CN1539861A - Method for modifying inorganic particles through grafting in situ by ball milling method - Google Patents
Method for modifying inorganic particles through grafting in situ by ball milling method Download PDFInfo
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- CN1539861A CN1539861A CNA2003101119325A CN200310111932A CN1539861A CN 1539861 A CN1539861 A CN 1539861A CN A2003101119325 A CNA2003101119325 A CN A2003101119325A CN 200310111932 A CN200310111932 A CN 200310111932A CN 1539861 A CN1539861 A CN 1539861A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000000498 ball milling Methods 0.000 title claims description 9
- 238000011065 in-situ storage Methods 0.000 title abstract description 3
- 239000010954 inorganic particle Substances 0.000 title 1
- 239000002105 nanoparticle Substances 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 19
- 239000012716 precipitator Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000005543 nano-size silicon particle Substances 0.000 claims description 11
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- -1 acrylic ester Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 230000001960 triggered effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000003701 mechanical milling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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Abstract
A process for modifying the inorganic nanoparticles features that the inorganic nanoparticles, acrylate and low-temp trigger are mixed in ball grinder while the in-situ graft reaction its triggered to change the surface affinity of nanoparticles, and reinforce the coagulated structure of nanoparticles.
Description
Technical field
The present invention relates to a kind of method that adopts ball milling method to carry out in-situ grafting polymerization reaction modifying nano inoganic particle.
Background technology
Nanoparticle (size between 1～100nm) because of having small-size effect, surface interface effect and the interfacial interaction strong with polymkeric substance, if can be in polymkeric substance with the nanoparticle good distribution, the strong interaction interface of huge amount will be formed, thereby significantly improve the mechanical property of polymkeric substance and produce effects such as special light, electricity, magnetic under very low loading level, therefore the researchdevelopment of nano-particles filled polymer composites is rapid in recent years.
Yet, big just because of specific surface area, the surface energy height, very easy gathering of nanoparticle self and reunion, the consistency of polymeric matrix that adds the nano particle of surface hydrophilicity and surperficial hydrophobicity is relatively poor, nanoparticle often is scattered in the matrix resin with the form of big coacervate, is difficult to obtain having the matrix material of dispersive nanostructure.Compare with traditional micron particle strongthener, the matrix material that contains the nanoparticle coacervate can't show the special excellent properties that it should have, and the possibility performance is poorer.At present relatively effective means is that nanoparticle surface is handled, and essence is to reduce the gravitational potential energy between the particle or increase repulsion potential energy between the particle.
According to having or not chemical reaction between surface treatment agent and the nanoparticle, the surface treatment method of nanoparticle can be divided into surface physics modification and surface chemical modification two big classes.The surface physics modification is meant between surface treatment agent and nanoparticle except Van der Waals force, hydrogen bond or coordinate bond interact, there is not the combination of ionic linkage, covalent linkage, its essence is that surface adsorption coats, and properties-correcting agent can't enter nanoparticle coacervate inside, and modified effect is relatively poor.The surfactivity that nanoparticle is high utilizes chemical reaction method that nanoparticle is carried out surface modification to people provides favourable condition.Chemical modification method has multiple again, and wherein being considered to preferably, method mainly contains coupling agent modified and graft modification.Coupling agent treatment nanoparticles such as coupling agent modified common employing silicane, titanate ester or phosphoric acid ester.Usually contain two kinds of groups of different nature in the coupling agent molecule structure.A kind of group can have an effect with inorganic material surface (physical adsorption or chemical reaction), another group can have an effect with macromolecular material (chemical reaction or physical adsorption), thereby can on the interface of inorganic materials and macromolecular material, play the molecule bridge joint, improve the bonding interface of material.But because used coupling agent all is small-molecule substances, the many mechanical properties that can influence material of consumption, and that consumption can disperse less is inhomogeneous, influence treatment effect, and price is more expensive, makes the cost increase.Graft modification is meant by various means at nano inoganic particle surface grafting polymerization thing.Utilize this method, the grafting process helps strutting the coacervate of nanoparticle on the one hand, has also changed the surface property of particle, has increased the consistency between particle and matrix, dispersion of particles is improved, thereby give its some new function.On the other hand, make nanoparticle reunite intravital each particle surface, strengthened the structure of loose coacervate all with the grafts of going up chemical bonding.
