CN102659322A - Preparation method of glass/polymethyl methacrylate (PMMA) micro-nano interface structure laminated material - Google Patents
Preparation method of glass/polymethyl methacrylate (PMMA) micro-nano interface structure laminated material Download PDFInfo
- Publication number
- CN102659322A CN102659322A CN2012100978104A CN201210097810A CN102659322A CN 102659322 A CN102659322 A CN 102659322A CN 2012100978104 A CN2012100978104 A CN 2012100978104A CN 201210097810 A CN201210097810 A CN 201210097810A CN 102659322 A CN102659322 A CN 102659322A
- Authority
- CN
- China
- Prior art keywords
- pmma
- glass
- interface structure
- micro
- nano interface
- 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
Abstract
The invention relates to the field of composite materials and especially relates to a preparation method of a glass/polymethyl methacrylate (PMMA) micro-nano interface structure laminated material. The preparation method comprises the following steps that 1, polymethylhydrosiloxane and ethyl orthosilicate undergo a hydrolysis reaction under the alkaline conditions to produce silica sol; and the silica sol is coated on the surface of glass to form a silica porous film having aperture sizes of 0.2 to 2mm; 2, a methyl methacrylate monomer, a plasticizer and an initiator are mixed according to a certain ratio and then undergo prepolymerization to produce a PMMA prepolymer; 3, the silica porous film is coated with the PMMA prepolymer and then is subjected to heat treatment in vacuum; and 4, the silica porous film with the PMMA prepolymer undergoes heat treatment polymerization in a high-pressure nitrogen atmosphere to produce the glass/PMMA micro-nano interface structure laminated material. The glass/PMMA micro-nano interface structure laminated material has excellent performances of high transparency, impact resistance, fatigue resistance and aging resistance.
Description
Technical field
The present invention relates to a kind of glass/PMMA laminate preparation method, relate in particular to a kind of glass/PMMA micro-nano interface structure laminate preparation method.
Background technology
Glass (inorganic) has better hardness, intensity, optical property and chemicalstability, but fragility is big, shock resistance is poor; And synthetic glass (polymethylmethacrylate, PMMA) easily moulding have good toughness and shock resistance, but hardness is low, the surface is prone to scratch, it is aging to be prone to.The organic and inorganic laminate has been taken into account advantages such as high, high temperature resistant, the corrosion-resistant and synthetic glass lightweight of glass hard (HRC65, shock resistance, easy-formation; Obtain the optimum optimization combination at aspects such as intensity, loss of weight, high temperature resistant, shock resistance, long lifetives; Can substitute the conventional transparent material, be applied to fields such as aircraft windscreen, shellproof door and window, vehicle glass, the transparent floor of top-grade building.
Because the Young's modulus and the thermal expansivity of glass and synthetic glass differ an one magnitude, the hot pressing layer closes very high glass coating thermal stresses and the interface layer stress (interface normal stress and interfacial sheat stress) of appearance in the process.In use laminate bears envrionment temperature and external load effect, produces reciprocal fatigue deformation, and coming unstuck appears in interface easily after for some time.The interface major cause that lost efficacy of coming unstuck is that interlayer shear lost efficacy, and invalid position is positioned at layer and closes position, edge, interface.Improve the interface binding intensity of glass/synthetic glass, reduce interfacial stress, for preventing that the interface from coming unstuck most important.Prior art mainly utilizes interface modification (to increase interfacial adhesion! ) improve the bonding interface performance, but cause easily interface shearing-resistance cut performance and shock resistance reduce (Ou Yingchun, Feng Haibing, Lan Zhiwei, etc., " research of polyurethane pellicle and synthetic glass interface binding intensity ", Wuhan University of Technology's journal, 2009,
31, 103-105.), therefore, be necessary angle from interface structure, examine the solution route that comes unstuck and lost efficacy in the interface again closely.
