CN102352097B - Organic rectorite/polyurea nanocomposite - Google Patents
Organic rectorite/polyurea nanocomposite Download PDFInfo
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- CN102352097B CN102352097B CN 201110274736 CN201110274736A CN102352097B CN 102352097 B CN102352097 B CN 102352097B CN 201110274736 CN201110274736 CN 201110274736 CN 201110274736 A CN201110274736 A CN 201110274736A CN 102352097 B CN102352097 B CN 102352097B
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Abstract
The invention relates to an organic rectorite/polyurea nanocomposite. The nanocomposite is technically characterized in that: rectorite silicate is used as an additive, the organic diamine or quaternary ammonium salt containing a C12-C18 molecular chain is selected for modification, and the in-situ polymerization method is adopted to prepare the organic rectorite/polyurea nanocomposite. The prepared polyurea composite has the characteristics that the technological process is simple, the cost is low; and compared with pure polyurea, the nanocomposite has high tensile strength, elongation at break, initial decomposition temperature, etc.
Description
Technical field
The present invention relates to a kind of organic rectorite/polyureas nano composite material, is the preparation method of a kind of HS, high temperature resistant organic rectorite/polyureas nano composite material, belongs to the high-temperature anticorrosion field.
Background technology
The Spray Polyurea Elastomer technology is a kind of solvent-free, free of contamination novel operating technique that has.Coating application compared with techniques with traditional has many good qualities: fast setting, 100% solid content, easy construction etc.It generally is made up of A component and R component.The A component generally is the semi-prepolymer that is generated by isocyanic ester and polyether glycol, and the R component generally is to contain Amino Terminated polyether(ATPE), liquid amine chain extender and other auxiliary agents.During use A component and R component are mixed spraying.Along with the development of spray polyurea technology, need the more carbamide paint of HS, anti-higher temperature, be applied to more wide field, like thermal power plant's chimney anticorrosion, storage tank insulation etc.
Polymer based nanocomposites is to be matrix with the polymkeric substance, and nano material is a kind of matrix material of disperse phase.Because the dimensional effect of nano material wherein; Big specific surface area and strong interface keying action; Can make polymer based nanocomposites have the not available excellent properties of general polymerization thing based composites; Thereby having very wide application prospect and business development value, polymer based nanocomposites has become one of technology of the highest realization industry of nanotechnology at present.Wherein, utilize layered silicate natural clay and polymer manufacture nano composite material to become the focus of nearly decades of research.A lot of correlative studys show that under the few situation of natural clay addition, the mechanical property of polymer materials, resistance toheat and gas barrier property etc. all have significant improvement.The maximum natural clay of research mainly is polynite at present, and rectorite leng is a kind of and the natural mineral polynite similar, and is abundant at China's reserves, has very wide application prospect in the polymer modification field.
Summary of the invention
The technical problem that solves
For fear of the weak point of prior art, the present invention proposes a kind of organic rectorite/polyureas nano composite material, and organic rectorite clay/polyureas nano composite material that a kind of intensity is high, high temperature resistant, cost is relatively low and preparation method thereof is provided.
Technical scheme
A kind of organic rectorite/polyureas nano composite material is characterized in that each constituent mass umber per-cent is: organic rectorite clay 1～10, polyureas 90～99; Said organic rectorite clay adopts C
12～C
18Long-chain organic quaternary ammonium salt or C
12～C
18The organic diamine of long-chain carries out organic cation exchange intercalation processing to the sodium rectorite leng and obtains; Concrete preparation process is following:
Step 1: sodium rectorite leng and 400～1000ml water are added stirring pulping in the reactor drum, with organic modifiers C
12Join after water-soluble in the slurries, homogeneous disperseed 3～15 minutes, and at 80～100 ℃ of following insulation reaction 3～12h; The ratio of said sodium rectorite leng, organic modifiers is: the add-on of organic modifiers is 1～3 times of sodium rectorite leng cation exchange capacity.