The method of at present common graft modification has: (1) passes through linked reaction, organic group that can direct polymerization on the inorganic particulate surface grafting (as vinyl or contain the organo-functional group of vinyl), or the treated organo-functional group that produces free radical (as-ROH ,-RNH
2,-R-O-O-R ' etc.).(2) directly utilize the hydroxyl on inorganic particulate surface
[97]Various types of polymkeric substance in the nanoparticle surface grafting.Aforesaid method often is to carry out graft reaction in solution, also must remove the solvent that is added behind the processing nanoparticle, and technology is complicated, and cost is increased.(3) a certain amount of hydroxyl is generally contained on the surface of inorganic nano-particle, and methods such as high-energy radiation, Cement Composite Treated by Plasma can make the hydroxyl of nanoparticle surface or lattice imperfection place produce the spike with initiating activity, and trigger monomer is at its surface aggregate.Its shortcoming is the equipment requirements height, is difficult to suitability for industrialized production.
Summary of the invention
The method that the purpose of this invention is to provide a kind of situ-formed graft modified Nano inorganic particulate, by ball-milling processing at nanometer SiO
2The surface grafting acrylic polymer, change the surperficial affinity of nanoparticle, strengthen the interface interaction of nanoparticle and polymeric matrix, thereby improve the dispersion of nanoparticle in polymkeric substance, so that further prepare the nano-particles filled polymer composites.
Purpose of the present invention can realize by following measure: adopt ball mill with reactive treatment agent (double bond containing monomer and radical polymerization initiator) nano inoganic particle to be handled.Monomer and initiator and nanoparticle are mixed and the surface of the abundant wetting particle of auxiliary agent liquid, and in mechanical milling process, utilize monomers such as the high heat that produced and mechanical force initiating methacrylates class that the chemical graft of nanoparticle surface is reacted.This will help the dispersion (changed particle surface affinity) of nanoparticle in follow-up and matrix melt blending process, and this grafts will be had an effect with polymeric matrix (physical entanglement and initiator effect be the chemical reaction of appropriateness down), thereby strengthen bonding interface; Inner grafting obtains to strengthen the open structure that makes the nanoparticle coacervate simultaneously because of monomer infiltrates, and finally reaches to help the purpose that nanoparticle disperses and strengthen coacervate.
Concrete grammar of the present invention is: with nano inoganic particle, monomer and radical initiator join in the ball mill, rotating speed 300～500rpm, 1～4 hour ball milling time; Used monomer is esters of acrylic acid, vinylformic acid (AA), methacrylic acid or maleic anhydride (MA) etc.; Used radical initiator is azo-initiator or peroxide initiator; Used each proportioning components is: the monomer consumption is 20～300wt% of nanoparticle consumption, and the consumption of radical initiator is 0.1～0.5wt% of monomer consumption, and solvent load is 10～30wt% of nanoparticle consumption.
Used nano inoganic particle can be nano-silicon dioxide particle or Nano particles of calcium carbonate etc. in the aforesaid method, nano-silicon dioxide particle can be precipitator method nano silicon or fumed nano silicon-dioxide, median size is 7～50nm, and specific surface area is 150～640m
2/ g; Used acrylic ester monomer is generally ethyl propenoate (EA), butyl acrylate (BA), Isooctyl acrylate monomer (2-EHA) or methyl acrylic ester; Used initiator is generally Diisopropyl azodicarboxylate or benzoyl peroxide.
According to the method described above, when the consumption of reactive treatment agent more after a little while, can when adding monomer and radical initiator, add solvent, with the surface that guarantees that treatment agent can abundant wetting nano inoganic particle, and can play certain processing aid effect.The preferred dimixo-octyl phthalate of used solvent.
Because the present invention adopts liquid acrylic ester monomer to deal with agent, thereby treatment agent and nano inoganic particle are mixed by ball milling method, the even wetting nanoparticle surface of treatment agent and distribute at surperficial lamellar, simultaneously in mechanical milling process, treatment agent monomer generation graft polymerization reaction, method is simple and treatment effect good.Chemical graft has changed the surperficial affinity of nanoparticle, and this will help the dispersion of nanoparticle in follow-up and matrix melt blending process, and inner grafting obtains to strengthen because of monomer infiltrates to make the open structure of nanoparticle coacervate simultaneously.Nanoparticle behind the ball milling modification can directly utilize, and need not further processing, has simplified technology, and cost is reduced.When modified Nano particle and polymeric matrix at high temperature during Compound Machining, graftomer will descend the chemical reaction of appropriateness with matrix polymer generation physical entanglement and initiator effect, combine with interface between matrix resin thereby strengthened Nano filling, the mechanical property of material is improved.
