CN105348533A - Novel organic and inorganic hybrid silicon resin nano particles and preparation method - Google Patents

Novel organic and inorganic hybrid silicon resin nano particles and preparation method Download PDF

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Publication number
CN105348533A
CN105348533A CN201510867262.2A CN201510867262A CN105348533A CN 105348533 A CN105348533 A CN 105348533A CN 201510867262 A CN201510867262 A CN 201510867262A CN 105348533 A CN105348533 A CN 105348533A
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China
Prior art keywords
particles
alcohol
silicone resin
preparation
inorganic hybridization
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CN201510867262.2A
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Chinese (zh)
Inventor
陈道伟
郑云峰
高翔
侯建超
胡家啟
纪建华
吴惠
郭欢
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ZHEJIANG KAIHUA SYNTHETIC MATERIALS CO Ltd
Zhejiang Xinan Chemical Industrial Group Co Ltd
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ZHEJIANG KAIHUA SYNTHETIC MATERIALS CO Ltd
Zhejiang Xinan Chemical Industrial Group Co Ltd
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Priority to CN201510867262.2A priority Critical patent/CN105348533A/en
Publication of CN105348533A publication Critical patent/CN105348533A/en
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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
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses organic and inorganic hybrid silicon resin nano particles and a preparation method. The organic and inorganic hybrid silicon resin nano particles of which the particle size ranges from 300 nm to 900 nm are obtained through a one-step method of conducting hydrolysis and precipitation on bis(trichlorosilyl)ethane in an alcohol-water solution. The nano particles have the advantage that inorganic white carbon black modifies the mechanical property of a polymer, an organic carbon chain is directly introduced into a molecular chain structure, the compatibility of the particles and polymer materials can be improved, the degree of dispersion of the particles is improved, the strength between the particles and a polymer chain is strengthened, the modification effect of the particles is improved, and the great application potential on toughness and modification of the polymer is achieved. According to the preparation method, the production process is simple, the requirements on raw materials and equipment are low, and a polycondensation reaction of silicon hydroxyl is reduced by adopting the alcohol-water solution; the nano-size particles can be obtained, and the nano-size particles have the advantages of being small in particle size, large in specific surface area and high in degree of dispersion; a large amount of alcohol is adopted for treatment in later period, the number of silicon hydroxyl on the surfaces of the nano particles is decreased, and the compatibility of the particles and the polymer is improved.

Description

A kind of novel organic inorganic hybridization silicone resin nanoparticle and preparation method
Technical field
The present invention relates to a kind of new texture silicone resin nano material, particularly relate to a kind of method that precipitator method prepare organic inorganic hybridization silicone resin nanoparticle.
Background technology
White carbon black is a kind of important polymer modification material.White carbon black and unformed hydrated SiO 2, molecular formula is SiO 2h 2o, it is a kind of white, tasteless, powder material, the advantageous property such as there is polymolecularity, chemical stability, high temperature resistant, electrical insulating property is good, often be used to the modification of the materials such as plastics, rubber, coating, binding agent, have the mechaanical property of materials and very significantly improve, its tear strength, tensile break strength etc. can be improved.
White carbon black surface often has great amount of hydroxy group to exist; therefore wetting ability is stronger; and industrial use white carbon black and polymer materials is blended prepare matrix material to improve polymer materials character time; due to the hydrophobicity of most of plastics, rubber, often can there is the serious agglomeration problem of white carbon black and cause modified effect not good.Therefore, the consistency in order to increase white carbon black and hydrophobic polymer material often needs to carry out modification to white carbon black.Method common at present has alcohol esterification process, reactive organic silicon compound method, ion surface polymer graft method etc.These method successfuls, can strengthen the reactive force between white carbon black and organic polymer molecules chain.But because needs are twice-modified, not only add cost, secondary processing also affects to some extent on character such as the particle diameters of white carbon black, very easily causes the reunion of white carbon black and causes modified effect to reduce.
Therefore, this patent proposes a kind of novel organic inorganic hybridization silicone resin nanoparticle and preparation method thereof, this product can regard a kind of novel organic white carbon black as, organic carbochain is introduced siloxane bond main chain, the consistency of the organic white carbon black of gained and polymkeric substance can be improved by the mutual winding of this carbochain and polymer molecular chain, can be used for the modification of the polymer materials such as plastics, rubber, improve its mechanical property.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of novel organic inorganic hybridization silicone resin nanoparticle and preparation method thereof is provided.
Organic inorganic hybridization silicone resin nanoparticle of the present invention, average particle diameter is 300 ~ 900nm, has cross-linked network molecular chain structure, and its network repeat unit structure is
Lattice chain end structure is-O-R, R be hydrogen atom and carbonatoms is the alkyl of two to six.
Object of the present invention also comprises a kind of described organic inorganic hybridization silicone resin nanoparticle preparation method, comprises the steps:
1) alcohol of the water of 50-100 weight part and 10-50 weight part being mixed with alcohol solution adds in reactor, passes into the HCl that nitrogen gas stirring generates to remove reaction, controls temperature of reaction at 20-60 degree Celsius, preferred 20-40 DEG C;
2) two (trichlorine is silica-based) ethane of 10-30 weight part were added drop-wise in reactor in 10-60 minute react, the alcohol adding 10-50 weight part after dropwising continues reaction 10-30 minute, be precipitated thing to filter, and wash with water, dry, obtain organic inorganic hybridization silicone resin nanoparticle.
Described alcohol to be carbon atom quantity be two to six Organic Alcohol.
The invention has the beneficial effects as follows, the present invention utilizes alcohol-water system to adopt the precipitator method to prepare organic inorganic hybridization silicone resin nanoparticle.There is following feature:
1, this technology proposes a kind of novel organic inorganic hybridization silicone resin molecular chain structure, this resin nano particle possesses the advantage of inorganic white carbon black to the modification of polymkeric substance mechanical property, organic carbon connection is directly introduced molecular chain structure simultaneously, the consistency of this particle and polymer materials can be improved, the intensity improve dispersion of particles degree, strengthening between particle and polymer chain, improves particle modified effect;
2, the precipitator method one step prepares nanoparticle, and production process is simple, low to the requirement of raw material, equipment;
3, adopt alcohol solution to reduce the polycondensation of silicone hydroxyl, can nanometer particle be obtained, possess the advantage that particle diameter is little, reference area is large, degree of scatter is high;
4, the later stage adopts a large amount of alcohol process, reduces the quantity of nanoparticle surface silicone hydroxyl, improves the consistency of nanoparticle and polymkeric substance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of two (trichlorine the is silica-based) ethane of raw material;
Fig. 2 is the infrared spectrum of the organic inorganic hybridization silicone resin nanoparticle that the embodiment of the present invention 1 obtains;
Fig. 3 is the scanning electron microscope (SEM) photograph of the organic inorganic hybridization silicone resin nanoparticle that the embodiment of the present invention 1 obtains;
Fig. 4 is the particle size dispersion figure of the organic inorganic hybridization silicone resin nanoparticle that the embodiment of the present invention 1 obtains;
Fig. 5 is the organic inorganic hybridization silicone resin nanoparticle that obtains of the present invention to the stress-strain diagram of this polymkeric substance of copolymer-modified front and back of vinylbenzene and n-butyl acrylate.
Embodiment
The present invention be a kind of precipitator method to prepare the method for organic inorganic hybridization silicone resin nanoparticle, comprise the steps:
A kind of organic inorganic hybridization silicone resin nanoparticle preparation method according to claim 1, is characterized in that, comprise the steps:
1) alcohol of the water of 50-100 weight part and 10-50 weight part being mixed with alcohol solution adds in reactor, passes into the HCl that nitrogen gas stirring generates to remove reaction, controls temperature of reaction at 20-40 degree Celsius;
2) two (trichlorine is silica-based) ethane of 10-30 weight part were added drop-wise in reactor in 10-60 minute react, the alcohol adding 10-50 weight part after dropwising continues reaction 10-30 minute, be precipitated thing to filter, and wash with water, dry, obtain organic inorganic hybridization silicone resin nanoparticle.
