CN1408762A - Inorganic nano particle-high molecular composite material and its preparing method and use - Google Patents
Inorganic nano particle-high molecular composite material and its preparing method and use Download PDFInfo
- Publication number
- CN1408762A CN1408762A CN 01133287 CN01133287A CN1408762A CN 1408762 A CN1408762 A CN 1408762A CN 01133287 CN01133287 CN 01133287 CN 01133287 A CN01133287 A CN 01133287A CN 1408762 A CN1408762 A CN 1408762A
- Authority
- CN
- China
- Prior art keywords
- latex
- salt
- nano
- modifying agent
- weight percentage
- 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.)
- Granted
Links
Images
Landscapes
- Paper (AREA)
Abstract
The nano composite material consists of nano material 1.00-5.00 wt%, surface modifier 0.04-1.00 wt% and latex mixed together 94.00-98.96 wt%. The preparation process includes supersonic wave dispersion of nano material sluryy, heating to the temperature 10-30 deg.c over the melting point of the surface modifier, adding the surface modifier for reaction for 1-3 hr, cooling before stopping reaction, mixing with latex at normal temperature and high speed dispersion for homogeneous mixing. The present invention can shield paint to reach the aim of resisting ultraviolet ageing and heat ageing and increasing the heat insulation of paint. It is used to paint paper to raise the performance of paper.
Description
(1) technical field:
The present invention relates to inorganic nano particle-high molecular composite material, its preparation method and as the age inhibiting application of paper coating.
(2) background technology:
Nano material is the novel material that has just grown up the eighties in 20th century, is born from one, just is described as " the most promising material of 21 century " by U.S. material association because of the wide range of commercial prospect.Nano material becomes the focus of Materials science research because its special small-size effect, surface effects, quantum size effect and macro quanta tunnel effect have caused attention widely in many scientific domains.Simultaneously, it has also increased new content for conventional composite study.
In recent years, for improving the over-all properties of material, the research of inorganic nano particle-high molecular composite material has caused people's attention, and becomes the new direction of current nano material and matrix material development gradually.The conventional method for preparing inorganic nano particle-high molecular composite material mainly contains: blending method, graft process, sol-gel method and dispersion copolymerization method on the throne etc.
Inorganic nano particle-high molecular composite material adopts high molecular stable composition effect that nanoparticle is compound in the polymkeric substance, makes mixture have secular stability.Nanoparticle combines with polymer support, not only can control the stability of the radius and the particulate of crystal grain, and the compound back of polymer materials and nano material demonstrates bigger advantage at aspects such as optics, mechanical propertys, with its as coating have that film-forming temperature is low, advantage such as glued membrane resistance to blocking, water tolerance, thermotolerance, flame retardant resistance and mechanical property are good.
Simultaneously, because nanoparticle has the not available special optical performance of macrobead, ubiquity " blue shift " phenomenon not only has stronger ultraviolet radiation absorption characteristic, but also has infrared reflective properties.It adds in the latex, can form shielding effect to coating, reaches the purpose of anti-ultraviolet ageing and thermal ageing, increases the thermal insulation of coating simultaneously.
Today, abroad, nano material in industry widespread uses such as rubber, plastics, printing ink, papermaking, coating, is improved aspect of performance but concentrate on mostly, and the application in the paper anti-aging still belongs to the first time.At home, progressively develop CaCO in recent years
3, ZnO, Fe
2O
3, SiO
2And TiO
2Etc. nano material, and begun to carry out the exploration application, but still belonged to blank in the application of papermaking and coating industry in rubber, plastics and medicine and other fields.
U.S. Pat-5596032 has been reported a kind of slow solidified cationic asphalt emulsion, chemistry, machinery, rheology and thixotroping stability with height, with itself and ultra-fine bone meal or clay blend, the matrix material that obtains is applicable to coating, floor, house and road seal gum.Compare with this patent, its applied inorganic materials particle diameter is not mentioned, and purposes is also different.
U.S. Pat-6113682 has been reported a kind of preparation method of composite pigment particle, surface-coated polysiloxane at stratiform silica and titanium dioxide complex particle, wherein the median size of titanium dioxide is 100nm, use it for makeup preparations, can improve skin slickness, glossiness, water resisting property and with the bonding force of skin.Compare this preparation methods difference, and purposes difference with this patent.
U.S. Pat-5552469 has been reported a kind of polymer-based carbon/laminated nano composition, its preparation method is an insertion polymerization thing melt in layered silicate material, distance between the lamella is 1-10nm, is preferably 3-4.5nm, like this since platelet can relatively be easy to peel off.Compare its preparation method difference with this patent.