The present invention is further illustrated to reach accompanying drawing by the following examples.
Description of drawings
Fig. 1 is the infrared spectra graphic representation of embodiment 5 and comparative example sample; Wherein a is embodiment 5, and b is a comparative example.
Embodiment
Table 1 is the character of the nano silicon of various embodiments of the present invention use.Table 2 is each composition consumption proportion and processing condition of part embodiment of the present invention, and getting nano silicon weight is 10g.The concrete steps of each embodiment are: by required proportioning, initiator (Diisopropyl azodicarboxylate AIBN or benzoyl peroxide BPO) is added in the acrylic ester monomer after the dissolving, again with nano silicon in ball mill by predetermined processing condition ball milling to mixing.Among the embodiment 9 the solvent dimixo-octyl phthalate is added in the acrylic ester monomer.Table 3 is the monomer conversion and the percentage of grafting of embodiment sample; Each embodiment sample uses the acetone extracting after 48 hours in Soxhlet extractor in the table 3, carry out thermogravimetic analysis (TGA) with Netzsch TG 209 thermogravimetric analyzers, monomer conversion=total polymer weight/monomer weight, percentage of grafting=graftomer weight/silica weight.
With Bruker Equinox 55 Fourier infrared spectrographs record through the infrared spectra curve of acetone extracting embodiment 5 samples and comparative example sample (undressed precipitator method nano silicon) after 48 hours as shown in Figure 1.Compare 1717cm in the infrared spectrum of embodiment with the infrared spectrum of comparative example
-1The absorption peak that the place occurs shows the existence of carbonyl, proves that the butyl polyacrylate chemical graft changes the chemical structure of nano inoganic particle at nano-silica surface to some extent in mechanical milling process.Illustrate that ball milled situ-formed graft modified Nano inorganic particulate is a kind of simple possible, easily the method for implementing.
The character of table 1 nano silicon
Trade mark median size (nm) specific surface area (m
2/ g) production method
MN1P 10 640 ± 50 precipitator method
Aerosil200 7 200 ± 30 vapor phase processs
Table 2 part embodiment each composition consumption proportion and processing condition
The two ball mushroom rotating speed ball milling times of nano-silica vinylformic acid fourth initiator phthalic acid
Change the silicon weight ester weight different monooctyl ester weight of weight (rpm) (hr)
(g) (g) (g) (g)
Embodiment 1 10 30 BPO 500 2
(precipitator method) 0.060
Embodiment 2 10 20 BPO 400 4
(precipitator method) 0.040
Embodiment 3 10 10 BPO 400 3
(precipitator method) 0.050
Embodiment 4 10 30 AIBN 400 1
(precipitator method) 0.150
Embodiment 5 10 20 AIBN 500 3
(precipitator method) 0.100
Embodiment 6 10 10 AIBN 500 4
(precipitator method) 0.020
Embodiment 7 10 5 AIBN 400 4
(precipitator method) 0.025
Embodiment 8 10 2 AIBN 400 4
(precipitator method) 0.010
Embodiment 9 10 2 BPO 3 400 4
(precipitator method) 0.010
Embodiment 10 10 10 BPO 400 3
(vapor phase process) 0.050
Monomer conversion and the percentage of grafting of table 3 part embodiment
Monomer conversion (%) percentage of grafting (%)
Embodiment 1 6.39 3.38
Embodiment 2 12.48 2.38
Embodiment 3 9.94 2.41
Embodiment 4 16.87 3.20
Embodiment 5 20.85 5.96
Embodiment 6 16.13 3.17
Embodiment 7 19.81 1.09
Embodiment 8 21.63 0.62
Embodiment 9 25.42 1.52
Embodiment 10 38.96 20.65
Claims (7)
1. the method for a ball milled situ-formed graft modified Nano inorganic particulate is characterized in that with nano inoganic particle monomer and radical initiator join in the ball mill, rotating speed 300～500rpm, 1～4 hour ball milling time; Used monomer is esters of acrylic acid, vinylformic acid, methacrylic acid or maleic anhydride; Used radical initiator is azo-initiator or peroxide initiator; Used each proportioning components is: the monomer consumption is 20～300wt% of nanoparticle consumption, and the consumption of radical initiator is 0.1～0.5wt% of monomer consumption, and solvent load is 10～30wt% of nanoparticle consumption.
