A Hybrid Coating Agent for the Surface of Hollow Glass Microspheres, Its Preparation Method and Application

Abstract

The present invention provides a surface hybrid coating agent for hollow glass microspheres, which comprises the following raw material components in parts by mass: 20 to 40 parts of aqueous amino acrylate emulsion, 10 to 15 parts of tetraethyl orthosilicate (TEOS), 1 to 1.5 parts of aluminum sec-butoxide (ASB), a silane coupling agent (KH550), and 0.15 to 0.3 parts of p-toluenesulfonic acid (PTSA). The surface modifier for hollow glass microspheres provided by the present invention is green and environmentally friendly, simple to prepare, and can effectively improve the wettability and interfacial bonding performance between the microspheres and the resin. The present invention also provides a preparation method and application of the surface hybrid coating agent for hollow glass microspheres.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and particularly relates to a hybrid coating agent for the surface of hollow glass microspheres, a preparation method thereof, and an application thereof. Background Art

[0002] Due to their excellent properties, polymer materials have been widely used in the automotive field. However, with the development of automotive lightweighting, the requirements for materials are getting higher and higher. How to further prepare polymer materials with lower density and suitable for the automotive field has become a research hotspot in the polymer modification industry.

[0003] At present, there are roughly two ways to achieve lightweighting of polymer resin materials: one is to reduce the specific gravity by foaming. However, problems such as difficult control of the foaming process, high cost, and strength loss of the material after foaming are not conducive to the realization of lightweighting; the other is to achieve lightweighting by adding lightweight fillers such as hollow glass microspheres. However, the surface of hollow glass microspheres is smooth and has few chemical groups, and the interfacial bonding performance with the resin matrix is weak, making it difficult for the prepared hollow glass microsphere / resin composite material to meet the mechanical property requirements. Therefore, surface modification of hollow microspheres to improve their wettability with resins and improve the interfacial properties of their composite materials, and preparing hollow glass microsphere / resin composite materials with light weight and high strength are of great significance for promoting the development of automotive lightweighting. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a hybrid coating agent for the surface of hollow glass microspheres, a preparation method thereof, and an application thereof. The coating agent provided by the present invention can improve the interfacial bonding performance of microsphere and resin composite materials.

[0005] The present invention provides a hybrid coating agent for the surface of hollow glass microspheres, which includes, by weight:

[0006] 20 - 40 parts of waterborne amino acrylic acid;

[0007] 15 - 30 parts of tetraethyl orthosilicate;

[0008] 15 - 30 parts of aluminum sec-butoxide;

[0009] 3 - 6 parts of silane coupling agent;

[0010] 0.15 - 0.3 part of p-toluenesulfonic acid.

[0011] The present invention provides a preparation method of the hybrid coating agent for the surface of hollow glass microspheres according to the above technical solution, which includes:

[0012] Carrying out a first mixing of tetraethyl orthosilicate and ethanol to obtain solution A;

[0013] The silane coupling agent, p-toluenesulfonic acid and ethanol are mixed for the second time to obtain solution B;

[0014] The solution B is added dropwise to solution A for the first time to obtain silica sol;

[0015] Aluminum sec-butoxide and ethanol are mixed for the third time to obtain solution C;

[0016] p-Toluenesulfonic acid and ethanol are mixed for the fourth time to obtain solution D;

[0017] The solution D is added dropwise to solution C for the second time to obtain aluminum sol;

[0018] The silica sol is added dropwise to the aluminum sol for the third time to obtain silica-alumina hybrid sol;

[0019] Waterborne amino acrylic acid and water are mixed for the fifth time to obtain a waterborne amino acrylic acid emulsion;

[0020] The silica-alumina hybrid sol is added dropwise to the waterborne amino acrylic acid emulsion and stirred to obtain a hybrid coating agent on the surface of hollow glass microspheres.

[0021] Preferably, the dosage ratio of tetraethyl orthosilicate to ethanol is (15 - 30) g : (1000 - 2000) mL;

[0022] The dosage ratio of the silane coupling agent, p-toluenesulfonic acid and ethanol is (3 - 6) g : (0.15 - 0.3) g : (100 - 200) mL;

[0023] The volume ratio of solution A to solution B is (100 - 200) : (100 - 200);

[0024] The dosage ratio of aluminum sec-butoxide to ethanol is (15 - 30) g : (1000 - 2000) mL;

[0025] The dosage ratio of p-toluenesulfonic acid to ethanol is (0.15 - 0.3) g : 100 mL;

[0026] The volume ratio of solution C to solution D is (100 - 200) : (100 - 200);

[0027] The volume ratio of the silica sol to the aluminum sol is (100 - 50) : (50 - 100);

[0028] The dosage ratio of the waterborne amino acrylic acid to water is (20 - 40) g : (1000 - 2000) mL;

[0029] The mass ratio of the silica-alumina hybrid sol to the waterborne amino acrylic acid emulsion is (5 - 10) : (100 - 200).

