CN110144028B - Production process for preparing organic-inorganic composite water-retaining agent - Google Patents
Production process for preparing organic-inorganic composite water-retaining agent Download PDFInfo
- Publication number
- CN110144028B CN110144028B CN201910445778.6A CN201910445778A CN110144028B CN 110144028 B CN110144028 B CN 110144028B CN 201910445778 A CN201910445778 A CN 201910445778A CN 110144028 B CN110144028 B CN 110144028B
- Authority
- CN
- China
- Prior art keywords
- product
- water
- retaining agent
- mixing
- parts
- 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.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 177
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 80
- 238000002156 mixing Methods 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000008367 deionised water Substances 0.000 claims abstract description 63
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 63
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 37
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 18
- 230000001678 irradiating effect Effects 0.000 claims abstract description 18
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010453 quartz Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000005457 ice water Substances 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 239000012467 final product Substances 0.000 claims abstract description 15
- 238000000643 oven drying Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 17
- 239000000178 monomer Substances 0.000 description 12
- 238000007865 diluting Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000010954 inorganic particle Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- -1 sodium carboxylate Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2107/00—Impermeabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a production process for preparing an organic-inorganic composite water-retaining agent. a. Mixing sodium hydroxide and deionized water, and adding into acrylic acid under the condition of ice-water bath to obtain product A; b. mixing the titanium dioxide dispersion liquid with deionized water to obtain a product B; c. mixing the product A, the product B and acrylamide, pouring into a quartz tube, and irradiating with ultraviolet light under nitrogen atmosphere to obtain photopolymerization product C; d. mixing N, N-methylene bisacrylamide, ammonium persulfate and deionized water to obtain a product D; e. mixing the product C and the product D in nitrogen atmosphere, and heating to obtain a product e; f. soaking product e in ethanol, and oven drying to obtain the final product. The invention solves the problems that the organic-inorganic interface of the water-retaining agent is not tightly combined and is difficult to degrade after being used for many times, prevents the water-retaining agent from becoming the next 'white pollution', and has great significance in improving the tight combination degree of the organic-inorganic interface of the water-retaining agent and realizing the degradation after being used for many times.
Description
Technical Field
The invention relates to a water-retaining agent, in particular to a novel production process for preparing an organic-inorganic composite water-retaining agent.
Background
The problems of drought land, water and soil loss, desertification, sand storm and the like increasingly become main ecological problems facing the world. Especially in water resource shortage areas, agricultural production activities are greatly limited, so that solving the problems of soil drought resistance and water retention becomes a hotspot of current research.
The water-retaining agent is a high molecular compound, can absorb hundreds of even thousands of times of water of the self mass in a short time, can be slowly released, has excellent water absorption and water retention performances, and is widely applied to the aspects of agricultural production, drug delivery, daily life and the like. The traditional water-retaining agent has excellent water-retaining property, but has the defects of poor strength, monomer residue, difficult degradation and the like. Research shows that inorganic particles are doped in the traditional water-retaining agent, so that the water absorption and mechanical properties can be improved, and the water-retaining agent can be endowed with unique functions. Huang, P prepares the organic-inorganic double-network water-retaining agent of graphene and polyacrylic acid in two steps, and because the organic-inorganic double-network water-retaining agent has unique first network (graphene) and second network (polyacrylamide) structures, the mechanical property is obviously improved, and a thought is provided for designing a novel network structure. The fanli kernel is doped with inorganic montmorillonite into the water-retaining agent, the water-retaining agent is prepared by adopting an aqueous solution method, the preparation method is convenient to control, the container is not stuck, and the prepared water-retaining agent has strong water absorption and salt tolerance. At present, inorganic substances and monomers are grafted and crosslinked to prepare the organic-inorganic composite water-retaining agent, and the preparation process is simple and is easy to realize large-scale production. However, the grafting efficiency is low, the organic-inorganic interface is not tightly combined, the inorganic matter can not be uniformly dispersed in the system by a stirring method, and the existing water-retaining agent is difficult to degrade after being used for many times. Therefore, the development of a novel production process is particularly important. Based on the above problems, it is important to develop a novel production process for preparing organic-inorganic composite water-retaining agent.
