CN103819991A - Novel protection material suitable for dinosaur fossil and preparation method thereof - Google Patents
Novel protection material suitable for dinosaur fossil and preparation method thereof Download PDFInfo
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- CN103819991A CN103819991A CN201310630117.3A CN201310630117A CN103819991A CN 103819991 A CN103819991 A CN 103819991A CN 201310630117 A CN201310630117 A CN 201310630117A CN 103819991 A CN103819991 A CN 103819991A
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Abstract
The invention discloses a novel protection material suitable for a dinosaur fossil and a preparation method of the novel protection material. The material is compounded from acrylic polymer and modified nanosilicon dioxide. According to the method, an emulsion polymerization manner is adopted, methyl methacrylate, butyl methacrylate, methyl acrylate and crylic acid are taken as main monomers for polymerization, a modified nano SiO2 solution is added before or after the polymerization reaction, and the mixture is stirred and blended uniformly. The preparation process is simple, the raw materials are easily available, the cost is low, the method is environmentally friendly, and the industrial production is easily implemented. The novel protection material has an excellent chemical stability, a film formed by the novel protection material has the advantages of excellent corrosion resistance, weather resistance, adhesiveness and heat stability, the original appearance of the fossil is kept, the efflorescence of the dinosaur fossil caused by the environment factor is avoided, and the service life of the fossil is prolonged.
Description
Technical field
The present invention relates to a kind of material for the protection of dinosaur fossil, belong to Material Field.
Technical background
Dinosaur fossil is the non-renewable treasure that the Nature is vouchsafed the mankind.China is the abundantest country of dinosaur fossil resource in the world; all find abundant dinosaur fossil in more than 20 provinces (city, autonomous region); to the end of the year 2012, China's approved has been set up national geological parks and the UNESCO Geopark of family more than 20 take geological vestige such as dinosaur fossil, Largescale Dinosaur Footprints fossil, fossil dinosaur eggs as main object of protection.Meanwhile, also have the museum of natural history, geological museum and the special dinosaur museum collection of One's name is legion to have a large amount of dinosaur fossils.Development of new material is applied to the protections such as dinosaur's bone fossil, paleontological fossil, has important scientific value and huge using value.
Dinosaur fossil protecting materials should possess the features such as the transparency is good, weathering resistance is good, solidity to corrosion good, maintenance fossil original appearance.For this reason, experiment determines that dinosaur fossil protecting materials is made up of two portions, i.e. polymer matrix and nano inorganic material.The nano inorganic material overwhelming majority selects silicon-dioxide, and this is closely related by the special structure properties of nano silicon.Polymer matrix is the integral part of protecting materials; polymer-based material is the main part that forms protecting materials; for nano inorganic material provides suitable carrier, make it produce suitable network structure, therefore polymer-based material and inorganic nano material should complement one another.Select substrate material mainly to consider following three aspects: raw material is easy to get, with low cost, prepare easy etc.The matrix of protecting materials, mainly contains silicone resin, acrylate, epoxy resin, zapon varnish etc.These materials have provide protection in various degree, but have some limitations, and its use range is restricted, and result of use has been subject to impact.As epoxy resin, adhesive power extensive chemical good stability, there is good alkali resistance, acid resistance and solvent resistance, reinforcement effect is good, but ventilation property is poor, can stop the evaporation of fossil internal moisture and the exchange of gas at fossil surface filming, can cause that for a long time fossil surface comes off, and easy to change under the uviolizing of sunlight, resistance to neutral salt spray corrodibility is poor, and light transmission is general.Zapon varnish is a kind of by nitro-cotton, Synolac, softening agent and organic solvent are modulated the clear lacquer forming, belong to volatility paint, there is fast drying, gloss is soft, the features such as resistance to acids and bases and neutral salt spray corrodibility are better, but it is airtight, color and luster is dark, not ageing-resistant, after using, affect fossil outward appearance, increase in time, color becomes darker and darker, to such an extent as to be difficult to find out the style of fossil, be unfavorable for observing and scientific research, simultaneously, it is not a kind of environment-friendly type coating, when use, toxicity is larger, although so also using, but can not think desirable protecting materials.Organosilicon material is due to production process complexity, and cost is very high, and resistance to neutral salt spray corrodibility is poor, and light transmission is general, thereby limits its application.Therefore, make the more diversion of people's handle to the research of the protecting materials take acrylic resin as matrix.Acrylic resin-based protecting materials has that preparation technology is simple, weathering resistance, gloss retention, film-forming properties are good, the advantage of normal temperature self-drying and remarkable mechanical property.These advantages make to study under normal conditions and produce fossil protecting materials becomes possibility, is subject to extensive concern.
