CN103159413B - A kind of glass fibre adds treating compound and the preparation thereof of carbon nanotube - Google Patents
A kind of glass fibre adds treating compound and the preparation thereof of carbon nanotube Download PDFInfo
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- CN103159413B CN103159413B CN201210553280.XA CN201210553280A CN103159413B CN 103159413 B CN103159413 B CN 103159413B CN 201210553280 A CN201210553280 A CN 201210553280A CN 103159413 B CN103159413 B CN 103159413B
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Abstract
The present invention relates to the treating compound that a kind of glass fibre adds carbon nanotube, this treating compound is composed of the following components by weight percentage: laking agent 3%-10%, epoxy resin 3%-10%, cats product 0.5%-5%, coupling agent 0.1%-5%, carbon nanotube 0.1%-1%, deionized water 69%-93.3%.Preparation method: bisphenol A type epoxy resin, add in ionized water, temperature keeps 60 ~ 80 DEG C, 1 ~ 2h is stirred under 200 ~ 500r/min, then add the carbon nanotube of Dyhard RU 100 formaldehyde resin, cats product, silane coupling agent, modification successively, stir, finally add deionized water, stir, obtain treating compound.The formula that the inventive method adopts is simple, practical, is applicable to suitability for industrialized production; The treating compound of preparation effectively can improve the intensity of glass fibre; And the intensity of glass fiber compound material can be improved.
Description
Technical field
The invention belongs to treating compound and preparation field thereof, particularly a kind of glass fibre adds carbon nanotube treating compound and preparation thereof.
Background technology
In glass fibre actual production, in drawing process the sharply decline of temperature can make glass fibre produce surface stress, thus formed crizzle fibre property is declined, therefore usual stretching while fiber surface spray or dip-coating one deck treating compound.Treating compound mainly contains two effects: prevent on the one hand the generation of fiberglass surfacing tiny crack and diffusion, the interfibrous frictionally damage of minimizing, improve the intensity of fiber; Treating compound can improve the cohesive strength between fiber and matrix on the other hand.
CNTs has fabulous mechanical property, as tensile strength (200GPa), Young's modulus (200 ~ 500GPa) and breaking strain (10 ~ 30%), is the ideal chose being used as modifying interface.More and more report about the research of CNTs/ nanocomposite, in resin, add the performance that a small amount of CNTs just obviously can improve material.CNTs has huge specific surface area, plays obvious interfacial effect, bridging action, Anticrack, thus improve the strength of materials in the middle of resin.There is report, by electrophoretic deposition (EPD) method, CNTs is deposited to fiberglass surfacing, think that nanoparticle is similar to the mineral substance in biological bone, the suitable nano level interfacial energy formed thus improves the cohesive strength of fiber and resin, improves the intensity of glass filament reinforced plastics.
When CNTs adds in treating compound, modified CNTs and glass fibre are combined closely, and play bridging action in cracks, improve the tensile strength of fiber; Also can improve the interface structure between glass fibre and resin simultaneously, improve cohesive strength.In a word, when adding CNTs in treating compound, can greatly improve fiberglass products quality.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of glass fibre and adds carbon nanotube treating compound and preparation method thereof, and the formula that the present invention adopts is simple, practical, is applicable to suitability for industrialized production; The treating compound of preparation effectively can improve the intensity of glass fibre; And the intensity of glass fiber compound material can be improved.
A kind of glass fibre of the present invention adds carbon nanotube treating compound, it is characterized in that: this treating compound is composed of the following components by weight percentage:
Described laking agent is Dyhard RU 100 formaldehyde resin, and density is 1.198g/cm
3, viscosity is 500 ~ 560mPas.
Described epoxy resin is bisphenol A type epoxy resin emulsion, and relative molecular mass is 350 ~ 1000, and median size is 0.2 ~ 2.0 μm.
Described cats product is palmityl trimethyl ammonium chloride.
Described coupling agent is silane coupling agent, and model is KH-550, KH-560 or A186.