Disclosure of Invention
The invention aims to provide a novel production process for preparing an organic-inorganic composite water-retaining agent. The invention solves the problems that the organic-inorganic interface of the water-retaining agent is not tightly combined and is difficult to degrade after being used for many times, prevents the water-retaining agent from becoming the next 'white pollution', and has great significance in improving the tight combination degree of the organic-inorganic interface of the water-retaining agent and realizing the degradation after being used for many times.
The technical scheme of the invention is as follows: a novel production process for preparing an organic-inorganic composite water-retaining agent is prepared according to the following method;
a. mixing sodium hydroxide and deionized water, and adding into acrylic acid under the condition of ice-water bath to obtain product A;
b. mixing the titanium dioxide dispersion liquid with deionized water to obtain a product B;
c. mixing the product A, the product B and acrylamide, pouring the mixture into a quartz tube at constant volume, and irradiating the mixture with ultraviolet light in nitrogen atmosphere to obtain a photopolymerization product, namely a product C;
d. mixing N, N-methylene bisacrylamide, ammonium persulfate and deionized water to obtain a product D;
e. mixing the product C and the product D in nitrogen atmosphere, and heating to obtain a product e;
f. soaking product e in ethanol, and oven drying to obtain the final product.
In the production process of the novel organic-inorganic composite water-retaining agent, in the step a, 6 to 12 parts by weight of sodium hydroxide and 18 to 24 parts by weight of deionized water are mixed and then added to 24 to 30 parts by weight of acrylic acid under the condition of ice-water bath.
In the production process for preparing the novel organic-inorganic composite water-retaining agent, in the step b, 1 to 3 parts by weight of titanium dioxide dispersion liquid and 5 to 7 parts by weight of deionized water are mixed; the titanium dioxide dispersion liquid contains 15-25% of titanium dioxide solid content and 10-20nm of particle size.
In the production process for preparing the novel organic-inorganic composite water-retaining agent, in the step c, 8-10 parts by weight of the product A, 0.1-2.5 parts by weight of the product B and 0.5-1.5 parts by weight of acrylamide are mixed, and deionized water is adopted to fix the volume to 45-50 parts and poured into a quartz tube.
In the aforementioned production process for preparing the organic-inorganic composite water-retaining agent, in the step c, 200-500W ultraviolet light is used for irradiating for 30-40min under the nitrogen atmosphere.
In the production process for preparing the novel organic-inorganic composite water-retaining agent, in the step d, 0.03-0.04 parts by weight of N, N-methylene bisacrylamide, 0.2-0.3 parts by weight of ammonium persulfate and 45-50 parts by weight of deionized water are mixed.
In the production process for preparing the novel organic-inorganic composite water-retaining agent, in the step e, 45-50 parts by weight of the product C and 4-6 parts by weight of the product D are mixed.
In the production process of the novel organic-inorganic composite water-retaining agent, in the step e, heating is performed for 2-4 hours at the temperature of 60-70 ℃.
In the production process for preparing the novel organic-inorganic composite water-retaining agent, in the step f, the alcohol soaking time is 110-130min, and the drying temperature is 75-85 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention relates to a novel production process for preparing an organic-inorganic composite water-retaining agent, which is prepared according to the following method; a. mixing sodium hydroxide and deionized water, and adding into acrylic acid under the condition of ice-water bath to obtain product A; b. mixing the titanium dioxide dispersion liquid with deionized water to obtain a product B; c. mixing the product A, the product B and acrylamide, pouring into a quartz tube, and irradiating with ultraviolet light under nitrogen atmosphere to obtain photopolymerization product C; d. mixing N, N-methylene bisacrylamide, ammonium persulfate and deionized water to obtain a product D; e. mixing the product C and the product D in nitrogen atmosphere, and heating to obtain a product e; f. soaking the product e in ethanol, and oven drying to obtain the final product; titanium dioxide inorganic particles are used as a photoinitiator in the early stage, free radicals are generated on the surface through ultraviolet illumination to promote AA and AM monomers to generate polymerization reaction and graft on the surface, so that a copolymer grows on the surface of titanium dioxide, at the moment, the polymer and the titanium dioxide are connected together in a bonding mode, an organic-inorganic interface is combined more tightly, organic-inorganic compatibility is increased, and then the inorganic particles are uniformly dispersed in a system to obtain a photopolymerization product; and adding initiator ammonium persulfate and cross-linking agent N, N-methylene bisacrylamide into the photopolymerization product at the later stage, polymerizing the monomer which is not completely reacted at the earlier stage, and forming a three-dimensional network structure by the polymerization product under the action of the cross-linking agent.