(3) summary of the invention:
The object of the present invention is to provide a kind of inorganic nano particle-high molecular composite material and preparation method thereof, and as the age inhibiting application of paper coating.
The invention provides a kind of inorganic nano particle-high molecular composite material, formed by nano material, surface-modifying agent and latex blending, wherein nano material is selected from nanometer CaCO
3, TiO
2, SiO
2, ZnO or Fe
2O
3, particle diameter is 40-60nm, preferred nanometer CaCO
3, TiO
2, ZnO, weight percentage is 1.00%-5.00%, is preferably 3.00%-5.00%; Surface-modifying agent is selected from silane coupling agent, titanate coupling agent, lipid acid (salt), preferred fatty acid (salt), it is selected from stearic acid (salt), palmitinic acid (salt), tetradecanoic acid (salt), lauric acid (salt), most preferably be stearic acid (salt) or lauric acid (salt), weight percentage is 0.04%-1.00%, is preferably 0.12%-1.00%; Latex is selected from acrylic ester emulsion, benzene emulsion, styrene-butadiene latex, carboxylic styrene butadiene latex, is preferably styrene-butadiene latex or carboxylic styrene butadiene latex, and weight percentage is 94.00%-98.96%, is preferably 94.00%-96.88%.
The preparation method of inorganic nano particle-high molecular composite material is, at first with the slurries of nano material through ultrasonic dispersing 5-15 minute, preferred 8-12 minute, be warmed up to the above 10-30 of surface-modifying agent fusing point ℃ then, preferred 15-25 ℃, add surface-modifying agent and carry out modification, react after 1-3 hour, preferred 1.5-2.5 hour, cooling, cooling, stopped reaction, then with the directly blending at normal temperatures of itself and latex, by high speed dispersion with its uniform mixing, stirring velocity between 2000-4000rpm, preferred 2500-3500rpm, churning time is 5-30 minute, preferred 10-20 minute.
Inorganic nano particle-high molecular composite material is as the age inhibiting application of paper coating.
The present invention adopts the dispersion stabilization that earlier nano-material modified method is improved nano material, the method for selecting direct blending then for use with its with modification after the blending of nano material slurries, form stablize, the nano particle-high molecular dispersion system of homogeneous.Because high molecular stable composition effect, by the inorganic nano ion is compound in the high molecular polymer, again nanoparticle is added in the latex, can form shielding effect to coating, reach the effect of anti-ultraviolet ageing and thermal ageing, increase the thermal insulation of coating simultaneously.Be applied to paper coating, the paper performance after the coating is greatly enhanced.
(4) description of drawings: Fig. 1 is the ultraviolet ray ageing graphic representation of the embodiment of the invention 1.Fig. 2 is the thermal ageing graphic representation of the embodiment of the invention 1.Fig. 3 is the ultraviolet ray ageing graphic representation of the embodiment of the invention 2.Fig. 4 is the thermal ageing graphic representation of the embodiment of the invention 2.
(5) embodiment:
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.Embodiment 1:a. preparation method
With the slurries of 1g nano-calcium carbonate through ultrasonic dispersing 5 minutes, be warmed up to the stearic fusing point of surface-modifying agent then more than 20 ℃, add the 0.04g stearic acid, react after 2 hours cooling, cooling, the 98.96g styrene-butadiene latex is directly added wherein, high-speed stirring 20 minutes, stirring velocity 2000rpm promptly gets nano particle-high molecular composite material.B. coating property
Wherein 1-5-1 is unmodified sample, and 1-5-2 is the modification sample, does 1. coating physical property measurement of art paper primary coat
2. small-sized knife coater physicals test:
1. from the coating test-results, the coating water-retention value of employing modified latex exceeds nearly 5 seconds than the coating water-retention value of unmodified latex.Other performance of coating is close.
2. from the White Board test, it is lower slightly that the White Board of the unmodified latex of White Board ratio employing of employing modified latex is torn speed (plucking test), and the moisture-resistant frictional behaviour is better.C. 1. ultraviolet ray ageing of aging resistance:
As seen from Figure 1, whiteness, lightness behind the latex ultraviolet ray ageing after the modification are better than unmodified latex, illustrate that the adding of nano-calcium carbonate has influenced the aging resistance of White Board.Nano-calcium carbonate as can be seen from the figure is not too big to the influence of whiteness, but certain contribution is arranged, and nano-calcium carbonate is obviously bigger to the influence of blue degree, and the obvious integral body that decays of the latex indigo plant degree after the modification is better than unmodified latex.2. thermal ageing:
As can be seen from Figure 2, under the thermal ageing environment, the adding of nano-calcium carbonate all has certain contribution to whiteness and Lan Du.And as can be seen, the thermal ageing curve of modification sample obviously is better than unmodified sample.