Described carbon nanotube is modified carbon nano-tube, and method of modifying is: (1) carbon nanotube adds acid with strong oxidizing property, then heats, and stirs 20 ~ 30h, and then centrifugal or natural subsidence cleaning, obtains the black mixed solution of carbon nanotube and water; (2) in obtained black mixed solution, second diene triamine, polyvinyl pyrilodone is added, 5 ~ 10h is stirred under 70 DEG C ~ 110 DEG C conditions, namely the CNT (carbon nano-tube) of modification is obtained, wherein the mass ratio of carbon nanotube and acid with strong oxidizing property is 1:50 ~ 1:300, and the mass ratio of polyvinyl pyrilodone and carbon nanotube is 1:20 ~ 1:10; The mass ratio of second diene triamine and carbon nanotube is 1:15 ~ 1:10.
Described acid with strong oxidizing property is concentrated nitric acid.
A kind of glass fibre of the present invention adds the treating compound preparation method of carbon nanotube, comprise: add bisphenol A type epoxy resin 3%-10% by weight percentage, add in ionized water, temperature keeps 60 ~ 80 DEG C, 1 ~ 2h is stirred under 200 ~ 500r/min, then the carbon nanotube 0.1%-1% of Dyhard RU 100 formaldehyde resin 3%-10%, cats product 0.5%-5%, silane coupling agent 0.1%-5%, modification is added successively, stir, finally add deionized water, stir, obtain treating compound, wherein the total weight percent of deionized water is 69%-93.3%.
The present invention is by the intensity of multifilament strength tester tested glass fiber, and precursor brute force (N/TEX) represents the intensity of glass fibre, gets 10 groups of samples and records fibre strength, and getting its mean value is glass fiber strength.
The present invention, by the organic assembling of several raw material, improves the intensity of glass fibre.Dyhard RU 100 formaldehyde resin is the polymkeric substance of the strong positive charge of a kind of lower molecular weight ,-CONH
2hydrophilic radical coordinates distinctive dual quaternary amine type cationic reactive groups, makes there is very strong bonding force between itself and fiber.Membrane-forming agent epoxy resin and laking agent form the higher resin film of one deck intensity at fiber surface, and with the addition of the carbon nanotube of modification, can realize the effect of effective reinforcing glass fiber.This formula is simple, practical, not only can improve the intensity of glass fibre, the Fiber In Composite Material made and the cohesive strength of resin higher, the quality of glass fiber product can be improved to a great extent.
beneficial effect
(1) formula of the present invention's employing is simple, practical, is applicable to suitability for industrialized production;
(2) treating compound that prepared by the present invention effectively can improve the intensity of glass fibre;
(3) treating compound that prepared by the present invention can improve the intensity of glass fiber compound material.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope photo of the glass fibre being coated with interpolation 0.3% carbon nanotube treating compound.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
5g carbon nanotube is put into there-necked flask, adds 250ml concentrated nitric acid, then stir 20h in a heated condition, then or natural subsidence cleaning centrifugal with dehydrated alcohol, deionized water repeatedly, finally obtains the black mixed solution of carbon nanotube and water.In obtained black mixed solution, add 0.5g second diene triamine, 1.0g polyvinyl pyrilodone stirs 10h under 70 DEG C of conditions, obtain the CNT (carbon nano-tube) of modification.
Per distribution ratio takes the bisphenol A type epoxy resin of 5% by weight, and add to and add in container that weight percent is the deionized water of 50%, temperature keeps 60 DEG C, stirs 1h under 500r/min.Then Dyhard RU 100 formaldehyde resin 5%, cats product 1%, silane resin acceptor kh-550 0.3%, modified carbon nano-tube 0.1% is added by weight percentage successively, each stirring 0.5h, its cationic surfactant dilutes with deionized water in advance, finally add the deionized water that weight percent is 38.6%, stir 2.5h, obtain treating compound, intensity N/TEX is 0.52.
