CN105524300B - A kind of modified manometer silicon dioxide and preparation method thereof - Google Patents
A kind of modified manometer silicon dioxide and preparation method thereof Download PDFInfo
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- CN105524300B CN105524300B CN201610047610.6A CN201610047610A CN105524300B CN 105524300 B CN105524300 B CN 105524300B CN 201610047610 A CN201610047610 A CN 201610047610A CN 105524300 B CN105524300 B CN 105524300B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
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Abstract
The invention belongs to the modification technology of the nano silicon of composite, more particularly to suitable for ring-type mutual-phenenyl two acid bromide two alcohol ester's nano composite material nano silicon modification technology.The synthetic method that the present invention designs is reasonable, and obtained modified nano silicon dioxide particles have dispersiveness well；The modified nano silicon dioxide particles that the present invention obtains, that is, serve as filler and serve as catalyst again, the polybutylene terephthalate (PBT)/nanometer silicon dioxide composite material being prepared has good toughness.
Description
Technical field
The invention belongs to the modification technology of the nano silicon of composite, more particularly to suitable for ring-type to benzene two
The modification technology of the nano silicon of formic acid butanediol ester nano composite material.
Background technology
Ring-type mutual-phenenyl two acid bromide two alcohol ester oligomer (CBT) is a kind of to have high flowing, high infiltration, high filling capacity concurrently
Composite matrix resin, the cyclic oligomer being made up of dimer to heptamer.CBT melt viscosities it is low (24mPas,
190 DEG C), various reinforcements can be infiltrated after melting rapidly；Catalyst is added, can the ring-opening polymerisation at a temperature of less than product fusing point
Obtain polybutylene terephthalate (PBT) (PBT, the polybutylene terephthalate (PBT) mark for polymerizeing to obtain by CBT of HMW
PCBT is designated as, with the conventional PBT of difference), reaction is easily controlled and discharged without small molecule by-product, reactionless heat, can be rapid-result soon
Type.CBT has very strong representativeness, causes industrial quarters and as currently the only industrialized aromatic radical cyclic oligoester
The common research interest of art circle.But CBT occur polymerisation it is usual while polymerization while crystallize, it is intermolecular not tie up knot, therefore
PCBT fragility is very big and comprehensive mechanical property is inadequate.
Nano silicon (SiO2) there is big, inexpensive, nontoxic, the good Environmental compatibility of specific surface area and high temperature resistant
It is a kind of excellent reinforcing material etc. excellent specific property.In view of SiO2Surface energy is high, easily reunites, difficult with general blend method
To obtain the dispersed and Nano-meter SiO_2 on nanoscale2Particle and the good interfacial adhesion of macromolecule matrix storeroom.Cause
This is preparing SiO2During nano composite material, surface modification need to be carried out to it, to improve SiO2The interface compatibility of particle and matrix
And its dispersiveness in the base, this is to realize SiO2Key of the particle to the activeness and quietness of matrix material.
The content of the invention
The nanometer silicon dioxide particle modified it is an object of the invention to provide a kind of surface containing catalyst and its synthesis side
Method, the main reunion for breaking nano silicon using surfactant, then carries out silane coupler in silica surface
It is modified, then carry out the graft modification of tin catalyst.This nanometer silicon dioxide particle, it can both be directly used as poly- terephthaldehyde
The filler of sour butanediol ester, can serve as the catalyst of reaction again, therefore be advantageous to improve the processability of composite, and more
Add environmental protection.
The present inventor passes through in-depth study, by specific method of modifying, obtains the nanometer two of tin catalyst modification
Silica.Pass through conventional composite material and preparation method thereof, you can the polybutylene terephthalate (PBT) of high tenacity/receive is prepared
Rice silicon dioxide composite material.
That is, the nano silicon that tin catalyst of the invention is modified has following molecular structure：
The preparation method for the nano silicon that a kind of tin catalyst is modified, passes through three following step reactions
It is made, step (1)：Nano silicon and cationic surfactant are formed into dispersed mixing in organic solvent
Liquid；Step (2)：Isocyanates silane coupler is added in step (1) described mixed liquor, reaction obtains isocyanates
Silane coupler modified nano silicon；Step (3)：The isocyanates that step (2) is obtained is silane coupler modified
Nano silicon and catalyst reaction, obtain the nano silicon of catalyst modification.
The present invention has advantages below compared with prior art：
The synthetic method that the present invention designs is reasonable, and obtained modified nano silicon dioxide particles have dispersiveness well；
The modified nano silicon dioxide particles that the present invention obtains, that is, serve as filler and serve as catalyst again, be prepared
Polybutylene terephthalate (PBT)/nanometer silicon dioxide composite material has good toughness.