Described alcohol to be carbon atom quantity be two to six Organic Alcohol.
The characteristic group of material characterizes and is obtained by Nicolet5700 infrared spectrometer sign, and adopt transmitted light detection method to operate at ambient temperature, sweep limit is 4000 ~ 500cm -1, resolving power is 4cm -1, scanning times is 16 times.
Nanoparticle pattern adopts the observation of FDAC SU-70 field emission scanning electron microscope to obtain, and through gold-plated instrument gold-plated (the metal spraying time is 90s), directly uses scanning electron microscopic observation.
Nano particle diameter is tested by Britain Malvern company Zetasizer3000HSA nanometer laser particle size analyzer and is obtained, and is sent out measure at 25 DEG C by dynamic light scattering, and particle diameter is three mean values measured.
Nanoparticle and polymer composites prepare by German ThermoElectron (Karlsruhe) GmbH company HAAKEMiniLabII miniature high performance composite mixing moulding system melt is blended, processing conditions is: extrusion temperature 210-230 DEG C, screw speed 60-120rpm.The injection moulding of material carries out in HAAKEMiniJet miniature high performance composite mixing moulding system, processing conditions is: injection temperature 260-280 DEG C, injection pressure 1050-1150bar, injection time 10-15 second, die temperature 50 DEG C-70 DEG C, dwell pressure 850-950bar, dwell time 10-15 second.
The tensile stress strain curve of polymkeric substance is obtained by German Zwick company Zwick/RoellZ020 universal testing machine test, testing method is with reference to GB9341-2000, and probe temperature is 20 DEG C, and force transducer type is 20KN, Elongation test speed is 1mm/min, and preload force is 1N.
The multipolymer of vinylbenzene and n-butyl acrylate is that commerical prod directly obtains, and molecular weight is 100,000, and vinylbenzene mass fraction is 40%.
Describe the present invention in detail according to drawings and embodiments below, object of the present invention and effect will become more obvious.
Embodiment 1:
Add in reactor after the ethanol of the water of 100 weight parts and 10 weight parts is mixed with alcohol solution, pass into the HCl that nitrogen gas stirring generates to remove reaction, control temperature of reaction at 20 degrees Celsius, two (trichlorine is silica-based) ethane of 10 weight parts were added drop-wise in reactor in 30 minutes and react, the ethanol adding 50 weight parts after dropwising continues reaction 20 minutes, be precipitated thing to filter, and wash with water, dry, obtain organic inorganic hybridization silicone resin nanoparticle.Comparison diagram 1 and Fig. 2 can find out, the Si-Cl key characteristic peak that reaction terminates two (trichlorine the is silica-based) ethane of rear raw material disappears, Si-O-Si and Si-OH base key characteristic peak is obvious, at 1130-1000cm -1place has gone out a wider peak and complicated, and illustrate that on Si-O-Si key, Si is with side chain, result is identical with expected product structure.Fig. 3 is the electron-microscope scanning figure of organic inorganic hybridization silicone resin nanoparticle in water after ultrasonic, can find out that this product primary particle size is less than 1 micron, be agglomerated into the particle of several microns in water.The grain size distribution of what Fig. 4 provided is ultrasonic measurement, can find out that particle diameter is mainly at about 500nm, calculating averaging of income particle diameter is 640nm.
Embodiment 2:
Add in reactor after the ethanol of the water of 50 weight parts and 50 weight parts is mixed with alcohol solution, pass into the HCl that nitrogen gas stirring generates to remove reaction, control temperature of reaction at 20 degrees Celsius, two (trichlorine is silica-based) ethane of 30 weight parts were added drop-wise in reactor in 60 minutes and react, the propyl carbinol adding 10 weight parts after dropwising continues reaction 30 minutes, be precipitated thing to filter, and wash with water, dry, obtain organic inorganic hybridization silicone resin nanoparticle, median size is 310nm.
Embodiment 3:
Add in reactor after the propyl carbinol of the water of 100 weight parts and 50 weight parts is mixed with alcohol solution, pass into the HCl that nitrogen gas stirring generates to remove reaction, control temperature of reaction at 40 degrees Celsius, two (trichlorine is silica-based) ethane of 30 weight parts were added drop-wise in reactor in 10 minutes and react, the propyl carbinol adding 50 weight parts after dropwising continues reaction 30 minutes, be precipitated thing to filter, and wash with water, dry, obtain organic inorganic hybridization silicone resin nanoparticle, median size is 870nm.
Embodiment 4:
Add in reactor after the ethanol of the water of 100 weight parts and 10 weight parts is mixed with alcohol solution, pass into the HCl that nitrogen gas stirring generates to remove reaction, control temperature of reaction at 40 degrees Celsius, two (trichlorine is silica-based) ethane of 10 weight parts were added drop-wise in reactor in 50 minutes and react, the ethanol adding 10 weight parts after dropwising continues reaction 10 minutes, be precipitated thing to filter, and wash with water, dry, obtain organic inorganic hybridization silicone resin nanoparticle, median size is 710nm.
Embodiment 5:
Add in reactor after the propyl carbinol of the water of 70 weight parts and 30 weight parts is mixed with alcohol solution, pass into the HCl that nitrogen gas stirring generates to remove reaction, control temperature of reaction at 20 degrees Celsius, two (trichlorine is silica-based) ethane of 10 weight parts were added drop-wise in reactor in 30 minutes and react, the propyl carbinol adding 50 weight parts after dropwising continues reaction 30 minutes, be precipitated thing to filter, and wash with water, dry, obtain organic inorganic hybridization silicone resin nanoparticle, median size is 430nm.The multipolymer of the organic inorganic hybridization silicone resin nanoparticle obtained and vinylbenzene and n-butyl acrylate is carried out blended processing by miniature high performance composite mixing moulding system, wherein the parts by weight of organic inorganic hybridization silicone resin nanoparticle are 5%, Fig. 5 is the stretching mechanical curve adding this polymkeric substance before and after resin nano particle.Can find out, the interpolation of this organic inorganic hybridization silicone resin nanoparticle improves obviously the mechanical property of polymkeric substance, and its modulus significantly improves, and elongation at break improves.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.

