CN102786647B - Biodegradable polyurethane oil-absorbing material and preparation method thereof - Google Patents
Biodegradable polyurethane oil-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a biodegradable polyurethane oil-absorbing material. The oil-absorbing material is prepared from raw materials comprising biodegradable oligomer polyol with hydroxyl value of 200-400 mgKOH / g, diisocyanate, polyether polysiloxane dihydric alcohol, a catalyst, a foam stabilizing agent and a foaming agent through a polymerization reaction. The oil-absorbing material has density of 30-100Kg / m<3> and diesel absorption ratio of 50-100 times. The biodegradable polyurethane oil-absorbing material has advantages of biodegradability, no toxicity, no pollution, low cost, and capability of on-site foam. As an ecological polyurethane oil-absorbing material, it can be used for adsorption of water surface spill oil, and is especially suitable for emergency treatment of surface oil spill for river and lake water.
Description
Technical field
The invention belongs to oil absorption material field, be specifically related to the preparation method of a kind of biodegradable polyurethane oil absorption material and this material.
Background technology
Along with the development of world industry, greasy dirt discharge increases day by day, and the approach of oil leak and chance are also more and more, and particularly maritime shipping causes lets out oil accident on a large scale.As hitting a submerged reef in Alaska, in March, 1,989 21.4 ten thousand tons of giant tanker of the 24 U.S. " Ai Kesong Valdez " number cause approximately 3.5 ten thousand tons of crude oil leakages; On January 21st, 1993,25 ton Denmark oil tankers of fully loaded crude oil bumped against with another oil tanker in marine site, the Sumatra north and 2.9 ten thousand tons of leakage crude oil; L999 Maltese oil tanker on December 12 " Ai Lika " number leaks nearly ten thousand tons, heavy oil in Atlantic Ocean fracture sinking; In November, 2002 Liberia's nationality oil tanker " prestige " number disintegrates and sinks in marine site, the Spain northwestward, at least 6.3 ten thousand tons of heavy oil spills, and it is contaminated that France, Spain and Portugal amount to thousands of kilometers of seashores, tens thousand of seabird death; The Russian oil tanker " volga oil 139 " number that loads 4700 tons of heavy oil in November, 2007 meets with blast in straits, Kerch, the sinking of disintegrating, and more than 3000 ton of heavy oil spill, causes accident sea area and suffers severe contamination; On April 20th, 2010, the drilling unit that British Petroleum Company p.l.c. rents in the U.S. Gulfian " deep water local horizon " is blasted, and causes bulk petroleum to leak, and leads to an economy and environment tragedy; On July 16th, 2010, oil pipeline blast in Dalian causes 1500 tons of crude oil leakages and enters sea.According to Chinese maritime patrol ship, within 13: 30 on the 19th, monitor that result shows, approximately 430 square kilometres, contaminated marine site, wherein serious pollution marine site is about 12 square kilometres, generally pollutes marine site and is about 52 square kilometres.
At present, serious threat of marine oil pollution is to the ecotope in coastal waters, and the oil pollution of administering near sea water environment has been very urgent.But sea pollution by oil is administered and also lacked effective method, main dependence reduced opportunities for contamination, and the oily(waste)water of source of pollution is carried out to pre-treatment, controls greasy dirt and arranges extra large total amount etc.The problem for preventing that pollution of the sea solution from leaking crude oil proposing in developed country's summit meeting in July, 1989, has nowadays become one and has looked steadily throughout the world white great research topic.Oil absorption material causes wide people's great attention just in this case.As the application number patent of invention that is 200510040379.X disclose a kind of by long alkyl chain methacrylates, vinylformic acid short-chain ester as monomer, take water as disperse phase, the porous high oil adsorption resin that adds dispersion agent, initiator, linking agent and organic solvent to obtain through polymerization.Its oil suction multiplying power and oil suction efficiency are high, resin can be reused simultaneously.
The cost of high oil-absorbing resin is compared higher with common oil absorption material (as polypropylene fibre, bombax cotton etc.), when how to improve oil absorptiveness, reducing costs is the key issue of high oil absorbency Materials.
