TW202122347A - Method for processing porous silica , porous silica made, and application of the porous silica - Google Patents

Abstract

A method for progressing porous silica includes steps: providing water-soluble template agent and solvent, dissolve the water-soluble template agent in the solvent to obtain mixed solution. Adding first silane compound, second silane compound, and third silane compound to the mixed solution. The concentration of the first silane compound is 0.02 mol/L-0.08 mol/L, and the concentration of the second silane compound is 0.02 mol/L-0.08 mol/L, the concentration of the third silane compound is 0.002mol/L-0.006mol/L; sol-gel reaction with water-soluble template as template to obtain intermediate product. The second silane compound includes a hydrophobic group and the third silane compound includes an amine group. And washing and drying the intermediate product to obtain porous silica. The disclosure also provides the porous silica and the application of the porous silica.

Description

Porous silica, its preparation method and its application

The invention relates to the field of polymer materials, in particular to a porous silicon dioxide, its preparation method and its application.

Generally, non-porous silicon dioxide is made from tetraethyl orthosilicate (TEOS) by the sol-gel process (Sol-gel process), and the dielectric constant of the silicon dioxide powder itself is 3.9 When it is introduced into an insulating resin material (for example, polyimide) to form a composite material, the dielectric constant of the insulating resin material cannot be reduced.

Silica with pores generally uses organic compounds with hydrophilic and lipophilic amphoteric properties, that is, so-called surfactants as organic templates. In an acidic, alkaline or organic solution environment, the organic interface active agent itself is used to self-assemble in the solvent environment to stack into templates of different shapes, and the hydrolyzed organosilicon compound polymerizes (that is, Sol-gel method) on the outside of the template, and finally remove the template by high-temperature sintering to obtain a silicon dioxide material with holes. Using the air introduced in the hole (air dielectric constant is 1), the silicon dioxide can be introduced into the insulating resin material to form a composite material to reduce the dielectric constant. However, high-temperature sintering will cause the -Si-OH groups on the surface of the silica powder to transform into -Si-O-Si-, and the remaining unconverted -Si-OH groups will not be sufficient for surface modification with the silane coupling agent. Sex.

Therefore, it is necessary to provide a method for preparing porous silica. The porous silica prepared by the method has a hydrophilic group, a hydrophobic group and a -Si-OH group to solve the above-mentioned problems.

In addition, it is necessary to provide a porous silica.

In addition, it is also necessary to provide an application of the porous silica.

A preparation method of porous silica includes the following steps:

Provide a water-soluble template and a solvent, and dissolve the water-soluble template in the solvent to obtain a mixed solution;

The first silane compound, the second silane compound, and the third silane compound are added to the mixed solution, and the molar concentration of the first silane compound in the mixed solution is 0.02 mol/L-0.08 mol/L. The molar concentration of the second silane compound in the mixed solution is 0.02 mol/L-0.08 mol/L, and the molar concentration of the third silane compound in the mixed solution is 0.002 mol/L-0.006 mol/L, The first silane compound, the second silane compound, and the third silane compound are all hydrolyzed to generate silicon dioxide, and the water-soluble template is used as a template to perform a sol-gel reaction to obtain an intermediate product; wherein, the first The disilane compound includes a hydrophobic group, and the third silane compound includes an amine group;

The intermediate product is washed and dried, so that the water-soluble template is dissolved and removed to obtain the porous silica.

Further, the chemical formula of the first silane compound is Si-(OR) ₄ , wherein R is a saturated alkane group, and the number of carbon atoms of the saturated alkane group is n, where n is an integer, and 1≤n≤2 .

Further, the chemical formula of the second silane compound is R ₁ -Si-(OR) ₃ , wherein R ₁ is a hydrophobic group, and the R ₁ includes linear alkane groups, cycloalkyl groups, vinyl groups, and phenyl groups. R is a saturated alkane group, and the number of carbon atoms of the saturated alkane group is n, where n is an integer, and 1≤n≤2.

Further, the chemical formula of the third silane compound is R ₂ -Si-(OR) ₃ , wherein R ₂ includes -NH ₂ , R is a saturated alkane group, and the number of carbon atoms of the saturated alkane group is n, where n Is an integer, and 1≤n≤2.

Further, the water-soluble template is a saccharide, and the molar concentration of the water-soluble template in the mixed solution is 0.05 mol/L-0.20 mol/L.

Further, before adding the first silane compound, the second silane compound, and the third silane compound, the preparation method further includes adding a catalyst to the mixed solution, and the catalyst includes an acid or a salt, The molar concentration of the catalyst in the mixed solution is 0.1 mol/L-0.5 mol/L.

The solvent is a mixture of an inorganic solvent and an organic solvent, and the volume ratio of the inorganic solvent to the organic solvent is 1-3:1-5.

Further, the reaction temperature of the sol-gel reaction is 25°C-100°C.

A porous silica, the porous silica includes a silica main structure and a hydrophobic group and an amine group connected to the silica main structure; the silica main structure includes a plurality of pores The pore diameter of the hole is 2nm-50nm; the molar ratio of the hydrophobic group to the amine group is 3.33-4.0.

Further, the hydrophobic group includes at least one of a linear alkane group, a cycloalkyl group, a vinyl group, and a phenyl group.

An application of the porous silica in insulating resin.

