CN103772638B - By bisphenol F epoxy resin composition and preparation and the application of polyurethane structural modification - Google Patents
By bisphenol F epoxy resin composition and preparation and the application of polyurethane structural modification Download PDFInfo
- Publication number
- CN103772638B CN103772638B CN201210417588.1A CN201210417588A CN103772638B CN 103772638 B CN103772638 B CN 103772638B CN 201210417588 A CN201210417588 A CN 201210417588A CN 103772638 B CN103772638 B CN 103772638B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- bisphenol
- preparation
- resin composition
- polyurethane structural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000012986 modification Methods 0.000 title claims abstract description 20
- 230000004048 modification Effects 0.000 title claims abstract description 20
- 239000004842 bisphenol F epoxy resin Substances 0.000 title claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 13
- 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 abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 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 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- -1 alicyclic isocyanate Chemical class 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 17
- 239000004917 carbon fiber Substances 0.000 abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000004513 sizing Methods 0.000 abstract description 17
- 239000003795 chemical substances by application Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000013459 approach Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 8
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical class O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 238000009955 starching Methods 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 238000009835 boiling Methods 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
- 238000005516 engineering process Methods 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
- 238000011156 evaluation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 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
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 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
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 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
- 238000001035 drying 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
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 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
- 239000002002 slurry Substances 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 present invention relates to a kind of bisphenol F epoxy resin composition by polyurethane structural modification, its component comprises: the isocyanates of the bisphenol f type epoxy resin of mass percent 88-99% and mass percent 1-12%; Its preparation comprises: bisphenol f type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation; After cooling, under nitrogen protection, add isocyanate reaction thing, prior to 50-70 DEG C of stirring reaction 1-2 hour, be then warming up to 80-100 DEG C, continue reaction more than 2 hours, make the bisphenol F epoxy resin composition by polyurethane structural modification. The present invention is 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 permeability of sizing agent, improve convergence and the anti-wear performance 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 materials.
Description
Technical field
The invention belongs to the modification preparation field of epoxy resin in high-molecular organic material, particularly a kind of by polyurethane structuralThe bisphenol F epoxy resin composition of modification and preparation and application.
Background technology
Epoxy resin has higher intensity, good adhesive property, chemical stability, easily machine-shaping and with low cost etc.Advantage, its polymer composites is by a large number for many industrial circles. But because the curing rear crosslink density of pure epoxy resin is high,There is the shortcomings such as internal stress is large, curing material is crisp, heat resistance is poor, limited its application in fibre reinforced composites.Boundary layer plays an important role in composite, and it is the transition zone that reinforcement is connected with matrix, is to transmit stress simultaneouslyBridge, so its structure and performance directly have influence on 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 materialImportance in application, sizing agent has become the important supplementary material of carbon fiber, graphite fibre through engineering approaches, its performance impact carbonThe manufacturability of fiber manufacturing engineering and the comprehensive mechanical property of composite are also that current high-performance carbon fibre and graphite fibre produceThe important focus of industry technical research. Chinese invention patent application 200510063352.2,201010300131.3,201010234852.9,2009102158.33,201010202372.4 disclose respectively with epoxy resin, aqueous epoxy resins,The preparation method of the carbon fiber sizing agent that glycidol ether-ether, polypropylene nitrile, epoxy vinyl compound resin are key componentAnd application. In addition, in order further to improve the performance of emulsion property and starching carbon fiber, Chinese invention patent application201010217247.0,201110102007.0,201110085545.3,200410064587.9 disclose respectively adopt polynaryThe preparation method and application of the emulsion pasting agent of the modifications such as alcohol, Graphene, CNT, nano silicon. Meanwhile, inState's application for a patent for invention 201010217240.9 and 201010125199.2 discloses respectively two kinds of self-emulsifying type epoxy radicals carbon fibresThe synthesis preparation method of Wesy's sizing agent. But from current application feature, adopt above-mentioned resin formula to prepare the upper of gained, while being applied to carbon fiber, graphite fibre, there is convergence and wear-resisting under normal fiber starching amount (< 1.40%) condition in slurry agentProperty poor, open the problems such as fibre and expanding performance shortcoming and resilience toughness deficiency, especially at the carbon of 12K and above tow numberUbiquity in the through engineering approaches application of fiber, has restricted the practical engineering application of above-mentioned sizing agent.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of bisphenol F epoxy resin composition by polyurethane structural modification andIts preparation and application, by the method for the in-situ modified composition epoxy resin of polyurethane structural, introduce polarity carbamate groupsGroup, be applied to the preparation of carbon fiber sizing agent, can improve the technique permeability of sizing agent, improve sizing technique andThe convergence of carbon fiber and anti-wear performance, be conducive to 12K and above tow and count the application of carbon fiber through engineering approaches and high-performance composite woodThe manufacture of material; And preparation technology is simple for this composition epoxy resin, reaction raw materials convenient sources, can be complete in common apparatusBecome preparation process, 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: mass percentThe isocyanates of the bisphenol f type epoxy resin of 88-99% and mass percent 1-12%.