[0030] Preferably, the first mixing is carried out by sealed stirring; the time of the sealed stirring is 30 to 40 min;

[0031] The second mixing is carried out by sealed stirring; the time of the sealed stirring is 0.3 to 0.7 hours;

[0032] The third mixing is carried out by sealed stirring; the time of the sealed stirring is 0.3 to 0.7 hours;

[0033] The fourth mixing is carried out by sealed stirring; the time of the sealed stirring is 0.3 to 0.7 hours;

[0034] The fifth mixing is carried out under stirring conditions; the time of the stirring is 20 to 30 min.

[0035] Preferably, the dropping rate of the first dropping is 1 to 3 mL / min;

[0036] The dropping rate of the second dropping is 1 to 3 mL / min;

[0037] The dropping rate of the third dropping is 1 to 2 mL / min;

[0038] The dropping rate of the fourth dropping is 0.3 to 0.7 mL / min.

[0039] Preferably, after the fourth dropping is completed, it further includes:

[0040] Ultrasonic treatment is carried out on the obtained mixed solution to obtain a hybrid coating agent on the surface of hollow glass microspheres;

[0041] The time of the ultrasonic treatment is 20 to 40 min.

[0042] The present invention provides a modified hollow glass microsphere, including:

[0043] Hollow glass microspheres;

[0044] A coating disposed on the surface of the hollow glass microspheres; the coating is formed by the hybrid coating agent on the surface of the hollow glass microspheres described in the above technical solution.

[0045] Preferably, the thickness of the coating is 1 to 2 μm.

[0046] The present invention provides a composite material, including:

[0047] Resin and the modified hollow glass microspheres described in the above technical solution.

[0048] Preferably, the mass content of the modified hollow glass microspheres in the composite material is 8 to 10%.

[0049] The present invention provides a surface modifier for hollow glass microspheres. After modifying the surface of the hollow microspheres, it can improve the wetting performance between the microspheres and the resin matrix, as well as the surface roughness of the microspheres, thereby enhancing the mechanical locking force between the microspheres and the resin matrix and improving the interfacial bonding performance of the microsphere / resin composite material. Detailed implementation mode

[0050] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0051] The present invention provides a surface hybrid coating agent for hollow glass microspheres, which includes, by weight:

[0052] 20 to 40 parts of waterborne amino acrylic acid;

[0053] 15 to 30 parts of tetraethyl orthosilicate (TEOS);

[0054] 15 to 30 parts of aluminum sec-butoxide (ASB);

[0055] 3 to 6 parts of silane coupling agent (KH550);

[0056] 0.15 to 0.3 parts of p-toluenesulfonic acid (PTSA).

[0057] In the present invention, the weight fraction of the waterborne amino acrylic acid is preferably 25 to 35 parts, more preferably 28 to 32 parts, and most preferably 30 parts. In the present invention, the waterborne amino acrylic acid can be a commercially available product, such as the product with the model BH-831 provided by Dongguan Heima Chemical Co., Ltd.

[0058] In the present invention, the weight fraction of the tetraethyl orthosilicate is preferably 20 to 25 parts, more preferably 22 to 23 parts.

[0059] In the present invention, the weight fraction of the aluminum sec-butoxide is preferably 20 to 25 parts, more preferably 22 to 23 parts.

[0060] In the present invention, the weight fraction of the silane coupling agent is preferably 3 to 6 parts. In the present invention, the silane coupling agent is preferably KH550.

[0061] In the present invention, the weight fraction of the p-toluenesulfonic acid is preferably 0.15 to 0.3 parts.

[0062] The present invention provides a milky white waterborne surface modifier for hollow glass microspheres (surface hybrid coating agent for hollow glass microspheres).

[0063] The present invention provides a method for preparing a hybrid coating agent on the surface of hollow glass microspheres according to the above technical solution, including:

[0064] Carry out a first mixing of tetraethyl orthosilicate and ethanol to obtain solution A;

[0065] Carry out a second mixing of a silane coupling agent, p-toluenesulfonic acid and ethanol to obtain solution B;

[0066] Carry out a first dropwise addition of the solution B into solution A to obtain silica sol;

[0067] Carry out a third mixing of aluminum sec-butoxide and ethanol to obtain solution C;

[0068] Carry out a fourth mixing of p-toluenesulfonic acid and ethanol to obtain solution D;

[0069] Carry out a second dropwise addition of the solution D into solution C to obtain aluminum sol;

[0070] Carry out a third dropwise addition of the silica sol into the aluminum sol to obtain a silica-aluminum hybrid sol;

[0071] Carry out a fifth mixing of waterborne amino acrylic acid and water to obtain a waterborne amino acrylic acid emulsion;

[0072] Carry out a fourth dropwise addition of the silica-aluminum hybrid sol into the waterborne amino acrylic acid emulsion and stir to obtain a milky white waterborne surface modifier for hollow microspheres (hybrid coating agent on the surface of hollow glass microspheres).

