CN108071018A - A kind of aramid fiber water-soluble epoxy resin sizing agent - Google Patents
A kind of aramid fiber water-soluble epoxy resin sizing agent Download PDFInfo
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- CN108071018A CN108071018A CN201711442951.4A CN201711442951A CN108071018A CN 108071018 A CN108071018 A CN 108071018A CN 201711442951 A CN201711442951 A CN 201711442951A CN 108071018 A CN108071018 A CN 108071018A
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- water
- epoxy resin
- sizing agent
- soluble epoxy
- aramid fiber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
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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
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention provides a kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, sizing agent key component is water-soluble epoxy resin, surfactant and distilled water form, and wherein the mass ratio of both water-soluble epoxy resin and surfactant is 20~30: 0.6~15.The surfactant is anion surfactant polyacrylamide or aliphatic alcohol polyoxyvinethene phosphate sylvite and nonionic surfactant polyethylene oxide PEO.Concrete scheme is uniformly to mix water-soluble epoxy resin and surfactant at 30~50 DEG C in 20~30: 0.6~15 ratio, adds in distilled water and is diluted to solid content 20~30%, so as to obtain aramid fiber water-soluble epoxy resin sizing agent.This sizing agent stability is good, at low cost, free from environmental pollution, and preparation method is simple.
Description
Technical field
The present invention relates to a kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, more particularly to a kind of aramid fibers
The preparation method of fiber water-soluble epoxy resin sizing agent.
Background technology
Aramid fiber is a kind of high-tech special type organic fiber haveing excellent performance, and has high ratio modulus, repels the corrupting influence, anti-drop
Many excellent properties such as solution, high temperature resistant, shock resistance are widely used in the fields such as space flight and aviation, war industry, life protection, such as
Make the composite reinforcing materials such as rocket engine cast, tank armor, bulletproof jacket, the helmet, optical fiber.
However, the fragile material of aramid fiber category high-strength and high-modulus low elongation, surface-active functional group is less, and chemistry is presented
Inertia, while crystallinity is very high, amorphous region is less, thus with resin-bonded poor performance, so as to cause composite material obtained
Mechanical property is not good enough.In order to solve this problem, in actual application, it will usually which aramid fiber is done at surface size
, there is the phenomenon that lousiness in reason, to reduce drawing of fiber when, improve the boundling of fiber, improve processing performance and fiber and interlaminar resin
Chemical bond ability is greatly promoted the interaction of fibre reinforcement and basis material, and it is interface characteristics to improve fibrous composite
Energy.
Common sizing agent has two kinds of solvent-borne type and emulsion-type.Have in solvent-borne type sizing agent containing largely inflammable volatile
Solvent, environment easy to pollute are mostly used emulsion-type sizing agent now.Wherein using water as the soluble epoxide tree of solvent or decentralized medium
Fat sizing agent is more and more taken seriously.
The methods of water-soluble epoxy resin is generally with Mechanical Method, phase inversion, chemical modification, by epoxy with particle or liquid
The stable dispersion system matched somebody with somebody in drop ground being dispersed in using water as the decentralized medium of continuous phase of form stable, to a certain degree
On not only retain the excellent properties of most epoxy resin, but also can preferably be dissolved or dispersed in water, avoid as far as possible
The use of organic solvent, improves the level of resources utilization.But since epoxy resin itself is not soluble in water, its water solubility is main
Come from introduced in its molecule segment such as-COOH ,-OH ,-NH2It waits hydrophilic radicals or adds in suitable solubilizer to realize.
To the exploitation of water-soluble epoxy resin also in development phase, industrial water requirement is big, still needs to the external production of a large amount of imports in China at present
Product, so there are very wide Research Prospects to water-soluble epoxy resin and with the Compositional type sizing agent of other substances.
The content of the invention
In order to improve the combination power between aramid fiber and matrix resin, so as to improve the performance of composite material, the present invention
Provide a kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent.Using water-soluble epoxy resin as main slurry with it is non-
Ionic surface active agent polyethylene glycol oxide, anion surfactant polyacrylamide, wetting agent etc. are compounded to prepare virtue
The compound sizing agent of synthetic fibre fiber.Aramid fiber provided by the invention is stablized with sizing agent performance, has preferable wetability, together
When aramid fiber can also be made to maintain preferable mechanical property.
The present invention provides a kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, which is characterized in that by weight
Percentage meter is measured, component includes：
Water-soluble resin：20~30wt%
Water：0~80wt%
Surfactant：0.6~15wt%
The total weight of said components meets 100%, wherein：
The water-soluble resin is bonderite modified soluble epoxy resin PAEK, epoxide number 0.44mol/100g.Its
Structural formula is：
The surfactant is anion surfactant or nonionic surfactant.
The anion surfactant is polyacrylamide or aliphatic alcohol polyoxyvinethene phosphate sylvite.
