CN113336912A - Carbon fiber composite material based on cyclic acetal polyurethane and preparation method thereof - Google Patents
Carbon fiber composite material based on cyclic acetal polyurethane and preparation method thereof Download PDFInfo
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a carbon fiber composite material based on cyclic acetal polyurethane and a preparation method thereof. The carbon fiber composite material is prepared from the following components in parts by mass: 100 parts of degradable dihydroxy monomer based on cyclic acetal, 20-200 parts of curing agent, 0-6 parts of curing accelerator, 0-300 parts of organic solvent and 20-500 parts of carbon fiber. The preparation method comprises the following steps: uniformly mixing the degradable dihydroxy monomer based on the cyclic acetal, the curing agent, the curing accelerator, the carbon fiber and the organic solvent, and then curing to obtain the carbon fiber composite material based on the cyclic acetal polyurethane. The carbon fiber composite material can remove the matrix resin bonded with the carbon fibers under very mild conditions, so that the carbon fibers can be well recovered, and the recovered carbon fibers can keep the original excellent performance; and simultaneously endows the carbon fiber composite material with the reworkability, and solves the problem of short service life of the prepreg.
Description
Technical Field
The invention relates to a carbon fiber composite material, in particular to an easily-recycled and reprocessable carbon fiber composite material based on cyclic acetal polyurethane and a preparation method thereof, and belongs to the technical field of high polymers and composite materials.
Background
Carbon fiber reinforced resin based Composites (CFRP) are one of the most advanced composite materials at present. It has the advantages of light weight, high strength, high temperature resistance, corrosion resistance and the like. Such materials are widely used in high-end sporting and entertainment fields including rackets, golf clubs, bicycles, and the like; general industrial fields such as automobile manufacturing, wind power generation, power transmission, civil construction, offshore oil fields, medical equipment, and the like; the aerospace fields such as aircraft structural members, satellite and space station components, missiles and rocket fairings are still continuously expanding to new application fields at present and are in a rapid expansion period.
The demand for carbon fiber has increased significantly over the past decade, with an estimated annual compound growth rate of 12%, which will increase from 58000 tons in 2015 to 11600 tons in 2021. It is thus understood that the amount of carbon fiber composite material that is discarded is also quite surprising, but the current recycling of such waste is quite rudimentary, mostly by incineration and landfill. But as environmental legislation becomes more stringent, the enormous environmental impact of landfill and incineration disposal makes more industrialized solutions desirable. The degradation and recovery of the carbon fiber composite material are degradation of the resin matrix in nature, and the carbon fiber is not damaged as far as possible while the resin is degraded.
In the currently reported techniques, degradable groups such as schiff base bonds, disulfide bonds, acetal structures, etc. have been introduced into a thermosetting resin matrix by molecular design to impart degradability to the thermosetting resin matrix. The carbon fiber composite material can be degraded under mild conditions, and the recycling of the carbon fiber is realized. In addition, some bonds such as disulfide bonds, Schiff base bonds, etc. in these degradation groups have unique chemical properties. By introducing such exchangeable groups, the thermosetting resin can be imparted with repairable, reworkable, or the like properties. After the prepreg is applied to the carbon fiber composite material, the problems that the prepreg of the composite material is short in service life and cannot be processed again after being formed are solved. However, the introduction of these degradable groups can result in the thermal stability and mechanical properties of the prepared composite material, which can not be compared with the traditional thermosetting resin-based composite material.
Disclosure of Invention
The invention mainly aims to provide a carbon fiber composite material based on cyclic acetal polyurethane and a preparation method thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a carbon fiber composite material based on cyclic acetal polyurethane, which is prepared from the following components in parts by mass:
wherein the degradable dihydroxy monomer has a structure shown in formula I:
wherein R comprises H or methoxy.
The embodiment of the invention also provides a preparation method of the carbon fiber composite material based on the cyclic acetal polyurethane, which comprises the following steps:
uniformly mixing a degradable dihydroxy monomer based on cyclic acetal, a curing agent, a curing accelerator, carbon fiber and an organic solvent, and then curing to obtain a carbon fiber composite material based on cyclic acetal polyurethane;
wherein the degradable dihydroxy monomer has a structure shown in formula I:
wherein R comprises H or methoxy;
the mass ratio of the degradable dihydroxy monomer to the curing agent to the curing accelerator to the organic solvent to the carbon fiber is 100: (20-200): (0-6): (0-300): (20-500).
