CN103819683A - A novel titanium nanometer polymer alloy material and a preparation method thereof - Google Patents
A novel titanium nanometer polymer alloy material and a preparation method thereof Download PDFInfo
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Abstract
The invention relates to a synthesis preparation technology of a novel titanium nanometer polymer alloy material. According to the technology, nanometer organotitanium oligomer used as a precursor is blended with nanometer aluminium oxide modified fluorine-containing polyaryletherketone, and subjected to an ultrasonic-assisted microwave solid-liquid milling reaction process to obtain a titanium nanometer fluorine-containing polyaryletherketone copolymer. The novel polymer alloy material shows a series of excellent physical and chemical characteristics. The material has following characteristics: high hardness, abrasion resistance, high-temperature resistance, resistance to high-pressure steam, capability of preventing sticky dirty, scale resistance, ageing resistance, and the like and is particularly suitable for substrate materials of special coatings.
Description
Technical field
The invention belongs to novel material and advanced manufacturing technology field, what relate to is the nano fluorine-contained poly (aryl ether ketone) copolymer of a kind of titanium, is applicable to prepare the matrix film forming material of special coating.
Background technology
Underground deep layer crude oil or gas extraction, geological condition and corrosive environment are very complicated.Owing to being subject to the strong osmotic effect of high temperature (80～250 ℃) and high pressure (> 5MPa) hot steam, all kinds of corrosive mediums in crude oil and sewage are (as SO in addition
4 2-, NO
3 -, Cl
-, F
-, CN
-, Ba
+, Ca
+deng) and the erosion of unwanted bacteria, oil-gas field down-hole equipment, tubing string, pipeline and chemical corrosion and the deposition fouling of oil/gas pipe line, container basin are on the ground accelerated, not only shorten the work-ing life of winning apparatus, cause increasing of exploitation of oil-gas field cost, and seriously affect the normal production of enterprise.Research shows according to investigations: underground deep layer oil extraction pipeline, be subject to the impact of tectonic structure and reservoir condition, corrode very serious, the average corrosion rate of buried oil pipe line is up to 1.5～3.3mm/a, spot corrosion speed is up to 5～15mm/a, corrosion condition is perforation in 3～6 months, within 6～12 months, just needs overhaul, within 1～2 year, scraps.Recover the oil with the mean lifetime of buried oil pipe line at 9～18 months not etc., the shortest only has 3 months.Deep layer underground pipeline Anticorrosion Problems becomes the normal key of recovering the oil and reducing cost for oil production in oil field.
In petroleum industry, recover the oil more more complex than earth's surface Buried Oil Pipelines with the Working environment of underground pipeline, therefore, the anticorrosive work of deep layer underground mining oil-piping is also much bigger than the difficulty of earth's surface oil pipeline.Although oilfield applications is paid much attention to the corrosion and protection of oil extraction pipeline at present, existing oil pipe anti-corrosive erosion technology is carried out to constantly Improvement and perfection, to seek the breakthrough of new anticorrosion technique.But owing to being fallen behind
The restriction of anticorrosive, solve the heavy corrosion problem of oil extraction pipeline, become the century difficult problem that alleviate oil crisis and accelerates the urgency of energy industry development the world today.
The present invention is originally an industrial brainstorm subject research of carrying out for a corrosion and protection difficult problem for oil-gas field deep-well drill tool and the defeated pipeline of underground mining.By adopting previous patent of invention achievement---nano organic titanium polymer and the copolymerization of nanometer alumina modified fluorinated poly arylene ether ketone, prepare the nano fluorine-contained polyaryletherketone high polymer alloy of a kind of titanium novel material.The titanium nano-high molecule alloy coating that utilizes this novel material to make has obtained successful application in the corrosion-proof coating protection works of oil-gas field well casing.Product innovation is in Karamay Oil Fields in Xinjiang, Tarim Oilfield, soil is breathed out the application test in oil field, performance than the current product (phenol aldehyde modified corrosion-resistant epoxy paint) in use is more excellent, protection life several times, spoke reduces cost of winning and the maintenance of equipment expense of oil and natural gas greatly, thereby improve significantly the production efficiency of oil-gas mining, capture the technical barrier of the corrosion and protection of underground high sulfur content exploitation of oil-gas field equipment, obtain the effect that user is satisfied with very much, also for the production domesticization of China's oil and the selected high-performance protective coating of natural-gas field deep mining equipment provides novel body material.