2. The invention relates to a titanium dioxide water-retaining agent, which is mainly characterized in that titanium dioxide and the water-retaining agent are difficult to uniformly disperse, the invention uses light to initiate polymerization, a polymer grows on the surface of inorganic particles, TiO2 plays a role in enhancing, and the titanium dioxide has good photodegradability and simultaneously plays a role in photocatalytic degradation, so the water-retaining agent can be self-degraded under illumination, and the environmental pollution is reduced.
Experiments prove that:
the invention adopts a Fourier transform infrared spectrometer with model number 8400S manufactured by Shimadzu corporation of Japan to measure the infrared spectrum. An XPS analyzer model ESCALB 250, manufactured by Thermo VG corporation of the United states, was used. Thermogravimetric and differential thermal characterization was performed using a thermogravimetric analyzer TGA-4000 and a simultaneous thermogravimetric analyzer HCT-2. Finally, a transmission electron microscope (Tecnal G2F 20, FEI) was used to collect high resolution images at an accelerating voltage of 200 kV.
1. In the present invention, TiO (a) is a mixture obtained by mixing A, B and acrylamide2- (AA-AM); mixing A product, B product and acrylamide, pouring into a quartz tube, and irradiating by ultraviolet light under nitrogen atmosphere to obtain a photopolymerization product (B), namely TiO2- (AA-AM), respectively carrying out infrared spectrometer measurement to obtain (a) TiO2- (AA-AM) and (b) TiO2(AA-AM) infrared spectrum, as shown in FIG. 1, 1641cm in FIG. 1-1，989cm-1The vibration absorption peaks of (a) TiO are generated by C ═ C and C-H vibration in olefin, respectively2- (AA-AM) and (b) TiO2- (AA-AM) comparison, (b) TiO2The two absorption peak intensities in (AA-AM) are obviously reduced, and because free radicals are generated on the surface of titanium dioxide under ultraviolet light, carbon-carbon double bonds of monomers are broken, and the monomers are subjected to polymerization reaction with each other, so that TiO (shown in figure 1 (b)) is prepared from TiO2The peak intensity of the- (AA-AM) curve is obviously weakened.
2. For TiO prepared in examples 1 to 62the-P (AA-AM) organic-inorganic composite water-retaining agent is measured by an infrared spectrometer to obtain the organic-inorganic composite water-retaining agentThe infrared spectrum of the water agent is shown in FIG. 2, 3435cm in FIG. 2-1The vibration peak is caused by the stretching vibration of OH-and N-H in amide group, and is 2923cm-1，2852cm-1Two newly generated methylene peaks, 1454cm-1The characteristic absorption peak of sodium carboxylate is shown above, and the polymerization of the monomer to produce TiO is described2-P (AA-AM) organic-inorganic composite water retention agent.