The method for preparing porous silica provided by the present invention can generate holes in the main structure of silica by cleaning the water-soluble template, instead of the high-temperature sintering step of the traditional method, and prevent -Si-OH on the surface of the silica It is uncontrollable due to high-temperature sintering, and simplifies the process and saves costs; secondly, the preparation method uses a second silane compound and a third silane compound with a hydrophobic group and an amine group, respectively, so as to directly use the second silane compound. Hydrophobic groups and hydrophilic groups are formed on the main structure of silicon oxide. The traditional surface modification steps required after high-temperature sintering are omitted. Moreover, by controlling the addition ratio of the second silane compound and the third silane compound, that is, Porous silica with a balance of hydrophobic groups and hydrophilic groups can be obtained; the porous silica prepared by the preparation method has pores (the dielectric constant of the air in the pores is about 1), when the porous silica is used When preparing composite materials, it is beneficial to reduce the dielectric constant of composite materials. Since the porous silica provided by the present invention has both a hydrophobic group and a hydrophilic group, when the porous silica is used to prepare an insulating resin, it can not only ensure the dispersibility of the porous silica, but also ensure compatibility. It can also reduce the dielectric constant of the insulating resin.

Referring to Fig. 1, an embodiment of the present invention provides a method for preparing porous silica, which includes the following steps:

Step S11: Provide a solvent, and add a water-soluble template and a catalyst to the solvent to obtain a mixed solution.

The solvent is a mixture of an inorganic solvent and an organic solvent. The volume ratio of the inorganic solvent to the organic solvent is 1-3:1-5. In a specific embodiment, the inorganic solvent is deionized water, and the organic solvent is ethanol.

The water-soluble template is sugars, such as glucose, maltose, fructose, and sucrose. Preferably, the water-soluble template is at least one of D-glucose, D-maltose, D-fructose and sucrose. The water-soluble templating agent is a non-interfacially active templating agent, and the water-soluble templating agent can be dissolved and removed by an aqueous solution, so that the subsequently prepared silica has pores to form a porous structure of silica; The templating agent can create holes in the main structure of the silicon dioxide, instead of the high-temperature sintering step of the traditional method, prevent the -Si-OH on the surface of the silicon dioxide from being uncontrollable due to the high-temperature sintering, simplify the manufacturing process, and save costs.

The catalyst is an acid or a salt. In a specific embodiment, the salt is ammonia water. The molar concentration of the acid or the acid in the mixed solution is 0.1 mol/L-0.5 mol/L.

Specifically, a mixture of deionized water and ethanol is provided, the water-soluble templating agent is added to the mixture, and the water-soluble templating agent is dissolved in the solvent; then an acid or a salt is added, and the pH test paper is used to detect the The pH value of the mixed solution.

Step S12: adding the first silane compound, the second silane compound, and the third silane compound to the mixed solution to perform a sol-gel reaction to obtain an intermediate product.

The first silane compound, the second silane compound, and the third silane compound can all be hydrolyzed to generate silicon dioxide.

The chemical formula of the first silane compound is Si-(OR) ₄ , wherein R is a saturated alkane group, and the number of carbon atoms of the saturated alkane group is n, where n is an integer and 1≤n≤2, that is, Said R is -CH ₃ or -CH ₂ CH ₃ . That is, the first silane compound may be tetramethoxysilane or tetraethoxysilane. The first silane compound is hydrolyzed and polymerized in the mixed solution, and the water-soluble template is used as a template to coat the water-soluble template to form the main body of the porous silica, which is then precipitated . Wherein, the molar concentration of the first silane compound in the mixed solution is 0.02 mol/L-0.08 mol/L.

The chemical formula of the second silane compound is R ₁ -Si-(OR) ₃ , wherein R ₁ is at least one of a linear alkane group, a cycloalkyl group, a vinyl group, and a phenyl group, such as -CH ₃ ; R is saturated The alkane group, the number of carbon atoms of the saturated alkane group is n, where n is an integer, and 1≤n≤2. The second silane compound includes, but is not limited to, at least one of methyltrimethoxysilane (MTMS), silane cross-linked polyethylene (VTMS), and phenyltrimethoxysilane (PTMS). The second silane compound facilitates the preparation of porous silica having hydrophobic groups on the surface, reducing the hygroscopicity of the porous silica, thereby reducing the influence of moisture on the dielectric properties of the porous silica. Wherein, the molar concentration of the second silane compound in the mixed solution is 0.02 mol/L-0.08 mol/L.

The chemical formula of the third silane compound is R ₂ -Si-(OR) ₃ , wherein R ₂ includes an amine group, such as -CH ₂ CH ₂ CH ₂ NH ₂ ; R is a saturated alkane group, the saturated alkane group The number of carbon atoms in is n, where n is an integer and 1≤n≤2. The third silane compound includes, but is not limited to, 3-aminopropyltriethoxysilane (APTES). The amine group in the third silane compound helps to avoid the precipitation of porous silica when the porous silica is subsequently combined with polyimide or epoxy resin. Wherein, the molar concentration of the third silane compound in the mixed solution is 0.002 mol/L-0.006 mol/L.

Further, in the same set of experiments, the R in the first silane compound, the second silane compound, and the third silane compound are the same, that is, all of them are -CH ₃ or all of them are -CH ₂ CH ₃ at the same time.

Wherein, the second silane compound provides a hydrophobic group, and the third silane compound provides an amine group, which is a hydrophilic group. By adjusting the ratio of the second silane compound to the third silane compound, the final preparation is adjusted The ratio of hydrophobic groups to hydrophilic groups on the porous silica can balance the water absorption and dispersibility of the porous silica.

Wherein, the molar concentration of the water-soluble template in the mixed solution is 0.05 mol/L-0.20 mol/L.

