CN100455516C - Prepn process of silica sol modified nanometer CaCO3 composite particle - Google Patents
Prepn process of silica sol modified nanometer CaCO3 composite particle Download PDFInfo
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- CN100455516C CN100455516C CNB2006100983287A CN200610098328A CN100455516C CN 100455516 C CN100455516 C CN 100455516C CN B2006100983287 A CNB2006100983287 A CN B2006100983287A CN 200610098328 A CN200610098328 A CN 200610098328A CN 100455516 C CN100455516 C CN 100455516C
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- caco
- nanometer
- silica sol
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Abstract
The present invention relates to preparation process of nanometer CaCO3/SiO2 composite particle. Through mixing nanometer CaCO3 water suspension and silica sol in certain stoichiometric ratio via powerful stirring, ultrasonic dispersing treatment, heating while further stirring to dewater and condensate small size nanometer silica sol with high surface activity, and depositing on the surface of nanometer CaCO3 to prepare nanometer CaCO3/SiO2 composite particle of size 40-60 nm and high surface activity. The nanometer CaCO3/SiO2 composite particle in core-shell structure has high stability in water, capacity of being dispersed homogeneously in polymer, high storage stability, excellent heat resistance and dispersivity in water soluble polymer, and is used in preparing organic-inorganic hybridized material.
Description
Technical field
The present invention relates to a kind of shelf-stable, excellent heat resistance, in the aqueous high molecular compound good dispersion, have the silica sol modified nanometer CaCO of nucleocapsid structure
3The preparation method of composite particles.
Background technology
In recent years, along with deepening continuously of organic-inorganic hybrid material research, to nanometer CaCO
3Research become the research focus in this field.But because nanometer CaCO
3Particle diameter is little, and specific surface area is little, and surface energy is big, makes them be easy to flock together, and has caused at preparation polymkeric substance/nanometer CaCO
3Dispersed bad problem during matrix material, there is the high shortcoming of poor, the surperficial PH of acid resistance in nanometer simultaneously, has also limited its use range.Although at present about nano level CaCO
3Study on the modification to superpolymer makes rapid progress, and has obtained considerable progress on certain degree, but dispersed quality is the first element of modified-high polymer, also is the bottleneck that the restriction composite materials property improves.
Aerospace material technology, 2003.2:P57 has characterized sol-gel method modified Nano CaCO
3Performance, the result show properties-correcting agent with chemical bond in conjunction with in the lime carbonate surface.Since the limitation of preparation process, prepared nanometer CaCO
3Modified Nano CaCO when the properties-correcting agent add-on is 6% (massfraction)
3Reverse with the contact angle of polar solvent, but the non-silicon sol of the present invention of the properties-correcting agent that this institute uses, this research was not simultaneously mentioned dispersiveness, stability and the application performance thereof of prepared modified particle.
Summary of the invention
The purpose of this invention is to provide a kind of silica sol modified nanometer CaCO
3The preparation method of composite particles has the less silicon sol of particle diameter of activity hydroxy by the surface, according to defined terms to nanometer CaCO
3Particle carries out modification, makes it have nucleocapsid structure, has improved its coagulation stability in water, and shelf-stable, excellent heat resistance, good dispersion in the aqueous high molecular compound.
Preparation method of the present invention is:
Under brute force stirs, according to stoichiometric ratio, with the nanometer CaCO of certain solid content
3Aqeous suspension mixes with silicon sol, and after ultrasonic dispersing was handled, elevated temperature continued powerful the stirring, promptly obtains silica sol modified nanometer CaCO again
3(composite water dispersion).Wherein use the modified Nano CaCO of silicon sol preparation
3Aqueous dispersions is called for short modified Nano CaCO
3/ SiO
2Aqueous dispersions.
Nanometer CaCO
3The particle diameter of aqeous suspension can be 10-100nm, and solid content can be 8-80%, is preferably in 10-30%.
Used silicon sol is a kind of nano silicon aqueous dispersions by the ion exchange method preparation in the preparation process of the present invention, and its particle diameter is 3～100nm, and solid content can be 20-80%, is preferably in 20-40%.
The modified Nano CaCO of the present invention's preparation
3In the aqeous suspension, the quality of nano silicon accounts for modified Nano CaCO
31%～100%, be preferably in 5%～20%.
The pH value of silicon sol before using can be 2.5-11, is preferably 3-9.
