CN113736015A - Bionic polymer containing dopamine functional group and preparation method thereof - Google Patents

Bionic polymer containing dopamine functional group and preparation method thereof Download PDF

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CN113736015A
CN113736015A CN202111043296.1A CN202111043296A CN113736015A CN 113736015 A CN113736015 A CN 113736015A CN 202111043296 A CN202111043296 A CN 202111043296A CN 113736015 A CN113736015 A CN 113736015A
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polymerization
functional groups
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CN113736015B (en
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钟蔚华
朱波
张鹏
朱晓琳
宫平
叶丽莎
白昌龙
孙宗宝
金子明
曲志敏
虢忠仁
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Shandong Non Metallic Material Research Institute
University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention belongs to the field of bionic high molecular materials, and particularly provides a bionic polymer containing dopamine functional groups and a preparation method thereof.

Description

Bionic polymer containing dopamine functional group and preparation method thereof
Technical Field
The invention belongs to the field of bionic high polymer materials, and particularly relates to a bionic polymer containing dopamine functional groups and a preparation method thereof.
Background
The aramid fiber reinforced composite material has excellent comprehensive performance and is widely applied to the research, development and production of new-generation weaponry in China. The aramid fiber reinforced composite material has excellent elasticity resistance, light weight, impact resistance and stealth performance, and is widely applied to missile shells, composite armors and airplane structure shells; meanwhile, the composite material has the characteristics of high strength, high toughness, low density, high heat resistance and the like, and can greatly improve the impact resistance of shells of airplanes and rockets, the characteristic coefficient of containers and the like; the high-dielectric-constant high-voltage dielectric ceramic has the properties of low dielectric constant, low dielectric loss factor, high corrosion resistance and the like, and is also widely applied to the fields of aircraft radar radomes and the like. The aramid fiber reinforced resin composite material is also applied to main bearing structures of American and French fighters, vehicle bodies of combat vehicles and other important parts, and missile shells such as SS-24, SS-25, SS-27 and the like. A large amount of aramid fiber composite materials are laid on the surface of the B-2A fuselage of the American stealth bomber, so that the stealth effect of the American stealth bomber is improved. In addition, the aramid fiber composite material is also applied to a dual-grid antenna grid front reflecting surface on the communication satellite of 'Venus 1' and 'Xinnuo 6'.
Although the aramid fiber composite material is widely applied to military equipment, the surface of the aramid fiber composite material is lack of active groups based on the characteristics of high symmetry, high orientation degree and crystallinity of aramid fiber molecules, so that the bonding strength of the aramid fiber and a resin interface is low, the interlayer shear strength is poor, and the further application of the aramid fiber composite material is limited. At present, the technical field of aramid fiber interface modification in China has been advanced to a certain extent, and the aramid fiber interface performance can be better improved, but the modification technology has the defects of easy damage to the mechanical property of a fiber body, complex and time-consuming modification steps and difficulty in meeting the requirements of in-situ continuous treatment of fiber spinning. How under the condition that does not harm aramid fiber body, realize quick, the high efficiency modification to aramid fiber surface, promote aramid fiber and resin's interfacial properties by a wide margin, be the main point place in this field.
Through observation of adhesion of mussels (Mussel) on rocks, the Mussel secreted foot proteins (Mfps) are found to have extremely strong adhesion, and the adhesion is mainly derived from dopamine and lysine-rich proteins contained in the foot proteins. The mussel foot protein not only can have strong adhesiveness in a dry environment, but also can be firmly adhered to rocks even in a humid environment or even underwater. Polydopamine is widely applied in the biomedical field, such as antifouling and antibacterial, cell engineering, tissue engineering, biological glue and other fields. In 2007, researchers synthesize polydopamine for the first time, the polydopamine has very strong adhesiveness, the dopamine can undergo spontaneous oxidative polymerization under the weak alkaline aerobic condition in a buffer solution, the polymerization is simple, other reagents are not needed, a sample to be processed is directly placed into the buffer solution, the self polymerization of the dopamine can be initiated under the weak alkaline aerobic condition, and the polymerized dopamine can be adhered to almost all substrates of macromolecules, metals and inorganic non-metals, and even can be adhered to cells (Science, 2007, 318(5849): 426-30).