Compared with the prior art, the invention has the following beneficial effects:
1) the recyclable and reprocessable carbon fiber composite material based on the cyclic acetal polyurethane can remove matrix resin bonded with carbon fibers under a very mild condition, so that the carbon fibers can be well recycled, and the recycled carbon fibers can keep the original excellent performance;
2) the recyclable and reprocessable carbon fiber composite material based on the cyclic acetal polyurethane can be reprocessed and molded at a certain temperature, so that the carbon fiber composite material can be reprocessed, the prepared prepreg can be placed for a long time, and the problem of short service life of the prepreg is solved;
3) the recyclable and reprocessable carbon fiber composite material based on the cyclic acetal polyurethane can also obtain matrix resin degradation fragments with relatively small components under mild conditions, wherein active groups are very clear and are aldehyde groups and alcoholic hydroxyl groups obtained by acetal structure degradation, and the recycled resin matrix can be conveniently recycled in the subsequent process;
4) the preparation of the recyclable and reprocessable carbon fiber composite material based on the cyclic acetal polyurethane provided by the invention can adopt the existing general carbon fiber composite material processing and preparing method, has strong operability and good controllability, is easy to implement and is beneficial to industrial large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a FIRT spectrum of a cyclic acetal polyurethane-based carbon fiber composite material obtained in example 1 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the present inventors have conducted extensive research and practice to propose a technical solution of the present invention, which mainly introduces a cyclic acetal structure similar to a spiro acetal and a dynamic bond such as a urethane bond into a resin structure. The material performance is ensured, meanwhile, the carbon fiber composite material is endowed with degradability and reworkability, and the problem of short service life of the prepreg is solved. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a carbon fiber composite material based on cyclic acetal polyurethane, which is prepared from the following components in parts by mass:
wherein the degradable dihydroxy monomer has a structure shown in formula I:
wherein R comprises H or methoxy.
As one of the preferred embodiments, the carbon fiber composite material based on the cyclic acetal polyurethane is prepared from the following components in parts by mass:
further, the carbon fiber composite material based on the cyclic acetal polyurethane is prepared from the following components in parts by mass:
as one of preferred embodiments, the curing agent includes a polyisocyanate having a radical functionality of not less than 3, preferably any one or a combination of two or more of L-lysine triisocyanate, triphenylmethane triisocyanate, HDI trimer, and the like, but is not limited thereto.
As one of preferred embodiments, the curing accelerator includes an organic metal compound, preferably any one or a combination of two or more of stannous 2-ethyl hexanoate, bismuth neododecanoate, iron (III) acetylacetonate, dibutyltin dilaurate, and the like, but is not limited thereto. The curing accelerator is added in the scheme of the invention, so that the curing reaction time can be greatly shortened, the efficiency of preparing the composite material is improved, and the invention has great economic benefit in actual industrial production.
As one of the preferred embodiments, the organic solvent includes any one or a combination of two or more of benzene-based organic solvents, halogenated hydrocarbon-based organic solvents, ether-based organic solvents, and the like, preferably any one or a combination of two or more of toluene, xylene, chloroform, dichloroethane, tetrahydrofuran, ethanol, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, and the like, but is not limited thereto.
As one of the preferred embodiments, the carbon fiber is short fiber, carbon fiber unidirectional cloth, carbon fiber bidirectional cloth, or carbon fiber felt, but is not limited thereto.
Further, the cyclic acetal polyurethane-based carbon fiber composite material has a resin matrix cross-linked structure including a cyclic acetal structure and a urethane bond.
The recyclable and reprocessable carbon fiber composite material of the cyclic acetal polyurethane is formed by solidifying the degradable dihydroxy monomer, the curing agent and the carbon fiber, and the easily degradable cyclic acetal structure is introduced into a resin matrix cross-linked network of the composite material in the solidification process, so that the matrix resin for bonding the carbon fiber can be removed from the composite material under mild conditions, the carbon fiber can be well recycled, and the recycled carbon fiber can keep high quality. And simultaneously endows the carbon fiber composite material with the reworkability, and solves the problem of short service life of the prepreg.
