CN101531767B - Micro-nano granules dispersion method in polymer basal body using liquid-liquid interface - Google Patents
Micro-nano granules dispersion method in polymer basal body using liquid-liquid interface Download PDFInfo
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- CN101531767B CN101531767B CN200910113999XA CN200910113999A CN101531767B CN 101531767 B CN101531767 B CN 101531767B CN 200910113999X A CN200910113999X A CN 200910113999XA CN 200910113999 A CN200910113999 A CN 200910113999A CN 101531767 B CN101531767 B CN 101531767B
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- 239000007788 liquid Substances 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000006185 dispersion Substances 0.000 title claims description 3
- 239000008187 granular material Substances 0.000 title description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract 5
- 239000007853 buffer solution Substances 0.000 claims abstract 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 10
- 229910052681 coesite Inorganic materials 0.000 claims 5
- 229910052906 cristobalite Inorganic materials 0.000 claims 5
- 239000000377 silicon dioxide Substances 0.000 claims 5
- 235000012239 silicon dioxide Nutrition 0.000 claims 5
- 229910052682 stishovite Inorganic materials 0.000 claims 5
- 229910052905 tridymite Inorganic materials 0.000 claims 5
- 229920006254 polymer film Polymers 0.000 claims 4
- 239000012154 double-distilled water Substances 0.000 claims 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000003505 polymerization initiator Substances 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种利用液-液界面进行微纳米颗粒在聚合物基体中分散的方法。以化学方法合成SiO2微米或纳米级颗粒，并通过离心分离和超声分散，将其制备成乙醇胶体溶液；将乙醇胶体溶液加入到甲苯/水液-液界面，利用界面的物理化学特性使微纳米颗粒均匀分散；将聚合物单体溶解在与水不互溶的有机溶剂中，将引发剂等溶解在缓冲溶液中。引发液-液界面上的现场聚合反应，生成聚合物/SiO2颗粒复合膜；将制备的聚合物/SiO2颗粒复合膜及不含SiO2颗粒的聚合物空白膜模压成型，制成具有SiO2微纳米颗粒均匀分布的聚合物复合材料。本发明工艺简单，解决了微纳米颗粒在聚合物基体中分散困难，容易结团的问题。The invention discloses a method for dispersing micronano particles in a polymer matrix by using a liquid-liquid interface. Synthesize SiO 2 micron or nano-sized particles by chemical method, and prepare it into ethanol colloid solution through centrifugation and ultrasonic dispersion; add ethanol colloid solution to toluene/water liquid-liquid interface, make use of the physical and chemical properties of the interface to make the micro The nanoparticles are uniformly dispersed; the polymer monomer is dissolved in a water-immiscible organic solvent, and the initiator is dissolved in a buffer solution. Initiate the on-site polymerization reaction on the liquid-liquid interface to form a polymer/SiO 2 particle composite film; the prepared polymer/SiO 2 particle composite film and the polymer blank film without SiO 2 particles are molded to form a SiO 2 Polymer composite material with uniform distribution of micro-nano particles. The invention has a simple process and solves the problems of difficulty in dispersing the micro-nano particles in the polymer matrix and easy agglomeration.
Description
Technical field
The present invention relates to a kind of liquid-liquid interface that utilizes and carry out micro-nano granules dispersive method in polymeric matrix.
Background technology
Polymer matrix composite has been widely used in fields such as industry, national defence and aerospace at present.Bibliographical information adds nano particle (as SiO in polymeric matrix
2Nano particle) can significantly improve the mechanical property of polymeric matrix.Polymeric matrix after the modification can also be further carries out compoundly with other various fillers or toughener, makes the high performance polymer composite material with practical value.But nano particle is difficult to disperse in polymeric matrix owing to have bigger serface and surfactivity, is easy to occur clustering phenomena, thereby influences modified effect.Utilize micro-nano granules characterization of adsorption and dissemination on the profit liquid-liquid interface,, can effectively prevent to reunite, realize the homodisperse of micro-nano granules in polymeric matrix, make polymkeric substance/micro-nano granules composite membrane by the polymerized in-situ method.The multi-disc composite membrane can and then prepare polymkeric substance/micro-nano granules matrix material through compression molding.The method of disperseing micro-nano granules to prepare polymkeric substance/micro-nano granules matrix material with liquid-liquid interface yet there are no report at present.
Summary of the invention
Purpose of the present invention just provides a kind of micro-nano granules dispersive method in polymeric matrix.The steps include:
1, with the tetraethoxy being main raw material, is ammoniacal liquor, 50-55ml dehydrated alcohol and the mixing of 100ml redistilled water of 25%-28% with the 160-175ml volume percent, stirs 3-10 minute in the constant temperature magnetic stirrer, dropwise adds 18-22ml again with SiO
2The meter volume percent is the tetraethoxy of 20%-30%, continues to stir 5-48 hour, and control reaction temperature is between 12-30 ℃; Product changes with 3000 and carries out centrifugation, after the gained precipitation washing three times in ethanol ultra-sonic dispersion 20-60min, obtain SiO
2Colloidal sol;
2, the 3-6ml organic monomer is dissolved in 30-60ml and the immiscible organic solvent of water, make organic solution, described organic solvent is a kind of in toluene, benzene and the oil of mirbane, and described organic monomer is a kind of in vinylbenzene and the aniline; Get redistilled water 30-60ml, add 1.5-2.5g organic monomer polymerization starter and make initiator solution A, described organic monomer polymerization starter is a Potassium Persulfate; In the 30-60ml redistilled water, dissolve 0.06-0.10g NaHCO in addition
3Make buffered soln B;
3, organic solution that equal-volume step (2) is made and buffering solution B are put into beaker and are left standstill 5-10min to two and be separated, and drip the SiO that 2-20ul step (1) makes at liquid-liquid interface
2Colloidal sol; Treat SiO behind the 4-20min
2Particle is after liquid-liquid interface disperses to finish, and the initiator solution A that 1-3mL step (2) is made directly injects water with pipettor, causes the polymerized in-situ reaction; After 24 hours, the composite membrane that floats over liquid-liquid interface is shifted out, make and contain SiO
2The particulate polymeric film; Do not add SiO in addition
2Colloidal sol prepares blank polymeric film with identical step;
What 4, step (3) is made contains SiO
2SiO is prepared in particulate polymeric film and blank polymeric film compression molding
2The homodisperse polymer composites of nano particle.
