CN103772638A - Polyurethane-structure-modified bisphenol F epoxy resin composite, as well as preparation and application thereof - Google Patents
Polyurethane-structure-modified bisphenol F epoxy resin composite, as well as preparation and application thereof Download PDFInfo
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- CN103772638A CN103772638A CN201210417588.1A CN201210417588A CN103772638A CN 103772638 A CN103772638 A CN 103772638A CN 201210417588 A CN201210417588 A CN 201210417588A CN 103772638 A CN103772638 A CN 103772638A
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- bisphenol
- epoxy resin
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Polymers C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000004842 bisphenol F epoxy resin Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 238000012986 modification Methods 0.000 claims abstract description 31
- 230000004048 modification Effects 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 23
- 239000004917 carbon fiber Substances 0.000 claims abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000004513 sizing Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 43
- 229930185605 Bisphenol Natural products 0.000 claims description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- -1 alicyclic isocyanate Chemical class 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000006260 foam Substances 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000009955 starching Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane-structure-modified bisphenol F epoxy resin composite which comprises the following components in percentage by mass: 88-99% of bisphenol F epoxy resin and 1-12% of isocyanate. The preparation method of the polyurethane-structure-modified bisphenol F epoxy resin composite comprises the following steps: vacuumizing and dewatering the bisphenol F epoxy resin reactant at high temperature until no foam is generated; cooling, under the protection of nitrogen, adding the isocyanate reactant, reacting for 1-2 hours at 50-70 DEG C in a stirring manner, raising the temperature to 80-100 DEG C, and continuing the reaction for more than 2 hours to prepare the polyurethane-structure-modified bisphenol F epoxy resin composite. According to the invention, through the method of in-situ modification of the epoxy resin composite by the polyurethane structure, the polarity carbamic acid ester group is introduced to be applied to preparation of a carbon fiber sizing agent, so that the technological permeability of the sizing agent is improved, the sizing technology capability and the bundling and the wear resistance of the carbon fiber are improved, engineering application of the carbon fiber with 12K and more tows and manufacture of a high-performance composite material are facilitated.
Description
Technical field
The invention belongs to the modification preparation field of epoxy resin in organic polymer material, particularly a kind of bisphenol F epoxy resin composition by polyurethane structural modification and preparation and application.
Background technology
Epoxy resin has higher intensity, good adhesiveproperties, chemical stability, easily machine-shaping and the advantage such as with low cost, and its polymer composites is by a large number for many industrial circles.But because the curing rear cross-linking density of pure epoxy resin is high, there is the shortcomings such as internal stress is large, curing material is crisp, thermotolerance is poor, limited its application in fibre reinforced composites.Interfacial layer plays an important role in matrix material, and it is the transition layer that reinforcement is connected with matrix, is the bridge that transmits stress, so its structure and performance directly have influence on the performance of matrix material simultaneously.
At present, importance based on sizing agent in high-performance carbon fibre and graphite fibre manufacturing engineering and fiber-reinforced resin matrix compound material application, sizing agent has become the important supplementary material of carbon fiber, graphite fibre through engineering approaches, the manufacturability of its performance impact carbon fiber manufacturing engineering and the comprehensive mechanical property of matrix material are also the important focuses of current high-performance carbon fibre and the research of graphite fibre industrialization technology.Chinese invention patent application 200510063352.2,201010300131.3,201010234852.9,2009102158.33,201010202372.4 discloses respectively preparation method and the application take epoxy resin, aqueous epoxy resins, Racemic glycidol ether-ether, polypropylene nitrile, epoxy vinyl compound resin as the carbon fiber sizing agent of main ingredient.In addition, in order further to improve the performance of emulsion property and starching carbon fiber, Chinese invention patent application 201010217247.0,201110102007.0,201110085545.3,200410064587.9 discloses respectively the preparation method and application that adopt the emulsion pasting agent of the modifications such as polyvalent alcohol, Graphene, carbon nanotube, nano silicon.Meanwhile, Chinese invention patent application 201010217240.9 and 201010125199.2 discloses respectively the synthesis preparation method of two kinds of self-emulsifying type epoxy group(ing) carbon fiber sizing agents.But from current application feature, adopt above-mentioned resin formula to prepare the sizing agent of gained, while being applied to carbon fiber, graphite fibre, there is under normal fiber starching amount (<1.40%) condition convergency and wear no resistance, open fibre and the problem such as expanding performance shortcoming and resilience toughness deficiency, especially ubiquity in the through engineering approaches application of the carbon fiber of 12K and above tow number, has restricted the practical engineering application of above-mentioned sizing agent.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of bisphenol F epoxy resin composition by polyurethane structural modification and preparation and application, by the method for the in-situ modified composition epoxy resin of polyurethane structural, introduce polarity carbamate groups, be applied to the preparation of carbon fiber sizing agent, can improve the technique perviousness of sizing agent, improve convergency and the wear resisting property of sizing technique and carbon fiber, the manufacture that is conducive to 12K and above tow and counts carbon fiber through engineering approaches application and high performance composite; And preparation technology is simple for this composition epoxy resin, reaction raw materials convenient sources can complete preparation process in general-purpose equipment, and economic benefit is good, is conducive to realize suitability for industrialized production.
A kind of bisphenol F epoxy resin composition by polyurethane structural modification of the present invention, its component comprises: the isocyanic ester of the bisphenol f type epoxy resin of mass percent 88-99% and mass percent 1-12%.
Described bisphenol f type epoxy resin is selected from one or more the mixture in Bisphenol F type 6458, Bisphenol F type 6445, Bisphenol F type 6420, Bisphenol F type 6421;
Described bisphenol f type epoxy resin, its molecular-weight average is 350～2500 grams/mol, preferably molecular-weight average is 350～1500 grams/mol;
Described isocyanic ester is aromatic series, aliphatics or alicyclic isocyanate;
Preferred isocyanic ester is aromatic series tolylene diisocyanate (TDI), aromatic series diphenylmethanediisocyanate (MDI), six methylene diisocyanates of aliphatics (HDI) or alicyclic isophorone diisocyanate (IPDI).
The preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification of the present invention, comprising:
(1) bisphenol f type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, the temperature of its vacuum hydro-extraction is 90-150 ℃, and the vacuum pressure of dehydration is 100-0.1mmHg;
(2) respectively the dry epoxy resin of above-mentioned vacuum hydro-extraction gained is cooled to 50 ~ 70 ℃; under the drying nitrogen protection of purity 99.999%, add isocyanate reaction thing; wherein the mass ratio of epoxy resin and isocyanic ester is 88 ~ 99:1 ~ 12; prior to 50 ~ 70 ℃; stirring reaction 1 ~ 2 hour; then be warming up to 80 ~ 100 ℃; continue reaction more than 2 hours; isocyanate functional group's content of controlling reaction product is less than 0.1% stopped reaction, makes the bisphenol F epoxy resin composition of polyurethane structural modification.
In described step (1) bisphenol f type epoxy resin be selected from one or more the mixture in Bisphenol F type 6458, Bisphenol F type 6445, Bisphenol F type 6420, Bisphenol F type 6421;
In described step (1) bisphenol f type epoxy resin, its molecular-weight average is 350～2500 grams/mol, preferably molecular-weight average is 350～1500 grams/mol;
The temperature of the vacuum hydro-extraction in described step (1) is 90-120 ℃, and the vacuum pressure of dehydration is 10-0.5mmHg;
Isocyanic ester in described step (2) is aromatic series, aliphatics or alicyclic isocyanate;
Preferred isocyanic ester is aromatic series tolylene diisocyanate (TDI), aromatic series diphenylmethanediisocyanate (MDI), six methylene diisocyanates of aliphatics (HDI) or alicyclic isophorone diisocyanate (IPDI).
A kind of bisphenol F epoxy resin composition by polyurethane structural modification of the present invention preparation have good convergency and wear resistance epoxy group(ing) carbon fiber sizing agent in application.
Beneficial effect
(1) the present invention, by the method for the in-situ modified composition epoxy resin of polyurethane structural, introduces polarity carbamate groups, is applied to the preparation of sizing agent, can improve the technique perviousness of sizing agent; Meanwhile, by the molecular-weight average of free adjustment composition epoxy resin, improve convergency and the wear resisting property of sizing technique and carbon fiber, the manufacture that is conducive to 12K and above tow and counts carbon fiber through engineering approaches application and high performance composite;
(2) this preparation technology is simple, and reaction raw materials convenient sources can complete preparation process in general-purpose equipment, and economic benefit is good, is conducive to realize suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1-12
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 70 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative six methylene diisocyanates (HDI) are added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 70 ℃; be warming up to again 95 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol F epoxy resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, two or six methylene diisocyanates (HDI) consumption are in table 1.
Table 1, reaction raw materials quality table
Embodiment 13-24
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 70 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative isophorone diisocyanate (IPDI) is added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 70 ℃; be warming up to again 95 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol F epoxy resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, isophorone diisocyanate (IPDI) consumption are in table 2.
Table 2, reaction raw materials quality table
Embodiment 25-36
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 50 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative diphenylmethanediisocyanate (MDI) is added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 50 ℃; be warming up to again 85 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol F epoxy resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, diphenylmethanediisocyanate (MDI) consumption are in table 3.
Table 3, reaction raw materials quality table
Embodiment 37-48
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 50 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative tolylene diisocyanate (TDI) is added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 50 ℃; be warming up to again 85 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol F epoxy resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, tolylene diisocyanate (TDI) consumption are in table 4.
Table 4, reaction raw materials quality table
Application Example
One, the preparation of epoxy group(ing) carbon fiber sizing agent
Get 60g above-described embodiment and prepare the composition epoxy resin of the polyurethane structural modification of gained, add 0.32g 2,6-ditertbutylparacresol (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) stirs 1 hour at 90 ℃.Then be cooled to 80 ℃, slowly drip the high-speed stirring emulsification simultaneously of 100g deionized water, after completing, add 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(to be produced by BNK company of the U.S.), 0.32g butyl glycol ether (group produces by traditional Chinese medicines), prepare water-based emulsion.
The viscosity that the present embodiment is prepared gained water-based emulsion adopts the test of Brookfield DV-II Pro rotational viscosimeter to obtain, emulsion PH adopts the examination of the U.S. DELTA 320pH of Mettler Toledo Inc. instrumentation to obtain, emulsion surface tension adopts the DCAT21 type dynamic contact angle of German DataPhysics company and surface tension instrument test to obtain, emulsion median size adopts the Zetasizer NanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company of Britain to obtain, and prepared emulsion property indices is in table 5.
Table 5, emulsion property index test result
Two, the starching of carbon fiber
The above-mentioned gained emulsion pasting agent of preparing is carried out to starching in self-control on small-sized starching instrument, and selected fiber is 12K T300 grade carbon fiber, dipping time 30s, 130 ℃ of drying temperatures, time of drying 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341; Exercise question: temp, resisting type carbon fibre emulsion sizing agent) method test obtains wear resistance, lousiness figureofmerit; According to GB 3357-1982 unidirectional fibre reinforced plastics interlayer shear strength test method test carbon-fibre composite interlaminar shear strength ILSS; After adopting feel appearance method to starching, carbon fiber cluster performance is graded, and gained starching carbon fiber Evaluation results is in table 6.
Table 6, starching carbon fiber Evaluation results
| Convergency | Wear resistance/time | Lousiness amount/mg | ILSS/Mpa | |
| Comparative example 1 | × | 2036 | 3.31 | 66.5 |
| Comparative example 2 | × | 2017 | 3.35 | 68.3 |
| Comparative example 3 | × | 2053 | 3.29 | 67.9 |
| Comparative example 4 | × | 2042 | 3.06 | 67.0 |
| Embodiment 3 | ● | 4492 | 0.45 | 119.1 |
| Embodiment 11 | ● | 4534 | 0.42 | 111.3 |
| Embodiment 17 | ● | 4020 | 0.23 | 108.6 |
| Embodiment 24 | ● | 4106 | 0.48 | 109.4 |
| Embodiment 28 | ● | 3730 | 0.56 | 99.9 |
| Embodiment 36 | ● | 3285 | 0.61 | 100.8 |
| Embodiment 41 | ● | 3349 | 0.32 | 84.6 |
| Embodiment 47 | ○ | 3092 | 0.73 | 91.1 |
Note: convergency Index grading ●-fine zero-good △-bad ×-poor
Although the present invention discloses preferred embodiment as above; so it is not in order to limit content of the present invention; anyly be familiar with this skill person; not departing from main spirits of the present invention and context; when doing various changes and retouching, therefore the protection domain of invention should be as the criterion with the basic right claimed range of applying for a patent.
Claims (14)
1. by a bisphenol F epoxy resin composition for polyurethane structural modification, its component comprises: the isocyanic ester of the bisphenol f type epoxy resin of mass percent 88-99% and mass percent 1-12%.
2. a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 1, is characterized in that: described bisphenol f type epoxy resin is selected from one or more the mixture in Bisphenol F type 6458, Bisphenol F type 6445, Bisphenol F type 6420, Bisphenol F type 6421.
3. a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 1 and 2, is characterized in that: described bisphenol f type epoxy resin, its molecular-weight average is 350～2500 grams/mol.
4. a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 3, is characterized in that: described bisphenol f type epoxy resin, its molecular-weight average is 350～1500 grams/mol.
5. a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 1, is characterized in that: described isocyanic ester is aromatic series, aliphatics or alicyclic isocyanate.
6. a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 5, is characterized in that: described isocyanic ester is aromatic series tolylene diisocyanate TDI, aromatic series diphenylmethanediisocyanate MDI, six methylene diisocyanate HDI of aliphatics or alicyclic isophorone diisocyanate IPDI.
7. by a preparation method for the bisphenol F epoxy resin composition of polyurethane structural modification, comprising:
(1) bisphenol f type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, the temperature of its vacuum hydro-extraction is 90-150 ℃, and the vacuum pressure of dehydration is 100-0.1mmHg;
(2) respectively the dry epoxy resin of above-mentioned vacuum hydro-extraction gained is cooled to 50 ~ 70 ℃; under the drying nitrogen protection of purity 99.999%, add isocyanate reaction thing; wherein the mass ratio of epoxy resin and isocyanic ester is 88 ~ 99:1 ~ 12; prior to 50 ~ 70 ℃; stirring reaction 1 ~ 2 hour; then be warming up to 80 ~ 100 ℃; continue reaction more than 2 hours; isocyanate functional group's content of controlling reaction product is less than 0.1% stopped reaction, makes the bisphenol F epoxy resin composition of polyurethane structural modification.
8. the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 7, is characterized in that: in described step (1) bisphenol f type epoxy resin be selected from one or more the mixture in Bisphenol F type 6458, Bisphenol F type 6445, Bisphenol F type 6420, Bisphenol F type 6421.
9. according to the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification described in claim 7 or 8, it is characterized in that: in described step (1) bisphenol f type epoxy resin, its molecular-weight average is 350～2500 grams/mol.
10. the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 9, is characterized in that: described bisphenol f type epoxy resin, its molecular-weight average is 350～1500 grams/mol.
The preparation method of 11. a kind of bisphenol F epoxy resin compositions by polyurethane structural modification according to claim 7, is characterized in that: the temperature of the vacuum hydro-extraction in described step (1) is 90-120 ℃, and the vacuum pressure of dehydration is 10-0.5mmHg.
The preparation method of 12. a kind of bisphenol F epoxy resin compositions by polyurethane structural modification according to claim 7, is characterized in that: the isocyanic ester in described step (2) is aromatic series, aliphatics or alicyclic isocyanate.
The preparation method of 13. a kind of bisphenol F epoxy resin compositions by polyurethane structural modification according to claim 12, is characterized in that: described isocyanic ester is aromatic series tolylene diisocyanate TDI, aromatic series diphenylmethanediisocyanate MDI, six methylene diisocyanate HDI of aliphatics or alicyclic isophorone diisocyanate IPDI.
The application in preparation epoxy group(ing) carbon fiber sizing agent of 14. 1 kinds of bisphenol F epoxy resin compositions by polyurethane structural modification.
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