US patent 8784895 discloses a method for modifying a fiber with polydopamine, which can achieve better modification results and almost does not damage the mechanical properties of the fiber body. But the method is also difficult to be used for the rapid continuous surface treatment of aramid fibers. Firstly, the time of the dopamine spontaneous oxidation polymerization deposition process is long, a 40 nm-thick polydopamine film can be formed only after 24 hours, and the method cannot be suitable for the requirements of continuous sizing modification of aramid fibers. Meanwhile, under the action of an oxidant, the catechol group of dopamine is oxidized into catechol, so that the adhesion effect with organic fibers is weakened.
Therefore, developing a more suitable dopamine modification method for aramid fibers becomes one of the problems to be solved in the field.
Disclosure of Invention
Aiming at various defects in the prior art, the invention provides a bionic polymer containing dopamine functional groups and a preparation method thereof, the bionic polymer is a random copolymer and contains the dopamine functional groups, and has a series of advantages of good phenolic hydroxyl controllability, strong adhesiveness, small using amount, simple process, suitability for industrial production and the like.
The main principle of the invention is as follows:
aiming at the problems of the existing fiber surface modification technology, the inventor prepares the water-soluble bionic mussel polymer modified fiber surface by taking a methacrylic acid polymer as a main chain so as to realize the rapid surface modification of the fiber and the strong combination of the fiber and the epoxy resin. The functional side group of dopamine is introduced into the main chain, so that the functional side group of dopamine can be rapidly assembled on the surface of the fiber in a water phase and has a strong adhesion effect, and the polymer is anchored on the surface of the fiber, so that the defects of long modification time and easy oxidation failure of the traditional dopamine-like modified polymer are avoided, and the rapid, efficient and in-situ modification of the surface of the fiber can be realized on the premise of not damaging an aramid fiber body.
The specific technical scheme of the invention is as follows:
a bionic polymer containing dopamine functional groups and a preparation method thereof, the bionic polymer is a random copolymer, and the structural general formula (I) is as follows:
Figure 169033DEST_PATH_IMAGE001
wherein: m and n are positive integers, m is more than or equal to 10 and less than or equal to 5000, n is more than or equal to 10 and less than or equal to 5000, m: n = 1: 99-99: 1; a is more than or equal to 0 and less than or equal to 20;
when a is more than or equal to 0 and less than or equal to 20, the influence of the alkylene chain length on the solubility and the hydrophilicity of the polymer and the subsequent bonding force between the polymer and the resin can be better controlled;
further, in view of adhesion control and polymer molecular weight and solubility problems, m in the above general formula (I): n is 20:80 to 60: 40.
The invention fills the blank of the field, and obtains the polymer for the first time, wherein a dopamine-like structure-catechol group is introduced into the main chain of the polymer, so that the polymer has an adhesion effect, can react with sulfydryl or amino to form a covalent bond, and is strongly adhered to the surface of an inorganic or organic material. The polymer obtained by the invention is designed from molecules, avoids the problem of dopamine structure oxidation, thereby greatly improving the polymerization efficiency, and is quite different from the existing dopamine-like biomimetic polymer.
In addition, the inventor also provides a preparation method of the polymer, which comprises the following steps:
carrying out free radical polymerization reaction on a modified methacrylamide monomer and a modified methacrylic acid-based monomer in the presence of an initiator to obtain a biomimetic polymer containing dopamine or dopamine-like functional groups;
the structural formula of the modified methacrylamide monomer is as follows:
Figure 371955DEST_PATH_IMAGE002
；
the structural formula of the modified methacrylic acid-based monomer is as follows:
Figure 758200DEST_PATH_IMAGE003
wherein a is more than or equal to 0 and less than or equal to 20.