3. For the TiO prepared in example 32-A X ray photoelectron spectroscopy measurement of P (AA-AM) organic-inorganic composite water retention agent, xps spectrum of B C1 s; c O1 spectrum xps of 1 s; d N1 spectrum xps of 1s, as shown in FIG. 3, there are four distinct peaks at 1076.8eV, 536.7eV,405.24eV and 284.6eV in FIG. 3A, respectively corresponding to Na, O, N and C elements constituting the water-retaining agent, the area ratio is consistent with the actual ratio, 284.6eV corresponds to C1s peak in the polymer, which has four sub-peaks corresponding to four different valence states of the polymer chain shown in FIG. 3B, and the curve fitting degree is high, which proves that the carbon forming four different valence states after the monomer polymerization reaction is consistent with the structure of the polymer chain. In fig. 3C, there are three oxygen peaks corresponding to three different valence oxygen in two monomers, respectively, where the area ratio of the total area of O in the carboxyl group to O in the amide group is 1:0.24, and the area ratio of O in two valence states in the carboxyl group is 1:1, which meets the monomer raw material ratio. Finally amide and carboxyl groups can be observed in D. So that the two monomers polymerize to form TiO2the-P (AA-AM) organic-inorganic composite water-retaining agent is consistent with infrared spectrum analysis, and TiO is successfully prepared2-P (AA-AM) organic-inorganic composite water retention agent.
4. For the TiO prepared in example 32Thermogravimetric analysis and differential thermal analysis are carried out on the-P (AA-AM) organic-inorganic composite water-retaining agent, as shown in figure 4, the temperature of 37-200 ℃ in figure 4 is the first stage, the reason of weight loss is evaporation of water adsorbed on the surface of the water-retaining agent and decomposition of small molecules which do not completely participate in the reaction, and the weight loss in the stage is about 20%. There are three absorption peaks between 300 ℃ and 600 ℃ corresponding to the cleavage of the bonds in the three branches N-H, O-H and C ═ O, and there are three distinct exothermic peaks I during this period, indicating the evolution of heat while weight loss occurs. Weight loss at 600 deg.CThe weight loss was found to be about 15% as the carbon backbone started to decompose, releasing a large amount of heat with release of carbon dioxide, which was similar to the theoretical 14.41% carbon content on the backbone. Meanwhile, the anatase titanium dioxide is converted into rutile at about 600 ℃, and partial heat is also released, so the exothermic peak II is generated by overlapping two parts.
5. For the TiO prepared in example 32The transmission electron microscope picture of the-P (AA-AM) organic-inorganic composite water retaining agent is shown in figure 5, the interplanar spacing in the left picture of figure 5 is measured for a plurality of times and is about 0.342nm, and the diffraction pattern d is 2.8985nm-1Together demonstrate the (101) crystal plane of the anatase form and therefore have good photocatalytic properties.
As shown in the transmission electron microscope of the right side of FIG. 5, the particle size of a single organic-inorganic particle is about 10.7nm, and no obvious agglomeration occurs. Since the inorganic particulate titanium dioxide acts as a photoinitiator in the photoinitiated polymerization stage, the monomer is grafted onto its surface by photoinitiated polymerization. The organic and inorganic compatibility is increased, so that titanium dioxide inorganic particles are uniformly dispersed in a three-dimensional network structure, and the liquid absorption performance of the water-retaining agent is promoted together. Because the inorganic particles are uniformly dispersed, the contact area of photocatalysis is increased, and the degradation rate of the water-retaining agent is improved.
6. For TiO prepared in examples 1 to 62The water absorption rate curve of the-P (AA-AM) organic-inorganic composite water-retaining agent is shown in figure 6, and the liquid absorption rate in the whole system generally shows the trends of quick liquid absorption at the early stage and slow liquid absorption at the later stage.
7. For TiO prepared in examples 1 to 62When the-P (AA-AM) organic-inorganic composite water-retaining agent is subjected to a salt absorption (0.9 wt% NaCl) test, a salt absorption rate curve is shown in figure 7, the liquid absorption rate in the whole system generally shows the tendency of quick liquid absorption in the early stage and slow liquid absorption in the later stage, and meanwhile, the time required for salt absorption is obviously shorter than the time required for water absorption.
The applicant also carried out the experimental tests and analysis described in 1-7 above on the water-retaining agents prepared in other examples, and the obtained results are equivalent to the above tests and analysis results.
In conclusion, the invention solves the problems that the organic-inorganic interface of the water-retaining agent is not tightly combined and is difficult to degrade after being used for many times, prevents the water-retaining agent from becoming the next 'white pollution', and has the beneficial effects of improving the tight combination degree of the organic-inorganic interface of the water-retaining agent and realizing the degradation after being used for many times.
