CN104788933B - A kind of preparation method of polymer/SiO2 nano composite material - Google Patents

A kind of preparation method of polymer/SiO2 nano composite material Download PDF

Info

Publication number
CN104788933B
CN104788933B CN201510234226.2A CN201510234226A CN104788933B CN 104788933 B CN104788933 B CN 104788933B CN 201510234226 A CN201510234226 A CN 201510234226A CN 104788933 B CN104788933 B CN 104788933B
Authority
CN
China
Prior art keywords
sio
polymer
nano
preparation
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510234226.2A
Other languages
Chinese (zh)
Other versions
CN104788933A (en
Inventor
王波
冯跃战
陈阳
陈薇薇
孙瑞洲
刘春太
申长雨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University
Original Assignee
Zhengzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou University filed Critical Zhengzhou University
Priority to CN201510234226.2A priority Critical patent/CN104788933B/en
Publication of CN104788933A publication Critical patent/CN104788933A/en
Application granted granted Critical
Publication of CN104788933B publication Critical patent/CN104788933B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

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

Abstract

The preparation method that the present invention relates to a kind of inorganic nanometer particle compesite, the preparation method being specifically related to polymer/silicon dioxide nano composite material.The present invention provides a kind of new polymer/SiO2The preparation method of nano composite material, by polymer and functionalization SiO2Nanoparticle prepares polymer/SiO by solution blending or melt blending2Nano composite material, polymer and functionalization SiO2The mass ratio of nanoparticle is: 100 1～6；Wherein, functionalization SiO2Nanoparticle is the SiO of polymer surface modification2Nanoparticle, is utilize the degraded of polymer in physics melt Blending Processes, it is achieved polymer molecular chain is chemically grafted to Nano-meter SiO_22On surface.The inventive method make the method preparing polymer based nanocomposites be more suitable for quantify produce, process simple and with low cost.