The method comprises the following specific steps:
adopting free radical polymerization under the photo-initiation or thermal initiation reaction condition to obtain a polymerization product under the photo-initiation or thermal initiation reaction condition, dissolving a solid part obtained by the reaction in a methanol solution, titrating the solution into cold anhydrous ether for precipitation to purify, centrifugally collecting insoluble substances at 3000-10000 rpm, and vacuumizing and drying the obtained precipitation product to obtain a final bionic polymer;
the amount of methanol is: the volume ratio of the total monomer feeding mass to the methanol is 0.01 g/ml-0.1 g/ml;
the dosage of the anhydrous ether is as follows: the volume ratio of the total monomer feeding mass to the anhydrous ether is 0.0005-0.005 g/ml, and the temperature of the anhydrous ether is 0-25oC；
Wherein the initiator: the molar ratio of the total monomers was 1: 15; among the monomers, modified methacrylamide monomer: molar ratio of modified methacrylic acid monomer 1: 99-99: 1.
the modified methacrylamide monomer has a molar mass of 221g/mol, and the modified methacrylate-based monomer is methyl-terminated oligo-ethylene glycol methacrylate, and the molar mass of the oligo-ethylene glycol methacrylate is 100-980 g/mol.
The photoinitiator is one of benzoin, benzoin dimethyl ether and thiopropoxy thioxanthone.
The thermal initiator is one of azobisisobutyronitrile, benzoyl peroxide and azobisisocyano valeric acid.
The polymerization condition of photo-initiation is ultraviolet irradiation polymerization reaction for 0.5-24 h under the protection of inert gas at 0-100 ℃.
The thermal-initiated polymerization condition is 0-100 ℃ under the protection of inert gas for 0.1-72 hours.
Further, the photoinitiated polymerization condition is ultraviolet irradiation polymerization reaction for 10-20 hours at 20-50 ℃ under the protection of inert gas; the thermal-initiated polymerization condition is that the reaction is carried out for 1-20 hours under the protection of inert gas at the temperature of 60-80 ℃.
Preferably, the polymerization method of the polymer is free radical polymerization under thermal initiation in consideration of polymerization process and cost, and in this case, the preferred initiator is azobisisobutyronitrile, the photo-initiation polymerization temperature is 75 ℃, and the polymerization time is 3 h.
The inventor applies the obtained bionic polymer to aramid fiber modification, and finds that the surface-modified aramid fiber has strong adhesion due to the fact that the polymer contains dopamine-like groups, namely catechol groups, and can be rapidly assembled on the surface of the aramid fiber, and fiber modification can be completed after the polymer is soaked in a polymer solution for 30 seconds, so that the requirements of continuous and in-situ sizing modification of fiber monofilaments are met; meanwhile, the water phase sizing is green and environment-friendly, and meets the industrial production requirement.
The aramid fiber surface after modification was compared to untreated aramid fiber surface by X-ray photoelectron spectroscopy (XPS) test (see figure 3), and unique groups O = C-O-and C-O appeared in the two polymer sizing agents, demonstrating successful polymer sizing. Compared with untreated aramid fibers, the modified aramid fibers have the advantages that the interfacial shear strength of the modified aramid fibers and resin is improved by 51% to the maximum extent through a monofilament extraction (IFSS) test, the modification effect is remarkable, and the mechanical properties of the fibers are not damaged while the bonding strength of the fibers and the resin is improved.
In conclusion, the bionic polymer containing the dopamine functional group provided by the invention is a random copolymer, contains the dopamine functional group, has a series of advantages of good phenolic hydroxyl controllability, strong adhesiveness, small usage amount, simple process, suitability for industrial production and the like, can effectively improve the interlaminar shear strength of the fiber reinforced composite material when used as a fiber sizing agent, and has a wide application prospect.
Drawings
FIG. 1 is a drawing of Compound II1An H-NMR spectrum of the mixture is shown,
FIG. 2 is a drawing of Compound III1An H-NMR spectrum of the mixture is shown,
FIG. 3 is an XPS spectrum of surface element changes of aramid fibers before and after sizing modification of a biomimetic polymer obtained by the invention.
Detailed Description
In order to better understand the invention, the following embodiments further illustrate the content of the invention, and the invention described herein is only for explaining the invention, not for limiting the invention.
The various reagents used in the examples below are specified below:
name (R) Purity/specification Manufacturer of the product
Na2B4O7 99% Aladdin
NaHCO3 AR Shanghai Lingfeng Chemicals Co., Ltd
Methacrylic anhydride 99% Preparation by the existing method
NaOH AR Reagent plant for the chemical industry of the Pinghu lake
HCl AR KUNSHAN JINGKE MICRO-ELECTRONICS MATERIAL Co.,Ltd.