The utilisation technology that the present invention is intended to by adopting nano material is prepared a kind of high-performance polymer, and develops special coating material product as matrix, for having opened up a new way in industrial antisepsis erosion field.
Summary of the invention
Object of the present invention, being intended to provides a kind of high performance coated substrate material for special anticorrosive erosion technical field.The technological line designing and implement is to adopt mechanochemistry principle, by the ultrasonic wave assisted microwave synthesis solid-liquid ball-milling reaction device of making by oneself and changing a social system, by nano organic titanium (presoma) polymkeric substance and nanometer alumina modified fluorinated poly arylene ether ketone blend ball milling generation copolyreaction, obtain a kind of high polymer alloy state polymer matrices material, and by the nano fluorine-contained polyaryletherketone high polymer alloy of its called after titanium novel material, be called for short the nano fluorine-contained poly (aryl ether ketone) copolymer of titanium.Its skeleton symbol is abbreviated as (TPEKF), and its chemical structural formula is:
Wherein, m value is that 2～20, n value is 6～30.
In formula-(Al
2o
2) be nano aluminium oxide, polymeric system is take NMP as solvent carrier.In its chemical structure, containing organic titanium, organic fluorine block and polyethersulfone, polyetherketone functional group, be that one dissolves in polar solvent (DMF, DMAC, NMP, THF, CHCl
3deng) film forming body material.
TPEKF is a kind of novel thermoplastic high molecule alloy material, and its preparation method comprises the following steps:
The first step takes each component according to formula ratio, packs in order homemade ultrasonic wave assisted microwave synthesis solid-liquid ball-milling reaction device into, then adds sealed tank cap after the Stainless Steel Ball of different-grain diameter by proportioning.
Second step starts ball-milling reaction device and enters normal operation, grinds and must not be less than 6h working time.After operation 1h, shutdown inspection.Upper end metallic thermometer of later every operation 1h shutdown inspection record and barometric data.Prepolymer is under the effect of carrier NMP and ultrasonic wave, microwave and mechanical force, when in tank, temperature, accumulation of pressure are to the required temperature and pressure of reaction (180 ℃ of temperature >, pressure for vaporization > 0.6MPa in tank), polycondensation starts.Then allowing the ball milling reaction times continue to 6h can shut down.
The 3rd step question response tank naturally cools to after normal temperature, and can opening filters out Stainless Steel Ball, obtains the polymerisate of black mud shape, and its particle diameter is 200～300nm, solids content >=65%.
The 4th step is transferred to nano bead mill by product and grinds, and grinds 3h, can reach requirement fineness (50～80nm), for subsequent use with 300 order screen cloths filtrations.
Accompanying drawing explanation
Raw material IR analysis chart before the ultrasonic ball milling of Fig. 1.
The XRD figure of Fig. 2 raw material and ultrasonic ball milling 30h sample.
The IR spectrum of Fig. 3 planetary ball mill 30h sample.
The IR spectrum of the ultrasonic ball milling 30h of Fig. 4 sample.
The TEM pattern of the ultrasonic ball milling 30h of Fig. 5 sample.
Fig. 6 ultrasonic wave solid-liquid ball-milling reaction device schematic diagram.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
The preparation method of the nano fluorine-contained poly (aryl ether ketone) copolymer of titanium of the present invention, its feature comprises chemical following reaction formula:
For completing above chemosynthesis reaction, concrete implementation step is as follows:
The first step is prepared required experimental installation and starting material:
1. major equipment: 1. homemade ultrasonic wave/microwave solid-liquid ball-milling reaction device (device); 2. the PHN10L nano material ball mill that (Guangzhou) Machinery Manufacturing Co., Ltd. produces is strangled by group;
2. main raw material(s): 1. base-material raw material: nano organic titanium high molecular polymer (HTH); Nanometer alumina modified fluorinated poly arylene ether ketone (self-control).2. auxiliary agent class: nanometer alumina modified dose, commercially available PBT catalyzer, ZD-401, KH560 coupling agent; 3. grinding medium: ф 20mm, ф 15mm, ф 10mm, tetra-kinds of Stainless Steel Balls of ф 5mm, its proportioning is: 10: 20: 30: 40 (wt, %);
Second step is prepared nano organic titanium polymer by the already described method in patent of invention ZL200810029936.1 " nano organic titanium polymer and coating thereof and manufacture method " of authorizing;