Step 2: obtaining filter cake with deionized water repetitive scrubbing and filtration, is the AgNO of 0.1mol/L when adopting concentration
3Solution is checked in washings less than till behind the halide-ions; Filter cake oven dry grinding is made particle size is: the organic rectorite clay of 1～15 μ m;
Step 3: with 1～10 part of organic rectorite clay, join among 45～58.5 parts of carbamide paint component R, utilize high speed homogenization whisking appliance homogeneous to disperse 5～15 minutes; Mix stirring with 45～58.5 parts of carbamide paint component A again after being uniformly dispersed; The mass ratio of said R component and A component is 0.8～1.2;
Step 4: utilized vacuum outgas again 3～5 minutes, and be poured on the sheet glass, casting film-forming makes organic rectorite/polyureas nano composite material.
The sodium base rectorite leng that said sodium rectorite leng is a purity 70%.
Organic modifiers in the said step 1 is C
16Or C
18
Beneficial effect
A kind of organic rectorite/polyureas nano composite material that the present invention proposes, prior art has following advantage relatively:
1), with respect to pure carbamide paint, the tensile strength of this nano composite material has significantly and to improve.Add-on at organic rectorite is merely at 5% o'clock, and the tensile strength of matrix material is brought up to 10.10Mpa by original 5.84MPa, and amplification reaches 72.95%.
2), with respect to pure carbamide paint, the elongation at break of this nano composite material improves.Add-on at organic rectorite is merely at 5% o'clock, and the elongation at break of matrix material brings up to 318.52% by original 292.92%, and amplification reaches 8.74%.
3), with respect to pure carbamide paint, in the thermogravimetic analysis (TGA) process, be merely at 5% o'clock in the add-on of organic rectorite, weightless 5% o'clock temperature of nano composite material has had large increase, brings up to 294.1 ℃ by original 273.6 ℃, has improved 20.5 ℃.
4), with respect to pure carbamide paint, in the thermogravimetic analysis (TGA) process, be merely at 5% o'clock in the add-on of organic rectorite, weightless 50% o'clock temperature of nano composite material is greatly improved, and brings up to 421.5 ℃ by original 412.1 ℃, has improved 9.4 ℃.
5), the present invention adopts situ aggregation method to prepare nano composite material, is a kind of direct, simple, pollution-free, method that operating procedure simply prepares nano composite material.
Description of drawings
Fig. 1 is the modified technique of organic rectorite among the present invention;
Fig. 2 is the preparation technology of organic rectorite/polyureas nano composite material among the present invention;
The thermogravimetric curve of the nano composite material that Fig. 3 makes.
Embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
Organic rectorite clay in the nano composite material of the present invention is to use C
12～C
18Long-chain organic quaternary ammonium salt or C
12～～C
18The organic diamine of long-chain carries out to rectorite leng that organic cation exchange intercalation processing obtains.Used rectorite leng is that a kind of purity is 70% sodium base rectorite leng.Used organic intercalation agent is that to contain a carbon atom number in the molecular structure be 12～18 straight chained alkyl quaternary ammonium salt or to contain two carbon atom numbers be 12～18 branched-chain alkyl diamine.
The preparation method of the organic rectorite described in the present invention is: with 100g sodium base rectorite leng is benchmark, and rectorite leng and 400～1000ml water are added stirring pulping in the reactor drum, and with organic modifiers C
12(or C
16, C
18) join in the slurries after water-soluble, homogeneous disperseed 3～15 minutes, and at 80～100 ℃ of following insulation reaction 3～12h.Filter then and use the deionized water repetitive scrubbing in washings, to use the AgNO of concentration as 0.1mol/L
3The solution inspection is less than halide-ions.Afterwards, oven dry is ground and to be made particle size and be: the organic rectorite clay of 1～15 μ m.
With 1～10 part of organic rectorite clay, join carbamide paint component R45～58.5 parts, utilize high speed homogenization whisking appliance homogeneous to disperse 5～15 minutes.After being uniformly dispersed again with carbamide paint component A45～58.5 parts, keeping the mass ratio of R component and A component is 0.8～1.2.Mix and stir, utilized vacuum outgas 3～5 minutes, film, make nano composite material.