Silicon dioxide porous membrane has been successfully applied to submicron high speed integrated circuit, optics, catalysis, separation, heat insulation and insulation and field of nanocomposite materials.Through selecting different material and preparation technology, the aperture is adjustable continuously from the nanoscale to the micro-meter scale.CN1272245 discloses with Z 150PH and has prepared the method for silicon dioxide porous membrane as template, and pore size distribution is in 2-100 nm scope.People such as Dongjiang Yang are raw material with polymethyl hydrogen siloxane and tetraethoxy; Prepare aperture adjustable porous silica between 50-500 nm; And controlled (the D J Yang of thin-film hydrophobic performance; Y Xu, W J Xu, et al. Tuning pore size and hydrophobicity of macroporous hybrid silica films with high optical transmittance by a non-template route. Journal of Materials Chemistry; 2008
18,5557 – 5562.).People such as Yong Liu are through glass and hydrochloric acid and ydrogen peroxide 50 generation hydro-thermal reaction (Y Liu; H Wang; Y C Wang; Et al. A non-template hydrothermal route to uniform 3D macroporous films with switchable optical properties. Journal of Non-Crystalline Solids, 2011
357, 1768 – 1773.), at the silicon-dioxide macropore film of glass surface formation aperture 1-7 mm.
Through on glass/synthetic glass interface, introducing the aperture is the silicon dioxide porous membrane of micrometer/nanometer yardstick, because main chemical compositions (SiO between silica membrane and the glass
2) similar with chemical bond, interface bond strength is high, can form hard membrane layer; Meanwhile, the useful area that the duct of porous silica has increased glass/synthetic glass bonding interface improves the bonding interface performance.Glass/PMMA interface is changed three-dimensional micro-nano structure into by original two-dimension plane structure, and (PMMA gets into SiO
2In the duct), reduced interfacial sheat stress, improve the anti-aging and anti-fatigue performance in interface, thereby help the safety and the work-ing life of lifting glass/synthetic glass laminate.
Summary of the invention
The objective of the invention is to through introduce the porous silica film in micro/nano-scale aperture at glass surface; Improve glass/synthetic glass interface structure; Utilize the PMMA performed polymer polymerization in the porous-film perforate duct, prepare glass/PMMA laminate with micro-nano interface structure.
The objective of the invention is to realize like this, it is characterized in that method steps is:
1) utilizes polymethyl hydrogen siloxane (PMHS) and tetraethoxy (TEOS) hydrolysis under alcohol solvent neutral and alkali condition, prepare solid content and be 10% SiO
2Colloidal sol, and be coated on glass surface, under vacuum, solidify, prepare SiO
2Porous membrane;
2) MMA MONOMER (MMA), plasticizer phthalic acid dibutylester (DBP) and initiator Lucidol (BPO) are mixed the back pre-polymerization according to a certain percentage, prepare polymethylmethacrylate (PMMA) performed polymer;
3) at porous SiO
2Film surface applies the PMMA performed polymer, and places the following 50 ℃ of thermal treatment 1-7 h of vacuum;
4) under high pressure nitrogen atmosphere, heat-treat polymerization, prepare glass/PMMA laminate with micro-nano interface structure.
The mass ratio of described TEOS and PMHS is 1～10, and alkaline condition is solution acid alkalinity pH=10;
Described glass material is Sodelimesilica Glass or alumina silicate glass;
Described SiO
2The porous membrane coating method is a spin-coating method, spin coating rotating speed 1000～3000 rpm, 60-80 ℃ of vacuum solidification temperature;
The mass ratio of the raw material MMA of described PMMA performed polymer, DBP, BPO is 92.9:0.3:6.8, and the pre-polymerization temperature is 85 ℃, pre-polymerization time 10-30 min;
Described PMMA performed polymer coating method is spin coating, and the spin coating rotating speed is 500～1000 rpm.
Described nitrogen pressure is 1.1～2.0 MPa, and the thermal treatment polymerization process condition is 90-100 ℃ of insulation 1 h.
