CN112480416B - Preparation method of polyborosilazane shear thickening liquid - Google Patents
Preparation method of polyborosilazane shear thickening liquid Download PDFInfo
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- CN112480416B CN112480416B CN202011344140.2A CN202011344140A CN112480416B CN 112480416 B CN112480416 B CN 112480416B CN 202011344140 A CN202011344140 A CN 202011344140A CN 112480416 B CN112480416 B CN 112480416B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/56—Boron-containing linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/14—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Abstract
The invention belongs to the technical field of preparation of organosilicon materials, and particularly relates to a preparation method of a polyborosilazane shear thickening liquid, which comprises the following steps: uniformly stirring an aminosilane coupling agent and water, and heating; adding boric acid, heating and then carrying out heat preservation reaction; and reducing the pressure of the reaction product to obtain the polyborosiloxane shear thickening liquid. The method has the advantages of simple process, in-situ formation of the dispersion phase in the dispersion medium, no impurities, good compatibility of the dispersion phase and the dispersion medium, environmental friendliness, yield of more than 95 percent, suitability for large-scale industrial production and wide application prospect; the content of the dispersed phase is controllable, the viscosity is controllable, the raw materials are easy to obtain, and the price is low; the invention does not need to add additional dispersed phase, and the liquid is not layered and has high stability.
Description
Technical Field
The invention belongs to the technical field of preparation of organosilicon materials, and particularly relates to a preparation method of a polyborosilazane shear thickening liquid.
Background
Shear thickening fluids are non-newtonian fluids, and the viscosity of the fluid increases with increasing shear force when the shear force applied to the fluid reaches a certain threshold. Based on the special characteristics of the shear thickening fluid, damping devices such as shock absorbers, soft protective clothing, cushioning devices and the like are developed in succession. The thickening of shear thickening fluids is generally accomplished by the interaction of the dispersed phase and the dispersing medium. The dispersed phase is composed of silicon dioxide, calcium carbonate, polystyrene and polymethyl methacrylate particles with spherical shapes, and the dispersion medium is composed of polyethylene glycol, polyalcohol, water and the like. The uniform dispersion of the dispersed phase in the dispersion medium is a major factor in determining the performance of the shear thickening fluid. For example, the invention patent (CN201911362143.6) discloses an ionic liquid-based shear thickening liquid and a preparation method thereof, wherein polymethyl methacrylate (PMMA) particles are used as a disperse phase, and imidazole-based ionic liquid is used as a dispersion medium; the invention patent (CN201811235892.8) discloses a preparation method of a shear thickening liquid, polyethylene glycol is used as a dispersion medium, NiAl-LDH/SiO2 nano particles are used as a dispersion phase, a polymer oxidation layer weakens the electrostatic repulsion between particles to a certain extent, and a stronger shear thickening effect is generated; the invention patent (CN201710156357.2) discloses a preparation method of high-impact-resistance shear thickening liquid, which mainly comprises mixed liquid of nano silicon dioxide and polyethylene glycol, and adopts a method of combining mechanical mixing and ultrasonic oscillation to prepare the shear thickening liquid with stable structure and good impact resistance; the invention patent (CN201910307737.0) discloses a high-viscosity heat-dissipation ultraviolet-resistant shear thickening liquid and a preparation method thereof, wherein the high-viscosity heat-dissipation ultraviolet-resistant shear thickening liquid comprises spherical silicon dioxide, polyethylene glycol, graphene and montmorillonite, and has excellent heat-conducting property; the invention patent (CN201710723695.X) discloses a method for preparing shear thickening liquid, which comprises the steps of adding nano silicon dioxide microspheres and a silane coupling agent, and obtaining the shear thickening liquid with stable performance by adopting a mode of directly heating a dispersion medium.
Shear thickening fluids are currently composed of a dispersed phase and a dispersion medium. The system compatibility of the dispersion phase and the dispersion medium has great influence on the performance of the shear thickening liquid, and as the dispersion phase and the dispersion medium in the liquid are secondarily mixed and do not form chemical bonds and actions between the dispersion phase and the dispersion medium, the dispersion phase is easy to agglomerate and separate out again in the dispersion medium, and the structure is unstable.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a preparation method of polyborosilazane shear thickening liquid, which solves the technical problems of poor compatibility between a dispersed phase and a dispersion medium and unstable structure in the preparation of the prior art, and has the advantages of environment-friendly preparation method, high yield, suitability for large-scale industrial production and wide application field.
The preparation method of the polyborosilazane shear thickening liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly stirring an aminosilane coupling agent and water, and heating;
(2) adding boric acid, heating and then carrying out heat preservation reaction;
(3) and reducing the pressure of the reaction product to obtain the polyborosiloxane shear thickening liquid.