Further, the reaction temperature of the sol-gel reaction is controlled to be 25°C to 100°C.

Wherein, the reaction process of the first silane compound in the solvent is shown in FIG. 2A. The first silane compound is hydrolyzed in water to form the main structure of silicon dioxide; please refer to FIG. 2B, the first silane compound and the second silane compound The silane compound and the third silane compound are jointly hydrolyzed in the solvent to form silicon dioxide with a hydrophobic group and an amine group. In FIG. 2B, R'represents R ₁ and the third silane in the second silane compound. _{R 2} in the compound.

Step S13: washing the intermediate product and drying to obtain the porous silica.

Specifically, the intermediate product is centrifuged. In other embodiments, other methods (such as filtration) may be used to separate the porous silica. Then the separated product is first cleaned with ethanol to remove the organic matter on the surface of the product; then cleaned with deionized water, the water-soluble template in the porous silica is dissolved in deionized water to form porous silica with pores .

The surface of the porous silica prepared by the preparation method has -Si-OH, a pore structure, a hydrophobic group and an amine group at the same time.

The present invention also provides a porous silica. The porous silica includes a silica main structure and a group connected to the silica main structure. The main structure of silicon dioxide includes a plurality of holes. The group includes at least a hydrophilic group and a hydrophobic group. The hydrophobic group includes at least one of a linear alkane group, a cycloalkyl group, a vinyl group, and a phenyl group. The hydrophobic group is used to increase the hydrophobic performance of the porous silica and reduce the porous silica Hygroscopicity, thereby reducing the influence of moisture on the dielectric properties of porous silica; the hydrophilic group includes an amine group, and the amine group is used for the subsequent porous silica as a precursor and When combined with polyimide or epoxy resin, avoid the precipitation of porous silica.

Further, the molar ratio of the hydrophobic group to the amino group is 3.33-4.0.

Further, the pore diameter of the hole is 2nm-50nm.

The present invention also provides applications including the porous silicon dioxide in insulating resins, and the insulating resins include but are not limited to polyimide composite materials, epoxy resin composite materials, and the like.

The embodiment of the present invention also provides a method for preparing a polyimide composite material including the porous silica, which includes the following steps:

Step S21: dissolving the diamine monomer in a polar aprotic solvent, and dispersing the porous silica in the polar aprotic solvent.

Wherein, the diamine monomer includes 4,4-diaminodiphenyl ether (ODA), p-phenylenediamine, 4,4-diaminodiphenylmethane, 2,2-bis[4-(4-amino At least one of phenoxy)phenyl]propane. The polar aprotic solvent includes but is not limited to N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like.

Step S22: Dissolve the dianhydride monomer in the polar aprotic solvent to obtain a polyamide acid solution (PAA).

The dianhydride monomers include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-two At least one of phenketotetracarboxylic dianhydride (BTDA), 4,4'-diphenyl ether dianhydride (ODPA), and 4,4'-(hexafluoroisopropylene) diphthalic anhydride (6FPA).

Step S23: subject the polyamide acid solution to a film forming process.

In a specific embodiment, the polyamide acid solution is coated on a copper foil for pre-baking, and then the thermal imidization reaction is performed at a high temperature. Specifically, the polyamide acid solution coated on the copper foil was pre-baked at 140°C for 10 minutes, and then baked in a high-temperature nitrogen oven at 150°C for 5 minutes, 200°C for 5 minutes, and 250°C. Bake for 5 minutes, 300°C for 30 minutes, and 350°C for 30 minutes. Finally, an etching solution is used to remove the copper foil to obtain a polyimide composite material.

The silica has a hydrophobic group to improve the hydrophobic performance of the silica; the silica has an amine group, and the amine group is used to synthesize the monomer of the polyimide composite material The molecules (ie, diamine monomer and dianhydride monomer) are bonded to improve the dispersibility of the silica in the polyamide acid solution. Since the amine group is a water-absorbing group, it is necessary to balance the water absorption and dispersibility of silica by controlling the ratio of the hydrophobic group to the amine group.

Doping in the polyimide composite material can reduce the dielectric constant of the polyimide composite material.

The present invention also provides a polyimide composite material. The polyimide composite material includes the porous silica.

The embodiment of the present invention also provides a method for preparing an epoxy resin composite material including the porous silica, which includes the following steps:

Step S31: providing bisphenol A epoxy resin, dicyclopentadiene phenol epoxy resin and fillers, dissolving the bisphenol A epoxy resin and the dicyclopentadiene phenol epoxy resin in an organic solvent, The filler is dispersed in the organic solvent.

The organic solvent includes at least one of acetone, methyl ethyl ketone (MEK), cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, and ethyl acetate.

The filler includes at least one of aluminum hydroxide, the porous silica, magnesium hydroxide, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay, talc and mica.

In a specific embodiment, the filler is aluminum hydroxide and the porous silica provided by the present invention. The silicon dioxide has a hydrophobic group to improve the hydrophobic performance of the silicon dioxide; the silicon dioxide has an amine group, and the amine group is used to synthesize the precursor of the epoxy resin composite material ( That is, the bisphenol A epoxy resin and the dicyclopentadiene phenol type epoxy resin are bonded to improve the dispersibility of the silicon dioxide in the epoxy resin precursor. Since the amine group is a water-absorbing group, it is necessary to balance the water absorption and dispersibility of silica by controlling the ratio of the hydrophobic group to the amine group.

Step S32: adding a curing agent and a rubber solution to obtain an epoxy resin precursor.