Embodiment
The present invention is described in detail below.
The modified manometer silicon dioxide of the present invention has following molecular structure：
Left side in structural formula be connected with three hydroxyls for silica, be can be seen that from structural formula on silica
It is grafted with hydroxyl and modified group.
The preparation method for the nano silicon that the tin catalyst of the present invention is modified comprises the following steps：
Step (1)：Nano silicon and cationic surfactant be scattered obtain in organic solvent it is dispersed
Mixed liquor；
Step (2)：Isocyanates silane coupler is added in step (1) described mixed liquor, reaction obtains isocyanide
The silane coupler modified nano silicon of esters of gallic acid；
Step (3)：Isocyanates that step (2) is obtained silane coupler modified nano silicon and catalyst
Reaction, obtains the nano silicon of catalyst modification.
【Step (1)：Nano silicon and cationic surfactant be scattered obtain in organic solvent it is dispersed
Mixed liquor】
A certain amount of cationic surfactant is added in appropriate organic solvent, electromagnetic agitation speed is 400-
600r/min, temperature are 50-70 DEG C, mixing time 10-60min, obtain mixed liquor；Then by a certain amount of nanometer titanium dioxide
Silicon is added in above-mentioned mixed liquor, ultrasonic disperse processing 0.5-2h, obtains dispersed nano silicon mixed liquor.
Nano silicon used in the step (1) is the hydroxyl nano silicon in surface, and its particle diameter is
10-100nm。
Cationic surfactant used in the step (1), it is in quaternary cationic surfactant
It is one or more kinds of mixed in alkyl trimethyl ammonium salt type, dialkyl dimethyl ammonium salt type, alkyl dimethyl benzyl ammonium type
Compound.Relative to the nano silicon of 100 mass parts, the addition of cationic surfactant is 5-30 mass parts, preferably
10-24 mass parts.
Organic solvent used in the step (1) is one or more kinds of mixing in benzene,toluene,xylene
Thing.
【Step (2)：Isocyanates silane coupler is added in step (1) described mixed liquor, reaction obtains isocyanide
The silane coupler modified nano silicon of esters of gallic acid】
The dispersed mixed liquor of nano silicon that step (1) is obtained is fitted into condensation reflux unit, in nitrogen
Appropriate isocyanates silane coupler is added dropwise under protection, electromagnetic agitation speed is 100-300r/min, temperature 70-
90 DEG C, reaction time 6-24h.React after terminating through centrifuging, cleaning, obtain the silane coupler modified nanometer of isocyanates
Silica.
Described isocyanates silane coupler is in isocyanic acid triethoxy silica alkane, isocyanic acid trimethoxy silane
One kind or two kinds of mixture.Relative to 100 grams of nano silicon, the addition of the isocyanates silane coupler
For 5-30 milliliters, preferably 10-30 milliliters.
【Step (3)：The silane coupler modified nano silicon of isocyanates that step (2) is obtained and catalysis
Agent is reacted, and obtains the nano silicon of catalyst modification】
The silane coupler modified nano silicon of isocyanates that step (2) is obtained evenly spreads to organic molten
In agent, nitrogen is protected and under the conditions of 100-300r/min magnetic agitation, adds appropriate catalyst, and temperature is 70-90 DEG C,
Reaction time is 6-8h.Reaction terminate after through centrifuging, dry, obtain the nano silicon of catalyst modification.
The catalyst, can be tin catalyst or titanium class catalyst, it is contemplated that the stability of catalyst and industrial
Easy degree, preferably tin catalyst are obtained, the tin catalyst is tin cycloalkanes, dihydroxy chlorine in organic tin catalyst
Change one kind or two kinds of mixture in butyl tin, preferably dihydroxy chlorinated butyl tin.Relative to the nano-silica of 100 mass parts
SiClx, the tin catalyst addition are 5-40 mass parts, preferably 10-30 mass parts.
The one kind or two kinds of mixture that can also be added in cerous acetate or cerium oxalate in the reaction of the step (3), 100
Addition in the silane coupler modified nano silicon of mass parts is 3-5 mass parts.Catalysis can be improved after addition
The stability that agent is combined with silica, and follow-up polymerisation is had no adverse effect.
Bis cyclopentadienyl zirconium dichloride can also be added in the reaction of the step (3), the silane coupler modified of 100 mass parts receives
Addition in rice silica is 5-8 mass parts.Bis cyclopentadienyl zirconium dichloride can not only be accelerated between catalyst and silica
Reaction rate, and the grafting rate of catalyst on silica can be effectively improved.
Described drying can select the methods of constant pressure and dry, vacuum drying.
The temperature of described drying should be 50-70 DEG C.
Embodiment
Below, the present invention is more specifically described by following examples.Here, embodiment is merely to illustrate the present invention, no
It is construed that limiting the scope of the invention.It is that can be carried out in the case of without departing from its spirit and scope to implement the present invention
Various changes and modifications.These change and improvement within the scope of the appended claims, it should be understood that into be the present invention one
Part.
Embodiment 1
10g ammonium bromide and tetraoctyl ammonium bromide is dispersed in 1500ml dimethylbenzene, electromagnetic agitation speed is 500r/min, and magnetic force stirs
20min is mixed, obtains solution A；50g nano silicon is added in solution A, 1h is ultrasonically treated, obtains finely dispersed
Mixed liquid B.
Mixed liquid B is fitted into condensation reflux unit, in N210ml isocyanic acid triethoxysilicane is added dropwise under protection
Alkane coupling agent, the oil bath reaction 24h under the conditions of 80 DEG C.After the completion of reaction, product is separated, cleaned repeatedly with dimethylbenzene, is obtained
The coupling agent modified nano silicon of grafted silane.
By the above-mentioned nano silicon being modified, ultrasonic disperse is into dimethylbenzene again, N2Simultaneously magnetic agitation is protected, is added
Enter 15g catalyst, 80 DEG C of reaction temperature, react 6h.After the completion of reaction, product is separated, with THF clean remove it is non-grafted
Catalyst, finally with alcohol washes product.After drying 12h in 60 DEG C of vacuum drying ovens, the nanometer titanium dioxide of catalyst modification is obtained
Silicon.
Then the nano silicon of catalyst modification is added to CBT in-situ polymerizations generation pCBT nano composite materials,
And standard tensile batten is made using the micro- injection of Haake.Using universal testing machine to batten extension test, stress-strain song is obtained
Line, the toughness of composite is drawn by curve integration.The pCBT of the wherein nano silicon of the catalyst modification containing 2wt% receives
The absorption at break of nano composite material can be 591J, and relative to the 370J of pure pCBT composites, its toughening effect improves about
60%.
Embodiment 2
The nano silicon of the catalyst modification prepared using embodiment 1, prepare the nanometer two of 5wt% catalyst modifications
The pCBT nano composite materials of silica.The absorption at break of this composite can be 610J, relative to pure pCBT composites
370J, its toughening effect improve about 65%.
Embodiment 3
12g ammonium bromide and tetraoctyl ammonium bromide is dispersed in 1500ml dimethylbenzene, electromagnetic agitation speed is 500r/min, and magnetic force stirs
20min is mixed, obtains solution A.50g nano silicon is added in solution A, 1h is ultrasonically treated, obtains finely dispersed
Mixed liquid B.
Mixed liquid B is fitted into condensation reflux unit, in N215ml isocyanic acid triethoxysilicane is added dropwise under protection
Alkane coupling agent, the oil bath reaction 24h under the conditions of 80 DEG C.After the completion of reaction, product is separated, cleaned repeatedly with dimethylbenzene, is obtained
The coupling agent modified nano silicon of grafted silane.
By the above-mentioned nano silicon being modified, ultrasonic disperse is into dimethylbenzene again, N2Simultaneously magnetic agitation is protected, is added
Enter 15g catalyst, 80 DEG C of reaction temperature, react 6h.After the completion of reaction, product is separated, with THF clean remove it is non-grafted
Catalyst, finally with alcohol washes product.After drying 12h in 60 DEG C of vacuum drying ovens, the nanometer titanium dioxide of catalyst modification is obtained
Silicon.
Then the nano silicon of catalyst modification is added to CBT in-situ polymerizations generation pCBT nano composite materials,
And standard tensile batten is made using the micro- injection of Haake.Using universal testing machine to batten extension test, stress-strain song is obtained
Line, the toughness of composite is drawn by curve integration.The pCBT of the wherein nano silicon of the catalyst modification containing 3wt% receives
Nano composite material, relative to pure pCBT composites, its toughening effect improves about 56%.
Embodiment 4
5g ammonium bromide and tetraoctyl ammonium bromide is dispersed in 1500ml dimethylbenzene, electromagnetic agitation speed is 500r/min, and magnetic force stirs
20min is mixed, obtains solution A.50g nano silicon is added in solution A, 1h is ultrasonically treated, obtains finely dispersed
Mixed liquid B.