The 3rd step is prepared nanometer alumina modified fluorinated poly arylene ether ketone; its feature is as follows: adopting fluorophenyl Resorcinol monomer and difluoro benzophenone is raw material; take nano aluminium oxide as catalytic modification agent; a kind of high-performance nano hydridization soluble polymer novel material that reaction makes under nitrogen atmosphere protection, its preparation process is as follows:
Fill 32% reagent hydrochloric acid 240mL and with amount frozen water mechanical stirring synthesizer in, constant pressure quantitative drips the para-fluoroaniline of 0.6mol and 30% sodium nitrite solution of 0.6mol successively, under lasting whipped state, maintain the temperature between 0～5 ℃, the reaction times is 2h, and suction filtration obtains product A;
2. in mechanical stirring synthesizer, add successively the benzoquinone of sodium bicarbonate and the 0.55mol of 3500mL distilled water, 1.2mol, under whipped state, drip product A, temperature control stirs 1.5h at 12 ℃, then at room temperature continue stirring reaction 1.5h, pour out reactant and carry out suction filtration, repeatedly use distilled water wash, put into vacuum drying oven after 60 ℃ of vacuum-drying, obtain product B (fluorophenyl benzoquinone) with propyl carbinol dissolving-recrystallization;
3. is being furnished with magnetic stirring apparatus, in the synthesizer of cool solidifying pipe and constant voltage Liquid dropping bottle, add successively 0.25mol product B, 0.75mol zinc powder and 500mL distilled water, heated for controlling temperature refluxes between 90～95 ℃, then slowly drip 32% reagent hydrochloric acid 175mL, drip rear continuation backflow 4～5h, take out while hot suction filtration, filtrate bottle is cooled to 1～5 ℃ with frozen water, adularescent crystal is separated out, and keep 2h, then suction filtration, with distilled water repetitive scrubbing pressed powder, put into vacuum drying oven in 60 ℃ of vacuum-dryings, obtain white monomeric products C (4-fluorophenyl Resorcinol),
4. the toluene, the 20% nano-dispersed agent nano alumina powder jointed, 10% that take successively total amount 70% are placed in beaker, moving to stirrer mixes, by nano bead mill grinding distribution, process is monitored nanoparticle distributional pattern or is detected nanoparticle with laser particle size analyzer by Electronic Speculum and enters uniform dispersion state, can stop grinding distribution, whole grinding distribution process approximately needs 1～1.5h, obtains translucent nano dispersion fluid;
5. in the dry synthesizer that prolong, water trap and nitrogen ingress pipe are housed, add successively the Resorcinol of 0.5mol product C (4-fluorophenyl Resorcinol), 0.5mol, 4, the 4 '-difluoro benzophenone (DFK) of 0.5mol, the Anhydrous potassium carbonate (K of nanometer alumina modified dose of (dispersion liquid) 70g, 0.6mol
2cO
3), 230mL NMP and 1500mL toluene, at N
2under gas protection and under magnetic agitation, azeotropic dehydration 2.5～3h after being warming up to 160 ℃, be heated to 170 ℃, distill out toluene and take the residual water-content in system out of, continue reaction 2h, until polymerization system viscosity no longer raises, obtain the nanometer alumina modified fluorinated poly arylene ether ketone solution of solid content 60% left and right;
The 4th step is prepared the nano fluorine-contained poly (aryl ether ketone) copolymer of titanium: take HTH600g, NMP230g, MEK70g, nanometer alumina modified fluorinated poly arylene ether ketone solution 360g, PBT catalyzer 40g, nano aluminium oxide 40g, ZD-401 auxiliary agent 10g, KH-560 auxiliary agent 10g, add up to 1360g, pack in ultrasonic wave/microwave solid-liquid ball-milling reaction device (device), add 3/4ths places of Stainless Steel Ball to tank internal volume by proportioning, then screw bolt seal cover.Start ball-milling reaction device and enter normal operation, the reaction times of grinding operation needs 6h.After operation 3h, the airtight situation of shutdown inspection also records metallic thermometer and the barometric data on grinding pot top.Later every operation 1h shutdown inspection also records a secondary data.In the time that temperature in tank reaches reaction temperature required (180 ℃) and pressure (0.6MPa), allow the ball milling reaction times continue 1h and shut down.Question response tank naturally cools to after normal temperature, and can opening filters out steel ball, and the particle diameter that obtains black mud shape is about the nano fluorine-contained poly (aryl ether ketone) copolymer of titanium of 60～80nm, solids content >=65%.