Description

A kind of preparation method of polymer/SiO2 nano composite material
Technical field:
The preparation method that the present invention relates to a kind of inorganic nanometer particle compesite, the preparation method being specifically related to polymer/silicon dioxide nano composite material.
Background technology:
In order to polymeric matrix is strengthened, toughness reinforcing and increasing is firm, and makes polymer represent nano effect, adds inorganic nano-particle generally in the polymer.But for the character of nanoparticle itself, owing to its surface high can frequently result in the reunion of nanoparticle, thus affecting the performance of performance.In recent years, having had a lot of research in the surface modification and scattering problem of inorganic nano-particle, some simple and easy to do dispersibility characterizing methods also produce therewith accordingly.Existing inorganic nano particle modified method mainly includes chemical method and physical method, wherein, owing to having the wellability extremely similar with polymeric matrix, the modified inorganic nano-particle of surface grafting polymerization thing is considered as prepare one of optimal filler of high-performance polymer/inorganic nanometer particle compesite.Relevant report has: Feng etc. utilize silane coupler GPS and ethanol at nano silicon (SiO2) surface introducing alcoholic extract hydroxyl group, by esterification grafting PMMA under catalytic condition, result shows that polymer graft rate is up to 55% (FengL, HeL, MaY, etal.MaterialsChemistryandPhysics, 2009,116 (1): 158-163)；Rong etc. utilize silane coupling A PTS at Nano-meter SiO_22Surface introduces amino, by melt condensation methods at SiO2Surface introduces hyperbranched aromatic urethane, and percent grafting is up to 32.8% (YuY, RongMZ, ZhangMQ.Polymer, 2010,51 (2): 492-499).But, above-mentioned method of modifying or because process is complicated, relatively costly, or it is not suitable for batch production composite because effect is undesirable etc..Therefore, explore a kind of applicable inorganic nanoparticle surface modification method and become one of key issue urgently to be resolved hurrily in polymer/inorganic nanometer particle compesite course of industrialization.
Summary of the invention:
The preparation method that the present invention provides a kind of new polymer/silicon dioxide nano composite material, prepared by Nano particles of silicon dioxide solution blending or the melt blending of polymer and polymer surface modification, it is grafted in inorganic nano-particle sub-surface (namely utilizes the degraded of polymer in physics melt Blending Processes, it is achieved polymer molecular chain is chemically grafted to Nano-meter SiO_2 owing to the Nano particles of silicon dioxide of Inventive polymers surface modification adopts physical blending to realize polymer chemistry2On surface) so that prepare the method for polymer nanocomposites be more suitable for quantifying producing, process simple and with low cost.
Technical scheme:
The present invention provides a kind of polymer/SiO2The preparation method of nano composite material, by polymer and functionalization SiO2Nanoparticle prepares polymer/SiO by solution blending or melt blending2Nano composite material, polymer and functionalization SiO2The mass ratio of nanoparticle is: 100 1～6；Wherein, functionalization SiO2Nanoparticle is the SiO of described polymer (being about to preparation compound) surface modification2Nanoparticle, its preparation method comprises the steps:
A is by Nano-meter SiO_22With described polymer in solvent by solution blending, make polymer be completely dissolved, be subsequently adding precipitant and precipitate out precipitation, finally precipitate is filtered, namely dried obtains Polymer/nano SiO2Pre-composition；Wherein, polymer and Nano-meter SiO_22Mass ratio be: 100 10～20；
The pre-composition that step a prepares is obtained Polymer/nano SiO at the following melt blending 5～30min of the above decomposition temperature of melting point polymer by b2Blend；
The blend that step b is obtained by c is dissolved in solvent, obtains functionalization SiO by high speed centrifugation2Nanoparticle；Wherein, high speed centrifugation condition is: centrifugation rate 8000～11000rpm, centrifugation time 10～30min；
