CN108164710B - SiO (silicon dioxide)2Preparation method of/polysiloxane acrylate composite material - Google Patents
SiO (silicon dioxide)2Preparation method of/polysiloxane acrylate composite material Download PDFInfo
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- CN108164710B CN108164710B CN201711441034.4A CN201711441034A CN108164710B CN 108164710 B CN108164710 B CN 108164710B CN 201711441034 A CN201711441034 A CN 201711441034A CN 108164710 B CN108164710 B CN 108164710B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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Abstract
The invention provides SiO2The preparation method of the/polysiloxane acrylate composite material comprises the following steps: A) will be provided withNano SiO2Adding polyethylene glycol acrylate compound, stirring to obtain SiO2Modified polyethylene glycol acrylates; B) subjecting the SiO2Adding the modified polyethylene glycol acrylate compound into the polymethylhydrosiloxane solution, introducing nitrogen and stirring, and carrying out hydrosilylation reaction under the conditions of no water and no oxygen and the presence of a catalyst to obtain SiO2A polysiloxane acrylate composite material. O and SiO of ether bond in polyethylene glycol acrylate compound2The silanol bond of (A) forms a hydrogen bond, SiO2The method is favorable for attracting the polyethylene glycol acrylate to be orderly arranged, increases the contact probability of double bonds and active hydrogen, and improves the addition conversion rate. Meanwhile, the production method of continuously dripping raw materials in the market is improved, and the production process is simplified.
Description
Technical Field
The invention belongs to the technical field of organic silicon synthesis, and particularly relates to SiO2A preparation method of a polysiloxane acrylate composite material.
Background
In recent years, the reaction of organic silicon and acrylate becomes a great research hotspot of material science, and a great deal of research shows that the organic silicon acrylate has wide application prospects in the fields of surface treatment, fabric finishing agents, crosslinking agents and the like. Burzyhiski, Robert et al have made many studies on the polymerization of double bond-containing organosiloxane and acrylate monomers; since Sonmjer et al first discovered that trichlorosilane forms Si-C bonds with 1-octene under the catalysis of diacetyl peroxide, the hydrosilylation reaction became one of the most important reactions in silicone chemistry since 1947. The hydrosilylation method is mild in condition, safe and high in catalytic activity. In order to solve the problems of hydrosilylation reaction technology, scholars at home and abroad make a lot of researches on hydrosilylation reaction catalysts and catalytic mechanisms, so that the activity and selectivity of hydrosilylation reaction are improved to a great extent, and the attention on the properties of reactants is less.
Because the polymethylhydrosiloxane molecule is in a spiral shape, the whole molecule has very low polarity and very strong hydrophobicity, so that the polymethylhydrosiloxane molecule is poorly combined with the unsaturated double bond-containing acrylate and is a typical immiscible system. Therefore, the two phases need to be slowly converted into one phase along with time in the addition reaction process, so that the phenomenon of incomplete reaction and delamination can occur in the reaction of the polymethylhydrosiloxane and the polyethylene glycol acrylate, and the reaction conversion rate is low and the reaction time is long.
Disclosure of Invention
The invention aims to provide SiO2The method for preparing the polysiloxane acrylate composite material has the advantages of fast reaction and high conversion rate.
The invention provides SiO2The preparation method of the/polysiloxane acrylate composite material comprises the following steps:
A) mixing nano SiO2Adding polyethylene glycol acrylate compound, stirring to obtain SiO2Modified polyethylene glycol acrylates;
B) subjecting the SiO2Adding the modified polyethylene glycol acrylate compound into the polymethylhydrosiloxane solution, introducing nitrogen and stirring, and carrying out hydrosilylation reaction in the presence of a catalyst to obtain SiO2A polysiloxane acrylate composite material.
Preferably, the nano SiO2Is nano SiO2Powder or silica sol;
the nano SiO2The particle size of (A) is 20 to 100 nm.
Preferably, the polyethylene glycol acrylate compound comprises one or more of methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate and polyethylene glycol methacrylate.
Preferably, the number average molecular weight of the polyethylene glycol acrylate compound is 350-1500.
Preferably, the polyethylene glycol acrylate compound, the polymethylhydrosiloxane and the nano SiO2The mass ratio of (50-100): (50-200): (1-5).