Ultrasonic wave/Microwave Irradiation Assisted Chemical of the present invention synthesizes solid-liquid ball-milling reaction device, and ultrasonic device mainly plays the aid dispersion effect of nanoparticle, and equipment mainly plays assistant chemical Synthesis (another outer patent is examined and asked case).Microwave is hertzian wave, has electromagnetically induced agent catalytic affect effect, also should have the properties influence of ripple simultaneously; Microwave is a kind of electromagnetic energy in electromagnetic spectrum end.Although microwave is comprising an electric field and a magnetic field, only have electric field that energy is shifted to the material in order to heating.Compare with the energy (80～120kcal/mol) of usual chemical bond, the energy equivalence little (0.03kcal/mol) of microwave photon, so can directly not exert an influence to molecular structure.Therefore having absorbed the caused effect of microwave only limits on molecule activity.
Microwave is wavelength hertzian wave of (0.3GHz～300GHz) between 1mm～1m, comprises Electric and magnetic fields two components.Micro-wave energy produces 2.0 × 109s
-1higher frequency electromagnetic field, in this higher frequency electromagnetic field, to there is orientation polarization and divertical motion in polar molecule, but due to the thermal motion of intermolecular interaction and molecule, make molecule divertical motion be obstructed and produce frictional force, molecule self is shown as to hot generation, carry out so-called molecule " interior heating ".The phenomenon that electromagnetic energy is converted into heat energy by material is a kind of micro-wave dielectric heat effect.
Micro-wave dielectric heat effect is a kind of " interior heating " mechanism, thereby avoid thermal conduction and the transmission of heat by convection in traditional heating, because of but one evenly, type of heating rapidly, the effect of microwave and different substances is different simultaneously, micro-wave dielectric heat effect changes with the difference of molecular property, often the polarity of material is stronger, and its micro-wave dielectric heat effect is stronger.Microwave comes from it to the high efficiency of chemical reaction and can be widely used among heterogeneous building-up reactions polarity thing microwave, the especially reaction on polymer support, and microwave is Reaction time shorten significantly.Owing to having such characteristic, microwave becomes the best thermal source of solid-state and solvent-free building-up reactions.
The speed of microwave heating has other advantage.It can allow chemists have sufficient time to analytical reaction, reacts and improves productive rate to optimize.This modern technique makes its user have sufficient time to thinking and innovation.
Microwave Irradiation Assisted Chemical is synthetic be one at perfect gradually emerging field.Its feature comprises:
(1) microwave is not simple heat effect on the impact of chemical reaction, also exist selectivity heating problem (being the matching relationship of material molecular structure and microwave frequency), exist some specific non-thermal effect, or the activation of molecule is affected.Some current experimental studies show: microwave can be induced the generation of some selective reactions, prepare the chemical reaction of water soluble sulfonated CuPc title complex as microwave-assisted, have just shown the non-thermal effect of microwave radiation to chemical reaction.
Therefore, in microwave chemical reaction, should both exist heat effect, also existing some has the non-thermal effect of special role.
(2) microwave causes molecular vibration, can cause chemical bond resonance, and the violent resonance of molecule can cause chemical bond rupture.It can cause can contribute the rotation of (exciting) molecule to the fracture of chemical bond.Explain from kinetics: once molecule obtains energy and transition, will become a kind of metastable state state, now molecularity is very active, intermolecular collision frequency and effective collision frequency increase greatly, thereby promote the carrying out of reaction, therefore, can think that microwave has activation to molecule; Vibration, the rotation etc. of molecule should be quantized on energy, and microwave chemical should have photochemical some characteristic.
(3) when molecule is dissociated into after Molecular fragments (or charged particle) in reaction process, it also can change in the polarized situation of elect magnetic field, and this is also to affect a kind of factor that some reaction preference strengthens.
In sum, the impact of microwave on chemical reaction, except thermal effect, also should there is nonthermal effect, theoretically, microwave not only can be accelerated chemical reaction, and can also suppress the generation of chemical reaction (reaction of certain direction) under certain condition.The mechanism that microwave accelerates (slowing down) chemical reaction is very complicated, and from this view point, the impact of nonthermal effect will make microwave chemical have more characteristic, have profound significance.
In order to verify this chemical action, do IR, XRD and tem analysis by preparing product, test result is as Fig. 1 to Fig. 5.
As shown in Figure 2, after ultrasonic ball milling 30h, the diffraction peak intensity of sample weakens greatly, and halfwidth increases, and this grain-size that shows titanium hydride powder reduces, and lattice distortion increases.