Current research general choice abundant raw material, the Acrylic Acid Monomer that is easy to preparation are through being polymerized to protecting materials matrix, and weathering resistance, gloss retention, film-forming properties, normal temperature self-drying and mechanical property that it has had, can better resist the corrosion of various soda acids.But acrylic resin molecule mostly is linear structure; lack cross-linking set; thereby water tolerance; weathering resistance and heat impedance have to be optimized; adopt nano silicon compounding technology to carry out modification to this material for this reason; it is being kept on the basis of original good characteristic, significantly improve the performance such as water-fast, weather-proof and heat resistanceheat resistant of protecting materials.In domestic research report, all select at present take stone cultural artifact and relics as research object.And dinosaur fossil main composition thing is calcite and phosphatic rock, thereby to require novel protected material be neutrality or weakly alkaline, to prevent the destruction of protecting materials to fossil; Dinosaur fossil now uses protecting materials to be mostly zapon varnish, and this material is poisonous, and the feature of environmental protection is poor, and meanwhile, after it applies fossil surface for some time, color deepens gradually, reduces the transparency, can not keep fossil original appearance, and impact is observed and research; In existing research, there are no the characteristic for dinosaur fossil, detailed formula and application report with nano-silicon dioxide modified acrylic ester for the protection of fossil.
Summary of the invention
The present invention is directed to the problems referred to above, a kind of novel protected material that is applicable to dinosaur fossil and preparation method thereof is provided.
The present invention is achieved through the following technical solutions:
A novel protected material that is applicable to dinosaur fossil, described material is composited by acrylic ester polymer and modified manometer silicon dioxide.
Due to nanometer SiO
2a kind of nontoxic, tasteless non-metallic material, for unformed white powder, microstructure is cotton-shaped and netted accurate grain pattern, for spherical form, this special construction makes it have unique character: to wavelength 490 nm with interior ultraviolet reflection rate up to 70% ~ 80%, be added in macromolecular material, can reach the object of anti-ultraviolet aging and thermal ageing; Small-size effect and macro quanta tunnel effect make it produce the effect of oozing of becoming silted up, can be deep near the unsaturated link(age) of macromolecular chain, and have an effect with the electronic cloud of unsaturated link(age), improve heat, light stability and the chemical stability of macromolecular material, thereby improve resistance to deterioration and the chemical resistant properties of product; At high temperature still there is the feature that intensity, toughness and stability are high, be dispersed in material, be combined with macromolecular chain and form tridimensional network, thereby the fundamental property such as intensity, elasticity of raising material also improves water resistance simultaneously greatly; Three-dimensional silica stone structure, bigger serface, undersaturated ligancy, make it have extremely strong adsorption to pigment ion, can reduce the pigment decay causing because of uviolizing.Other nano materials do not have the character of these aspects.Therefore the deficiency that protecting materials exists in order to promote straight polymer-acrylate, keeps fossil original appearance, shows that according to experimental study in acrylate matrix polymeric material, adding nano silicon can significantly improve correlated performance.Increase the degree of branching of acrylic ester polymer by composite silicon dioxide; increase cross-linking set; significantly improve the performances such as water-fast, the weather-proof and heat resistanceheat resistant of protecting materials; and silicon-dioxide is through forming covalent bonds between modification and olefine acid ester polymer; inorganic component is more firm with combination, is conducive to guarantee the stability of material.
As optional mode, described modified manometer silicon dioxide is evenly distributed in described acrylic ester polymer, and described modified manometer silicon dioxide combines by chemical bond with described acrylic ester polymer, forms three dimensional network structure.Modified manometer silicon dioxide is uniformly distributed in three dimensional network structure, is conducive to guarantee the performance homogeneity of material, also can improve the over-all properties of protecting materials.
As optional mode, described acrylic ester polymer is mainly formed by the copolymerization of core-shell by methyl methacrylate, butyl methacrylate, methyl acrylate, four kinds of monomers of vinylformic acid.By selecting various of monomer copolymerization to be also conducive to improve acrylic ester polymer degree of branching, more easily form three dimensional network structure.
As optional mode, described four kinds of monomers form by following mass parts: 39 ~ 45 parts of methyl methacrylates; 20 ~ 43 parts of butyl methacrylate; 15 ~ 39 parts of methyl acrylates; Vinylformic acid 1-2 part.
As optional mode, described material was emulsion form before being coated to fossil surface, is coated to fossil surface and forms transparent protective membrane on fossil surface after solidifying.Easy to use, be conducive to keep the original appearance of fossil.
The present invention also provides a kind of method of preparing the above-mentioned novel protected material that is applicable to dinosaur fossil: adopt emulsion polymerization way; carry out polymerization take methyl methacrylate, butyl methacrylate, methyl acrylate and vinylformic acid as principal monomer, and before polyreaction starts or polyreaction add modified Nano SiO after finishing
2liquid stirring and evenly mixing.