Described bisphenol f type epoxy resin is selected from Bisphenol F type 6458, Bisphenol F type 6445, Bisphenol F type 6420, bis-phenolThe mixture of one or more in F type 6421;
Described bisphenol f type epoxy resin, its mean molecule quantity is 350～2500 grams/mol, preferably mean molecule quantity is350～1500 grams/mol;
Described isocyanates is aromatic series, aliphatic or alicyclic isocyanate;
Preferred isocyanates is aromatic series toluene di-isocyanate(TDI) (TDI), aromatic series methyl diphenylene diisocyanate(MDI), six methylene diisocyanates of aliphatic (HDI) or alicyclic IPDI (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, its vacuum dehydrationTemperature 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 of purity 99.999%Under dry nitrogen protection, add isocyanate reaction thing, wherein the mass ratio of epoxy resin and isocyanates is 88 ~ 99:1 ~ 12, firstIn 50 ~ 70 DEG C, stirring reaction 1 ~ 2 hour, is then warming up to 80 ~ 100 DEG C, continues reaction more than 2 hours, controls reactionIsocyanate functional group's content of product is less than 0.1% stopped reaction, makes the bisphenol F epoxy resin group of polyurethane structural modificationCompound.
In described step (1) bisphenol f type epoxy resin be selected from Bisphenol F type 6458, Bisphenol F type 6445, Bisphenol FThe mixture of one or more in type 6420, Bisphenol F type 6421;
In described step (1) bisphenol f type epoxy resin, its mean molecule quantity is 350～2500 grams/mol, preferably flatAverage molecular weight 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;
Preferred isocyanates is aromatic series toluene di-isocyanate(TDI) (TDI), aromatic series methyl diphenylene diisocyanate(MDI), six methylene diisocyanates of aliphatic (HDI) or alicyclic IPDI (IPDI).
A kind of bisphenol F epoxy resin composition by polyurethane structural modification of the present invention has good convergence and resistance in preparationApplication in the epoxy radicals carbon fiber sizing agent of mill property.
Beneficial effect
(1) the present invention, by the method for the in-situ modified composition epoxy resin of polyurethane structural, introduces polarity carbamate groups,Be applied to the preparation of sizing agent, can improve the technique permeability of sizing agent; Meanwhile, by free adjustment epoxy resinThe mean molecule quantity of composition, improves convergence and the anti-wear performance of sizing technique and carbon fiber, be conducive to 12K and more thanTow is counted the manufacture of the application of carbon fiber through engineering approaches and high-performance composite materials;
(2) this preparation technology is simple, and reaction raw materials convenient sources can complete preparation process, economic benefit in common apparatusWell, be conducive to realize suitability for industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention. Should be understood that these embodiment are only for illustrating the present inventionLimit the scope of the invention and be not used in. In addition should be understood that after having read the content of the present invention's instruction art technologyPersonnel can make various changes or modifications the present invention, and these equivalent form of values fall within equally the application's appended claims and limitFixed scope.
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 DEG C,Control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation. Be cooled to 70 DEG C, removal vacuumizesDevice, inserts condenser pipe. Under high pure nitrogen protection, by trace for quantitative six methylene diisocyanates (HDI)Measuring pump is added drop-wise in flask very lentamente, dropwises rear elder generation and at 70 DEG C, reacts 1 hour, then be warming up to 95 DEG C of reactions 2More than hour, infrared analysis is carried out in sampling, when result shows nothing-NCO group, makes the Bisphenol F of polyurethane structural modificationComposition epoxy resin. Epoxy resin composition kind used and consumption, two or six methylene diisocyanates (HDI) are usedAmount is in table 1.