Another aspect of an embodiment of the present invention provides a method for preparing a carbon fiber composite material based on cyclic acetal polyurethane, including:
uniformly mixing a degradable dihydroxy monomer based on cyclic acetal, a curing agent, a curing accelerator, carbon fiber and an organic solvent, and then curing to obtain a carbon fiber composite material based on cyclic acetal polyurethane;
wherein the degradable dihydroxy monomer has a structure shown in formula I:
wherein R comprises H or methoxy;
the mass ratio of the degradable dihydroxy monomer to the curing agent to the curing accelerator to the organic solvent to the carbon fiber is 100: (5-200): (0-6): (0-300): (20-500).
As one of the preferred embodiments, the mass ratio of the degradable dihydroxy monomer, the curing agent, the curing accelerator, the organic solvent and the carbon fiber is 100: (100-200): (3-6): (0-300): (20-500).
Further, the mass ratio of the degradable dihydroxy monomer, the curing agent, the curing accelerator, the organic solvent and the carbon fiber is 100: (100-200): (3-6): (60-300): (20-500).
As one of preferred embodiments, the method for preparing the degradable dihydroxy monomer comprises:
mixing 500g of vanillin with 302g of glycerol according to a molar ratio of 1: 1, adding 1000g of DMF, 1000g of petroleum ether and 30g of p-toluenesulfonic acid, carrying out water division reflux reaction for 12 hours by adopting a Dean-Stark device, and settling and washing by using a saturated sodium bicarbonate aqueous solution to obtain 560g of dihydroxy monomer. The structural formula is as follows:
as another preferred embodiment, the method for preparing the degradable dihydroxy monomer comprises:
500g of p-hydroxybenzaldehyde and 377g of glycerol are mixed according to a molar ratio of 1: 1, adding 1000g of DMF, 1000g of petroleum ether and 30g of p-toluenesulfonic acid, carrying out water division reflux reaction for 12 hours by adopting a Dean-Stark device, and settling and washing by using a saturated sodium bicarbonate aqueous solution to obtain 650g of dihydroxy monomer. The structural formula is as follows:
as one of preferred embodiments, the curing agent includes a polyisocyanate having a radical functionality of not less than 3, preferably any one or a combination of two or more of L-lysine triisocyanate, triphenylmethane triisocyanate, HDI trimer, and the like, but is not limited thereto.
As one of preferred embodiments, the curing accelerator includes an organic metal compound, preferably any one or a combination of two or more of stannous 2-ethyl hexanoate, bismuth neododecanoate, iron (III) acetylacetonate, dibutyltin dilaurate, and the like, but is not limited thereto. The curing accelerator is added in the scheme of the invention, so that the curing reaction time can be greatly shortened, the efficiency of preparing the composite material is improved, and the invention has great economic benefit in actual industrial production.
As one of the preferred embodiments, the organic solvent includes any one or a combination of two or more of benzene-based organic solvents, halogenated hydrocarbon-based organic solvents, ether-based organic solvents, and the like, preferably any one or a combination of two or more of toluene, xylene, chloroform, dichloroethane, tetrahydrofuran, ethanol, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, and the like, but is not limited thereto.
As one of the preferred embodiments, the carbon fiber is short fiber, carbon fiber unidirectional cloth, carbon fiber bidirectional cloth, or carbon fiber felt, but is not limited thereto.
Further, the preparation method of the carbon fiber composite material based on the cyclic acetal polyurethane specifically comprises the following steps:
uniformly mixing a degradable dihydroxy monomer based on cyclic acetal, a curing agent, a curing accelerator, carbon fiber and an organic solvent, then carrying out hot pressing at 80-180 ℃ for 0.5-2 h, or curing at 80-120 ℃ for 1-2 h, then curing at 120-180 ℃ for 2-3 h, and finally curing at 150-200 ℃ for 2-3 h to obtain the carbon fiber composite material based on cyclic acetal polyurethane.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments, drawings, and comparative examples, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
In the following examples, the monofilament stretch of carbon fiber unidirectional cloth was measured at a stretch speed of 5mm/min with a span of 25 mm.