Embodiment 1: with 100g purity is that 70% rectorite leng places reactor drum, adds 800ml water, stirs and processes slurries, gets the C of 45g
18Organic quaternary ammonium salt, and it is dissolved with suitable quantity of water, slowly join in the slurries, stir after the 5min with high speed homogenization whisking appliance homogeneous, reactor drum is warming up to 80 ℃, insulation reaction 6h filters, and uses the deionized water repetitive scrubbing, until using AgNO
3Drips of solution is added to and does not occur white precipitate in the washings, with the organic rectorite oven dry that makes, and pulverizes and grinds.
Get 1 part of levigated organic clay rectorite leng, join 49.5 parts of carbamide paint R components, stir.Disperse 5min with high speed homogenization whisking appliance homogeneous again, add 49.5 parts again and get carbamide paint A component, vacuum outgas 5min films, and makes nano composite material.
Embodiment 2: with 100g purity is that 70% rectorite leng places reactor drum, adds 800ml water, stirs and processes slurries, gets the C of 45g
18Organic quaternary ammonium salt, and it is dissolved with suitable quantity of water, slowly join in the slurries, stir after the 5min with high speed homogenization whisking appliance homogeneous, reactor drum is warming up to 80 ℃, insulation reaction 6h filters, and uses the deionized water repetitive scrubbing, until using AgNO
3Drips of solution is added to and does not occur white precipitate in the washings, with the organic rectorite oven dry that makes, and pulverizes and grinds.
Get 2 parts of levigated organic clay rectorite lengs, join 49 parts of carbamide paint R components, stir.Disperse 5min with high speed homogenization whisking appliance homogeneous again, add 49 parts again and get carbamide paint A component, vacuum outgas 5min films, and makes nano composite material.
Embodiment 3: with 100g purity is that 70% rectorite leng places reactor drum, adds 800ml water, stirs and processes slurries, gets the C of 45g
18Organic quaternary ammonium salt, and it is dissolved with suitable quantity of water, slowly join in the slurries, stir after the 5min with high speed homogenization whisking appliance homogeneous, reactor drum is warming up to 80 ℃, insulation reaction 6h filters, and uses the deionized water repetitive scrubbing, until using AgNO
3Drips of solution is added to and does not occur white precipitate in the washings, with the organic rectorite oven dry that makes, and pulverizes and grinds.
Get 4 parts of levigated organic clay rectorite lengs, join 48 parts of carbamide paint R components, stir.Disperse 5min with high speed homogenization whisking appliance homogeneous again, add 48 parts again and get carbamide paint A component, vacuum outgas 5min films, and makes nano composite material.
Embodiment 4: with 100g purity is that 70% rectorite leng places reactor drum, adds 800ml water, stirs and processes slurries, gets the C of 45g
18Organic quaternary ammonium salt, and it is dissolved with suitable quantity of water, slowly join in the slurries, stir after the 5min with high speed homogenization whisking appliance homogeneous, reactor drum is warming up to 80 ℃, insulation reaction 6h filters, and uses the deionized water repetitive scrubbing, until using AgNO
3Drips of solution is added to and does not occur white precipitate in the washings, with the organic rectorite oven dry that makes, and pulverizes and grinds.
Get 5 parts of levigated organic clay rectorite lengs, join 47.5 parts of carbamide paint R components, stir.Disperse 5min with high speed homogenization whisking appliance homogeneous again, add 47.5 parts again and get carbamide paint A component, vacuum outgas 5min films, and makes nano composite material.
In the process of preparation nano composite material, the C that adopts
18The rectorite leng of modification.Add organic rectorite massfraction be 3%, 4% and 5%, the nano composite material that makes is designated as respectively: 2-polyureas, 4-polyureas and 5-polyureas.
The mechanical property of the nano composite material that makes is following:
| Tensile strength (MPa) | Elongation at break (%) | |
| Pure polyureas | 5.84 | ?292.92 |
| The 3-polyureas | 6.08 | ?295.62 |
| The 4-polyureas | 7.80 | ?320.80 |
| The 5-polyureas | 10.10 | ?318.52 |
Matrix material thermal weight loss data:
| Weightless 5% temperature | Weightless 50% temperature | |
| Pure polyureas | 273.6 | ?412.1 |
| The 5-polyureas | 294.1 | ?421.5 |
Nano polyurea coating after the modification can be widely used in fields such as anticorrosion, thermal power plant's chimney anticorrosion, storage tank insulation of breakout tank.
Claims (2)
1. organic rectorite/polyureas nano composite material is characterized in that each constituent mass umber per-cent is: organic rectorite clay 1～10, polyureas 90～99; Said organic rectorite clay adopts C
18The long-chain organic quaternary ammonium salt carries out organic cation exchange intercalation processing to the sodium rectorite leng and obtains; Concrete preparation process is following:
Step 1: sodium rectorite leng and 400～1000ml water are added stirring pulping in the reactor drum, with organic modifiers C
18Join in the slurries after the long-chain organic quaternary ammonium salt is water-soluble, homogeneous disperseed 3～15 minutes, and at 80～100 ℃ of following insulation reaction 3～12h; The ratio of said sodium rectorite leng, organic modifiers is: the add-on of organic modifiers is 1～3 times of sodium rectorite leng cation exchange capacity;
Step 2: obtaining filter cake with deionized water repetitive scrubbing and filtration, is the AgNO of 0.1mol/L when adopting concentration
3Solution is checked in washings less than till behind the halide-ions; Filter cake oven dry grinding is made particle size is: the organic rectorite clay of 1～15 μ m;
Step 3: with 1～10 part of organic rectorite clay, join among 45～58.5 parts of carbamide paint component R, utilize high speed homogenization whisking appliance homogeneous to disperse 5～15 minutes; Mix stirring with 45～58.5 parts of carbamide paint component A again after being uniformly dispersed; The mass ratio of said R component and A component is 0.8～1.2;
Step 4: utilized vacuum outgas again 3～5 minutes, and be poured on the sheet glass, casting film-forming makes organic rectorite/polyureas nano composite material.
2. organic rectorite according to claim 1/polyureas nano composite material is characterized in that: the sodium base rectorite leng that said sodium rectorite leng is a purity 70%.
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| CN104592740A (en) * | 2015-02-18 | 2015-05-06 | 中国科学院长春应用化学研究所 | Carbon dioxide based polyurea composite material and preparation method thereof |
| CN108342149A (en) * | 2018-03-07 | 2018-07-31 | 成都福兰特电子技术股份有限公司 | A kind of ceramic crystal powdery paints, preparation method and its construction technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473872A (en) * | 2002-08-08 | 2004-02-11 | 马晓燕 | Rectorte/polypropylene nano comoposite material and its preparing method |
| CN101702448A (en) * | 2009-10-29 | 2010-05-05 | 西北工业大学 | Organic rectorite modified composite gel type electrolyte and preparation method thereof |
| CN101712785A (en) * | 2008-10-06 | 2010-05-26 | 常琛 | Novel super absorbent resin/inorganic nanoparticle composite material, preparation method thereof and usage thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473872A (en) * | 2002-08-08 | 2004-02-11 | 马晓燕 | Rectorte/polypropylene nano comoposite material and its preparing method |
| CN101712785A (en) * | 2008-10-06 | 2010-05-26 | 常琛 | Novel super absorbent resin/inorganic nanoparticle composite material, preparation method thereof and usage thereof |
| CN101702448A (en) * | 2009-10-29 | 2010-05-05 | 西北工业大学 | Organic rectorite modified composite gel type electrolyte and preparation method thereof |
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Effective date of registration: 20141210 Address after: Danfeng road Haian town Haian County Jiangsu city Nantong province No. 29 226600 Patentee after: NANTONG XINYUAN ELECTRIC APPLIANCE MANUFACTURING CO., LTD. Patentee after: Northwestern Polytechnical University Address before: 710072 Xi'an friendship West Road, Shaanxi, No. 127 Patentee before: Northwestern Polytechnical University |