CN109912838A - A kind of automatically cleaning TPU foamed composite and preparation method thereof - Google Patents
A kind of automatically cleaning TPU foamed composite and preparation method thereof Download PDFInfo
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- CN109912838A CN109912838A CN201910209879.3A CN201910209879A CN109912838A CN 109912838 A CN109912838 A CN 109912838A CN 201910209879 A CN201910209879 A CN 201910209879A CN 109912838 A CN109912838 A CN 109912838A
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Abstract
The invention discloses a kind of automatically cleaning TPU foamed composites and preparation method thereof, belong to polymeric composite foam field, raw materials used to be calculated by weight as: 150-200 parts of TPU, 3-8 parts of foaming agent, 5 parts of photocatalytic self-cleaning PVDF coating agent.Formula is scientific and reasonable for automatically cleaning TPU foamed composite prepared by the present invention, and environment-protecting and non-poisonous, process flow is simple and practical, using novel rGO-TiO2/ PVDF photocatalysis coating agent is coated, substantially increase the self-cleaning ability of PVDF, it is improved the mechanical property of TPU foam simultaneously, and graphene itself has antibacterial ability, the stain resistance of TPU foam can more be improved, new thinking is provided for Future Development novel foam material, and there are huge economic results in society in practical applications.
Description
Technical field
The invention belongs to polymeric composite foam fields, and in particular to a kind of automatically cleaning TPU foamed composite and
Preparation method.
Background technique
Foamed plastics is since the 1940s comes out, due to many excellent performances, such as energy absorption
Well, density is small, sound absorbing performance is good etc., obtains in fields such as metal electrode, adsorbent material, structural material, energy absorbing materials
It is widely applied.Thermoplastic polyurethane (TPU) is the elastocopolymer of polyester-diol or polyetherdiol and dihydric alcohol block composition.
The plasticity and elasticity that this special soft or hard block structure promotes TPU that there are other thermoplastics to hardly match.In addition, TPU
The degradability that also there are foamed material other foamed materials not have meets the reason of current sustainable development, environment-friendly type development
It reads.Therefore, TPU foamed material has become research hotspot in recent years, is often applied to the gentle punching of athletic shoe industry, athletic protective
Product etc..With the continuous improvement that the special dimensions such as Aeronautics and Astronautics require foam performance, traditional foamed plastics is
It is not able to satisfy these fields to the particular/special requirement of the strength of materials, rigidity and heat resistance etc..Therefore, high performance has become foam plastic
Expect the new direction and hot spot of research.
Containing F atom in the strand of PVDF, the surrounding of carbochain is surrounded by F atom, enable the surface very little of PVDF, and
The crystallinity of PVDF is relatively high, can form hackly microspike in the PVDF of surface portion crystallization, these protrusions can drop
Low-surface-energy makes contact angle become larger, and is conducive to hydrophobic.Drops can be formed when water droplet falls in the surface of PVDF, can be taken away
Most dust.Meanwhile bacterium and greasy dirt are easy to be adhered to the surface of TPU foam in a humidity environment, make foam
There is spot and mechanical properties decrease in surface, therefore not only takes away the dust for being adsorbed on foam surface in research, but also
It is also contemplated that the greasy dirt and bacterial decomposition that foam surface will be adsorbed on.
In numerous semiconductor light-catalysts, TiO2With its oxidability is strong, photocatalytic activity is high, good (resistance toization of stability
Learn and photoetch), but also have many advantages, such as safe and non-toxic, low in cost, be acknowledged as before environment pollution treatment field most develops
The environment-friendly type catalysis material on way.But TiO2It is a kind of wide band gap semiconducter, only absorption accounts for very at least part of in sunlight
Ultraviolet light, so improving TiO2Its visible light catalysis activity can be improved in absorption of the semiconductor material in visible light region.It influences
TiO2Another key factor of photocatalytic activity is the compound of photo-generate electron-hole.Since light excites TiO2The photoproduction electricity of generation
Son-hole is to easily compound, so reducing the compound of photo-generated carrier can also be improved TiO2Photocatalysis efficiency.In recent years, it grinds
Discovery is studied carefully by semiconductor light-catalyst TiO2With Carbon Materials (such as carbon nanotube, carbon black, graphene, the oxidation of different shape, structure
Graphene etc.) it is compound be that one kind effectively improves TiO2One of approach of photocatalytic activity.
Summary of the invention
The purpose of the present invention is to provide a kind of automatically cleaning TPU foamed composites and preparation method thereof.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of automatically cleaning TPU foamed composite, it is raw materials used to be calculated by weight as: 150-200 parts of TPU, foaming agent 3-
8 parts, 5 parts of photocatalytic self-cleaning PVDF coating agent.
The foaming agent is that sodium bicarbonate is mixed with 4,4 '-oxobenzenesulfonyl hydrazide 1:1 in mass ratio.
The photocatalytic self-cleaning PVDF coating agent it is specific the preparation method comprises the following steps:
1) 1mL isopropyl titanate is added in 5mL dehydrated alcohol, is then slowly dropped into 5mL ammonium chloride containing 4mg under agitation
Aqueous solution, obtain part A；
2) 50mg GO is added in 50mL deionized water and is ultrasonically treated 30min, then with 1000 r/min high-speed stirred 1h,
100mg glucose and 1mL ammonium hydroxide are added, part B is obtained；
3) part A and part B are mixed, then mixture is put into autoclave, heat 12h at 160 DEG C；
4) after reduction reaction, product pure water and ethanol washing for several times, and dry 12h at 90 DEG C, obtain rGO-TiO2；
5) 2.5g Kynoar (PVDF) powder, 22.5g dimethylformamide (DMF) and 0.125g rGO-TiO are weighed2In
In single port bottle, it is condensed back 3h in 65 DEG C of water-bath, the photocatalytic self-cleaning coating agent is made.
Gained TiO2Partial size be 9nm-12nm.
The preparation method of the automatically cleaning TPU foamed composite the following steps are included:
1) TPU, foaming agent are dried at 80 DEG C；
2) TPU, foaming agent are sufficiently mixed in a high speed mixer；
3) mixture for obtaining step 2 is quickly transferred in preheated casting machine, and temperature of each section is arranged, obtains TPU foam
Composite material；
4) it takes a monolith TPU foamed composite to be placed on film applicator, adjusts film applicator thickness knob and floating rule speed adjustment knob, adjust
Then photocatalytic self-cleaning PVDF coating agent is placed in film applicator floating rule leading edge by whole to suitable gear, open film applicator,
TPU foamed composite surface coats 1g/cm2Automatically cleaning PVDF coating agent, then the foam is placed in 65 DEG C of vacuum ovens
Dry 20min, is made the automatically cleaning TPU foamed composite.
Casting machine Zhong-1 block, 2nd area, 3rd area, four areas He Wu, area setting temperature be followed successively by 115 DEG C, 125 DEG C, 155 DEG C,
160 DEG C and 150 DEG C.
Application of the automatically cleaning TPU foamed composite in packaging material, membrane structure material and article of footwear.
The present invention first passes through one step hydro thermal method, and redox graphene is added in the synthesis process of titanium dioxide, makes two
Titanium oxide is grown on the surface of graphene, gained rGO-TiO2Obvious red shift occurs for the ABSORPTION EDGE of composite photo-catalyst object, while big
Catalyst is improved in the absorption intensity of visible region greatly, so that the application range of catalyst be allow effectively to expand to visible
Light area (such as Fig. 1).This is primarily due to be enriched with sp in one side graphene2Hydridization carbon, in the photocatalytic process, due to sp2Hydridization
The σ key that carbon is formed is easier to polarize, thus has very big Raman section.Meanwhile when using excited by visible light, π state can occur altogether
Vibration enhancing, to improve it in the absorption intensity of visible region.Sp contained in graphene2What hydbridized carbon atoms bonded together to form is total to
The big pi bond of yoke can carry out significant response to visible light, to improve the utilization efficiency to visible light.Again by rGO-TiO2It is added to
In PVDF, it is greatly improved the stain resistance of PVDF.
The beneficial effects of the present invention are:
(1) present invention uses isopropyl titanate as titanium source, prepares rGO-TiO by one step hydro thermal method2Photochemical catalyst, preparation process
Simply, asepsis environment-protecting, TiO2Particle energy homoepitaxial is on rGO, and uniform particle diameter (partial size 9nm-12nm, such as Fig. 2), so that
TiO2Photocatalysis efficiency it is high.
(2) automatically cleaning TPU foamed composite prepared by the present invention, formula is scientific and reasonable, environment-protecting and non-poisonous, process flow letter
It is single practical, using novel rGO-TiO2/ PVDF photocatalysis coating agent is coated, and the self-cleaning ability of PVDF is substantially increased,
It is improved the mechanical property of TPU foam simultaneously, and graphene itself has antibacterial ability, can more improve TPU foam
Stain resistance to provide new thinking from now on for exploitation novel foam material, and has huge society in practical applications
Economic benefit.
Detailed description of the invention
Fig. 1 is rGO-TiO2(a) and TiO2(b) ultraviolet-visible absorption spectroscopy figure；
Fig. 2 is prepared TiO2Grain size distribution；
Fig. 3 is prepared rGO-TiO2XRD diagram；
Fig. 4 is rGO(a) and prepared rGO-TiO2(b) SEM figure；
Fig. 5 is different rGO-TiO2(wherein, a is 0% rGO-TiO to the minimal contact angle picture of the PVDF coating agent of content2/
PVDF, b PVDF, c are 1% rGO-TiO2/ PVDF, d is 3% rGO-TiO2/ PVDF, e is 4% rGO-TiO2/ PVDF, f 5%
rGO-TiO2/ PVDF)；
Fig. 6 is degradation rate of the different materials to methylene blue.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
A method of preparing automatically cleaning TPU foamed composite, specific steps are as follows:
1) 1mL isopropyl titanate is added in 5mL dehydrated alcohol, is then slowly dropped into 5mL ammonium chloride containing 4mg under agitation
Aqueous solution, obtain part A；50mg GO is added in 50mL deionized water and is ultrasonically treated 30min, then 1000 r/min
High-speed stirred 1h adds 100mg glucose and 1mL ammonium hydroxide, obtains part B；Part A and part B are mixed and are put into height
It presses in kettle, heats 12h at 160 DEG C；After reduction reaction, product pure water and ethanol washing for several times, and are done at 90 DEG C
Dry 12h, obtains rGO-TiO2；Weigh 2.5g PVDF powder, 22.5g DMF and 0.025g rGO-TiO2In single port bottle, at 65 DEG C
Water-bath in be condensed back 3h, 1% rGO-TiO is made2Photocatalytic self-cleaning coating agent；
2) 150 parts by weight TPU, 1.5 parts by weight sodium bicarbonates, 1.5 4,4 '-oxobenzenesulfonyl hydrazide of parts by weight are dried at 80 DEG C
After dry, it is sufficiently mixed in a high speed mixer；Obtained mixture is quickly transferred in preheated casting machine, and each section of temperature is arranged
Degree is 115 DEG C, 125 DEG C, 155 DEG C, 160 DEG C and 150 DEG C, obtains TPU foamed composite；
3) it takes a monolith TPU foamed composite to be placed on film applicator, adjusts film applicator thickness knob and floating rule speed adjustment knob, adjust
Then photocatalytic self-cleaning PVDF coating agent is placed in film applicator floating rule leading edge by whole to suitable gear, open film applicator,
TPU foamed composite surface coats one layer 1% of rGO-TiO2Automatically cleaning PVDF coating agent, then the foam is placed in 65 DEG C very
Dry 20min, is made automatically cleaning TPU foamed composite in empty drying box.
Embodiment 2
A method of preparing automatically cleaning TPU foamed composite, specific steps are as follows:
1) 1mL isopropyl titanate is added in 5mL dehydrated alcohol, is then slowly dropped into 5mL ammonium chloride containing 4mg under agitation
Aqueous solution, obtain part A；50mg GO is added in 50mL deionized water and is ultrasonically treated 30min, then with 1000 r/
Min high-speed stirred 1h, adds 100mg glucose and 1mL ammonium hydroxide, obtains part B；Part A and part B are mixed and are put into
In autoclave, 12h is heated at 160 DEG C；After reduction reaction, product pure water and ethanol washing for several times, and at 90 DEG C
Dry 12h, obtains rGO-TiO2；Weigh 2.5g PVDF powder, 22.5g DMF and 0.075g rGO-TiO2In single port bottle, 65
DEG C water-bath in be condensed back 3h, 3% rGO-TiO is made2Photocatalytic self-cleaning coating agent；
2) 150 parts by weight TPU, 1.5 parts by weight sodium bicarbonates, 1.5 4,4 '-oxobenzenesulfonyl hydrazide of parts by weight are dried at 80 DEG C
After dry, it is sufficiently mixed in a high speed mixer；Obtained mixture is quickly transferred in preheated casting machine, and each section of temperature is arranged
Degree is 115 DEG C, 125 DEG C, 155 DEG C, 160 DEG C and 150 DEG C, obtains TPU foamed composite；
3) it takes a monolith TPU foamed composite to be placed on film applicator, adjusts film applicator thickness knob and floating rule speed adjustment knob, adjust
Then photocatalytic self-cleaning PVDF coating agent is placed in film applicator floating rule leading edge by whole to suitable gear, open film applicator,
TPU foamed composite surface coats one layer 3% of rGO-TiO2Automatically cleaning PVDF coating agent, then the foam is placed in 65 DEG C very
Dry 20min, is made automatically cleaning TPU foamed composite in empty drying box.
Embodiment 3
A method of preparing automatically cleaning TPU foamed composite, specific steps are as follows:
1) 1mL isopropyl titanate is added in 5mL dehydrated alcohol, is then slowly dropped into 5mL ammonium chloride containing 4mg under agitation
Aqueous solution, obtain part A；50mg GO is added in 50mL deionized water and is ultrasonically treated 30min, then 1000 r/min
High-speed stirred 1h adds 100mg glucose and 1mL ammonium hydroxide, obtains part B；Part A and part B are mixed and are put into height
It presses in kettle, heats 12h at 160 DEG C；After reduction reaction, product pure water and ethanol washing for several times, and are done at 90 DEG C
Dry 12h, obtains rGO-TiO2；Weigh 2.5g PVDF powder, 22.5g DMF and 0.1g rGO-TiO2In single port bottle, at 65 DEG C
It is condensed back 3h in water-bath, 4% rGO-TiO is made2Photocatalytic self-cleaning coating agent；
2) 150 parts by weight TPU, 1.5 parts by weight sodium bicarbonates, 1.5 4,4 '-oxobenzenesulfonyl hydrazide of parts by weight are dried at 80 DEG C
After dry, it is sufficiently mixed in a high speed mixer；Obtained mixture is quickly transferred in preheated casting machine, and each section of temperature is arranged
Degree is 115 DEG C, 125 DEG C, 155 DEG C, 160 DEG C and 150 DEG C, obtains TPU foamed composite；
3) it takes a monolith TPU foamed composite to be placed on film applicator, adjusts film applicator thickness knob and floating rule speed adjustment knob, adjust
Then photocatalytic self-cleaning PVDF coating agent is placed in film applicator floating rule leading edge by whole to suitable gear, open film applicator,
TPU foamed composite surface coats one layer 4% of rGO-TiO2Automatically cleaning PVDF coating agent, then the foam is placed in 65 DEG C very
Dry 20min, is made automatically cleaning TPU foamed composite in empty drying box.
Embodiment 4
A method of preparing automatically cleaning TPU foamed composite, specific steps are as follows:
1) 1mL isopropyl titanate is added in 5mL dehydrated alcohol, is then slowly dropped into 5mL ammonium chloride containing 4mg under agitation
Aqueous solution, obtain part A；50mg GO is added in 50mL deionized water and is ultrasonically treated 30min, then 1000 r/min
High-speed stirred 1h adds 100mg glucose and 1mL ammonium hydroxide, obtains part B；Part A and part B are mixed and are put into height
It presses in kettle, heats 12h at 160 DEG C；After reduction reaction, product pure water and ethanol washing for several times, and are done at 90 DEG C
Dry 12h, obtains rGO-TiO2；Weigh 2.5g PVDF powder, 22.5g DMF and 0.125g rGO-TiO2In single port bottle, at 65 DEG C
Water-bath in be condensed back 3h, 5% rGO-TiO is made2Photocatalytic self-cleaning coating agent；
2) 150 parts by weight TPU, 1.5 parts by weight sodium bicarbonates, 1.5 4,4 '-oxobenzenesulfonyl hydrazide of parts by weight are dried at 80 DEG C
After dry, it is sufficiently mixed in a high speed mixer；Obtained mixture is quickly transferred in preheated casting machine, and each section of temperature is arranged
Degree is 115 DEG C, 125 DEG C, 155 DEG C, 160 DEG C and 150 DEG C, obtains TPU foamed composite；
3) it takes a monolith TPU foamed composite to be placed on film applicator, adjusts film applicator thickness knob and floating rule speed adjustment knob, adjust
Then photocatalytic self-cleaning PVDF coating agent is placed in film applicator floating rule leading edge by whole to suitable gear, open film applicator,
TPU foamed composite surface coats one layer 5% of rGO-TiO2Automatically cleaning PVDF coating agent, then the foam is placed in 65 DEG C very
Dry 20min, is made automatically cleaning TPU foamed composite in empty drying box.
Comparative example 1
A method of preparing TPU foamed composite, specific steps are as follows: by 150 parts by weight TPU, 1.5 parts by weight bicarbonates
After sodium, 1.5 parts by weight, 4,4 '-oxobenzenesulfonyl hydrazide are dried at 80 DEG C, it is sufficiently mixed in a high speed mixer；What is obtained is mixed
Object to be closed to be quickly transferred in preheated casting machine, setting temperature of each section is 115 DEG C, 125 DEG C, 155 DEG C, 160 DEG C and 150 DEG C,
Obtain TPU foamed composite.
Comparative example 2
A method of preparing TPU foamed composite, specific steps are as follows:
1) weigh 2.5g PVDF powder, 22.5g DMF is placed in single port bottle, 3h is condensed back in 65 DEG C of water-bath, prepare
At without rGO-TiO2PVDF coating agent；
2) 150 parts by weight TPU, 1.5 parts by weight sodium bicarbonates, 1.5 4,4 '-oxobenzenesulfonyl hydrazide of parts by weight are dried at 80 DEG C
After dry, it is sufficiently mixed in a high speed mixer；Obtained mixture is quickly transferred in preheated casting machine, and each section of temperature is arranged
Degree is 115 DEG C, 125 DEG C, 155 DEG C, 160 DEG C and 150 DEG C, obtains TPU foamed composite；
5) it takes a monolith TPU foamed composite to be placed on film applicator, adjusts film applicator thickness knob and floating rule speed adjustment knob, adjust
Then photocatalytic self-cleaning PVDF coating agent is placed in film applicator floating rule leading edge by whole to suitable gear, open film applicator,
TPU foam surface coats one layer of PVDF coating agent, and the foam is then placed in 20min in 65 DEG C of vacuum ovens, is made from clear
Clean TPU foamed composite.
Performance test
1 automatically cleaning TPU foamed composite mechanical property of table
Fig. 5 is containing not same amount rGO-TiO2The corresponding minimal contact angle picture of the PVDF coating agent of photochemical catalyst.Wherein a be
TPU foam surface is not coated by PVDF coating agent, directly coats the minimal contact angle picture that oleic acid measures；B is in TPU foam surface
One layer of PVDF coating agent without containing photochemical catalyst of coating；C is to coat one layer containing 1% photochemical catalyst in TPU foam surface
PVDF coating agent；D is to coat one layer of PVDF coating agent containing 3% photochemical catalyst in TPU foam surface；E is in TPU foam table
Face coats one layer of PVDF coating agent containing 4% photochemical catalyst；F is to coat one layer containing 5% photochemical catalyst in TPU foam surface
PVDF coating agent.(a), (b), (c), (d), (e) corresponding minimal contact angle be 78.4 ° respectively, 77.9 °, 58.6 °, 38.8 °,
39.0°.It follows that being not coated by the coating agent of PVDF coating agent or coating without containing photochemical catalyst in TPU foam surface, most
The contact angle measured eventually is all larger, without self-cleaning property, and coats the PVDF coating containing photochemical catalyst in TPU foam surface
Agent, the contact angle measured are all smaller.Illustrate that oleic acid molecular is decomposed by photochemical catalyst under light illumination, so contact angle is smaller.It is added
Catalyst it is excessive, the photocatalysis contact point of PVDF coating surface reaches saturation, and minimal contact angle does not continue to become smaller.So
In PVDF coating agent, the optimum content of photochemical catalyst is 4%.
Fig. 6 is different materials under visible light to degradation rate (wherein, the rGO-TiO of methylene blue24%) content is.
As can be seen from the figure pure TPU foam hardly has the ability of degradation of methylene blue；By the compound titanium dioxide of graphene
Fast to the degradation speed of methylene blue, degradation rate is high；It is coated with rGO-TiO2The TPU foam of/PVDF coating agent has degradation methylene
The ability of base indigo plant.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (7)
1. a kind of automatically cleaning TPU foamed composite, it is characterised in that: raw materials used to be calculated by weight as: TPU 150-
200 parts, 3-8 parts of foaming agent, 5 parts of photocatalytic self-cleaning PVDF coating agent.
2. automatically cleaning TPU foamed composite according to claim 1, it is characterised in that: the foaming agent is bicarbonate
Sodium is mixed with 4,4 '-oxobenzenesulfonyl hydrazide 1:1 in mass ratio.
3. automatically cleaning TPU foamed composite according to claim 1, it is characterised in that: the photocatalytic self-cleaning
PVDF coating agent it is specific the preparation method comprises the following steps:
1) 1mL isopropyl titanate is added in 5mL dehydrated alcohol, is then slowly dropped into 5mL ammonium chloride containing 4mg under agitation
Aqueous solution, obtain part A；
2) 50mg GO is added in 50mL deionized water and is ultrasonically treated 30min, then with 1000 r/min high-speed stirred 1h,
100mg glucose and 1mL ammonium hydroxide are added, part B is obtained；
3) part A and part B are mixed, then mixture is put into autoclave, heat 12h at 160 DEG C；
4) after reduction reaction, product pure water and ethanol washing, and the dry 12h at 90 DEG C, obtain rGO-TiO2；
5) rGO-TiO of 2.5g PVDF powder, 22.5g DMF and 0.125g is weighed2In 65 DEG C of condensing reflux 3h, the light is made
It is catalyzed automatic cleaning coating agent.
4. automatically cleaning TPU foamed composite according to claim 3, it is characterised in that: gained TiO2Partial size be 9nm-
12nm。
5. a kind of preparation method of automatically cleaning TPU foamed composite according to any one of claims 1-4, feature exist
In: the following steps are included:
1) TPU, foaming agent are dried at 80 DEG C；
2) TPU, foaming agent are sufficiently mixed in a high speed mixer；
3) mixture for obtaining step 2 is quickly transferred in preheated casting machine, and temperature of each section is arranged, obtains TPU foam
Composite material；
4) 1g/cm is coated on gained TPU foamed composite surface2Photocatalytic self-cleaning PVDF coating agent is subsequently placed in 65 DEG C very
Dry 20min, is made the automatically cleaning TPU foamed composite in empty drying box.
6. automatically cleaning TPU foamed composite according to claim 5, it is characterised in that: each section of setting in casting machine
Temperature is followed successively by 115 DEG C, 125 DEG C, 155 DEG C, 160 DEG C and 150 DEG C.
7. a kind of automatically cleaning TPU foamed composite as described in claim 1 is in packaging material, membrane structure material and shoes system
Application in product.
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| CN113736330A (en) * | 2021-09-29 | 2021-12-03 | 哈尔滨工程大学 | Flower-like TiO2Photocatalytic self-polishing resin-based composite coating and preparation method thereof |
| CN115069310A (en) * | 2022-03-21 | 2022-09-20 | 福建工程学院 | TPU/TiO 2 Preparation method and application of/PDA (personal digital Assistant) composite three-dimensional porous foam |
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| 李轶: "聚氨酯海绵负载二氧化钛/石墨烯复合蒙脱土漂浮材料可见光降解17α-乙炔基雌二醇", 《河海大学学报》 * |
| 肖建伟: "染料敏化太阳能电池二氧化钛光阳极构筑即界面调控研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736330A (en) * | 2021-09-29 | 2021-12-03 | 哈尔滨工程大学 | Flower-like TiO2Photocatalytic self-polishing resin-based composite coating and preparation method thereof |
| CN113736330B (en) * | 2021-09-29 | 2022-09-27 | 哈尔滨工程大学 | Flower-like TiO 2 Photocatalytic self-polishing resin-based composite coating and preparation method thereof |
| CN115069310A (en) * | 2022-03-21 | 2022-09-20 | 福建工程学院 | TPU/TiO 2 Preparation method and application of/PDA (personal digital Assistant) composite three-dimensional porous foam |
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