Drawings
FIG. 1 shows (a) TiO of the present invention2- (AA-AM) and (b) TiO2-infrared spectrogram of (AA-AM);
FIG. 2 shows TiO of the present invention2-infrared spectrogram of P (AA-AM) organic-inorganic composite water-retaining agent;
FIG. 3 is ray photoelectron spectroscopy measurement of A X and xps spectrum of B C1s of the TiO2-P (AA-AM) organic-inorganic composite water-retaining agent of the invention; c O1 spectrum xps of 1 s; d N1 spectrum xps of 1 s;
FIG. 4 shows TiO of the present invention2-thermogravimetric analysis and differential thermogram of the P (AA-AM) organic-inorganic composite water retention agent;
FIG. 5 shows TiO of the present invention2-transmission electron microscopy of P (AA-AM) organic-inorganic composite water retaining agent;
FIG. 6 shows TiO of the present invention2-water absorption rate curve of P (AA-AM) organic-inorganic composite water retention agent;
FIG. 7 shows TiO of the present invention2-P (AA-AM) organic-inorganic composite water retention agent salt absorption (0.9 wt% NaCl) rate curve.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Example 1, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 9g of sodium hydroxide and 21g of deionized water, and adding the mixture into 27g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 6g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 20%, and the particle size is 15 nm;
c. mixing 9g of product A, 0.2g of product B and 1g of acrylamide, diluting to a constant volume of 40ml with deionized water, pouring into a quartz tube, and irradiating with 300W ultraviolet light in nitrogen atmosphere for 35min to obtain a photopolymerization product, namely product C;
d. mixing 0.036g of N, N-methylene bisacrylamide, 0.24g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing product D5 g with product C under nitrogen atmosphere, and heating at 70 deg.C for 3 hr to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 2, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 9g of sodium hydroxide and 21g of deionized water, and adding the mixture into 27g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 6g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 20%, and the particle size is 15 nm;
c. mixing 9g of product A, 0.6g of product B and 1g of acrylamide, diluting to a constant volume of 40ml with deionized water, pouring into a quartz tube, and irradiating with 300W ultraviolet light in nitrogen atmosphere for 35min to obtain a photopolymerization product, namely product C;
d. mixing 0.036g of N, N-methylene bisacrylamide, 0.24g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing product D5 g with product C under nitrogen atmosphere, and heating at 70 deg.C for 3 hr to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 3, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 9g of sodium hydroxide and 21g of deionized water, and adding the mixture into 27g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 6g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 20%, and the particle size is 15 nm;
c. mixing 9g of the product A, 1g of the product B and 1g of acrylamide, diluting to a constant volume of 40ml by using deionized water, pouring into a quartz tube, and irradiating for 35min by using 300W ultraviolet light under the nitrogen atmosphere to obtain a photopolymerisable product, namely a product C;
d. mixing 0.036g of N, N-methylene bisacrylamide, 0.24g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing product D5 g with product C under nitrogen atmosphere, and heating at 70 deg.C for 3 hr to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 4, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 9g of sodium hydroxide and 21g of deionized water, and adding the mixture into 27g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 6g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 20%, and the particle size is 15 nm;
c. mixing 9g of the product A, 1.4g of the product B and 1g of acrylamide, diluting to a constant volume of 40ml with deionized water, pouring into a quartz tube, and irradiating with 300W ultraviolet light for 35min under the nitrogen atmosphere to obtain a photopolymerization product, namely a product C;
d. mixing 0.036g of N, N-methylene bisacrylamide, 0.24g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing product D5 g with product C under nitrogen atmosphere, and heating at 70 deg.C for 3 hr to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 5, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 9g of sodium hydroxide and 21g of deionized water, and adding the mixture into 27g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 6g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 20%, and the particle size is 15 nm;
c. mixing 9g of the product A, 1.8g of the product B and 1g of acrylamide, diluting to a constant volume of 40ml with deionized water, pouring into a quartz tube, and irradiating with 300W ultraviolet light for 35min under the nitrogen atmosphere to obtain a photopolymerization product, namely a product C;
