CN106519195A - Preparing method of pectinate polyester and modified polylactic acid fibers - Google Patents
Preparing method of pectinate polyester and modified polylactic acid fibers Download PDFInfo
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- CN106519195A CN106519195A CN201611018543.1A CN201611018543A CN106519195A CN 106519195 A CN106519195 A CN 106519195A CN 201611018543 A CN201611018543 A CN 201611018543A CN 106519195 A CN106519195 A CN 106519195A
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- polyester
- polylactic acid
- pectination
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Materials For Medical Uses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparing method of pectinate polyester and modified polylactic acid fibers. The preparing method is characterized in that methyl methacrylate and hydroxyethyl methylacrylate monomers react, a macromolecular initiator of which the side chains contain terminal hydroxyl groups is obtained, and accordingly, the ring opening polymerization of cyclic ester monomers (for example, glycolide, lactide or caprolactone) is initiated to obtain pectinate polyester; and then, blending electrospinning is carried out on the pectinate polyester and polylactic acid to obtain modified polylactic acid fibers. First, the main chain of the pectinate polyester is a methyl methacrylate and hydroxyethyl methylacrylate copolymerized structure, is flexible and elastic and performs toughening and reinforcing functions on a polylactic acid base body, and the polylactic acid fibers with different modified effects can be obtained by regulating the ratio of poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate) chain segments in the copolymerized structure; secondly, the pectinate polyester carries the polyester side chains, and the problem of poor compatibility of the main chain and the polylactic acid is solved; and therefore, the modified polylactic acid fibers have better mechanical properties than common polylactic acid fibers.
Description
Technical field
A kind of the invention belongs to polymeric material field, more particularly to the preparation side of pectination polyester and modified polylactic acid fiber
Method.
Background technology
Since 21st century, plastic is flooded with the life of the mankind, serves as highly important effect, but traditional modeling
Time needed for material products degraded is generally up to upper century-old even more long, accumulations of a large amount of waste or used plastics result in it is serious " in vain
Color pollutes ".In addition, the raw material of conventional plastic derives from the non-renewable resources such as oil, with the day by day exhausted of fossil resources,
Traditional plastics industry will also be on the hazard, therefore the friendly Biodegradable material petroleum replacing base plastics of development environment are produced
Product, are increasingly becoming the focus of research and development.
Polylactic acid（PLA）With good biocompatibility and biodegradability, therefore which is in pharmaceutical carrier, tissue work
Each field such as journey, engineering plastics obtains extensive concern.But due to polylactic acid fragility is high, hardness is big, thermal property is bad etc. because
Element is restricted its range of application, and simple polylactic acid can not meet the demand that people use.
Hydroxyethyl methylacrylate（HEMA）Polymer be a kind of hydrophilic flexible gel state polymer, with good
Describing property of biology, is mainly used as the medical macromolecular materials of ophthalmology and dentistry, is the main material for manufacturing contact lenss.But its
Body polymerizate is a kind of gel state cross-linked structure, it is impossible to dissolves and does not melt, thus is difficult to be introduced into polylactic acid-based biology
Degradable poly ester structure；Methyl methacrylate (MMA) is the monomer of synthetic lucite, and it can be with other vinyl monomers altogether
It is poly- to obtain flexible and resilient material, but itself does not have the functional group for causing ring-type esters monomer ring-opening polymerisation.On
State bi-material incompatible with polylactic acid, using conventional meanses it is difficult to individually be applied in poly-lactic acid material, reach and change
The purpose of kind acid fiber by polylactic.
The content of the invention
The present invention gives the preparation method of a kind of pectination polyester and modified polylactic acid fiber, prepared by the method modified poly-
Acid fiber has more preferable mechanical property.
The invention provides a kind of preparation method of pectination polyester, comprises the following steps：
A) methyl methacrylate and hydroxyethyl methylacrylate are entered under the first catalyst action in solvents tetrahydrofurane
Row reaction, obtains macromole evocating agent, and the catalyst is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile)；
B) by above-mentioned made macromole evocating agent and ring-type esters monomer under the second catalyst action, carry out in solvent anti-
Should, combed polyester is obtained, the catalyst is stannous chloride or stannous octoate, and the solvent is toluene, dichloromethane or trichlorine
One kind in methane.