The anion surfactant polyacrylamide PAM, molecular weight are 1500~18,000,000, are a kind of having for wire
Machine macromolecular water-soluble polymer, white powder can dissolve in any proportion in water, and dissolving is not affected by temperature, water-soluble
Liquid is homogeneous limpid high viscosity liquid, nontoxic, non-corrosive, with superiority such as thickening property, endurance of cutting, dispersivenesses
Energy.The molecular formula of PAM is as follows：
The anion surfactant aliphatic alcohol polyethenoxy phosphate kalium salt, be alcohol ether type it is nonionic modified be one
Kind phosphate type anion surfactant, there is preferable wetting action.
The nonionic surfactant is polyethylene oxide PEO, and molecular weight 10~500,000 are a kind of white water-solubles
Thermoplastic material, low toxicity and with complete water-soluble have a flexibility, excellent rheology of solution, can be used as spinning sizing agent,
Thickener, lubricant, antistatic agent etc. have preferable compatibility with other resins, can improve the bonding between matrix and fiber
Property.More importantly it can enhance surface activity of aramid fiber containing hydrophilic and hydrophobic grouping in PEO molecules, reduce surface
Power contributes to wettability of the aqueous solution to aramid fiber, and, to aramid fiber in water scattered particularly useful, addition is suitable for this
Ratio can be such that slurry preferably sprawls.
The preparation of aramid fiber sizing agent designed by the present invention is by the way that main slurry is dissolved in the water realization, specifically
Following technique：
Water-soluble epoxy resin and surfactant are blended in 30~50 DEG C uniformly in 20~30: 0.6~15 ratio
Mixing adds in distilled water and is diluted to solid content 20~30%, you can obtains aramid fiber water-soluble epoxy resin sizing agent.
The key of the present invention is using the water-soluble epoxy resin of environment-friendly type as main slurry, and then adds in macromolecular water-soluble
Anion surfactant PAM or the preferable nonionic surfactant PEO of molecular flexibility, to each component coordinate compounding come
The water-soluble sizing agent suitable for aramid fiber is obtained, and by changing the content of PEO and PAM aramid fiber can be made to have not
Same aft-loaded airfoil performance, to meet different technique and purposes.
Sizing agent provided by the present invention is water-soluble sizing agent, and preparation is simple, it is short to take, at low cost, free from environmental pollution,
The advantages that easy to use.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, experimental procedure are as follows：
Water-soluble epoxy resin is uniformly mixed for 1: 0.05 in mass ratio with anion surfactant PAM at 40 DEG C,
Distilled water dilution uniform stirring 30min is added in, obtains aramid fiber sizing agent.
The content of each component is as follows in final aramid fiber sizing agent obtained：
Water-soluble epoxy resin：20wt%
Water：79wt%
Polyacrylamide PAM：1wt%
Embodiment 2
A kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, experimental procedure are as follows：
Water-soluble epoxy resin is uniformly mixed for 1: 0.03 in mass ratio with anion surfactant PAM at 40 DEG C,
Distilled water is added to dilute uniform stirring 30min, obtains aramid fiber sizing agent.
The content of each component is as follows in final aramid fiber sizing agent obtained：
Water-soluble epoxy resin：20wt%
Water：79.4wt%
Polyacrylamide PAM：0.6wt%
Embodiment 3
A kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, experimental procedure are as follows：
Water-soluble epoxy resin and aliphatic alcohol polyoxyvinethene phosphate sylvite is uniformly mixed in mass ratio for 9: 1 at 30 DEG C
It closes and is uniformly mixed, distilled water is added to dilute uniform stirring 30min, obtains aramid fiber sizing agent.
The content of each component is as follows in final aramid fiber sizing agent obtained：
Water-soluble epoxy resin：90wt%
Aliphatic alcohol polyoxyvinethene phosphate sylvite：10wt%
Embodiment 4
A kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, experimental procedure are as follows：
Water-soluble epoxy resin and aliphatic alcohol polyoxyvinethene phosphate sylvite is uniform in mass ratio for 95: 5 at 30 DEG C
Mixing is uniformly mixed, and distilled water is added to dilute uniform stirring 30min, obtains aramid fiber sizing agent.
The content of each component is as follows in final aramid fiber sizing agent obtained：
Water-soluble epoxy resin：95wt%
Aliphatic alcohol polyoxyvinethene phosphate sylvite：5wt%
Embodiment 5
A kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, reaction step are as follows：
Water-soluble epoxy resin with polyethylene oxide at 45 DEG C for 2: 1 is uniformly mixed in mass ratio, distilled water is added to dilute
Uniform stirring 40min obtains aramid fiber sizing agent.
The content of each component is as follows in final aramid fiber sizing agent obtained：
Water-soluble epoxy resin：20wt%
Water：70wt%
Polyethylene oxide：10wt%
Embodiment 6
A kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, reaction step are as follows：
Water-soluble epoxy resin with polyethylene oxide at 45 DEG C for 3: 2 is uniformly mixed in mass ratio, distilled water is added to dilute
Uniform stirring 40min obtains aramid fiber sizing agent.