D is by the functionalization SiO of step c gained2Nanoparticle is distributed in solvent, repeats step c until functionalized nano SiO2Till surface is absent from free polymers give strand.
Preferably, the blended method of described polymer and functionalized SiO 2 nano-particle solution is: by functionalized SiO 2 nanoparticle ultrasonic disperse to solvent, it is subsequently adding polymer and obtains suspension, polymer is made to be completely dissolved under stirring, adding precipitant and precipitate out precipitation, precipitate is through filtering, being drying to obtain polymer/silicon dioxide nano composite material；Wherein, solvent is can with the solvent of described polymer-compatible, and precipitant is the non-solvent of polymer, it is preferred to methanol, ethanol or water.
Preferably, described polymer is polyester polymer.
It is furthermore preferred that described polymer is selected from Merlon (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polylactic acid (PLA) or polymethyl methacrylate (PMMA).
Wherein, solvent described in step a, c and d is can with the solvent of described polymer-compatible.
Precipitant described in step a is the non-solvent of polymer, it is preferred to methanol, ethanol or water.
Preferably, in step a, the method for solution blending is: Nano-meter SiO_22First ultrasonic disperse processes to obtain Nano-meter SiO_2 in a solvent2Dispersion liquid, then by described polymer and Nano-meter SiO_22Dispersion liquid blended under agitation.
Preferably, step b adopts double screw extruder or banbury to carry out melt blending, blended time 10～20min.
Preferably, in said method, polymer is bisphenol A polycarbonate, Nano-meter SiO_22For gas phase nano SiO2(namely prepared by vapor phase method, is characterized as being surface and contains a large amount of silicone hydroxyl), solvent is oxolane (THF), and precipitant is methanol.
Preferably, when polymer is PC, Nano-meter SiO_22For gas phase nano SiO2Time, pre-composition melt blending 10min in step b, melt temperature 240～280 DEG C.
Preferably, when polymer is PC, Nano-meter SiO_22For gas phase nano SiO2Time, centrifugation time 30min in step c, centrifugation rate 10000rpm.
Preferably, step d repetition step c is purified process at least 4 times.
The invention have the benefit that
The preparation method that the present invention provides a kind of new polymer/silicon dioxide nano composite material, polymer/silicon dioxide nano composite material is prepared with functionalized SiO 2 nanoparticle (Nano particles of silicon dioxide of polymer surface modification) solution blending or melt blending by polymer, it is grafted in inorganic nano-particle sub-surface (namely utilizes the degraded of polymer in physics melt Blending Processes, it is achieved polymer molecular chain is chemically grafted to Nano-meter SiO_2 owing to functionalized SiO 2 nanoparticle of the present invention adopts physical blending to realize polymer chemistry2On surface) so that prepare the method for polymer nanocomposites be more suitable for quantifying producing, process simple and with low cost.
Accompanying drawing explanation
The original SiO of Fig. 12With functionalization SiO2Nanoparticle (the SiO of polymer surface modification2Nanoparticle) thermogravimetric (TG) curve, illustration is thermogravimetric (TG) curve (note: nitrogen protection, 20 DEG C/min of heating rate) of pure PC.
Fig. 2 Nano-meter SiO_22With pure PC infrared spectrogram (a) and carbonyl region (C=O) infrared spectrum (b).
Fig. 3 Nano-meter SiO_22XPS swarming fitted figure with the XPS spectrum figure (a) of pure PC and C1s (b), Si2p (c) position.
The original SiO of Fig. 42(a) and SiO2Transmission electron microscope (TEM) picture of-10 (b) and static contact angle (illustration).
Stresses typical-the strain curve of pure PC and the PCS composite of Fig. 5.
The hot strength of pure PC and the PCS composite of Fig. 6 and fracture elongation.
Detailed description of the invention:
The present invention provides a kind of polymer/SiO2The preparation method of nano composite material, by polymer and functionalization SiO2Nanoparticle prepares polymer/SiO by solution blending or melt blending2Nano composite material, polymer and functionalization SiO2The mass ratio of nanoparticle is: 100 1～6 (being preferably 100 1～3)；