Comparison diagram 3 and Fig. 4 are known, the characteristic peak of epoxy resin 1246.56,1035.26,912.78cm
-1after ultrasonic ball milling 30h, become 1241.60,1032.65,910.42cm
-1this shows, in ultrasonic mechanical milling process, nano-titanium is because surfactivity is higher, the oxygen of locating with epoxy group(ing), ether etc. more active in epoxy resin molecule interacts, thereby grafting the epoxy resin molecule of fracture, or adsorb by oxygen more active in epoxy group(ing), thereby cause the peak position of these functional groups in infrared spectra to be offset.
Fig. 6 is ultrasonic wave solid-liquid ball-milling reaction device schematic diagram, and it comprises: 1-ultrasonic generator; 2-energy dress parallel operation; 3-ball grinder or cylinder; 4-transmission shaft; 5-buncher; 6-horizontal stand; 7-vertical support frame; 8-tongued and grooved flanges; 9-water coolant; 10-agitator arm; 11-stationary bearing.
The foregoing is only preferred embodiments of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. the nano fluorine-contained polyether sulphone ketone copolymers of titanium, it has following structural formula:
Wherein, m value is that 2～20, n value is 6～30.
2. for the preparation of a nanometer alumina modified fluorinated poly arylene ether ketone for the nano fluorine-contained polyether sulphone ketone copolymers of titanium claimed in claim 1, it has following structural formula:
Wherein, m value is that 2～20, n value is 6～30.
3. nanometer alumina modified fluorinated poly arylene ether ketone preparation method claimed in claim 2, take fluorophenyl Resorcinol monomer and difluoro benzophenone as raw material, take nano aluminium oxide as catalytic modification agent, reaction preparation under nitrogen atmosphere protection, it comprises the following steps:
1) frozen water of the hydrochloric acid that is 32% by every 240mL quality percentage composition and same amount mixes in mechanical stirring synthesizer, and constant pressure quantitative drips the sodium nitrite solution that the para-fluoroaniline of 0.6mol and the quality percentage composition of 0.6mol are 30% successively, under lasting whipped state, maintain the temperature between 0～5 ℃, reaction times is 2h, and suction filtration obtains head product;
2) in churned mechanically synthesizer, add successively the benzoquinone of sodium bicarbonate and the 0.55mol of 3500mL distilled water, 1.2mol, under whipped state, drip the head product that step 1) obtains, temperature control stirs 1.5h at 12 ℃, then at room temperature continue stirring reaction 1.5h, pour out reactant and carry out suction filtration, repeatedly use distilled water wash, put into vacuum drying oven after 60 ℃ of vacuum-drying, obtain product fluorophenyl benzoquinone with propyl carbinol dissolving-recrystallization;
3) is being furnished with magnetic stirring apparatus, in the synthesizer of cool solidifying pipe and constant voltage Liquid dropping bottle, add successively 0.25mol product fluorophenyl benzoquinone, 0.75mol zinc powder and 500mL distilled water, heated for controlling temperature refluxes between 90～95 ℃, then slowly drip quality percentage composition and be 32% hydrochloric acid 175mL, drip rear continuation backflow 4～5h, take out while hot suction filtration, filtrate bottle is cooled to 1～5 ℃ with frozen water, adularescent crystal is separated out, and keep 2h, then suction filtration, with distilled water repetitive scrubbing pressed powder, put into vacuum drying oven in 60 ℃ of vacuum-dryings, obtain white monomeric products 4-fluorophenyl Resorcinol,
4) toluene, the 20% nano-dispersed agent nano alumina powder jointed, 10% that take successively total amount 70% are placed in beaker, moving to stirrer mixes, by nano bead mill grinding distribution, process is monitored nanoparticle distributional pattern or is detected nanoparticle with laser particle size analyzer by Electronic Speculum and enters uniform dispersion state, can stop grinding distribution, whole grinding distribution process approximately needs 1～1.5h, obtains the translucent nano dispersion fluid of oyster white;
5) in the dry synthesizer that prolong, water trap and nitrogen ingress pipe are housed, add successively 0.5mol product 4-fluorophenyl Resorcinol, 0.5mol Resorcinol, 0.5mol 4, Anhydrous potassium carbonate, 230mLNMP and the 1500mL toluene of 4 '-difluoro benzophenone, nano dispersion fluid 70g, 0.6mol that step 4) obtains, at N
2under gas protection and under magnetic agitation; azeotropic dehydration 2.5～3h after being warming up to 160 ℃; be heated to 170 ℃; distill out toluene and take the residual water-content in system out of; continue reaction 2h; until polymerization system viscosity no longer raises, obtain the nanometer alumina modified fluorinated poly arylene ether ketone solution of solid content 60% left and right.
4. the preparation method of the nano fluorine-contained polyether sulphone ketone copolymers of titanium claimed in claim 1, comprises the following steps:
1) take each component and pack in order in ultrasonic wave/microwave solid-liquid ball-milling reaction device by formula ratio, add nano organic titanium high molecular polymer HTH, again with the blend of nanometer alumina modified fluorinated poly arylene ether ketone, then add sealed tank cap after the Stainless Steel Ball of different-grain diameter by proportioning;
2) start ultrasonic wave/microwave solid-liquid ball-milling reaction device, grind and be no less than 6h working time, after operation 1h, shutdown inspection, upper end metallic thermometer of later every operation 1h shutdown inspection record and barometric data, prepolymer is under the effect of carrier NMP or tetramethylene sulfone and catalyst, heat up through grinding, when in tank, temperature, accumulation of pressure are to 180 ℃ of the interior temperature > of tank, pressure for vaporization > 20MPa, polycondensation starts, then, allowing the ball milling reaction times continue 1h can shut down again;
3) question response tank naturally cools to after normal temperature, and can opening filters out Stainless Steel Ball, obtains the polymerisate of black mud shape, and its particle diameter D50 is about 50～80nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108841234A (en) * | 2018-05-25 | 2018-11-20 | 中国人民解放军陆军装甲兵学院 | A kind of titanium-based hybrid material preparation method |
| WO2019210528A1 (en) * | 2018-05-02 | 2019-11-07 | 江苏金陵特种涂料有限公司 | Preparation method for organic titanium precursor polymer tpp-ii and application thereof in special coating |
| CN118006211A (en) * | 2024-04-08 | 2024-05-10 | 北京市建筑工程研究院有限责任公司 | Polyurethane modified epoxy resin composition and steel strand suitable for circumferential arrangement of wind power mixing tower |
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| CN101067021A (en) * | 2006-09-19 | 2007-11-07 | 张驰 | Nanometer alumina modified polyether ketone and its nanometer ceramic film paint |
| CN101638483A (en) * | 2008-08-01 | 2010-02-03 | 张驰 | Nano organic titanium polymer, coating thereof and manufacturing method thereof |
| CN101671438A (en) * | 2008-09-08 | 2010-03-17 | 张驰 | Titanium and nano fluorine-containing poly (aryl ether ketone) copolymer, coating made thereof and manufacturing method thereof |
| CN103130616A (en) * | 2013-02-04 | 2013-06-05 | 江苏金陵特种涂料有限公司 | Preparing method for fluorine-containing monomer synthesis and nanometer aluminum oxide modified fluorine-containing polyaryletherketone |
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|---|---|---|---|---|
| CN101067021A (en) * | 2006-09-19 | 2007-11-07 | 张驰 | Nanometer alumina modified polyether ketone and its nanometer ceramic film paint |
| CN101638483A (en) * | 2008-08-01 | 2010-02-03 | 张驰 | Nano organic titanium polymer, coating thereof and manufacturing method thereof |
| CN101671438A (en) * | 2008-09-08 | 2010-03-17 | 张驰 | Titanium and nano fluorine-containing poly (aryl ether ketone) copolymer, coating made thereof and manufacturing method thereof |
| CN103130616A (en) * | 2013-02-04 | 2013-06-05 | 江苏金陵特种涂料有限公司 | Preparing method for fluorine-containing monomer synthesis and nanometer aluminum oxide modified fluorine-containing polyaryletherketone |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019210528A1 (en) * | 2018-05-02 | 2019-11-07 | 江苏金陵特种涂料有限公司 | Preparation method for organic titanium precursor polymer tpp-ii and application thereof in special coating |
| CN108841234A (en) * | 2018-05-25 | 2018-11-20 | 中国人民解放军陆军装甲兵学院 | A kind of titanium-based hybrid material preparation method |
| CN118006211A (en) * | 2024-04-08 | 2024-05-10 | 北京市建筑工程研究院有限责任公司 | Polyurethane modified epoxy resin composition and steel strand suitable for circumferential arrangement of wind power mixing tower |
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