Synthesis of degradable dihydroxy monomers
As one of preferred embodiments, the method for preparing the degradable dihydroxy monomer comprises:
mixing 500g of vanillin with 302g of glycerol according to a molar ratio of 1: 1, adding 1000g of DMF, 1000g of petroleum ether and 30g of p-toluenesulfonic acid, carrying out water division reflux reaction for 12 hours by adopting a Dean-Stark device, and settling and washing by using a saturated sodium bicarbonate aqueous solution to obtain 560g of dihydroxy monomer. The structural formula is as follows:
as another preferred embodiment, the method for preparing the degradable dihydroxy monomer comprises:
500g of p-hydroxybenzaldehyde and 377g of glycerol are mixed according to a molar ratio of 1: 1, adding 1000g of DMF, 1000g of petroleum ether and 30g of p-toluenesulfonic acid, carrying out water division reflux reaction for 12 hours by adopting a Dean-Stark device, and settling and washing by using a saturated sodium bicarbonate aqueous solution to obtain 650g of dihydroxy monomer. The structural formula is as follows:
example 1:
100g of dihydroxy monomer (formula I-1), 200g of HDI trimer and 500g of short carbon fiber are mixed and stirred uniformly, and then are cured for 2 hours at 120 ℃, 2 hours at 150 ℃ and 2 hours at 180 ℃ to obtain the carbon fiber composite material, wherein the FIRT spectrum is shown in figure 1, and absorption peaks corresponding to carbamate bonds and acetal bonds exist in the figure.
The obtained carbon fiber composite material is placed in a mixed solution of 0.1mol/L HCl water and tetrahydrofuran (the volume ratio of water to tetrahydrofuran is 2: 8), and is completely degraded at room temperature for 6 hours, and the recovered short carbon fiber is obtained after washing, and the appearance of the recovered short carbon fiber is not different from that of the original short carbon fiber.
Example 2:
100g of dihydroxy monomer (formula I-2), 100g of HDI trimer, 6g of dibutyltin dilaurate and 20g of short carbon fiber are mixed and stirred uniformly, and then cured at 80 ℃ for 1 hour, 120 ℃ for 3 hours and 150 ℃ for 3 hours to obtain the carbon fiber composite material.
The obtained carbon fiber composite material is placed in a mixed solution of 0.1mol/L HCl water and acetone (the volume ratio of water to acetone is 2: 8), and is completely degraded at room temperature for 4 hours, and the recovered short carbon fiber is obtained after washing, and the appearance of the recovered short carbon fiber is not different from that of the original short carbon fiber.
The carbon fiber composite material plate prepared by the embodiment is hot-pressed for 2 hours at the temperature of 180 ℃ and under the pressure of 10MPa by using a non-planar die, so that the non-planar carbon fiber composite material can be obtained. And placing the prepreg for 72 hours, and hot-pressing the prepreg for 2 hours at the temperature of 180 ℃ and under the pressure of 10MPa by using a flat vulcanizing instrument to obtain the carbon fiber composite material plate with excellent performance.
Example 3:
100g of dihydroxy monomer (formula I-1), 20g of triphenylmethane triisocyanate, 3g of stannous 2-ethyl hexanoate and 60g of dimethylformamide are mixed and stirred uniformly, then the mixture and 50g of carbon fiber felt are prepared into carbon fiber felt prepreg, and the carbon fiber felt prepreg is hot-pressed at 130 ℃ for 2 hours, cured at 130 ℃ for 2.5 hours and cured at 160 ℃ for 2.5 hours, thus obtaining the carbon fiber composite material.
Placing the obtained carbon fiber composite material at 0.1mol/L H2SO4And (3) completely degrading the mixture of water and tetrahydrofuran (the volume ratio of water to tetrahydrofuran is 2: 8) at room temperature for 6 hours, and washing to obtain the recycled carbon fiber felt, wherein the appearance of the recycled carbon fiber felt is not different from that of the original carbon fiber felt.
The carbon fiber composite material plate prepared by the embodiment is hot-pressed for 1 hour at the temperature of 160 ℃ and under the pressure of 10MPa by using a non-planar die, and then the non-planar carbon fiber composite material can be obtained. And placing the prepreg for 72 hours, and hot-pressing the prepreg for 1 hour at the temperature of 160 ℃ and under the pressure of 10MPa by using a flat vulcanizing instrument to obtain the carbon fiber composite material plate with excellent performance.