[0073] In the present invention, the ethanol used in the preparation process of the hybrid coating agent on the surface of hollow glass microspheres is preferably anhydrous ethanol; the dosage ratio of tetraethyl orthosilicate and ethanol is preferably (15 - 30) g:

[0074] (1000 - 2000) mL, more preferably (20 - 25) g: (1300 - 1700) mL, and most preferably (22 - 23) g: 1500 mL; the first mixing is preferably sealed stirring; the time of the sealed stirring is preferably 30 - 40 min, more preferably 33 - 37 min, and most preferably 35 min.

[0075] In the present invention, the dosage ratio of the silane coupling agent, p-toluenesulfonic acid and ethanol is preferably (3 - 6) g: (0.15 - 0.3) g: (100 - 200) mL, more preferably (4 - 5) g: (0.20 - 0.25) g:

[0076] (130 - 170) mL, most preferably 4.5 g:(0.22 - 0.23) g:150 mL; the second mixing is preferably carried out with stirring in a sealed container; the time for the sealed stirring is preferably 0.3 - 0.7 hours, more preferably 0.4 - 0.6 hours, and most preferably 0.5 hours.

[0077] In the present invention, the volume ratio of solution A to solution B is preferably (100 - 200):(100 - 200), more preferably (130 - 170):(130 - 170), and most preferably 150:150.

[0078] In the present invention, the first dropping is preferably carried out using a peristaltic pump; the dropping speed of the first dropping is preferably 1 - 3 mL / min, more preferably 1.5 - 2.5 mL / min, and most preferably 2.0 mL / min; the first dropping is preferably accompanied by strong magnetic stirring.

[0079] In the present invention, the dosage ratio of aluminum sec - butoxide to ethanol is preferably (15 - 30) g:(1000 - 2000) mL, more preferably (20 - 25) g:(1300 - 1700) mL, and most preferably (22 - 23) g:1500 mL; the third mixing is preferably carried out with stirring in a sealed container; the time for the sealed stirring is preferably 0.3 - 0.7 hours, more preferably 0.4 - 0.6 hours, and most preferably 0.5 hours.

[0080] In the present invention, the dosage ratio of p - toluenesulfonic acid to ethanol is preferably (0.15 - 0.3) g:100 mL, more preferably (0.2 - 0.25) g:100 mL; the fourth mixing is preferably carried out with stirring in a sealed container; the time for the sealed stirring is preferably 0.3 - 0.7 hours, more preferably 0.4 - 0.6 hours, and most preferably 0.5 hours.

[0081] In the present invention, the volume ratio of solution C to solution D is preferably (100 - 200):(100 - 200), more preferably (130 - 170):(130 - 170), and most preferably 150:150.

[0082] In the present invention, the second dropping is preferably carried out using a peristaltic pump, and the dropping speed of the second dropping is preferably 1 - 3 mL / min, more preferably 1.5 - 2.5 mL / min, and most preferably 2 mL / min.

[0083] In the present invention, the volume ratio of silica sol to alumina sol is preferably (100 - 50):(50 - 100), more preferably (90 - 60):(60 - 90), and most preferably (80 - 70):(70 - 90).

[0084] In the present invention, the dropping rate of the third addition is preferably 1 to 2 mL / min, more preferably 1.5 mL / min.

[0085] In the present invention, the water is preferably deionized water; the dosage ratio of the aqueous amino acrylate to water is preferably (20 - 40) g : (1000 - 2000) mL, more preferably (25 - 35) g : (1300 - 1700) mL, and most preferably 30 g : 1500 mL; the fifth mixing is preferably carried out under stirring; the stirring time is preferably 20 to 30 min, more preferably 25 min.

[0086] In the present invention, the mass concentration of the aqueous amino acrylate emulsion is preferably 1 to 3%, more preferably 1.5 to 2.5%, and most preferably 2%.

[0087] In the present invention, the mass ratio of the silicon-aluminum hybrid sol to the aqueous amino acrylate emulsion is preferably (5 - 10) : (100 - 200), more preferably (6 - 9) : (130 - 170), and most preferably (7 - 8) : 150.

[0088] In the present invention, the dropping rate of the fourth addition is preferably 0.3 to 0.7 mL / min, more preferably 0.4 to 0.6 mL / min, and most preferably 0.5 mL / min; the fourth addition is preferably accompanied by strong magnetic stirring to prevent the sol particles from aggregating due to excessive hydrolysis in the aqueous amino acrylate solution.

[0089] In the present invention, after the fourth addition is completed, it preferably further includes:

[0090] Ultrasonic treatment of the obtained mixed solution to obtain a milky white surface modifier for hollow aqueous microspheres.

[0091] In the present invention, the ultrasonic treatment is preferably carried out in an ultrasonic cleaner; the ultrasonic treatment time is preferably 20 to 40 min, more preferably 25 to 35 min, and most preferably 30 min.