Methacrylic acid monomer 90% Acros Organics
Benzoinum 99% Bailingwei Tech Co Ltd
Thiopropoxy thioxanthone 99% Bailingwei Tech Co Ltd
Benzoinum dimethyl ether 99% Anyingji chemical
Azobisisobutyronitrile 98% Anyingji chemical
Benzoyl peroxide 97% Anyingji chemical
Azobiscyanovaleric acid 98% Anyingji chemical
2- (3, 4-dihydroxyphenyl) ethylamine 99% Anyingji chemical
The monomers used and the structural formula are as follows:
dihydroxybenzene Compound (II)
Figure 87550DEST_PATH_IMAGE004
；
Modified methacrylamide monomer (III)
Figure 348767DEST_PATH_IMAGE005
；
Modified methacrylic acid based monomer (IV)
Figure 79962DEST_PATH_IMAGE006
；
The synthesis method of the modified methacrylamide monomer (III) comprises the following specific steps:
10g of Na was taken2B4O7，4g NaHCO3Into a reaction flask, then 100ml of ultrapure water was added, followed by addition of 5g of the compound (II) (of II) containing a dihydroxyphenyl group1H-NMR chart shown in FIG. 1); then 4.7ml of methacrylic anhydride is dissolved in 25ml of THF and is added into the solution drop by drop; then preparing 1M NaOH, dropwise adding the NaOH into the solution, adjusting the pH to 8-9, introducing nitrogen at room temperature, and magnetically stirring for reacting for 17 hours; after the reaction is finished, adding 50ml of ethyl acetate into the reaction solution, standing for layering, taking the lower-layer water phase, and repeating for 2 times; then 6M HCl is added into the filtrate dropwise to adjust the pH = 2; then transferring the filtrate to a round-bottom flask, adding 50ml of ethyl acetate, and extracting for 3 times; finally precipitating into cold 500ml n-hexane, filtering, and takingFiltering the residue, and drying to obtain modified methacrylamide monomer (III) (of III)1FIG. 2 shows an H-NMR chart 5.6g, yield 80%.
The structural general formula of the biomimetic polymer containing dopamine functional groups prepared in the following examples 1-9 is shown as follows
Figure 73326DEST_PATH_IMAGE007
Wherein m, n and a and the initiator adopted in the reaction are respectively as follows:
value of a in initiator monomer IV the molar ratio m of units III to units IV in polymer I: n is
Example 1 Thiopropoxylthiothioxanthone 31: 99
Example 2 Thiopropoxy thioxanthone 1099: 1
Example 3 Benzoinum 840: 60
Example 4 Benzoinum bismethyl ether 520: 80
Example 5 Benzoinum bismethyl Ether 020: 80
Example 6 azobisisobutyronitrile 2020: 80
Example 7 azobisisobutyronitrile 550: 50
Example 8 benzoyl peroxide 550: 50
Example 9 azobisisocyano valeric acid 360: 40.
Example 1
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
adopting photo-initiation polymerization, adding 0.0189g (0.07 mmol) of thiopropoxy thioxanthone, 0.022g (0.1 mmol) of modified methacrylamide monomer (III) and 0.232g (1 mmol) of modified methacrylic acid monomer (IV) (a = 3) into a reaction tube, injecting 10ml of DMF, carrying out ultraviolet illumination polymerization reaction for 24h under the inert gas environment at the temperature of 0 ℃, and reacting to obtain the thiopropoxy thioxanthoneThe obtained solid part is dissolved in 18.4ml of methanol solution and then titrated to 368ml of 10-15oC, precipitating in anhydrous ether for purification, centrifuging at 8000rpm to collect insoluble substances, and placing the obtained precipitation product on a vacuum line for vacuum drying overnight to obtain 0.184g of biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 28.6 MPa, which is 11.37% higher than that of the aramid fiber which is not treated. The sizing agent improves the bonding strength of the fiber and the resin, and does not damage the mechanical property of the fiber.