The invention has the advantages that: (1) utilizes PMHS and TEOS to be raw material, prepares aperture adjustable porous silica film between 0.2～2 mm at glass surface; (2) through the PMMA performed polymer polymerization in the porous silica duct; Not only form the three-D micro-nano interface structure; And the interface contact area of glass through porous silica film and synthetic glass increase substantially, and bonding interface performance, shock resistance and anti-aging and anti-fatigue performance significantly improve; (3) because the SiO in the duct
2Form the refractive index gradient layer with two kinds of compositions of PMMA, help reducing the interface luminous reflectance, the transparency of laminate is up to 92%, guarantees to meet the high transparent requirement of Transparent Parts in Aviation and covil construction glass, vehicle glass.
Specific embodiment
Embodiment 1
With mass ratio is that 5 TEOS and PMHS are raw material, hydrolysis under the pH=10 condition in alcohol solvent, and the preparation solid content is 10% SiO
2Colloidal sol, and be coated on the thick Sodelimesilica Glass surface of 3 mm, SiO is prepared in 80 ℃ of curing under vacuum
2Porous membrane.Mass polymerization synthetic PMMA performed polymer is coated on the porous membrane, and 50 ℃ of thermal pretreatment are 2 hours under vacuum, are 95 ℃ of insulation 1 h under the nitrogen atmosphere of 1.5 MPa at air pressure then, prepare glass/PMMA laminate.The scanning electron microscope analysis in sample transverse section shows, SiO
2Thickness is 560 nm, and aperture size is 200-340 nm; The transparency of ultraviolet-visible pectrophotometer test shows glass/PMMA laminate (total thickness 3.1 mm) is 92% (550 nm).
Embodiment 2
With mass ratio is that 1 TEOS and PMHS are raw material, hydrolysis under the pH=10 condition in alcohol solvent, and solid content is 10% SiO
2Colloidal sol, and be coated on the thick Sodelimesilica Glass surface of 3 mm, SiO is prepared in 80 ℃ of curing under vacuum
2Porous membrane.Mass polymerization synthetic PMMA performed polymer is coated on the porous membrane, and 50 ℃ of thermal pretreatment are 2 hours under vacuum, are 95 ℃ of insulation 1 h under the nitrogen atmosphere of 2.0 MPa at air pressure then, prepare glass/PMMA laminate.The scanning electron microscope analysis in sample transverse section shows, SiO
2Thickness is 1.6 mm, and aperture size is 0.6-1.2 mm; The transparency of ultraviolet-visible pectrophotometer test shows laminate (total thickness 3.1 mm) is 90% (550 nm).
Claims (6)
1. glass/PMMA micro-nano interface structure laminate preparation method is characterized in that process step is:
1) utilizes polymethyl hydrogen siloxane (PMHS) and tetraethoxy (TEOS) hydrolysis under alcohol solvent neutral and alkali condition, prepare solid content and be 10% SiO
2Colloidal sol, and be coated on glass surface, under vacuum, solidify, prepare SiO
2Porous membrane;
2) MMA MONOMER (MMA), plasticizer phthalic acid dibutylester (DBP) and initiator Lucidol (BPO) are mixed the back pre-polymerization according to a certain percentage, prepare polymethylmethacrylate (PMMA) performed polymer;
3) at porous SiO
2Film surface applies the PMMA performed polymer, and places the following 50 ℃ of thermal treatment 1-7 h of vacuum;
4) under high pressure nitrogen atmosphere, heat-treat polymerization, prepare glass/PMMA laminate with micro-nano interface structure.
2. glass according to claim 1/PMMA micro-nano interface structure laminate preparation method, the mass ratio that it is characterized in that TEOS and PMHS is 1～10, alkaline condition is solution acid alkalinity pH=10.
3. glass according to claim 1/PMMA micro-nano interface structure laminate preparation method is characterized in that glass material is Sodelimesilica Glass or alumina silicate glass; SiO
2The porous membrane coating method is a spin-coating method, spin coating rotating speed 1000～3000 rpm, 60-80 ℃ of vacuum solidification temperature.
4. glass according to claim 1/PMMA micro-nano interface structure laminate preparation method is characterized in that raw material MMA, the DBP of PMMA performed polymer, the mass ratio of BPO are 92.9:0.3:6.8, and the pre-polymerization temperature is 85 ℃, pre-polymerization time 10-30 min.
5. glass according to claim 1/PMMA micro-nano interface structure laminate preparation method is characterized in that PMMA performed polymer coating method is spin coating, and the spin coating rotating speed is 500～1000 rpm.
6. glass according to claim 1/PMMA micro-nano interface structure laminate preparation method is characterized in that nitrogen pressure is 1.1～2.0 MPa, and the thermal treatment polymerization process condition is 90-100 ℃ of insulation 1 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210097810.4A CN102659322B (en) | 2012-04-06 | 2012-04-06 | Preparation method of glass/polymethyl methacrylate (PMMA) micro-nano interface structure laminated material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210097810.4A CN102659322B (en) | 2012-04-06 | 2012-04-06 | Preparation method of glass/polymethyl methacrylate (PMMA) micro-nano interface structure laminated material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102659322A true CN102659322A (en) | 2012-09-12 |
| CN102659322B CN102659322B (en) | 2014-04-02 |
Family
ID=46768937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210097810.4A Expired - Fee Related CN102659322B (en) | 2012-04-06 | 2012-04-06 | Preparation method of glass/polymethyl methacrylate (PMMA) micro-nano interface structure laminated material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659322B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030915A (en) * | 2012-12-05 | 2013-04-10 | 常州大学 | Preparation method of plasticized, copolymerized and modified organic glass |
| CN105664994A (en) * | 2016-02-29 | 2016-06-15 | 暨南大学 | Amino-functionalization magnetic photocatalyst and preparing method and application thereof |
| CN111881613A (en) * | 2020-08-05 | 2020-11-03 | 武汉市政工程设计研究院有限责任公司 | Inversion method and system for three-dimensional stress field with different weights of normal stress and shear stress |
| CN113698094A (en) * | 2021-08-31 | 2021-11-26 | 北京航空航天大学 | Preparation method of high-strength high-toughness high-light transmittance composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5893329A (en) * | 1981-11-30 | 1983-06-03 | Toshiba Corp | Method for flattening insulating layer |
| US6284382B1 (en) * | 1997-11-27 | 2001-09-04 | Sony Corporation | Antireflection film and manufacturing method thereof |
| CN1740823A (en) * | 2005-07-15 | 2006-03-01 | 复旦大学 | A multiwindow wideband anti-reflection PMMA-SiO2 thin film and producing method thereof |
| CN101062773A (en) * | 2007-04-13 | 2007-10-31 | 中国科学院山西煤炭化学研究所 | Method for preparing mesoporous material by non-surface activator process |
| CN101450973A (en) * | 2007-11-28 | 2009-06-10 | 郭晴晴 | Synthetic method of nano SiO2/PMMA |
-
2012
- 2012-04-06 CN CN201210097810.4A patent/CN102659322B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5893329A (en) * | 1981-11-30 | 1983-06-03 | Toshiba Corp | Method for flattening insulating layer |
| US6284382B1 (en) * | 1997-11-27 | 2001-09-04 | Sony Corporation | Antireflection film and manufacturing method thereof |
| CN1740823A (en) * | 2005-07-15 | 2006-03-01 | 复旦大学 | A multiwindow wideband anti-reflection PMMA-SiO2 thin film and producing method thereof |
| CN101062773A (en) * | 2007-04-13 | 2007-10-31 | 中国科学院山西煤炭化学研究所 | Method for preparing mesoporous material by non-surface activator process |
| CN101450973A (en) * | 2007-11-28 | 2009-06-10 | 郭晴晴 | Synthetic method of nano SiO2/PMMA |
Non-Patent Citations (1)
| Title |
|---|
| 王华林等: "PMMA/SiO2有机-无机杂化玻璃的研究", 《高分子材料科学与工程》, vol. 16, no. 4, 31 July 2000 (2000-07-31), pages 114 - 116 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030915A (en) * | 2012-12-05 | 2013-04-10 | 常州大学 | Preparation method of plasticized, copolymerized and modified organic glass |