Claims (4)

1. an organic inorganic hybridization silicone resin nanoparticle, it is characterized in that, organic inorganic hybridization silicone resin exists with nanoparticle form, and average particle diameter is 300 ~ 900nm, this organic inorganic hybridization silicone resin has cross-linked network molecular chain structure, and its network repeat unit structure is:
Lattice chain end structure is-O-R, R be hydrogen atom and carbonatoms is the alkyl of two to six.
2. a preparation method for organic inorganic hybridization silicone resin nanoparticle according to claim 1, is characterized in that, comprise the steps:
1) alcohol of the water of 50-100 weight part and 10-50 weight part being mixed into alcohol solution adds in reactor, controls temperature of reaction at 20-60 degree Celsius, passes into nitrogen gas stirring;
2) two (trichlorine is silica-based) ethane of 10-30 weight part were added drop-wise in reactor in 10-60 minute react, the alcohol adding 10-50 weight part after dropwising continues reaction 10-30 minute, reaction terminates rear filtration and is precipitated thing, water washing, drying, obtain organic inorganic hybridization silicone resin nanoparticle.
3. preparation method according to claim 2, is characterized in that described alcohol to be carbon atom quantity is the Organic Alcohol of two to six.
4. the preparation method as described in claim 2-3, is characterized in that described two (trichlorine is silica-based) ethane can be the high products obtained through rectifying that boils of by-product being rich in two (trichlorine is silica-based) ethane obtained in vinyl silanes preparation process.
CN201510867262.2A 2015-11-27 2015-11-27 Novel organic and inorganic hybrid silicon resin nano particles and preparation method Pending CN105348533A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109266211A (en) * 2018-08-28 2019-01-25 淮阴工学院 Organopolysiloxane super hydrophobic coating and preparation method thereof
CN114181557A (en) * 2021-09-30 2022-03-15 中国海洋石油集团有限公司 Water-based fireproof radiation-resistant coating system and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603787A (en) * 2012-02-14 2012-07-25 长安大学 Synthesis method of monodisperse bridged polysilsesquioxanes microspheres

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603787A (en) * 2012-02-14 2012-07-25 长安大学 Synthesis method of monodisperse bridged polysilsesquioxanes microspheres

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
OVIATT, HW: "ALKYLENE-BRIDGED SILSESQUIOXANE SOL-GEL SYNTHESIS AND XEROGEL CHARACTERIZATION - MOLECULAR REQUIREMENTS FOR POROSITY", 《CHEMISTRY OF MATERIALS》 *
关士友: "桥联聚倍半硅氧烷的发展", 《高分子通报》 *
吕志卿: "桥联聚倍半硅氧烷（BPS）的研究进展", 《材料导报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109266211A (en) * 2018-08-28 2019-01-25 淮阴工学院 Organopolysiloxane super hydrophobic coating and preparation method thereof
CN109266211B (en) * 2018-08-28 2020-07-24 淮阴工学院 Organopolysiloxane super-hydrophobic coating and preparation method thereof
CN114181557A (en) * 2021-09-30 2022-03-15 中国海洋石油集团有限公司 Water-based fireproof radiation-resistant coating system and preparation method thereof

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