CN110240618B - Phosphorus-containing amination coupling agent and preparation method and application thereof - Google Patents
Phosphorus-containing amination coupling agent and preparation method and application thereof Download PDFInfo
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- CN110240618B CN110240618B CN201910505672.0A CN201910505672A CN110240618B CN 110240618 B CN110240618 B CN 110240618B CN 201910505672 A CN201910505672 A CN 201910505672A CN 110240618 B CN110240618 B CN 110240618B
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- 239000007822 coupling agent Substances 0.000 title claims abstract description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 20
- 239000011574 phosphorus Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005576 amination reaction Methods 0.000 title claims abstract description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 15
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004513 sizing Methods 0.000 claims abstract description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- 239000003822 epoxy resin Substances 0.000 abstract description 6
- 229920000647 polyepoxide Polymers 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 150000003017 phosphorus Chemical class 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- -1 sizing treatment Chemical compound 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a phosphorus-containing amination coupling agent and a preparation method and application thereof, wherein a carbon fiber adopts a surface sizing treatment method of the substances, the phosphorus-containing amination coupling agent is synthesized by taking phosphoric triamide and an epoxy group coupling agent as raw materials, and the preparation method of the phosphoric triamide comprises the following steps: phosphate and ethylenediamine are used as raw materials and are prepared by a heating reflux mode. The application of the phosphorus-containing amination coupling agent not only can keep the interface bonding performance between the carbon fiber and the epoxy resin, but also obviously enhances the flame retardant performance of the carbon fiber epoxy resin composite material.
Description
Technical Field
The invention relates to the field of preparation of a phosphorus-nitrogen coupling agent and material fibers, in particular to a phosphorus-nitrogen coupling agent for flame-retardant modification of a carbon fiber surface, a preparation method thereof and application thereof on the carbon fiber surface.
Background
The carbon fiber has a series of excellent performances such as high specific strength, specific modulus, low density, corrosion resistance, electric and heat conduction, small thermal expansion coefficient and the like, and the advanced composite material prepared by taking the carbon fiber as a reinforcement has irreplaceable and wide application in the fields of aerospace, national defense, national economy and the like, and is an important assistance for promoting the development of new materials in China. With the trend of the integrated development of the structure and the function of the composite material, the carbon fiber composite material also faces the same problem. Because the surface of the carbon fiber is inert, in order to improve the wettability between the fiber and the matrix, the most commonly adopted modification means is the surface modification of the carbon fiber, such as sizing treatment, coupling agent modification, electrochemical oxidation, plasma oxidation and the like. The coupling agent modification has the advantages of high reaction speed, good dispersibility, low price and the like, is suitable for industrial application, has two functional groups on a chemical structure, and can connect the fiber and the matrix in a chemical bond mode, so that the interface combination is firmer.
At present, the research on the coupling agent modified composite material is available at foreign countries but not much, and the research on the coupling agent modified carbon fiber epoxy composite material system at home is very little, so that the system and the reference are difficult to realize. Most of the researches are focused on the research of modified amino silane coupling agents, and only the improvement of the interface performance is focused on, but the demands for the functionalization of the composite material in different fields are rarely focused on. Due to the important application of carbon fiber epoxy composite materials in the aerospace field, in addition to focusing on interface properties, the composite materials are expected to have certain flame retardant properties, and the research on materials meeting such requirements is urgent.
Disclosure of Invention
In order to solve the problems in the prior art and enable the interfacial property and the flame retardant property of the carbon fiber composite material to meet the requirements at the same time, the invention provides a phosphorus-containing aminated coupling agent for fiber surface flame retardant modification and a preparation method and application thereof. The synthesis method is simple, feasible, stable and controllable. The coupling agent synthesized by the method is used for treating the surface of the fiber, so that the bonding capability between the fiber and the resin matrix can be maintained, and the flame retardant property of the composite material can be obviously improved.
The invention adopts the following technical scheme: a method for preparing a phosphorus-containing aminated coupling agent, comprising: adding the phosphoric triamide into a reactor, slowly heating under the protection of nitrogen, dropwise adding an epoxy group coupling agent into a reaction system, keeping a constant stirring speed, and reacting at 40-60 ℃ for 30 min-1 h.
In a preferred embodiment of the invention, the phosphoric triamide is prepared by reacting phosphate with ethylenediamine under the protection of nitrogen for 1-3 hours at the boiling point of ethylenediamine.
The structural formula of the phosphate is as follows:
the structural formula of the ethylenediamine is as follows:
the structural formula of the phosphoric triamide is as follows:
in a preferred embodiment of the present invention, the epoxy-based coupling agent is γ - (2, 3-epoxypropoxy) propyltrimethoxysilane, i.e., KH560, which has the formula:
in a preferred embodiment of the invention, phosphoric triamides are prepared with or without a solvent; when a solvent is used, the solvent is toluene.
In a preferred embodiment of the invention, the reaction molar ratio of the phosphoric triamide to the epoxy coupling agent is 1: 1-3: 1.
The invention also protects the phosphorus-containing amination coupling agent prepared by the preparation method.
The invention also protects the application of the phosphorus-containing amination coupling agent on the surface of the carbon fiber, and the phosphorus-containing amination coupling agent is used for preparing a sizing agent for flame-retardant modification of the surface of the carbon fiber, wherein the volume fraction of the phosphorus-containing amination coupling agent is 2-7%, and the mixture is uniformly stirred and hydrolyzed for 0.5-2 h.
In a preferred embodiment of the invention, the carbon fiber is obtained by using polyacrylonitrile-based raw material and the final heat treatment temperature is within 1200-3000 ℃.