Temperature of reaction can be preferably in 80-100 ℃ between 20-110 ℃.
The present invention can be with nanometer CaCO
3Aqueous dispersions adds the generation dehydration condensation that heats up again in the silicon sol earlier, also can will add nanometer CaCO again after the silicon sol intensification earlier
3Aqueous dispersions carries out dehydration condensation.
The modified Nano CaCO that the present invention is prepared
3When aqueous dispersions was used for the hybrid inorganic-organic modification of aqueous polymer, selected high molecular polymer can be aqueous polyurethane, acrylate, polyvinyl alcohol etc.
The benefit that the present invention uses ultrasonic dispersing to handle is that it has further improved degree of scatter.Improved modified Nano CaCO
3The dispersiveness of particle in water.When being used for situ aggregation method and preparing the hybrid inorganic-organic materials of aqueous polymer, can increase organic phase and inorganic alternate consistency, improve the dispersiveness of inorganic particulate in superpolymer.
Embodiment
The present invention is described in detail below in conjunction with example, but the present invention is not limited to following example.
Embodiment 1
Take by weighing 5g silicon sol (this laboratory is synthetic, and the pH value is 2.5, and particle diameter is that 3nm, solid content are 20%), elevated temperature to 20 ℃ is of a size of 400g 10nm nanometer CaCO under powerful stirring action
3Aqueous dispersions (solid content is 8%) slowly adds, and after ultrasonic dispersing is handled 1.5h, continues can obtain having the nanometer CaCO of nucleocapsid structure more than the powerful 2h of stirring again
3/ SiO
2Composite particles (SiO
2Account for CaCO
3Consumption 3.1%) aqueous dispersions, its solid content is about 8.1%.
Embodiment 2
Take by weighing 18g silicon sol (this laboratory is synthetic, and the pH value is 4.0, and particle diameter is that 10nm, solid content are 35%), elevated temperature to 40 ℃ is of a size of 400g 30nm nanometer CaCO under powerful stirring action
3Aqueous dispersions (solid content is 15%) slowly adds, again after ultrasonic dispersing is handled 1.5h, and, continue can obtain having the nanometer CaCO of nucleocapsid structure more than the powerful 2h of stirring
3/ SiO
2Composite particles (SiO
2Account for CaCO
3Consumption 10.5%) aqueous dispersions, its solid content is about 15.9%.
Embodiment 3
Take by weighing 30g silicon sol (this laboratory is synthetic, and the pH value is 5.5, and particle diameter is that 25nm, solid content are 40%), elevated temperature to 65 ℃ is of a size of 400g 50nm nanometer CaCO under powerful stirring action
3Aqueous dispersions (solid content is 30%) slowly adds, again after ultrasonic dispersing is handled 1.5h, and, continue can obtain having the nanometer CaCO of nucleocapsid structure more than the powerful 2h of stirring
3/ SiO
2Composite particles (SiO
2Account for CaCO
3Consumption 10%) aqueous dispersions, its solid content are 30.7%.
Embodiment 4
Take by weighing 100g silicon sol (this laboratory is synthetic, and the pH value is 7.0, and particle diameter is that 40nm, solid content are 48%), elevated temperature to 85 ℃ is of a size of 200g 60nm nanometer CaCO under powerful stirring action
3Aqueous dispersions (solid content is 50%) slowly adds, again after ultrasonic dispersing is handled 1.5h, and, continue can obtain having the nanometer CaCO of nucleocapsid structure more than the powerful 2h of stirring
3/ SiO
2Composite particles (SiO
2Account for CaCO
3Consumption 48%) aqueous dispersions, its solid content is about 49.3%.
Embodiment 5
Take by weighing 150g silicon sol (this laboratory is synthetic, and the pH value is 8.5, and particle diameter is that 68nm, solid content are 60%), elevated temperature to 98 ℃ is of a size of 200g 75nm nanometer CaCO under powerful stirring action
3Aqueous dispersions (solid content is 65%) slowly adds, again after ultrasonic dispersing is handled 1.5h, and, continue can obtain having the nanometer CaCO of nucleocapsid structure more than the powerful 2h of stirring
3/ SiO
2Composite particles (SiO
2Account for CaCO
3Consumption 69.2%) aqueous dispersions, its solid content is about 62.9%.