[0092] The present invention provides a modified hollow glass microsphere, comprising:

[0093] Hollow glass microspheres;

[0094] A coating provided on the surface of the hollow glass microspheres, and the coating is a coating formed by the hybrid coating agent for the surface of the hollow glass microspheres as described in the above technical solution.

[0095] In the present invention, the thickness of the coating is preferably 1 to 2 μm, more preferably 1.5 μm.

[0096] In the present invention, the preparation method of the modified hollow glass microspheres preferably includes:

[0097] Add hollow glass microspheres to the hybrid coating agent on the surface of the hollow glass microspheres and stir to obtain a stirred product;

[0098] Let the stirred product stand, then dry and screen it to obtain (hybrid coating) modified hollow glass microspheres.

[0099] In the present invention, the addition is preferably carried out while slowly adding with stirring.

[0100] In the present invention, the stirring is preferably mechanical stirring. The stirring rate is preferably 300 - 500 r / min, more preferably 350 - 450 r / min, and most preferably 400 r / min; the stirring time is preferably 20 - 30 minutes, more preferably 25 minutes.

[0101] In the present invention, the standing time is preferably 15 - 30 minutes, more preferably 20 - 25 minutes.

[0102] In the present invention, the drying is preferably carried out by drying in a tray; the drying temperature is preferably 100 - 120 °C, more preferably 105 - 115 °C, and most preferably 110 °C; the drying time is preferably 3 - 6 h, more preferably 4 - 5 h.

[0103] In the present invention, the preparation method of the modified hollow glass microspheres more preferably includes:

[0104] Dissolve 15 - 30 g of the precursor (TEOS) in 1000 - 2000 ml of absolute ethanol, seal and stir for 30 - 40 min to prepare solution A; at the same time, dissolve 3 - 6 g of silane coupling agent (KH550) and 0.15 - 0.3 g of catalyst (PTSA) in 100 - 200 ml of absolute ethanol, seal and stir for half an hour to prepare solution B; then drip solution B into solution A at a speed of 2 ml / min with a peristaltic pump and mix to prepare silica sol under strong magnetic stirring;

[0105] Dissolve 15 - 30 g of the precursor (ASB) in 1000 - 2000 ml of absolute ethanol, seal and stir for 30 min to prepare solution C; dissolve 0.15 - 0.3 g of catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution D; use a peristaltic pump to drip catalyst solution D into solution C at a speed of 2 ml / min to prepare alumina sol;

[0106] Add silica sol to alumina sol according to a certain volume ratio and mix to obtain silica-alumina hybrid sol;

[0107] Take 20 - 40 g of waterborne amino acrylic acid and dissolve it in 1000 - 2000 ml of deionized water. After stirring for 20 - 30 min, a waterborne amino acrylic acid emulsion with a mass fraction of 2% is prepared. Drop 50 g of silica-alumina hybrid sol with different ratios into the waterborne amino acrylic acid emulsion at a rate of 0.5 ml / min, and stir strongly to prevent the sol particles from coagulating due to excessive hydrolysis in the waterborne amino acrylic acid solution. After the dropping is completed, place the mixed solution in an ultrasonic cleaner and ultrasonicate for 20 - 40 min to prepare a milky white waterborne hollow microsphere surface modifier.

[0108] Slowly add hollow glass microspheres to the milky white waterborne hybrid sizing agent while stirring. The mechanical stirring rate is 300 - 500 r / min, and the stirring time is 20 - 30 minutes;

[0109] After standing for 15 - 30 minutes, take out the microspheres and place them in a tray, and dry them at 100 - 120 °C for 3 - 6 h before taking them out;

[0110] After sieving with a sieve, the hollow glass microspheres modified with a hybrid coating are obtained.

[0111] The present invention provides a composite material, comprising:

[0112] Resin and the modified hollow glass microspheres as described in the above technical solution.

[0113] In the present invention, the resin is preferably selected from one or more of polyamide 6 (PA6), acrylonitrile-butadiene-styrene copolymer (ABS), and high impact polystyrene (HIPS).

[0114] In the present invention, the mass content of the modified hollow glass microspheres in the composite material is preferably 8 - 12%, more preferably 9 - 11%, and most preferably 10%.

[0115] In the present invention, the preparation method of the composite material preferably includes:

[0116] Mix the resin and the antioxidant to obtain a mixture;

[0117] Extrude the mixture and the modified hollow glass microspheres to obtain the composite material.

[0118] In the present invention, the composition of the resin is the same as that described in the above technical solution. In the present invention, the antioxidant is preferably antioxidant B215; the mass of the antioxidant is preferably 0.2 - 0.5%, more preferably 0.3 - 0.4%; the mass ratio of the resin to the modified hollow glass microspheres is preferably (88 - 90):(8 - 12), more preferably 89:10.

