Inorganic-organic hybrid glass fiber and high-temperature-resistant polypropylene dispensing cylinder

Abstract

The invention provides a siloxane-terminated polymer and a preparation method thereof, an inorganic-organic hybrid glass fiber impregnated with the polymer, a polypropylene composite material, a preparation method of the polypropylene composite material and a corresponding high-temperature-resistant polypropylene dispensing cylinder. A siloxane-terminated polymer is synthesized through hydrosilylation, two ends of a molecular chain of the siloxane-terminated polymer contain hydrolyzable siloxane groups, the middle of the molecular chain contains hydroxyl capable of being subjected to cross-linking reaction, glass fibers are subjected to dipping treatment by using the polymer, a coating is formed on the surfaces of the glass fibers, and the inorganic-organic hybrid glass fibers are obtained. The hybrid glass fiber is added into the polypropylene composite material, and the glass fiber and a polypropylene matrix are bonded through the chemical bond action, so that the compatibility of the glass fiber and the polypropylene matrix is greatly improved, and the mechanical property and the thermal deformation temperature of the polypropylene composite material are further improved. And the thermal deformation temperature of the polypropylene composite material can reach more than 160 DEG C, so that the requirement of a high-temperature sizing process on the high-temperature resistance of the dispensing cylinder material can be met.

Description

Technical Field

[0001] The present invention relates to the technical field of polypropylene modification, and specifically to a siloxane-terminated polymer and a preparation method thereof, an inorganic-organic hybrid glass fiber, a polypropylene composite material and a preparation method thereof, and a corresponding high-temperature resistant polypropylene dispensing cartridge. Background Art

[0002] Hot melt adhesive (HMA) is a solvent-free, plastic adhesive whose physical state changes with temperature within a certain temperature range, while its chemical properties remain unchanged. This makes it not only environmentally friendly, but also allows the colloid to solidify quickly after heating stops. Hot melt adhesive is stored in solid form. When used, it is heated to a specific temperature using a heating device (the melting point of hot melt adhesive is between 100°C and 200°C, depending on the specific formulation) to turn it into a liquid or viscous state to obtain sufficient fluidity, allowing it to pass smoothly through the dispensing needle and form the desired pattern or coating area as needed. Therefore, unlike many other types of adhesives, hot melt adhesive must be heated to a molten state before it can be applied. The hot melt adhesive needs to be continuously heated throughout the dispensing process to ensure that the hot melt adhesive in the molten state has a mobile phase, thereby ensuring the accuracy and effectiveness of dispensing.

[0003] On the other hand, the adhesive coating process in the fields of semiconductor packaging and testing, surface mount technology (SMT) and electronic components requires high yield and high precision. Commonly used adhesives have high viscosity and low fluidity at room temperature. For these high-viscosity adhesives, it is necessary to reduce their viscosity and improve fluidity under heating to reduce bubbles in the adhesive, which helps to fill tiny gaps more evenly or achieve finer patterned coating, thereby improving the dispensing accuracy and coating consistency of the adhesive.

[0004] Given the characteristics of adhesive coating processes in fields such as hot melt adhesives and semiconductor packaging and testing, there is an increasing demand for materials that can load adhesives under high temperature conditions (above 160°C). Hot melt adhesives and electronic adhesives that require precision in dispensing require high-temperature gluing processes. However, the polypropylene used in dispensing cartridges is a thermoplastic material and is difficult to withstand temperatures above 160°C. In addition, the thermal deformation temperature of the dispensing cartridge material is too low, which can lead to glue dripping and stringing at the dispensing nozzle at high temperatures, greatly affecting the quality and efficiency of dispensing. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above shortcomings and propose a siloxane-terminated polymer and its preparation method, an inorganic-organic hybrid glass fiber, a polypropylene composite material and its preparation method, and a corresponding high-temperature resistant polypropylene dispensing cartridge. By adjusting the formula, the heat deformation temperature of the polypropylene dispensing cartridge can be increased to above 160°C, which can meet the heat resistance requirements of the high-temperature gluing process for the dispensing cartridge material.