Wherein, functionalization SiO2Nanoparticle is the SiO of described polymer surface modification2Nanoparticle, its preparation method comprises the steps:
A is by Nano-meter SiO_22With polymer in solvent by solution blending, make polymer be completely dissolved, be subsequently adding precipitant and precipitate out precipitation, finally precipitate is filtered, namely dried obtains Polymer/nano SiO2Pre-composition；Wherein, polymer and Nano-meter SiO_22Mass ratio be: 100 10～20；
The pre-composition that step a prepares is obtained Polymer/nano SiO at the following melt blending 5～30min of the above decomposition temperature of melting point polymer by b2Blend；
The blend that step b is obtained by c is dissolved in solvent, obtains functionalization SiO by high speed centrifugation2Nanoparticle；Wherein, high speed centrifugation condition is: centrifugation rate 8000～11000rpm, centrifugation time 10～30min；
D is by the functionalization SiO of step c gained2Nanoparticle is distributed in solvent, repeats step c until functionalized nano SiO2Till surface is absent from free polymers give strand.
In the present invention, the addition of solvent fully dissolves to meet polymer；The addition of precipitant is as the criterion precipitating out precipitation completely.
In the present invention, the method for polymer and functionalized SiO 2 nanoparticle melt blending adopts existing melt-mixing method.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
The embodiment of the present invention adopts bisphenol A polycarbonate (PC) (the concrete trade mark is WonderlitePC-110, Taiwan Qi Mei industrial corporation) as polymer, adopt gas phase nano SiO2(particle diameter and specific surface area respectively 15 ± 5nm and 250 ± 30m2/ g, Shanghai Mai Kun Chemical Co., Ltd.) as SiO2Nanoparticle, it is also known as original SiO2。
Comparative example 1PC/ Nano-meter SiO_22The preparation of composite
One, PC surface modification SiO2The method of nanoparticle, concretely comprises the following steps:
1) ultrasonic disperse 5～10g Nano-meter SiO_22SiO is obtained in 500mlTHF solvent2Dispersion liquid, ultrasonic power and time respectively 100W and 1h；Subsequently 40～45gPC pellet is dissolved under mechanical agitation above-mentioned SiO2Dispersion liquid, is stirred at room temperature 4h；PC adds 500ml methanol after being completely dissolved and promotes PC/SiO2Pre-composition Precipitation, standby after filtration drying；
2) by dry for 5g PC/SiO2Pre-composition is dissolved in 200mlTHF again, the nanoparticle in high speed centrifugation (10000rpm, 30min) separation and Extraction mixture；In order to ensure that the nanoparticle surface separated is absent from free PC strand, by in the centrifugal precipitate redispersion obtained first to THF solvent, ultrasonic 15min separates to recentrifuge after homogeneous solution, repeat above-mentioned centrifugal-purification process of dispersion-centrifugal at least 4 times, the Nano-meter SiO_2 obtained2Particle is referred to as SiO2-0 (namely pre-composition is without melt blending, and the melt blending time is 0min).
By gained SiO2-0 carries out thermogravimetric test (specific experiment according to ISO11358-1997 standard perform), result as it is shown in figure 1, as shown in Figure 1, SiO2The thermogravimetric curve of-0 almost with original SiO2Thermogravimetric curve overlap, (50～700 DEG C), SiO in Range of measuring temp2-0 mass loss only having about 2.3wt%, illustrate solution blending process can not graft polymers to Nano-meter SiO_22Surface.
Two, PC/ Nano-meter SiO_22The preparation of composite
By the original SiO in step one2And SiO2-0 mixes with PC Matrix Solution: the SiO of 100mg2SiO with 100mg2-0 is added separately in 200mlTHF, ultrasonic 1h (ultrasonic power 100W), dissolve 9.9gPC pellet subsequently respectively and obtain nanoparticle suspension, until completely dissolved (2h), add 200ml methanol extraction under mechanical agitation respectively and precipitate out composite, equal vacuum drying 24h under 80 DEG C of conditions after filtration, obtains PC/SiO2Nano composite material (abbreviation PCS) PCSp and PCS0.