The curing agent includes at least one of 4,4'-diaminodiphenyl sulfide (DDS), 3,3'-diaminodiphenyl sulfide (DAS), and diphenylmethane diamine (DDM).

Step S33: subjecting the epoxy resin precursor to a film forming process.

In a specific embodiment, the epoxy resin precursor is coated on a copper foil for pre-baking, and then the thermal curing reaction is performed in an oven. Specifically, the epoxy resin precursor coated on the copper foil was pre-baked at 140° C. for 2 min, and then baked in an oven at 160° C. for 2 h to cause the epoxy resin precursor to undergo a thermal curing reaction. Finally, an etching solution is used to remove the copper foil to obtain an epoxy resin composite material.

The present invention also provides an epoxy resin composite material. The epoxy resin composite material includes the porous silica.

The present invention will be described below with specific embodiments.

Example 1

Take a 500mL double-layer beaker and use cooling water to control the temperature in the beaker to 35°C. After adding 200 mL of ethanol and 100 mL of deionized water to the double-layer beaker, 7.0 g of D-fructose was added as a water-soluble template to obtain a mixed solution, and the molar concentration of D-fructose in the mixed solution was 0.130 mol/ L. After uniformly stirring by magnetic force, 9.0 mL of ammonia water is added to the mixed solution, and the molar concentration of the ammonia water in the mixed solution is 0.231 mol/L.

Then, 1.87 g of TEOS (first silane compound), 2.45 g of MTMS (second silane compound) and 0.1 g of APTES (third silane compound) were added in sequence, and reacted at a reaction temperature of 35°C for 48 hours, where the TEOS, the The molar concentrations of MTMS and the APTES in the mixed solution are 0.030 mol/L, 0.060 mol/L, and 0.002 mol/L, respectively.

Centrifuge the reaction product, take out the paste and put it in a 500 mL beaker, add 400 mL of ethanol to ultrasonically clean for 30 minutes and centrifuge, and repeat the procedure 3 times. The product after ethanol washing and centrifugation was ultrasonically cleaned with 400 mL of deionized water for 30 minutes and then centrifuged, and this was repeated 10 times. The product after washing and centrifuging with deionized water is freeze-dried to obtain silicon dioxide with pores and methyl groups.

Example 2

The difference from Example 1 is: the molar concentration of D-fructose is 0.096mol/L, the quality of D-fructose is 5.2g; the molar concentration of TEOS is 0.060mol/L, the quality of TEOS is 3.74g; the second silane compound It is VTMS, the molar concentration of VTMS is 0.023 mol/L, and the quality of VTMS is 1.34g; the silicon dioxide with pores and vinyl groups is obtained.

Others are the same as in Embodiment 1, and will not be repeated here.

Example 3

The difference from Example 1 is: the molar concentration of D-fructose is 0.096mol/L, the quality of D-fructose is 5.2g; the molar concentration of TEOS is 0.060mol/L, the quality of TEOS is 3.74g; the second silane compound It is PTMS, the molar concentration of PTMS is 0.039mol/L, the quality of PTMS is 2.30g, and the silica with pores and phenyl groups is obtained.

Others are the same as in Embodiment 1, and will not be repeated here.

Comparative example 1

The difference from Example 1 is: the molar concentration of D-fructose is 0.096mol/L, the quality of D-fructose is 5.2g; the molar concentration of TEOS is 0.090mol/L, the quality of TEOS is 5.62g, and the quality of VTMS is 0g (that is, without adding the second silane compound), a silica with pores but no hydrophobic group is obtained.

Others are the same as in Embodiment 1, and will not be repeated here.

Comparative example 2

The difference from Example 1 is that the quality of APTES is 0 g (that is, the third silane compound is not added), and silicon dioxide with pores and methyl groups but no amine groups is obtained.

Others are the same as in Embodiment 1, and will not be repeated here.

Comparative example 3

The difference from Example 1 is that the quality of D-fructose is 0 g (that is, no water-soluble templating agent is added), and silica without pores but with methyl groups and amine groups is obtained.

Others are the same as in Embodiment 1, and will not be repeated here.

The specific treatment conditions of Examples 1-3 and Comparative Examples 1-3 are shown in Table 1, and the molar concentrations of the components used in Examples 1-3 and Comparative Examples 1-3 are shown in Table 2. Table 1 The quality of D-fructose (g) TEOS quality (g) The second type of silane compound The quality of the second type of silane compound (g) Quality of APTES (g) Example 1 7.0 1.87 MTMS 2.45 0.1 Example 2 5.2 3.74 VTMS 1.34 0.1 Example 3 5.2 3.74 PTMS 2.30 0.1 Comparative example 1 5.2 5.62 — — 0.1 Comparative example 2 7.0 1.87 MTMS 2.45 — Comparative example 3 — 1.87 MTMS 2.45 0.1 Table 2 Molar concentration of D-fructose (mol/L) Molar concentration of TEOS (mol/L) The molar concentration of the second silane compound (mol/L) Molar concentration of APTES (mol/L) Example 1 0.130 0.030 0.060 0.002 Example 2 0.096 0.060 0.023 0.002 Example 3 0.096 0.060 0.039 0.002 Comparative example 1 0.096 0.090 0 0.002 Comparative example 2 0.130 0.030 0.060 0 Comparative example 3 0 0.030 0.060 0.002

According to the preparation methods of Examples 1-3 and Comparative Examples 1-3, partial structures of Examples 1-3 and Comparative Examples 1-3 can be inferred, and the results are shown in Table 3. table 3 Whether there are holes Is there a hydrophobic group Types of hydrophobic groups Is there an amine group Example 1 Yes Yes methyl Yes Example 2 Yes Yes Vinyl Yes Example 3 Yes Yes Phenyl Yes Comparative example 1 Yes no — Yes Comparative example 2 Yes Yes methyl no Comparative example 3 no Yes methyl Yes

The infrared test was performed on the silica prepared in Examples 1-3 and Comparative Example 1, please refer to FIG. 3 and FIG. 4, and the positions of the absorption peaks and the corresponding groups are shown in Tables 4 and 5. Table 4 Group The position of the absorption peak (cm ^-1 ) -OH 3500 Asymmetric C=C 1594 Symmetrical C=C 1417 Si-O-Si 1030 and 1130 Si-CH ₃ 1287 NH 3000

Since the porous silica prepared in Example 1 has a methyl group compared to other silicas, ^{the characteristic peak at 1287 cm -1} (belonging to Si-CH ₃ ) is obvious; compared with the porous silica prepared in Example 2 Other silicon dioxides have vinyl ^{groups, and the characteristic peaks at 1594 cm -1} (belonging to asymmetric C=C) and 1417 cm ^-1 (belonging to symmetric C=C) are obvious; the silicon dioxide prepared in Comparative Example 1 has an amine group and There is no hydrophobic group, so ^{the characteristic peak at 3000 cm -1} (belonging to NH) is obvious. table 5 Group The position of the absorption peak (cm ^-1 ) Alkane CH 747 Si-O-Si 1049 and 1134 Aromatic C=C 1508 and 1603 CN 1325 Aromatic CH 3020 and 3047 NH 3412

Porous silicon dioxide prepared in Example 1 compared to other silicon dioxide having a phenyl group, and a characteristic peak located 1508cm ^-1 1603cm ^-1 C = C aromatic belonging obvious located 3020cm ^-1 and 3047cm ^-1 belonging to an aromatic The characteristic peak of group CH is obvious.

The silicon dioxide prepared in Example 1-2 and Comparative Example 1 were subjected to nuclear magnetic resonance tests respectively, and the test results are shown in FIG. 5A and FIG. 5C. Figure 5A is a silicon spectrum test, and Figure 5C is a carbon spectrum test.

Among them, in the silicon spectrum test, T represents the displacement of organic silicon, Q represents the displacement of inorganic silicon, and the positions of silicon in the compound represented by _{T 2} , T ₃ , Q ₃ and Q _{4 are shown in Fig. 5B. In Example 1, the displacements of T 2} , T ₃ , Q ₃ and Q ₄ in Example 2 and Comparative Example 1 are shown in Table 6. It can be seen from Comparative Example 1 that the hydrolysis and polymerization of the first silane compound completely has Q ₃ (-111.70 ppm) and Q ₄ (-120.87 ppm), and the hydrolysis and polymerization of the third silane compound completely has T ₃ (-76.69 ppm). ); The hydrolysis polymerization of the first silane compound of Example 1 completely has Q ₃ (-111.40 ppm) and Q ₄ (-122.14 ppm), and the hydrolysis and polymerization of the second silane compound and the third silane compound completely have T ₃ (-76.46 ppm) The hydrolysis and polymerization of the first silane compound of Example 2 completely have Q ₃ (-112.14 ppm) and Q ₄ (-122.89 ppm), and the hydrolysis and polymerization of the second silane compound and the third silane compound completely have T ₃ (-92.32 ppm). From Example 1 and Example 2 Q ₃ signal with respect to Comparative Example 1 significantly reduced, described in Example 1 of the second full Silane compound of Example 2 in conjunction with the third Silane Silane compound with a first compound. Table 6 Q ₄ (ppm) Q ₃ (ppm) T ₃ (ppm) T ₂ (ppm) Example 1 -122.14 -111.40 -76.46 -67.96 Example 2 -122.89 -122.14 -92.32 -83.41 Comparative example 1 -120.87 -111.70 -76.69 -70.94

It can be seen from Figure 5C that the porous silica prepared in Example 1 has a methyl group, and the characteristic peak at -2.2609ppm (belonging to the carbon in the methyl group) is obvious; the porous silica prepared in Example 2 has a vinyl group, The characteristic peaks at 131.2644ppm and 136.7204 (respectively belong to the carbon in the vinyl group) are obvious; the silica prepared in Comparative Example 1 only has amine groups, located at 10.7371ppm, 22.6561 ppm and 43.9768 ppm (respectively belong to -CH ₂ CH ₂ CH ₂ NH ₂ carbon) characteristic peaks are obvious.

The specific surface area and pore diameter of the silica prepared in Examples 1-3 and Comparative Example 1 were tested respectively. Among them, Figure 6A, Figure 7A, Figure 8A and Figure 9A are the specific surface area test diagrams of the silicon dioxide prepared in Examples 1-3 and Comparative Example 1, respectively; Figure 6B, Figure 7B, Figure 8B and Figure 9B are respectively the implementation Pore size distribution diagrams of the silica prepared in Examples 1-3 and Comparative Example 1. In addition, the water absorption rate of the silica prepared in Examples 1-3 and Comparative Example 1 was tested at 100°C. The test results of specific surface area, pore size and water absorption are shown in Table 7. Table 7 Specific surface area (m ² /g) Aperture (nm) Water absorption rate (%) Example 1 754.43 5.80 0.29 Example 2 558.23 6.03 1.82 Example 3 87.92 12.89 0.58 Comparative example 1 423.78 4.90 7.56

It can be seen from the results in Table 7 that the porous silica prepared in Examples 1-3 all have a relatively large specific surface area, and the pores are all mesopores.