Preferably, the content of active hydrogen in the polymethylhydrosiloxane is 0.18-1.58 wt%.
Preferably, the catalyst is an isopropanol solution of chloroplatinic acid.
Preferably, the chloroplatinic acid accounts for 5-40 ppm of the total reactant mass.
Preferably, the temperature of the hydrosilylation reaction is 70-90 ℃;
the hydrosilylation reaction time is 6-10 hours.
Preferably, the hydrosilylation reaction is carried out in the absence of water and oxygen.
The invention provides SiO2The preparation method of the/polysiloxane acrylate composite material comprises the following steps: A) mixing nano SiO2Adding polyethylene glycol acrylate compound, stirring to obtain SiO2Modified polyethylene glycol acrylates; B) subjecting the SiO2Adding the modified polyethylene glycol acrylate compound into the polymethylhydrosiloxane solution, introducing nitrogen and stirring, and carrying out hydrosilylation reaction under the conditions of no water and no oxygen and the presence of a catalyst to obtain SiO2A polysiloxane acrylate composite material. O and SiO of ether bond in polyethylene glycol acrylate compound2The silanol bond of (A) forms a hydrogen bond, SiO2The method is favorable for attracting the polyethylene glycol acrylate to be orderly arranged, increases the contact probability of double bonds and active hydrogen, and improves the addition conversion rate. Meanwhile, the production method of continuously dripping raw materials in the market is improved, and the production process is simplified. Experimental results show that the conversion rate of the preparation method is as high as 97.2%.
In addition, SiO produced by the present application2The/polysiloxane acrylate composite material has a polysiloxane hydrophobic main chain and a polyoxyethylene hydrophilic side chain, and the hydrophilic and hydrophobic properties of the product can be adjusted by controlling the length of a polyoxyethylene chain segment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an IR spectrum of the product of example 3 of the present invention.
Detailed Description
The invention provides SiO2The preparation method of the/polysiloxane acrylate composite material comprises the following steps:
A) mixing nano SiO2Adding polyethylene glycol acrylate compound, stirring to obtain SiO2Modified polyethylene glycol acrylates;
B) subjecting the SiO2Adding the modified polyethylene glycol acrylate compound into the polymethylhydrosiloxane solution, introducing nitrogen and stirring, and carrying out hydrosilylation reaction under the conditions of no water and no oxygen and the presence of a catalyst to obtain SiO2A polysiloxane acrylate composite material.
In the invention, the nano SiO2The particle size of (A) is preferably 20 to 100nm, more preferably 30 to 80nm, and most preferably 50 to 70 nm; the nano SiO2Can be nano SiO2The powder can be added in the form of silica sol.
In the invention, the polyethylene glycol acrylate compound comprises one or more of methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate and polyethylene glycol methacrylate; the number average molecular weight of the polyethylene glycol acrylate compound is preferably 350-1500, more preferably 350-1000, and most preferably 350-500.
The stirring is preferably magnetic stirring, and the stirring time is preferably 0.5-1 hour.
In the invention, the polymethylhydrosiloxane solution is preferably an isopropanol solution of polymethylhydrosiloxane, and the content of active hydrogen in the polymethylhydrosiloxane is preferably 0.18-1.58 wt%, more preferably 0.18-1.0 wt%, and most preferably 0.18-0.5 wt%.
The polyethylene glycol acrylate compound, the polymethylhydrosiloxane and the nano SiO2The mass ratio of (b) is preferably (50-100): (50-200): (1-5), specifically, the mass ratio of the polyethylene glycol acrylate compound to the polymethylhydrosiloxane is preferably 1: (1-3), in the embodiment of the invention, can be 1:2, 1:275, 1:1.3 or 1: 1.83; the SiO2The mass ratio of the compound to the polyethylene glycol acrylate compound is preferably (0.01-0.05): 1, more preferably (0.015 to 0.03): 1, in embodiments of the present invention, may be 0.017:1 or 0.025: 1.
In the present invention, the catalyst is preferably chloroplatinic acid (H)2PtCl6·6H2O) in isopropanol; the chloroplatinic acid (H)2PtCl6·6H2The mass fraction of chloroplatinic acid in the isopropanol solution of O) is preferably 0.5-1%, and more preferably 0.7-0.8%; the chloroplatinic acid in the catalyst accounts for 5-40 ppm, preferably 5-10 ppm, of the total reactant, and the total reactant refers to polyethylene glycol acrylate compounds, polymethylhydrosiloxane and nano SiO2。
In the present invention, the hydrosilylation is preferably performed under anhydrous and oxygen-free conditions when the nano SiO is2When the catalyst is in the form of silica sol, a certain amount of water is contained in the silica sol, so that a certain influence is generated on the reaction, the conversion rate of the reaction is reduced, but the reaction is still obviously higher than that of the prior art which does not use nano SiO2The conversion of (a); meanwhile, the use of the silica sol can reduce the requirement of the environment on anhydrous conditions and greatly reduce the production cost. The temperature of the hydrosilylation reaction is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 80 ℃; the time of the hydrosilylation reaction is preferably 6 to 10 hours, more preferably 7 to 9 hours, and most preferably 8 hours.
After the hydrosilylation reaction is finished, removing the solvent by rotary evaporation to obtain SiO2A polysiloxane acrylate composite material.
SiO in the invention2The/polysiloxane acrylate composite material has a structure shown in a formula I:
wherein X is the polymerization degree of polyethylene glycol (X is more than or equal to 7 and less than or equal to 30), R is-H, -CH3，-CH2CH3And the like.
Because the polyethylene glycol acrylate compound contains a polyoxyethylene chain segment, the invention can realize the adjustment of the hydrophile and the hydrophobicity of the product by controlling the length of the polyoxyethylene chain segment.
Inorganic SiO as described above2Use of a composite silicone acrylate material: the skin-care product has amphipathy, physiological inertia and good skin feel, and simultaneously has the characteristics of inorganic and organic property, can be used as a surface treating agent, a fabric finishing agent and a cross-linking agent, and can also be directly applied to a biocompatible material, a leveling agent and daily cosmetics.
The invention provides SiO2The preparation method of the/polysiloxane acrylate composite material comprises the following steps: A) mixing nano SiO2Adding polyethylene glycol acrylate compound, stirring to obtain SiO2Modified polyethylene glycol acrylates; B) subjecting the SiO2Adding the modified polyethylene glycol acrylate compound into the polymethylhydrosiloxane solution, introducing nitrogen and stirring, and carrying out hydrosilylation reaction under the conditions of no water and no oxygen and the presence of a catalyst to obtain SiO2A polysiloxane acrylate composite material. O and SiO of ether bond in polyethylene glycol acrylate compound2The silanol bond of (A) forms a hydrogen bond, SiO2The method is favorable for attracting the polyethylene glycol acrylate to be orderly arranged, increases the contact probability of double bonds and active hydrogen, and improves the addition conversion rate. Meanwhile, the production method of continuously dripping raw materials in the market is improved, and the production process is simplified. Experimental results show that the conversion rate of the preparation method is as high as 97.2%.
In addition, SiO produced by the present application2The/polysiloxane acrylate composite material has a polysiloxane hydrophobic main chain and a polyoxyethylene hydrophilic side chain, and the hydrophilic and hydrophobic properties of the product can be adjusted by controlling the length of a polyoxyethylene chain segment.
To further illustrate the present invention, the following examples are provided to illustrate the present invention2The method of preparing the/polysiloxane acrylate composite material is described in detail, but it should not be construed as limiting the scope of the invention.
The products of the examples were titrated by iodometry and the conversion was calculated:
(1) 0.1g of the sample was dissolved in 10mL of CCl4Poured into a 250mL iodine vial and then added with 10mL CCl4Washing and pouring into an iodine bottle; then 10mL (0.2mol/L) of bromine-acetic acid is added; sealing the iodine bottle with 1mL of water, shaking up, and placing in the dark for reaction for 30 min;
(2) adding 25mL (10% solution) of potassium iodide into a sample iodometry bottle, and washing with deionized water and pouring into the iodometry bottle;
(3) titrating with 0.1mol/L sodium thiosulfate as standard solution, adding 1% starch solution as indicator (1mL) when the color is lightened, and continuing to titrate until the solution becomes colorless, wherein the consumed standard solution has a volume V1The mean value was taken three times for each titration. (blank titration was performed simultaneously, the volume of standard solution consumed was V0)
Calculating the mass fraction of active hydrogen:
wherein, V0-blank run consumes volume of sodium thiosulfate standard solution, mL;
V1sample set experiments consumed the volume of sodium thiosulfate standard solution, mL;
c is the concentration of the standard solution of sodium thiosulfate, mol/L;
m-the measured mass of the sample, g;
calculating the content of active hydrogen according to the formula, and calculating the hydrosilylation conversion rate of the product according to the following formula:
example 1
Adding 10g of methoxypolyethylene glycol (350) acrylate into a beaker, then adding 1g of alkaline silica sol, and magnetically stirring for 0.5h at room temperature; to obtain a firstOxyethylene glycol acrylate coated SiO2Marking as A liquid; adding 20g of polymethylhydrosiloxane (0.18 wt%) and 35ml of isopropanol serving as a solvent into a 250ml three-neck flask, directly adding the solution A into the three-neck flask, introducing nitrogen and stirring, adding 3 drops of 0.74% by mass of an isopropanol solution serving as a catalyst of chloroplatinic acid (the chloroplatinic acid accounts for 5-10 ppm of the total mass of the reaction mass) under the anhydrous and oxygen-free conditions, and reacting for 8 hours at the temperature of 70 ℃. After the reaction is finished, removing the isopropanol solvent by rotary evaporation to obtain the inorganic SiO2The bottom of the obtained product has floccule, and the iodometric titration conversion rate is 79.0%.
Example 2
10g of methoxypolyethylene glycol (350) acrylate and 0.25g of nano SiO were added to the beaker2(50nm), magnetically stirring for 1h at room temperature to obtain SiO coated with methoxypolyethylene glycol acrylate2Marking as A liquid; 27.5g of polymethylhydrosiloxane (0.18 wt%) and 35ml of isopropanol as a solvent were charged into a 250ml three-necked flask, and the solution A was directly charged into the three-necked flask, introduced with nitrogen and stirred, passed through a hydrogen peroxide solution under anhydrous and oxygen-free conditions2PtCl6·6H2Carrying out hydrosilylation reaction under the catalysis of O (5-10 ppm). The reaction was carried out at 70 ℃ for 8 h. After the reaction is finished, removing the isopropanol solvent by rotary evaporation to obtain the inorganic SiO2The obtained product is relatively stable by the composite polysiloxane acrylate graft copolymer, and the iodometry titration conversion rate is 91.7%.
Example 3
15g of methoxypolyethylene glycol (350) acrylate and 0.25g of nano SiO were added to the beaker2(50nm), magnetically stirring at room temperature for 0.5h to obtain SiO coated with methoxypolyethylene glycol acrylate2Marking as A liquid; 20g of polymethylhydrosiloxane (0.18 wt%) and 35ml of isopropanol as a solvent were added into a 250ml three-neck flask, and the solution A was directly added into the three-neck flask, introduced with nitrogen and stirred, and passed through a H-flow reactor under anhydrous and oxygen-free conditions2PtCl6(5-10 ppm) catalyzing to perform hydrosilylation. The reaction was carried out at 70 ℃ for 8 h. After the reaction is finished, the isopropanol solvent is removed by rotary evaporation to obtain uniform and stable inorganic SiO2The conversion of the compounded silicone acrylate graft copolymer was 97.2% by iodometric titration.
The infrared detection is carried out on the product prepared in the example 3, the result is shown in figure 1, and figure 1 is an infrared spectrogram of the product in the example 3 of the invention; wherein (A) is an infrared spectrum of methoxy polyethylene glycol acrylate, (B) is an infrared spectrum of polymethylhydrosiloxane having active Si-H groups, and (C) is an infrared spectrum of an addition product prepared in example 3. Comparing B and C, 1000-1093 cm-1、1260cm-1And 2963cm-1Strong absorption peaks respectively belonging to a polysiloxane main chain skeleton Si-O-Si and a side group Si-CH3And C-H stretching vibration peak. The spectrum of the polymethylhydrosiloxane PHMS (B) is 2156cm-1And 912cm-1The two absorption peaks are respectively attributed to stretching and bending vibration of Si-H, and the intensity is very large, but is very weak in the spectrogram of the product (C), which indicates that the active Si-H group is completely replaced by methoxy polyethylene glycol acrylate. Comparison of A and C, 1603cm-1The peak is a stretching vibration peak of C ═ C of methoxypolyethylene glycol acrylate, and the peak is weakened in a spectrum of the product (C) and is 1100-1150 cm-1An absorption peak of polyoxyethylene ether bond appears nearby and is partially overlapped with a double-shoulder peak of a Si-O-Si bond, which also indicates that the methoxypolyethylene glycol acrylate has relatively fully performed addition reaction, and a target product is synthesized.
Example 4
Adding 15g of methoxypolyethylene glycol (350) acrylate and 1g of acidic silica sol into a beaker, and magnetically stirring for 1 hour at room temperature to obtain SiO coated with methoxypolyethylene glycol acrylate2(50nm) as solution A; 27.5g of polymethylhydrosiloxane (0.18 wt%) and 35ml of isopropanol as a solvent were charged into a 250ml three-necked flask, and the solution A was directly charged into the three-necked flask, introduced with nitrogen and stirred, passed through a hydrogen peroxide solution under anhydrous and oxygen-free conditions2PtCl6·6H2Carrying out hydrosilylation reaction under the catalysis of O (5-10 ppm). The reaction was carried out at 70 ℃ for 8 h. After the reaction is finished, removing the isopropanol solvent by rotary evaporation to obtain the inorganic SiO2Composite silicone acrylate graft copolymers with floc on the bottom and delamination of the resulting productsThe iodometric titration conversion was 84.6%.
Comparative example 1
In a 250ml three-necked flask, 15g of methoxypolyethylene glycol (350) acrylate was directly charged, followed by 20g of polymethylhydrosiloxane (0.18 wt%) and 35ml of isopropanol as a solvent, passed through nitrogen and stirred, and then passed through H under anhydrous and oxygen-free conditions2PtCl6·6H2Carrying out hydrosilylation reaction under the catalysis of O (5-10 ppm), reacting for 8 hours at the temperature of 70 ℃, and obtaining a product with a layering phenomenon, wherein the iodometry titration conversion rate is 69.5%.
TABLE 1 conversion rates of inventive examples 1 to 4 and comparative example 1
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. SiO (silicon dioxide)2The preparation method of the/polysiloxane acrylate composite material comprises the following steps:
A) mixing nano SiO2Adding polyethylene glycol acrylate compound, stirring to obtain SiO2Modified polyethylene glycol acrylates;
the number average molecular weight of the polyethylene glycol acrylate compound is 350-1500;
B) subjecting the SiO2Adding the modified polyethylene glycol acrylate compound into the polymethylhydrosiloxane solution, introducing nitrogen and stirring, and carrying out hydrosilylation reaction in the presence of a catalyst to obtain SiO2Polysiloxane propyleneAn acid ester composite;
the polyethylene glycol acrylate compound, the polymethylhydrosiloxane and the nano SiO2The mass ratio of (50-100): (50-200): (1-5).
2. The method of claim 1, wherein the nano SiO is2Is nano SiO2Powder or silica sol;
the nano SiO2The particle size of (A) is 20 to 100 nm.
3. The preparation method according to claim 1, wherein the polyethylene glycol acrylate compound comprises one or more of methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate and polyethylene glycol methacrylate.
4. The preparation method according to claim 1, wherein the active hydrogen content of the polymethylhydrosiloxane is 0.18-1.58 wt%.
5. The method of claim 1, wherein the catalyst is a solution of chloroplatinic acid in isopropanol.
6. The method according to claim 5, wherein the chloroplatinic acid is 5 to 40ppm based on the total reaction mass.
7. The method according to claim 1, wherein the temperature of the hydrosilylation reaction is 70 to 90 ℃;
the hydrosilylation reaction time is 6-10 hours.
8. The method according to any one of claims 1 to 7, wherein the hydrosilylation reaction is carried out under anhydrous and oxygen-free conditions.
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