Prepare polymer-based material with reference to coatings chemistry and coatings chemistry and technology; the characteristic mainly being formed by phosphatic rock and calcite in conjunction with dinosaur fossil and historical relic's protection " maintenance original appearance " principle; selecting methyl methacrylate, butyl methacrylate and butyl acrylate in abundant raw material, the easy acrylate monomer reacting is main monomer, is protecting materials matrix through copolymerization.Weathering resistance, gloss retention, film-forming properties, normal temperature self-drying and mechanical property that it has had, can better resist the corrosion of various soda acids.Butyl acrylate is soft monomer, gives multipolymer with tenacity and flexibility; Methyl methacrylate is hard monomer, gives multipolymer with hardness, also gives the water resistance that multipolymer is good simultaneously.Be soft monomer butyl acrylate content when many, the snappiness of film can improve, and when hard monomer methyl methacrylate is large, the water-absorbent of film can diminish, and water tolerance can increase.Butyl acrylate and methyl methacrylate weight ratio should be advisable between 1.0 ~ 1.5; Water is 70/30 ~ 60/40 with monomer ratio; Emulsification dosage is 3.5% ~ 5% of monomer mass, and the ratio of anionic emulsifier and nonionic emulsifying agent is 1:2, and its consumption is monomer 5%; Initiator potassium persulfate consumption can improve its transformation efficiency with 0.5% of monomer mass.
As optional mode, described modified Nano SiO
2liquid adopts the one in following two kinds of methods to prepare:
Method a: by nanometer SiO
2with 1:1(volume ratio) alcohol water-dispersion, add Sodium hexametaphosphate 99, utilize ultra-sonic oscillation fully to disperse solution, obtain modified Nano SiO
2liquid;
Method b: under 200r/min agitation condition, dehydrated alcohol and dispersion agent 731A are added to deionized water for stirring 10 minutes, slowly add nano silicon with 1g/min speed again, then add silane coupling agent YGO-1204 to continue to stir 30 minutes, pH of mixed value is adjusted to 7.8, and ultrasonic concussion obtains modified Nano SiO for 5 minutes
2liquid, wherein the add-on of dispersion agent 731A accounts for 2% of silicon-dioxide quality, and the add-on of silane coupling agent YGO-1204 accounts for 10% of silicon-dioxide quality.
As optional mode, above-mentioned preparation method's concrete steps are as follows:
1) get the raw materials ready by following mass parts: methyl methacrylate 39 ~ 45; Butyl methacrylate 20 ~ 43; Methyl acrylate 15 ~ 39; Vinylformic acid 1 ~ 2; Polyoxyethylene octyl phenyl ether (OP-10) 2 ~ 3; Dodecyl sulphate potassium (k12) 1 ~ 2; Potassium Persulphate (Kps) 0.2 ~ 0.5(initiator); Sulfothiorine 0.2 ~ 0.5(promotor); Deionized water 180 ~ 200; Sodium bicarbonate 0.2 ~ 0.5(neutralizing agent); Sodium polyacrylate 2 ~ 4(stablizer); Matting agent 1 ~ 4;
2) 10 parts of water dissolution Kps of the each use of difference, sodium bicarbonate, Sulfothiorine, stand-by;
3) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing of 2～3 times of amounts, remove stopper, then add vinylformic acid, anabolic reaction monomer;
4) hybrid reaction monomer is added to OP-10, k
12, sodium polyacrylate and 100 parts of water stirring and emulsifying.Get emulsion 30% and add reactor, separately add 70 parts of deionized waters and enter reactor, turn on agitator simultaneously.
5) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) middle Kps solution and the hypo solution configuring, in still, reaction starts slowly to drip remaining 70% pre-emulsion, simultaneously, get respectively 6 parts of steps 2) in configuration initiator solution and accelerator solution by 0.5 part of speed dropping in 10 minutes, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control temperature in the kettle 70-80 ℃ of insulation 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, in this process, add residue initiator solution and accelerator solution,
6) be cooled to 50 ℃ after having reacted, add 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, i.e. acrylic ester polymerization emulsion;
7) by nanometer SiO
2quality accounts for 5% ratio of reaction monomers total amount, by modified Nano SiO
2liquid and matting agent add in acrylic ester polymerization emulsion under agitation condition, obtain nano-silicon dioxide modified acrylic ester polymerization emulsion protecting materials.
Adopt initiator of the present invention, the add-on of promotor and neutralizing agent and add mode, the over-all properties that is conducive to control the particle diameter of gained emulsion and guarantees product.
As optional mode, in above-mentioned preparation method's step 1), get the raw materials ready by following mass parts: methyl methacrylate 39; Butyl methacrylate 20; Methyl acrylate 39; Vinylformic acid 2; Polyoxyethylene octyl phenyl ether (OP-10) 3; Dodecyl sulphate potassium (k
12) 2; Potassium Persulphate (KPS) 0.4; Sulfothiorine 0.4; Deionized water 200; Sodium bicarbonate 0.4; Sodium polyacrylate 4; Matting agent 3.Adopt this proportioning raw materials be conducive to guarantee resulting materials have the good transparency, chemical stability, with the over-all properties such as the sticking power of fossil, to adapt to better protect the application needs of dinosaur fossil.