Mixed liquid B is fitted into condensation reflux unit, in N215ml isocyanic acid triethoxysilicane is added dropwise under protection
Alkane coupling agent, the oil bath reaction 24h under the conditions of 80 DEG C.After the completion of reaction, product is separated and cleaned repeatedly with dimethylbenzene, is obtained
The nano silicon coupling agent modified to grafted silane.
By the above-mentioned nano silicon being modified, ultrasonic disperse is into dimethylbenzene again, N2Simultaneously magnetic agitation is protected, is added
Enter 20g catalyst, 2g cerous acetates, 4g bis cyclopentadienyl zirconium dichlorides, 80 DEG C of reaction temperature, react 6h.After the completion of reaction, by product point
From, cleaned with THF and remove non-grafted catalyst, finally with alcohol washes product.After drying 12h in 60 DEG C of vacuum drying ovens, obtain
To the nano silicon of catalyst modification.
Then the nano silicon of catalyst modification is added to CBT in-situ polymerizations generation pCBT nano composite materials,
And standard tensile batten is made using the micro- injection of Haake.Using universal testing machine to batten extension test, stress-strain song is obtained
Line, the toughness of composite is drawn by curve integration.The pCBT of the wherein nano silicon of the catalyst modification containing 2wt% receives
Nano composite material, relative to pure pCBT composites, its toughening effect improves about 62%.
Claims (2)
1. the preparation method for the nano silicon that a kind of tin catalyst is modified, it is characterised in that pass through three following steps
Rapid reaction is made,
Step (1)：Nano silicon forms dispersed mixed solution in organic solvent with cationic surfactant,
Wherein relative to the nano silicon of 100 mass parts, the addition of cationic surfactant is 5-30 mass parts；
Step (2)：Isocyanates silane coupler is added in step (1) described mixed solution, reaction obtains isocyanic acid
The silane coupler modified silica of esters；
Step (3)：The silane coupler modified silica of isocyanates that step (2) is obtained and tin catalyst are anti-
Should, the nano silicon of tin catalyst modification is obtained, is additionally added in the reaction of the step (3) in cerous acetate or cerium oxalate
One or more mixtures, the addition in the silane coupler modified nano silicon of 100 mass parts is 3-5 matter
Measure part.
2. the preparation method for the nano silicon that a kind of tin catalyst according to claim 1 is modified, its feature exist
In, it is made by three following step reactions,
Step (1)：5-12g ammonium bromide and tetraoctyl ammonium bromide is dispersed in 1500ml dimethylbenzene, electromagnetic agitation speed is 500r/min,
Magnetic agitation 20min, obtains solution A, and 50g nano silicon is added in solution A, is ultrasonically treated 1h, is disperseed
Uniform mixed liquid B；
Step (2)：Mixed liquid B is fitted into condensation reflux unit, in N2The 15ml ethoxy of isocyanic acid three is added dropwise under protection
Base silane coupling agent, the oil bath reaction 24h under the conditions of 80C；After after the completion of reaction, product is separated, being cleaned with dimethylbenzene, obtain
Silane coupler modified nano silicon；
Step (3)：By the above-mentioned nano silicon being modified, ultrasonic disperse is into dimethylbenzene again, N2Simultaneously magnetic agitation is protected,
Add 15g catalyst, 80 DEG C of reaction temperature, react 6h, after the completion of reaction, product is separated, with THF clean removing it is non-grafted
Catalyst, finally with alcohol washes product；After drying 12h in 60 DEG C of vacuum drying ovens, the nano-silica of catalyst modification is obtained
SiClx.
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| CN106632776B (en) * | 2016-09-19 | 2019-02-22 | 宁波大学 | A kind of silica/Polydicyclopentadiencomposite composite material and preparation method thereof |
| CN107670656B (en) * | 2017-09-25 | 2020-08-11 | 莱恩创科（北京）科技有限公司 | Photocatalyst loading method |
| CN107955412B (en) * | 2017-11-20 | 2020-01-14 | 苏州太湖电工新材料股份有限公司 | Preparation method and application of modified nano silicon dioxide |
| EP3718623A4 (en) | 2017-11-30 | 2020-12-02 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences | Molecular sieve-based catalyst modification apparatus, and method |
| CN110283278B (en) * | 2019-06-11 | 2021-03-23 | 宁波大学 | Polydicyclopentadiene composite material and preparation method thereof |
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