Example 2
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
adopting photo-initiated polymerization, adding 0.0189g (0.07 mmol) of thiopropoxy thioxanthone, 0.221g (1 mmol) of modified methacrylamide monomer (III) and 0.054g (0.1 mmol) of modified methacrylic acid monomer (IV) (a = 10) into a reaction tube, injecting 10ml of DMF, carrying out ultraviolet irradiation polymerization reaction for 0.5h under the inert gas environment at the temperature of 0 ℃, dissolving the solid part obtained by the reaction in 14.5ml of methanol solution, and titrating to 290ml of 0-10oC, precipitating in anhydrous ether for purification, centrifuging at 8000rpm to collect insoluble substances, and placing the obtained precipitate on a vacuum line for vacuum drying overnight to obtain 0.145g of biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 34.2 MPa which is improved by 33.18 percent compared with that of the aramid fiber which is not treated. The sizing agent improves the bonding strength of the fiber and the resin, and does not damage the mechanical property of the fiber.
Example 3
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
adopting light-initiated polymerization, adding 0.0282g (0.133 mmol) of benzoin, 0.176g (0.8 mmol) of modified methacrylamide monomer (III) and 0.542g (1.2 mmol) of modified methacrylic acid monomer (IV) (a = 8) into a reaction tube, injecting 10ml of DMF, carrying out ultraviolet irradiation polymerization reaction for 12h at 30 ℃ in an inert gas environment, dissolving the solid part obtained by the reaction in 3.1ml of methanol solution, and titrating to 62ml of 5-10oC, precipitating in anhydrous ether for purification, centrifuging at 8000rpm to collect insoluble substances, and placing the obtained precipitation product on a vacuum line for vacuum drying overnight to obtain 0.310g of biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
Monofilament pull-out test is an important means for representing the interface bonding strength of fiber and resin, and the interface shear strength IFSS of the modified aramid fiber is 34.6 MPa, which is improved by 34.74 percent compared with that of the aramid fiber which is not treated. The sizing agent improves the bonding strength of the fiber and the resin, and does not damage the mechanical property of the fiber.
Example 4
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
0.034g (0.133 mmol) of benzoin dimethyl ether, 0.088g (0.4 mol) of modified methacrylamide monomer (III) and modified methacrylic acid monomer(IV) (a = 5) 0.512g (1.6 mmol) was added to a reaction tube, 10ml of DMF was injected, ultraviolet polymerization was performed at 25 ℃ under an inert gas atmosphere for 16 hours, the solid portion obtained by the reaction was dissolved in 13.35ml of methanol solution, and then, the solution was titrated to 445ml of 20-25 mloC in anhydrous ether precipitation for purification, 3000rpm centrifugation to collect insoluble substances, the obtained precipitation product in vacuum line vacuum drying overnight to obtain 0.267g biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 32.3MPa, which is improved by 25.78% compared with that of the aramid fiber which is not processed. The sizing agent improves the bonding strength of the fiber and the resin, and does not damage the mechanical property of the fiber.
Example 5
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
adding 0.034g (0.133 mmol) of benzoin dimethyl ether, 0.088g (0.4 mmol) of modified methacrylamide monomer (III) and 0.163g (1.6 mmol) of modified methacrylic acid monomer (IV) (a = 0) into a reaction tube by adopting free radical polymerization, injecting 10ml of DMF, carrying out ultraviolet irradiation polymerization reaction for 3h at 100 ℃ in an inert gas environment, dissolving the solid part obtained by the reaction in 3.4ml of methanol solution, and titrating to 170ml of 10-15oC, precipitating in anhydrous ether for purification, centrifuging at 3000rpm to collect insoluble substances, and placing the obtained precipitation product on a vacuum line for vacuum drying overnight to obtain 0.102g of biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 33.12 MPa, which is improved by 28.97 percent compared with that of the aramid fiber which is not treated. The sizing agent improves the bonding strength of the fiber and the resin, and does not damage the mechanical property of the fiber.