Embodiment 2
5g carbon nanotube is put into there-necked flask, adds 300ml concentrated nitric acid, then stir 30h in a heated condition, then or natural subsidence cleaning centrifugal with dehydrated alcohol, deionized water repeatedly, finally obtains the black mixed solution of carbon nanotube and water.In obtained black mixed solution, add 0.7g second diene triamine, 0.9g polyvinyl pyrilodone stirs 5h under 110 DEG C of conditions, obtain the CNT (carbon nano-tube) of modification.
Per distribution ratio takes the bisphenol A type epoxy resin of 5% by weight, and add to and add in container that weight percent is the deionized water of 50%, temperature keeps 80 DEG C, stirs 2h under 200r/min.Then Dyhard RU 100 formaldehyde resin 5%, cats product 1%, silane coupling agent KH-5600.3%, modified carbon nano-tube 0.3% is added by weight percentage successively, each stirring 0.5h, its cationic surfactant dilutes with deionized water in advance, finally add the deionized water that weight percent is 38.4%, stir 2.5h, obtain treating compound, intensity N/TEX is 0.57.
Embodiment 3
5g carbon nanotube is put into there-necked flask, adds 350ml concentrated nitric acid, then stir 30h in a heated condition, then or natural subsidence cleaning centrifugal with dehydrated alcohol, deionized water repeatedly, finally obtains the black mixed solution of carbon nanotube and water.In obtained black mixed solution, add 0.9g second diene triamine, 0.8g polyvinyl pyrilodone stirs 5h under 110 DEG C of conditions, obtain the CNT (carbon nano-tube) of modification.
Per distribution ratio takes the bisphenol A type epoxy resin of 5% by weight, and add to and add in container that weight percent is the deionized water of 50%, temperature keeps 60 DEG C, stirs 1h under 250r/min.Then Dyhard RU 100 formaldehyde resin 5%, cats product 1%, silane resin acceptor kh-550 0.3%, modified carbon nano-tube 0.5% is added by weight percentage successively, each stirring 0.5h, its cationic surfactant dilutes with deionized water in advance, finally add the deionized water that weight percent is 38.2%, stir 2.5h, obtain treating compound, intensity N/TEX is 0.61.
Embodiment 4
5g carbon nanotube is put into there-necked flask, adds 400ml concentrated nitric acid, then stir 30h in a heated condition, then or natural subsidence cleaning centrifugal with dehydrated alcohol, deionized water repeatedly, finally obtains the black mixed solution of carbon nanotube and water.In obtained black mixed solution, add that 1.0g enters second diene triamine, 0.7g polyvinyl pyrilodone stirs 5h under 110 DEG C of conditions, obtain the CNT (carbon nano-tube) of modification.
Per distribution ratio takes the bisphenol A type epoxy resin of 5% by weight, and add to and add in container that weight percent is the deionized water of 50%, temperature keeps 60 DEG C, stirs 1h under 250r/min.Then Dyhard RU 100 formaldehyde resin 5%, cats product 1%, silane resin acceptor kh-550 0.3%, modified carbon nano-tube 0.9% is added by weight percentage successively, each stirring 0.5h, its cationic surfactant dilutes with deionized water in advance, finally add the deionized water that weight percent is 37.8%, stir 2.5h, obtain treating compound, intensity N/TEX is 0.60.
Comparative example 1
Take the bisphenol A type epoxy resin of 3.5% by weight percentage, add to and add in container that weight percent is the deionized water of 50%, temperature keeps 60 DEG C, stirs 1h under 250r/min.Then add by weight percentage successively Dyhard RU 100 formaldehyde resin 3.5%, cats product 1%, silane resin acceptor kh-550 0.3%, respectively stir 0.5h.Cats product with deionized water dilution, finally adds the deionized water of 41.7% in advance by weight percentage, and stir 2.5h, obtain treating compound, intensity N/TEX is 0.42.