[0006] In order to achieve the above technical objectives, the technical solutions adopted by the present invention are as follows:

[0007] In the first aspect, a siloxane-terminated polymer is provided, wherein each end of the polymer has at least two siloxane groups and the middle of the polymer chain contains at least one hydroxyl group, and the corresponding structural formula is:

[0008]

[0009] wherein R1, R2, and R3 are the same or different and contain 1 to 20 atoms, and the groups of R1, R2, and R3 are selected from hydrogen atoms, alkyl groups, or alkoxy groups, and at least one of R1, R2, and R3 is selected from alkoxy groups, preferably, at least one of R1, R2, and R3 is selected from methoxy groups or ethoxy groups;

[0010] R4, R5, R6, and R7 are the same or different and contain 1 to 20 carbon atoms. The groups of R4, R5, R6, and R7 are selected from: alkyl groups or phenyl groups with 1 to 20 carbon atoms; preferably, R4, R5, R6, and R7 are selected from any one of methyl, ethyl, and phenyl groups, and more preferably, R4, R5, R6, and R7 are selected from methyl groups.

[0011] R8 contains 4 to 54 atoms, and R9 does not contain N, S, or P elements. Preferably, R8 contains at least one ester bond or ether bond;

[0012] R9 is different from R8. R9 contains 4 to 54 atoms, R9 contains at least one hydroxyl group, and R9 does not contain N, S, or P elements.

[0013] m and n are the same or different and are selected from non-zero positive integers.

[0014] Preferably, said R8 is selected from or Any one or more of .

[0015] Preferably, said R9 is selected from or Any one or more of .

[0016] In a second aspect, the method for preparing the above-mentioned siloxane-terminated polymer comprises: subjecting a capping agent, a diene monomer and a hydrogen-containing silicone oil to a hydrosilylation reaction to obtain the polymer.

[0017] Preferably, the hydrogen-containing silicone oil is 1,1,3,3-tetramethyldisiloxane (hydrogen-containing double-headed);

[0018] Preferably, the diene monomer is a terminal diene monomer, that is, the unsaturated double bonds are located at both ends of the molecule; more preferably, the diene monomer is selected from: or Any one or more of .

[0019] Preferably, the end-capping agent is selected from any one or more of vinyldimethylmethoxysilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane and vinyltriisopropoxysilane.

[0020] Furthermore, the preparation method of the siloxane-terminated polymer includes: conducting a hydrosilylation reaction of hydrogenated silicone oil and a diene monomer according to a molar ratio of n(Si-H):n(C=C)=(0.8-1):1;

[0021] Preferably, the hydrogenated silicone oil and the diene monomer are subjected to a hydrosilylation reaction in a molar ratio of n(Si-H):n(C=C)=(0.9-1):1;

[0022] Furthermore, the preparation method of the siloxane-terminated polymer includes: adding an inhibitor and a catalyst to the hydrosilylation reaction, reacting the hydrosilylation reaction at 70-90° C. for 2-6 hours, and then heating to 80-100° C. and keeping the temperature for 1-4 hours.

[0023] Wherein, the polymerization inhibitor is selected from p-methylanisole;

[0024] The catalyst is selected from any one of chloroplatinic acid and chloroplatinic acid vinyl complex; preferably, the catalyst is selected from chloroplatinic acid-divinyltetramethyldisiloxane complex.

[0025] The third aspect is a use, including: use of the above-mentioned siloxane-terminated polymer in the preparation of inorganic-organic hybrid materials.

[0026] In a fourth aspect, an inorganic-organic hybrid glass fiber is obtained by impregnating glass fiber in the above-mentioned siloxane-terminated polymer solution, and then taking out the impregnated glass fiber and drying it.

[0027] The drying includes: standing drying at room temperature and drying at a high temperature of 100-200°C.

[0028] Preferably, the immersion time is 1-4 hours;

[0029] Preferably, the drying time at room temperature is 0.5-1 hour;

[0030] Preferably, the drying time at a high temperature of 100-200° C. is 1-4 hours;

[0031] Preferably, the solvent of the siloxane-terminated polymer solution is toluene, ethyl acetate, butyl acetate or propylene glycol methyl ether acetate.

[0032] A fifth aspect is a use, including: use of the above-mentioned inorganic-organic hybrid glass fiber in the preparation of a polyolefin composite material.

[0033] In a sixth aspect, a polypropylene composite material comprises the following raw materials: polypropylene pellets, a compatibilizer, an antioxidant, and the inorganic-organic hybrid glass fiber described above.

[0034] Preferably, the melt index of the polypropylene pellets is 1-20 g / 10 min, and the test standard for the melt index is ASTM D1238:2023;

[0035] Preferably, the compatibilizer is selected from any one or both of polyethylene grafted maleic anhydride (PE-g-MAH) and polypropylene grafted maleic anhydride (PP-g-MAH).

[0036] Preferably, the antioxidant is selected from any one or both of phosphite antioxidants and hindered phenol antioxidants. More preferably, the antioxidant is selected from a composite antioxidant obtained by combining a phosphite antioxidant and a hindered phenol antioxidant.

[0037] Furthermore, the polypropylene composite material is composed of the following components in parts by weight: 90-110 parts of polypropylene pellets, 2-10 parts of a compatibilizer, 0.1-2 parts of an antioxidant, and 10-50 parts of inorganic-organic hybrid glass fibers.

[0038] Preferably, the polypropylene composite material is composed of the following components in parts by weight: 90-110 parts of polypropylene pellets, 3-8 parts of a compatibilizer, 0.1-1 part of an antioxidant, and 10-40 parts of inorganic-organic hybrid glass fibers.

[0039] In a seventh aspect, the method for preparing the polypropylene composite material mentioned above comprises: uniformly mixing all components in proportion, adding the components into a plastic mixer for plasticizing and mixing.

[0040] Wherein, the plasticizing temperature is 200-300°C, preferably, the plasticizing temperature is 250°C.

[0041] In an eighth aspect, a use is provided, namely, application of the above-mentioned polypropylene composite material in hot melt adhesive dispensing equipment.

[0042] A ninth aspect is a use, which is the application of the above-mentioned polypropylene composite material in the fields of semiconductor packaging, surface mount technology (SMT) and electronic components.

[0043] In a tenth aspect, a high-temperature resistant polypropylene dispensing cylinder is obtained by processing and molding the above-mentioned polypropylene composite material.

[0044] Wherein, the processing and molding includes: injection molding or extrusion molding.

[0045] The beneficial effects of the present invention are as follows: a siloxane-terminated polymer is synthesized by hydrosilylation, wherein the ends of the molecular chain contain hydrolyzable siloxane groups, and the middle of the molecular chain contains cross-linkable hydroxyl groups. This polymer is used to impregnate glass fibers to form a coating on the surface, thereby obtaining inorganic-organic hybrid glass fibers. When the hybrid glass fibers are added to a polypropylene composite material, the hydroxyl groups in the middle of the polymer molecular chain react with the maleic anhydride grafted to the compatibilizer molecules at high temperatures, bonding the glass fibers to the polypropylene matrix through chemical bonding, significantly improving the compatibility between the two, and thereby improving the mechanical properties and heat deformation temperature of the polypropylene composite material. The heat deformation temperature of the polypropylene composite material used as a dispensing tube can reach above 160°C, which can meet the high temperature resistance requirements of the dispensing tube material in high-temperature sizing processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is a comparison of the infrared spectra of the siloxane-terminated polymer solution and its cured product prepared in Example 5.

[0047] Figure 2 These are SEM observation pictures of glass fibers that were not impregnated with polymer and glass fibers that were impregnated with the siloxane-terminated polymer solution of Example 5.

[0048] Figure 3 These are SEM observation images of the fracture cross sections of the glass fiber-polypropylene composite material strips of Examples 6-9 and Comparative Examples 1-5. DETAILED DESCRIPTION

[0049] The technical solutions in the embodiments are clearly and completely described below in conjunction with the embodiments of the present invention. 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 in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. It should be noted that the terms used here are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0050] If the specific experimental conditions are not specified in the examples, they are usually based on conventional conditions in the field or conditions recommended by the reagent company; the materials, reagents, etc. used in the examples can be purchased through commercial channels unless otherwise specified.

[0051] Example 1

[0052] Synthesis of siloxane-terminated polymer: 0.87 g of p-methylanisole, an inhibitor, and 0.09 g of a catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (Pt atom effective content is 3000 ppm) were added to a flask and dissolved with 50 mL of toluene. 64.47 g (0.48 mol) of a hydrogenated double end cap, 19.63 g (0.2 mol) of diallyl ether, 42.86 g (0.2 mol) of trimethylolpropane diallyl ether, and 47.58 g (0.25 mol) of vinyltriethoxysilane were dissolved in 100 mL of toluene and added dropwise to a flask at 85 ° C. The reaction was protected by nitrogen gas, and the materials were added dropwise for a total of 2.5 hours. After the addition, the temperature was raised to 92 ° C. and the temperature was kept at 1.5 hours to terminate the reaction. The siloxane-terminated polymer was obtained after cooling to room temperature.

[0053] Preparation of organic-inorganic hybrid glass fiber: EDR17-2400-362K alkali-free glass fiber (linear density 2400, fiber diameter 17 μm) of Jushi Co., Ltd. was placed in a drying oven at 100°C and dried for 2 hours. After that, it was added to the above-mentioned siloxane-terminated polymer solution at room temperature and immersed for 0.5 hours. The glass fiber was taken out and allowed to stand at room temperature for 0.5 hours. The glass fiber impregnated with the polymer solution was then placed in a 140°C oven and vacuum dried for 2 hours to obtain organic-inorganic hybrid glass fiber.

[0054] Example 2

[0055] Synthesis of siloxane-terminated polymer: 0.87 g of p-methylanisole, a polymerization inhibitor, and 0.09 g of a catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (Pt atom effective content of 3000 ppm) were added to a flask and dissolved with 50 mL of toluene. 64.47 g (0.48 mol) of a hydrogenated double-capped end cap, 19.63 g (0.2 mol) of diallyl ether, 34.44 g (0.2 mol) of glycerol-A,A'-diallyl ether, and 47.58 g (0.25 mol) of vinyltriethoxysilane were dissolved with 100 mL of toluene and added dropwise to a flask at 85° C. The reaction was protected by nitrogen gas in the flask. The materials were added dropwise over a total of 2.5 hours, and the temperature was raised to 92° C. and kept for 1.5 hours to terminate the reaction. The siloxane-terminated polymer was obtained after cooling to room temperature.

[0056] Preparation of organic-inorganic hybrid glass fiber: The preparation method is the same as that in Example 1.

[0057] Example 3

[0058] Synthesis of siloxane-terminated polymer: 0.87 g of p-methylanisole, a polymerization inhibitor, and 0.09 g of a catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (Pt atom effective content is 3000 ppm) were added to a flask and dissolved with 50 mL of toluene. 64.47 g (0.48 mol) of a hydrogenated double end cap, 28.44 g (0.2 mol) of ethylene glycol diallyl ether, 42.86 g (0.2 mol) of trimethylolpropane diallyl ether, and 47.58 g (0.25 mol) of vinyltriethoxysilane were dissolved in 100 mL of toluene and added dropwise to a flask at 85 ° C. The reaction was protected by nitrogen gas, and the dropwise addition of the materials was completed in a total of 2.5 hours. After completion of the dripping, the temperature was raised to 92 ° C. and the reaction was maintained for 1.5 hours to terminate the reaction. The siloxane-terminated polymer was obtained after cooling to room temperature.

[0059] Preparation of organic-inorganic hybrid glass fiber: The preparation method is the same as that in Example 1.

[0060] Example 4

[0061] Synthesis of siloxane-terminated polymer: 0.87 g of p-methylanisole, a polymerization inhibitor, and 0.09 g of a chloroplatinic acid-divinyltetramethyldisiloxane complex (Pt atom effective content of 3000 ppm) were added to a flask and dissolved with 50 mL of toluene. 64.47 g (0.48 mol) of a hydrogenated double-capped end cap, 61.68 g (0.2 mol) of bisphenol A diallyl ether, 34.44 g (0.2 mol) of glycerol-A,A'-diallyl ether, and 47.58 g (0.25 mol) of vinyltriethoxysilane were dissolved in 100 mL of toluene and added dropwise to a flask at 85° C. The reaction was protected by nitrogen gas in the flask. The materials were added dropwise over a total of 2.5 hours. After completion of the addition, the temperature was raised to 92° C. and maintained for 1.5 hours to terminate the reaction. The siloxane-terminated polymer was obtained after the temperature was cooled to room temperature.

[0062] Preparation of organic-inorganic hybrid glass fiber: The preparation method is the same as that in Example 1.

[0063] Example 5

[0064] Synthesis of siloxane-terminated polymer: 0.87 g of p-methylanisole, an inhibitor, and 0.09 g of a catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (Pt atom effective content is 3000 ppm) were added to a flask and dissolved with 100 mL of toluene. 64.47 g (0.48 mol) of a hydrogenated double end cap, 30.84 g (0.1 mol) of bisphenol A diallyl ether, 9.81 g (0.1 mol) of diallyl ether, 42.86 g (0.2 mol) of trimethylolpropane diallyl ether, and 47.58 g (0.25 mol) of vinyltriethoxysilane were dissolved with 80 mL of toluene and added dropwise to a flask at 85 ° C. The reaction was protected by nitrogen gas, and the materials were added dropwise for a total of 2.5 hours. After the addition, the temperature was raised to 92 ° C. and the reaction was maintained for 1.5 hours to terminate the reaction. The siloxane-terminated polymer was obtained after cooling to room temperature.

[0065] Preparation of organic-inorganic hybrid glass fiber: The preparation method is the same as that in Example 1.

[0066] The siloxane-terminated polymer solution of Example 5 and the dried siloxane-terminated polymer were subjected to infrared spectroscopy analysis, and it was found that the siloxane-terminated polymer solution had a wavelength of 3300-3600 cm -1 There is an obvious hydroxyl absorption peak at 3300-3600 cm-1 in the infrared spectrum of the siloxane-terminated polymer after drying at 160℃*30min. -1 The hydroxyl absorption peak at the bottom is significantly reduced, which is due to the hydrolysis of the siloxane group and condensation with the hydroxyl group, indicating that the siloxane-terminated polymer has introduced hydroxyl groups and can undergo condensation reaction with the hydroxyl groups produced after the hydrolysis of the siloxane and solidify into a film.

[0067] Example 6

[0068] A glass fiber-polypropylene composite material comprises: 100 parts of CNOOC Shell HP500NA-Z polypropylene pellets with a melt index of 12 g / 10 min (melt index test standard is ASTM D1238:2023), 3 parts of a compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH), 0.5 parts of a composite antioxidant, the composite antioxidant comprising antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1, and 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 1.

[0069] Example 7

[0070] A glass fiber-polypropylene composite material comprises: 5 parts of a compatibilizer, maleic anhydride grafted polypropylene (PP-g-MAH), 24.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 1, and the remaining formula components are the same as those in Example 6.

[0071] Example 8

[0072] The glass fiber-polypropylene composite material comprises: 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 2, and the remaining formula components are the same as those in Example 6.

[0073] Example 9

[0074] A glass fiber-polypropylene composite material comprises: 5 parts of a compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH), 24.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 2, and the remaining formula components are the same as those in Example 6.

[0075] Example 10

[0076] The glass fiber-polypropylene composite material comprises: 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 3, and the remaining formula components are the same as those in Example 6.

[0077] Example 11

[0078] A glass fiber-polypropylene composite material comprises: 5 parts of a compatibilizer, maleic anhydride grafted polypropylene (PP-g-MAH), 24.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 3, and the remaining formula components are the same as those in Example 6.

[0079] Example 12

[0080] The glass fiber-polypropylene composite material comprises: 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 4, and the remaining formula components are the same as those in Example 6.

[0081] Example 13

[0082] A glass fiber-polypropylene composite material comprises: 5 parts of a compatibilizer, maleic anhydride grafted polypropylene (PP-g-MAH), 24.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 4, and the remaining formula components are the same as those in Example 6.

[0083] Example 14

[0084] The glass fiber-polypropylene composite material comprises: 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 5, and the remaining formula components are the same as those in Example 6.

[0085] Example 15

[0086] A glass fiber-polypropylene composite material comprises: 5 parts of a compatibilizer, maleic anhydride grafted polypropylene (PP-g-MAH), 24.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 5, and the remaining formula components are the same as those in Example 6.

[0087] Comparative Example 1

[0088] A glass fiber-polypropylene composite material comprises: 100 parts of CNOOC Shell HP500NA-Z polypropylene pellets with a melt index of 12 g / 10 min, 3 parts of a compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH), 0.5 parts of a composite antioxidant (the composite antioxidant comprises antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1), and 16.5 parts of untreated EDR17-2400-362K alkali-free glass fiber.

[0089] Comparative Example 2

[0090] A glass fiber-polypropylene composite material includes: 100 parts of CNOOC Shell HP500NA-Z polypropylene pellets with a melt index of 12 g / 10 min, 0.5 parts of a composite antioxidant, the composite antioxidant including antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1, and 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 1.

[0091] Comparative Example 3

[0092] A glass fiber-polypropylene composite material comprises: 100 parts of CNOOC Shell HP500NA-Z polypropylene pellets with a melt index of 12 g / 10 min, 0.5 parts of a compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH), 0.5 parts of a composite antioxidant, the composite antioxidant comprising antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1, and 24.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 1.

[0093] Comparative Example 4

[0094] Synthesis of siloxane-terminated polymer: 0.20 g of the polymerization inhibitor p-methylanisole and 0.06 g of the catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex were added to a flask and dissolved with 50 mL of toluene. 64.47 g (0.48 mol) of hydrogen-containing double head, 19.63 g (0.2 mol) of diallyl ether, 28.44 g (0.2 mol) of ethylene glycol diallyl ether, and 24.74 g (0.13 mol) of vinyltriethoxysilane were dissolved with 80 mL of toluene and added dropwise to the flask at 85° C. During the reaction, nitrogen was used to protect the reactants in the flask. The materials were added dropwise for a total of 2.5 hours. After the addition was completed, the temperature was raised to 92° C. and kept warm for 1.5 hours to terminate the reaction. The siloxane-terminated polymer was obtained after cooling to room temperature.

[0095] Preparation of organic-inorganic hybrid glass fiber: The preparation method is the same as that in Example 1.

[0096] Comparative Example 5

[0097] A glass fiber-polypropylene composite material comprises: 100 parts of CNOOC Shell HP500NA-Z polypropylene pellets with a melt index of 12 g / 10 min, 3 parts of a compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH), 0.5 parts of a composite antioxidant, the composite antioxidant comprising antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1, and 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Comparative Example 4.

[0098] Processing and molding of the glass fiber-polypropylene composite materials of Examples 6-15 and Comparative Examples 1-5:

[0099] Polypropylene, PP-g-MAH and antioxidant are uniformly mixed in a certain proportion, and added from the barrel feeding port by the starvation feeding method for plasticization at a plasticizing temperature of 250°C. Organic-inorganic hybrid glass fiber is added from the fiber feeding port and plasticized by fully mixing with the polypropylene melt.

[0100] A screw speed of 15 r / min was selected for direct injection molding experiments, an injection pressure of 100 MPa, an injection speed of 15 mm / s, a nozzle aperture of 5 mm, and performance tests were performed on standard specimens obtained by injection molding.

[0101] Performance tests of the glass fiber-polypropylene composite materials of Examples 6-15 and Comparative Examples 1-5:

[0102] SEM micromorphology: The surface morphology of the raw material EDR17-2400-362K alkali-free glass fiber and the glass fiber impregnated with the siloxane-terminated polymer solution prepared in Example 5 was observed by SEM. The observation results are listed in Figure 2, and the surface morphology of the glass fiber before and after being immersed in the siloxane-terminated polymer solution was analyzed.

[0103] The cross section of the glass fiber-polypropylene composite material was obtained by injection molding using liquid nitrogen brittle fracture and then subjected to gold spraying. The micromorphology of the sample cross section was observed using a scanning electron microscope (SEM). The observation results are listed in Figure 3 , thereby evaluating the distribution and interface bonding of the doped glass fibers in the polypropylene resin matrix.

[0104] Tensile Strength: The tensile strength of glass fiber-polypropylene composites was tested using a universal materials testing machine in accordance with GB / T1447-2005. The specimen dimensions were 150 × 10 × 4 mm, with a spacing of 115 mm, a gauge length of 80 mm, and a test speed of 10 mm / min.

[0105] Flexural Strength: The tensile strength of glass fiber-polypropylene composites was tested using a universal materials testing machine in accordance with GB / T1447-2005. The specimen dimensions were 80 × 10 × 4 mm, with a gauge length of 64 mm.

[0106] Unnotched impact strength: Referring to GB / T1451-2005, the simply supported unnotched impact strength of glass fiber-polypropylene composites was tested using a pendulum impact tester. The specimen dimensions were 80 × 10 × 4 mm, with a gauge length of 70 mm.

[0107] Heat resistance test: Referring to ASTM D 648, an oil bath heating apparatus and a device for generating bending stress were used to test the load deflection temperature of the glass fiber-polypropylene composite material, thereby evaluating its heat resistance.

[0108] The performance test results of the glass fiber-polypropylene composite materials of Examples 6-15 and Comparative Examples 1-5 are listed in Table 1.

[0109] Table 1

[0110]

[0111] From the analysis of the results in Table 1, it can be seen that in Examples 6-15, a siloxane-terminated polymer is designed and dip-coated on the surface of the glass fiber. The Si-OR siloxane groups are hydrolyzed and condensed to form an anchoring effect with the hydroxyl groups on the surface of the glass fiber, and the hydroxyl groups in the polymer segments can undergo a ring-opening reaction with the maleic anhydride in the compatibilizer PP-g-MAH at high temperature, thereby improving the compatibility of the glass fiber and the polypropylene matrix. The corresponding mechanical strength, impact resistance and heat resistance are also significantly increased. Among them, the heat deformation temperature of the samples prepared in Examples 6-15 are all higher than 150°C, the heat deformation temperature of the sample with 16.5 parts of inorganic-organic hybrid glass fiber is between 150-160°C, and the heat deformation temperature of the sample with the inorganic-organic hybrid glass fiber content increased to 24.5 parts is between 160-170°C. The increase in heat deformation temperature indicates that the sample requires a higher temperature to deform under a certain load, and its heat resistance is improved.

[0112] from Figure 2 It can be seen from the SEM image that the glass fiber not impregnated with the polymer is composed of silicon dioxide and other oxides and has a smooth appearance. The glass fiber impregnated with the siloxane-terminated polymer solution prepared in Example 5 has a rough appearance, and the polymer molecules will be deposited on the surface of the glass fiber, changing the smooth appearance characteristics of the glass fiber.

[0113] Regarding the compatibility of glass fiber with polypropylene matrix, Figure 3 The SEM images also show that the glass fibers of Examples 6-9 are not only more evenly dispersed in the polypropylene melt but also form a very tight interface with the polypropylene. In contrast, the glass fibers of Comparative Examples 1-5 have larger gaps between them and the polypropylene, indicating poor interface bonding. While Comparative Examples 1-5 also improve the mechanical properties and heat resistance of polypropylene composites by adding glass fibers or inorganic-organic hybrid glass fibers, the glass fibers, as inorganic materials, do not form a strong bond with the polypropylene matrix, thus failing to achieve the desired modification goal. There is still room for improvement in performance.

[0114] Comparative Example 1 did not use the siloxane-terminated polymer to impregnate the glass fiber. Instead, the original glass fiber was directly blended with polypropylene and a compatibilizer. The resulting composite material had a poor interface bonding effect between the glass fiber and the polypropylene ( Figure 3 ), and the mechanical properties, impact resistance and heat resistance corresponding to Comparative Example 1 are significantly lower than those of Examples 6-15.

[0115] Comparative Example 2 did not use PP-g-MAH compatibilizer, resulting in poor interface bonding between glass fiber and polypropylene in the composite material ( Figure 3 ), and the mechanical properties, impact resistance and heat resistance corresponding to Comparative Example 2 are significantly lower than those of Examples 6-15.

[0116] The amount of compatibilizer used in Comparative Example 3 is only 0.5 parts, which is obviously too low, resulting in poor interface bonding between glass fiber and polypropylene in the composite material ( Figure 3 ), and the mechanical properties, impact resistance and heat resistance corresponding to Comparative Example 3 are significantly lower than those of Examples 6-15.

[0117] Comparative Example 4 synthesized a siloxane-terminated polymer, using diallyl ether and ethylene glycol diallyl ether as diene monomers to undergo a hydrosilylation reaction with hydrogenated silicone oil, and using vinyl triethoxysilane as a capping agent. No hydroxyl group was introduced into the polymer backbone, resulting in a lack of chemical linking sites with the PP-g-MAH compatibilizer. However, Figure 3 From the SEM images, it can be seen that the interface gap between the inorganic-organic hybrid glass fiber and polypropylene prepared in Example 4 is significantly smaller, which is slightly different from that in Examples 6-9. The mechanical properties, impact resistance and heat resistance of the composite material corresponding to Example 5 are still lower than those in Examples 6-15, but relatively closer.

[0118] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or make equivalent replacements for parts thereof. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention. Although the above describes the specific implementation methods of the present invention, it is not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that, based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. A siloxane-terminated polymer, characterized in that Each end of the polymer has at least two siloxane groups, and the middle of the polymer chain contains at least one hydroxyl group. The corresponding structural formula is: wherein R1, R2, and R3 are the same or different and contain 1 to 20 atoms, and the groups of R1, R2, and R3 are selected from hydrogen atoms, alkyl groups, or alkoxy groups, and at least one of R1, R2, and R3 is selected from alkoxy groups; R4, R5, R6, and R7 are the same or different and contain 1 to 20 carbon atoms. The groups of R4, R5, R6, and R7 are selected from: alkyl groups of 1 to 20 carbon atoms or phenyl groups; R8 contains 4 to 54 atoms, and R9 does not contain nitrogen, sulfur, or phosphorus; R9 is different from R8. R9 contains 4 to 54 atoms, R9 contains at least one hydroxyl group, and R9 does not contain N, S, or P elements. m and n are the same or different and are selected from non-zero positive integers.