By dry PCSp and PCS0 composite by hot-forming, hot-forming condition: preheat 10min at 240 DEG C, then hot pressing 5min under 15MPa pressure, is cooled to glass transition temperature (145 DEG C) rear pressure release, sampling below subsequently at this pressure；The nanoparticle impact on composite materials property, stretching condition: under room temperature, draw speed is 10mm/min is observed by extension test；Fig. 5 is the stresses typical-strain curve of pure PC and PCS composite；Fig. 6 is hot strength and the fracture elongation of pure PC and PCS composite；The tensile property of composite is specifically tested and is performed according to GB/T1040-2006 standard.By Fig. 5 and Fig. 6 it can be seen that add original SiO2And SiO2After-0 particle, the hot strength of PC is kept approximately constant in range of error；But due to the non-grafted polymer of nanoparticle surface, surface can cause more greatly the reason reunited, and tensile toughness sharply worsens；73.8% and 72% is declined respectively compared to pure PC, PCSp and PCS0 fracture of composite materials elongation percentage.
Embodiment 1PC/ functionalized nano SiO2The preparation of composite
One, functionalized nano SiO2Preparation
In this embodiment, the preparation of pre-composition and centrifugal treating method are with comparative example 1, simply by pre-composition (weighing 20g therein) melt blending 10min on the twin screw extruder, wherein, screw speed 30rpm, melt temperature 250 DEG C, pelletize after extrusion；The functional nanoparticle that this embodiment obtains is referred to as SiO2-10。
By gained SiO2-10 carry out thermogravimetric test (method is with comparative example 1), result as it is shown in figure 1, as shown in Figure 1, SiO2The thermogravimetric curve of-10 is compared to original SiO2Having significant difference, have obvious mass loss within the scope of 350～550 DEG C, the physics chemical action illustrated in melt blending 10min process promotes organic polymer to be grafted on Nano-meter SiO_22Surface.
Additionally, SiO2FTIR (Fig. 2 (a), the SiO of-102There is PC characteristic peak in the FTIR curve of-10, such as 2972,1779,1226cm-1Deng) and XPS (Fig. 3 (a) and (b), SiO2The appearance of-10 surface typical case's PC strand feature keys, such as C-C, C-O-C, C=O etc.) result all shows that the PC strand of Partial digestion is grafted to Nano-meter SiO_2 in melt blending process2Surface.In conjunction with original SiO2With the thermogravimetric curve of pure PC, be computed SiO2The surface grafting rate of-10 is 30.2%.
Fig. 2 (b) is SiO2-10 and pure PC carbonyl region (C=O) infrared spectrum, as shown in Fig. 2 (b), SiO2Carbonyl group (C=O) the infrared signature purer PC in peak position of-10 surface PC strands offsets；Fig. 3 (b) and Fig. 3 (c) is Nano-meter SiO_22With the pure PC XPS swarming fitted figure in C1s, Si2p position, as shown in Fig. 3 (b) and (c), SiO2The XPS characteristic peak of-10 surface PC strand C=O and C-O-C key also there occurs skew, and the Si-OH key of particle surface is changed into Si-O-C key.Result above proves that melt blending makes PC and Nano-meter SiO_22There occurs ester exchange reaction, this is due to Nano-meter SiO_22Surface silanol group (Si-OH) when the melt blending of high temperature Strong shear, and carbonate group generation alcoholysis in PC strand, cause PC strand covalence graft to Nano-meter SiO_22Surface.Additionally, original SiO2The lower valency Si atom that surface exists is oxidized to Si in melt blending process4+(Fig. 3 (c)).
It addition, our com-parison and analysis pure PC, pure PC fusion plastification 10min and PC/SiO2Exterior appearance after melt blending 10min；Result shows, PC granule is after melt blending 10min, particularly at Nano-meter SiO_22Under existence condition, there is notable change in appearance color, illustrates that thermal degradation occurs PC in melt blending process, and Nano-meter SiO_22Introducing accelerate above-mentioned thermal degradation process.Additionally, SiO2The thermogravimetric curve (Fig. 1) of-10 shows that the thermal degradation temperature of its Surface coating polymer molecular chain is lower than pure PC, and this also illustrates that the PC strand of degraded is grafted on Nano-meter SiO_22Surface.This is likely due to PC strand and occurs degraded to form terminal hydroxyl in melt blending process, then with Nano-meter SiO_22The silicone hydroxyl generation condensation reaction on surface is grafted to nanoparticle surface.
Fig. 4 is original SiO2(a) and SiO2Transmission electron microscope (TEM) picture of-10 (b) and static contact angle (illustration), as shown in Figure 4, due to the speciality of surface hydrophilicity, original SiO2(Fig. 4 (a)) and SiO2-10 (Fig. 4 (b)) all show as typically " chain " structure, and carefully contrast is it is observed that SiO2-10 particle profiles are more smooth, and mean diameter is higher than original SiO2(25.8nm > 21.5nm)；More significantly difference can be passed through the feature of the inside and outside particle of comparison diagram 4 (b) circle and obtain.Two kinds of particle surface water-wet behaviors are by static contact angle (Fig. 4 illustration) display, due to the existence of surface grafting polymerization thing, SiO2-10 surface hydrophilicities are lower than original SiO2, this is beneficial to adopt SiO2-10 prepare polymer matrix composite.
Two, PC/ functionalized nano SiO2The preparation of composite
Further, by SiO2-10 nanoparticles are introduced back into PC matrix, prepare PCS10 composite.Preparation process is consistent with preparation PCSp and PCS0 composite in comparative example 1 with condition.Fig. 5 is the stresses typical-strain curve of pure PC and PCS composite；Fig. 6 is hot strength and the fracture elongation of pure PC and PCS composite；By Fig. 5 and Fig. 6 it can be seen that the hot strength of PCS10 composite and the purer PC of fracture elongation all improve a lot, increase rate reaches 16.8% and 241.1% respectively；This key factor is in SiO2Define caused by strong bonding interface between PC strand and the PC matrix of-10 surface graftings, it was shown that the present invention utilizes functionalization SiO2When nanoparticle prepares composite, hot strength and fracture elongation to PC matrix serve bigger raising effect.
Embodiment 2PC/ functionalized nano SiO2The preparation of composite
One, functionalized nano SiO2Preparation
In this embodiment, except being 20min except the melt blending time, all the other operations are all identical with embodiment 1, and gained functional nanoparticle is called for short SiO2-20, gained composite is PCS20.
By gained SiO2-20 carry out thermogravimetric test (method is with comparative example 1), result as it is shown in figure 1, as shown in Figure 1, compared to original SiO2, SiO2The thermogravimetric curve of-20 shows that it has comparatively significantly mass loss within the scope of 350-550 DEG C；But, SiO2Thermal degradation temperature and the mass loss of-20 are respectively less than SiO2-10, illustrate that melt blending overlong time is unfavorable for the increase of polymer graft rate, this is primarily due to the longer melt blending time and can cause that grafting molecules chain degradation degree increases；This result also illustrates, by melt blending, PC strand is grafted to SiO2There is optimal case in the method for modifying of nanoparticle surface, according to experimental result, the optimum melt blending time is 10min on the blended time.
Two, PC/ functionalized nano SiO2The preparation of composite
Further, by SiO2-20 nanoparticles are introduced back into PC matrix, prepare PCS20 composite.Preparation process is consistent with preparation PCSp and PCS0 composite in comparative example 1 with condition.Fig. 5 is the stresses typical-strain curve of pure PC and PCS composite；Fig. 6 is hot strength and the fracture elongation of pure PC and PCS composite；By Fig. 5 and Fig. 6 it can be seen that SiO2-20 introduce the hot strength and toughness that also are able to reinforcing material simultaneously in PC matrix, but increase rate is less than PCS10, i.e. SiO2-20 pairs of PC matrix potentiation are weaker than SiO2-10。
In the present invention, each comparative example and embodiment ensure SiO in PCS composite2Content is identical, and concrete proportioning raw materials is as shown in table 1:
Table 1 composite Raw proportioning
Comparative example 1 PCSp The original SiO of PC/2 9900mg PC/100mg SiO2
Comparative example 1 PCS0 PC/SiO2-0 9900mg PC/100mg SiO2-0
Embodiment 1 PCS10 PC/SiO2-10 9857mg PC/143mg SiO2-10
Embodiment 2 PCS20 PC/SiO2-20 9870mg PC/130mg SiO2-20
Note: SiO2-0 is isolated Nano-meter SiO_2 in pre-composition2Particle (namely the melt blending time is 0min)；SiO2-10 and SiO2-20 is the melt blending time respectively is 10, isolated functionalized nano SiO in 20min blend2Particle.

Claims (24)

1. polymer/SiO2The preparation method of nano composite material, it is characterised in that by polymer and functionalization SiO2Nanoparticle prepares polymer/SiO by solution blending or melt blending2Nano composite material, polymer and functionalization SiO2The mass ratio of nanoparticle is: 100 1～6；Wherein, functionalization SiO2Nanoparticle is the SiO of described polymer surface modification2Nanoparticle, its preparation method comprises the steps:
A is by Nano-meter SiO_22With described polymer in solvent by solution blending, make polymer be completely dissolved, be subsequently adding precipitant and precipitate out precipitation, finally precipitate is filtered, namely dried obtains Polymer/nano SiO2Pre-composition；Wherein, polymer and Nano-meter SiO_22Mass ratio be: 100 10～20；
The pre-composition that step a prepares is obtained Polymer/nano SiO at the following melt blending 5～30min of the above decomposition temperature of melting point polymer by b2Blend；
The blend that step b is obtained by c is dissolved in solvent, obtains functionalization SiO by high speed centrifugation2Nanoparticle；Wherein, high speed centrifugation condition is: centrifugation rate 8000～11000rpm, centrifugation time 10～30min；
D is by the functionalization SiO of step c gained2Nanoparticle is distributed in solvent, repeats step c until functionalized nano SiO2Till surface is absent from free polymers give strand.
2. polymer/SiO according to claim 12The preparation method of nano composite material, it is characterised in that described polymer and functionalization SiO2The blended method of nano-particle solution is: by functionalization SiO2Nanoparticle ultrasonic disperse, in solvent, is subsequently adding polymer and obtains suspension, make polymer be completely dissolved under stirring, adds precipitant and precipitates out precipitation, and precipitate is through filtering, being drying to obtain polymer/SiO2Nano composite material；Wherein, solvent is can with the solvent of described polymer-compatible, and precipitant is the non-solvent of polymer.
3. polymer/SiO according to claim 22The preparation method of nano composite material, it is characterised in that described precipitant is methanol, ethanol or water.
4. polymer/SiO according to claim 1 and 22The preparation method of nano composite material, it is characterised in that described polymer is selected from Merlon, polyethylene terephthalate, polybutylene terephthalate (PBT), polylactic acid or polymethyl methacrylate.
5. polymer/SiO according to claim 32The preparation method of nano composite material, it is characterised in that described polymer is selected from Merlon, polyethylene terephthalate, polybutylene terephthalate (PBT), polylactic acid or polymethyl methacrylate.
6. polymer/the SiO according to any one of claims 1 to 32The preparation method of nano composite material, it is characterised in that solvent described in step a, c and d is can with the solvent of described polymer-compatible.
7. polymer/SiO according to claim 42The preparation method of nano composite material, it is characterised in that solvent described in step a, c and d is can with the solvent of described polymer-compatible.
8. polymer/SiO according to claim 52The preparation method of nano composite material, it is characterised in that solvent described in step a, c and d is can with the solvent of described polymer-compatible.
9. polymer/the SiO according to any one of claims 1 to 32The preparation method of nano composite material, it is characterised in that in step a, the method for solution blending is: Nano-meter SiO_22First ultrasonic disperse processes to obtain Nano-meter SiO_2 in a solvent2Dispersion liquid, then by described polymer and Nano-meter SiO_22Dispersion liquid blended under agitation.
10. polymer/SiO according to claim 42The preparation method of nano composite material, it is characterised in that in step a, the method for solution blending is: Nano-meter SiO_22First ultrasonic disperse processes to obtain Nano-meter SiO_2 in a solvent2Dispersion liquid, then by described polymer and Nano-meter SiO_22Dispersion liquid blended under agitation.
11. polymer/SiO according to claim 52The preparation method of nano composite material, it is characterised in that in step a, the method for solution blending is: Nano-meter SiO_22First ultrasonic disperse processes to obtain Nano-meter SiO_2 in a solvent2Dispersion liquid, then by described polymer and Nano-meter SiO_22Dispersion liquid blended under agitation.
12. polymer/SiO according to claim 62The preparation method of nano composite material, it is characterised in that in step a, the method for solution blending is: Nano-meter SiO_22First ultrasonic disperse processes to obtain Nano-meter SiO_2 in a solvent2Dispersion liquid, then by described polymer and Nano-meter SiO_22Dispersion liquid blended under agitation.
13. the polymer/SiO according to any one of claims 1 to 32The preparation method of nano composite material, it is characterised in that step b adopts double screw extruder or banbury to carry out melt blending, blended time 10～20min.
14. polymer/SiO according to claim 42The preparation method of nano composite material, it is characterised in that step b adopts double screw extruder or banbury to carry out melt blending, blended time 10～20min.
15. polymer/SiO according to claim 52The preparation method of nano composite material, it is characterised in that step b adopts double screw extruder or banbury to carry out melt blending, blended time 10～20min.
16. polymer/SiO according to claim 62The preparation method of nano composite material, it is characterised in that step b adopts double screw extruder or banbury to carry out melt blending, blended time 10～20min.
17. polymer/SiO according to claim 92The preparation method of nano composite material, it is characterised in that step b adopts double screw extruder or banbury to carry out melt blending, blended time 10～20min.
18. polymer/SiO according to claim 52The preparation method of nano composite material, it is characterised in that described polymer is bisphenol A polycarbonate, Nano-meter SiO_22For gas phase nano SiO2, solvent is oxolane, and precipitant is methanol.
19. polymer/SiO according to claim 62The preparation method of nano composite material, it is characterised in that described polymer is bisphenol A polycarbonate, Nano-meter SiO_22For gas phase nano SiO2, solvent is oxolane, and precipitant is methanol.
20. polymer/SiO according to claim 92The preparation method of nano composite material, it is characterised in that described polymer is bisphenol A polycarbonate, Nano-meter SiO_22For gas phase nano SiO2, solvent is oxolane, and precipitant is methanol.
21. polymer/SiO according to claim 132The preparation method of nano composite material, it is characterised in that described polymer is bisphenol A polycarbonate, Nano-meter SiO_22For gas phase nano SiO2, solvent is oxolane, and precipitant is methanol.
22. the polymer/SiO according to any one of claim 18～212The preparation method of nano composite material, it is characterised in that pre-composition melt blending 10min in step b, melt temperature 240～280 DEG C.
23. the polymer/SiO according to any one of claim 18～212The preparation method of nano composite material, it is characterised in that centrifugation time 30min in step c, centrifugation rate 10000rpm.
24. polymer/SiO according to claim 222The preparation method of nano composite material, it is characterised in that centrifugation time 30min in step c, centrifugation rate 10000rpm.
CN201510234226.2A 2015-05-08 2015-05-08 A kind of preparation method of polymer/SiO2 nano composite material Active CN104788933B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510234226.2A CN104788933B (en) 2015-05-08 2015-05-08 A kind of preparation method of polymer/SiO2 nano composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510234226.2A CN104788933B (en) 2015-05-08 2015-05-08 A kind of preparation method of polymer/SiO2 nano composite material

Publications (2)

Publication Number Publication Date
CN104788933A CN104788933A (en) 2015-07-22
CN104788933B true CN104788933B (en) 2016-06-29

Family

ID=53554144

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510234226.2A Active CN104788933B (en) 2015-05-08 2015-05-08 A kind of preparation method of polymer/SiO2 nano composite material

Country Status (1)

Country Link
CN (1) CN104788933B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106633707B (en) * 2015-10-30 2018-08-17 天津大学 Reduce the method and its application of polylactic acid melt viscosity
CN109456586B (en) * 2018-09-21 2020-12-29 浙江大学宁波理工学院 Melt blending method modified carbon nano particle/polycarbonate nano composite film and preparation method thereof
CN111171486A (en) * 2020-01-13 2020-05-19 杭州电子科技大学 Preparation and performance test research method of modified PMMA composite material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006299126A (en) * 2005-04-21 2006-11-02 Nissan Motor Co Ltd Method for modifying surface of nano-filler, polymer nano-composite and method for producing polymer nano-composite
CN101481494B (en) * 2009-01-16 2012-04-25 华东理工大学 Thermoplastic polyester alloy nano composite material and preparation thereof
US8586183B2 (en) * 2011-01-13 2013-11-19 Sabic Innovative Plastics Ip B.V. Thermoplastic compositions, method of manufacture, and uses thereof
CZ2013758A3 (en) * 2013-09-30 2015-04-29 Vysoké Učení Technické V Brně Thermoplastic material and process for preparing thereof

Also Published As

Publication number Publication date
CN104788933A (en) 2015-07-22

Similar Documents

Publication Publication Date Title
Kedzior et al. Poly (methyl methacrylate)‐grafted cellulose nanocrystals: One‐step synthesis, nanocomposite preparation, and characterization
Xu et al. Design of healable epoxy composite based on β-hydroxyl esters crosslinked networks by using carboxylated cellulose nanocrystals as crosslinker
CN106192048B (en) Preparation method of graphene oxide modified polypropylene fiber
CN104788933B (en) A kind of preparation method of polymer/SiO2 nano composite material
CN105820519A (en) PET-based graphene composite material, preparation method thereof, and aerostat
CN111511980A (en) Method for producing finely-divided hydrophobically modified cellulose fiber
CN111454556A (en) Preparation method of polycaprolactone nanofiber composite material
JP2009261993A (en) Method of pulverizing polysaccharides, method of modifying polysaccharides, resin reinforcing agent and resin composition
CN102408658A (en) Graphene modified poly-methyl methacrylate composite and preparation method thereof
CN111073245B (en) Regenerated polycarbonate composite material and preparation method thereof
Long et al. Enhancing the performance of polylactic acid composites through self-assembly lignin nanospheres for fused deposition modeling
CN113943458B (en) Polycarbonate/polypropylene alloy material and preparation method thereof
Ju et al. Thermal and mechanical properties of polyethylene glycol (PEG)-modified lignin/polylactic acid (PLA) biocomposites
CN113788914B (en) SEBS/AT composite toughening agent, preparation method thereof and high-performance PET/PA6 foaming material
CN104844824B (en) Nano-meter SiO_2 based on polymer melt degraded2Surface modifying method
CN111349304B (en) Polycarbonate styrene resin alloy and preparation method thereof
CN116478523B (en) Preparation process of nano hybrid particle reinforced polycarbonate
CN110283426B (en) Bio-based degradable starch filled epoxy resin composite material and preparation method thereof
CN109593339B (en) PC composition with high hardness and high transparency and preparation method thereof
CN116675936A (en) Wear-resistant plastic with ageing resistance
CN113462021B (en) Natural filler, high-strength and high-toughness polymer composite material thereof, and preparation method and application thereof
Li et al. Preparation and molecular dynamics simulation of 3-isocyanatopropyltrimethoxysilane-modified sisal microcrystalline cellulose/natural rubber composites
CN114318577A (en) Using GO-SiO2Method for improving crystallization performance of polyester fiber by composite nucleus-forming additive
CN108530850B (en) A kind of fire retardant PBT with no halogen/ASA alloy and preparation method thereof
Qu et al. Physical modifications of cellulose nanocrystals by poly (d-lactic acid) and poly (ethylene glycol)(PDLA-PEG-PDLA) block copolymer to improve the mechanical properties of polylactide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CB03 Change of inventor or designer information

Inventor after: Wang Bo

Inventor after: Feng Yuezhan

Inventor after: Chen Yang

Inventor after: Chen Weiwei

Inventor after: Sun Ruizhou

Inventor after: Liu Chuntai

Inventor before: Wang Bo

Inventor before: Feng Yuezhan

Inventor before: Chen Yang

Inventor before: Chen Weiwei

Inventor before: Sun Ruizhou

Inventor before: Liu Chuntai

Inventor before: Shen Changyu

CB03 Change of inventor or designer information