Comparative example 2
Per distribution ratio takes the bisphenol A type epoxy resin of 5% by weight, and add to and add in container that weight percent is the deionized water of 50%, temperature keeps 60 DEG C, stirs 1h under 250r/min.Then add Dyhard RU 100 formaldehyde resin 5%, cats product 1%, silane resin acceptor kh-550 0.3% by weight percentage successively, respectively stir 0.5h, its cationic surfactant dilutes with deionized water in advance, finally add the deionized water of 38.7% by weight percentage, stir 2.5h, obtain treating compound, intensity N/TEX is 0.45.
Claims (4)
1. the glass fibre treating compound adding carbon nanotube, this treating compound is composed of the following components by weight percentage: laking agent 3%-10%, epoxy resin 3%-10%, cats product 0.5%-5%, coupling agent 0.1%-5%, carbon nanotube 0.1%-1%, deionized water 69%-93.3%; Wherein laking agent is Dyhard RU 100 formaldehyde resin, and density is 1.198g/cm
3, viscosity is 500 ~ 560mPas; Epoxy resin is bisphenol A type epoxy resin emulsion, and relative molecular mass is 350 ~ 1000, and median size is 0.2 ~ 2.0 μm; Cats product is palmityl trimethyl ammonium chloride;
Wherein carbon nanotube is modified carbon nano-tube, and method of modifying is: (1) carbon nanotube adds acid with strong oxidizing property, then heats, and stirs 20 ~ 30h, and then centrifugal or natural subsidence cleaning, obtains the black mixed solution of carbon nanotube and water; (2) in obtained black mixed solution, second diene triamine, polyvinyl pyrilodone is added, 5 ~ 10h is stirred under 70 DEG C ~ 110 DEG C conditions, namely the CNT (carbon nano-tube) of modification is obtained, wherein the mass ratio of carbon nanotube and acid with strong oxidizing property is 1:50 ~ 1:300, and the mass ratio of polyvinyl pyrilodone and carbon nanotube is 1:20 ~ 1:10; The mass ratio of second diene triamine and carbon nanotube is 1:15 ~ 1:10.
2. a kind of glass fibre according to claim 1 adds the treating compound of carbon nanotube, and it is characterized in that: described coupling agent is silane coupling agent, model is KH-550, KH-560 or A186.
3. a kind of glass fibre according to claim 1 adds the treating compound of carbon nanotube, it is characterized in that: described acid with strong oxidizing property is concentrated nitric acid.
4. glass fibre as claimed in claim 1 adds a treating compound preparation method for carbon nanotube, comprising:
Add bisphenol A type epoxy resin 3%-10% by weight percentage, add in ionized water, temperature keeps 60 ~ 80 DEG C, stir 1 ~ 2h under 200 ~ 500r/min, then add the carbon nanotube 0.1%-1% of Dyhard RU 100 formaldehyde resin 3%-10%, cats product 0.5%-5%, silane coupling agent 0.1%-5%, modification successively, stir, finally add deionized water, stir, obtain treating compound, wherein the total weight percent of deionized water is 69%-93.3%.
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| CN104086094B (en) * | 2014-07-16 | 2016-09-14 | 哈尔滨工业大学 | A kind of glass fiber infiltration agent of carbon nanotubes and preparation method thereof |
| CN107141977A (en) * | 2017-05-08 | 2017-09-08 | 河海大学 | A kind of carbon nano-tube modification coating and preparation method and application |
| CN108658480A (en) * | 2018-05-30 | 2018-10-16 | 陈毅忠 | A kind of preparation method of high combination basalt cladded type size |
| CN111620571A (en) * | 2020-06-04 | 2020-09-04 | 苏州北美国际高级中学 | Anti-ultraviolet magnetic glass fiber and manufacturing method thereof |
| CN115011041B (en) * | 2022-07-15 | 2023-07-21 | 中广核俊尔(浙江)新材料有限公司 | Environment-friendly high-gloss low-fiber-floating continuous-reinforced long glass fiber polypropylene composite material |
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