Modified glass microsphere and preparation method thereof and method for preparing composite resin product by using modified glass microsphere

[0034] Example 1

[0035] The preparation of yellowing resistant products includes the following steps:

[0036] (1) Preparation of modified glass beads

[0037] 1) Preparation of a class of glass beads

[0038] The mixed glass beads obtained by mixing solid glass beads with a particle size of 10.0 μm and hollow glass beads are subjected to surface pretreatment. Among the mixed glass beads, solid glass beads accounted for 50.0%, and hollow glass beads accounted for 50.0%. The surface pretreatment specifically includes alkaline washing (NaOH), water washing, and ammonia fluoride (NH 4 F) and hydrofluoric acid (HF) in the mixture of coarsening, washing, tin chloride (SnCl 2 ) And hydrochloric acid (HCl) mixed solution sensitized, washed with water, silver nitrate-containing ammonia solution (AgNO 3 +NH 3 ·H 2 O) The activation step is processed.

[0039] The surface pretreatment of the glass beads enhances the chemical activity of the surface, and then the pretreated glass beads are coated with a metal aluminum film by chemical coating, and the surface is covered with a uniform and dense metal aluminum layer. Glass beads.

[0040] Put the prepared metal-plated glass beads in a stirring tank for stirring, the speed of the stirring tank is 50 rpm, and spray nitric acid (HNO 3 ) Solution, to partially pickle the metal layer coated on the surface of the glass beads for a certain period of time to control the final metal coverage of the glass beads to 80%.

[0041] After pickling, the glass beads coated with the metal layer are ultrasonically cleaned for more than 10 minutes to remove the residual nitric acid and metal film on the surface; after drying the obtained glass beads, pour a certain concentration of UV absorber solution into Into the stirring tank, stir for 10 minutes and then dry at 100°C for 3 hours to prepare a class of glass beads.

[0042] 2) Preparation of Class II glass beads

[0043] The surface of the mixed glass beads obtained by mixing solid glass beads with a particle size of 10.0μm and hollow glass beads is dewaxed, alkalized and ultrasonically cleaned, and then a layer of perfluoropolyether material is evaporated by the PVD process , The second type of glass beads was prepared.

[0044] 3) Preparation of modified glass beads

[0045] Weigh 85% of the first type of glass beads and 15% of the second type of glass beads according to the mass percentage, and mix them evenly to obtain modified glass beads;

[0046] (2) Surface activation treatment of modified glass beads

[0047] Put the modified glass beads prepared above into a high-speed kneader, and add them to the mixed coupling agent solution of silane coupling agent and aluminate coupling agent with a mass ratio of 1:1, and perform ultrasonic for 40 minutes After being dispersed, it was dried at 120°C for 2 hours to obtain surface-activated modified glass beads.

[0048] Among them, the coupling agent is a commonly used coupling agent, specifically, it can be a silane coupling agent, a titanate coupling agent, a zirconate coupling agent, an aluminate coupling agent, a bimetal coupling agent (aluminum- Zirconate, aluminum-titanium composite coupling agent), rare earth coupling agent, phosphorus-containing coupling agent, boron-containing coupling agent, one or more kinds of mixture.

[0049] (3) Preparation of yellowing resistant masterbatch

[0050] Weigh 55.0% of polypropylene masterbatch, 15.0% of ultraviolet absorber, 25.0% of antioxidant, and 5.0% of light stabilizer according to mass percentage. After drying at 50℃-60℃ for 6 hours, mix them uniformly, and adopt extrusion granulation process. Must be yellowing resistant masterbatch. UV531/UV770=1:1 in ultraviolet absorbers, antioxidants can be the main anti-sterically hindered phenols, specifically antioxidant 1010, auxiliary anti-phosphites, thiolipids, antioxidant 168 One or more of the light stabilizers are hindered amine stabilizers, and light stabilizer 770 can be used.

[0051] The first class glass beads, the second class glass beads, and yellowing resistant masterbatch are prepared in advance and used for injection molding to prepare yellowing resistant products.

[0052] (4) Preparation of anti-yellowing products

[0053] Weigh the activated modified glass beads, polypropylene resin, polymethyl methacrylate resin, maleic anhydride grafted polypropylene, and anti-yellowing masterbatch according to the weight parts of the components in Example 1 of Table 1, and mix them evenly After 15 minutes or more, use the injection molding process to form a yellowing resistant product of the desired shape. The yellowing resistance and mechanical properties of the products were tested, and the test results are listed in Table 1.

[0054] Example 2 to Example 6

[0055] According to the components specified in Table 1, the weight ratio of the modified glass beads was appropriately adjusted, and the preparation method in Example 1 was repeated. Table 1 lists the corresponding test results.

[0064] Example 7-13

[0065] Under the condition that the content of each component of Example 4 in Table 1 remains unchanged, only the weight ratio of the first type of glass beads to the second type of glass beads is changed, and the preparation method in Example 4 is repeated for the other steps. Table 2 lists The corresponding test result.

[0066] Table 2 The influence of the content of the first class glass beads and the second class glass beads on the yellowing resistance and easy-to-clean performance

[0067]

[0068] It can be seen that in a certain range, the more the content of Class I glass beads, the better the yellowing resistance, and the more the content of Class II glass beads, the better the easy-to-clean performance. However, considering the acceptable yellowing resistance and easy-to-clean performance range of the product, the content of the first type glass beads is 70%-85%, the content of the second type glass beads is 15%-30%, and the first type glass beads When the beads are 85%, the yellowing resistance is better, and the easy-to-clean performance of the product is also within the acceptable range.

[0069] Because a type of glass beads has a discontinuous metal layer on the surface, when ultraviolet rays are incident on the surface of a type of glass beads, part of it is directly reflected by the metal layer, and the other part is injected into the glass through the gap between the metal layers. Inside the microbeads, multiple reflections are formed inside a type of glass microbeads (the metal-coated part of the surface of a type of glass microbeads also reflects the ultraviolet light entering the interior), which is indirectly consumed and reduces ultraviolet rays The aging effect on resin products improves the yellowing resistance of the products. The surface of the second type of glass microbeads is coated with a hydrophobic material. Because of its hydrophobic effect, the sewage is not easy to adhere, so that the product can achieve the effect of stain resistance and easy cleaning. For the proportion of modified glass beads, within the allowable range, the larger the weight of the first type of glass beads, the better the yellowing resistance of the product, and vice versa, the better the product is easy to clean.