2. in accordance with the method for claim 1, it is characterized in that used acrylic ester monomer is ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer or methyl acrylic ester.
3. in accordance with the method for claim 1, it is characterized in that used radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
4. according to the described method of claim 1,2 or 3, it is characterized in that used nano inoganic particle is nano-silicon dioxide particle or Nano particles of calcium carbonate, median size is 7～50nm, and specific surface area is 150～640m
2/ g.
5. in accordance with the method for claim 4, it is characterized in that used nano-silicon dioxide particle is precipitator method nano silicon or fumed nano silicon-dioxide.
6. according to the described method of claim 1,2 or 3, it is characterized in that when adding monomer and radical initiator, adding solvent.
7. in accordance with the method for claim 6, it is characterized in that described solvent is a dimixo-octyl phthalate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310111932 CN1273509C (en) | 2003-10-29 | 2003-10-29 | Method for modifying inorganic particles through grafting in situ by ball milling method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310111932 CN1273509C (en) | 2003-10-29 | 2003-10-29 | Method for modifying inorganic particles through grafting in situ by ball milling method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1539861A true CN1539861A (en) | 2004-10-27 |
| CN1273509C CN1273509C (en) | 2006-09-06 |
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ID=34336306
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|---|---|---|---|
| CN 200310111932 Expired - Fee Related CN1273509C (en) | 2003-10-29 | 2003-10-29 | Method for modifying inorganic particles through grafting in situ by ball milling method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810718A (en) * | 2015-11-27 | 2017-06-09 | 衡阳凯新特种材料科技有限公司 | A kind of surface treatment method of nano-silicon nitride powder |
| CN106833026A (en) * | 2017-02-08 | 2017-06-13 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of PVC powdered whitings |
| CN108794707A (en) * | 2018-07-16 | 2018-11-13 | 太仓美克斯机械设备有限公司 | A kind of calcium carbonate powder of graft modification |
| CN110452419A (en) * | 2019-08-07 | 2019-11-15 | 安徽工程大学宣城产业技术研究院有限公司 | A kind of surface grafting has the preparation method of the nano silica of liquid rubber |
| CN110845676A (en) * | 2018-08-20 | 2020-02-28 | 广州悦纳科技有限公司 | Nano particle polymer composite microsphere and preparation method and application thereof |
| CN113802207A (en) * | 2021-09-24 | 2021-12-17 | 孙大伟 | Nano antibacterial composite fiber for processing non-woven fabric and preparation method thereof |
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2003
- 2003-10-29 CN CN 200310111932 patent/CN1273509C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810718A (en) * | 2015-11-27 | 2017-06-09 | 衡阳凯新特种材料科技有限公司 | A kind of surface treatment method of nano-silicon nitride powder |
| CN106833026A (en) * | 2017-02-08 | 2017-06-13 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of PVC powdered whitings |
| CN108794707A (en) * | 2018-07-16 | 2018-11-13 | 太仓美克斯机械设备有限公司 | A kind of calcium carbonate powder of graft modification |
| CN110845676A (en) * | 2018-08-20 | 2020-02-28 | 广州悦纳科技有限公司 | Nano particle polymer composite microsphere and preparation method and application thereof |
| CN110845676B (en) * | 2018-08-20 | 2022-08-26 | 广州艾信特实业有限公司 | Nano particle polymer composite microsphere and preparation method and application thereof |
| CN110452419A (en) * | 2019-08-07 | 2019-11-15 | 安徽工程大学宣城产业技术研究院有限公司 | A kind of surface grafting has the preparation method of the nano silica of liquid rubber |
| CN113802207A (en) * | 2021-09-24 | 2021-12-17 | 孙大伟 | Nano antibacterial composite fiber for processing non-woven fabric and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1273509C (en) | 2006-09-06 |
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