Concrete feature of the present invention:
(1) SiO
2Nano particle can make nano particle fully be disperseed after introducing the profit liquid-liquid interface by colloidal sol.
(2) SiO
2The content of nano particle in polymkeric substance can pass through SiO
2The addition of colloidal sol is adjusted.
(3) on-site polymerization helps to realize well compound between nano particle and the polymeric matrix.
Technology of the present invention is simple, and nano particle fully disperses in polymeric matrix, and the addition controllability is strong, and may realize the continuous output of polymeric film by the device design, has solved nano particle effectively and has disperseed difficult problem at polymeric matrix.
Embodiment
Embodiment:
1, with the tetraethoxy is main raw material, ammoniacal liquor, the 51.2ml volume percent that with the 168ml volume percent is 25%-28% earlier is 99.7% ethanol and the mixing of 100ml redistilled water, in the constant temperature magnetic stirrer, stirred 5 minutes, and dropwise added the 20ml volume percent again and be 28.0% (with SiO
2Meter) tetraethoxy with 60 rev/mins rotating speed, continues to stir 48 hours, and control reaction temperature is at 25 ℃.Product changes with 3000 and carries out centrifugation and (after reaction finishes, carry out centrifugation immediately, in order to avoid SiO
2The colloidal sol conglomeration is assembled), with deionized water ultra-sonic dispersion 1h in ethanol time afterwards that gives a baby a bath on the third day after its birth, obtain the SiO of stable existence in ethanol
2Colloidal sol;
2, be that to dissolve in the 50ml volume percent be in 99.5% the toluene, to make toluene solution for 98.0% vinylbenzene with the 5ml volume percent.Adding 2g mass percent is 99.5% Potassium Persulfate in the 50ml redistilled water, makes initiator solution A; In the 50ml redistilled water, dissolve 0.08g NaHCO in addition
3, make buffered soln B and be used for SiO
2Nano particle is in the dispersion of liquid-liquid interface;
3, the toluene solution that step (2) is made and buffering solution B each 50ml put into beaker and leave standstill 10min to two and be separated, and injecting 2ul content at liquid-liquid interface is the SiO that 6.2g/L step (1) makes
2Colloidal sol.Treat SiO behind the 15min
2Particle is after liquid-liquid interface disperses to finish, and the initiator solution A that 2ml step (2) is made directly injects water, causes the polymerized in-situ reaction.After 24 hours, the film that floats over liquid-liquid interface is shifted out, make and contain SiO
2The particulate polymeric film; Do not add SiO in addition
2Colloidal sol prepares blank polymeric film with identical step;
4. what step (3) is made contains SiO
2SiO is prepared in particulate polymeric film and blank polymeric film compression molding
2The homodisperse polymer composites of nano particle.
The mechanical property of compound back polystyrene has obtained efficient hardening.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910113999XA CN101531767B (en) | 2009-04-17 | 2009-04-17 | Micro-nano granules dispersion method in polymer basal body using liquid-liquid interface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910113999XA CN101531767B (en) | 2009-04-17 | 2009-04-17 | Micro-nano granules dispersion method in polymer basal body using liquid-liquid interface |
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| Publication Number | Publication Date |
|---|---|
| CN101531767A CN101531767A (en) | 2009-09-16 |
| CN101531767B true CN101531767B (en) | 2011-05-18 |
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|---|---|---|---|
| CN200910113999XA Expired - Fee Related CN101531767B (en) | 2009-04-17 | 2009-04-17 | Micro-nano granules dispersion method in polymer basal body using liquid-liquid interface |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018163071A1 (en) * | 2017-03-06 | 2018-09-13 | Uti Limited Partnership | Device and method of manufacturing a device for detecting hydrocarbons |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7323540B2 (en) * | 2004-06-16 | 2008-01-29 | North Carolina State University | Process for preparing microrods using liquid-liquid dispersion |
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2009
- 2009-04-17 CN CN200910113999XA patent/CN101531767B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7323540B2 (en) * | 2004-06-16 | 2008-01-29 | North Carolina State University | Process for preparing microrods using liquid-liquid dispersion |
Non-Patent Citations (2)
| Title |
|---|
| Darsh Wasan et al..Colloidal dispersions:Sturcture,stability and geometric confinement.《Powder Technology》.2005,第153卷135-141. * |
| DarshWasanetal..Colloidaldispersions:Sturcture stability and geometric confinement.《Powder Technology》.2005 |
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| CN101531767A (en) | 2009-09-16 |
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