Table 1, reaction material 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 DEG C,Control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation. Be cooled to 70 DEG C, removal vacuumizesDevice, inserts condenser pipe. Under high pure nitrogen protection, quantitative IPDI (IPDI) is used to microflowmeterAmount pump is added drop-wise in flask very lentamente, dropwises rear elder generation and at 70 DEG C, reacts 1 hour, then be warming up to 95 DEG C of reactions 2More than hour, infrared analysis is carried out in sampling, when result shows nothing-NCO group, makes the Bisphenol F of polyurethane structural modificationComposition epoxy resin. Epoxy resin composition kind used and consumption, IPDI (IPDI) consumption are shown inTable 2.
Table 2, reaction material 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 DEG C,Control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation. Be cooled to 50 DEG C, removal vacuumizesDevice, inserts condenser pipe. Under high pure nitrogen protection, by trace for quantitative methyl diphenylene diisocyanate (MDI)Measuring pump is added drop-wise in flask very lentamente, dropwises rear elder generation and at 50 DEG C, reacts 1 hour, then be warming up to 85 DEG C of reactions 2More than hour, infrared analysis is carried out in sampling, when result shows nothing-NCO group, makes the Bisphenol F of polyurethane structural modificationComposition epoxy resin. Epoxy resin composition kind used and consumption, methyl diphenylene diisocyanate (MDI) consumptionIn table 3.
Table 3, reaction material 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 DEG C,Control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation. Be cooled to 50 DEG C, removal vacuumizesDevice, inserts condenser pipe. Under high pure nitrogen protection, quantitative toluene di-isocyanate(TDI) (TDI) is used to Micro-metering PumpsBe added drop-wise to very lentamente in flask, dropwise rear elder generation and at 50 DEG C, react 1 hour, then be warming up to 85 DEG C of reactions 2 hoursAbove, infrared analysis is carried out in sampling, when result shows nothing-NCO group, makes the Bisphenol F epoxy of polyurethane structural modificationResin combination. Epoxy resin composition kind used and consumption, toluene di-isocyanate(TDI) (TDI) consumption are in table 4.
Table 4, reaction material quality table
Application Example
One, the preparation of epoxy radicals carbon fiber sizing agent
Get 60g above-described embodiment and prepare the composition epoxy resin of the polyurethane structural modification of gained, add 0.32g2,6-bis-unclesButyl paracresol (group produces by traditional Chinese medicines), 21.30g octadecanol polyoxyethylene ether surface active agent (ethylene oxide polymerizationDegree 20) (being produced by Hai'an, Jiangsu petrochemical plant), at 90 DEG C, stir 1 hour. Then be cooled to 80 DEG C, slowly dripThe simultaneously high-speed stirred emulsification of 100g deionized water, after completing, add 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(byBNK company of the U.S. produce), 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 BrookfieldDV-IIPro rotation viscometer to obtain, breastLiquid PH adopts the examination of the U.S. DELTA320pH of Mettler Toledo Inc. instrumentation to obtain, and emulsion surface tension adopts GermanyThe DCAT21 type dynamic contact angle of DataPhysics company and surface tension instrument test obtain, and emulsion average grain diameter adopts BritainThe ZetasizerNanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company obtains, the every property of prepared emulsionEnergy index 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 on the small-sized starching instrument of self-control, and selected fiber is 12KT300 levelCarbon fiber, dipping time 30s, 130 DEG C of baking temperatures, drying time 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341; Exercise question: temp, resisting type carbon fibre breastLiquid sizing agent) method test obtains wearability, lousiness figureofmerit; According to GB3357-1982 unidirectional fibre reinforced plastics interlayerShear strength test method test carbon fibre composite interlaminar shear strength ILSS; Carbon fibre after adopting feel ocular estimate to starchingDimension cluster performance is graded, and gained starching carbon fiber Evaluation results is in table 6.
