Epoxy group-containing fluorosiloxane and application thereof in improving performance of nylon / polyester

Abstract

The invention provides epoxy group-containing fluorosiloxane and application thereof in improvement of nylon / polyester performance, and belongs to the technical field of new materials. According to the technical scheme, the epoxy modified polysiloxane auxiliary agent is synthesized. Polysiloxane has excellent high and low temperature resistance, wear resistance, lubricating property, weather resistance and the like. After epoxy modification, an epoxy group on a molecular chain can be subjected to a chemical chain extension reaction with an amino-terminated group and a carboxyl-terminated group in molecular structures of materials such as PA6 / PA66 / PET. The reaction not only improves the viscosity of the to-be-modified molecules, but also significantly improves the processability and low-temperature flexibility of the to-be-modified molecules. Meanwhile, the compatibility of polysiloxane and molecules to be modified is increased due to the introduction of the epoxy group, so that the synthesized epoxy modified polysiloxane cannot be separated out in a system, the stability of the material performance is ensured, and the effective modification of the nylon / polyester performance is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of new materials, and particularly to fluorosiloxanes containing epoxy groups and their applications in enhancing the properties of nylon / polyester. Background Art

[0002] In the field of materials science, nylon (such as PA6, PA66) and polyester (such as PET), as widely used polymer materials, play an important role in many industries. However, they have certain deficiencies in aspects such as their own wear resistance, and it is difficult to meet the requirements of some high-end application scenarios. Therefore, the research on enhancing their properties has always been the focus of the industry.

[0003] Currently, the methods for enhancing the properties of nylon / polyester mainly include the following several, but all have obvious defects:

[0004] Physical blending with wear-resistant additives method: The commonly used method is to physically blend some wear-resistant additives, such as silicone powder, molybdenum disulfide, polytetrafluoroethylene powder, ultra-high molecular weight polyethylene, graphite, etc. Due to the poor compatibility of these powders with nylon / polyester, they are likely to cause migration and precipitation during actual use, affecting the performance stability of the material. More critically, during the melt spinning process, problems such as broken filaments and unstable wire diameters occur, seriously restricting the processing and application of the material.

[0005] Chemical copolymerization method: By grafting some chemical groups during the synthesis of PA6 / PA66 / PET raw materials, the wear resistance of the material can be improved. However, this method often causes a significant increase in product cost, lacks sufficient competitiveness in terms of economy, has low practical value, and is difficult to achieve large-scale industrial application.

[0006] Chemical tackifying method: The industry also uses chemical tackifying and other schemes to improve the wear resistance of PA6 / PA66 / PET. However, on the one hand, this method requires a large investment in equipment and causes high energy consumption during the production process, increasing the production cost. On the other hand, when high-viscosity PA6 / PA66 / PET is subjected to wire drawing and extrusion, it has very high requirements for production equipment, processes, etc. Often, due to high viscosity, raw materials are blocked at the die head and other phenomena, seriously affecting production efficiency and product quality.

[0007] In summary, the existing methods for enhancing the properties of nylon / polyester have many problems, and there is an urgent need to develop a more efficient, economical, and feasible technical solution to meet the market demand for high-performance nylon / polyester materials. Summary of the Invention

[0008] The purpose of the present invention is to provide fluorosiloxanes containing epoxy groups and their applications in enhancing the properties of nylon / polyester, which can effectively enhance the properties of nylon / polyester.

[0009] To achieve the above-mentioned invention object, the present invention provides the following technical solutions:

[0010] The present invention provides a preparation method of a fluorosiloxane containing epoxy groups, comprising the following steps:

[0011] S1. Mix methyl / phenyltrimethoxysilane, tetramethyltetrahydrocyclotetrasiloxane and hexamethyldisiloxane, add catalyst 1, and carry out a first reaction to obtain product 1;

[0012] S2. Mix allyl glycidyl ether monomer, solvent and catalyst 2, add product 1, and carry out a second reaction to obtain product 2;

[0013] S3. Mix product 2, fluorinated acrylate monomer, acrylate monomer, crosslinking agent and initiator, and carry out a third reaction to obtain a fluorosiloxane containing epoxy groups.

[0014] Preferably, in S1, the catalyst 1 is concentrated sulfuric acid.

[0015] Preferably, the temperature of the first reaction is 70-90 °C;

[0016] The time of the first reaction is 3-4 h.

[0017] Preferably, in S1, purification treatment of product 1 is further included.

[0018] Preferably, in S2, the catalyst 2 is chloroplatinic acid-isopropanol;

[0019] The solvent is toluene.

[0020] Preferably, in S2, the temperature of the second reaction is 70-90 °C;

[0021] The time of the second reaction is 3-15 h;

[0022] In S2, purification treatment of product 2 is further included.

[0023] Preferably, in S3, the fluorinated acrylate monomer includes one or more of dodecafluoroheptyl methacrylate, hexafluorobutyl methacrylate or octafluoropentyl methacrylate;

[0024] The acrylate monomer includes one or more of 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, TAC, butyl acrylate, HEA, HPA, HEMA, HPMA or MMA;

[0025] The crosslinking agent includes vinyl monomers or vinyl siloxane coupling agents. The vinyl monomers include acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, N-methylol acrylamide or diacetone acrylamide;

[0026] The vinyl siloxane coupling agents include vinyltriethoxysilane, vinyltrimethoxysilane or vinyltris(β-methoxyethoxy)silane;

[0027] The initiator is a free radical polymerization initiator, and the free radical polymerization initiator includes azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-butyl peroxybenzoyl or methyl ethyl ketone peroxide;

[0028] The temperature of the third reaction is 60-80 °C;

[0029] The time of the third reaction is 3-12 h.

[0030] The present invention also provides an epoxy group-containing fluorosiloxane prepared by the above preparation method.

[0031] The present invention also provides the application of the above epoxy group-containing fluorosiloxane in improving the performance of nylon or polyester materials.

[0032] The nylon or polyester materials include but are not limited to PA6, PA66, PA11, PA12, PA46, PA6T, PA9T, PA10T, PBT, PET, PCT, PEN, PTT, PA6 / 66, PA610, PA612, PPA, PARA, PETG or PCTG, etc.

[0033] The present invention also provides a method for modifying nylon or polyester, including the following steps:

[0034] Mix the above epoxy group-containing fluorosiloxane with nylon or polyester materials and extrude to obtain a modified material.

[0035] The technical effects and advantages of the present invention:

[0036] This technical solution synthesizes an epoxy-modified polysiloxane auxiliary. Polysiloxane itself has excellent high and low temperature resistance, wear resistance, lubrication performance, weather resistance, etc. After epoxy modification, the epoxy groups on its molecular chain can carry out chemical chain extension reactions with the terminal amino groups and terminal carboxyl groups in the molecular structures of PA6 / PA66 / PET. This reaction not only increases the viscosity of PA6 / PA66 / PET molecules, but also significantly improves their processing performance and low temperature toughness. At the same time, the introduction of epoxy groups increases the compatibility between polysiloxane and PA6 / PA66 / PET, ensuring that the synthesized epoxy-modified polysiloxane does not precipitate in the PA6 / PA66 / PET system and guaranteeing the stability of material properties.

[0037] Due to the good lubrication performance of siloxane, the synthesized epoxy-modified polysiloxane greatly improves the processing and extrusion performance of PA6 / PA66 / PET. Compared with traditional chemical viscosity-increasing methods, this solution does not have the phenomenon of raw material blockage at the die head due to high viscosity, reduces the requirements for production equipment and processes, reduces equipment investment and energy consumption, improves production efficiency, and reduces production costs.

[0038] The fluorosilicon group containing epoxy groups synthesized in this invention significantly improves the wear resistance of the prepared nylon / polyester braided network tubes due to the high wear resistance of fluorosilicon elements. This enables the modified nylon / polyester materials to meet more application scenarios with high wear resistance requirements, such as high-end textile products, mechanical parts, aerospace and other fields, and has broad application prospects and market value.

[0039] In the preparation process of the solution provided by this invention, the raw materials and reaction conditions used are relatively mild, reducing environmental pollution. Through the effective modification of nylon and polyester materials, the service life of the materials is extended, material waste and waste generation are reduced, which conforms to the development concept of green environmental protection and has good social benefits. Specific embodiments

[0040] This invention provides a preparation method of a fluorosiloxane containing epoxy groups, which includes the following steps:

[0041] S1. Mix methyl / phenyltrimethoxysilane, tetramethyltetrahydrocyclotetrasiloxane and hexamethyldisiloxane, add catalyst 1, and carry out the first reaction to obtain product 1;

[0042] S2. Mix allyl glycidyl ether monomer, solvent and catalyst 2, add product 1, and carry out the second reaction to obtain product 2;

[0043] S3. Mix product 2, fluorinated acrylate monomer, acrylate monomer, crosslinking agent and initiator, and carry out the third reaction to obtain a fluorosiloxane containing epoxy groups.

[0044] In the present invention, preferably, in S1, the catalyst 1 is concentrated sulfuric acid. Preferably, the temperature of the first reaction is 70-90°C; the time of the first reaction is 3-4 h. Preferably, in S1, it also includes purifying the product 1. Preferably, in S2, the catalyst 2 is chloroplatinic acid-isopropanol; the solvent is toluene. Preferably, in S2, the temperature of the second reaction is 70-90°C; the time of the second reaction is 3-15 h; in S2, it also includes purifying the product 2.

[0045] Preferably, in S3, the fluorinated acrylate monomer includes one or more of dodecafluoroheptyl methacrylate, hexafluorobutyl methacrylate, or octafluoropentyl methacrylate; the acrylate monomer includes one or more of 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, TAC, butyl acrylate, HEA, HPA, HEMA, HPMA, or MMA; the crosslinking agent includes an olefin monomer or a vinyl siloxane coupling agent, and the olefin monomer includes acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, N-methylol acrylamide, or diacetone acrylamide; the vinyl siloxane coupling agent includes vinyltriethoxysilane, vinyltrimethoxysilane, or vinyltris(β-methoxyethoxy)silane; the initiator is a free radical polymerization initiator, and the free radical polymerization initiator includes azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-butyl peroxyacetate, or methyl ethyl ketone peroxide; the temperature of the third reaction is 60-80°C; the time of the third reaction is 3-12 h.

[0046] The present invention also provides a fluorosiloxane containing epoxy groups prepared by the above preparation method.

[0047] The present invention also provides the application of the above fluorosiloxane containing epoxy groups in improving the performance of nylon or polyester materials.

[0048] The present invention also provides a method for modifying nylon or polyester, including the following steps:

[0049] Mix the above fluorosiloxane containing epoxy groups with nylon or polyester materials, and extrude and mold to obtain a modified material.

[0050] Preferably, the modified material is a monofilament;

[0051] More preferably, the monofilament is prepared into a braided network tube for application.

[0052] The technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0053] Example 1

[0054] 1. Preparation of epoxy group-containing fluorosiloxane:

[0055] (1) Preparation of hydrogen-containing polysiloxane:

[0056] Using 0.6 mol of methyltrimethoxysilane and 0.2 mol of tetramethyltetrahydrocyclotetrasiloxane as synthesis raw materials, and 0.02 mol of hexamethyldisiloxane (MM) as a macromolecular chain terminator to synthesize high molecular weight hydrogen-containing polysiloxane. Add methyltrimethoxysilane, tetramethyltetrahydrocyclotetrasiloxane, and hexamethyldisiloxane into a flask, use 0.1 mol (0.5 - 1.5% of the total mass) of p-toluenesulfonic acid as a catalyst, react at 80 °C for 4 hours under nitrogen protection, and carry out an equilibration reaction at 0 - 20 °C until the end point. The product is dissolved in toluene, neutralized with 5% NaHCO3 solution to pH = 6.5 - 7.5 to avoid residual acid damaging subsequent reactions, and washed with water until neutral; the layers are separated to remove water, the water in the toluene layer is removed with a water-absorbing desiccant, filtered, and toluene is distilled off to obtain the product.

[0057] Product structure: Linear-based, branched polysiloxane with Me3SiO- at the end and Si-H and Si-CH3 units in the main chain:

[0058] Me3SiO-[Si(CH3)2O] m -[Si(CH3)HO] n -SiMe3

[0059] Product of step (1): 1 The Si-H content (δ 4.7 ppm) is detected by 1H NMR to ensure that the hydrogen content is 0.5 - 1.2%; the Mn is measured by GPC to be in the range of 1×10 4 - 5×10 4 g / mol.

[0060] (2) Preparation of epoxy group-containing siloxane:

[0061] In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, add Karstedt catalyst (Pt concentration 10 - 30 ppm) and the solvent toluene (30 - 50% of the total mass). Add (1.05 - 1.2 eq) of allyl glycidyl ether and 0.1 monomethacryloxypropyltrimethoxysilane monomer to the flask and stir to heat up. After the temperature reaches 70 °C, slowly dropwise add the hydrogen-containing polysiloxane prepared in step (1) (1.0 eq (calculated as Si-H)) into the flask, and finish the dropping in about 2 hours to avoid local Si-H excess leading to gelation. Control the whole reaction process at a temperature of 60 - 70 °C to avoid epoxy ring opening (>80 °C risk). Maintain a N2 atmosphere during the dropping of the hydrogen-containing polysiloxane to prevent the Pt catalyst from deactivating. Monitor by FTIR the disappearance of the Si-H peak at 2270 cm -1 and the stability of the epoxy peak (910 cm -1 ) to ensure complete reaction. The reaction is completed after about 6 hours. Keep the temperature of the reaction product at 100 °C and use a rotary evaporator to remove the solvent and unreacted raw materials under vacuum, and add 0.1% dibutylhydroxytoluene (BHT) stabilizer to prevent epoxy ring thermal opening until there is no distillate, obtaining a modified silicone oil containing epoxy groups.

[0062] Product structure: Epoxypropyl ether groups grafted on the silicone backbone:

[0063] Me3SiO-[Si(CH3)2O] m -[Si(CH3)(O-CH2-CH(O)CH2-O-C3H6)O] n -SiMe3

[0064] Product of step (2): Epoxy value determination (hydrochloric acid - acetone method), target value 0.2 - 0.4 mol / 100 g; FTIR confirmation of the epoxy characteristic peak at 910 cm-1.

[0065] (3) Preparation of fluorosilicone containing epoxy groups:

[0066] Mix (20 - 40 parts, by mass ratio) of hexafluorobutyl methacrylate (HFBMA), (2 - 5 parts, by mass ratio) of divinylbenzene (DVB), and (5 - 10 parts, by mass ratio) of methyl methacrylate (MMA) monomers and perform pre-emulsification for 30 minutes to improve the copolymerization uniformity;

[0067] Mix the modified silicone oil containing epoxy groups prepared in step (2) (100 parts, by mass ratio) with the above pre-emulsion and add them to the flask. Introduce a nitrogen atmosphere and add (0.5 - 1% parts, by mass ratio) of azobisisobutyronitrile (AIBN) initiator.

[0068] The specific ratio is as follows: epoxy-modified silicone oil: hexafluorobutyl methacrylate (HFMA): methyl methacrylate (MMA): divinylbenzene (DVB) = 100:30:10:5;

[0069] Initiator (AIBN): 1 wt% (based on the total mass of monomers).

[0070] Segmented temperature increase is adopted: Initially, react AIBN (half-life 10 h) at 60 °C for 4 hours, and then raise the temperature to 70 °C in the later stage to accelerate the reaction for 4 hours. Add (0.1 - 0.3% parts, mass ratio) 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a polymerization inhibitor to protect the epoxy group from free radical attack. The total reaction time is 6 - 8 hours. Take the precipitate, and after precipitation, wash it ultrasonically 3 times with a 50% ethanol / water mixture, and then extract it with acetone in a Soxhlet extractor for 24 hours to completely remove unreacted monomers, obtaining fluorosiloxane containing epoxy groups;

[0071] Final product of step (3): The content of F element detected by XPS is (target 10 - 15%), the Tg is observed by DSC in the range of -40 to -20 °C, and the thermal decomposition temperature is verified by TGA to be ≥250 °C.

[0072] 2. Blending modification of fluorosiloxane containing epoxy groups with nylon / polyester

[0073] Preparation of wear-resistant masterbatch: Add 20% of the above-mentioned wear-resistant additive to PA6 / 2.8 viscosity chips, mix evenly, and then granulate them with a twin-screw extruder to make the modified wear-resistant masterbatch SFPA20. The temperature settings for each zone of the twin-screw from zone 1 to zone 10 are respectively:

[0074] 225 °C - 230 °C - 230 °C - 230 °C - 225 °C - 225 °C - 220 °C - 215 °C - 225 °C - 235 °C.

[0075] The screw speed is 300 r / min.

[0076] Preparation of monofilament: First, dehumidify and dry PA66 raw materials / 3.4 viscosity, PA66 antioxidant masterbatch, PA color masterbatch, and SFPA20 wear-resistant masterbatch in an environment of 120 °C / 8H until the moisture content is controlled below 500 ppm. Set the temperature for each zone of the wire drawing extruder from zone 1 to zone 8 as:

[0077] 280 °C - 285 °C - 285 °C - 280 °C - 280 °C - 280 °C - 280 °C - 285 °C.

[0078] The length-diameter ratio of the screw is 30:1, the temperature of the cold water tank is set at 35°C, the temperature of the hot water tank is set at 95°C (length is 4 meters), the temperature of the first hot air box is 200°C (length is 4 meters), and the temperatures of the second and third hot air boxes are both 220°C (lengths are 4 meters each). 3% of PA66 antioxidant masterbatch, 2% of PA color masterbatch, 3% of SFPA20 wear-resistant masterbatch, and 92% of PA66 raw material are metered and fed through a loss-in-weight feeder, blended, and then put into the screw for further plasticizing and blending before extrusion. After cooling in the cold water tank, stretching 3 times in the hot water tank, stretching 1 time in the hot air box, and negative stretching by -0.5 times, it is wound up. The actual rotation speeds of the 1-4 traction machines are 20m / min - 60m / min - 80m / min - 70m / min.

[0079] Example 2

[0080] The difference from Example 1 is only that:

[0081] Preparation of wear-resistant masterbatch: In PA6 / 2.8 viscosity chips, 20% of the above-mentioned wear-resistant additives are added. After blending evenly, it is granulated by a twin-screw extruder to make the modified wear-resistant masterbatch SFPA20. The temperature settings of each zone of the twin-screw from 1-10 are as follows:

[0082] 225°C - 230°C - 230°C - 230°C - 225°C - 225°C - 220°C - 215°C - 225°C - 235°C.

[0083] The screw rotation speed is 300r / min.

[0084] Monofilament preparation: PA66 raw material / 3.4 viscosity, PA66 antioxidant masterbatch, PA color masterbatch, and SFPA20 wear-resistant masterbatch are all dehumidified and dried in an environment of 120°C / 8H until the moisture content is controlled below 500ppm. The temperature settings of each zone of the wire drawing and extrusion machine from 1-8 are 280°C - 285°C - 285°C - 280°C - 280°C - 280°C - 280°C - 285°C. The length-diameter ratio of the screw is 30:1, the temperature of the cold water tank is set at 35°C, the temperature of the hot water tank is set at 95°C (length is 4 meters), the temperature of the first hot air box is 200°C (length is 4 meters), and the temperatures of the second and third hot air boxes are both 220°C (lengths are 4 meters each). 3% of PA66 antioxidant masterbatch, 2% of PA color masterbatch, 5% of SFPA20 wear-resistant masterbatch, and 90% of PA66 raw material are metered and fed through a loss-in-weight feeder, blended, and then put into the screw for further plasticizing and blending before extrusion. After cooling in the cold water tank, stretching 3 times in the hot water tank, stretching 1 time in the hot air box, and negative stretching by -0.5 times, it is wound up. The actual rotation speeds of the 1-4 traction machines are 20m / min - 60m / min - 80m / min - 70m / min.

[0085] Example 3

[0086] The difference from Example 1 is only that:

[0087] Preparation of wear-resistant masterbatch: 20% of the above-mentioned wear-resistant additive is added to PA6 / 2.8 viscosity chips. After being evenly blended, it is granulated by a twin-screw extruder to produce the modified wear-resistant masterbatch SFPA20. The temperature settings for each zone of the twin-screw from zone 1 to zone 10 are respectively:

[0088] 225°C - 230°C - 230°C - 230°C - 225°C - 225°C - 220°C - 215°C - 225°C - 235°C.

[0089] The screw speed is 300 r / min.

[0090] Preparation of monofilament: PA66 raw material / 3.4 viscosity, PA66 antioxidant masterbatch, PA color masterbatch, and SFPA20 wear-resistant masterbatch are all dehumidified and dried in an environment of 120°C / 8H until the moisture content is controlled below 500 ppm. The temperature settings for each zone of the wire drawing extruder from zone 1 to zone 8 are 280°C - 285°C - 285°C - 280°C - 280°C - 280°C - 280°C - 285°C. The length-diameter ratio of the screw is 30:1. The temperature of the cold water tank is set at 35°C, and the temperature of the hot water tank is set at 95°C (length is 4 meters). The temperature of the first hot air box is 200°C (length is 4 meters), and the temperatures of the second and third hot air boxes are both 220°C (lengths are 4 meters each). 3% of PA66 antioxidant masterbatch, 2% of PA color masterbatch, 8% of SFPA20 wear-resistant masterbatch, and 87% of PA66 raw material are metered and fed through a loss-in-weight feeder, blended, and then put into the screw for further plasticization and blending before being extruded. After cooling in the cold water tank, stretching 3 times in the hot water tank, stretching 1 time in the hot air box, and negative stretching -0.5 times, it is wound up. The actual speeds of the traction machines for 1 - 4 traction are 20 m / min - 60 m / min - 80 m / min - 70 m / min.

[0091] Comparative Example 1

[0092] The difference from Example 1 is only that:

[0093] Preparation of monofilament: PA66 raw material / 3.4 viscosity, PA66 antioxidant masterbatch, and PA color masterbatch are all dehumidified and dried in an environment of 120°C / 8H until the moisture content is controlled below 500 ppm. The temperature settings for each zone of the wire drawing extruder from zone 1 to zone 8 are:

[0094] 280°C - 285°C - 285°C - 280°C - 280°C - 280°C - 280°C - 285°C.

[0095] The length-diameter ratio of the screw is 30:1. The temperature of the cold water tank is set at 35°C, and the temperature of the hot water tank is set at 95°C (with a length of 4 meters). The temperature of the first hot air box is 200°C (with a length of 4 meters), and the temperatures of the second and third hot air boxes are both 220°C (each with a length of 4 meters). 3% of PA66 antioxidant masterbatch, 2% of PA color masterbatch, and 95% of PA66 raw material are metered and fed through a loss-in-weight feeder, blended, and then put into the screw for further plasticizing and blending before extrusion. After cooling in the cold water tank, stretching 3 times in the hot water tank, stretching 1 time in the hot air box, and negative stretching by -0.5 times, it is wound up. The actual rotational speeds of the traction machines for 1-4 traction are 20m / min - 60m / min - 80m / min - 70m / min respectively.

[0096] Experimental Example

[0097] Wear resistance test:

[0098] The above-mentioned monofilaments (Examples 1-3 and Comparative Example 1) are all spun into round filaments with a wire diameter of 0.25 mm. After being pieced together into 3 filaments per strand, they are woven into a 48-spindle network tube by a weaving process, with a folding diameter of 10 mm and a mesh count of 10. The ISO-6722 needle abrasion standard is used to test the number of wear-resistant times, which is used as the basis for wear-resistant determination.

[0099] The results are shown in Table 1 below:

[0100] Table 1 Results of Wear Resistance Test Data

[0101]

[0102] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of an epoxy group-containing fluorosiloxane, characterized in that, It includes the following steps: S1. Mix methyl / phenyltrimethoxysilane, tetramethyltetrahydrocyclotetrasiloxane and hexamethyldisiloxane, add catalyst 1, and carry out the first reaction to obtain product 1; S2. Mix allyl glycidyl ether monomer, solvent and catalyst 2, add product 1, and carry out the second reaction to obtain product 2; S3. Mix product 2, fluorinated acrylate monomer, acrylate monomer, crosslinking agent and initiator, and carry out the third reaction to obtain epoxy group-containing fluorosiloxane.

2. The preparation method of the epoxy group-containing fluorosiloxane according to claim 1, characterized in that, In S1, the catalyst 1 is concentrated sulfuric acid.

3. The preparation method of the epoxy group-containing fluorosiloxane according to claim 1 or 2, characterized in that, The temperature of the first reaction is 70-90 °C; The time of the first reaction is 3-4 h.

4. The preparation method of the epoxy group-containing fluorosiloxane according to claim 1, characterized in that, In S1, it also includes purifying product 1.

5. The preparation method of the epoxy group-containing fluorosiloxane according to claim 1, wherein, In S2, the catalyst 2 is chloroplatinic acid-isopropanol; The solvent is toluene.

6. The preparation method of the epoxy group-containing fluorosiloxane according to claim 5, characterized in that, In S2, the temperature of the second reaction is 70-90 °C; The time of the second reaction is 3-15 h; In S2, it also includes purifying product 2.

7. The preparation method of the epoxy group-containing fluorosiloxane according to claim 1, characterized in that, In S3, the fluorinated acrylate monomer includes one or more of dodecafluoroheptyl methacrylate, hexafluorobutyl methacrylate or octafluoropentyl methacrylate; The acrylate monomer includes one or more of 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, TAC, butyl acrylate, HEA, HPA, HEMA, HPMA or MMA; The crosslinking agent includes olefin monomers or vinyl siloxane coupling agents. The olefin monomers include acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, N-hydroxymethylacrylamide or diacetone acrylamide; The vinyl siloxane coupling agents include vinyltriethoxysilane, vinyltrimethoxysilane or vinyltris(β-methoxyethoxy)silane; The initiator is a free radical polymerization initiator, and the free radical polymerization initiator includes azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-butyl peroxybenzene or methyl ethyl ketone peroxide; The temperature of the third reaction is 60-80 °C; The time of the third reaction is 3-12 h.

8. The epoxy group-containing fluorosiloxane prepared by the preparation method according to any one of claims 1-7.

9. The application of the epoxy group-containing fluorosiloxane according to claim 8 in improving the performance of nylon or polyester materials.

10. A method for modifying nylon or polyester, characterized in that, It includes the following steps: Blend the epoxy group-containing fluorosiloxane according to claim 8 with nylon or polyester materials, and extrude and mold to obtain a modified material.

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