Compared with the prior art, the preparation process of the phosphorus-containing amination coupling agent is simple, the reaction is stable, the surface sizing coating process is applied to the surface of the carbon fiber, the interface performance between the carbon fiber and the epoxy resin can be maintained, the flame retardant performance of the carbon fiber epoxy resin composite material is obviously enhanced, and the interface performance and the flame retardant performance of the material are met.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is an FTIR spectrum of the phosphorus-containing aminated coupling agent obtained in example 1.
Detailed Description
The following examples are further described below.
In the following examples, two carbon fibers with different surface conditions were used, respectively:
carbon fiber 1: polyacrylonitrile-based carbon fibers with epoxy sizing glue layers.
Carbon fiber 2: high-temperature degumming, and no glue layer on the surface.
The invention has the effects that the interface bonding performance of the material is evaluated through the interlaminar shear strength, and the flame retardant performance of the material is evaluated through the value of the limiting oxygen index. The results of the flame retardant modification of the surfaces of the two carbon fibers are shown in table 1.
Example 1
The reaction equation for this example is as follows:
in the reaction process, phosphoric triamide and KH560 are used as raw materials, 19ml of phosphoric triamide is added into a 100ml three-neck flask, 22ml of KH560 is added dropwise under the protection of nitrogen, the temperature is raised to 60 ℃ while stirring, and the reaction is stopped after 30min of reaction. As shown in fig. 1, the structure is characterized as follows: FTIR (KBr) (cm)-1): 3347 and 3297 (-NH)2) 2940 and 2840 (-CH)2），1562（-NH），1201（P=O），1083（Si-O），1056（P-C-O）。
The modified phosphorus-containing amination coupling agent with the structure is used for surface flame-retardant treatment of carbon fibers. The carbon fiber 1 is treated by a surface sizing method, and the solution preparation method comprises the following steps: 5ml of the modified phosphorus-containing aminated coupling agent is dropwise added into a mixed solution of 10ml of methanol and 85ml of water, and hydrolysis is carried out for 1h under uniform stirring. The fiber after surface treatment is compounded with epoxy 6101 resin, triethylene tetramine is used as a curing agent to prepare an interlaminar shear and limiting oxygen index experiment sample band, and the test results are shown in table 1.
Example 2
The same treatment conditions as in example 1 were used except that the kind of the fiber used in example 1 was changed and carbon fiber 2 was used.
Comparative example 1
The carbon fiber 1 is compounded with epoxy 6101 resin, triethylene tetramine is used as a curing agent to prepare an interlaminar shear and limiting oxygen index experiment sample strip, and the test results are shown in table 1.
Comparative example 2
By changing the mixture ratio of the solution in example 1, 15ml of the modified phosphorus-containing aminated coupling agent was added dropwise to a mixed solution of 30ml of methanol and 55ml of water, and hydrolysis was carried out for 1 hour with uniform stirring. The remaining processing conditions were the same as in example 1.
TABLE 1 interlaminar shear strength and limiting oxygen index of composite materials
From the results in table 1, it can be seen that the carbon fiber epoxy resin composite material prepared by satisfying the conditions of the present invention has excellent interfacial properties and flame retardant properties. The carbon fiber epoxy resin composite material which is not modified by the phosphorus-containing aminated coupling agent and the parameters of the modification of which are out of the limited range cannot realize excellent interface and flame retardant performance.
The foregoing embodiments illustrate and describe the principles and general features of the present invention and its advantages. It will be understood by those skilled in the art that the present invention is not limited by the embodiments described above, which are given by way of illustration of the principles of the invention and are not to be taken as limiting the scope of the invention in any way, and that various changes and modifications may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of a phosphorus-containing aminated coupling agent is characterized by comprising the following steps: adding the phosphoric triamide into a reactor, slowly heating under the protection of nitrogen, dropwise adding an epoxy group coupling agent into a reaction system, keeping a constant stirring speed, and reacting at 40-60 ℃ for 30 min-1 h; the epoxy group coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the structural formula of the epoxy group coupling agent is as follows:
the structural formula of the phosphoric triamide is as follows:
the structural formula of the phosphorus-containing amination coupling agent is as follows:
2. the preparation method of claim 1, wherein the phosphoric triamide is prepared by reacting phosphoric acid ester with ethylenediamine under the protection of nitrogen for 1-3 hours at the boiling point of ethylenediamine.
3. The process according to claim 2, wherein the phosphoric triamide is prepared with or without a solvent; when a solvent is used, the solvent is toluene.
4. The preparation method according to claim 1, wherein the molar ratio of the phosphoric triamide to the epoxy coupling agent is 1: 1-3: 1.
5. The aminated coupling agent containing phosphorus prepared by the process according to any one of claims 1 to 4.
6. The application of the phosphorus-containing aminated coupling agent on the surface of carbon fibers as claimed in claim 5, characterized in that the phosphorus-containing aminated coupling agent is used to prepare a sizing agent for flame-retardant modification of the surface of carbon fibers, wherein the volume fraction of the phosphorus-containing aminated coupling agent is 2-7%, and the mixture is uniformly stirred and hydrolyzed for 0.5-2 h.
7. The application of claim 6, wherein the carbon fiber is a carbon fiber obtained from polyacrylonitrile-based raw material at a final heat treatment temperature of 1200-3000 ℃.
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| 石墨烯的功能化及其环氧树脂复合材料的阻燃性能及机理研究;王鑫;《中国科学技术大学硕士学位论文》;20131231;第2-4章 * |
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