[0119] In the present invention, the extrusion is preferably carried out in a twin-screw extruder; the modified hollow glass microspheres are preferably mixed by side feeding; the temperature of each section during the extrusion process is preferably 230 to 240 °C, more preferably 235 °C; the rotation speed is preferably 100 to 150 r / min, more preferably 110 to 140 r / min, and most preferably 120 to 130 r / min.

[0120] The present invention provides a surface modifier for hollow glass microspheres. After modifying the surface of the hollow microspheres, the wetting performance between the microspheres and the resin matrix and the surface roughness of the microspheres can be improved, thereby enhancing the mechanical locking force between the microspheres and the resin matrix and improving the interfacial bonding performance of the microsphere / resin composite material.

[0121] The performance measurement and measurement method of the weight-reducing composite material prepared in the following examples of the present invention are as follows:

[0122] 1. Apparent density: Refer to ISO1183 (Determination method for density of non-foamed plastics);

[0123] 2. Notched impact strength: Refer to ISO 179 (Determination of Charpy impact strength);

[0124] 3. Tensile strength: Refer to ISO 527 (Determination of tensile properties of plastics);

[0125] 4. Flexural modulus: Refer to ISO 178 (Determination of flexural properties of plastics).

[0126] Comparative Example 1

[0127] First, 90 parts by weight of polyamide 6 (PA6) and 0.5% antioxidant B215 parts are fully mixed in a high-speed mixer; after mixing evenly, the mixed material is fed into a twin-screw extruder, and 10 parts by weight of untreated hollow glass microspheres are added to the melt through side feeding. Finally, the PA6 masterbatch containing hollow glass microspheres is extruded to obtain the composite material, where the temperature setting range of each section of the twin-screw extruder is 230 to 240 °C and the rotation speed is 100 r / min.

[0128] Example 1

[0129] Dissolve 15 g of the precursor (TEOS) in 1000 - 2000 ml of absolute ethanol, seal and stir for 30 min to prepare solution A; simultaneously, dissolve 3 g of the silane coupling agent (KH550) and 0.15 g of the catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution B; then, drip solution B into solution A at a rate of 2 ml / min using a peristaltic pump, and prepare silica sol under strong magnetic stirring; take 20 g of waterborne amino acrylic acid and dissolve it in 1000 ml of deionized water, and prepare a 2% waterborne amino acrylic acid emulsion after magnetic stirring for 30 min. Drip 50 g of silica sol into the waterborne amino acrylic acid emulsion at a rate of 0.5 ml / min, and stir strongly to prevent the sol particles from aggregating due to excessive hydrolysis in the waterborne amino acrylic acid solution. After the dripping is completed, place the mixed solution in an ultrasonic machine and ultrasonicate for 30 min to prepare a milky white waterborne hollow microsphere surface modifier.

[0130] Slowly add hollow glass microspheres to the milky white waterborne hollow microsphere surface modifier while stirring, with a mechanical stirring rate of 400 r / min and a stirring time of 30 minutes;

[0131] After standing for 30 minutes, take out the microspheres and place them on a tray, dry them at 140 °C for 2 h, and then take them out; after sieving with a sieve, the hollow glass microspheres modified with a hybrid coating, denoted as H1, are obtained.

[0132] Fully mix 90 parts by weight of polyamide 6 (PA6) and 0.5% antioxidant B215 in a high-speed mixer; after mixing evenly, feed the mixed material into a twin-screw extruder, and respectively add 10 parts by weight of the surface-treated H1 hollow glass microspheres to the melt through side feeding. Finally, extrude the PA6 masterbatch containing hollow glass microspheres to obtain the composite material, where the temperature setting range of each section of the twin-screw extruder is 230 - 240 °C and the rotation speed is 100 r / min.

[0133] Example 2

[0134] Dissolve 15 g of the precursor (ASB) in 1000 ml of absolute ethanol, seal and stir for 30 min to prepare solution C; dissolve 0.15 g of the catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution D; use a peristaltic pump to add solution D of the catalyst dropwise to solution C at a rate of 2 ml / min to prepare an aluminum sol; take 20 g of waterborne amino acrylic acid and dissolve it in 1000 ml of deionized water, magnetically stir for 30 min to prepare a 2% waterborne amino acrylic acid emulsion, add 50 g of the aluminum sol dropwise to the waterborne amino acrylic acid emulsion at a rate of 0.5 ml / min, and stir strongly to prevent the sol particles from aggregating due to excessive hydrolysis in the waterborne amino acrylate solution. After the addition is complete, place the mixed solution in an ultrasonic machine and ultrasonicate for 30 min to prepare a milky white waterborne hollow microsphere surface modifier.

[0135] Slowly add hollow glass microspheres to the milky white waterborne hollow microsphere surface modifier while stirring, with a mechanical stirring rate of 400 r / min and a stirring time of 30 minutes;

[0136] After standing for 30 minutes, take out the microspheres and place them on a tray, dry them at 140 °C for 2 h and then take them out; after screening with a sieve, the hollow glass microspheres modified with a hybrid coating are obtained, denoted as H2.

[0137] Fully mix 90 parts by weight of polyamide 6 (PA6) with 0.5% antioxidant B215 parts in a high-speed mixer; after mixing evenly, feed the mixed material into a twin-screw extruder, and add 10 parts by weight of surface-treated H2 hollow glass microspheres to the melt through side feeding respectively. Finally, extrude the PA6 masterbatch containing hollow glass microspheres to obtain the composite material, where the temperature setting range of each section of the twin-screw extruder is 230 - 240 °C and the rotation speed is 100 r / min.

[0138] Example 3

[0139] Dissolve 15 g of the precursor (TEOS) in 1000 - 2000 ml of absolute ethanol, seal and stir for 30 min to prepare solution A; at the same time, dissolve 3 g of silane coupling agent (KH550) and 0.15 g of catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution B; then add solution B dropwise to solution A at a rate of 2 ml / min with a peristaltic pump, and prepare silica sol under strong magnetic stirring; dissolve 15 g of the precursor (ASB) in 1000 ml of absolute ethanol, seal and stir for 30 min to prepare solution C; dissolve 0.15 g of catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution D, and add catalyst D solution dropwise to solution C at a rate of 2 ml / min with a peristaltic pump to prepare alumina sol. Add silica sol to alumina sol at a volume ratio of 2:1 at a rate of 2 ml / min to obtain a silica-alumina hybrid sol; take 20 g of waterborne amino acrylic acid and dissolve it in 1000 ml of deionized water, stir magnetically for 30 min to prepare a 2% waterborne amino acrylic acid emulsion. Then take 50 g of silica-alumina sol and add it dropwise to the waterborne amino acrylic acid emulsion at a rate of 0.5 ml / min, and stir strongly to prevent the sol particles from aggregating due to excessive hydrolysis in the waterborne amino acrylic acid solution. After the addition is complete, place the mixed solution in an ultrasonic machine and ultrasonicate for 30 min to prepare a milky white waterborne hollow microsphere surface modifier.

[0140] Slowly add hollow glass microspheres to the milky white waterborne hollow microsphere surface modifier while stirring, with a mechanical stirring rate of 400 r / min and a stirring time of 30 minutes;

[0141] After standing for 30 minutes, take out the microspheres and place them on a tray, dry them at 140 °C for 2 h and then take them out; after screening with a sieve, hybrid coating-modified hollow glass microspheres are obtained, denoted as H3.

[0142] Fully mix 90 parts by weight of polyamide 6 (PA6) and 0.5% antioxidant B215 in a high-speed mixer; after mixing evenly, feed the mixed material into a twin-screw extruder, and add 10 parts by weight of surface-treated H3 hollow glass microspheres to the melt through side feeding. Finally, extrude the PA6 masterbatch containing hollow glass microspheres to obtain a composite material, where the temperature setting range for each section of the twin-screw extruder is 230 - 240 °C and the rotation speed is 100 r / min.

[0143] Example 4

[0144] Dissolve 15 g of the precursor (TEOS) in 1000 - 2000 ml of absolute ethanol, seal and stir for 30 min to prepare solution A; simultaneously, dissolve 3 g of silane coupling agent (KH550) and 0.15 g of catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution B; then add solution B dropwise to solution A at a rate of 2 ml / min using a peristaltic pump, and prepare silica sol under strong magnetic stirring; dissolve 15 g of the precursor (ASB) in 1000 ml of absolute ethanol, seal and stir for 30 min to prepare solution C; dissolve 0.15 g of catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution D, and add catalyst solution D dropwise to solution C at a rate of 2 ml / min using a peristaltic pump to prepare alumina sol. Add silica sol to alumina sol at a volume ratio of 2:2, with silica sol being added at a rate of 2 ml / min, to obtain a silica-alumina hybrid sol; take 20 g of waterborne aminoacrylate and dissolve it in 1000 ml of deionized water, stir magnetically for 30 min to prepare a 2% waterborne aminoacrylate emulsion. Then take 50 g of silica-alumina sol and add it dropwise to the waterborne aminoacrylate emulsion at a rate of 0.5 ml / min, with strong magnetic stirring to prevent the sol particles from aggregating due to excessive hydrolysis in the waterborne acrylate solution. After the addition is complete, place the mixed solution in an ultrasonic machine and ultrasonicate for 30 min to prepare a milky white waterborne hollow microsphere surface modifier.

[0145] Slowly add hollow glass microspheres to the milky white waterborne hollow microsphere surface modifier while stirring, with a mechanical stirring rate of 400 r / min and a stirring time of 30 minutes;

[0146] After standing for 30 minutes, take out the microspheres and place them on a tray, dry them at 140 °C for 2 h and then take them out; after screening with a sieve, hybrid coating-modified hollow glass microspheres are obtained, denoted as H4.

[0147] Fully mix 90 parts by weight of polyamide 6 (PA6) with 0.5% antioxidant B215 in a high-speed mixer; after mixing evenly, feed the mixed material into a twin-screw extruder, and add 10 parts by weight of surface-treated H4 hollow glass microspheres to the melt through side feeding. Finally, extrude the PA6 masterbatch containing hollow glass microspheres to obtain the composite material; the temperature setting range for each section of the twin-screw extruder is 230 - 240 °C, and the rotation speed is 100 r / min.

[0148] Example 5

[0149] Dissolve 15 g of the precursor (TEOS) in 1000 - 2000 ml of absolute ethanol, seal and stir for 30 min to prepare solution A; at the same time, dissolve 3 g of silane coupling agent (KH550) and 0.15 g of catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution B; then drip solution B into solution A at a rate of 2 ml / min with a peristaltic pump and prepare silica sol under strong magnetic stirring; dissolve 15 g of the precursor (ASB) in 1000 ml of absolute ethanol, seal and stir for 30 min to prepare solution C; dissolve 0.15 g of catalyst (PTSA) in 100 ml of absolute ethanol, seal and stir for half an hour to prepare solution D, and drip catalyst solution D into solution C at a rate of 2 ml / min with a peristaltic pump to prepare alumina sol. Drip silica sol into alumina sol at a volume ratio of 1:2 at a rate of 2 ml / min to obtain a silica-alumina hybrid sol; take 20 g of waterborne amino acrylic acid and dissolve it in 1000 ml of deionized water, stir magnetically for 30 min to prepare a 2% waterborne amino acrylic acid emulsion. Then take 50 g of silica-alumina sol and drip it into the waterborne amino acrylic acid emulsion at a rate of 0.5 ml / min, and stir strongly to prevent the sol particles from aggregating due to excessive hydrolysis in the waterborne amino acrylic acid solution. After dripping, place the mixed solution in an ultrasonic machine and ultrasonicate for 30 min to prepare a milky white waterborne hollow microsphere surface modifier.

[0150] Slowly add hollow glass microspheres to the milky white waterborne hollow microsphere surface modifier while stirring, with a mechanical stirring rate of 400 r / min and a stirring time of 30 minutes;

[0151] After standing for 30 minutes, take out the microspheres and place them on a tray, dry them at 140 °C for 2 h and then take them out; after screening with a sieve, the hollow glass microspheres modified with a hybrid coating, denoted as H5, are obtained.

[0152] Fully mix 90 parts by weight of polyamide 6 (PA6) with 0.5% antioxidant B215 in a high-speed mixer; after mixing evenly, feed the mixed material into a twin-screw extruder, and add 10 parts by weight of surface-treated H5 hollow glass microspheres to the melt through side feeding respectively. Finally, extrude the PA6 masterbatch containing hollow glass microspheres, which is the composite material; the temperature setting range of each section of the twin-screw extruder is 230 - 240 °C and the rotation speed is 100 r / min.

[0153] The test results are as follows:

[0154]

[0155] It can be seen that Comparative Example 1 is hollow glass microspheres without surface modification, and Examples 1 and 2 are hollow glass microspheres modified with a single silica sol and a single alumina sol hybrid coating agent respectively. Examples 3, 4, and 5 are the test data of hollow glass microspheres modified with silica sol and alumina sol in a ratio of 2:1, 2:2, and 1:2 respectively. In order to verify and compare the improvement of the surface properties of the modified glass microspheres, the above unmodified microspheres and the hollow glass microsphere samples obtained in the examples were respectively blended with polyamide-6 (PA6) (the content of the hollow glass microspheres was 10 wt%), and hollow glass microsphere / PA6 composites were prepared and their properties were tested. After comparison, for the hollow glass microspheres prepared with the surface modifier of the present invention, the tensile strength, tensile modulus, flexural strength, flexural modulus, and IZOD notched impact strength of the corresponding composite materials have been greatly improved. The properties of the hollow glass microspheres prepared in Example 3 are the best, which can effectively improve the compatibility and interfacial bonding properties between the microspheres and the resin matrix.

[0156] Although the present invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration do not limit the present invention. Those skilled in the art will clearly understand that various changes can be made without departing from the true spirit and scope of the present invention as defined by the appended claims, so as to adapt a particular situation, material, composition of matter, substance, method, or process to the objectives, spirit, and scope of the present application. All such modifications are intended to be within the scope of the appended claims. Although the methods disclosed herein have been described with reference to specific operations performed in a specific order, it should be understood that these operations can be combined, subdivided, or reordered without departing from the teachings of the present invention to form equivalent methods. Therefore, unless specifically indicated herein, the order and grouping of operations are not limitations of the present application.