Embodiment 6
Take by weighing 200g silicon sol (this laboratory is synthetic, and the pH value is 10.5, and particle diameter is that 86nm, solid content are 75%), elevated temperature to 105 ℃ is of a size of 250g 88nm nanometer CaCO under powerful stirring action
3Aqueous dispersions (solid content is 72%) slowly adds, again after ultrasonic dispersing is handled 1.5h, and, continue can obtain having the nanometer CaCO of nucleocapsid structure more than the powerful 2h of stirring
3/ SiO
2Composite particles (SiO
2Account for CaCO
3Consumption 83.3%) aqueous dispersions, its solid content is about 73.3%.
Embodiment 7
Take by weighing 250g silicon sol (this laboratory is synthetic, and the pH value is 11.0, and particle diameter is that 100nm, solid content are 80%), elevated temperature to 110 ℃ is of a size of 250g 100nm nanometer CaCO under powerful stirring action
3Aqueous dispersions (solid content is 80%) slowly adds, again after ultrasonic dispersing is handled 1.5h, and, continue can obtain having the nanometer CaCO of nucleocapsid structure more than the powerful 2h of stirring
3/ SiO
2Composite particles (SiO
2Account for CaCO
3Consumption 100%) aqueous dispersions, its solid content are 80%.
Comparative example 1
1, takes by weighing the modified Nano CaCO of a certain amount of example 1
3/ SiO
2The composite particles aqueous dispersions, with separating with 3000r/min in the HIMAC type whizzer, the sedimentary time appears in the record emulsion, investigates its package stability.Make: compare 1
#Sample.
2, in like manner take by weighing the modified Nano CaCO of example 2
3/ SiO
2The composite particles aqueous dispersions.Make: compare 2
#Sample.
3, in like manner take by weighing the modified Nano CaCO of example 3
3/ SiO
2The composite particles aqueous dispersions.Make: compare 3
#Sample.
4, in like manner take by weighing the modified Nano CaCO of example 4
3/ SiO
2The composite particles aqueous dispersions.Make: compare 4
#Sample.
5, in like manner take by weighing the modified Nano CaCO of example 4
3/ SiO
2The composite particles aqueous dispersions.Make: compare 5
#Sample.
6, in like manner take by weighing the modified Nano CaCO of example 4
3/ SiO
2The composite particles aqueous dispersions.Make: compare 6
#Sample.
7, in like manner take by weighing the modified Nano CaCO of example 4
3/ SiO
2The composite particles aqueous dispersions.Make: compare 7
#Sample.
8, in like manner take by weighing unmodified nanometer CaCO
3Aqueous dispersions.Make: compare 8
#Sample
Following table is being for to have under the condition of ultrasonication, different nanometer CaCO
3/ SiO
2The stability of composite particles emulsion sample.By finding out in the table, along with the increase of Nano silica sol add-on, modification CaCO
3Stability strengthen gradually, can be in whizzer separate 120 minutes no coagulations with 3000r/min, show that working as the silicon sol consumption is CaCO
3Can realize CaCO at 10% o'clock
3Particle in water homodisperse and have preferably stability.
Silica sol modified nanometer CaCO
3The stability of aqueous dispersions
| Sample | Nano silica sol content (accounts for nanometer CaCO 3％) | Centrifugal stability (min) |
| 1 # | 5 | 60 |
| 2 # | 8 | 90 |
| 3 # | 10 b) | 120 do not precipitate |
| 4 # | 50 | 120 do not precipitate |
| 5 # | 60 | 120 do not precipitate |
| 6 # | 80 | 120 do not precipitate |
| 7 # | 100 | 120 do not precipitate |
| 8 # | 0 | / a) |
A) "/" expression promptly produces precipitation without centrifugally operated.
B) room temperature is placed the precipitated and separated phenomenon was not taken place in 6 months.
Studies show that product modified Nano CaCO of the present invention
3/ SiO
2The composite particles emulsion has package stability and accumulation stability preferably.
Claims (6)
1. silica sol modified nanometer CaCO
3The preparation method of composite particles is characterized in that under brute force stirs, according to stoichiometric ratio, with the nanometer CaCO of certain solid content
3Aqeous suspension mixes with silicon sol, and after ultrasonic dispersing was handled, elevated temperature continued powerful the stirring, promptly obtains silica sol modified nanometer CaCO again
3Composite water dispersion be modified Nano CaCO
3/ SiO2 aqueous dispersions; Nanometer CaCO
3The particle diameter of aqeous suspension is 10-100nm, and solid content is 8-80%, and used silicon sol is a kind of nano silicon aqueous dispersions by the ion exchange method preparation in the preparation process, and its particle diameter is 3～100nm, and solid content is 20-80%; Wherein said modified Nano CaCO
3In/SiO2 the aqeous suspension, the quality of nano silicon accounts for modified Nano CaCO
31%～100%; The pH value of silicon sol before using is 2.5-11, and temperature of reaction is between 20-110 ℃.