Example 6
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
adopting thermal initiation free radical polymerization, adding 0.0218g (0.133 mmol) of azobisisobutyronitrile, 0.088g (0.4 mmol) of modified methacrylamide monomer (III) and 1.571g (1.6 mmol) of modified methacrylic acid monomer (IV) (a = 20) into a reaction tube, injecting 10ml of DMF, carrying out polymerization reaction for 72h at 0 ℃ under an inert gas environment, dissolving the solid part obtained by the reaction in 14.24ml of methanol solution, and titrating to 259ml of 5-10 mloC in anhydrous ether for purification, 3000rpm centrifugation to collect insoluble substances, and the obtained precipitation product was placed on a vacuum line and vacuum-dried overnight to obtain 0.712g of biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 32.24 MPa, which is improved by 25.55 percent compared with that of the aramid fiber which is not processed. The sizing agent can improve the bonding strength of the fiber and the resin without damaging the mechanical property of the fiber.
Example 7
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
by the use of heatInitiating free radical polymerization, adding 0.0218g (0.133 mmol) of azobisisobutyronitrile, 0.221g (1 mmol) of modified methacrylamide monomer (III) and 0.32g (1 mmol) of modified methacrylic acid monomer (IV) (a = 5) into a reaction tube, injecting 10ml of DMF, carrying out polymerization reaction for 12h at 60 ℃ under an inert gas environment, dissolving the solid part obtained by the reaction in 5.32ml of methanol solution, and titrating to 97ml of 0-5oC in anhydrous ether for purification, the insoluble matter was collected by centrifugation at 3000rpm, and the resulting precipitate was dried on a vacuum line under vacuum overnight to give 0.266g of a biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 38.78 MPa, which is improved by 51.01 percent compared with that of the aramid fiber which is not treated. The sizing agent improves the bonding strength of the fiber and the resin, and does not damage the mechanical property of the fiber.
Example 8
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
adopting thermal initiation free radical polymerization, adding 0.0322g (0.133 mmol) of benzoyl peroxide, 0.221g (1 mmol) of modified methacrylamide monomer (III) and 0.32g (1 mmol) of modified methacrylic acid monomer (IV) (a = 5) into a reaction tube, injecting 10ml of DMF, carrying out polymerization reaction for 0.1h at 100 ℃ under an inert gas environment, dissolving the solid part obtained by the reaction in 23.9ml of methanol solution, and titrating to 239ml of 0-25oC, precipitating in anhydrous ether for purification, centrifuging at 3000rpm to collect insoluble substances, and placing the obtained precipitation product on a vacuum line for vacuum drying overnight to obtain 0.239g of biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 36.23 MPa, which is improved by 41.08% compared with that of the aramid fiber which is not treated. The sizing agent can improve the bonding strength of the fiber and the resin without damaging the mechanical property of the fiber.
Example 9
A preparation method of a biomimetic polymer containing dopamine functional groups comprises the following specific steps:
adopting thermal initiation free radical polymerization, adding 0.0342g (0.133 mmol) of azobisisocyano valeric acid, 0.221g (1 mmol) of modified methacrylamide monomer (III) and 0.232g (1 mmol) of modified methacrylic acid monomer (IV) (a = 3) into a reaction tube, injecting 10ml of DMF, carrying out polymerization reaction for 5h at 80 ℃ in an inert gas environment, dissolving the solid part obtained by the reaction in 12.65ml of methanol solution, and titrating to 361ml of 5-10 mloC in anhydrous ether for purification, centrifugal collection of insoluble substances at 3000rpm, and vacuum drying the obtained precipitate overnight in a vacuum line to obtain 0.253g of biomimetic polymer.
Fiber sizing: weighing 0.1g of the polymer, dissolving the polymer in 100ml of acetic acid buffer solution with pH =5.5, soaking and sizing each fiber bundle in a fiber sizing mode, putting 500g of aramid fiber on a creel, passing each fiber bundle through a sizing tank in sequence under the pulling force of a traction device, soaking the fiber in the solution for 30s, soaking the fiber in deionized water for 5min, and drying the fiber at 100 ℃ for 3 h.
The monofilament extraction test is an important means for representing the interface bonding strength of the fiber and the resin, and the interface shear strength IFSS of the modified aramid fiber is 36.9MPa, which is 43.69 percent higher than that of the aramid fiber which is not treated. The sizing agent can improve the bonding strength of the fiber and the resin without damaging the mechanical property of the fiber.
In conclusion, the bionic polymer provided by the invention contains dopamine functional groups, has a series of advantages of good controllability of phenolic hydroxyl groups, strong adhesiveness, small usage amount, simple process, suitability for industrial production and the like, can effectively improve the interlaminar shear strength of the fiber reinforced composite material when being used as a fiber sizing agent, and has wide application prospects.

Claims (8)

1. A bionic polymer containing dopamine functional groups is characterized in that: the general structural formula (I) is as follows:
Figure 330707DEST_PATH_IMAGE001
wherein: m and n are positive integers, m is more than or equal to 10 and less than or equal to 5000, n is more than or equal to 10 and less than or equal to 5000, m: n = 1: 99-99: 1; a is more than or equal to 0 and less than or equal to 20.
2. The dopamine-functional-group-containing biomimetic polymer according to claim 1, characterized in that: m in the above general formula (I): n is 20:80 to 60: 40.
3. The method for preparing the biomimetic polymer containing dopamine functional groups according to claim 1, characterized in that: the method comprises the following steps:
carrying out free radical polymerization reaction on a modified methacrylamide monomer and a modified methacrylic acid-based monomer in the presence of an initiator to obtain a biomimetic polymer containing dopamine or dopamine-like functional groups;
the structural formula of the modified methacrylamide monomer is as follows:
Figure 130036DEST_PATH_IMAGE002
；
the structural formula of the modified methacrylic acid-based monomer is as follows:
Figure 715738DEST_PATH_IMAGE003
wherein a is more than or equal to 0 and less than or equal to 20.
4. The method for preparing the biomimetic polymer containing dopamine functional groups according to claim 3, wherein the method comprises the following steps: the method comprises the following specific steps:
adopting free radical polymerization under the photo-initiation or thermal initiation reaction condition to obtain a polymerization product under the photo-initiation or thermal initiation reaction condition, dissolving a solid part obtained by the reaction in a methanol solution, titrating the solution into cold anhydrous ether for precipitation to purify, centrifugally collecting insoluble substances at 3000-10000 rpm, and vacuumizing and drying the obtained precipitation product to obtain a final bionic polymer;
the amount of methanol is: the volume ratio of the total monomer feeding mass to the methanol is 0.01 g/ml-0.1 g/ml;
the dosage of the anhydrous ether is as follows: the volume ratio of the total monomer feeding mass to the anhydrous ether is 0.0005-0.005 g/ml, and the temperature of the anhydrous ether is 0-25oC；
Wherein the initiator: the molar ratio of the total monomers was 1: 15; among the monomers, modified methacrylamide monomer: molar ratio of modified methacrylic acid monomer 1: 99-99: 1;
the modified methacrylic acid-based monomer is methyl-terminated oligo-polyethylene glycol methacrylate, and the molar mass of the oligo-polyethylene glycol methacrylate is 100-980 g/mol.
5. The method for preparing the biomimetic polymer containing dopamine functional groups according to claim 4, wherein the method comprises the following steps: the photoinitiator is one of benzoin, benzoin dimethyl ether and thiopropoxy thioxanthone; the thermal initiator is one of azobisisobutyronitrile, benzoyl peroxide and azobisisocyano valeric acid.
6. The method for preparing the biomimetic polymer containing dopamine functional groups according to claim 4, wherein the method comprises the following steps: the polymerization condition of photo-initiation is that the polymerization reaction is carried out for 0.5 to 24 hours under the protection of inert gas at the temperature of 0 to 100 ℃; the thermal-initiated polymerization condition is 0-100 ℃ under the protection of inert gas for 0.1-72 hours.
7. The method for preparing a biomimetic polymer comprising dopamine functional groups according to claim 5 or 6, characterized in that: the polymerization condition of photo-initiation is ultraviolet irradiation polymerization reaction for 10-20 h under the protection of inert gas at 20-50 ℃; the thermal-initiated polymerization condition is that the reaction is carried out for 1-20 hours under the protection of inert gas at the temperature of 60-80 ℃.
8. The method for preparing a biomimetic polymer comprising dopamine functional groups according to claim 5 or 6, characterized in that: the reaction condition is thermal initiation, the initiator is preferably azobisisobutyronitrile, the thermal initiation polymerization temperature is 75 ℃, and the polymerization time is 3 hours.
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