As optional mode, above-mentioned preparation method can also comprise concrete steps:
1) get the raw materials ready by following mass parts: methyl methacrylate 39 ~ 40; Butyl methacrylate 42 ~ 43; Methyl acrylate 15 ~ 16; Vinylformic acid 1 ~ 2; Polyoxyethylene octyl phenyl ether (OP-10) 1 ~ 3; Dodecyl sulphate potassium (k
12) 1 ~ 2; Potassium Persulphate (KPS) 0.3 ~ 0.4(initiator); Sulfothiorine 0.4 ~ 0.5(promotor); Deionized water 190 ~ 200; Sodium bicarbonate 0.2 ~ 0.4(neutralizing agent); Sodium polyacrylate 4 ~ 5(stablizer); Matting agent 1 ~ 4;
2) use respectively 10 parts of water dissolution Kps, sodium bicarbonate, Sulfothiorine, stand-by;
3) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing, remove stopper, then add vinylformic acid and modified Nano SiO
2liquid anabolic reaction body, wherein modified Nano SiO
2liquid is by nanometer SiO
25% the ratio that quality accounts for reaction monomers total amount adds;
4) hybrid reaction body is added to OP-10, k12, sodium polyacrylate and 100 parts of water stirring and emulsifying; Get emulsion 30% and add reactor, add 70 parts of deionized water reactors, turn on agitator simultaneously.
5) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) middle Kps solution and the hypo solution configuring, in still, reaction starts slowly to drip remaining 70% pre-emulsion, simultaneously, get respectively 6 parts of steps 2) in configuration initiator solution and accelerator solution by 0.5 part of speed dropping in 10 minutes, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control temperature in the kettle 70-80 ℃ of insulation 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, in the time starting to heat up, add residue initiator and promotor.
6) be cooled to 50 ℃ after having reacted, add 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, adds matting agent to stir and obtains nano-silicon dioxide modified polyacrylate dispersion protecting materials.
By add modified Nano SiO before polyreaction
2liquid is that reaction system is with modification SiO
2for core carries out in-situ polymerization, the homogeneity of resulting materials is better, and gained emulsion is not easy precipitation, and the shelf time is longer, and the over-all properties of protecting materials is also better.
Disclosed all features in this specification sheets, or step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Beneficial effect of the present invention:
1, compared to existing technology; novel protected material of the present invention is the Water Soluble Compound material of a kind of easy construction, low cost, less energy-consumption, nontoxic, the feature of environmental protection; there is higher chemical stability; it forms film and has good solidity to corrosion, weathering resistance, tack and thermostability; can keep fossil original appearance, reduce because of the weathering of environmental factors to dinosaur fossil, extend the fossil life-span; experiment shows that described material can improve fossil fastening strength 10%, extends 1 ~ 2 times of fossil life-span.
2, material preparation process of the present invention is scientific and reasonable, and preparation technology is simple, and raw material is easy to get, with low cost, and environmental friendliness is easy to realize suitability for industrialized production.Can also make nanometer titanium dioxide silicon materials finely dispersed dinosaur fossil protecting materials in polymkeric substance.
embodiment:
Embodiment is by the following examples described in further detail foregoing of the present invention again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following example.Do not departing from any modification of making within the spirit and principles in the present invention, and being equal to of making according to ordinary skill knowledge and customary means replace or improve, all should be included in protection scope of the present invention.Related per-cent in embodiment, is mass percent if no special instructions.So raw material is commercial goods in following embodiment, matting agent used is conventional matting agent in commercially available letex polymerization.
Embodiment 1:
1) get the raw materials ready by following mass parts: 39 parts of methyl methacrylates; 42 parts of butyl methacrylate; 17 parts of methyl acrylates; 2 parts, vinylformic acid; 3 parts of polyoxyethylene octyl phenyl ethers (OP-10); 2 parts, dodecyl sulphate potassium (k12); 0.4 part of Potassium Persulphate (Kps); 0.4 part, Sulfothiorine; 200 parts of deionized waters; 0.4 part of sodium bicarbonate; 5 parts of sodium polyacrylates; 4 parts of matting agents;
2) use respectively 10 parts of water dissolution KPS, sodium bicarbonate, Sulfothiorine, stand-by;
3) under 200r/min agitation condition, dehydrated alcohol and dispersion agent 731A(are purchased to Shanghai City Xiang Lan Chemical Co., Ltd.) add deionized water for stirring 10 minutes, slowly add nano silicon with 1g/min speed again, then add silane coupling agent YGO-1204 to continue to stir 30 minutes, pH of mixed value is adjusted to 7.8, and ultrasonic concussion obtains modified Nano SiO for 5 minutes
2liquid, wherein the add-on of dispersion agent 731A accounts for 2% of silicon-dioxide quality, and the add-on of silane coupling agent YGO-1204 accounts for 10% of silicon-dioxide quality.
4) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing, remove stopper, then add vinylformic acid and modified Nano SiO
2liquid anabolic reaction body.
5) hybrid reaction body is added to OP-10, k12, sodium polyacrylate and 100 parts of water stirring and emulsifying.Get emulsion 30% and add reactor, add 70 parts of deionized water reactors, turn on agitator simultaneously.
6) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) middle Kps solution and the hypo solution configuring, in still, reaction starts slowly to drip remaining 70% pre-emulsion, simultaneously, get respectively 6 parts of steps 2) in configuration initiator solution and accelerator solution by 0.5 part of speed dropping in 10 minutes, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control 70 ~ 80 ℃ of insulations of temperature in the kettle 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, this process adds residue initiator and promotor.
7) reacted and be cooled to 50 ℃, added 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, adds matting agent to stir and obtains the novel protected material that is applicable to dinosaur fossil, rear material is carried out to performance test.
Sample is measured by material corrosion and protection Key Laboratory of Sichuan Province.Sample is carried out to integration test, produce NDJ-1 rotational viscosimeter viscosimetric with Shanghai Geology instrument institute respectively; Japan produces SPA400 scan-probe and measures particle footpath; The anti-corrosion mensuration of film is carried out in upper marine products FQY050 salt fog sulphur corrosion proofing box; Germany produces STA 409 PC Thermal Synthetic Analysis instrument and measures film decomposition temperature; Carry out film weathering test with ultraviolet case; By GB GB1720-79, GB/T 1731-93 measures film adhesive and paint film flexibility, with coating film gloss degree changing value after vancometer mensuration certain hour.
Its detected result is in table 1 and table 2:
the novel protected material emulsion performance measurement of table 1
| Test event | Emulsion viscosity | Emulsion average diameter | Emulsion film decomposition temperature |
| Test result | 20 mpa.s | 85nm | 365.5℃ |
the novel protected material film of table 2 and traditional material (zapon varnish) performance comparison
| Test event | Apply traditional zapon varnish | Apply novel protected material |
| 96h water-intake rate/% | 1.91 | 1.42 |
| 0.5%H 2SO 4Soak | 48h bubbles | 96h bubbles |
| 0.5%NaOH soaks | 192h is unchanged | 192h is unchanged |
| Film ultraviolet ageing | 240h yellowing | 720h yellowing |
| Film adhesive | 2 grades | 1 grade |
| Film salt air corrosion 0.5%NaCl pH value of solution=3 | 4h bubbles | 40h bubbles |
| 1 year decrement of glossiness | 5% | 1% |
Protecting materials after adopting scanning electronic microscope to film forming is observed, and result shows that nano silicon is evenly distributed in described acrylic ester polymer, and combines closely with acrylic ester polymer, forms three dimensional network structure.
Embodiment 2:
1) get the raw materials ready by following mass parts: 40 parts of methyl methacrylates; 43 parts of butyl methacrylate; 16 parts of methyl acrylates; 1 part, vinylformic acid; 1 part of polyoxyethylene octyl phenyl ether (OP-10); 1 part, dodecyl sulphate potassium (k12); 0.3 part of Potassium Persulphate (Kps); 0.5 part, Sulfothiorine; 190 parts of deionized waters; 0.2 part of sodium bicarbonate; 4 parts of sodium polyacrylates; 1 part of matting agent;
2) use respectively 10 parts of water dissolution KPS, sodium bicarbonate, Sulfothiorine, stand-by;
3) by nanometer SiO
2with 1:1(volume ratio) alcohol water-dispersion, add Sodium hexametaphosphate 99, utilize ultra-sonic oscillation fully to disperse solution, obtain modified Nano SiO
2liquid;
4) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing, remove stopper, then add vinylformic acid and modified Nano SiO
2liquid anabolic reaction body.
5) hybrid reaction body is added to OP-10, k12, sodium polyacrylate and 100 parts of water stirring and emulsifying.Get emulsion 30% and add reactor, add 70 parts of deionized water reactors, turn on agitator simultaneously.
6) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) middle Kps solution and the hypo solution configuring, in still, reaction starts slowly to drip remaining 70% pre-emulsion, simultaneously, get respectively 6 parts of steps 2) in configuration initiator solution and accelerator solution by 0.5 part of speed dropping in 10 minutes, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control 70 ~ 80 ℃ of insulations of temperature in the kettle 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, this process adds residue initiator and promotor.
7) reacted and be cooled to 50 ℃, added 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, adds matting agent to stir and obtains the novel protected material that is applicable to dinosaur fossil.Resulting materials over-all properties slightly inferior with material described in embodiment 1, wherein emulsion forms protection film decomposition temperature and declines 2 ~ 3 ℃ compared with embodiment 1, but still can meet the application requiring of protection dinosaur fossil.
Embodiment 3:
1) get the raw materials ready by following mass parts: 39 parts of methyl methacrylates; 20 parts of butyl methacrylate; 39 parts of methyl acrylates; 2 parts, vinylformic acid; 3 parts of polyoxyethylene octyl phenyl ethers (OP-10); Dodecyl sulphate potassium (k
12) 2 parts; 0.4 part of Potassium Persulphate (KPS); 0.4 part, Sulfothiorine; 200 parts of deionized waters; 0.4 part of sodium bicarbonate; 4 parts of sodium polyacrylates; 3 parts of matting agents;
2) 10 parts of water dissolution Kps of the each use of difference, sodium bicarbonate, Sulfothiorine, stand-by;
3) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing of 2～3 times of amounts, remove stopper, then add vinylformic acid, anabolic reaction monomer;
4) hybrid reaction monomer is added to OP-10, k
12, sodium polyacrylate and 100 parts of water stirring and emulsifying.Get emulsion 30% and add reactor, separately add 70 parts of deionized waters and enter reactor, turn on agitator simultaneously.
5) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) middle Kps solution and the hypo solution configuring, in still, reaction starts slowly to drip remaining 70% pre-emulsion, get 6 parts of initiators and 6 parts of promotor by 0.5 part of speed dropping in 10 minutes simultaneously, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control temperature in the kettle 70-80 ℃ of insulation 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, in this process, add residue initiator and promotor;
6) be cooled to 50 ℃ after having reacted, add 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, i.e. acrylic ester polymerization emulsion;
7) under 200r/min agitation condition, dehydrated alcohol and dispersion agent 731A are added to deionized water for stirring 10 minutes, slowly add nano silicon with 1g/min speed again, then add silane coupling agent YGO-1204 to continue to stir 30 minutes, pH of mixed value is adjusted to 7.8, and ultrasonic concussion obtains modified Nano SiO for 5 minutes
2liquid, wherein the add-on of dispersion agent 731A accounts for 2% of silicon-dioxide quality, and the add-on of silane coupling agent YGO-1204 accounts for 10% of silicon-dioxide quality;
8) by nanometer SiO
2quality accounts for 5% ratio of reaction monomers total amount, by modified Nano SiO
2liquid and matting agent add in acrylic ester polymerization emulsion under agitation condition, obtain nano-silicon dioxide modified acrylic ester polymerization emulsion protecting materials.Compared with resulting materials in embodiment 1, material filming thing hardness is bigger, more easy to crack, and film adhesive is reduced to 3 grades.
Embodiment 4:
1) get the raw materials ready by following mass parts: 45 parts of methyl methacrylates; 39 parts of butyl methacrylate; 15 parts of methyl acrylates; 1 part, vinylformic acid; 2 parts of polyoxyethylene octyl phenyl ethers (OP-10); Dodecyl sulphate potassium (k
12) 1 part; 0.2 part of Potassium Persulphate (KPS); 0.4 part, Sulfothiorine; 180 parts of deionized waters; 0.2 part of sodium bicarbonate; 2 parts of sodium polyacrylates; 1 part of matting agent;
2) 10 parts of water dissolution Kps of the each use of difference, sodium bicarbonate, Sulfothiorine, stand-by;
3) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing of 2～3 times of amounts, remove stopper, then add vinylformic acid, anabolic reaction monomer;
4) hybrid reaction monomer is added to OP-10, k
12, sodium polyacrylate and 100 parts of water stirring and emulsifying.Get emulsion 30% and add reactor, separately add 70 parts of deionized waters and enter reactor, turn on agitator simultaneously.
5) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) middle Kps solution and the hypo solution configuring, in still, reaction starts slowly to drip remaining 70% pre-emulsion, simultaneously, get respectively 6 parts of steps 2) in configuration initiator solution and accelerator solution by 0.5 part of speed dropping in 10 minutes, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control temperature in the kettle 70-80 ℃ of insulation 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, in this process, add residue initiator and promotor,
6) be cooled to 50 ℃ after having reacted, add 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, i.e. acrylic ester polymerization emulsion;
7) by nanometer SiO
2with 1:1(volume ratio) alcohol water-dispersion, add Sodium hexametaphosphate 99, utilize ultra-sonic oscillation fully to disperse solution, obtain modified Nano SiO
2liquid;
8) by nanometer SiO
2quality accounts for 5% ratio of reaction monomers total amount, by modified Nano SiO
2liquid and matting agent add in acrylic ester polymerization emulsion under agitation condition, obtain nano-silicon dioxide modified acrylic ester polymerization emulsion protecting materials.Resulting materials less stable, easily precipitation, 2 grades of film adhesives.
In embodiment 3 or 4, make the over-all properties of material slightly inferior with embodiment 1 resulting materials, particularly nanometer SiO
2the homogeneity of disperseing in gained emulsion is slightly poor, and mixed emulsion more easily precipitates with respect to gained emulsion in embodiment 1 and 2, but joins shortly in the situation of i.e. use, is still well positioned to meet the application requiring of protection dinosaur fossil.
Embodiment 5:
A novel protected material that is applicable to dinosaur fossil, described material is composited by acrylic ester polymer and modified manometer silicon dioxide.
As optional mode, described acrylic ester polymer can adopt the correlation method in above-described embodiment to obtain by letex polymerization, can be also the emulsion of being made up of commercially available acrylic ester polymer.
The foregoing is only the preferred embodiments of the present invention, is only illustrative for the purpose of the present invention, and nonrestrictive; Those of ordinary skills understand, and in the spirit and scope that limit, can carry out many changes to it in the claims in the present invention, revise, and even equivalence is changed, but all will fall into protection scope of the present invention.
Claims (10)
1. a novel protected material that is applicable to dinosaur fossil, is characterized in that, described material is composited by acrylic polymer and modified manometer silicon dioxide.
2. the novel protected material that is applicable to dinosaur fossil according to claim 1; it is characterized in that; described modified manometer silicon dioxide is evenly distributed in described acrylic ester polymer; and described modified manometer silicon dioxide combines by chemical bond with described acrylic ester polymer, form three dimensional network structure.
3. the novel protected material that is applicable to dinosaur fossil according to claim 1; it is characterized in that, described acrylic polymer is mainly formed by the copolymerization of core-shell by methyl methacrylate, butyl methacrylate, methyl acrylate, four kinds of monomers of vinylformic acid.
4. the novel protected material that is applicable to dinosaur fossil according to claim 3, is characterized in that, described four kinds of monomers form by following mass parts: 39 ~ 45 parts of methyl methacrylates; 20 ~ 43 parts of butyl methacrylate; 15 ~ 39 parts of methyl acrylates; Vinylformic acid 1-2 part.
5. the novel protected material that is applicable to dinosaur fossil according to claim 1, is characterized in that, described material was emulsion form before being coated to fossil surface, is coated to fossil surface and forms transparent protective membrane on fossil surface after certainly dry.
6. prepare the method for the novel protected material that is applicable to dinosaur fossil claimed in claim 1 for one kind; it is characterized in that; adopt emulsion polymerization way; carry out polymerization take methyl methacrylate, butyl methacrylate, methyl acrylate and vinylformic acid as principal monomer, and before polyreaction starts or polyreaction add modified Nano SiO after finishing
2liquid stirring and evenly mixing.
7. preparation method according to claim 6, is characterized in that described modified Nano SiO
2liquid adopts the one in following two kinds of methods to prepare:
Method a: by nanometer SiO
2with the water-dispersion of 1:1 alcohol, add Sodium hexametaphosphate 99, utilize ultra-sonic oscillation fully to disperse solution, obtain modified Nano SiO
2liquid;
Method b: under 200r/min agitation condition, dehydrated alcohol and dispersion agent 731A are added to deionized water for stirring 10 minutes, slowly add nano silicon with 1g/min speed again, then add silane coupling agent YGO-1204 to continue to stir 30 minutes, pH of mixed value is adjusted to 7.8, and ultrasonic concussion obtains modified Nano SiO for 5 minutes
2liquid, wherein the add-on of dispersion agent 731A accounts for 2% of silicon-dioxide quality, and the add-on of silane coupling agent YGO-1204 accounts for 10% of silicon-dioxide quality.
8. preparation method according to claim 7, is characterized in that, concrete steps are as follows:
1) get the raw materials ready by following mass parts: methyl methacrylate 39 ~ 45; Butyl methacrylate 20 ~ 43; Methyl acrylate 15 ~ 39; Vinylformic acid 1 ~ 2; Polyoxyethylene octyl phenyl ether (OP-10) 2 ~ 3; Dodecyl sulphate potassium (k12) 1 ~ 2; Potassium Persulphate (Kps) 0.2 ~ 0.5; Sulfothiorine 0.2 ~ 0.5; Deionized water 180 ~ 200; Sodium bicarbonate (neutralizing agent) 0.2 ~ 0.5; Sodium polyacrylate (stablizer) 2 ~ 4; Matting agent 1 ~ 4;
2) 10 parts of water dissolution Kps of the each use of difference, sodium bicarbonate, Sulfothiorine, stand-by;
3) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing of 2～3 times of amounts, remove stopper, then add vinylformic acid, anabolic reaction monomer;
4) hybrid reaction monomer is added to OP-10, k
12, sodium polyacrylate and 100 parts of water stirring and emulsifying, get emulsion 30% and add reactor, separately add 70 parts of deionized waters and enter reactor, turn on agitator simultaneously;
5) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) the middle Kps(initiator configuring) solution and Sulfothiorine (promotor) solution, in still, reaction starts slowly to drip remaining 70% pre-emulsion, simultaneously, get respectively 6 parts of steps 2) in configuration initiator solution and accelerator solution by 0.5 part of speed dropping in 10 minutes, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control temperature in the kettle 70-80 ℃ of insulation 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, in this process, add residue initiator solution and accelerator solution,
6) be cooled to 50 ℃ after having reacted, add 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, i.e. acrylic ester polymerization emulsion;
7) by nanometer SiO
2quality accounts for 5% ratio of reaction monomers total amount, by modified Nano SiO
2liquid and matting agent add in acrylic ester polymerization emulsion under agitation condition, obtain nano-silicon dioxide modified acrylic ester polymerization emulsion protecting materials.
9. preparation method according to claim 8, is characterized in that, gets the raw materials ready: methyl methacrylate 39 in described step 1) by following mass parts; Butyl methacrylate 20; Methyl acrylate 39; Vinylformic acid 2; Polyoxyethylene octyl phenyl ether (OP-10) 3; Dodecyl sulphate potassium (k
12) 2; Potassium Persulphate (KPS) 0.4; Sulfothiorine 0.4; Deionized water 200; Sodium bicarbonate 0.4; Sodium polyacrylate 4; Matting agent 3.
10. preparation method according to claim 7, is characterized in that, concrete steps are as follows:
1) get the raw materials ready by following mass parts: methyl methacrylate 39 ~ 40; Butyl methacrylate 42 ~ 43; Methyl acrylate 15 ~ 16; Vinylformic acid 1 ~ 2; Polyoxyethylene octyl phenyl ether (OP-10) 1 ~ 3; Dodecyl sulphate potassium (k
12) 1 ~ 2; Potassium Persulphate (KPS) 0.3 ~ 0.4(initiator); Sulfothiorine 0.4 ~ 0.5(promotor); Deionized water 190 ~ 200; Sodium bicarbonate 0.2 ~ 0.4; Sodium polyacrylate 4 ~ 5; Matting agent 1 ~ 4;
2) use respectively 10 parts of water dissolution Kps, sodium bicarbonate, Sulfothiorine, stand-by;
3) methyl methacrylate, butyl methacrylate, methacrylate monomer metering are mixed, with 5% sodium hydroxide solution washing, remove stopper, then add vinylformic acid and modified Nano SiO
2liquid anabolic reaction body, wherein modified Nano SiO
2liquid is by nanometer SiO
25% the ratio that quality accounts for reaction monomers total amount adds;
4) hybrid reaction body is added to OP-10, k12, sodium polyacrylate and 100 parts of water stirring and emulsifying; Get emulsion 30% and add reactor, add 70 parts of deionized water reactors, turn on agitator simultaneously;
5) open reactor well heater, treat that temperature in the kettle rises to 70 ℃, stop heating, now add respectively 2 parts of steps 2) middle Kps solution and the hypo solution configuring, in still, reaction starts slowly to drip remaining 70% pre-emulsion, simultaneously, get respectively 6 parts of steps 2) in configuration initiator solution and accelerator solution by 0.5 part of speed dropping in 10 minutes, in the time that also remaining 50%, pre-emulsion adds sodium hydrogen carbonate solution, after being added dropwise to complete, control temperature in the kettle 70-80 ℃ of insulation 30 minutes, then be warming up to 90 ℃ of insulations 30 minutes, in the time starting to heat up, add residue initiator solution and accelerator solution,
6) be cooled to 50 ℃ after having reacted, add 5% ammoniacal liquor to regulate pH=7.5 ~ 8, blowing, crosses 200 order nylon mesh, adds matting agent to stir and obtains nano-silicon dioxide modified polyacrylate dispersion protecting materials.
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| CN109967323A (en) * | 2019-03-14 | 2019-07-05 | 四川轻化工大学 | A kind of construction method for fossil wood protection |
| CN110698191A (en) * | 2019-10-28 | 2020-01-17 | 南京航空航天大学 | Biological ceramic material with ultraviolet high reflection |
| CN113881304A (en) * | 2021-10-14 | 2022-01-04 | 江苏乐离新材料科技有限公司 | Nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution and preparation method thereof |
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Cited By (3)
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| CN109967323A (en) * | 2019-03-14 | 2019-07-05 | 四川轻化工大学 | A kind of construction method for fossil wood protection |
| CN110698191A (en) * | 2019-10-28 | 2020-01-17 | 南京航空航天大学 | Biological ceramic material with ultraviolet high reflection |
| CN113881304A (en) * | 2021-10-14 | 2022-01-04 | 江苏乐离新材料科技有限公司 | Nano silicon dioxide modified polyacrylate water-soluble equipment protective film solution and preparation method thereof |
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| CN103819991B (en) | 2017-01-18 |
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