Generally speaking, the adding of nanoparticle becomes just to influence to the paper aging performance after the coating, but amount more after a little while, influences also less.
Embodiment 2:a. preparation method
With the slurries of 5g nano-calcium carbonate through ultrasonic dispersing 15 minutes, be warmed up to the lauric fusing point of surface-modifying agent then more than 20 ℃, add the 0.05g lauric acid, react after 3 hours cooling, cooling, 94.95 parts of latex are directly added wherein, high-speed stirring 15 minutes, stirring velocity 3000rpm promptly gets nano particle-high molecular composite material.B. coating property
Wherein 1# is unmodified sample, and 2# is the modification sample, does the ivory board face and is coated with 1. coating physical property measurement
2. paper performance test:
| Project and numbering | ????1# | ????2# |
| Solid content: % | ????61.9 | ????61.8 |
| PH value: 25 ℃ | ????8.21 | ????8.48 |
| Viscosity: 25 ℃, 60rpm | ????2500 | ????2700 |
| Project and numbering | ????1# | ????2# |
| Whiteness | ????85.5 | ????87.3 |
| Ink absorption (K﹠N value) | ????23.3 | ????25.0 |
| Smoothness (s) | ????31.0 | ????26.0 |
| Roughness (μ) | ????5.40 | ????5.44 |
| Glossiness | ????36.0 | ????30.2 |
| Water absorbent surface (g/ml) | ????31.0 | ????26.0 |
| ????IGT | ????3.0 | ????3.0 |
1. by experiment as can be seen, modification is more or less the same with the different coating rerum naturas that unmodified latex is prepared, and the adding of nano-calcium carbonate slightly improves viscosity, but amplitude is less.
2. the coating experimental result shows, the introducing of nano-calcium carbonate has brought bigger influence to the ink absorption and the water absorbent surface of paper, because the hydrophobic oleophylic of nano material after the modification, so the water absorbent surface of paper reduces significantly, thereby paper water resisting property is improved greatly.Because ink absorption increases, therefore caused the reduction of sheet gloss.C. aging resistance
Wherein series one is unmodified sample, and series two is nono calcium carbonate modified sample, and series three contrasts 1. ultraviolet ray ageing of sample for BASF AG:
As seen from Figure 3, in ultraviolet ray ageing, nano-calcium carbonate has begun to show its anti-ultraviolet effect, and unmodified sample obviously is inferior to the modification sample, and BASF AG's product is suitable with the modification sample.Because the adding of nano material, stoped ultraviolet ray aging to paper, the lightness of paper and whiteness obviously decay are little.2. thermal ageing:
As seen from Figure 4, the thermal ageing effect of unmodified sample is obviously poor than other two samples, BASF AG's sample secondly, the lightness and the whiteness rate of decay are apparently higher than nano-material modified sample.
Can think that thus the adding of nano material has bigger influence to the heat aging performance of paper, and confirm the thermal insulation and the anti ageing property of nano material that the paper aging performance of having added after the latex coating of nanoparticle obviously is better than unmodified sample.
Embodiment 3:a. preparation method
With the slurries of 6g nano-calcium carbonate through ultrasonic dispersing 15 minutes, be warmed up to the lauric fusing point of surface-modifying agent then more than 20 ℃, add the 0.06g lauric acid, react after 3 hours cooling, cooling, 93.94 parts of latex are directly added wherein, high-speed stirring 15 minutes, stirring velocity 3000rpm promptly gets nano particle-high molecular composite material.Experiment is found, when the add-on of nano material is 6% (weight percent), have in latex and separate out the phenomenon generation, so the add-on of nano material should not be greater than 5%.
Claims (5)
1. an inorganic nano particle-high molecular composite material is formed by nano material, surface-modifying agent and latex blending, and wherein nano material is selected from nanometer CaCO
3, TiO
2, SiO
2, ZnO or Fe
2O
3, particle diameter is 40-60nm, weight percentage is 1.00%-5.00%; Surface-modifying agent is selected from silane coupling agent, titanate coupling agent, lipid acid (salt), and weight percentage is 0.04%-1.00%; Latex is selected from acrylic ester emulsion, benzene emulsion, styrene-butadiene latex, carboxylic styrene butadiene latex, and weight percentage is 94.00%-98.96%.
2. inorganic nano particle-high molecular composite material according to claim 1, wherein nano material is selected from nanometer CaCO
3, TiO
2, ZnO, weight percentage is 3.00%-5.00%; Surface-modifying agent is lipid acid (salt), is selected from stearic acid (salt), palmitinic acid (salt), tetradecanoic acid (salt), lauric acid (salt), is preferably stearic acid (salt) or lauric acid (salt), and weight percentage is 0.12%-1.00%; Latex is selected from styrene-butadiene latex or carboxylic styrene butadiene latex, and weight percentage is 94.00%-96.88%.
3. the preparation method of the matrix material of a claim 1, at first with the slurries of nano material through ultrasonic dispersing 5-15 minute, be warmed up to the above 10-30 of surface-modifying agent fusing point ℃ then, add surface-modifying agent and carry out modification, react after 1-3 hour, cooling, cooling, stopped reaction, then with the directly blending at normal temperatures of itself and latex, with its uniform mixing, stirring velocity is between 2000-4000rpm by high speed dispersion, and churning time is 5-30 minute.
4. the preparation method of matrix material according to claim 3, wherein the ultrasonic dispersing time is 8-12 minute, and temperature is the above 15-25 of surface-modifying agent fusing point ℃, and the reaction times is 1.5-2.5 hour, the high-speed stirring motor speed is between the 2500-3500rpm, and churning time is 10-20 minute.
5. claim 1 or 2 matrix material are as the age inhibiting application of paper coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01133287 CN1207341C (en) | 2001-09-25 | 2001-09-25 | Inorganic nano particle-high molecular composite material and its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01133287 CN1207341C (en) | 2001-09-25 | 2001-09-25 | Inorganic nano particle-high molecular composite material and its preparing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1408762A true CN1408762A (en) | 2003-04-09 |
| CN1207341C CN1207341C (en) | 2005-06-22 |
Family
ID=4671676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01133287 Expired - Fee Related CN1207341C (en) | 2001-09-25 | 2001-09-25 | Inorganic nano particle-high molecular composite material and its preparing method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1207341C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307274C (en) * | 2003-03-14 | 2007-03-28 | 株式会社日本触媒 | Coating composition for heating dry |
| CN100371386C (en) * | 2006-09-01 | 2008-02-27 | 四川大学 | Polymer containing ultraviolet absorption group and titanium dioxide complex particle composition and method of preparing the same |
| CN100400590C (en) * | 2005-09-15 | 2008-07-09 | 复旦大学 | Nanometer composite acrylic resin with high solid content and low viscosity and the prepn of its coating |
| CN101824778A (en) * | 2010-05-05 | 2010-09-08 | 南通茂林医用材料有限公司 | Processing method for surface nano functionalization of cellulose reel |
| CN101161697B (en) * | 2007-09-30 | 2010-10-13 | 攀钢集团攀枝花钢铁研究院 | Method for preparing grafted nano titanium oxide functional particles |
| CN101423634B (en) * | 2008-12-18 | 2010-12-01 | 江南大学 | Method for preparing multifunctional nano composite material |
| CN101456961B (en) * | 2009-01-07 | 2011-01-19 | 中国热带农业科学院农产品加工研究所 | Method for preparing reactive nano calcium carbonate-native rubber composite material |
| CN102585638A (en) * | 2011-12-31 | 2012-07-18 | 东莞上海大学纳米技术研究院 | Preparation method for waterborne nano radiating and cooling environment-friendly coating, and coating |
| CN104452454A (en) * | 2014-11-28 | 2015-03-25 | 广西大学 | Preparation method of nano modified emulsion |
| CN109504222A (en) * | 2018-11-07 | 2019-03-22 | 山东益利油漆有限公司 | A kind of addition Nano-meter SiO_22The water-borne acrylic coatings of hollow microballoon |
| CN109749168A (en) * | 2017-11-03 | 2019-05-14 | 北京化工大学 | A kind of nano zine oxide/rubber composite material and preparation method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100365037C (en) * | 2006-03-14 | 2008-01-30 | 同济大学 | Process for in-situ preparation of nano silicon dioxide and boron modified phenol-formaldehyde resin nano composites |
| CN102030850B (en) * | 2010-10-29 | 2012-05-09 | 华南理工大学 | Method for preparing environmentally-friendly anhydrous phase paper coating |
-
2001
- 2001-09-25 CN CN 01133287 patent/CN1207341C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307274C (en) * | 2003-03-14 | 2007-03-28 | 株式会社日本触媒 | Coating composition for heating dry |