The amino silane coupling agent is one or a plurality of compounds of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, aminoethyl aminopropyl methyl dimethoxysilane, aminoethyl aminopropyl triethoxysilane, aminoethyl aminopropyl methyl diethoxysilane, phenylaminomethyl trimethoxysilane, phenylaminomethyl triethoxysilane, aminoethyl aminopropyl trimethoxysilane and amino coupling agent oligomer.
The molar ratio of the aminosilane coupling agent to water is 1: (0.01-0.50).
In the step (1), the temperature is increased to 40-60 ℃.
The molar ratio of the aminosilane coupling agent to the boric acid is as follows: 1: (0.05-1).
In the step (2), the temperature is raised to 60-90 ℃ and the reaction time is 1-5 hours.
The vacuum degree of the reduced pressure dehydration is lower than-0.085 MPa, the dehydration temperature is 90-120 ℃ until no fraction is produced.
The preparation method of the invention has the following mechanism:
the invention utilizes the reaction of amino group in amino silane coupling agent and boric acid to form bond, and then the silane coupling agent takes boron-oxygen radical as core and reacts with water to carry out in-situ polymerization on the surface. The invention utilizes the interaction of the in-situ formation of the dispersed phase particles in the dispersion medium to regulate and control the two, the formed clusters are uniformly dispersed in the silane coupling agent, and the chemical bonds and the action between the two lead the clusters to show the shear thickening performance in the shearing process.
Compared with the prior art, the invention has the following beneficial effects.
(1) The method has the advantages of simple process, in-situ formation of the dispersion phase in the dispersion medium, no impurities, good compatibility of the dispersion phase and the dispersion medium, environmental friendliness, yield of more than 95 percent, suitability for large-scale industrial production and wide application prospect;
(2) the content of the dispersed phase is controllable, the viscosity is controllable, the raw materials are easy to obtain, and the price is low;
(3) the invention does not need to add additional dispersed phase, and the liquid is not layered and has high stability.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
3.6g of water are added to 206g of aminoethylaminopropylmethyldimethoxysilane and heated to 50 ℃ with stirring. Then 30g of boric acid is added into the solvent, stirred rapidly, and heated to 80 ℃ for reaction for 3 h. Then heating to 100 ℃, and removing the fraction under the vacuum degree of-0.095 MPa until no fraction is obtained, thus obtaining the shear thickening polyborosilazane. Viscosity of 2040mm at the rotating speed of 10r/min2Viscosity 2200mm at 20r/min2Viscosity 2407mm at 50r/min2Viscosity 2655mm at 100r/min2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 97%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 2
Except that 54g of boric acid was added as described in example 1. The viscosity of the obtained shear thickening polyborosilazane is 52800mm at the rotating speed of 10r/min2/s, rotating speed of 20r/min, 55200mm2Viscosity 56100mm at a speed of 50r/min2S, 57020mm at a rotation speed of 100r/min2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 95%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 3
Except that 220g of aminoethylaminopropyltrimethoxysilane and 6g of boric acid were added as described in example 1. The obtained shear thickening polyborosilazane has the viscosity of 108mm at the rotating speed of 10r/min2At a rotational speed of 20r/min of 116 mm/s2Viscosity 132mm at a speed of 50 r/min/s2S, 148mm at a rotation speed of 100r/min2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 96%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 4
Except that 22g of gamma-aminopropyltriethoxysilane and 60g of boric acid were added as described in example 1. The viscosity of the obtained shear thickening polyborosilazane is 7800 at the rotating speed of 10r/minmm2(s) 7909mm at a rotation speed of 20r/min2Viscosity 8120mm at a rotation speed of 50r/min2(s) 8370mm at a rotation speed of 100r/min2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 97%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 5
Except that 201g of phenylaminomethyltrimethoxysilane and 60g of boric acid were added as described in example 1. The viscosity of the obtained shear thickening polyborosilazane is 3650mm at the rotating speed of 10r/min2(s) at a rotation speed of 20r/min of 3860mm2Viscosity 3900mm at a rotational speed of 50r/min2S, rotation speed of 100r/min 4020mm2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 97%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 6
As in example 1, except that 9g of water was added. The obtained shear thickening polyborosilazane has viscosity of 20500mm at the rotating speed of 10r/min2(s) 22600mm at a rotation speed of 20r/min2Viscosity 24960mm at a speed of 50r/min2(s) 25100mm at 100r/min2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 98%, and the liquid has no layering at the centrifugal rotating speed of 5000 r/min for 10min and has a stable structure.
Example 7
The reaction was carried out as described in example 1, except that the reaction temperature after the addition of boric acid was 60 ℃ for 1 hour. The viscosity of the obtained shear thickening polyborosilazane is 1450mm at the rotating speed of 10r/min2(s), rotation speed of 1480mm at 20r/min2(s) viscosity 1510mm at 50r/min2(s) 1620mm at a rotation speed of 100r/min2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 96%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 8
As described in example 1, except thatThe reaction temperature after adding boric acid was 90 ℃ and the reaction time was 5 hours. The viscosity of the obtained shear-thickening polyborosilazane is 3850mm at the rotating speed of 10r/min2S, rotating speed of 20r/min 4020mm2Viscosity of 4205mm at a speed of 50r/min24280mm at a rotation speed of 100 r/min/s2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 96%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 9
The procedure was as in example 1, except that the degree of vacuum in the vacuum degassing was-0.085 MPa and the degassing temperature was 120 ℃ until no distillate was obtained. Obtaining the viscosity of 2230mm of the shear thickening polyborosilazane at the rotating speed of 10r/min2Viscosity at 20r/min of 2400 mm/s2Viscosity 2490mm at 50r/min2Viscosity 2720mm at 100r/min2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 96%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Example 10
The procedure is as described in example 1, except that 100g of aminoethylaminopropylmethyldimethoxysilane and 100g of aminoethylaminopropyltriethoxysilane are used. The viscosity of the shear thickening polyborosilazane is 3100mm under the rotating speed of 10r/min2(s) viscosity at 20r/min 3520mm2Viscosity at 50r/min of 3690 mm/s2Viscosity at 100r/min of 3750 mm/s2/s。
The yield of the shear thickening polyborosilazane prepared by the embodiment reaches 95%, and the liquid has no layering at the centrifugal speed of 5000 r/min for 10min and has a stable structure.
Claims (2)
1. A preparation method of polyborosilazane shear thickening liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly stirring an aminosilane coupling agent and water, and heating to 40-60 ℃;
(2) adding boric acid, heating to 60-90 ℃, and then carrying out heat preservation reaction for 1-5 hours;
(3) reducing the pressure of the reaction product to a low degree, wherein the vacuum degree of the reduced pressure is lower than-0.085 MPa, the reduction temperature is 90-120 ℃, and the polyborosiloxane shear thickening liquid is obtained until no fraction is produced;
the molar ratio of the aminosilane coupling agent to the boric acid is as follows: 1: (0.05-1);
the molar ratio of the aminosilane coupling agent to water is 1: (0.01-0.50).
2. A method of preparing a polyborosilazane shear-thickening fluid according to claim 1, characterized in that: the amino silane coupling agent is one or a plurality of compounds of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, aminoethyl aminopropyl methyl dimethoxysilane, aminoethyl aminopropyl triethoxysilane, aminoethyl aminopropyl methyl diethoxysilane, phenylaminomethyl trimethoxysilane, phenylaminomethyl triethoxysilane, aminoethyl aminopropyl trimethoxysilane and amino coupling agent oligomer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101189283A (en) * | 2005-05-31 | 2008-05-28 | 日东纺绩株式会社 | Polymer made from organosilane compound and boron compound |
| JP2008133334A (en) * | 2006-11-28 | 2008-06-12 | Nitto Boseki Co Ltd | Imidazolesilane-containing rust-preventive agent |
| CN103145941A (en) * | 2013-03-19 | 2013-06-12 | 北京化工大学 | Preparation method of polyurethane energy-absorbing material |
| CN108892952A (en) * | 2018-07-17 | 2018-11-27 | 北京化工大学常州先进材料研究院 | A kind of preparation of the boron modified shock resistance organosilicon material of silicon |
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- 2020-11-26 CN CN202011344140.2A patent/CN112480416B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101189283A (en) * | 2005-05-31 | 2008-05-28 | 日东纺绩株式会社 | Polymer made from organosilane compound and boron compound |
| JP2008133334A (en) * | 2006-11-28 | 2008-06-12 | Nitto Boseki Co Ltd | Imidazolesilane-containing rust-preventive agent |
| CN103145941A (en) * | 2013-03-19 | 2013-06-12 | 北京化工大学 | Preparation method of polyurethane energy-absorbing material |
| CN108892952A (en) * | 2018-07-17 | 2018-11-27 | 北京化工大学常州先进材料研究院 | A kind of preparation of the boron modified shock resistance organosilicon material of silicon |
Non-Patent Citations (1)
| Title |
|---|
| Unimodal and bimodal networks of physically crosslinked polyborodimethylsiloxane: viscoelastic and equibiaxial extension behaviors;Nispa Seetapan等;《J Polym Res》;20130602;第20卷;第183(1/9)页右栏最后1段、第183(2/9)页左栏最后1段、第183(4/9)页右栏最后1段 * |
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Effective date of registration: 20221222 Address after: 541299 No. 18, North Welfare Road, Dingjiang Town, Lingchuan County, Guilin City, Guangxi Zhuang Autonomous Region Patentee after: Guilin Baolongda New Material Co.,Ltd. Address before: No.16 Haichuan Road, Jining high tech Zone, Shandong Province, 272001 Patentee before: JINING University |