Preferably, the methyl methacrylate of synthetic macromolecule initiator is 9 with the volume ratio of hydroxyethyl methylacrylate:
1、8:2、7:3、6:4。
Preferably, the macromole evocating agent is 1 with the mol ratio of caprolactone monomer reaction:18~1:90.
The invention provides a kind of preparation method of modified polylactic acid fiber, comprises the following steps：
A) methyl methacrylate and hydroxyethyl methylacrylate are entered under the first catalyst action in solvents tetrahydrofurane
Row reaction, obtains macromole evocating agent, and the catalyst is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile)；
B) by above-mentioned made macromole evocating agent and ring-type esters monomer under the second catalyst action, with solvent in carry out it is anti-
Should, pectination polyester is obtained, the catalyst is stannous chloride or stannous octoate, and the solvent is toluene, dichloromethane or trichlorine
One kind in methane；
C) by the pectination polyester, polylactic acid blended under agitation in chloroform, polydactyl acid is prepared by electrical spinning method
Fiber.
Preferably, the pectination polyester is 5 ~ 30 weight portions, and the polylactic acid is 70 ~ 95 weight portions.
The invention provides the preparation method of a kind of pectination polyester and modified polylactic acid fiber, the method is by methacrylic acid
Methyl ester is reacted under the first catalyst action with hydroxyethyl methylacrylate, obtains macromole evocating agent；Then, using upper
In the presence of the second initiator, in solvent, reaction obtains pectination polyester with ring-type esters monomer to state macromole evocating agent；Most
Afterwards, above-mentioned pectination polyester and polylactic acid are blended in chloroform, modified polylactic acid fiber is prepared using electrical spinning method.
Beneficial effects of the present invention are：
Main chain is prepared for for polymethyl methacrylate and hydroxyethyl methylacrylate, comb of the side chain for pla-pcl by copolymerization
Shape polyester, can control side chain density by adjusting methyl methacrylate with hydroxyethyl methylacrylate copolymerization ratios；Pectination
Polyester is existing flexible and flexible, solves its bottleneck with the poor compatibility of polylactic acid again；The pectination polyester and poly- breast
The characteristics of modified polylactic acid fiber film prepared by acid blending not only can preserve polylactic acid itself, while improve pure acid fiber by polylactic
Mechanical property.
Description of the drawings
Fig. 1 causes for the polymethyl methacrylate-hydroxyethyl methylacrylate macromole prepared in the embodiment of the present invention 1
Agent and methyl methacrylate, the infrared spectrogram of hydroxyethyl methylacrylate monomer.
The infrared spectrogram of pectination polycaprolactone co-polymers of the Fig. 2 for preparing in the embodiment of the present invention 5.
The hydrogen nuclear magnetic resonance spectrogram of pectination polycaprolactones of the Fig. 3 for preparing in the embodiment of the present invention 7.
The Polycaprolactone modified polylactic acid of pectination of different side chain density of the Fig. 4 for preparing in the embodiment of the present invention 10 ~ 13 is fine
The mechanical property comparison diagram of dimension.
Fig. 5 is that the polydactyl acid prepared in the pure acid fiber by polylactic for preparing and embodiment 10 in the embodiment of the present invention 9 is fine
The stress-strain diagram of dimension.
As shown in figure 1, methyl methacrylate（MMA）In 2956.33 cm in the infrared spectrogram of monomer-1、1726.53
cm-1、1637.23 cm-1、1325.65 cm-1Occurs strong absworption peak everywhere, C on the stretching vibration of C-H, ester group on point methylene
The stretching vibration of C-O on the stretching vibration of=O, the stretching vibration of C=C and ester group；, in hydroxyethyl methylacrylate（HEMA）Monomer
Infrared spectrogram in, in 3442.98 cm-1、2957.66 cm-1、1716.93 cm-1、1636.18 cm-1、1321.49 cm-1Occur strong absworption peak at five, be respectively belonging on the stretching vibration of-OH, methylene C=O on the stretching vibration of C-H, ester group
The stretching vibration of C-O on stretching vibration, the stretching vibration of C=C and ester group；And react the poly hydroxy ethyl acrylate after terminating
The contrast of infrared spectrogram and monomer understand, be in 1637.22 cm-1There is not absworption peak in left and right, and other wave numbers occur
Corresponding absworption peak, illustrate that C=C has disappeared, it was demonstrated that polymethyl methacrylate-hydroxyethyl methylacrylate macromole
The synthesis of initiator.
As shown in Fig. 2 the infrared spectrogram of the pectination polycaprolactone obtained by embodiment 5.2946.36cm in figure-1It is
Belong to the stretching vibration peak of C-H on the methylene of methyl methacrylate and hydroxyethyl methylacrylate on main chain, 1724.07
cm-1It is the absworption peak of carbonyl, partial dislocation, 1190.93 cm occurs before and after reaction-1It is the stretching vibration peak of C-O on ester group；
Product is in 731.92cm in addition-1On occur in that the stretching vibration peak of five connected methylene C-H on polycaprolactone, and original position in
3442.98cm-1The stretching vibration peak of-the OH at place disappears substantially, and in 3438.10cm-1Appearance is less to belong to polycaprolactone chain
The stretching vibration peak of-the OH of section end.Analysis shows, reaction product are pectination polycaprolactones.
As shown in figure 3, in 0.88-0.90ppm (- CH2-, a) place is the feature of methylene hydrogen after double bond disconnection on main chain
Peak, 1.28ppm（-CH3, b）Place is the characteristic peak of methyl hydrogen on the upside of main chain, 1.37-1.45ppm（-CH2-, f）、1.67-
1.68ppm（-CH2-, e）、2.31-2.35ppm（-CH2-, d）Place is the methylene on PCL chains in three kinds of diverse locations respectively
The characteristic peak of hydrogen, 3.62-3.69ppm（-OCH3, g）Place is the characteristic peak of the methyl that MMA surveyor's chains end is connected with ester group, in figure
On HEMA side chains, the displacement of two methylene hydrogen being connected with ester group is identical with c displacements on PCL chains, and characteristic peak is in same position
Put.Nuclear magnetic spectrogram analysis further demonstrates the synthesis of pectination polycaprolactone.
As shown in figure 4, the copolymerization ratios by adjusting pectination polyester backbone, can prepare changing for different mechanical properties
Property acid fiber by polylactic.
As shown in figure 5, the pure acid fiber by polylactic breakpoint percentage elongation prepared by embodiment 9 is 45%, and prepared by embodiment 10
Modified polylactic acid fiber breakpoint percentage elongation be changed into 69%, tensile strength also rises to 6.7Mpa from original 4.4Mpa, is modified poly-
The mechanical property of acid fiber is greatly improved.
Specific embodiment
Embodiment is given below to be specifically described to the present invention, it is worth pointing out that following examples be served only for it is right
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, person skilled in the art's root in the field
Protection scope of the present invention is still fallen within according to some nonessential modifications and adaptations that the invention described above content is made to the present invention.
The invention provides a kind of preparation method of pectination polyester, comprises the following steps：
A) methyl methacrylate and hydroxyethyl methylacrylate are entered under the first catalyst action in solvents tetrahydrofurane
Row reaction, obtains macromole evocating agent, and the catalyst is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile)；
B) by above-mentioned made macromole evocating agent and ring-type esters monomer under the second catalyst action, carry out in solvent anti-
Should, pectination polyester is obtained, the catalyst is stannous chloride or stannous octoate, and the solvent is toluene, dichloromethane or trichlorine
One kind in methane.
Wherein the methyl methacrylate of synthetic macromolecule initiator with the volume ratio of hydroxyethyl methylacrylate monomer is
9:1、8:2、7:3、6:4。
The macromole evocating agent is 1 with the mol ratio of ring-type esters monomer:18~1:90, with methyl methacrylate with
The volume ratio of hydroxyethyl methylacrylate monomer is 7:3, macromole evocating agent is 1 with the mol ratio of caprolactone monomer:As a example by 18,
Its reaction path is as follows.
In the preparation process of the macromole evocating agent, reaction temperature is 80 ~ 120 DEG C, and the response time is 10 ~ 16h.
Ring-type esters monomer ring opening polymerisation process temperature is 100-160 DEG C, and the response time is 12 ~ 48h, and the second catalyst adds
Dosage for caprolactone monomer quality 2 ~ 5 ‰.
Present invention also offers a kind of preparation method of modified polylactic acid fiber, by by pectination polyester and PLA solution
Blending electrostatic spinning is prepared.The preparation method of wherein described pectination polyester is same as above, repeats no more.
Polylactic acid of the polylactic acid of the present invention for commercialization, in parts by weight, the pectination polyester is 5 ~ 30 parts, is gathered
Lactic acid is 70 ~ 95 parts.
The blending adopts solution blending, and solution can be using in dichloromethane, chloroform or N-N dimethylformamides
One kind, solution temperature are 25 DEG C -35 DEG C, and mixing time is 10 ~ 18h, preferably 10 ~ 12h.
Embodiment 1
Equipped with magnetic stir bar 100ml flasks in add 0.1g azodiisobutyronitriles, 4.5ml methyl methacrylates,
0.5ml hydroxyethyl methylacrylates, 20ml tetrahydrofurans, a reflux condensing tube with gas inlet-outlet is quickly connected to
On bottle, logical nitrogen drives oxygen 30min out of, reduces nitrogen flow, and reaction is heated to 80 DEG C, stirring reaction 12 by water seal gas outlet
Hour, room temperature is cooled to, 12h is precipitated in 60ml normal hexane, sucking filtration, vacuum drying 12h obtain white powder polymer.
Embodiment 2
In adjustment macromole evocating agent building-up process, monomer addition is 4ml methyl methacrylates and 1ml hydroxyethyl methacrylates
Ethyl ester, other steps prepare macromole evocating agent with embodiment 1.
Embodiment 3
In adjustment macromole evocating agent building-up process, monomer addition is 3.5ml methyl methacrylates and 1.5ml metering systems
Sour hydroxyl ethyl ester, other steps prepare macromole evocating agent with embodiment 1.
Embodiment 4
In adjustment macromole evocating agent building-up process, monomer addition is 3ml methyl methacrylates and 2ml hydroxyethyl methacrylates
Ethyl ester, other steps prepare macromole evocating agent with embodiment 1.
Embodiment 5
The initiator PMMA-HEMA 1.1604g, close prepared during embodiment 1 is added in the reaction bulb equipped with magnetic stir bar
Envelope, three removing oxygen of the logical nitrogen of evacuation, stannous octoate 0.09g, caprolactone 5g and toluene solvant 30ml are used successively repeatedly
Syringe is added, adjustment reaction pressure of the inside of a bottle after being warming up to 120 DEG C, and stirring reaction 24h is cooled to room temperature, in 100ml petroleum ether
Interior precipitation 12h, room temperature in vacuo are dried 12h, obtain white crystalline polymer.
Embodiment 6
Using the macromole evocating agent prepared in embodiment 2, other steps synthesize pectination polycaprolactone with embodiment 5.
Embodiment 7
Using the macromole evocating agent prepared in embodiment 3, other steps synthesize pectination polycaprolactone with embodiment 5.
Embodiment 8
Using the macromole evocating agent prepared in embodiment 4, other steps synthesize pectination polycaprolactone with embodiment 5.
Embodiment 9
0.3871g polylactic acid, 0.02g benzyltriethylammoinium chlorides, 3ml are added in will be equipped with the 10ml vials of magnetic stir bar
Chloroform, is configured to the blend solution of 8wt% mass concentrations, 25 DEG C of stirring 12h；Pour the blend solution being stirred into 5ml medical
Syringe, on high-voltage electrostatic spinning device.Using the syringe needle of 0.9mm diameters, voltage 7KV, receiver board and syringe needle are set
Distance is 15cm, and spinning flow velocity is 6 μ L/min；The fibrous membrane that Electrospun is obtained is vacuum dried 24h in 30 DEG C, obtains pure poly- breast
Sour fiber.
Embodiment 10
The pectination polycaprolactone copolymerization prepared during 0.03871g embodiments 5 are added in will be equipped with the 10ml vials of magnetic stir bar
Thing, 0.3484g polylactic acid, 0.02g benzyltriethylammoinium chlorides, 3ml chloroforms, are configured to the blend solution of 8wt% mass concentrations,
25 DEG C of stirring 12h；Pour the blend solution being stirred the injector for medical purpose of 5ml into, on high-voltage electrostatic spinning device.Make
With the syringe needle of 0.9mm diameters, voltage 7KV is set, receiver board is 15cm with syringe needle distance, and spinning flow velocity is 6 μ L/min；Electrostatic
The fibrous membrane that spinning is obtained is vacuum dried 24h in 30 DEG C, obtains modified polylactic acid fiber.
Embodiment 11
Using the pectination polycaprolactone co-polymer prepared in embodiment 6, addition and step prepare modified poly- breast with embodiment 10
Sour fiber.
Embodiment 12
Using the pectination polycaprolactone co-polymer prepared in embodiment 7, addition and step prepare modified poly- breast with embodiment 10
Sour fiber.
Embodiment 13
Using the pectination polycaprolactone co-polymer prepared in embodiment 8, addition and step prepare modified poly- breast with embodiment 10
Sour fiber.
Finally it should be noted that above example is only to illustrate technical scheme and unrestricted, although reference
Embodiment has been described in detail to the present invention, it should be appreciated by those skilled in the art that can be to distributing bright technology
Scheme is modified or is replaced on an equal basis, and without deviating from the spirit and scope of technical solution of the present invention, which all should be covered at this
In the middle of bright right.
Claims (7)
1. a kind of preparation method of pectination polyester, it is characterised in that comprise the following steps：
A) methyl methacrylate and hydroxyethyl methylacrylate are entered under the first catalyst action in solvents tetrahydrofurane
Row reaction, obtains macromole evocating agent, and the catalyst is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile)；
B) by above-mentioned made macromole evocating agent and ring-type esters monomer under the second catalyst action, carry out in solvent anti-
Should, pectination polyester is obtained, the catalyst is stannous chloride or stannous octoate, and the solvent is toluene, dichloromethane or trichlorine
One kind in methane.
2. preparation method according to claim 1, it is characterised in that methyl methacrylate used can also be propylene
One kind of the acrylate apoplexy due to endogenous wind such as sour methyl ester, ethyl acrylate, ethyl methacrylate.
3. preparation method according to claim 1, it is characterised in that the methyl-prop of synthesis copolymeric structure macromole evocating agent
E pioic acid methyl ester is 9 with the volume ratio of hydroxyethyl methylacrylate:1、8:2、7:3、6:4.
4. preparation method according to claim 1, it is characterised in that the ring-type esters monomer be lactide, Acetic acid, hydroxy-, bimol. cyclic ester,
One or more of 6-caprolactone etc..
5. preparation method according to claim 1, it is characterised in that the macromole evocating agent is anti-with ring-type esters monomer
The mol ratio answered is 1:18~1:90.
6. a kind of preparation method of modified polylactic acid fiber, it is characterised in that comprise the following steps：
A) methyl methacrylate and hydroxyethyl methylacrylate are entered under the first catalyst action in solvents tetrahydrofurane
Row reaction, obtains macromole evocating agent, and the catalyst is azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile)；
B) by above-mentioned made macromole evocating agent and cyclic polyester monomer under the second catalyst action, carry out in solvent anti-
Should, pectination polyester is obtained, the catalyst is stannous chloride or stannous octoate, and the solvent is toluene, dichloromethane or trichlorine
One kind in methane；
C) by the pectination polyester, polylactic acid blended under agitation in chloroform, polydactyl acid is prepared by electrical spinning method
Fiber.
7. preparation method according to claim 6, it is characterised in that the pectination polyester is 5 ~ 30 weight portions, it is described poly-
Lactic acid is 70 ~ 95 weight portions.
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| CN113801308A (en) * | 2021-09-28 | 2021-12-17 | 长春工业大学 | Fluorine-containing polyester copolymer |
| CN115449021A (en) * | 2022-09-21 | 2022-12-09 | 襄阳三沃航天薄膜材料有限公司 | Side chain crystalline acrylate copolymer, and preparation method and application thereof |
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| CN108250383A (en) * | 2018-01-19 | 2018-07-06 | 盐城工学院 | More degree of cross linking polyurethane elastomers and preparation method thereof |
| CN108250383B (en) * | 2018-01-19 | 2020-09-08 | 盐城工学院 | Polyurethane elastomer with multiple crosslinking degrees and preparation method thereof |
| CN112111036A (en) * | 2020-09-14 | 2020-12-22 | 长春工业大学 | Polymer for endowing amphiphobicity of polylactic acid |
| CN113603869A (en) * | 2021-07-13 | 2021-11-05 | 华中科技大学 | Polyester brush-shaped polymer, one-pot synthesis method and application thereof |
| CN113603869B (en) * | 2021-07-13 | 2022-04-26 | 华中科技大学 | Polyester brush-shaped polymer, one-pot synthesis method and application thereof |
| CN113801308A (en) * | 2021-09-28 | 2021-12-17 | 长春工业大学 | Fluorine-containing polyester copolymer |
| CN115449021A (en) * | 2022-09-21 | 2022-12-09 | 襄阳三沃航天薄膜材料有限公司 | Side chain crystalline acrylate copolymer, and preparation method and application thereof |
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