| CN100400590C (en) * | 2005-09-15 | 2008-07-09 | 复旦大学 | Nanometer composite acrylic resin with high solid content and low viscosity and the prepn of its coating |
| CN100371386C (en) * | 2006-09-01 | 2008-02-27 | 四川大学 | Polymer containing ultraviolet absorption group and titanium dioxide complex particle composition and method of preparing the same |
| CN101161697B (en) * | 2007-09-30 | 2010-10-13 | 攀钢集团攀枝花钢铁研究院 | Method for preparing grafted nano titanium oxide functional particles |
| CN101423634B (en) * | 2008-12-18 | 2010-12-01 | 江南大学 | Method for preparing multifunctional nano composite material |
| CN101456961B (en) * | 2009-01-07 | 2011-01-19 | 中国热带农业科学院农产品加工研究所 | Method for preparing reactive nano calcium carbonate-native rubber composite material |
| CN101824778A (en) * | 2010-05-05 | 2010-09-08 | 南通茂林医用材料有限公司 | Processing method for surface nano functionalization of cellulose reel |
| CN102585638A (en) * | 2011-12-31 | 2012-07-18 | 东莞上海大学纳米技术研究院 | Preparation method for waterborne nano radiating and cooling environment-friendly coating, and coating |
| CN104452454A (en) * | 2014-11-28 | 2015-03-25 | 广西大学 | Preparation method of nano modified emulsion |
| CN109749168A (en) * | 2017-11-03 | 2019-05-14 | 北京化工大学 | A kind of nano zine oxide/rubber composite material and preparation method |
| CN109504222A (en) * | 2018-11-07 | 2019-03-22 | 山东益利油漆有限公司 | A kind of addition Nano-meter SiO_22The water-borne acrylic coatings of hollow microballoon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1207341C (en) | 2005-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1207341C (en) | Inorganic nano particle-high molecular composite material and its preparing method and use | |
| Chen et al. | Synthesis of ZnO/polystyrene composites particles by Pickering emulsion polymerization | |
| US6432535B1 (en) | Pigment in thin flakes and a method for manufacturing the same | |
| Liu et al. | Fabrication and properties of transparent polymethylmethacrylate/cellulose nanocrystals composites | |
| Goikuria et al. | Thermal stability increase in metallic nanoparticles-loaded cellulose nanocrystal nanocomposites | |
| Fernando | Nanocomposite and nanostructured coatings: Recent advancements | |
| JP3745688B2 (en) | Cosmetic extender pigment and method for producing the same | |
| Huang et al. | Fabrication and characterization of superhydrophobic high opacity paper with titanium dioxide nanoparticles | |
| JP2005539131A (en) | Effect pigments surface modified with LCST and / or UCST polymers | |
| Muzny et al. | Clay platelet dispersion in a polymer matrix | |
| Suhailath et al. | Synthesis, characterisation and flame, thermal and electrical properties of poly (n-butyl methacrylate)/titanium dioxide nanocomposites | |
| CN1263808C (en) | Surface nano modifying method for micrometer granule | |
| Yamamoto et al. | Soft polymer-silica nanocomposite particles as filler for pressure-sensitive adhesives | |
| Eslami et al. | Optical and mechanical properties of transparent acrylic based polyurethane nano Silica composite coatings | |
| DE10241510A1 (en) | Preparation of nano composites by organic modification of nano filler useful as a paint, adhesive, casting composition, in aircraft construction, electronics, automobile finishing, and as a parquet flooring lacquer | |
| CN1824699A (en) | Method of lowering acrylate material surface energy | |
| US6011087A (en) | Modified mineral filler for thermosets | |
| KR20200078149A (en) | Composite Particles of Cellulose Nanofiber and Polymer, and A Process for Preparing Same | |
| Wu et al. | Synthesis and film performances of SiO2/P (MMA-BA) core–shell structural latex | |
| CN113698669B (en) | White carbon black modified nano barium sulfate and preparation method and application thereof | |
| CN108531059A (en) | A kind of montmorillonite intercalation modified polyurethane paint of UV radiation | |
| Gibril et al. | Fabrication, physical and optical properties of functionalized cellulose based polymethylmethacrylate nanocomposites | |
| Kolesnik et al. | Reinforcement of polymer composite materials by titanium dioxide nanoparticles synthesized in plasma discharge under ultrasonic cavitation | |
| KR20020086516A (en) | Novel surface-modified pearl pigment and process for producing the same | |
| Samyn et al. | Application of polymer nanoparticle coating for tuning the hydrophobicity of cellulosic substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |