CN103788322B - The bisphenol A epoxide resin compositions modified by polyurethane structural and preparation thereof and application - Google Patents
The bisphenol A epoxide resin compositions modified by polyurethane structural and preparation thereof and application Download PDFInfo
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- CN103788322B CN103788322B CN201210417800.4A CN201210417800A CN103788322B CN 103788322 B CN103788322 B CN 103788322B CN 201210417800 A CN201210417800 A CN 201210417800A CN 103788322 B CN103788322 B CN 103788322B
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- bisphenol
- epoxy resin
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- polyurethane structural
- epoxide resin
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- 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
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
-
- 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
Abstract
The present invention relates to the epoxy resin sizing agent emulsion that a kind of polyurethane structural is modified, its component includes: the composition epoxy resin 55 ~ 78wt% of polyurethane structural modification, surfactant 20 ~ 40wt%, antioxidant 0.5 ~ 2wt%, levelling agent 1 ~ 2wt%, and antifreezing agent 0.5 ~ 1wt%；Its preparation includes: the dehydration of bisphenol A type epoxy resin evacuation produced to bubble-free, adds isocyanates, prepare composition epoxy resin after cooling；By above-mentioned material mark, surfactant and antioxidant are mixed homogenizing in a kettle., be then gradually adding deionized water, levelling agent and antifreezing agent, to obtain final product.Carbon fiber obtained by the epoxy resin sizing agent emulsion of the present invention has good convergence, wearability and toughness, and its convergence and wearability freely regulate easily by the consumption of isocyanate component；And this carbon fiber sizing agent need not add collecting agent and on-the-spot secondary mixing in the later stage, application has good stability, and carbon fiber starching wellability is good, and the beneficially stabilization of industry of carbon fiber produces.
Description
Technical field
The invention belongs to the modified preparation field of high-molecular organic material epoxy resin, particularly to one by polyurethane structural
Modified bisphenol A epoxide resin compositions and preparation thereof and application.
Background technology
Epoxy resin has higher intensity, excellent adhesive property, chemical stability, easy machine-shaping and with low cost etc.
Advantage, its polymer composites is largely used to many industrial circles.But crosslink density is high after solidifying because of pure epoxy resin,
There is the shortcomings such as internal stress is big, curing material is crisp, thermostability is poor, limit its application in fibre reinforced composites.
Boundary layer plays an important role in the composite, and it is the transition zone that reinforcement is connected with matrix, is transmission stress simultaneously
Bridge, so its structure and performance directly influence the performance of composite.
At present, based on sizing agent at high-performance carbon fibre and graphite fibre manufacturing engineering and fiber-reinforced resin matrix compound material
Importance in application, sizing agent has become the important supplementary material of carbon fiber, graphite fibre through engineering approaches, its performance impact carbon
The manufacturability of fiber manufacturing engineering and the comprehensive mechanical property of composite, be also current high-performance carbon fibre and graphite fibre product
The important focus of industry technical research.Chinese invention patent application 200510063352.2,201010300131.3,
201010234852.9,2009102158.33,201010202372.4 individually disclose with epoxy resin, aqueous epoxy resins,
(+)-2,3-Epoxy-1-propanol ether-ether, polypropylene nitrile, epoxy vinyl composite resin are the preparation method of the carbon fiber sizing agent of key component
And application.Additionally, in order to improve emulsion property and the performance of starching carbon fiber, Chinese invention patent application further
201010217247.0,201110102007.0,201110085545.3,200410064587.9 individually disclose employing polynary
The preparation method and application of the emulsion pasting agent that alcohol, Graphene, CNT, nano silicon etc. are modified.Meanwhile, in
It is fine that state's application for a patent for invention 201010217240.9 and 201010125199.2 individually discloses two kinds of self-emulsifying type epoxy radicals carbon
The synthesis preparation method of Wesy's sizing agent.But in terms of current application feature, use above-mentioned resin formula to prepare the upper of gained
, when being applied to carbon fiber, graphite fibre, there is under the conditions of normal fiber starching amount (< 1.40%) convergence and wear-resisting in slurry agent
Property poor, fibrillation and expanding performance shortcoming and the problem such as resilience toughness is not enough, especially at 12K and the carbon of above tow number
The through engineering approaches application of fiber generally exists, constrains the practical engineering application of above-mentioned sizing agent.
Summary of the invention
The technical problem to be solved be to provide a kind of bisphenol A epoxide resin compositions modified by polyurethane structural and
Its preparation and application, by the method for the in-situ modified composition epoxy resin of polyurethane structural, introduce Polar Amides formic acid ester group
Group, be applied to the preparation of carbon fiber sizing agent, the technique permeability of sizing agent can be improved, improve sizing technique and
The convergence of carbon fiber and anti-wear performance, beneficially 12K and the application of above tow number carbon fiber through engineering approaches and high performance composite
The manufacture of material；And this composition epoxy resin preparation technology is simple, reaction raw materials convenient sources, can be complete in common apparatus
Becoming preparation process, economic benefit is good, is advantageously implemented industrialized production.
A kind of bisphenol A epoxide resin compositions modified by polyurethane structural of the present invention, its component includes: mass percent
The bisphenol A type epoxy resin of 88-99% and the isocyanates of mass percent 1-12%.
Described bisphenol A type epoxy resin is selected from bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol-A
The mixture of one or more in type E51；
Described bisphenol A type epoxy resin, its mean molecule quantity is 350～2500 grams/mol, and preferably mean molecule quantity is
350～1500 grams/mol；
Described isocyanates is aromatic series, aliphatic or alicyclic isocyanate；
Preferably isocyanates is aromatic series toluene di-isocyanate(TDI) (TDI), aromatic series methyl diphenylene diisocyanate
(MDI), six methylene diisocyanates (HDI) of aliphatic or alicyclic isophorone diisocyanate (IPDI).
A kind of preparation method of the bisphenol A epoxide resin compositions modified by polyurethane structural of the present invention, including:
(1) dehydration of bisphenol A type epoxy resin reactant at high temperature evacuation is produced to bubble-free, its vacuum dehydration
Temperature is 90-150 DEG C, and the vacuum pressure of dehydration is 100-0.1mmHg；
(2) respectively the dry epoxy resin of above-mentioned vacuum dehydration gained is cooled to 50 ~ 70 DEG C, doing in purity 99.999%
The protection of dry nitrogen is lower adds isocyanates reactant, and its epoxy resin is 88 ~ 99:1 ~ 12 with the mass ratio of isocyanates, first
In 50 ~ 70 DEG C, stirring reaction 1 ~ 2 hour, then heat to 80 ~ 100 DEG C, continue reaction more than 2 hours, control reaction
Isocyanate functional group's content of product is less than 0.1% stopped reaction, prepares the bisphenol A epoxide resin that polyurethane structural is modified
Compositions.
In described step (1) bisphenol A type epoxy resin selected from bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44,
The mixture of one or more in bisphenol A-type E51；
In described step (1) bisphenol A type epoxy resin, its mean molecule quantity is 350～2500 grams/mol, preferably
Mean molecule quantity is 350～1500 grams/mol；
The temperature of the vacuum dehydration in described step (1) is 90-120 DEG C, and the vacuum pressure of dehydration is 10-0.5mmHg；
Isocyanates in described step (2) is aromatic series, aliphatic or alicyclic isocyanate；
Preferably isocyanates is aromatic series toluene di-isocyanate(TDI) (TDI), aromatic series methyl diphenylene diisocyanate
(MDI), six methylene diisocyanates (HDI) of aliphatic or alicyclic isophorone diisocyanate (IPDI).
A kind of bisphenol A epoxide resin compositions modified by polyurethane structural of the present invention has good convergence and resistance in preparation
Application in the epoxy radicals carbon fiber sizing agent of mill property.
Beneficial effect
(1) present invention method by the in-situ modified composition epoxy resin of polyurethane structural, introduces Polar Amides carbamate group,
It is applied to the preparation of sizing agent, the technique permeability of sizing agent can be improved；Meanwhile, by freely regulating epoxy resin
The mean molecule quantity of compositions, improves sizing technique and the convergence of carbon fiber and anti-wear performance, beneficially 12K and more than
The application of tow number carbon fiber through engineering approaches and the manufacture of high-performance composite materials；
(2) this preparation technology is simple, and reaction raw materials convenient sources can complete preparation process, economic benefit in common apparatus
Well, it is advantageously implemented industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology
The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited
Fixed scope.
Embodiment 1-12
Quantitative epoxy resin composition is placed in the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 DEG C,
Controlling vacuum pressure 100-0.1mmHg, evacuation is dehydrated 2 hours and produces to bubble-free.It is cooled to 70 DEG C, removes evacuation
Device, inserts condensing tube.Under high pure nitrogen is protected, six times quantitative methylene diisocyanates (HDI) are used trace
Dosing pump is added drop-wise in flask the most lentamente, first reacts 1 hour at 70 DEG C after dropping, then is warming up to 95 DEG C of reactions 2
More than hour, sampling carries out infrared analysis, during result display nothing-NCO group, prepares the bisphenol-A that polyurethane structural is modified
Composition epoxy resin.Epoxy resin composition kind used and consumption, six methylene diisocyanate (HDI) consumptions
It is shown in Table 1.
Raw materials quality table is used in table 1, reaction
Embodiment 13-24
Quantitative epoxy resin composition is placed in the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 DEG C,
Controlling vacuum pressure 100-0.1mmHg, evacuation is dehydrated 2 hours and produces to bubble-free.It is cooled to 70 DEG C, removes evacuation
Device, inserts condensing tube.Under high pure nitrogen is protected, quantitative isophorone diisocyanate (IPDI) is used microflowmeter
Amount pump is added drop-wise in flask the most lentamente, first reacts 1 hour at 70 DEG C after dropping, then is warming up to 95 DEG C of reactions 2
More than hour, sampling carries out infrared analysis, during result display nothing-NCO group, prepares the bisphenol-A that polyurethane structural is modified
Composition epoxy resin.Epoxy resin composition kind used and consumption, isophorone diisocyanate (IPDI) consumption are shown in
Table 2.
Raw materials quality table is used in table 2, reaction
Embodiment 25-36
Quantitative epoxy resin composition is placed in the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 DEG C,
Controlling vacuum pressure 100-0.1mmHg, evacuation is dehydrated 2 hours and produces to bubble-free.It is cooled to 50 DEG C, removes evacuation
Device, inserts condensing tube.Under high pure nitrogen is protected, quantitative methyl diphenylene diisocyanate (MDI) is used trace
Dosing pump is added drop-wise in flask the most lentamente, first reacts 1 hour at 50 DEG C after dropping, then is warming up to 85 DEG C of reactions 2
More than hour, sampling carries out infrared analysis, during result display nothing-NCO group, prepares the bisphenol-A that polyurethane structural is modified
Composition epoxy resin.Epoxy resin composition kind used and consumption, methyl diphenylene diisocyanate (MDI) consumption
It is shown in Table 3.
Raw materials quality table is used in table 3, reaction
Embodiment 37-48
Quantitative epoxy resin composition is placed in the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 DEG C,
Controlling vacuum pressure 100-0.1mmHg, evacuation is dehydrated 2 hours and produces to bubble-free.It is cooled to 50 DEG C, removes evacuation
Device, inserts condensing tube.Under high pure nitrogen is protected, quantitative toluene di-isocyanate(TDI) (TDI) is used Micro-metering Pumps
It is added drop-wise to the most lentamente in flask, first reacts 1 hour at 50 DEG C after dropping, then be warming up to 85 DEG C of reactions 2 hours
Above, sampling carries out infrared analysis, during result display nothing-NCO group, prepares the bisphenol-A epoxy that polyurethane structural is modified
Resin combination.Epoxy resin composition kind used and consumption, toluene di-isocyanate(TDI) (TDI) consumption are shown in Table 4.
Raw materials quality table is used in table 4, reaction
Application Example
One, the preparation of epoxy radicals carbon fiber sizing agent
Take 60g above-described embodiment and prepare the composition epoxy resin that the polyurethane structural of gained is modified, add 0.32g2,6-bis-uncle
Butyl paracresol (group produces by traditional Chinese medicines), 21.30g octadecanol polyoxyethylene ether surface active agent (ethylene oxide polymerization
Degree 20) (being produced by Hai'an, Jiangsu petrochemical plant), stir 1 hour at 90 DEG C.Then it is cooled to 80 DEG C, is slowly added dropwise
The simultaneously high-speed stirred emulsifying of 100g deionized water, add after completing 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(by
BNK company of the U.S. produce), 0.32g butyl glycol ether (group produces by traditional Chinese medicines), prepare water-based emulsion.
The present embodiment is prepared the viscosity of gained water-based emulsion and is used the test of Brookfield DV-II Pro rotating cylinder viscometer to obtain, breast
Liquid PH uses Mettler Toledo Inc. of U.S. DELTA 320pH measurement examination to obtain, and emulsion surface tension uses Germany
The DCAT21 type dynamic contact angle of DataPhysics company obtains with surface tension instrument test, and emulsion mean diameter uses Britain
The Zetasizer NanoZS90 type Dynamic laser scattering instrument test of Malvern instrument company obtains, the every property of prepared emulsion
Index can be shown in Table 5.
Table 5, emulsion property index test result
Two, the starching of carbon fiber
On the small-sized starching instrument of self-control, above-mentioned gained emulsion pasting agent of preparing is carried out starching, and selected fiber is 12K T300 level
Carbon fiber, dipping time 30s, baking temperature 130 DEG C, drying time 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341；Exercise question: temp, resisting type carbon fibre breast
Liquid sizing agent) method test obtain wearability, lousiness figureofmerit；According to GB3357-1982 unidirectional fibre reinforced plastics interlayer
Shear strength ILSS between shear strength test method test carbon fiber composite layer；Use feel ocular estimate fine to carbon after starching
Dimension cluster performance is graded, and gained starching carbon fiber Evaluation results is shown in Table 6.
Table 6, starching carbon fiber Evaluation results
Note: convergence Index grading ●-fine zero-good △-bad ×-poor
Although preferred embodiment is disclosed as above by the present invention, so it is not limited to present disclosure, any is familiar with this
Those skilled in the art, without departing from the main spirits of the present invention and context, when making various change and retouching, therefore invents
Protection domain should be as the criterion with the basic right claimed range applied for a patent.
Claims (7)
1. by a preparation method for the bisphenol A epoxide resin compositions of polyurethane structural modification, including:
(1) dehydration of bisphenol A type epoxy resin reactant at high temperature evacuation is produced to bubble-free, its vacuum dehydration
Temperature is 90-150 DEG C, and the vacuum pressure of dehydration is 100-0.1mmHg；
(2) respectively the dry epoxy resin of above-mentioned vacuum dehydration gained is cooled to 50～70 DEG C, doing in purity 99.999%
The protection of dry nitrogen is lower adds isocyanates reactant, and its epoxy resin is 88～99:1～12 with the mass ratio of isocyanates, first
In 50～70 DEG C, stirring reaction 1～2 hour, then heat to 80～100 DEG C, continue reaction more than 2 hours, control reaction
Isocyanate functional group's content of product is less than 0.1% stopped reaction, prepares the bisphenol A epoxide resin that polyurethane structural is modified
Compositions.
The preparation method of a kind of bisphenol A epoxide resin compositions modified by polyurethane structural the most according to claim 1, its
It is characterised by: the bisphenol A type epoxy resin in described step (1) is selected from bisphenol A-type E20, bisphenol A-type E21, double
The mixture of one or more in phenol A type E44, bisphenol A-type E51.
The preparation side of a kind of bisphenol A epoxide resin compositions modified by polyurethane structural the most according to claim 1 and 2
Method, it is characterised in that: the bisphenol A type epoxy resin in described step (1), its mean molecule quantity is 350～2500 grams/
Mole.
The preparation method of a kind of bisphenol A epoxide resin compositions modified by polyurethane structural the most according to claim 3, its
Being characterised by: described bisphenol A type epoxy resin, its mean molecule quantity is 350～1500 grams/mol.
The preparation method of a kind of bisphenol A epoxide resin compositions modified by polyurethane structural the most according to claim 1, its
Being characterised by: the temperature of the vacuum dehydration in described step (1) is 90-120 DEG C, the vacuum pressure of dehydration is 10-0.5mmHg.
The preparation method of a kind of bisphenol A epoxide resin compositions modified by polyurethane structural the most according to claim 1, its
It is characterised by: the isocyanates in described step (2) is aromatic series, aliphatic or alicyclic isocyanate.
The preparation method of a kind of bisphenol A epoxide resin compositions modified by polyurethane structural the most according to claim 6, its
It is characterised by: described isocyanates is aromatic series toluene di-isocyanate(TDI) TDI, aromatic series methyl diphenylene diisocyanate
MDI, aliphatic hexamethylene diisocyanate HDI or alicyclic isophorone diisocyanate IPDI.
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| CN106498740A (en) * | 2016-11-11 | 2017-03-15 | 北京化工大学 | A kind of polyurethane modified epoxy resin sizing agent and preparation method thereof |
| CN109957969B (en) * | 2017-12-25 | 2022-01-07 | 比亚迪股份有限公司 | Carbon fiber sizing agent, preparation method thereof, reinforced carbon fiber and carbon fiber composite material |
| CN110615988B (en) * | 2019-08-29 | 2022-03-11 | 江苏沃特新材料科技有限公司 | High-wear-resistance polyphenylene sulfide material and preparation method thereof |
| CN111574719B (en) * | 2020-04-09 | 2023-06-06 | 深圳航天科技创新研究院 | Thermoplastic epoxy resin and application thereof, and surface modifier for carbon fiber |
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