Table 6, starching carbon fiber Evaluation results
| Convergence | Wearability/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: convergence 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, is anyly familiar with thisSkill person, not departing from main spirits of the present invention and context, when doing various changes and retouching, therefore inventsProtection domain should be as the criterion with the basic right claimed range of applying for a patent.
Claims (7)
1. 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, its vacuum dehydrationTemperature 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 of purity 99.999%Under dry nitrogen protection, add isocyanate reaction thing, wherein the mass ratio of epoxy resin and isocyanates is 88～99:1～12, firstIn 50～70 DEG C, stirring reaction 1～2 hour, is then warming up to 80～100 DEG C, continues reaction more than 2 hours, controls reactionIsocyanate functional group's content of product is less than 0.1% stopped reaction, makes the bisphenol F epoxy resin group of polyurethane structural modificationCompound.
2. the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 1, itsBe characterised in that: the bisphenol f type epoxy resin in described step (1) is selected from Bisphenol F type 6458, Bisphenol F type 6445, twoThe mixture of one or more in phenol F type 6420, Bisphenol F type 6421.
3. the preparation side of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 1 and 2Method, is characterized in that: the bisphenol f type epoxy resin in described step (1), its mean molecule quantity be 350～2500 grams/Mole.
4. the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 3, itsBe characterised in that: described bisphenol f type epoxy resin, its mean molecule quantity is 350～1500 grams/mol.
5. the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 1, itsBe characterised in that: the temperature of the vacuum dehydration in described step (1) is 90-120 DEG C, the vacuum pressure of dehydration is 10-0.5mmHg.
6. the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 1, itsBe characterised in that: the isocyanates in described step (2) is aromatic series, aliphatic or alicyclic isocyanate.
7. the preparation method of a kind of bisphenol F epoxy resin composition by polyurethane structural modification according to claim 6, itsBe characterised in that: described isocyanates is aromatic series toluene di-isocyanate(TDI) TDI, aromatic series methyl diphenylene diisocyanateMDI, aliphatic hexamethylene diisocyanate HDI or alicyclic IPDI IPDI.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210417588.1A CN103772638B (en) | 2012-10-26 | 2012-10-26 | By bisphenol F epoxy resin composition and preparation and the application of polyurethane structural modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210417588.1A CN103772638B (en) | 2012-10-26 | 2012-10-26 | By bisphenol F epoxy resin composition and preparation and the application of polyurethane structural modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103772638A CN103772638A (en) | 2014-05-07 |
| CN103772638B true CN103772638B (en) | 2016-05-04 |
Family
ID=50565443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210417588.1A Active CN103772638B (en) | 2012-10-26 | 2012-10-26 | By bisphenol F epoxy resin composition and preparation and the application of polyurethane structural modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103772638B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482075A (en) * | 2015-12-15 | 2016-04-13 | 广东广山新材料有限公司 | Isocyanate modified epoxy resin and application |
| CN105669939A (en) * | 2016-02-29 | 2016-06-15 | 中简科技股份有限公司 | Preparation method for modified unsaturated polyester emulsion |
| 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 |
| CN110467711B (en) * | 2019-09-10 | 2021-09-28 | 武汉海威船舶与海洋工程科技有限公司 | Epoxy resin/polysiloxane/polyurethane polymer material and preparation method thereof |
| CN112760986A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of aqueous emulsion type carbon fiber sizing agent |
| CN112760983A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing aqueous emulsion type carbon fiber sizing agent |
| CN112760987A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing aqueous emulsion type carbon fiber sizing agent |
| CN112760985A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of aqueous emulsion type carbon fiber sizing agent |
| CN116180451B (en) * | 2023-03-01 | 2025-03-25 | 湖南泽睿新材料有限公司 | A continuous silicon carbide fiber sizing agent and its application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845755A (en) * | 2010-03-16 | 2010-09-29 | 天津碧海蓝天水性高分子材料有限公司 | Self-emulsifying polyurethanes epoxy sizing agent for carbon fibers and preparation method thereof |
| CN102206919A (en) * | 2011-04-22 | 2011-10-05 | 中国科学院宁波材料技术与工程研究所 | Graphene modified carbon fiber emulsion sizing agent and preparation method thereof |
| CN102459728A (en) * | 2009-06-10 | 2012-05-16 | 三菱丽阳株式会社 | Carbon fiber bundle with excellent mechanical properties |
| CN102675859A (en) * | 2012-05-10 | 2012-09-19 | 上海富朗化工科技发展有限公司 | Ultrahigh molecular weight single-component waterborne epoxy resin emulsion and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7465764B2 (en) * | 2004-06-18 | 2008-12-16 | Ocv Intellectual Captial, Llc | Epoxy sizing composition for filament winding |
-
2012
- 2012-10-26 CN CN201210417588.1A patent/CN103772638B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459728A (en) * | 2009-06-10 | 2012-05-16 | 三菱丽阳株式会社 | Carbon fiber bundle with excellent mechanical properties |
| CN101845755A (en) * | 2010-03-16 | 2010-09-29 | 天津碧海蓝天水性高分子材料有限公司 | Self-emulsifying polyurethanes epoxy sizing agent for carbon fibers and preparation method thereof |
| CN102206919A (en) * | 2011-04-22 | 2011-10-05 | 中国科学院宁波材料技术与工程研究所 | Graphene modified carbon fiber emulsion sizing agent and preparation method thereof |
| CN102675859A (en) * | 2012-05-10 | 2012-09-19 | 上海富朗化工科技发展有限公司 | Ultrahigh molecular weight single-component waterborne epoxy resin emulsion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 聚丙烯腈基碳纤维用环氧树脂上浆;张永刚等;《合成纤维》;20111231;第40卷(第12期);第6-9页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103772638A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103772638B (en) | By bisphenol F epoxy resin composition and preparation and the application of polyurethane structural modification | |
| CN103790020B (en) | Epoxy resin sizing agent emulsion that polyurethane structural is modified and preparation thereof and application | |
| CN103790019B (en) | A kind of epoxy radicals carbon fiber sizing agent emulsion and preparation and application | |
| CN111662633B (en) | Anti-static wear-resistant polyurethane floor coating and preparation method thereof | |
| Dai et al. | Synthesis of eugenol-based silicon-containing benzoxazines and their applications as bio-based organic coatings | |
| CN103788322B (en) | The bisphenol A epoxide resin compositions modified by polyurethane structural and preparation thereof and application | |
| EP3425005A1 (en) | Epoxy resin composition, molding material, and fiber-reinforced composite material | |
| CN104448183A (en) | Plant oil-based polyurethane composite material and preparation method thereof | |
| CN104987673A (en) | Epoxy resin composition for prepreg, carbon fiber prepreg and carbon fiber compound material | |
| CN111187428B (en) | Lignin-based polyol, modified lignin-based polyurethane material, modified lignin-based polyurethane film, and preparation method and application thereof | |
| CN109880295A (en) | An amino-terminated modified graphene oxide and its epoxy nanocomposite | |
| US20200157292A1 (en) | Epoxy resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material | |
| Monteserin et al. | Sustainable biobased epoxy thermosets with covalent dynamic imine bonds for green composite development | |
| CN109206573A (en) | A kind of flame-proof polyol and preparation method thereof and the application in polyurethane rigid foam plastic | |
| KR20190114807A (en) | Epoxy resin, epoxy resin composition and fiber-reinforced composite material using same | |
| Liu et al. | Synthesis and characterization of novel epoxy‐modified waterborne polyurethanes and their use in carbon fiber sizing | |
| Ren et al. | Silane-modified hyperbranched polyurethane with high strength, high transparency, and low viscosity | |
| US20230416521A1 (en) | Thermosetting epoxy resin composition, molded article from thermosetting epoxy resin, molding material for fiber-reinforced composite material, fiber-reinforced composite material, and method for producing fiber-reinforced composite material | |
| CA2521758C (en) | Epoxy resin composition | |
| CN110452307B (en) | A kind of modified nanocellulose and preparation method thereof | |
| CN112126194A (en) | Preparation method of toughened and modified epoxy resin composite material | |
| Li et al. | Synthesis and thermal properties of ethynyl phenyl azo phenol-biphenylene resin | |
| TWI734911B (en) | Epoxy resin composition, prepreg, fiber reinforced composite material and manufacturing method thereof | |
| CN114539762A (en) | MXene/polyurethane composite material with friction resistance and preparation method thereof | |
| He et al. | High performance toughened cyanate ester resin with low injection temperature for RTM process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |