CN110589839B

Movatterモバイル変換

Info

Publication number: CN110589839B
Application number: CN201910897257.4A
Authority: CN
Inventors: 郑四荣
Original assignee: Dongguan Chuangli Technology Development Co ltd
Current assignee: Dongguan Lixin Environmental Protection Technology Co ltd
Priority date: 2019-09-23
Filing date: 2019-09-23
Publication date: 2021-02-23
Anticipated expiration: 2039-09-23
Also published as: CN110589839A

Abstract

Translated fromChinese

本发明涉及二氧化硅领域，更具体地，本发明涉及一种二氧化硅增强剂及其制备方法和应用，制备原料至少包括硅源、硅烷化合物、酸性催化剂、碱性催化剂、乙醇、去离子水、有机溶剂。本发明在溶胶‑凝胶法制备纳米二氧化硅过程中，以正硅酸乙酯与长链氟烷基硅烷为硅源，又置于含有硅烷化合物溶液中对其进行进一步改性，最后将纳米二氧化硅粉体分散于有机溶剂中，其可应用于不饱和树脂、环氧树脂体系，不仅提高了材料的力学性能、抗冲压性能，而且也有助于材料的抗氧化以及耐水、耐油性能的改善。The present invention relates to the field of silica, more particularly, the present invention relates to a silica reinforcing agent and a preparation method and application thereof. The preparation raw materials at least include silicon source, silane compound, acidic catalyst, basic catalyst, ethanol, deionized water, organic solvents. In the present invention, in the process of preparing nano-silica by sol-gel method, ethyl orthosilicate and long-chain fluoroalkyl silane are used as silicon sources, and they are further modified by placing them in a solution containing a silane compound, and finally Nano-silica powder is dispersed in organic solvent, which can be used in unsaturated resin and epoxy resin system, which not only improves the mechanical properties and punching resistance of the material, but also contributes to the anti-oxidation, water resistance and oil resistance of the material. improvement.

Description

Silicon dioxide reinforcing agent and preparation method and application thereof

Technical Field

The invention relates to the field of silicon dioxide, in particular to a silicon dioxide reinforcing agent and a preparation method and application thereof.

Background

In order to reduce the cost of the high molecular material and improve the comprehensive performance of the high molecular material, a large amount of inorganic filler and organic functional auxiliary agent are often added into the polymer. The addition of certain scales of inorganic fillers such as calcium carbonate, talc, montmorillonite, vermiculite, silica, etc. to polymeric materials is an important direction in the development of polymeric composites, and the properties of polymeric composites depend to a large extent on the chemical structure of the fillers, the surface modification status and their dispersion status in the polymeric material.

The silicon dioxide is used as the main component of the silicon dioxide, and is an inorganic non-metallic material which is non-toxic, tasteless and pollution-free. Among them, the nano-silica has unique characteristics in many subjects and fields due to its small particle size, large specific surface area and high chemical purity, and thus has irreplaceable effect due to its excellent stability, reinforcement and thickening properties.

The nano silicon dioxide is used as an inorganic nano filler applied to a polymer, can improve the comprehensive performance of the polymer, but is difficult to be completely and uniformly dispersed into an adding system in a short time when in use due to large specific surface area, small particles and small bulk density, and shows strong hydrophilicity due to the existence of surface hydroxyl and unsaturated residual bonds, has poor compatibility when being compounded with the polymer, and is difficult to be uniformly dispersed. In addition, in the fields of quartz stone, artificial marble and the like, the composite material added with the auxiliary agent has high requirements on the anti-impact performance, the water resistance, the oil resistance and the oxidation resistance.

Disclosure of Invention

In order to solve the above technical problems, a first aspect of the present invention provides a silica reinforcing agent, which is prepared from at least: silicon source, silane compound, acid catalyst, alkaline catalyst, ethanol, deionized water and organic solvent.

As a preferable technical scheme of the invention, the silicon source comprises tetraethoxysilane and long-chain fluoroalkyl silane.

As a preferable technical scheme of the invention, the molar ratio of the ethyl orthosilicate, the long-chain fluoroalkylsilane and the silane compound is 1: (0.5-2): (0.5-2).

In a preferred embodiment of the present invention, the long-chain fluoroalkyl silane is selected from the group consisting of perfluorodecyltriethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, heptadecafluorodecyltriisopropoxysilane, perfluorooctyltriethoxysilane, heptadecafluorodecyltripropoxysilane, perfluorodecyltrimethoxysilane, and perfluorooctyltrimethoxysilane.

As a preferable technical scheme, the silane compound is prepared by reacting aminosilane and a cinnamic acid compound.

According to a preferable technical scheme of the invention, the molar ratio of the aminosilane to the cinnamic acid compound is (1-1.2): 1.

in a preferred embodiment of the present invention, the aminosilane is selected from one or more of aminopropyltrimethoxysilane, (4-amino-3, 3-dimethylbutyl) (methyl) dimethoxysilane, 4-amino-3, 3-dimethylbutyltrimethoxysilane, 4-aminobutyltriethoxysilane, (3-aminopropyl) dimethylmethoxysilane, 4-aminobutyldimethylmethoxysilane, (2-aminoisopropyl) triethoxysilane, and 3-aminopropyltriethoxysilane.

As a preferable technical scheme of the invention, the aminosilane is (3-aminopropyl) dimethylmethoxysilane and/or 4-aminobutyldimethylmethoxysilane.

The second aspect of the present invention provides a method for preparing a silica reinforcing agent, comprising at least the following steps:

(1) adding ethanol and deionized water into a silicon source, then adding an acid catalyst, and stirring for reaction to obtain a mixed solution, wherein the molar ratio of the silicon source to the ethanol to the deionized water is 1: (30-80): (3-5);

(2) adding an alkaline catalyst into the mixed solution obtained in the step (1), then adding the mixed solution into a solution containing a silane compound and ethanol, and stirring for reaction to obtain the modified nano-silica sol, wherein the weight ratio of the silane compound to the ethanol is 1: (3-6);

(3) drying, crushing, screening, washing, drying and grinding the nano-silica sol obtained in the step (2) to obtain in-situ modified nano-silica;

(4) and (4) adding the nano silicon dioxide obtained in the step (3) into a high-speed mixer, starting stirring, adding an organic solvent from a sample inlet, dispersing and stirring, and filtering to obtain the nano silicon dioxide.

The third aspect of the invention provides a silicon dioxide reinforcing agent applied to an unsaturated resin and epoxy resin system, which can obviously improve the mechanical property, the shock resistance, the oil resistance, the water resistance and the oxidation resistance of materials

Has the advantages that: the invention provides a silicon dioxide reinforcing agent and a preparation method and application thereof, in the process of preparing nano silicon dioxide by a sol-gel method, tetraethoxysilane and long-chain fluoroalkyl silane are taken as silicon sources and are further modified in a silane compound-containing solution, and finally nano silicon dioxide powder is dispersed in an organic solvent, so that the silicon dioxide reinforcing agent can be applied to unsaturated resin and epoxy resin systems, the problems of poor compatibility, difficult uniform dispersion and the like when the silicon dioxide reinforcing agent is compounded with a polymer are solved, the mechanical property and the impact pressure resistance of a material are improved, and the oxidation resistance, the water resistance and the oil resistance of the material are improved.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The silicon source is a main source substance for preparing silicon dioxide, and comprises tetraethoxysilane and long-chain fluoroalkyl silane.

Long chain fluoroalkylsilanes

The long-chain fluoroalkylsilane is long-chain fluoroalkylsilane containing fluorine atoms.

In one embodiment, the long chain fluoroalkylsilane is selected from one or more combinations of perfluorodecyltriethoxysilane (CAS: 101947-16-4), dodecafluoroheptylpropyltrimethoxysilane (CAS: 1105578-57-1), dodecafluoroheptylpropylmethyldimethoxysilane (CAS: 1374604-19-9), heptadecafluorodecyltriisopropoxysilane (CAS: 246234-80-0), perfluorooctyltriethoxysilane (CAS: 51851-37-7), heptadecafluorodecyltripropoxysilane (CAS: 521084-64-0), perfluorodecyltrimethoxysilane (CAS: 83048-65-1), perfluorooctyltrimethoxysilane (CAS: 85857-16-5).

In a preferred embodiment, the long chain fluoroalkylsilane is dodecafluoroheptylpropylmethyldimethoxysilane.

The silane compound of the present invention is a compound containing at least silicon, hydrogen, and oxygen atoms.

In one embodiment, the silane compound is prepared from an aminosilane.

In a preferred embodiment, the silane compound is prepared by reacting aminosilane with a cinnamic acid-based compound.

In a more preferred embodiment, the molar ratio of the aminosilane to the cinnamic acid compound is (1-1.2): 1; more preferably, the molar ratio of the aminosilane to the cinnamic acid compound is 1: 1.

amino silane

The aminosilane is a silane substance with amino.

In one embodiment, the aminosilane is selected from one or more combinations of 3-aminopropyltrimethoxysilane (CAS: 13822-56-5), (4-amino-3, 3-dimethylbutyl) (methyl) dimethoxysilane (CAS: 156849-43-3), 4-amino-3, 3-dimethylbutyltrimethoxysilane (CAS: 157923-74-5), 4-aminobutyltriethoxysilane (CAS: 3069-30-5), (3-aminopropyl) dimethylmethoxysilane (CAS: 31024-26-7), 4-aminobutyldimethylmethoxysilane (CAS: 3663-43-2), (2-aminoisopropyl) triethoxysilane (CAS: 36957-84-3), 3-aminopropyltriethoxysilane (CAS: 919-30-2).

In a preferred embodiment, the aminosilane is (3-aminopropyl) dimethylmethoxysilane and/or 4-aminobutyldimethylmethoxysilane.

In a more preferred embodiment, the aminosilane is (3-aminopropyl) dimethylmethoxysilane.

Cinnamic acid compound

The cinnamic acid compound is a polyphenol compound with acrylic acid group linked on benzene ring, and has a plurality of physiological activities, such as: antibacterial, anticancer, antiinflammatory, antiviral, antioxidant, antitumor and hepatoprotective effects.

In one embodiment, the cinnamic acid is 3, 5-di-tert-butyl-4-hydroxycinnamic Acid (AO) (CAS: 22014-01-3).

In a preferred embodiment, the cinnamic compound is the acid chloride 3, 5-di-tert-butyl-4-hydroxycinnamic acid (AO-Cl).

The preparation process of the AO-Cl comprises the following steps: placing AO (0.48mmol, 0.1g) into an anhydrous dry 25mL round bottom flask, adding anhydrous dry Dichloromethane (DCM) (4mL), adding dry anhydrous magneton, ultrasonic cleaning in an ultrasonic cleaner until the surface has no solid, placing on a magnetic stirrer, adding oxalyl chloride (200uL) in a ventilated place under stirring, reacting under normal temperature stirring to obtain yellow clear transparent liquid, plugging cotton in a dry explosion-proof ball (explosion-proof ball), and placing in an anhydrous dry CaCl₂) The rotary evaporator ofConcentrating under reduced pressure at 30 deg.C to dryness.

The preparation process of the silane compound of the invention is as follows: putting (3-aminopropyl) dimethylmethoxysilane (0.48mmol, 0.06g) into an anhydrous dry 25mL round-bottom flask, adding anhydrous dry DCM (2mL), adding magnetons, ultrasonically cleaning in an ultrasonic cleaner for a moment, placing on a magnetic stirrer, slowly dropping newly prepared AO-Cl (dissolving the newly prepared AO-Cl which is concentrated to be dry under reduced pressure with dry anhydrous DCM (2mL) while stirring, shaking the system, reacting for 3-4 h under normal temperature stirring, plugging cotton into a dry anti-explosion ball (the anti-explosion ball) after the reaction is finished, and filling anhydrous CaCl into the cotton₂) Concentrating the filtrate at 30 deg.C under reduced pressure to dryness.

In one embodiment, the molar ratio of ethyl orthosilicate, long chain fluoroalkylsilane, and silane compound is 1: (0.5-2): (0.5 to 2); more preferably, the molar ratio of the ethyl orthosilicate, the long-chain fluoroalkylsilane and the silane compound is 1: 1.3: 1.3.

The acidic catalyst of the invention is a substance which has acidity and can play a role of acid catalysis.

In some embodiments, the acidic catalyst is selected from one or more combinations of hydrochloric acid, phosphoric acid, oxalic acid, nitric acid.

In a preferred embodiment, the acidic catalyst is hydrochloric acid.

The basic catalyst of the invention is a substance which has alkalinity and can play a role of alkali catalysis.

In some embodiments, the basic catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia in combination.

In a preferred embodiment, the basic catalyst is ammonia.

The organic solvent is organic silane liquid.

In some embodiments, the organic solvent is selected from one or more combinations of methyldiethoxysilane (CAS: 2031-62-1), tetramethoxysilane (CAS: 681-84-5), tetraethoxysilane (CAS: 78-10-4), vinyltrimethylsilane (CAS: 754-05-2).

In a preferred embodiment, the organic solvent is tetramethoxysilane.

In a preferred embodiment, the method for preparing the silica reinforcing agent at least comprises the following steps:

(1) adding ethanol and deionized water into a silicon source, uniformly performing ultrasonic oscillation, then adding an acidic catalyst, adjusting the pH value to 3-4, stirring and reacting at 40-60 ℃ for 4-6 hours to obtain a mixed solution, wherein the molar ratio of the silicon source to the ethanol to the deionized water is 1: (30-80): (3-5);

(2) adding an alkaline catalyst into the mixed solution obtained in the step (1), adjusting the pH to 7-9, uniformly stirring, standing for 1-3h, adding into a solution containing a silane compound and ethanol, and stirring and reacting at 50-60 ℃ for 8-12h to obtain the modified nano-silica sol, wherein the weight ratio of the silane compound to the ethanol is 1: (3-6);

(3) drying, crushing and screening the nano-silica sol obtained in the step (2), centrifugally washing for 3-5 times by using ethanol, washing with water, drying in vacuum at 80 ℃ for 12-24h, and grinding to obtain in-situ modified nano-silica;

(4) adding the nano silicon dioxide obtained in the step (3) into a high-speed mixer, starting stirring, adding an organic solvent from a sample inlet, then dispersing and stirring for 1-2h, and filtering to obtain the nano silicon dioxide/organic solvent composite material, wherein the mass ratio of the nano silicon dioxide to the organic solvent is (2-4): 1.

in the experimental process, the inventor finds that the hydrophobic and oleophobic properties of the material obtained by compounding the prepared silicon dioxide reinforcing agent and resin are improved by regulating and controlling the type of the silicon source in the silicon dioxide forming process, namely adding long-chain fluoroalkylsilane containing fluorine atoms as one of the silicon sources, probably because alkoxy of the long-chain fluoroalkylsilane is hydrolyzed under the action of an acid catalyst to generate hydroxyl, the existence of the long-chain structure can bring steric hindrance and hinder the self polycondensation reaction, and the long-chain structure and hydroxyl of ethyl orthosilicate are subjected to dehydration condensation more, so that a surface layer consisting of low surface energy groups is formed on the surface and inside of silicon dioxide, the surface tension of solid can be obviously reduced, the solid is difficult to be wetted by liquid, and the effect of water and oil repellency is achieved. The inventor surprisingly finds that when the silane compound prepared by reacting aminosilane and cinnamic acid compounds is added into a reaction system, the oxidation resistance, the hydrophobicity of the system and the stamping resistance are obviously improved. The reason is probably that the silane compound is subjected to condensation polymerization with Si-OH on the surface of formed silicon dioxide after hydrolysis, on one hand, phenolic hydroxyl groups, -NH hydrogen donor groups and hydrophobic methyl groups can be grafted, and thus the oxidation resistance and the hydrophobicity are improved; on the other hand, the impact resistance of the material can be obviously improved because the addition of the silane compound can appropriately offset the influence of the long-chain fluoroalkyl silane on the impact resistance.

In addition, the inventor finds through experiments that when the silane compound is excessively added, the compounded material is easy to crack under the action of external force, and the impact and compression resistance performance is greatly reduced. The inventor finds that by regulating the molar ratio of ethyl orthosilicate, long-chain fluoroalkylsilane and silane compound to be 1: (0.5-2): (0.5-2), the prepared silicon dioxide reinforcing agent can enable the material to have good flexibility and strength, namely stamping resistance.

The third aspect of the invention provides an application of a silicon dioxide reinforcing agent, which is applied to unsaturated resin and epoxy resin systems and can obviously improve the mechanical property, the impact resistance, the oil resistance, the water resistance and the oxidation resistance of materials.

Examples

In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.

Example 1

The embodiment 1 of the invention provides a silicon dioxide reinforcing agent, which is prepared from the following raw materials: silicon source, silane compound, acid catalyst, alkaline catalyst, ethanol, deionized water and organic solvent.

The silicon source comprises tetraethoxysilane and long-chain fluoroalkyl silane; the long-chain fluoroalkylsilane is dodecafluoroheptyl-propyl-methyl-dimethoxysilane.

The preparation process of the silane compound is as follows: (3-aminopropyl) dimethylmethoxysilane (0.48mmol, 0.06g) was charged into an anhydrous dry 25mL round bottom flask, anhydrous dry DCM (2mL) was added, magnetons were added, sonicated in a sonicator for a while on a magnetic stirrer, freshly prepared AO-Cl (concentrated to dryness under reduced pressure) was slowly added dropwise with dry anhydrous AO-Cl while stirringDCM (2mL) is dissolved), a system is shaken, the mixture is stirred at normal temperature and reacts for 3-4 hours, and after the reaction is finished, a dry explosion-proof ball (cotton is filled in the explosion-proof ball, and anhydrous CaCl is filled in the mixture₂) Concentrating the filtrate at 30 deg.C under reduced pressure to dryness.

The preparation process of the AO-Cl comprises the following steps: placing AO (0.48mmol, 0.1g) into an anhydrous dry 25mL round bottom flask, adding anhydrous dry Dichloromethane (DCM) (4mL), adding dry anhydrous magneton, ultrasonic cleaning in an ultrasonic cleaner until the surface has no solid, placing on a magnetic stirrer, adding oxalyl chloride (200uL) in a ventilated place under stirring, reacting under normal temperature stirring to obtain yellow clear transparent liquid, plugging cotton in a dry explosion-proof ball (explosion-proof ball), and placing in an anhydrous dry CaCl₂) Concentrating the filtrate at 30 deg.C under reduced pressure to dryness.

The molar ratio of the ethyl orthosilicate to the long-chain fluoroalkylsilane to the silane compound is 1: 0.5: 0.5.

the acidic catalyst is hydrochloric acid.

The alkaline catalyst is ammonia water.

The organic solvent is tetramethoxysilane.

The preparation method of the silicon dioxide reinforcing agent comprises the following steps:

(1) adding ethanol and deionized water into a silicon source, uniformly oscillating with ultrasonic waves, then adding an acidic catalyst, adjusting the pH value to 3, stirring and reacting at 50 ℃ for 5 hours to obtain a mixed solution, wherein the molar ratio of the silicon source to the ethanol to the deionized water is 1: 55: 4;

(2) adding an alkaline catalyst into the mixed solution obtained in the step (1), adjusting the pH value to 8, uniformly stirring, standing for 2h, adding into a solution containing a silane compound and ethanol, and stirring and reacting at 55 ℃ for 10h to obtain the modified nano-silica sol, wherein the weight ratio of the silane compound to the ethanol is 1: 4;

(3) drying, crushing and screening the nano-silica sol obtained in the step (2), centrifugally washing for 4 times by using ethanol, washing by using water, drying for 18 hours in vacuum at 80 ℃, and grinding to obtain in-situ modified nano-silica;

(4) adding the nano silicon dioxide obtained in the step (3) into a high-speed mixer, starting stirring, adding an organic solvent from a sample inlet, then dispersing and stirring for 1h, and filtering to obtain the nano silicon dioxide/organic solvent mass ratio of 3: 1.

example 2

The embodiment 2 of the invention provides a silicon dioxide reinforcing agent, which comprises the following preparation raw materials: silicon source, silane compound, acid catalyst, alkaline catalyst, ethanol, deionized water and organic solvent.

The procedure of the preparation of the silane compound was the same as in example 1.

The molar ratio of the ethyl orthosilicate to the long-chain fluoroalkylsilane to the silane compound is 1: 1.3: 1.3.

the acidic catalyst is hydrochloric acid.

The alkaline catalyst is ammonia water.

The organic solvent is tetramethoxysilane.

The procedure of the preparation of the silica reinforcing agent was the same as in example 1.

Example 3

Embodiment 3 of the present invention provides a silica reinforcing agent, which is prepared from the following raw materials: silicon source, silane compound, acid catalyst, alkaline catalyst, ethanol, deionized water and organic solvent.

The molar ratio of the ethyl orthosilicate to the long-chain fluoroalkylsilane to the silane compound is 1: 2: 2.

the acidic catalyst is hydrochloric acid.

The alkaline catalyst is ammonia water.

The organic solvent is tetramethoxysilane.

Comparative example 1

Comparative example 1 compared to example 2, the molar ratio of ethyl orthosilicate, long chain fluoroalkylsilane, and silane compound was replaced with 1: 3: 1.3, otherwise as in example 2.

Comparative example 2

Comparative example 2 compared to example 2, the molar ratio of ethyl orthosilicate, long chain fluoroalkylsilane, and silane compound was replaced with 1: 1.3: 3, otherwise the same as in example 2.

Comparative example 3

Comparative example 3 is free of long chain fluoroalkyl silanes as compared to example 2, otherwise as described for example 2.

Comparative example 4

Comparative example 4 compared to example 2, there was no silane compound, and the other description is the same as example 2.

Comparative example 5

Comparative example 5 in comparison with example 2, the long-chain fluoroalkyl silane was replaced with methyl (3,3, 3-trifluoropropyl) diethoxysilane (CAS: 118162-95-1), otherwise the same as in example 2.

Comparative example 6

Comparative example 6 compared to example 2, the silane compound was replaced with propyltrimethoxysilane (CAS: 1067-25-0), otherwise as described for example 2.

Comparative example 7

Comparative example 7 in comparison with example 2, the silane compound was replaced with triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12, 12-heneicosyldodecyl) silane (CAS: 146090-84-8), otherwise the same as in example 2.

Evaluation of Performance

Adding epoxy resin into the silica reinforcing agent (3 wt% of the amount of epoxy resin) prepared in the above example, and stirring and mixing at 30 ℃ for 10 minutes to obtain an epoxy resin mixture; and then adding a DDM epoxy curing agent (35 wt% of the amount of the epoxy resin) which is heated and melted in a 100 ℃ oven for 15 minutes, stirring and mixing for 3 minutes, then placing the mixture into the 100 ℃ oven for curing for 10 hours, cooling to obtain the nano silicon dioxide modified epoxy resin composite material, setting a control example without adding a silicon dioxide reinforcing agent, and respectively carrying out performance test evaluation on the material.

1. Impact strength test

The material prepared was cut to give samples which were tested in 80 x 10 x 4mm impact test blocks and tested according to standard reference GB/T2571-1995 to record data.

2. Anti-aging test

The prepared material is made into an arbitrary size according to GB/T2567-1995, placed under an ultraviolet irradiation aging condition for 500 hours, placed in the middle of a support of a universal material testing machine, subjected to bending and tensile property tests according to GB/T2567-2008, and recorded with the bending strength and the tensile strength before and after ultraviolet irradiation.

3. Contact Angle testing

Water repellency is measured by the static contact angle (theta) of water on the surface of a material_{Water (W)}) Indicating the static contact angle (theta) of the oil-repellent material with heptane on the surface_Oil) This indicates that the droplet size was 5. mu.L, as measured at 25. + -. 2 ℃ by a contact angle measuring instrument (JC 2000C).

Table 1 performance characterization test

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

Translated fromChinese

1.一种二氧化硅增强剂，其特征在于，制备原料至少包括：硅源、硅烷化合物、酸性催化剂、碱性催化剂、乙醇、去离子水、有机溶剂；1. a silica reinforcing agent, it is characterized in that, preparation raw material comprises at least: silicon source, silane compound, acid catalyst, basic catalyst, ethanol, deionized water, organic solvent;

所述硅源包括正硅酸乙酯与长链氟烷基硅烷；The silicon source includes tetraethyl orthosilicate and long-chain fluoroalkyl silane;

所述正硅酸乙酯、长链氟烷基硅烷与硅烷化合物的摩尔比为1：(0.5～2)：(0.5～2)；The molar ratio of the ethyl orthosilicate, the long-chain fluoroalkyl silane and the silane compound is 1:(0.5-2):(0.5-2);

所述硅烷化合物由氨基硅烷与肉桂酸类化合物反应制备得到；The silane compound is prepared by reacting aminosilane with a cinnamic acid compound;

所述长链氟烷基硅烷选自全氟癸基三乙氧基硅烷、十二氟庚基丙基三甲氧基硅烷、十二氟庚基丙基甲基二甲氧基硅烷、十七氟癸基三异丙氧基硅烷、全氟辛基三乙氧基硅烷、十七氟癸基三丙氧基硅烷、全氟癸基三甲氧基硅烷、全氟辛基三甲氧基硅烷中的一种或多种组合；The long-chain fluoroalkyl silane is selected from the group consisting of perfluorodecyltriethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, dodecafluoroheptylpropylmethyldimethoxysilane, heptadecafluorosilane One of decyltriisopropoxysilane, perfluorooctyltriethoxysilane, heptadecafluorodecyltripropoxysilane, perfluorodecyltrimethoxysilane, perfluorooctyltrimethoxysilane one or more combinations;

所述氨基硅烷与肉桂酸类化合物的摩尔比为(1～1.2)：1；The molar ratio of the aminosilane to the cinnamic acid compound is (1-1.2): 1;

所述氨基硅烷为(3-氨基丙基)二甲基甲氧基硅烷和/或4-氨基丁基二甲基甲氧基硅烷；The aminosilane is (3-aminopropyl)dimethylmethoxysilane and/or 4-aminobutyldimethylmethoxysilane;

所述的二氧化硅增强剂的制备方法，至少包括以下步骤：The preparation method of described silica reinforcing agent, at least comprises the following steps:

(1)向硅源中加入乙醇、去离子水，然后加入酸性催化剂，搅拌反应，得混合溶液，其中，硅源、乙醇和去离子水的摩尔比为1：(30～80)：(3～5)；(1) Add ethanol and deionized water to the silicon source, then add an acidic catalyst, and stir the reaction to obtain a mixed solution, wherein the molar ratio of the silicon source, ethanol and deionized water is 1:(30～80):(3 ~5);

(2)向步骤(1)所得的混合溶液中加入碱性催化剂，然后加入到含有硅烷化合物和乙醇的溶液中，搅拌反应，得到改性的纳米二氧化硅溶胶，其中，硅烷化合物与乙醇的重量比为1：(3～6)；(2) adding a basic catalyst to the mixed solution obtained in step (1), then adding it to a solution containing a silane compound and ethanol, and stirring the reaction to obtain a modified nano-silica sol, wherein the silane compound and ethanol are The weight ratio is 1:(3～6);

(3)将步骤(2)所得的纳米二氧化硅溶胶干燥，粉碎，筛分，洗涤，干燥，研磨，得原位改性的纳米二氧化硅；(3) drying, pulverizing, sieving, washing, drying, and grinding the nano-silica sol obtained in step (2) to obtain in-situ modified nano-silica;

(4)将步骤(3)所得的纳米二氧化硅加入到高混机中，开启搅拌从进样口加入有机溶剂，分散搅拌，过滤，即得。(4) adding the nano-silicon dioxide obtained in step (3) into a high-speed mixer, turning on stirring, adding an organic solvent from the sample inlet, dispersing and stirring, and filtering to obtain the final product.