d. mixing 0.036g of N, N-methylene bisacrylamide, 0.24g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing product D5 g with product C under nitrogen atmosphere, and heating at 70 deg.C for 3 hr to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 6, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 9g of sodium hydroxide and 21g of deionized water, and adding the mixture into 27g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 6g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 20%, and the particle size is 15 nm;
c. mixing 9g of product A, 2.2g of product B and 1g of acrylamide, adding deionized water to a constant volume of 40ml, pouring into a quartz tube, and irradiating with 300W ultraviolet light in nitrogen atmosphere for 35min to obtain a photopolymerization product, namely product C;
d. mixing 0.036g of N, N-methylene bisacrylamide, 0.24g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing product D5 g with product C under nitrogen atmosphere, and heating at 70 deg.C for 3 hr to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 7, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 6g of sodium hydroxide and 18g of deionized water, and adding the mixture into 24g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 1g of titanium dioxide dispersion liquid with 5g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 15%, and the particle size is 10 nm;
c. mixing 8g of product A, 0.2g of product B and 0.5g of acrylamide, diluting to a constant volume of 45g by using deionized water, pouring into a quartz tube, and irradiating by using 200W ultraviolet light for 40min under the atmosphere of nitrogen to obtain a photopolymerization product, namely product C;
d. mixing 0.03g of N, N-methylene bisacrylamide, 0.2g of ammonium persulfate and 45g of deionized water to obtain a product D;
e. mixing product C45 g and product D4 g in nitrogen atmosphere, and heating at 60 deg.C for 4 hr to obtain product e;
f. soaking product e in ethanol for 110min, and oven drying at 75 deg.C to obtain the final product.
Example 8, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 8g of sodium hydroxide and 20g of deionized water, and adding the mixture into 26g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 5g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 18%, and the particle size is 13 nm;
c. mixing 8.5g of product A, 0.6g of product B and 0.8g of acrylamide, diluting to a constant volume of 46g by using deionized water, pouring into a quartz tube, and irradiating by using 300W ultraviolet light for 35min under the nitrogen atmosphere to obtain a photopolymerization product, namely product C;
d. mixing 0.035g of N, N-methylene bisacrylamide, 0.25g of ammonium persulfate and 47g of deionized water to obtain a product D;
e. mixing 46g of product C and 4.5g of product D under nitrogen atmosphere, and heating at 65 deg.C for 3h to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 9, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 9g of sodium hydroxide and 21g of deionized water, and adding the mixture into 27g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 2g of titanium dioxide dispersion liquid with 6g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 20%, and the particle size is 15 nm;
c. mixing 9g of the product A, 1.3g of the product B and 1g of acrylamide, diluting to 47g of deionized water, pouring into a quartz tube, and irradiating for 30min by 300W ultraviolet light in a nitrogen atmosphere to obtain a photopolymerization product, namely a product C;
d. mixing 0.036g of N, N-methylene bisacrylamide, 0.24g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing 47g of product C and 5g of product D under nitrogen atmosphere, and heating at 70 deg.C for 3h to obtain product e;
f. soaking product e in ethanol for 120min, and oven drying at 80 deg.C to obtain the final product.
Example 10, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 11g of sodium hydroxide and 22g of deionized water, and adding the mixture into 28g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 3g of titanium dioxide dispersion liquid with 5g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 23%, and the particle size is 18 nm;
c. mixing 9.5g of product A, 1.8g of product B and 1.3g of acrylamide, diluting to a constant volume of 48g by using deionized water, pouring into a quartz tube, and irradiating for 30min by using 500W ultraviolet light under the nitrogen atmosphere to obtain a photopolymerization product, namely product C;
d. mixing 0.032g of N, N-methylene bisacrylamide, 0.28g of ammonium persulfate and 48g of deionized water to obtain a product D;
e. mixing 48g of product C and 5.5g of product D in nitrogen atmosphere, and heating at 65 deg.C for 3h to obtain product e;
f. soaking product e in ethanol for 125min, and oven drying at 83 deg.C to obtain the final product.
