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

Abstract

The present application provides a siloxane-terminated polymer and a preparation method thereof, inorganic-organic hybrid glass fiber impregnated with the polymer, polypropylene composite material and a preparation method thereof, and a corresponding high-temperature-resistant polypropylene dispensing barrel. The siloxane-terminated polymer is synthesized by hydrosilylation, and contains hydrolysable siloxane groups at both ends of the molecular chain and cross-linkable hydroxyl groups in the middle of the molecular chain. The glass fiber is impregnated with the polymer to form a coating on the surface of the glass fiber to obtain inorganic-organic hybrid glass fiber. The hybrid glass fiber is added to the polypropylene composite material to bond the glass fiber and the polypropylene matrix through chemical bonds, greatly improving the compatibility of the two and further improving the mechanical properties and heat distortion temperature of the polypropylene composite material. The heat distortion temperature of the polypropylene composite material can reach more than 160 DEG C, thereby meeting the requirement of high-temperature sizing process on the high-temperature resistance of the dispensing barrel material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polypropylene modification, in particular 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 barrel. BACKGROUND

[0002] Hot melt adhesive (HMA) is a solvent-free, plastic adhesive. Its physical state changes with temperature within a certain temperature range, while its chemical properties remain unchanged. It is not only environmentally friendly, but also can quickly solidify after stopping heating. Hot melt adhesive is stored in solid form. When used, it is heated to a specific temperature (the melting point of hot melt adhesive is between 100℃ and 200℃, which varies due to different specific formulations) by a heating device, so that it becomes liquid or viscous state, so as to obtain sufficient flowability, thereby smoothly passing through the dispensing needle, and forming the required pattern or coating area as needed. Therefore, unlike many other types of adhesives, hot melt adhesive must be heated to a molten state before application, and hot melt adhesive needs to be continuously heated during the entire dispensing process to ensure that hot melt adhesive in a molten state has a flow phase, thereby ensuring the accuracy and effect of dispensing.

[0003] On the other hand, in the field of semiconductor packaging testing, surface mount technology (SMT) and electronic components, the adhesive coating requires high yield and high precision. The commonly used adhesives have high viscosity and low flowability at room temperature. For these high-viscosity adhesives, it is necessary to reduce the viscosity and improve the flowability of the adhesives under heating conditions, reduce the bubbles in the adhesives, and help to more uniformly fill the small gaps or achieve more fine patterned coating, thereby improving the dispensing accuracy and coating consistency of the adhesives.

[0004] In view of the characteristics of hot melt adhesive and adhesive coating process in the field of semiconductor packaging testing, there is an increasing demand for materials that can load adhesives under high temperature (above 160℃) conditions. Hot melt adhesive and electronic adhesives with high requirements on dispensing process precision require high-temperature adhesive application process. However, polypropylene used for dispensing barrels is a thermoplastic material, which is difficult to resist high temperature above 160℃. The low heat distortion temperature of the dispensing barrel material will cause dripping and stringing at the dispensing nozzle under high temperature, which has a great impact on the quality and efficiency of dispensing. SUMMARY

[0005] The purpose of this 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 distortion temperature of the polypropylene dispensing cartridge can be increased to above 160°C, which can meet the heat resistance requirements of the dispensing cartridge material in high-temperature dispensing processes.

[0006] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, a siloxane-terminated polymer, wherein each end of the polymer has at least two siloxane groups, and the polymer segment contains at least one hydroxyl group, with the corresponding structural formula as follows:

[0008]

[0009] R1, R2, and R3 may be the same or different, and contain 1 to 20 atoms. 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 or ethoxy groups.

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

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

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

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

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

[0016] Secondly, the preparation method of the siloxane-terminated polymer described above includes: performing a hydrosilylation reaction between a terminator, a diene monomer, and a hydrogen-containing silicone oil.

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

[0018] Preferably, the diene monomer is an end diene monomer, i.e. the unsaturated double bond is located at both ends of the molecule; more preferably, the diene monomer is selected from any one or more of: or

[0019] Preferably, the end capping agent is selected from any one or more of vinyl dimethyl methoxysilane, vinyl methyl dimethoxysilane, vinyl trimethoxysilane, vinyl dimethyl ethoxysilane, vinyl methyl diethoxysilane, vinyl triethoxysilane and vinyl triisopropoxysilane.

[0020] Further, the method for preparing the silicone end-capped polymer comprises: carrying out a hydrosilylation reaction between the hydrogen-containing silicone oil and the diene monomer at a molar ratio of n(Si-H):n(C=C)=(0.8-1):1;

[0021] Preferably, the hydrosilylation reaction is carried out at a molar ratio of n(Si-H):n(C=C)=(0.9-1):1;

[0022] Further, the method for preparing the silicone end-capped polymer comprises: adding a polymerization inhibitor and a catalyst in the hydrosilylation reaction, the hydrosilylation reaction is carried out at 70-90°C for 2-6 hours, and then the temperature is raised to 80-100°C for 1-4 hours.

[0023] Preferably, the polymerization inhibitor is selected from p-methyl anisole;

[0024] Preferably, the catalyst is selected from any one of chloroplatinic acid or vinyl complex of chloroplatinic acid; more preferably, the catalyst is selected from chloroplatinic acid-divinyl tetramethyl disiloxane complex.

[0025] In a third aspect, a use comprises: a use of the silicone end-capped polymer described above in the preparation of inorganic-organic hybrid materials.

[0026] In a fourth aspect, an inorganic-organic hybrid glass fiber is obtained by impregnating a glass fiber in a solution of the silicone end-capped polymer described above, and then taking out the impregnated glass fiber for drying.

[0027] Preferably, the drying comprises: static drying at room temperature and drying at a high temperature of 100-200°C.

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

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

[0030] Preferably, the drying time at high temperature of 100-200℃ 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] In the fifth aspect, a use, comprising: the use of the inorganic-organic hybrid glass fiber as described above in the preparation of a polyolefin composite material.

[0033] In the sixth aspect, a polypropylene composite material, comprising: polypropylene granules, a compatibilizer, an antioxidant, and the inorganic-organic hybrid glass fiber as described above.

[0034] Preferably, the polypropylene granules have a melt index of 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 phenolic antioxidants, and more preferably, the antioxidant is a composite antioxidant obtained by combining the phosphite antioxidant and the hindered phenolic antioxidant.

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

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

[0039] In the seventh aspect, a method for preparing the polypropylene composite material as described above, comprising: mixing all components uniformly according to the proportions, and feeding into a plastic mixing machine for plasticizing and mixing.

[0040] Preferably, the plasticizing temperature is 200-300℃, and more preferably, the plasticizing temperature is 250℃.

[0041] In the eighth aspect, a use, the application of the polypropylene composite material as described above to hot melt adhesive dispensing equipment.

[0042] In a ninth aspect, a use of the polypropylene composite material in the field of semiconductor packaging, surface mount technology (SMT) and electronic components.

[0043] In a tenth aspect, a high-temperature-resistant polypropylene glue dispensing barrel is formed by processing and molding the polypropylene composite material described above.

[0044] The processing and molding includes injection molding or extrusion molding.

[0045] The present application has the following advantages: a siloxane-terminated polymer is synthesized by hydrosilylation, which contains hydrolysable siloxane groups at both ends of the molecular chain and cross-linkable hydroxyl groups in the middle of the molecular chain, the polymer is used for impregnating treatment of glass fibers to form a coating on the surface of the glass fibers, and inorganic-organic hybrid glass fibers are obtained. The hydroxyl groups in the middle of the molecular chain of the polymer and the grafted maleic anhydride of the compatibilizer can react at high temperatures to bond the glass fibers and the polypropylene matrix through chemical bonds, greatly improving the compatibility of the two and further improving the mechanical properties and heat distortion temperature of the polypropylene composite material. The heat distortion temperature of the polypropylene composite material as a glue dispensing barrel can reach above 160℃, which can meet the requirements of high-temperature sizing process for the high-temperature resistance of the glue dispensing barrel material. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 The infrared spectrum comparison chart of the siloxane-terminated polymer solution prepared for Example 5 and the cured product thereof.

[0047] Figure 2 The SEM observation chart of the glass fibers impregnated with the siloxane-terminated polymer solution of Example 5 and the glass fibers without impregnating the polymer.

[0048] Figure 3 The SEM observation chart of the fracture cross section of the glass fiber-polypropylene composite material sample of Examples 6-9 and Comparative Examples 1-5. DETAILED DESCRIPTION

[0049] The technical solutions in the embodiments will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application. It should be noted that the terms used herein are only intended to describe the specific embodiments, and are not intended to limit the exemplary embodiments according to the present application. As used herein, the singular form is intended to include the plural form, unless the context clearly indicates otherwise, and it should also be understood that the terms "comprise" and / or "include" as used in the specification indicate the presence of the features, steps, operations, devices, components and / or their combinations.

[0050] If the specific conditions of the experiments in the embodiments are not specified, the general conditions in the art or the conditions recommended by the reagent companies are usually used; the materials, reagents and the like used in the embodiments can be purchased through commercial channels, unless otherwise specified.

[0051] Example 1

[0052] Synthesis of siloxane-terminated polymer: 0.87 g of polymerization inhibitor p-methylanisole and 0.09 g of catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (effective content of Pt atom is 3000 ppm) were added to a flask, dissolved in 50 mL of toluene, and 64.47 g (0.48 mol) of hydrogen-containing 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 the mixture was added dropwise into the flask at 85°C, and the reaction was protected by nitrogen during the reaction. The total dropwise time was 2.5 hours, and the reaction was completed by increasing the temperature to 92°C for 1.5 hours. After cooling to room temperature, the siloxane-terminated polymer was obtained.

[0053] Preparation of organic-inorganic hybrid glass fiber: EDR17-2400-362K alkali-free glass fiber (linear density 2400, fiber diameter 17 μm) from Corning Incorporated was dried in a dry box at 100°C for 2 hours, then added to the above siloxane-terminated polymer solution at room temperature, and the glass fiber was immersed in the polymer solution for 0.5 hours. The glass fiber was taken out and placed at room temperature for 0.5 hours. The glass fiber immersed in the polymer solution was placed in a 140°C oven for vacuum drying for 2 hours, and the organic-inorganic hybrid glass fiber was obtained.

[0054] Example 2

[0055] Synthesis of siloxane-terminated polymer: Add 0.87 g of polymerization inhibitor p-methyl anisole and 0.09 g of catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (3000 ppm effective content of Pt atom) into a flask, dissolve with 50 mL of toluene, dissolve 64.47 g (0.48 mol) of hydrogen-containing double end cap, 19.63 g (0.2 mol) of diallyl ether, 34.44 g (0.2 mol) of glycerol-Α,Α'-diallyl ether and 47.58 g (0.25 mol) of vinyltriethoxysilane with 100 mL of toluene, control the temperature at 85°C, drop into the flask, protect the reactants in the flask with nitrogen during the reaction, drop the total material for 2.5 hours, after dropping, raise the temperature to 92°C for 1.5 hours to end the reaction, cool to room temperature to obtain the siloxane-terminated polymer.

[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: Add 0.87 g of polymerization inhibitor p-methyl anisole and 0.09 g of catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (3000 ppm effective content of Pt atom) into a flask, dissolve with 50 mL of toluene, dissolve 64.47 g (0.48 mol) of hydrogen-containing double end cap, 19.63 g (0.2 mol) of diallyl ether, 34.44 g (0.2 mol) of glycerol-Α,Α'-diallyl ether and 47.58 g (0.25 mol) of vinyltriethoxysilane with 100 mL of toluene, control the temperature at 85°C, drop into the flask, protect the reactants in the flask with nitrogen during the reaction, drop the total material for 2.5 hours, after dropping, raise the temperature to 92°C for 1.5 hours to end the reaction, cool to room temperature to obtain the siloxane-terminated polymer.

[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: Add 0.87 g of polymerization inhibitor p-methyl anisole and 0.09 g of catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (effective content of Pt atom is 3000 ppm) into a flask, dissolve with 50 mL of toluene, dissolve 64.47 g (0.48 mol) of hydrogen-containing double seal head, 61.68 g (0.2 mol) of bisphenol A diallyl ether, 34.44 g (0.2 mol) of glycerol-Α,Α'-diallyl ether and 47.58 g (0.25 mol) of vinyltriethoxysilane with 100 mL of toluene, control the temperature at 85°C and drop into the flask, use nitrogen to protect the reactants in the flask during the reaction, drop the total material for 2.5 hours, after dropping, raise the temperature to 92°C for 1.5 hours to end the reaction, and then cool to room temperature to obtain the siloxane-terminated polymer.

[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: Add 0.87 g of polymerization inhibitor p-methyl anisole and 0.09 g of catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex (effective content of Pt atom is 3000 ppm) into a flask, dissolve with 50 mL of toluene, dissolve 64.47 g (0.48 mol) of hydrogen-containing double seal head, 61.68 g (0.2 mol) of bisphenol A diallyl ether, 34.44 g (0.2 mol) of glycerol-Α,Α'-diallyl ether and 47.58 g (0.25 mol) of vinyltriethoxysilane with 100 mL of toluene, control the temperature at 85°C and drop into the flask, use nitrogen to protect the reactants in the flask during the reaction, drop the total material for 2.5 hours, after dropping, raise the temperature to 92°C for 1.5 hours to end the reaction, and then cool to room temperature to obtain the siloxane-terminated polymer.

[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 are analyzed by infrared spectroscopy, and it is found that the siloxane-terminated polymer solution contains obvious hydroxyl absorption peaks at 3300-3600 cm -1 -1 after drying at 160°C for 30 minutes, the hydroxyl absorption peaks at 3300-3600 cm -1 -1 of the siloxane-terminated polymer are obviously reduced, which is due to the hydrolysis of siloxane groups and condensation with hydroxyl groups, indicating that the siloxane-terminated polymer has introduced hydroxyl groups and can undergo condensation reaction with the hydroxyl groups generated by the hydrolysis of siloxane and solidify into a film.

[0067] Example 6

[0068] Glass fiber-polypropylene composite material comprising: 100 parts of Zhonghai Shell HP500NA-Z type polypropylene granules with a melt index of 12 g / 10 min (the test standard for melt index 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, 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Example 1.

[0069] Example 7

[0070] Glass fiber-polypropylene composite material comprising: 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 formulation components are the same as in Example 6.

[0071] Example 8

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

[0073] Example 9

[0074] Glass fiber-polypropylene composite material comprising: 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 formulation components are the same as in Example 6.

[0075] Example 10

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

[0077] Example 11

[0078] Glass fiber-polypropylene composite material comprising: 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 formulation components are the same as in Example 6.

[0079] Example 12

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

[0081] Example 13

[0082] Glass fiber-polypropylene composite comprising: compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH) 5 parts, organic-inorganic hybrid glass fiber prepared in Example 5 24.5 parts, and the remaining formulation components are the same as in Example 6.

[0083] Example 14

[0084] Glass fiber-polypropylene composite comprising: organic-inorganic hybrid glass fiber prepared in Example 5 16.5 parts, and the remaining formulation components are the same as in Example 6.

[0085] Example 15

[0086] Glass fiber-polypropylene composite comprising: compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH) 5 parts, organic-inorganic hybrid glass fiber prepared in Example 5 24.5 parts, and the remaining formulation components are the same as in Example 6.

[0087] Comparative Example 1

[0088] Glass fiber-polypropylene composite comprising: CNOOC Shell HP500NA-Z polypropylene pellets 100 parts, melt index 12 g / 10 min, compatibilizer maleic anhydride grafted polypropylene (PP-g-MAH) 3 parts, composite antioxidant 0.5 parts, the composite antioxidant comprising antioxidant 168 and antioxidant 1010 in a mass ratio of 1 : 1, untreated EDR 17-2400-362K E-glass fiber 16.5 parts.

[0089] Comparative Example 2

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

[0091] Comparative Example 3

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

[0093] Comparative Example 4

[0094] Synthesis of siloxane end-capped polymer: The polymerization inhibitor p-methyl anisole 0.20 g and catalyst chloroplatinic acid-divinyltetramethyldisiloxane complex 0.06 g were added into a flask, dissolved in 50 mL of toluene, and the hydrogen-containing double end cap 64.47 g (0.48 mol), diallyl ether 19.63 g (0.2 mol), ethylene glycol diallyl ether 28.44 g (0.2 mol), and vinyltriethoxysilane 24.74 g (0.13 mol) were dissolved in 80 mL of toluene, and the mixture was added dropwise into the flask at 85°C, with nitrogen gas being used to protect the reaction in the flask. The total dropwise addition time was 2.5 hours, after which the temperature was increased to 92°C for 1.5 hours to complete the reaction. After cooling to room temperature, the siloxane end-capped polymer was obtained.

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

[0096] Comparative Example 5

[0097] Glass fiber-polypropylene composite material, comprising: 100 parts of Zhonghai Shell HP500NA-Z polypropylene pellets, having 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, and 16.5 parts of the organic-inorganic hybrid glass fiber prepared in Comparative Example 4, wherein the composite antioxidant comprises antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1.

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

[0099] The polypropylene, PP-g-MAH, and antioxidant were uniformly mixed in a certain proportion, and were plasticized by being added from the barrel feed port using a starved feeding method. The plasticization temperature was 250°C, and the organic-inorganic hybrid glass fiber was added from the fiber addition port and was plasticized by being fully mixed with the polypropylene melt.

[0100] Direct injection molding experiments were performed using a screw rotation speed of 15 r / min, an injection pressure of 100 MPa, an injection speed of 15 mm / s, and a nozzle aperture of 5 mm. The standard samples obtained by injection molding were tested for performance.

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

[0102] SEM micro-morphology: The raw material EDR17-2400-362K alkali-free glass fiber and the glass fiber after being impregnated with the siloxane end-capped polymer solution prepared in Example 5 were observed for surface morphology by SEM. The observation results are shown in Table 1. Figure 2The surface morphology of the glass fiber before and after the solution of the siloxane-terminated polymer was analyzed.

[0103] The glass fiber-polypropylene composite samples were broken by liquid nitrogen brittle fracture injection molding, and the cross sections were obtained and treated by gold spraying. The microstructure of the sample cross section was observed by using an electron scanning microscope (SEM), and the observation results are listed in Table 1. Figure 3 The distribution and interface bonding of the glass fiber doped therein in the polypropylene resin matrix were evaluated.

[0104] Tensile strength: The tensile strength of the glass fiber-polypropylene composite was detected by using a universal material testing machine according to the GB / T1447-2005 standard. The size of the sample was 150x10x4mm, the interval was 115mm, the gauge length was 80mm, and the test speed was 10mm / min.

[0105] Bending strength: The tensile strength of the glass fiber-polypropylene composite was detected by using a universal material testing machine according to the GB / T1447-2005 standard. The size of the sample was 80x10x4mm, and the gauge length was 64mm.

[0106] Notched impact strength: The notched impact strength of the glass fiber-polypropylene composite was detected by using a pendulum impact testing machine according to the GB / T1451-2005 standard. The size of the sample was 80x10x4mm, and the gauge length was 70mm.

[0107] Heat resistance test: The heat resistance of the glass fiber-polypropylene composite was evaluated by using an oil bath heating device and a bending stress generating device to test the load deformation temperature of the glass fiber-polypropylene composite according to the ASTM D 648 standard.

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

[0109] Table 1

[0110]

[0111] From the result analysis of Table 1, it can be seen that the Examples 6-15 are designed to coat the surface of the glass fiber with the siloxane group terminated polymer, in which the Si-OR siloxane group is hydrolyzed and condensed to form an anchor with the hydroxyl group on the surface of the glass fiber, and the hydroxyl group in the polymer segment can undergo ring-opening reaction with the maleic anhydride in the compatibilizer PP-g-MAH at high temperature, thereby improving the compatibility of the glass fiber with the polypropylene matrix, and the mechanical strength, impact resistance and heat resistance of the corresponding composite material are also significantly increased. In the Examples 6-15, the heat distortion temperature of the prepared sample is higher than 150°C, the heat distortion temperature of the sample with 16.5 parts of inorganic-organic hybrid glass fiber is between 150-160°C, and the heat distortion temperature of the sample with 24.5 parts of inorganic-organic hybrid glass fiber is between 160-170°C. The increase of the heat distortion temperature indicates that the sample needs a higher temperature to deform under a certain load, and the heat resistance is improved.

[0112] From the SEM images of Figure 2 It can be seen that the glass fiber without impregnating the polymer is composed of silicon dioxide and other oxides, and has a smooth appearance. After impregnation with the siloxane terminated polymer solution prepared in Example 5, the glass fiber has a rough and uneven appearance, and the polymer molecules are deposited on the surface of the glass fiber, changing the smooth appearance of the glass fiber.

[0113] For the compatibility of the glass fiber with the polypropylene matrix, it can also be seen from the SEM images of Figure 3 The glass fiber of Examples 6-9 can be more uniformly dispersed in the polypropylene melt, and the interface between the glass fiber and the polypropylene is very close. The gap between the glass fiber and the polypropylene in Comparative Examples 1-5 is larger, and the interface between the two is poor. Although Comparative Examples 1-5 also improve the mechanical properties and heat resistance of the polypropylene composite material by adding glass fiber or inorganic-organic hybrid glass fiber, the glass fiber as an inorganic material does not form strong adhesion with the polypropylene matrix, and the performance still has room for improvement.

[0114] Comparative Example 1 does not use siloxane group terminated polymer to coat the glass fiber, but uses the original glass fiber directly blended with polypropylene and compatibilizer, so that the interface bonding effect between the glass fiber and the polypropylene in the composite material is poor Figure 3 ), and the corresponding mechanical properties, impact resistance and heat resistance of Comparative Example 1 are significantly lower than those of Examples 6-15.

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

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

[0117] Comparative Example 4 synthesizes a siloxane-based capped polymer, using diallyl ether and ethylene glycol diallyl ether as a diene monomer and hydrogen-containing silicone oil for a silicon-hydrogen addition reaction, and using vinyl triethoxysilane as a capping agent, without introducing hydroxyl groups on the polymer main chain, resulting in a lack of chemical linking sites between the PP-g-MAH compatibilizer, but from the SEM image of Figure 3 , the interfacial gap between the inorganic-organic hybrid glass fiber prepared in Example 4 and the polypropylene is significantly smaller, and there is a slight gap compared to Examples 6-9, and the mechanical properties, impact resistance and heat resistance of the composite material corresponding to Example 5 are still lower than those of Examples 6-15, but are relatively closer.

[0118] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application, although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements of part thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application. Although the specific embodiments of the present application have been described above, they are not intended to limit the protection scope of the present application, and those skilled in the art should understand that various modifications or changes made to the technical solutions of the present application by those skilled in the art without creative labor are still within the protection scope of the present application.

Claims

1. A siloxane-terminated polymer characterized in that, Each end of the polymer is at least two siloxane groups, and at least one hydroxyl group is contained in the middle of the polymer chain segment, and the corresponding structural formula is: ； wherein R1, R2, R3 are the same or different, containing 1 to 20 atoms, and the groups of R1, R2, R3 are selected from: hydrogen atoms, alkyl groups or alkoxy groups, and at least one of R1, R2, R3 is selected from alkoxy groups; R4, R5, R6, R7 are the same or different, containing 1 to 20 carbon atoms, and the groups of R4, R5, R6, R7 are selected from: alkyl groups or phenyl groups with 1 to 20 carbon atoms; R8is selected from any one or more of , or . R9is selected from any one or more of or any one or more of m and n are the same or different, and are selected from positive integers other than zero.

2. The method of claim 1, wherein the siloxane-terminated polymer is prepared by the process comprising: The end-capping agent, the diene monomer and the hydrogen-containing silane are subjected to a hydrosilylation reaction to obtain; wherein the hydrogen-containing silane is 1,1,3,3-tetramethyldisiloxane; The diene monomer is an end diene monomer, and the unsaturated double bond is located at both ends of the molecule; The end-capping agent is selected from any one or more of vinyl dimethyl methoxysilane, vinyl methyl dimethoxysilane, vinyl trimethoxysilane, vinyl dimethyl ethoxysilane, vinyl methyl diethoxysilane, vinyl triethoxysilane and vinyl triisopropoxysilane.

3. The method for preparing the siloxane-terminated polymer according to claim 2, characterized in that, The preparation method comprises: subjecting the hydrogen-containing silane and the diene monomer to a hydrosilylation reaction at a molar ratio of n(Si-H):n(C=C)=(0.8-1):

1.

4. The method for preparing the siloxane-terminated polymer according to claim 3, characterized in that, The preparation method comprises: adding a polymerization inhibitor and a catalyst in the hydrosilylation reaction, the hydrosilylation reaction is carried out at 70-90℃ for 2-6 hours, and then the temperature is raised to 80-100℃ for 1-4 hours.

5. The method for preparing the siloxane-terminated polymer according to claim 4, characterized in that, The polymerization inhibitor is selected from p-methyl anisole; And / or, the catalyst is selected from any one of chloroplatinic acid or vinyl complex of chloroplatinic acid.

6. Use, characterized in that, Use of the siloxane-terminated polymer of claim 1 in the preparation of inorganic-organic hybrid materials.

7. An inorganic-organic hybrid glass fiber, characterized in that, The inorganic-organic hybrid glass fiber is obtained by impregnating a solution of the siloxane-terminated polymer of claim 1 into glass fiber, and then taking out the impregnated glass fiber for drying; The drying comprises: standing at room temperature and drying, and drying at a high temperature of 100-200℃.

8. The inorganic-organic hybrid glass fiber according to claim 7, wherein, The impregnation time is 1-4 hours; And / or, the standing at room temperature and drying time is 0.5-1 hour; And / or, the drying at a high temperature of 100-200℃ is 1-4 hours; And / or, the solvent in the solution of the siloxane-terminated polymer is toluene, ethyl acetate, butyl acetate or propylene glycol methyl ether acetate.

9. Use, characterized in that, Use of the inorganic-organic hybrid glass fiber of any one of claims 7-8 in the preparation of polyolefin composites.

10. A polypropylene composite, characterized in that, The composite material comprises the following raw materials: polypropylene pellets, a compatibilizer, an antioxidant, and the inorganic-organic hybrid glass fiber of any one of claims 7-8.

11. The polypropylene composite of claim 10, wherein, The melt index of the polypropylene pellets is 1-20 g / 10 min, and the test standard of the melt index is ASTM D1238:2023; And / or, the compatibilizer is selected from any one or both of polyethylene grafted maleic anhydride and polypropylene grafted maleic anhydride; And / or, the antioxidant is selected from any one or both of phosphite antioxidants and hindered phenolic antioxidants.

12. The polypropylene composite of claim 10, wherein, The polypropylene composite material is composed of the following components in parts by weight: polypropylene granules 90-110 parts, compatibilizer 2-10 parts, antioxidant 0.1-2 parts, inorganic-organic hybrid glass fiber 10-50 parts.

13. The polypropylene composite of claim 10, wherein, The polypropylene composite material is composed of the following components in parts by weight: polypropylene granules 90-110 parts, compatibilizer 2-10 parts, antioxidant 0.1-2 parts, inorganic-organic hybrid glass fiber 10-50 parts.

14. Process for the production of polypropylene composites according to any one of claims 10 to 13, characterized in that, All components are mixed uniformly in proportion, and are fed into a plastic mixer for plasticizing and mixing; The plasticizing temperature is 200-300 DEG C.

15. An application characterized in that, The polypropylene composite material according to any one of claims 10-13 is applied to hot melt glue dispensing equipment.

16. An application characterized in that, The polypropylene composite material according to any one of claims 10-13 is applied to the fields of semiconductor packaging, surface mount technology and electronic components.

17. A high temperature resistant polypropylene glue dispensing cartridge, characterized in that, The polypropylene composite material according to any one of claims 10-13 is processed and molded to obtain; The processing and molding includes injection molding or extrusion molding.

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