It can be seen from the results in Table 7 that Comparative Example 1 has the highest water absorption rate compared to Examples 1-3. This is because the second silane compound is not added during the preparation of Comparative Example 1, that is, no hydrophobic group is added. The water absorption rate is mainly due to the water absorption performance of the amine group; and the silica prepared in Examples 1-3 all have hydrophobic groups, so the water absorption rate decreases.

The following uses the silica prepared in Examples 1-3 and Comparative Examples 1-3 as raw materials to prepare polyimide composite materials and epoxy resin composite materials.

Example 4

Add 203.88g of NMP as solvent, 20.02g (0.1mol) ODA (diamine monomer) and 1.53g of silicon dioxide containing methyl group prepared in Example 1 into a 500mL four-neck round-bottomed reaction tank, and stir to The diamine monomer is completely dissolved. Among them, the quality of silicon dioxide accounts for 3% of the theoretical quality of synthetic polyimide composite materials.

Add 29.42g (0.1mol) BPDA (dianhydride monomer) and stir for 24h to obtain a polyamide acid solution.

The polyamide acid solution was coated on a copper foil and pre-baked at 140°C for 10 minutes; then in a high-temperature nitrogen oven, baked at 150°C for 5 minutes, 200°C for 5 minutes, and 250°C. Bake for 5 minutes, 300°C for 30 minutes, and 350°C for 30 minutes. Finally, an etching solution is used to remove the copper foil to obtain a polyimide composite material.

Example 5

The difference from Example 4 is that the silicon dioxide is the methyl group-containing silicon dioxide prepared in Example 1, and the quality of the silicon dioxide accounts for 5% of the theoretical quality of the synthetic polyimide composite material.

Others are the same as in Embodiment 4, and will not be repeated here.

Comparative example 4

The difference from Example 4 is that no silicon dioxide is added.

Others are the same as in Embodiment 4, and will not be repeated here.

Comparative example 5

The difference from Example 4 is that the silica is the silica prepared in Comparative Example 1 without hydrophobic groups, and the quality of the silica accounts for 5% of the theoretical quality of the synthetic polyimide composite material.

Others are the same as in Embodiment 4, and will not be repeated here.

Comparative example 6

The difference from Example 4 is that the silicon dioxide is the non-porous silicon dioxide prepared in Comparative Example 2, and the quality of the silicon dioxide accounts for 5% of the theoretical quality of the synthetic polyimide composite material.

Others are the same as in Embodiment 4, and will not be repeated here.

Comparative example 7

The difference from Example 4 is that the silicon dioxide is the silicon dioxide without amine groups prepared in Comparative Example 2, and the quality of the silicon dioxide accounts for 5% of the theoretical quality of the synthetic polyimide composite material.

Others are the same as in Embodiment 4, and will not be repeated here.

The specific treatment conditions of Examples 4-5 and Comparative Examples 4-7 are shown in Table 8. Table 8 Source of Silicon Dioxide Features of Silicon Dioxide Silica content Example 4 Example 1 With holes, methyl groups and amino groups 3% Example 5 Example 1 With holes, methyl groups and amino groups 5% Comparative example 4 — — — Comparative example 5 Comparative example 1 Possess pores and amine groups, but does not contain hydrophobic groups 5% Comparative example 6 Comparative example 3 No holes but with methyl and amino groups 5% Comparative example 7 Comparative example 2 Has holes and methyl groups, but does not contain amine groups 5%

The dielectric constant (Dk) and dielectric loss (Df) of the polyimide composite materials prepared in Examples 4-5 and Comparative Examples 4-7 were tested respectively, and the results are shown in Table 9. Table 9 Dk (10GHz) Df (10GHz) Example 4 2.85±0.01 0.009±0.001 Example 5 2.78±0.01 0.010±0.001 Comparative example 4 3.24±0.01 0.009±0.001 Comparative example 5 3.59±0.01 0.019±0.001 Comparative example 6 3.38±0.01 0.011±0.001 Comparative example 7 Poorly dispersed silica

According to the results of Examples 4-5 and Comparative Example 4, it can be seen that the silicon dioxide provided in Examples 4 and 5 has a methyl group as a hydrophobic group to reduce the influence of moisture on the dielectric constant; at the same time, Example 4 and implementation The silicon dioxide provided in Example 5 has holes, and the dielectric constant of the air filled in the holes is 1. With the increase of the amount of silicon dioxide, the dielectric constant is further reduced, thereby reducing the dielectric constant of the prepared polyimide composite material. Electric constant.

From the results of Example 5 and Comparative Example 5, it can be seen that although the silica in Comparative Example 5 has pores and an amine group, so that the silica has better compatibility, but because the amine group is The hydrophilic group increases the water absorption of the polyimide composite material, thereby increasing the influence of moisture on the Dk value and Df value.

From the results of Example 5, Comparative Example 4 and Comparative Example 6, it can be seen that the silica in Comparative Example 6 does not contain pores and cannot reduce the Dk value. Compared with Comparative Example 4, Comparative Example 6 has increased polyamide. Dk value of amine composite material. Among them, the Dk value of silicon dioxide itself is 3.9, and the Dk value of the polyimide composite material without adding silicon dioxide (ie, Example 4) is 3.24.

In Comparative Example 7, since silica did not contain amine groups, silica agglomerated, resulting in poor dispersibility of silica and poor compatibility with diamine monomers and dianhydride monomers.

Example 6

Add 1.77 g of bisphenol A epoxy resin and 1.23 g of dicyclopentadiene phenol type epoxy resin to a 250 mL plastic jar, then add 3.38 g of aluminum hydroxide, and finally add solvent MEK 7.83 g, and stir for 2 hours.

Add 0.66 g of the silicon dioxide containing methyl groups prepared in Example 1 and stir to disperse. Among them, the quality of silicon dioxide accounts for 3% of the theoretical quality of synthetic epoxy resin composites.

Then add 0.38g curing agent DDS and 15.42g rubber solution to make the solid content in the solvent MEK 17%.

The prepared epoxy resin precursor is coated on a copper foil, and pre-baked at 140° C. for 2 minutes; then, it is baked in an oven at 160° C. for 2 hours to make the epoxy resin precursor undergo a thermal curing reaction. Finally, an etching solution is used to remove the copper foil to obtain an epoxy resin composite material.

Example 7

The difference from Example 6 is that the silicon dioxide is the silicon dioxide containing vinyl groups prepared in Example 2.

Others are the same as in Embodiment 6, and will not be repeated here.

Example 8

The difference from Example 6 is that the silica is the silica prepared in Example 3 containing a phenyl group.

Others are the same as in Embodiment 6, and will not be repeated here.

Comparative example 8

The difference from Example 6 is that no silicon dioxide is added.

Others are the same as in Embodiment 6, and will not be repeated here.

The specific treatment conditions of Examples 6-8 and Comparative Example 8 are shown in Table 10. Table 10 Source of Silicon Dioxide Features of Silicon Dioxide Example 6 Example 1 With holes, methyl groups and amino groups Example 7 Example 2 With holes, vinyl groups and amino groups Example 8 Example 3 With holes, phenyl groups and amino groups Comparative example 8 — —

The dielectric constant (Dk) and dielectric loss (Df) of the epoxy resin composite materials prepared in Examples 6-8 and Comparative Example 8 were tested respectively, and the results are shown in Table 11. Table 11 Dk (10GHz) Df (10GHz) Example 6 4.64±0.01 0.058±0.01 Example 7 8.99±0.01 0.064±0.01 Example 8 8.33±0.01 0.060±0.01 Comparative example 8 5.09±0.01 0.071±0.01

From the results of Example 6 and Comparative Example 8, it can be seen that the silica provided in Example 6 has a methyl group as a hydrophobic group to reduce the influence of moisture on the dielectric constant; meanwhile, the silica provided in Example 6 has holes, The dielectric constant of the air filled in the hole is 1, which further reduces the dielectric constant, thereby reducing the dielectric constant of the prepared polyimide composite material.

From the results of Example 6 and Example 7-8, it can be seen that the silica provided in Examples 6-8 all have hydrophobic groups, which can reduce the influence of moisture on the Dk value and Df value. Among them, the vinyl group and the phenyl group have hydrophobic groups. All have C=C high molar susceptibility groups. According to the Claslius-Mosotti formula calculation, it can be seen that the high molar susceptibility groups can increase the Dk value. Among them, the Claslius-Mosotti formula is as follows:

Among them, P _m is the molar polarizability of the atomic group, V _m is the molar volume of the atomic group, and ε is the dielectric constant.

In addition, the wettability of the prepared polyimide composite was discussed by the content of added silica. Among them, some specific processing conditions and the test results of the contact angle are shown in Table 12. Table 12 Source of Silicon Dioxide Silicon dioxide content (%) Contact angle Example 9 Example 2 1 75.58 Example 10 Example 2 3 75.45 Example 11 Example 1 1 80.99 Example 12 Example 1 3 87.52 Comparative example 9 — — 74.81 Comparative example 10 Comparative example 1 1 53.62 Comparative example 11 Comparative example 1 3 26.39

It can be seen from Table 12 that compared to Comparative Examples 10-11, since the silica prepared in Comparative Example 1 is added, the silica prepared in Comparative Example 1 contains amine groups but no hydrophobic groups. Therefore, the hydrophilic properties of the composite material are increased, resulting in a decrease in the contact angle; compared with Comparative Example 9, Examples 9-12 are added with the silica with hydrophobic groups prepared in Example 1 or Example 2, thereby reducing The hydrophilicity of the composite material increases the contact angle.

The method for preparing porous silica provided by the present invention can generate pores in silica powder by cleaning the water-soluble template, instead of the high-temperature sintering step of the traditional method, and prevent -Si-OH on the surface of the silica It is uncontrollable due to high-temperature sintering, and simplifies the process and saves costs; secondly, the preparation method uses a second silane compound and a third silane compound with a hydrophobic group and an amine group, respectively, so as to directly use the second silane compound. Hydrophobic groups and hydrophilic groups are formed on the silica powder, and the traditional surface modification steps required after high-temperature sintering are omitted. Moreover, by controlling the addition ratio of the second silane compound and the third silane compound, that is, Porous silica with a balance of hydrophobic groups and hydrophilic groups can be obtained; the porous silica prepared by the preparation method has pores (the dielectric constant of the air in the pores is about 1), when the porous silica is used When preparing composite materials, it is beneficial to reduce the dielectric constant of composite materials. Since the porous silica provided by the present invention has both a hydrophobic group and a hydrophilic group, when the porous silica is used to prepare an insulating resin, it can not only ensure the dispersibility of the porous silica, but also ensure compatibility It can also reduce the dielectric constant of the insulating resin.

The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the above preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced. None should deviate from the spirit and scope of the technical solution of the present invention.

Fig. 1 is a flow chart of a method for preparing porous silica provided by an embodiment of the present invention. 2A is a schematic diagram of the reaction process of the first silane compound in a solvent. 2B is a schematic diagram of the reaction process of the first silane compound, the second silane compound, and the third silane compound in a solvent. FIG. 3 is an infrared test diagram of the silicon dioxide prepared in Example 1-2 and Comparative Example 1. FIG. 4 is an infrared test diagram of the silicon dioxide prepared in Example 3. FIG. 5A is a graph of silicon spectrum nuclear magnetic resonance test of the silicon dioxide prepared in Example 1-2 and Comparative Example 1. FIG. FIG. 5B is a schematic diagram of the positions of organic silicon and inorganic silicon in the compound in the silicon spectrum nuclear magnetic resonance. 5C is a carbon spectrum nuclear magnetic resonance test diagram of the silicon dioxide prepared in Example 1-2 and Comparative Example 1. FIG. 6A is a test diagram of the specific surface area of the silicon dioxide prepared in Example 1. FIG. FIG. 6B is a test diagram of the pore size distribution of the silicon dioxide prepared in Example 1. FIG. FIG. 7A is a test diagram of the specific surface area of the silicon dioxide prepared in Example 2. FIG. FIG. 7B is a test diagram of the pore size distribution of the silicon dioxide prepared in Example 2. FIG. FIG. 8A is a test diagram of the specific surface area of the silicon dioxide prepared in Example 3. FIG. FIG. 8B is a test diagram of the pore size distribution of the silicon dioxide prepared in Example 3. FIG. FIG. 9A is a test chart of the specific surface area of the silicon dioxide prepared in Comparative Example 1. FIG. FIG. 9B is a test diagram of the pore size distribution of the silicon dioxide prepared in Comparative Example 1. FIG.

no.

Claims (11)

A preparation method of porous silica, which is improved in that it includes the following steps: Provide a water-soluble template and a solvent, and dissolve the water-soluble template in the solvent to obtain a mixed solution; The first silane compound, the second silane compound, and the third silane compound are added to the mixed solution, and the molar concentration of the first silane compound in the mixed solution is 0.02 mol/L-0.08 mol/L. The molar concentration of the second silane compound in the mixed solution is 0.02 mol/L-0.08 mol/L, and the molar concentration of the third silane compound in the mixed solution is 0.002 mol/L-0.006 mol/L, The first silane compound, the second silane compound, and the third silane compound are all hydrolyzed to generate silicon dioxide, and the water-soluble template is used as a template to perform a sol-gel reaction to obtain an intermediate product; wherein, the first The disilane compound includes a hydrophobic group, and the third silane compound includes an amine group; and The intermediate product is washed and dried, so that the water-soluble template is dissolved and removed to obtain the porous silica. The method for preparing porous silica as described in item 1 of the scope of patent application, wherein the chemical formula of the first silane compound is Si-(OR) ₄ , wherein R is a saturated alkane group, and the carbon of the saturated alkane group is The number of atoms is n, where n is an integer, and 1≤n≤2. The method for preparing porous silica as described in item 1 of the scope of patent application, wherein the chemical formula of the second silane compound is R1-Si-(OR) ₃ , wherein R ₁ is the hydrophobic group, and R is A saturated alkane group, the number of carbon atoms of the saturated alkane group is n, where n is an integer and 1≤n≤2, and R ₁ includes at least one of a linear alkane group, a cycloalkyl group, a vinyl group, and a phenyl group. The method for preparing porous silica as described in item 1 of the scope of patent application, wherein the chemical formula of the third silane compound is R ₂ -Si-(OR) ₃ , wherein R is a saturated alkane group, and the saturated alkane The number of carbon atoms of the group is n, where n is an integer and 1≤n≤2; R ₂ includes -NH ₂ . The method for preparing porous silica as described in item 1 of the scope of patent application, wherein the water-soluble template is a carbohydrate, and the molar concentration of the water-soluble template in the mixed solution is 0.05 mol/L-0.20 mol/L. The method for preparing porous silica as described in item 1 of the scope of patent application, wherein before adding the first silane compound, the second silane compound, and the third silane compound, the preparation method further includes A catalyst is added to the mixed solution, the catalyst includes an acid or a salt, and the molar concentration of the catalyst in the mixed solution is 0.1 mol/L-0.5 mol/L. The method for preparing porous silica as described in item 1 of the scope of patent application, wherein the solvent is a mixture of an inorganic solvent and an organic solvent, and the volume ratio of the inorganic solvent to the organic solvent is 1-3:1- 5. The method for preparing porous silica as described in item 1 of the scope of patent application, wherein the reaction temperature of the sol-gel reaction is 25°C-100°C. A porous silica, which is improved in that the porous silica includes a silica main structure and a hydrophobic group and an amine group connected to the silica main structure; the silica main structure It includes a plurality of pores, the pore diameter of the pores is 2 nm-50 nm, and the molar ratio of the hydrophobic group to the amino group is 3.33-4.0. The porous silica described in item 9 of the scope of patent application, wherein the hydrophobic group includes at least one of a linear alkane group, a cycloalkyl group, a vinyl group, and a phenyl group. An application of the porous silica according to any one of items 9 to 10 in the scope of the patent application. The improvement is that the porous silica is used in an insulating resin.

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