阅读说明：本技术 一种聚合物包裹复合空心微球及其制备方法与应用 (Polymer-coated composite hollow microsphere and preparation method and application thereof ) 是由 苏榆钧 叶南飚 黄险波 马鹏涛 李成 唐磊 陈平绪 王林 于 2020-12-31 设计创作，主要内容包括：本发明提供了一种聚合物包裹复合空心微球及其制备方法与应用。所述聚合物包裹复合空心微球包括以下按重量份数计算的组分：无机空心微球、聚合物包裹层、助剂；所述无机空心微球为空心玻璃微球；所述聚合物包裹层是由聚合物分散液挥发溶剂干燥所得；所述聚合物分散液选自聚氨酯分散液、聚丙烯酸酯乳液、硅丙乳液、改性乙烯-醋酸乙烯酯乳液的一种或几种混合物。本发明采用聚氨酯分散液、聚丙烯酸酯乳液、硅丙乳液、改性乙烯-醋酸乙烯酯乳液的包裹脆性的无机空心微球,有效提高所得无机空心微球的抗破碎能力,能在塑料螺杆挤出共混改性过程中有效抑制无机空心微球的破损。(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 a plurality 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.)

1. The polymer-coated composite hollow microsphere is characterized by comprising 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 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.

2. The polymer-coated composite hollow microsphere according to claim 1, comprising 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.

3. The polymer-coated composite hollow microsphere according to claim 1, comprising 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.

4. The polymer-coated composite hollow microsphere of claim 1, wherein the auxiliary agent is one or more of a curing agent, a filler, a defoaming agent, a dispersing agent and an anti-settling agent.

5. The preparation method of the polymer-coated composite hollow microsphere of claims 1 to 4, which is characterized by comprising the following steps:

s1, adding pure water, inorganic hollow microspheres and an auxiliary agent into the polymer dispersion liquid in sequence to disperse and uniformly mix all the components to obtain the composite dispersion liquid.

S2, performing 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 ℃; to obtain the polymer-wrapped composite hollow microsphere.

6. The method according to claim 5, wherein the polymer dispersion has a solid content of 10 to 60 wt%.

7. Use of the polymer-coated composite hollow microspheres of claims 1-4 in the preparation of resin additives.

8. The use of the polymer-coated composite hollow microspheres of claims 1-4 in the preparation of drilling fluids.

9. A plastic product is characterized by comprising the following components in parts by weight: 69 to-89 parts of thermoplastic plastics, 10 to 30 parts of polymer-coated composite hollow microspheres according to claims 1 to 4, 0.5 to 0.9 part of antioxidant and 0.1 to 0.5 part of processing aid.

10. The plastic product of claim 9, wherein the thermoplastic is one or more of ABS resin, PP resin, or PS resin.

Technical Field

The invention relates to the technical field of high molecular 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 (CN103665747A) 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 phenolic resin has higher brittleness, the composite hollow microspheres prepared by the method have weaker resin melt shearing resistance, and are easy to break in the screw blending extrusion process 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 invention adopts the technical scheme that:

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-water sol is 1: 3.

the average particle size of the inorganic hollow microspheres is 5-80 μm, and 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, adding pure water, inorganic hollow microspheres and an auxiliary agent into the polymer dispersion liquid in sequence to disperse and uniformly mix all the components to obtain the composite dispersion liquid.

S2, performing 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 ℃; to obtain 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 of the spray drying 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: 69-89 parts of thermoplastic plastics, 10-30 parts of polymer-coated composite hollow microspheres, 0.5-0.9 part of antioxidant and 0.1-0.5 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/cm³Average particle size of 40 μ M, compressive strength of 5500psi, VS5500, 3M company;

2. polymer dispersion liquid:

polyurethane dispersion liquid: PU-608, 35% of solid content, Guangzhou Zhi;

polyacrylate emulsion: w-3230, solid content 45%, Badifu Co;

silicone-acrylic emulsion: RS-996AD, 48% solids content, Badifu corporation;

modified ethylene Vinyl Acetate (VAE) emulsion: CW40-705, solid content 55%, Chuanwei;

phenolic resin: the water-soluble phenolic resin PF005, the solid content is 55%, North China sea of Shandong;

3. auxiliary agent:

curing agent aziridine, RX-90, solid content is more than 99%, Dongguan cooperative chemical industry;

curing agent polyisocyanate, XP 2655, NCO content 21%, Bayer;

nano silicon dioxide solid hydrosol, JN-25, solid content 25%, Qingdao Yindao.

4. Antioxidant:

amine antioxidant 445, NAUGARD 445, dimifant;

hindered phenol antioxidant 1010, IRGANOX 1010, basf;

phosphate antioxidants 168, IRGANOX 168, basf;

5. processing aid:

oleic acid amide: ARMOSLIP CP, PMC Biogenix;

organosilicone lubricants: MB50-002, Dow;

zinc stearate lubricant: ZINC STEARATE (BS-2818), Zhongshan Huaming Tai.

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, sequentially 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 through 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 100ml/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 through a 1mm by 50mm die head and cooled to obtain continuous sheets, which were subjected to sample preparation to obtain sample examples, and the densities thereof 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 (XS104, 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 process³)。

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. And are neither required nor 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.