Example 11, a novel process for preparing an organic-inorganic composite water-retaining agent, prepared as follows;
a. mixing 12g of sodium hydroxide and 24g of deionized water, and adding the mixture into 30g of acrylic acid under the condition of ice-water bath to obtain a product A;
b. mixing 3g of titanium dioxide dispersion liquid with 7g of deionized water to obtain a product B; the solid content of titanium dioxide in the titanium dioxide dispersion liquid is 25%, and the particle size is 20 nm;
c. mixing 10g of product A, 2.2g of product B and 1.5g of acrylamide, metering to 50g, pouring into a quartz tube, and irradiating with 500W ultraviolet light for 40min under nitrogen atmosphere to obtain a photopolymerization product, namely product C;
d. mixing 0.04g of N, N-methylene bisacrylamide, 0.3g of ammonium persulfate and 50g of deionized water to obtain a product D;
e. mixing 50g of product C and 6g of product D under nitrogen atmosphere, and heating at 70 deg.C for 4h to obtain product e;
f. soaking product e in ethanol for 130min, and oven drying at 85 deg.C to obtain the final product.
Claims (9)
1. A production process for preparing an organic-inorganic composite water-retaining agent is characterized by comprising the following steps: the preparation method comprises the following steps;
a. mixing sodium hydroxide and deionized water, and adding into acrylic acid under the condition of ice-water bath to obtain product A;
b. mixing the titanium dioxide dispersion liquid with deionized water to obtain a product B;
c. mixing the product A, the product B and acrylamide, pouring the mixture into a quartz tube at constant volume, and irradiating the mixture with ultraviolet light in nitrogen atmosphere to obtain a photopolymerization product, namely a product C;
d. mixing N, N-methylene bisacrylamide, ammonium persulfate and deionized water to obtain a product D;
e. mixing the product C and the product D in nitrogen atmosphere, and heating to obtain a product e;
f. soaking product e in ethanol, and oven drying to obtain the final product.
2. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step a, 6-12 parts by weight of sodium hydroxide and 18-24 parts by weight of deionized water are mixed and then added into 24-30 parts by weight of acrylic acid under the condition of ice-water bath.
3. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step b, 1-3 parts of titanium dioxide dispersion liquid and 5-7 parts of deionized water are mixed according to parts by weight; the titanium dioxide dispersion liquid contains 15-25% of titanium dioxide solid content and 10-20nm of particle size.
4. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step c, 8 to 10 parts of the product A, 0.1 to 2.5 parts of the product B and 0.5 to 1.5 parts of acrylamide are mixed according to parts by weight, and deionized water is adopted to fix the volume to 45 to 50 parts and poured into a quartz tube.
5. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step c, 200-500W ultraviolet light is used for irradiating for 30-40min under the nitrogen atmosphere.
6. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step d, 0.03-0.04 part of N, N-methylene bisacrylamide, 0.2-0.3 part of ammonium persulfate and 45-50 parts of deionized water are mixed according to parts by weight.
7. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step e, 45-50 parts of the product C and 4-6 parts of the product D are mixed according to parts by weight.
8. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step e, the heating is carried out for 2 to 4 hours at the temperature of 60 to 70 ℃.
9. The production process for preparing organic-inorganic composite water-retaining agent according to claim 1, characterized in that: in the step f, the alcohol soaking time is 110-130min, and the drying temperature is 75-85 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910445778.6A CN110144028B (en) | 2019-05-27 | 2019-05-27 | Production process for preparing organic-inorganic composite water-retaining agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910445778.6A CN110144028B (en) | 2019-05-27 | 2019-05-27 | Production process for preparing organic-inorganic composite water-retaining agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110144028A CN110144028A (en) | 2019-08-20 |
| CN110144028B true CN110144028B (en) | 2021-09-24 |
Family
ID=67593244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910445778.6A Active CN110144028B (en) | 2019-05-27 | 2019-05-27 | Production process for preparing organic-inorganic composite water-retaining agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110144028B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113535A (en) * | 2013-02-07 | 2013-05-22 | 东北大学秦皇岛分校 | Compounding method of organic-inorganic nano composite material based on surface initiated polymerization (SIP) |
| CN106867171A (en) * | 2017-03-13 | 2017-06-20 | 东北大学秦皇岛分校 | A kind of method that utilization polyacrylamide nano composite titania material prepares hydrogel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2086693A2 (en) * | 2006-12-06 | 2009-08-12 | Ciba Holding Inc. | Changing surface properties by functionalized nanoparticles |
| WO2012153826A1 (en) * | 2011-05-06 | 2012-11-15 | Fujifilm Corporation | Dispersion composition, curable composition, composition, transparent film, microlens, solid-state image sensing device, method for manufacturing transparent film, method for manufacturing microlens and method for manufacturing solid-state image sensing device |
-
2019
- 2019-05-27 CN CN201910445778.6A patent/CN110144028B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113535A (en) * | 2013-02-07 | 2013-05-22 | 东北大学秦皇岛分校 | Compounding method of organic-inorganic nano composite material based on surface initiated polymerization (SIP) |
| CN106867171A (en) * | 2017-03-13 | 2017-06-20 | 东北大学秦皇岛分校 | A kind of method that utilization polyacrylamide nano composite titania material prepares hydrogel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110144028A (en) | 2019-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7447015B2 (en) | Polar monomer-grafted polypropylene resin, its manufacturing method and application | |
| DE69936408T2 (en) | polymer composition | |
| CN108276522A (en) | Can 3D printing the double cross-linked alginate-polyacrylamide acrylic acid high-performance water gels of iron ion preparation method | |
| CN111116824A (en) | High-toughness multifunctional hydrogel and preparation method and application thereof | |
| CN108192138B (en) | Modification method of carbon nano tube used as rubber filler | |
| CN103304939A (en) | Preparation method for nano-composite polytetrafluoroethylene anti-dripping agent | |
| EP1319026A1 (en) | Polystyrene microspheres and a method for their production | |
| CN112979869B (en) | Hexagonal boron nitride nanosheet hydrogel composite material, and preparation method and application thereof | |
| CN104829788A (en) | Preparation method for chitosan/2-acrylamido-2-methyl AMPS hydrogel | |
| CN108559018A (en) | Nano-scale water Narrow Molecular Weight Distribution acrylic acid copolymer ester and preparation method thereof | |
| CN102995488A (en) | Method for preparing cationic rosin/C9 petroleum resin sizing agent | |
| CN106012525A (en) | Super-hydrophobic modification method for polytetrafluoroethylene (PTTE) fibers applied to oily sewage treatment | |
| CN105985601A (en) | Polymethyl methacrylate-carboxylated carbon nanotube composite based on charge conjugation synergism and preparation method thereof | |
| CN110144028B (en) | Production process for preparing organic-inorganic composite water-retaining agent | |
| CN101864045A (en) | Preparation method of chemically crosslinked nanocomposite hydrogel | |
| CN106633373A (en) | Composite carbon nanotube/polypropylene powder material for SLS (selective laser sintering) and preparation method thereof | |
| CN108191993B (en) | A kind of sodium alginate and its preparation method and application | |
| CN108499543A (en) | A kind of preparation method for the cellulose base adsorbent for heavy metal that the degree of polymerization is controllable | |
| CN114409300B (en) | Method for preparing dispersing agent by using ultrasonic-assisted alkali catalysis sulfonated pennisetum sinese roxb separation waste liquid degradation product | |
| CN104710583A (en) | Preparation method for high-strength hydrogel | |
| CN105566553A (en) | Maleic anhydride-acrylic acid copolymer for washing agent and preparation method thereof | |
| CN114456326A (en) | Carboxylated polystyrene nano-microsphere and preparation method and application thereof | |
| CN109851965B (en) | Nano composite high water absorption material and preparation method thereof | |
| CN103525112A (en) | Method for preparing nano-plastic by waste plastic | |
| Thanoo et al. | Preparation of hydrogel beads from crosslinked poly (methyl methacrylate) microspheres by alkaline hydrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |