed with the thermoplastic resin, the antioxidant and the processing aid in a mixer according to the formulation shown in table 2, and then placed in a screw extruder to be kneaded and extruded, and extruded by a die of 1mm × 50mm and cooled to obtain continuous sheets, which were sampled to obtain sample samples, and the densities of the sample samples were measured, and the measurement results are shown in table 2.
The test methods or standards are specified below:
density: the density of the thermoplastic resin (matrix before addition of the inorganic hollow microspheres) and of the resulting sample cases was measured by an electronic densitometer (XS 104, mettler Toledo), which measures according to the archimedes principle.
TABLE 2
As can be seen from the test results in Table 2, in the control, the density of the product obtained by modifying the thermoplastic with the non-coated hollow glass microspheres filled therein is rather increased because the hollow glass microspheres are brittle and a considerable portion of the glass microspheres are broken into glass fragments (density 2.6 g/cm) during the screw blending extrusion process 3 )。
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. The polymer-coated composite hollow microsphere is characterized by comprising the following components in parts by weight:
40 to 60 parts of inorganic hollow microspheres;
38-55 parts of a polymer wrapping layer;
2-5 parts of an auxiliary agent;
the inorganic hollow microspheres are hollow glass microspheres;
the polymer coating layer is obtained by spray drying polymer dispersion liquid; the polymer dispersion liquid is selected from one or a mixture of a plurality of polyurethane dispersion liquid, polyacrylate emulsion, silicone-acrylic emulsion and modified ethylene-vinyl acetate emulsion;
the auxiliary agent consists of polyisocyanate and nano silicon dioxide solid hydrosol according to a mass ratio of 1;
the polymer-coated composite hollow microsphere is prepared by the following preparation method:
s1, sequentially adding pure water, inorganic hollow microspheres and an auxiliary agent into the polymer dispersion liquid to disperse and uniformly mix all the components to obtain a composite dispersion liquid;
s2, carrying out spray drying on the composite dispersion liquid obtained in the step S1, wherein the temperature of an air inlet of the spray drying is 120-300 ℃, and the temperature of an air outlet of the spray drying is 30-120 ℃; thus obtaining the polymer-wrapped composite hollow microsphere.
2. The polymer-encapsulated composite hollow microspheres of claim 1, wherein the polymer dispersion is a polyacrylate emulsion.
3. The method for preparing the polymer-coated composite hollow microspheres of claim 1 or 2, characterized by comprising the following steps:
s1, sequentially adding pure water, inorganic hollow microspheres and an auxiliary agent into the polymer dispersion liquid to disperse and uniformly mix all the components to obtain a composite dispersion liquid;
s2, carrying out spray drying on the composite dispersion liquid obtained in the step S1, wherein the temperature of an air inlet of the spray drying is 120 to 300 ℃, and the temperature of an air outlet of the spray drying is 30 to 120 ℃; to obtain the polymer-wrapped composite hollow microsphere.
4. The method according to claim 3, wherein the polymer dispersion has a solid content of 10 to 60wt%.
5. Use of the polymer-encapsulated composite hollow microspheres of claim 1 or 2 for the preparation of a resin additive.
6. Use of the polymer-coated composite hollow microspheres of claim 1 or 2 for the preparation of a drilling fluid.
7. A plastic product is characterized by comprising the following components in parts by weight: 69 to-89 parts of thermoplastic plastic, 10 to 30 parts of polymer-wrapped composite hollow microspheres according to claim 1 or 2, 0.5 to 0.9 part of antioxidant and 0.1 to 0.5 part of processing aid.
8. The plastic product of claim 7, wherein the thermoplastic plastic is one or more of ABS resin, PP resin or PS resin.
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| CN202011636887.5A CN112812369B (en) | 2020-12-31 | 2020-12-31 | Polymer-coated composite hollow microsphere and preparation method and application thereof |
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| CN202011636887.5A CN112812369B (en) | 2020-12-31 | 2020-12-31 | Polymer-coated composite hollow microsphere and preparation method and application thereof |
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| CN112812369B true CN112812369B (en) | 2023-03-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06254380A (en) * | 1993-03-03 | 1994-09-13 | Toagosei Chem Ind Co Ltd | Composite microballoon |
| CN103665747B (en) * | 2012-08-30 | 2015-10-21 | 中国石油化工股份有限公司 | A kind of compound hollow microballoon and its preparation method and application |
| CN104629088A (en) * | 2013-11-06 | 2015-05-20 | 金发科技股份有限公司 | Pearl essence coated polymer microspheres and preparation method and application thereof |
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