Summary of the invention
The object of the invention is do not there is biodegradable, contaminate environment, high in cost of production problem in order to overcome existing oil absorption material, provide a kind of have biodegradable, nontoxic, pollution-free, cost is low, can foam-in-place etc. the biodegradable polyurethane oil absorption material of advantage.
Object of the present invention can reach by following measures:
A kind of urethane oil absorption material, this oil absorption material is biodegradable polyurethane foam materials, it is raw material that this oil absorption material be take biodegradation type oligomeric polyols, vulcabond, polyethers polysiloxane binary alcohol, catalyzer, suds-stabilizing agent and the whipping agent that hydroxyl value is 200～400mgKOH/g, by polyreaction, prepares; The density of this oil absorption material is 30～100Kg/m
3, inhaling diesel oil multiplying power is 50～100 times.
The weight part consumption of each raw material of oil absorption material is: 100 parts of the biodegradation type oligomeric polyols that hydroxyl value is 200～400mgKOH/g, 20～80 parts of vulcabond, 5～40 parts of polyethers polysiloxane binary alcohols, 0.05～1.5 part of catalyzer, 0.3～2 part of suds-stabilizing agent, 1～10 part of whipping agent.Wherein the preferable amount of vulcabond is 30～70 parts, further preferably 35～60 parts; The preferable amount of polyethers polysiloxane binary alcohol is 10～35 parts, further preferably 15～30 parts; The preferable amount of catalyzer is 0.1～1.0 part, further preferably 0.2～0.8 part; The preferable amount of suds-stabilizing agent is 0.5～1.6 part; The preferable amount of whipping agent is 3～8 parts, further preferably 4.5～7.5 parts.
Hydroxyl value in the present invention is that the biodegradation type oligomeric polyols of 200～400mgKOH/g can make by the following method: polyoxyethylene glycol, glycerine and the vitriol oil are mixed and be made into compound liquefied reagent, again compound liquefied reagent and plant material are mixed, under heating and agitation condition, react.Wherein the mass ratio of each component polyoxyethylene glycol of compound liquefied reagent, glycerine and the vitriol oil is 100: 2～30: 1～6, preferably 100: 10～20: 3～6; The mass ratio of compound liquefied reagent and plant material is 3～6:1.The reaction of compound liquefied reagent and plant material, preferably reaction at 110～150 ℃, the reaction times is preferably 1～3h.
Plant material can be selected fibrous material for farming, fruits and seeds raw material, as is at least one in agricultural crop straw, bagasse, rice husk, xylon, W-Gum, green starch, tapioca (flour), sweet potato starch, sweet potato starch, yam starch, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch.
Polyoxyethylene glycol in the present invention further adopts poly(oxyethylene glycol) 400.
Polyethers polysiloxane binary alcohol in the present invention, claim again polyethersiloxanediol, this material is found in the development of the polyethers polysiloxane binary alcohol modified aqueous polyurethane coating-forming agent of Dong Qingqing etc., synthetic and the performance of the polyethersiloxanediol modified aqueous polyurethane of Song Haixiang etc., in the documents such as the Preparation of the Coating Agent on the Fabric with Polyurethane Modified by Polyethersiloxanediol of D Qing etc.
The vitriol oil in the present invention, unless otherwise indicated outside, generally refer to that mass concentration is more than or equal to 70% aqueous sulfuric acid; The vitriol oil in embodiment specifically refers to that massfraction is 98.3% the vitriol oil.
Vulcabond in the present invention can be one or more in tolylene diisocyanate, diphenylmethanediisocyanate, the many phenyl isocyanate of polymethine.The index of vulcabond need be controlled between 0.60～1.05, and the index of vulcabond refers to the ratio of the amount of vulcabond amount of substance and hydroxylated material.
The polyethers polysiloxane binary alcohol that the hydroxyl value that polyethers polysiloxane binary alcohol in the present invention is preferably selected is 50～200mgKOH/g.
Catalyzer in the present invention can in dibutyl tin laurate, stannous octoate, triethylene diamine, tetrem alkene triamine one or more.
Suds-stabilizing agent in the present invention is organic silicon modified by polyether tensio-active agent.Whipping agent is deionized water.
The polyreaction of each raw material of oil absorption material can adopt the polymerization process of urethane, its biodegradation type oligomeric polyols, polyethers polysiloxane binary alcohol, catalyzer, suds-stabilizing agent and whipping agent that further to comprise the steps: hydroxyl value be 200～400mgKOH/g in the present invention, at 20 ℃～30 ℃, stir, standing 10～60 minutes; Add rapidly vulcabond, stir 5～20s, pour immediately foaming mould into and foam; Foam is the slaking demoulding in 1～4 hour at 20 ℃～30 ℃, obtains biodegradable polyurethane oil absorption material.
The present invention further discloses the preparation method of above-mentioned biodegradable polyurethane oil absorption material: the biodegradation type oligomeric polyols that the hydroxyl value of take is 200～400mgKOH/g, vulcabond, polyethers polysiloxane binary alcohol, catalyzer, suds-stabilizing agent and whipping agent are raw material, by polyreaction, prepare; The density of the oil absorption material obtaining is 30～100Kg/m
3, inhaling diesel oil multiplying power is 50～100 times.Each optimum condition in this law and raw material are as mentioned above.
Beneficial effect of the present invention:
1, this biodegradable polyurethane oil absorption material adopts farm crop or agricultural waste material to make raw material, with low cost, has good using value and promotion prospect.
2, compare with existing general oil absorption material, urethane oil absorption material of the present invention has good biodegradable and environment friendliness.
3, this biodegradable polyurethane oil absorption material can be in oil spilling foam-in-place moulding, and convenient transportation is compared with existing oil absorption material, can greatly reduce storage and transport space.
4, this biodegradable polyurethane oil absorption material moulding process is simple, less investment, and production efficiency is high, is especially applicable to rivers,lakes and seas water surface emergency disposal of spill oil at sea.
Accompanying drawing explanation
Fig. 1 is the biological degradation effect contrast figure of embodiment 1 and comparative example 1.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but following content is not limitation of the present invention.
The suction diesel oil multiplying power testing method of each routine resulting materials is as follows:
The empty cloth bag of nonwoven is immersed in diesel oil after certain hour, take out to drip and drop down the m that weighs after 5min
1, then by m
0oil absorption material packs cloth bag into and immerses in oil product to be measured, when oil absorption material reaches saturated oil suction state, takes out and drips the m that weighs after dropping down
2.
Oil suction multiplying power (g oil/g oil absorption material)=(m
2-m
1-m
0)/m
0
In formula: m
0oil absorption material quality before-oil suction, g;
M
1empty bag quality after-oil suction, g;
M
2oil absorption material and empty bag quality, g after-saturated oil suction.
The density of oil absorption material is according to the mensuration of GB/T 6343-2009(porous plastics and rubber apparent density) measure.
Embodiment 1
By poly(oxyethylene glycol) 400, glycerine and the vitriol oil form compound liquefied reagent by the quality proportioning of 100: 20: 5.By ready liquefied reagent and W-Gum in mass ratio 4:1 transfer to agitator and condenser are housed, in advance in oil bath in the three-necked bottle of constant temperature to 120 ℃, under the condition that stirs and reflux, react 2h, after finishing, reaction transfers to immediately lower than in the cold water of 40 ℃, be cooled to room temperature, obtaining hydroxyl value is the biodegradation type oligomeric polyols of 280mgKOH/g.
In the reactor of agitator, thermometer, reflux exchanger is housed, add above-mentioned biodegradation type oligomeric polyols 100g, hydroxyl value is 100mgKOH/g polyethers polysiloxane binary alcohol 15g, stannous octoate 0.2g, triethylene diamine 0.5g, suds-stabilizing agent organic silicon modified by polyether tensio-active agent 0.5g, deionized water 5g, at room temperature stir, standing 25 minutes; Add rapidly tolylene diisocyanate 39g, stir 8s, pour immediately foaming mould into and foam; At room temperature slaking of the foam demoulding in 2 hours, obtains biodegradable polyurethane oil absorption material.Its performance is as follows: density is 50Kg/m
3, inhaling diesel oil multiplying power is 75 times.
By poly(oxyethylene glycol) 400, glycerine and the vitriol oil form compound liquefied reagent by the quality proportioning of 100: 10: 5.By ready liquefied reagent and bagasse in mass ratio 5:1 transfer to agitator and condenser are housed, in advance in oil bath in the three-necked bottle of constant temperature to 130 ℃, under the condition that stirs and reflux, react 1.5h, after finishing, reaction transfers to immediately lower than in the cold water of 40 ℃, be cooled to room temperature, obtaining hydroxyl value is the biodegradation type oligomeric polyols of 230mgKOH/g.
In the reactor of agitator, thermometer, reflux exchanger is housed, add above-mentioned biodegradation type oligomeric polyols 100g, hydroxyl value is 90mgKOH/g polyethers polysiloxane binary alcohol 18g, dibutyl tin laurate 0.3g, triethylene diamine 0.5g, suds-stabilizing agent organic silicon modified by polyether tensio-active agent 1.3g, deionized water 6.5g, at room temperature stir, standing 30 minutes; Add rapidly diphenylmethanediisocyanate 46g, stir 10s, pour immediately foaming mould into and foam; At room temperature slaking of the foam demoulding in 2.5 hours, obtains biodegradable polyurethane oil absorption material.Its performance is as follows: density is 45Kg/m
3, inhaling diesel oil multiplying power is 52 times.
Embodiment 3
By poly(oxyethylene glycol) 400, glycerine and the vitriol oil form compound liquefied reagent by the quality proportioning of 100: 18: 5.By ready liquefied reagent and bagasse in mass ratio 5:1 transfer to agitator and condenser are housed, in advance in oil bath in the three-necked bottle of constant temperature to 130 ℃, under the condition that stirs and reflux, react 1.5h, after finishing, reaction transfers to immediately lower than in the cold water of 40 ℃, be cooled to room temperature, obtaining hydroxyl value is the biodegradation type oligomeric polyols of 310mgKOH/g.
In the reactor of agitator, thermometer, reflux exchanger is housed, add above-mentioned biodegradation type oligomeric polyols 100g, hydroxyl value is 150mgKOH/g polyethers polysiloxane binary alcohol 30g, dibutyl tin laurate 0.35g, triethylene diamine 0.5g, suds-stabilizing agent organic silicon modified by polyether tensio-active agent 1.6g, deionized water 7.2g, at room temperature stir, standing 35 minutes; Add rapidly many phenyl isocyanate of polymethine 60g, stir 12s, pour immediately foaming mould into and foam; At room temperature slaking of the foam demoulding in 3 hours, obtains biodegradable polyurethane oil absorption material.Its performance is as follows: density is 45Kg/m
3, inhaling diesel oil multiplying power is 61 times.
By poly(oxyethylene glycol) 400, glycerine and the vitriol oil form compound liquefied reagent by the quality proportioning of 100: 16: 4.By ready liquefied reagent and bagasse in mass ratio 3.5:1 transfer to agitator and condenser are housed, in advance in oil bath in the three-necked bottle of constant temperature to 135 ℃, under the condition that stirs and reflux, react 2h, after finishing, reaction transfers to immediately lower than in the cold water of 40 ℃, be cooled to room temperature, obtaining hydroxyl value is the biodegradation type oligomeric polyols of 245mgKOH/g.
In the reactor of agitator, thermometer, reflux exchanger is housed, add above-mentioned biodegradation type oligomeric polyols 100g, hydroxyl value is 120mgKOH/g polyethers polysiloxane binary alcohol 20g, stannous octoate 0.4g, trolamine 1.1g, suds-stabilizing agent organic silicon modified by polyether tensio-active agent 0.8g, deionized water 4.5g, at room temperature stir, standing 15 minutes; Add rapidly tolylene diisocyanate 15g, diphenylmethanediisocyanate 26g, stirs 15s, pours immediately foaming mould into and foams; At room temperature slaking of the foam demoulding in 2.5 hours, obtains biodegradable polyurethane oil absorption material.Its performance is as follows: density is 80Kg/m
3, inhaling diesel oil multiplying power is 85 times.
Embodiment 5
By poly(oxyethylene glycol) 400, glycerine and the vitriol oil form compound liquefied reagent by the quality proportioning of 100: 10: 5.By ready liquefied reagent and bagasse in mass ratio 5:1 transfer to agitator and condenser are housed, in advance in oil bath in the three-necked bottle of constant temperature to 130 ℃, under the condition that stirs and reflux, react 1.5h, after finishing, reaction transfers to immediately lower than in the cold water of 40 ℃, be cooled to room temperature, obtaining hydroxyl value is the biodegradation type oligomeric polyols of 230mgKOH/g.
In the reactor of agitator, thermometer, reflux exchanger is housed, add above-mentioned biodegradation type oligomeric polyols 100g, hydroxyl value is 62mgKOH/g polyethers polysiloxane binary alcohol 25g, trolamine 0.8g, suds-stabilizing agent organic silicon modified by polyether tensio-active agent 0.6g, deionized water 6g, at room temperature stirs, standing 30 minutes; Add rapidly tolylene diisocyanate 15g, many phenyl isocyanate of polymethine 35g, stirs 8s, pours immediately foaming mould into and foams; At room temperature slaking of the foam demoulding in 3 hours, obtains biodegradable polyurethane oil absorption material.Its performance is as follows: density is 45Kg/m
3, inhaling diesel oil multiplying power is 75 times.
Comparative example 1
In the reactor of agitator, thermometer, reflux exchanger is housed, add polyether Glycols N210 (Jiangsu Zhongshang Chemical Co., Ltd.) 100g, hydroxyl value is 100mgKOH/g polyethers polysiloxane binary alcohol 15g, stannous octoate 0.2g, triethylene diamine 0.5g, suds-stabilizing agent organic silicon modified by polyether tensio-active agent 0.5g, deionized water 5g, at room temperature stir, standing 25 minutes; Add rapidly tolylene diisocyanate 39g, stir 8s, pour immediately foaming mould into and foam; At room temperature slaking of the foam demoulding in 2 hours, obtains urethane oil absorption material.Its performance is as follows: density is 50Kg/m
3, inhaling diesel oil multiplying power is 66 times.
Effect example 1
Embodiment 1, the synthetic urethane oil absorption material of comparative example 1 are accurately taken to the sample of 1g left and right, put into 50ml and contain (the preparation of buffered soln: 0.025moleNa of the diastatic buffered soln of 15mg
2hPO
4+ 0.025molekH
2pO
4with deionized water dissolving, be diluted to 1L, control PH=7), difference standing 18 in the Water Tank with Temp.-controlled of 27 ℃, after 36,72,120h, take out, with deionized water, repeatedly rinse for several times, again film is dried to constant weight in vacuum drying oven, calculate its rate of weight loss, rate of weight loss (%)=(sample weight after original sample weight-decomposition)/original sample weight * 100.Result as shown in Figure 1.Result shows, after standing degraded 120h, the biodegradable polyurethane oil absorption material rate of weight loss that embodiment 1 obtains is up to more than 20.6%, and the urethane oil absorption material that comparative example 1 obtains is after standing degraded 120h, and rate of weight loss is only 2.25% left and right.Illustrate that the starch-grafted aqueous polyurethane of the present invention is not only inhaled diesel oil multiplying power higher, and biological degradation successful is improved.
Claims (7)
1. a biodegradable polyurethane oil absorption material, it is characterized in that: it is raw material that this oil absorption material be take biodegradation type oligomeric polyols, vulcabond, polyethers polysiloxane binary alcohol, catalyzer, suds-stabilizing agent and the whipping agent that hydroxyl value is 200 ~ 400mgKOH/g, by polyreaction, prepares; The density of this oil absorption material is 30～100Kg/m
3, inhaling diesel oil multiplying power is 50～100 times;
The weight part consumption of this each raw material of oil absorption material is: 100 parts of the biodegradation type oligomeric polyols that hydroxyl value is 200 ~ 400mgKOH/g, 20～80 parts of vulcabond, 5～40 parts of polyethers polysiloxane binary alcohols, 0.05～1.5 part of catalyzer, 0.3～2 part of suds-stabilizing agent, 1～10 part of whipping agent;
Described hydroxyl value is that the biodegradation type oligomeric polyols of 200 ~ 400mgKOH/g makes by the following method: polyoxyethylene glycol, glycerine and the vitriol oil are mixed and be made into compound liquefied reagent, again compound liquefied reagent and plant material are mixed, under heating and agitation condition, react; Wherein said plant material is at least one in agricultural crop straw, bagasse, rice husk, xylon, W-Gum, green starch, tapioca (flour), sweet potato starch, sweet potato starch, yam starch, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch; Described polyoxyethylene glycol is poly(oxyethylene glycol) 400.
2. oil absorption material according to claim 1, is characterized in that the mass ratio of each component polyoxyethylene glycol of described compound liquefied reagent, glycerine and the vitriol oil is 100: 2～30: 1～6; The mass ratio of compound liquefied reagent and plant material is 3～6:1.
3. oil absorption material according to claim 1, is characterized in that described compound liquefied reagent and plant material react at 110～150 ℃, and the reaction times is 1～3h.
4. oil absorption material according to claim 1, it is characterized in that described vulcabond is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, the many phenyl isocyanate of polymethine, the index of vulcabond is in 0.60～1.05 scope; The hydroxyl value of described polyethers polysiloxane binary alcohol is 50 ~ 200mgKOH/g; Described catalyzer is one or more in dibutyl tin laurate, stannous octoate, triethylene diamine, tetrem alkene triamine.
5. oil absorption material according to claim 1, is characterized in that described suds-stabilizing agent is organic silicon modified by polyether tensio-active agent; Described whipping agent is deionized water.
6. oil absorption material according to claim 1, it is characterized in that described polyreaction biodegradation type oligomeric polyols, polyethers polysiloxane binary alcohol, catalyzer, suds-stabilizing agent and whipping agent that to comprise the steps: hydroxyl value be 200 ~ 400mgKOH/g, at 20 ℃～30 ℃, stir, standing 10～60 minutes; Add rapidly vulcabond, stir 5～20s, pour immediately foaming mould into and foam; Foam is the slaking demoulding in 1～4 hour at 20 ℃～30 ℃, obtains biodegradable polyurethane oil absorption material.
7. the preparation method of a biodegradable polyurethane oil absorption material, it is characterized in that: the biodegradation type oligomeric polyols that the hydroxyl value of take is 200 ~ 400mgKOH/g, vulcabond, polyethers polysiloxane binary alcohol, catalyzer, suds-stabilizing agent and whipping agent are raw material, by polyreaction, prepare; The density of the oil absorption material obtaining is 30～100Kg/m
3, inhaling diesel oil multiplying power is 50～100 times;
The weight part consumption of this each raw material of oil absorption material is: 100 parts of the biodegradation type oligomeric polyols that hydroxyl value is 200 ~ 400mgKOH/g, 20～80 parts of vulcabond, 5～40 parts of polyethers polysiloxane binary alcohols, 0.05～1.5 part of catalyzer, 0.3～2 part of suds-stabilizing agent, 1～10 part of whipping agent;
Described hydroxyl value is that the biodegradation type oligomeric polyols of 200 ~ 400mgKOH/g makes by the following method: polyoxyethylene glycol, glycerine and the vitriol oil are mixed and be made into compound liquefied reagent, again compound liquefied reagent and plant material are mixed, under heating and agitation condition, react; Wherein said plant material is at least one in agricultural crop straw, bagasse, rice husk, xylon, W-Gum, green starch, tapioca (flour), sweet potato starch, sweet potato starch, yam starch, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch; Described polyoxyethylene glycol is poly(oxyethylene glycol) 400.
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| CN104231213B (en) * | 2013-06-17 | 2016-12-28 | 江苏瑞丰科技实业有限公司 | A kind of preparation of low cost height oil absorptive function material |
| CN103360568B (en) * | 2013-07-24 | 2015-04-01 | 淮阴师范学院 | Polyurethane elastomer preparation method using starch liquefaction products |
| CN105315431A (en) * | 2014-07-29 | 2016-02-10 | 江苏瑞丰科技实业有限公司 | High-power oil absorption gel material and preparation method therefor |
| CN104530383A (en) * | 2014-12-31 | 2015-04-22 | 海南大学 | Method for preparing polyurethane foam through rice straw and prepared polyurethane foam |
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| CN107556772A (en) * | 2017-10-13 | 2018-01-09 | 重庆晋豪美耐皿制品有限公司 | Novel straw oil absorption material and preparation method thereof |
| CN107670653B (en) * | 2017-11-13 | 2020-09-11 | 太原理工大学 | Papermaking sludge fiber microporous oil absorption compound and preparation method and application thereof |
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