Example 4:
100g of dihydroxy monomer 2, 160g L-lysine triisocyanate, 5g of bismuth neododecanoate and 300g of tetrahydrofuran are mixed and stirred uniformly, then the mixture and 500g of carbon fiber unidirectional cloth are prepared into carbon fiber prepreg, the carbon fiber prepreg is cured for 0.5 hour at 180 ℃ by hot pressing, then the carbon fiber prepreg is post-cured for 2 hours at 180 ℃, and the carbon fiber composite material is obtained by post-curing for 2 hours at 200 ℃.
Placing the obtained carbon fiber composite material in a mixed solution of 0.1mol/L HCl water and dimethylformamide (the volume ratio of water to dimethylformamide is 2: 8), completely degrading at room temperature for 4 hours, and washing to obtain recycled carbon fiber unidirectional cloth; the tensile strength of the recycled carbon fiber unidirectional cloth monofilament is 3.17GPa, and the tensile strength of the original carbon fiber monofilament is 3.20 GPa.
The carbon fiber composite material plate prepared by the embodiment is hot-pressed for 2 hours at the temperature of 180 ℃ and under the pressure of 10MPa by using a non-planar die, so that the non-planar carbon fiber composite material can be obtained. And placing the prepreg for 72 hours, and hot-pressing the prepreg for 2 hours at the temperature of 180 ℃ and under the pressure of 10MPa by using a flat vulcanizing instrument to obtain the carbon fiber composite material plate with excellent performance.
Example 5:
100g of dihydroxy monomer 1, 170g L-lysine triisocyanate, 6g of iron (III) acetylacetonate and 200g of chloroform are mixed and stirred uniformly, then the mixture and 500g of carbon fiber unidirectional cloth are made into carbon fiber prepreg, the carbon fiber prepreg is cured for 1 hour at 80 ℃ by hot pressing, then the carbon fiber prepreg is post-cured for 2 hours at 120 ℃ and is post-cured for 2 hours at 150 ℃, and the carbon fiber composite material is obtained.
Putting the obtained carbon fiber composite material into a mixed solution of 0.1mol/L HCl water and ethanol (the volume ratio of water to ethanol is 2: 8), completely degrading at room temperature for 5 hours, and washing to obtain recycled carbon fiber unidirectional cloth; the tensile strength of the recycled carbon fiber unidirectional cloth monofilament is 3.17GPa, and the tensile strength of the original carbon fiber monofilament is 3.20 GPa.
The carbon fiber composite material plate prepared by the embodiment is hot-pressed for 2 hours at the temperature of 180 ℃ and under the pressure of 10MPa by using a non-planar die, so that the non-planar carbon fiber composite material can be obtained. And placing the prepreg for 48 hours, and hot-pressing the prepreg for 2 hours at the temperature of 180 ℃ and under the pressure of 10MPa by using a flat vulcanizing instrument to obtain the carbon fiber composite material plate with excellent performance.
Comparative example 1:
100g of bisphenol A (alatin), 170g L-lysine triisocyanate and 100g of dimethylformamide are mixed and stirred uniformly, then the mixture is mixed and stirred uniformly, and then the mixture and 300g of carbon fiber bidirectional plain cloth are made into carbon fiber prepreg, the carbon fiber prepreg is cured for 30min at 100 ℃ by hot pressing, and then the carbon fiber prepreg is post-cured for 2 hours at 120 ℃ and is post-cured for 2 hours at 140 ℃ to obtain the carbon fiber composite material.
The prepreg prepared in the comparative example was short in standing time and free from reworkability, and the obtained carbon fiber composite material was placed in a mixed solution of 0.1mol/L HCl water and tetrahydrofuran (water: methanol volume ratio 1: 9) without degradation at 50 ℃ for 30 days.
In conclusion, the carbon fiber composite material can remove the matrix resin bonded with the carbon fibers under very mild conditions, so that the carbon fibers can be well recovered, and the recovered carbon fibers can keep the original excellent performance; and simultaneously endows the carbon fiber composite material with the reworkability, and solves the problem of short service life of the prepreg.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. The carbon fiber composite material based on the cyclic acetal polyurethane is characterized by being prepared from the following components in parts by mass:
wherein the degradable dihydroxy monomer has a structure shown in formula I:
wherein R comprises H or methoxy.
2. The cyclic acetal polyurethane-based carbon fiber composite material according to claim 1, characterized in that: the composition is prepared from the following components in parts by mass:
3. the cyclic acetal polyurethane-based carbon fiber composite material according to claim 2, characterized in that: the composition is prepared from the following components in parts by mass:
4. the cyclic acetal polyurethane-based carbon fiber composite material according to any one of claims 1-3, characterized in that: the curing agent comprises polyisocyanate, the radical functionality of the polyisocyanate is not less than 3, and the curing agent is preferably any one or the combination of more than two of L-lysine triisocyanate, triphenylmethane triisocyanate and HDI trimer; and/or the curing accelerator comprises an organic metal compound, preferably any one or the combination of more than two of stannous 2-ethyl hexanoate, bismuth neododecanoate, ferric acetylacetonate and dibutyltin dilaurate.
5. The cyclic acetal polyurethane-based carbon fiber composite material according to any one of claims 1-3, characterized in that: the organic solvent comprises any one or the combination of more than two of benzene organic solvent, halogenated hydrocarbon organic solvent and ether organic solvent, preferably any one or the combination of more than two of toluene, xylene, trichloromethane, dichloroethane, tetrahydrofuran, ethanol, N-dimethylformamide, dimethyl sulfoxide and N, N-dimethylacetamide;
and/or the carbon fiber comprises short fiber, carbon fiber unidirectional cloth, carbon fiber bidirectional cloth or carbon fiber felt.
6. The cyclic acetal polyurethane-based carbon fiber composite material according to claim 1, characterized in that: the carbon fiber composite material based on the cyclic acetal polyurethane has a resin matrix cross-linked structure including a cyclic acetal structure and a urethane bond.
7. A preparation method of a carbon fiber composite material based on cyclic acetal polyurethane is characterized by comprising the following steps:
uniformly mixing a degradable dihydroxy monomer based on cyclic acetal, a curing agent, a curing accelerator, carbon fiber and an organic solvent, and then curing to obtain a carbon fiber composite material based on cyclic acetal polyurethane;
wherein the degradable dihydroxy monomer has a structure shown in formula I:
wherein R comprises H or methoxy;
the mass ratio of the degradable dihydroxy monomer to the curing agent to the curing accelerator to the organic solvent to the carbon fiber is 100: (20-200): (0-6): (0-300): (20-500).
8. The method of claim 7, wherein: the mass ratio of the degradable dihydroxy monomer to the curing agent to the curing accelerator to the organic solvent to the carbon fiber is 100: (100-200): (3-6): (0-300): (20-500), preferably 100: (100-200): (3-6): (60-300): (20-500).
9. The method of claim 7, wherein: the curing agent comprises polyisocyanate, the radical functionality of the polyisocyanate is not less than 3, and the curing agent is preferably any one or the combination of more than two of L-lysine triisocyanate, triphenylmethane triisocyanate and HDI trimer;
and/or the curing accelerator comprises an organic metal compound, preferably any one or the combination of more than two of stannous 2-ethyl hexanoate, bismuth neododecanoate, ferric acetylacetonate and dibutyltin dilaurate;
and/or the organic solvent comprises any one or the combination of more than two of benzene organic solvent, halogenated hydrocarbon organic solvent and ether organic solvent, preferably any one or the combination of more than two of toluene, xylene, trichloromethane, dichloroethane, tetrahydrofuran, ethanol, N-dimethylformamide, dimethyl sulfoxide and N, N-dimethylacetamide;
and/or the carbon fiber comprises short fiber, carbon fiber unidirectional cloth, carbon fiber bidirectional cloth or carbon fiber felt.
10. The production method according to claim 7, characterized by comprising: uniformly mixing a degradable dihydroxy monomer based on cyclic acetal, a curing agent, a curing accelerator, carbon fiber and an organic solvent, then carrying out hot pressing at 80-180 ℃ for 0.5-2 h or curing at 80-120 ℃ for 1-2 h, then curing at 120-180 ℃ for 2-3 h, and finally curing at 150-200 ℃ for 2-3 h to obtain the carbon fiber composite material based on cyclic acetal polyurethane.
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| CN114874589A (en) * | 2022-07-07 | 2022-08-09 | 中国科学院宁波材料技术与工程研究所 | Degradable carbon fiber reinforced resin matrix composite material and preparation method and application thereof |
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