The content of each component is as follows in final aramid fiber sizing agent obtained：
Water-soluble epoxy resin：21wt%
Water：65wt%
Polyethylene oxide：14wt%
Embodiment 7
A kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, reaction step are as follows：
Water-soluble epoxy resin and polyethylene oxide are pressed into quality with aliphatic alcohol polyoxyvinethene phosphate sylvite at 40 DEG C
Than uniformly being mixed for 4: 1: 1, distilled water is added to dilute uniform stirring 40min, obtains aramid fiber sizing agent.
The content of each component is as follows in final aramid fiber sizing agent obtained：
Claims (7)
1. a kind of preparation method of aramid fiber water-soluble epoxy resin sizing agent, which is characterized in that percentage,
Component includes：
2. aramid fiber water-soluble epoxy resin sizing agent according to claim 1, it is characterised in that the main slurry is
It is made of water-soluble epoxy resin and surfactant.
3. aramid fiber water-soluble epoxy resin sizing agent according to claim 1, it is characterised in that the water solubility ring
Oxygen resin is that the epoxide number of bonderite modified soluble epoxy resin PAEK, the PAEK are 0.44mol/100g.Its structural formula
For：
4. aramid fiber water-soluble epoxy resin sizing agent according to claim 1, which is characterized in that surfactant is cloudy
Ionic surface active agent or nonionic surfactant.The anion surfactant is polyacrylamide or fatty alcohol polyoxy
Vinethene phosphate kalium salt；The nonionic surfactant is polyethylene oxide PEO.
5. anion surfactant according to claim 4 is polyacrylamide PAM or fatty alcohol polyoxyethylene ether phosphorus
Acid esters sylvite.Wherein, aliphatic alcohol polyethenoxy phosphate kalium salt is a kind of nonionic modified phosphate type the moon for being of alcohol ether type from
Sub- surfactant has preferable wetting action.PAM molecular weight is 1500~18,000,000, is a kind of organic polymer of wire
Water-soluble polymer.Its molecular formula is as follows：
6. nonionic surfactant according to claim 4 is polyethylene oxide PEO, molecular weight 10~500,000 are one
The thermoplastic material of kind of white water-soluble, low toxicity and with complete water-soluble.
7. the preparation method of the aramid fiber water-soluble epoxy resin sizing agent according to claim 1-4, it is characterized in that will
Water-soluble epoxy resin and surfactant are blended in 30~50 DEG C of uniformly mixing in 20~30: 0.6~15 ratio, added in
Distilled water is diluted to solid content 20~30%, you can obtains aramid fiber water-soluble epoxy resin sizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711442951.4A CN108071018A (en) | 2017-12-27 | 2017-12-27 | A kind of aramid fiber water-soluble epoxy resin sizing agent |
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| CN201711442951.4A CN108071018A (en) | 2017-12-27 | 2017-12-27 | A kind of aramid fiber water-soluble epoxy resin sizing agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020143395A (en) * | 2019-03-06 | 2020-09-10 | 東レ・デュポン株式会社 | Aromatic polyamide fiber, aromatic polyamide fiber pulp and manufacturing method thereof |
| CN113480707A (en) * | 2021-06-08 | 2021-10-08 | 上海工程技术大学 | Aramid fiber water-soluble epoxy resin surface sizing agent and preparation and application thereof |
| CN113564923A (en) * | 2021-06-08 | 2021-10-29 | 上海工程技术大学 | Surface sizing agent for aramid fiber composite material and preparation and application thereof |
-
2017
- 2017-12-27 CN CN201711442951.4A patent/CN108071018A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020143395A (en) * | 2019-03-06 | 2020-09-10 | 東レ・デュポン株式会社 | Aromatic polyamide fiber, aromatic polyamide fiber pulp and manufacturing method thereof |
| JP7325161B2 (en) | 2019-03-06 | 2023-08-14 | 東レ・デュポン株式会社 | Aromatic polyamide fiber, aromatic polyamide fiber pulp, and method for producing the same |
| CN113480707A (en) * | 2021-06-08 | 2021-10-08 | 上海工程技术大学 | Aramid fiber water-soluble epoxy resin surface sizing agent and preparation and application thereof |
| CN113564923A (en) * | 2021-06-08 | 2021-10-29 | 上海工程技术大学 | Surface sizing agent for aramid fiber composite material and preparation and application thereof |
| CN113480707B (en) * | 2021-06-08 | 2022-04-26 | 上海工程技术大学 | Aramid fiber water-soluble epoxy resin surface sizing agent and preparation and application thereof |
| CN113564923B (en) * | 2021-06-08 | 2023-06-06 | 上海工程技术大学 | Surface sizing agent for aramid fiber composite material and preparation and application thereof |
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Application publication date: 20180525 |