2. silica sol modified nanometer CaCO according to claim 1
3The preparation method of composite particles is characterized in that nanometer CaCO
3The solid content of aqeous suspension is at 10-30%.
3. silica sol modified nanometer CaCO according to claim 1
3The preparation method of composite particles is characterized in that the quality of nano silicon accounts for modified Nano CaCO
35%～20%.
4. silica sol modified nanometer CaCO according to claim 1
3The preparation method of composite particles is characterized in that the pH value of silicon sol before using is for being 3-9.
5. silica sol modified nanometer CaCO according to claim 1
3The preparation method of composite particles is characterized in that temperature of reaction is at 80-100 ℃.
6. silica sol modified nanometer CaCO according to claim 1
3The preparation method of composite particles is characterized in that nanometer CaCO
3Aqueous dispersions adds the generation dehydration condensation that heats up again in the silicon sol earlier, or adds nanometer CaCO again after earlier silicon sol being heated up
3Aqueous dispersions carries out dehydration condensation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100983287A CN100455516C (en) | 2006-12-11 | 2006-12-11 | Prepn process of silica sol modified nanometer CaCO3 composite particle |
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|---|---|---|---|
| CNB2006100983287A CN100455516C (en) | 2006-12-11 | 2006-12-11 | Prepn process of silica sol modified nanometer CaCO3 composite particle |
Publications (2)
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|---|---|
| CN1974398A CN1974398A (en) | 2007-06-06 |
| CN100455516C true CN100455516C (en) | 2009-01-28 |
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|---|---|---|---|
| CNB2006100983287A Expired - Fee Related CN100455516C (en) | 2006-12-11 | 2006-12-11 | Prepn process of silica sol modified nanometer CaCO3 composite particle |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212197A (en) * | 2014-08-13 | 2014-12-17 | 浙江理工大学 | Method for preparing amphiphilic modified organic pigment based on discontinuous deposition of silica sol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102535243B (en) * | 2012-01-13 | 2014-02-26 | 东莞上海大学纳米技术研究院 | Method for reinforcing kraft with micro-nano inorganic crystal whiskers and kraft |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377921A (en) * | 2002-04-05 | 2002-11-06 | 中山大学 | Process for preparing nano CaCO3/SiO2 core-shell structure particle |
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- 2006-12-11 CN CNB2006100983287A patent/CN100455516C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377921A (en) * | 2002-04-05 | 2002-11-06 | 中山大学 | Process for preparing nano CaCO3/SiO2 core-shell structure particle |
Non-Patent Citations (2)
| Title |
|---|
| 纳米CaCO3/SiO2核－壳结构复合粒子的制备. 刘国军，曾汉民.宇航材料工艺，第3期. 2003 |
| 纳米CaCO3/SiO2核－壳结构复合粒子的制备. 刘国军，曾汉民.宇航材料工艺，第3期. 2003 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212197A (en) * | 2014-08-13 | 2014-12-17 | 浙江理工大学 | Method for preparing amphiphilic modified organic pigment based on discontinuous deposition of silica sol |
| CN104212197B (en) * | 2014-08-13 | 2016-08-24 | 浙江理工大学 | The method preparing amphipathic modified organic pigment based on the discontinuous deposition of Ludox |
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| CN1974398A (en) | 2007-06-06 |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jiangsu Hongchang Technology Co., Ltd. Assignor: Jiangsu University Contract fulfillment period: 2009.4.25 to 2015.4.24 contract change Contract record no.: 2009320001022 Denomination of invention: Prepn process of silica sol modified nanometer CaCO3 composite particle Granted publication date: 20090128 License type: Exclusive license Record date: 2009.6.23 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.4.25 TO 2015.4.24; CHANGE OF CONTRACT Name of requester: JIANGSU HONGCHANG SCIENCE AND TECHNOLOGY CO., LTD. Effective date: 20090623 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090128 Termination date: 20151211 |
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