Claims

1. A surface hybrid coating agent for hollow glass microspheres, by weight, comprising: 20 - 40 parts of aqueous amino acrylic acid; 15 - 30 parts of tetraethyl orthosilicate; 15 - 30 parts of aluminum sec-butoxide; 3 - 6 parts of silane coupling agent; 0.15 - 0.3 part of p-toluenesulfonic acid; The surface hybrid coating agent for hollow glass microspheres is prepared by the following preparation method: Perform a first mixing of tetraethyl orthosilicate and ethanol to obtain solution A; Perform a second mixing of the silane coupling agent, p-toluenesulfonic acid and ethanol to obtain solution B; Perform a first dropwise addition of the solution B to solution A to obtain silica sol; Perform a third mixing of aluminum sec-butoxide and ethanol to obtain solution C; Perform a fourth mixing of p-toluenesulfonic acid and ethanol to obtain solution D; Perform a second dropwise addition of the solution D to solution C to obtain aluminum sol; Perform a third dropwise addition of the silica sol to the aluminum sol to obtain a silica-aluminum hybrid sol; Perform a fifth mixing of aqueous amino acrylic acid and water to obtain an aqueous amino acrylic acid emulsion; Perform a fourth dropwise addition of the silica-aluminum hybrid sol to the aqueous amino acrylic acid emulsion and stir to obtain the surface hybrid coating agent for hollow glass microspheres.

2. A preparation method of the surface hybrid coating agent for hollow glass microspheres according to claim 1, comprising: Perform a first mixing of tetraethyl orthosilicate and ethanol to obtain solution A; Perform a second mixing of the silane coupling agent, p-toluenesulfonic acid and ethanol to obtain solution B; Perform a first dropwise addition of the solution B to solution A to obtain silica sol; Perform a third mixing of aluminum sec-butoxide and ethanol to obtain solution C; Perform a fourth mixing of p-toluenesulfonic acid and ethanol to obtain solution D; Perform a second dropwise addition of the solution D to solution C to obtain aluminum sol; Perform a third dropwise addition of the silica sol to the aluminum sol to obtain a silica-aluminum hybrid sol; Perform a fifth mixing of aqueous amino acrylic acid and water to obtain an aqueous amino acrylic acid emulsion; Perform a fourth dropwise addition of the silica-aluminum hybrid sol to the aqueous amino acrylic acid emulsion and stir to obtain the surface hybrid coating agent for hollow glass microspheres.

3. The method according to claim 2, wherein The dosage ratio of the tetraethyl orthosilicate and ethanol is (15 - 30) g : (1000 - 2000) mL; The dosage ratio of the silane coupling agent, p-toluenesulfonic acid and ethanol is (3 - 6) g : (0.15 - 0.3) g : (100 - 200) mL; The volume ratio of solution A and solution B is (100 - 200) : (100 - 200); The dosage ratio of the aluminum sec-butoxide and ethanol is (15 - 30) g : (1000 - 2000) mL; The dosage ratio of the p-toluenesulfonic acid and ethanol is (0.15 - 0.3) g : 100 mL; The volume ratio of solution C and solution D is (100 - 200) : (100 - 200); The volume ratio of the silica sol and the aluminum sol is (100 - 50) : (50 - 100); The dosage ratio of the aqueous amino acrylic acid and water is (20 - 40) g : (1000 - 2000) mL; The mass ratio of the silica-aluminum hybrid sol and the aqueous amino acrylic acid emulsion is (5 - 10) : (100 - 200).

4. The method according to claim 2, characterized in that The first mixing is a sealed stirring; the time of the sealed stirring is 30 to 40 minutes; The second mixing is a sealed stirring; the time of the sealed stirring is 0.3 to 0.7 hours; The third mixing is a sealed stirring; the time of the sealed stirring is 0.3 to 0.7 hours; The fourth mixing is a sealed stirring; the time of the sealed stirring is 0.3 to 0.7 hours; The fifth mixing is carried out under stirring conditions; the time of the stirring is 20 to 30 minutes.

5. The method according to claim 2, characterized in that, The dropping rate of the first dropping is 1 to 3 mL / min; The dropping rate of the second dropping is 1 to 3 mL / min; The dropping rate of the third dropping is 1 to 2 mL / min; The dropping rate of the fourth dropping is 0.3 to 0.7 mL / min.

6. The method according to claim 2, wherein After the fourth dropping is completed, it further includes: Ultrasonic treatment is performed on the obtained mixed solution to obtain a hybrid coating agent on the surface of the hollow glass microspheres; The time of the ultrasonic treatment is 20 to 40 minutes.

7. A modified hollow glass microsphere, comprising: Hollow glass microspheres; A coating disposed on the surface of the hollow glass microspheres; The coating is formed by the hybrid coating agent on the surface of the hollow glass microspheres according to claim 1.

8. The modified hollow glass microspheres according to claim 7, wherein, The thickness of the coating is 1 to 2 μm.

9. A composite material, comprising: A resin and the modified hollow glass microspheres according to claim 7.

10. The composite material according to claim 9, wherein, The mass content of the modified hollow glass microspheres in the composite material is 8 to 10%.

Images