2. The method for preparing a siloxane-terminated polymer according to claim 1, wherein The diene monomer is reacted with hydrogen-containing silicone oil to form a hydrosilylation reaction; Preferably, the hydrogen-containing silicone oil is 1,1,3,3-tetramethyldisiloxane (hydrogen-containing double-headed); Preferably, the diene monomer is a terminal diene monomer, and the unsaturated double bonds are located at both ends of the molecule; Preferably, the end-capping agent is selected from any one or more of vinyldimethylmethoxysilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane and vinyltriisopropoxysilane; Furthermore, the preparation method of the siloxane-terminated polymer includes: conducting a hydrosilylation reaction of hydrogenated silicone oil and a diene monomer according to a molar ratio of n(Si-H):n(C=C)=(0.8-1):1; Furthermore, the preparation method of the siloxane-terminated polymer includes: adding a polymerization inhibitor and a catalyst to a hydrosilylation reaction, reacting the hydrosilylation reaction at 70-90° C. for 2-6 hours, then heating to 80-100° C. and keeping the temperature for 1-4 hours; The polymerization inhibitor is selected from p-methylanisole; The catalyst is selected from any one of chloroplatinic acid or chloroplatinic acid vinyl complex.

3. A use, characterized in that, Use of the siloxane-terminated polymer according to claim 1 in the preparation of inorganic-organic hybrid materials.

4. An inorganic-organic hybrid glass fiber, characterized in that The inorganic-organic hybrid glass fiber is obtained by impregnating glass fiber with the siloxane-terminated polymer solution according to claim 1, and then taking out the impregnated glass fiber and drying it; The drying includes: standing drying at room temperature and drying at a high temperature of 100-200°C; Preferably, the immersion time is 1-4 hours; Preferably, the drying time at room temperature is 0.5-1 hour; Preferably, the drying time at a high temperature of 100-200° C. is 1-4 hours; Preferably, the solvent of the siloxane-terminated polymer solution is toluene, ethyl acetate, butyl acetate or propylene glycol methyl ether acetate.

5. A use, characterized in that, Use of the inorganic-organic hybrid glass fiber according to claim 4 in the preparation of polyolefin composite materials.

6. A polypropylene composite material, characterized in that The composite material comprises the following raw materials: polypropylene pellets, a compatibilizer, an antioxidant, and the above-mentioned inorganic-organic hybrid glass fiber; Preferably, the melt index of the polypropylene pellets is 1-20 g / 10 min, and the test standard for the melt index is ASTM D1238:2023; Preferably, the compatibilizer is selected from any one or two of polyethylene grafted maleic anhydride (PE-g-MAH) and polypropylene grafted maleic anhydride (PP-g-MAH); Preferably, the antioxidant is selected from any one or two of phosphite antioxidants and hindered phenol antioxidants; Furthermore, the polypropylene composite material is composed of the following components in parts by weight: 90-110 parts of polypropylene pellets, 2-10 parts of a compatibilizer, 0.1-2 parts of an antioxidant, and 10-50 parts of an inorganic-organic hybrid glass fiber; Preferably, the polypropylene composite material is composed of the following components in parts by weight: 90-110 parts of polypropylene pellets, 3-8 parts of a compatibilizer, 0.1-1 part of an antioxidant, and 10-40 parts of inorganic-organic hybrid glass fibers.

7. The method for preparing the polypropylene composite material according to claim 6, wherein: Mix all the components in proportion and add them into the plastic mixer for plasticizing and mixing; Wherein, the plasticizing temperature is 200-300°C.

8. A use, characterized in that, Use of the polypropylene composite material described in claim 6 in hot melt adhesive dispensing equipment.

9. A use, characterized in that, Application of the polypropylene composite material according to claim 6 in the fields of semiconductor packaging, surface mount technology (SMT) and electronic components.

10. High temperature resistant polypropylene dispensing cylinder, characterized in that: Obtained by processing and molding the polypropylene composite material according to claim 6; Wherein, the processing and molding includes: injection molding or extrusion molding.

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