| CN103030915B (en) * | 2012-12-05 | 2015-04-22 | 常州大学 | Preparation method of plasticized, copolymerized and modified organic glass |
| CN105664994A (en) * | 2016-02-29 | 2016-06-15 | 暨南大学 | Amino-functionalization magnetic photocatalyst and preparing method and application thereof |
| CN111881613A (en) * | 2020-08-05 | 2020-11-03 | 武汉市政工程设计研究院有限责任公司 | Inversion method and system for three-dimensional stress field with different weights of normal stress and shear stress |
| CN111881613B (en) * | 2020-08-05 | 2021-04-06 | 武汉市政工程设计研究院有限责任公司 | Inversion method and system for three-dimensional stress field with different weights of normal stress and shear stress |
| CN113698094A (en) * | 2021-08-31 | 2021-11-26 | 北京航空航天大学 | Preparation method of high-strength high-toughness high-light transmittance composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102659322B (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102659322B (en) | Preparation method of glass/polymethyl methacrylate (PMMA) micro-nano interface structure laminated material | |
| KR102494180B1 (en) | Low refractive index layer, laminated film, method for manufacturing low refractive index layer, method for manufacturing laminated film, optical member and image display device | |
| US6818306B2 (en) | Optically clear structural laminate | |
| RU2646641C2 (en) | Intermediate film for laminated glass, and laminated glass | |
| EP1984763B1 (en) | Method for preparing anti-reflective coatings and coating obtained therefrom | |
| KR102477728B1 (en) | Porous silicone object and process for producing same | |
| KR102477732B1 (en) | Void structured film bonded through catalytic action and method for manufacturing same | |
| KR102324896B1 (en) | Optical laminate, optical laminate manufacturing method, optical member, and image display device | |
| KR20130073898A (en) | Silicone-based material | |
| US11053127B2 (en) | Mechanically robust aerogels and preparation method thereof | |
| US20160046823A1 (en) | Nano-(Multifunctional) Solutions for Glass and Glass Products: Heterogeneous Nano-Self-Assembly and/or Coating | |
| KR102324895B1 (en) | Laminate film, optical member, and image display device | |
| CN107629491B (en) | Mesoporous SiO for flexible substrate2Wear-resistant anti-reflection coating and preparation method thereof | |
| CN114058199B (en) | UV-cured super-hydrophilic anti-fog coating and preparation method and application thereof | |
| Cai et al. | Transparent superhydrophobic hollow films (TSHFs) with superior thermal stability and moisture resistance | |
| Yang et al. | Fabrication of highly hydrophobic two-component thermosetting polyurethane surfaces with silica nanoparticles | |
| CN104591552A (en) | Laminated glass and preparation method thereof | |
| KR20200040895A (en) | Void layer, laminate, method for manufacturing void layer, optical member and optical device | |
| US20190232583A1 (en) | Method for producing optical laminate and optical laminate intermediate | |
| WO2017043496A1 (en) | Low-refractive-index layer, laminated film, method for producing low-refractive-index layer, method for producing laminated film, optical member, and image display device | |
| CN115380229A (en) | Optical laminate with double-sided adhesive layer and optical device | |
| CN112771413A (en) | Optical laminate with adhesive layers on both sides | |
| WO2017057331A1 (en) | Method for producing porous gel-containing liquid, porous gel-containing liquid, method for producing high-porosity layer, method for producing high-porosity porous body, and method for producing layered film roll | |
| CN112680124A (en) | Novel glass bonding method | |
| CN108623195B (en) | Heat insulation glass and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140402 Termination date: 20150406 |
|
| EXPY | Termination of patent right or utility model |