CN103790020A - Polyurethane structure modified epoxy resin sizing agent emulsion, and preparation and application - Google Patents
Polyurethane structure modified epoxy resin sizing agent emulsion, and preparation and application Download PDFInfo
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Abstract
The invention relates to a polyurethane structure modified epoxy resin sizing agent emulsion, which comprises the following ingredients: 55-78wt% of polyurethane structure modified epoxy resin composition, 20-40wt% of surfactant, 0.5-2wt% of anti-oxidant, 1-2wt% of levelling agent and 0.5-1wt% of antifreezing agent. The preparation method comprises the following steps: performing vacuum-pumping and dehydrating the bisphenol A epoxy resin to the condition that no bubbles can be generated, cooling and adding isocyanate to prepare a epoxy resin composition; mixing a surfactant and an antioxidant are mixed and homogenized in a reaction vessel according to the above material fraction, then adding deionized water, a levelling agent and an antifreezing agent gradually to obtain the polyurethane structure modified epoxy resin sizing agent emulsion. The carbon fiber prepared by the polyurethane structure modified epoxy resin sizing agent emulsion has good convergence, wear resistance and toughness, the convergence and wear resistance are easily and freely adjusted through the isocyanate component; a cluster agent is not required at the anaphase of the carbon fiber sizing agent, and on-site secondary mixing is not required, the application stability is good, the carbon fiber pasting wellability is good, and the polyurethane structure modified epoxy resin sizing agent emulsion is benefit for industrial stabilization and production of carbon fiber.
Description
Technical field
The invention belongs to the preparation field of water-base epoxy sizing agent emulsion, particularly a kind of epoxy resin sizing agent emulsion of the polyurethane structural modification with good convergence and ABRASION RESISTANCE and preparation and application.
Background technology
The important foundation reinforcement material of manufacture fiber-reinforced resin matrix compound material take carbon fiber, graphite fibre, glass fibre, aramid fiber etc. as the high-performance fiber of representative.Through engineering approaches with high-performance carbon fibre, graphite fibre is fabricated to example, in its technological process of production, the chemical surface treatment of fiber and starching are requisite links (" carbon fiber and graphite fibre " He Fuzhu, Chemical Industry Press, 2010) of research and production carbon fiber.By surface treatment of carbon fibers and upper slurry process, can improve on the one hand the convergence, ABRASION RESISTANCE, toughness, antistatic behaviour etc. of producing gained carbon fiber, can realize by the adjusting of sizing agent performance the balance regulation of opening fibre and expanding of gained carbon fiber simultaneously, meet carbon fiber, the graphite fibre performance requirement at composite material manufacturing technologies such as follow-up braiding, laying, windings.On the other hand, the processing on carbon fiber, graphite fibre surface is mated with the application performance of sizing agent, can, for different composite material resin system and shaping project process conditions in guaranteeing fiber manufacture and subsequent technique performance, improve carbon fiber, the matrix resin wettability of graphite fibre and the interface binding intensity of solidified forming gained fiber-reinforced resin matrix compound material.
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 composite 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, glycidol ether-ether, polypropylene nitrile, epoxy vinyl compound resin as the carbon fiber sizing agent of key component.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 polyalcohol, Graphene, CNT, 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 radicals carbon fiber sizing agents.But from current application feature, while adopting the sizing agent of above-mentioned resin formula and preparation method's gained to be applied to carbon fiber, graphite fibre, there is under normal fiber starching amount (<1.40%) condition convergence and wear no resistance, open fibre and the problem such as expanding performance shortcoming and resilience toughness deficiency, especially ubiquity in the carbon fiber through engineering approaches application of 12K and above tow number, has restricted the practical engineering application of above-mentioned sizing agent.
In order to improve convergence and the anti-wear performance deficiency of carbon fiber, graphite fibre, conventionally adopt and additionally add the auxiliary agents such as features bleeding agent, collecting agent in aqueous epoxy resins base emulsion sizing agent at present.Take carbon fiber collecting agent as example, at present commercially available product changes into the agent of the CHEMITYLEN of the company collection of filaments as Sanyo, and its active chemical is bisphenol type unsaturated polyester (UP).The technical problem such as in practical engineering application, after adding boundling function additive to mix, have that sizing agent stability of emulsion declines in water-based emulsion sizing agent, easily layering, solid content are wayward.Because the component of additional boundling function additive easily causes the sclerosis of starching carbon fiber, lose elasticity and ABRASION RESISTANCE that later stage fiber process moulding needs simultaneously, cannot meet the application demand of final composite.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of epoxy resin sizing agent emulsion and preparation and application of polyurethane structural modification, the obtained carbon fiber of this epoxy resin sizing agent emulsion has good convergence, ABRASION RESISTANCE and toughness, the chemical stability of sizing agent resin is good simultaneously, and the long term storage that is conducive to starching carbon fiber is guaranteed the quality; And preparation technology is simple, easy to operate, reaction raw materials convenient sources, cost is low, can in common apparatus, complete preparation process, and economic benefit is good, is conducive to realize suitability for industrialized production.
The epoxy resin sizing agent emulsion of a kind of polyurethane structural modification of the present invention, its component comprises:
Bisphenol A type epoxy resin 88 ~ 99wt%
Isocyanates 1 ~ 12wt%
Described bisphenol A type epoxy resin is selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51;
Described bisphenol A type epoxy resin, its mean molecule quantity is 350 ~ 2500 grams/mol, preferably mean molecule quantity is 350 ~ 1500 grams/mol;
Described isocyanates is aromatic series, aliphatic or alicyclic isocyanate; Preferred isocyanate is aromatic series toluene di-isocyanate(TDI) (TDI), aromatic series methyl diphenylene diisocyanate (MDI), six methylene diisocyanates of aliphatic (HDI) or alicyclic isophorone diisocyanate (IPDI);
Described surfactant is fatty alcohol-polyoxyethylene ether, the carbochain that its hydrophobic fat alcohol moiety is C1 ~ C18; Preferably hexadecanol polyoxyethylene ether, polyoxyethylene octadecanol;
In described fatty alcohol-polyoxyethylene ether, the degree of polymerization of oxirane is 5 ~ 100, and preferred degree of polymerization is 5 ~ 50;
Described antioxidant is BHT, and described levelling agent is Siloxane-Oxyalkylene Copolymers BNK-LK380, and described antifreezing agent is butyl glycol ether;
Described epoxy resin sizing agent emulsion, resin solid content is 30 ~ 60%, emulsion average grain diameter is 100 ~ 350nm, surface tension 30 ~ 50mN/m, emulsion room temperature rotary viscosity is 10 ~ 500cp.
The preparation method of the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification of the present invention, comprising:
(1) preparation of the composition epoxy resin of polyurethane structural modification
Bisphenol A type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, then the dry epoxy resin of vacuum dehydration 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 isocyanates 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 product is less than 0.1% stopped reaction, make the composition epoxy resin of polyurethane structural modification,
(2) preparation of the epoxy resin sizing agent emulsion of polyurethane structural modification
By the composition epoxy resin of above-mentioned polyurethane structural modification, in reactor, mix homogeneous by following quality of material umber with surfactant, antioxidant, homogeneous mixing temperature is controlled at 70 ~ 120 ℃, and homogeneous incorporation time is 0.5 ~ 2 hour; Then, uniform homogeneous blend is cooled to 60 ~ 90 ℃, progressively adds deionized water while high speed shear dispersion and emulsion, uniform homogeneous blend is 30 ~ 60:70 ~ 40 with deionized water quality ratio, after completing, add levelling agent and antifreezing agent, prepare the epoxy resin sizing agent emulsion of polyurethane structural modification;
In described step (1) bisphenol A type epoxy resin be selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, 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 ~ 150 ℃, and the vacuum pressure of dehydration is 100 ~ 0.1mmHg;
Isocyanates in described step (1) is aromatic series, aliphatic or alicyclic isocyanate; Preferred isocyanate is aromatic series toluene di-isocyanate(TDI) (TDI), aromatic series methyl diphenylene diisocyanate (MDI), six methylene diisocyanates of aliphatic (HDI) or alicyclic isophorone diisocyanate (IPDI);
Surfactant in described step (2) is fatty alcohol-polyoxyethylene ether, the carbochain that its hydrophobic fat alcohol moiety is C1 ~ C18; Preferably hexadecanol polyoxyethylene ether, polyoxyethylene octadecanol;
In described fatty alcohol-polyoxyethylene ether, the degree of polymerization of oxirane is 5 ~ 100, and preferred degree of polymerization is 5 ~ 50;
Described antioxidant is BHT, and described levelling agent is Siloxane-Oxyalkylene Copolymers BNK-LK380, and described antifreezing agent is butyl glycol ether;
Homogeneous mixing temperature in described step (2) is controlled at 70 ~ 120 ℃, preferably 85 ~ 120 ℃ of temperature;
In described step (2), deionized water pH value is 6.0 ~ 8.0, and resistance is for being greater than 1 megohm; Preferably pH value is 6.0 ~ 7.5, and resistance is for being greater than 10 megohms.
The epoxy resin sizing agent emulsion applications of a kind of polyurethane structural modification of the present invention is in the sizing technique of T300 ~ T1000 grade carbon fiber.
By the online impregnation of T300 ~ T1000 grade carbon fiber, impregnation time 10 ~ 50s, the temperature of heated-air drying is 100 ~ 170 ℃, 1 ~ 5 minute online dry time, can complete starching;
Described preferably 10 ~ 30s of online impregnation time, preferably 120 ~ 160 ℃ of the temperature of heated-air drying, preferably 1 ~ 3 minute online dry time.
Beneficial effect
(1) the epoxy resin sizing agent emulsion of polyurethane structural modification provided by the invention, its resin structure contains active epoxy group and polarity amino-formate bond, the obtained carbon fiber of sizing agent has good convergence, ABRASION RESISTANCE and toughness, and its convergence and ABRASION RESISTANCE are easily by the consumption free adjustment of isocyanate component; The chemical stability of above-mentioned sizing agent resin is good simultaneously, and the long term storage that is conducive to starching carbon fiber is guaranteed the quality;
(2) this carbon fiber sizing agent need to not add collecting agent and the mixing of on-the-spot secondary in the later stage, and the application of water-based emulsion sizing agent has good stability, and carbon fiber starching wettability is good, and the stabilization of industry that is beneficial to carbon fiber is produced;
(3) this preparation technology is simple, easy to operate, reaction raw materials convenient sources, and cost is low, can in common apparatus, complete preparation process, and economic benefit is good, is conducive to realize suitability for industrialized production.
The specific 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
One, the preparation of polyurethane-modified composition epoxy resin
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 condenser pipe.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 composition epoxy resin of polyurethane structural modification.Epoxy resin composition kind used and consumption, six methylene diisocyanates (HDI) consumption are in table 1.
Table 1, reaction material quality table
Two, 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 0.32g 2,6-BHT (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 stirred 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 rotation viscometer 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 average grain diameter 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 2.
Table 2, emulsion property index test result
Three, the starching of carbon fiber
Embodiment 1-12 is prepared to gained emulsion pasting agent and carry out starching in self-control on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, 130 ℃ 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 emulsion sizing agent) method test obtains ABRASION 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 ocular estimate to starching, carbon fiber cluster performance is graded, and gained starching carbon fiber Evaluation results is in table 3.
Table 3, starching carbon fiber Evaluation results
| ? | Convergence | ABRASION RESISTANCE/time | Lousiness amount/mg | ILSS/Mpa |
| Comparative example | × | 1831 | 3.79 | 67.1 |
| Embodiment 1 | ● | 4169 | 0.48 | 116.8 |
| Embodiment 2 | ● | 4411 | 0.20 | 111.9 |
| Embodiment 3 | ○ | 3717 | 0.94 | 114.7 |
| Embodiment 4 | ● | 4325 | 0.17 | 111.0 |
| Embodiment 5 | ● | 3723 | 0.90 | 115.5 |
| Embodiment 6 | ● | 3906 | 0.68 | 120.1 |
| Embodiment 7 | ○ | 3799 | 0.91 | 113.0 |
| Embodiment 8 | ● | 3982 | 0.70 | 111.3 |
| Embodiment 9 | ● | 4157 | 0.50 | 120.8 |
| Embodiment 10 | ● | 3835 | 0.74 | 118.7 |
| Embodiment 11 | ● | 4013 | 0.54 | 116.6 |
| Embodiment 12 | ● | 4274 | 0.15 | 120.7 |
Note: convergence Index grading ●-fine zero-good △-bad ×-poor
Embodiment 13-24
One, the preparation of polyurethane-modified composition epoxy resin
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 condenser pipe.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 composition epoxy resin of polyurethane structural modification.Epoxy resin composition kind used and consumption, isophorone diisocyanate (IPDI) consumption are in table 4.
Table 4. reacts uses material quality table
Two, 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 0.32g 2,6-BHT (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 stirred 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 rotation viscometer 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 average grain diameter adopts the ZetasizerNanoZS90 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
Three, the starching of carbon fiber
Embodiment 13-24 is prepared to gained emulsion pasting agent and carry out starching in self-control on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, 130 ℃ 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 emulsion sizing agent) method test obtains ABRASION 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 ocular estimate 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
| ? | Convergence | ABRASION RESISTANCE/time | Lousiness amount/mg | ILSS/Mpa |
| Comparative example | × | 1791 | 3.91 | 69.5 |
| Embodiment 13 | ● | 4004 | 0.23 | 103.6 |
| Embodiment 14 | ○ | 3308 | 1.15 | 110.0 |
| Embodiment 15 | ● | 3558 | 0.95 | 104.0 |
| Embodiment 16 | ○ | 3315 | 1.14 | 109.6 |
| Embodiment 17 | ● | 3621 | 0.89 | 104.7 |
| Embodiment 18 | ● | 3840 | 0.63 | 111.2 |
| Embodiment 19 | ● | 3467 | 0.91 | 108.8 |
| Embodiment 20 | ● | 3740 | 0.61 | 101.3 |
| Embodiment 21 | ● | 3978 | 0.25 | 104.6 |
| Embodiment 22 | ● | 3786 | 0.65 | 108.0 |
| Embodiment 23 | ● | 4030 | 0.28 | 103.2 |
| Embodiment 24 | ○ | 3374 | 1.19 | 103.9 |
Note: convergence Index grading ●-fine zero-good △-bad ×-poor
Embodiment 25-36
One, the preparation of polyurethane-modified composition epoxy resin
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 condenser pipe.Under high pure nitrogen protection; quantitative methyl diphenylene diisocyanate (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 composition epoxy resin of polyurethane structural modification.Epoxy resin composition kind used and consumption, methyl diphenylene diisocyanate (MDI) consumption are in table 7.
Table 7, reaction material quality table
Two, 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 0.32g 2,6-BHT (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 stirred 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 rotation viscometer 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 average grain diameter adopts the ZetasizerNanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company of Britain to obtain, and prepared emulsion property indices is in table 8.
Table 8, emulsion property index test result
Three, the starching of carbon fiber
Embodiment 25-36 is prepared to gained emulsion pasting agent and carry out starching in self-control on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, 130 ℃ 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 emulsion sizing agent) method test obtains ABRASION 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 ocular estimate to starching, carbon fiber cluster performance is graded, and gained starching carbon fiber Evaluation results is in table 9.
Table 9, starching carbon fiber Evaluation results
| ? | Convergence | ABRASION RESISTANCE/time | Lousiness amount/mg | ILSS/Mpa |
| Comparative example | × | 1803 | 3.57 | 68.8 |
| Embodiment 25 | ○ | 3105 | 0.99 | 92.8 |
| Embodiment 26 | ● | 3355 | 0.66 | 94.0 |
| Embodiment 27 | ● | 3617 | 0.33 | 92.7 |
| Embodiment 28 | ● | 3301 | 0.73 | 99.3 |
| Embodiment 29 | ● | 3631 | 0.31 | 98.4 |
| Embodiment 30 | ○ | 2903 | 1.25 | 95.8 |
| Embodiment 31 | ● | 3600 | 0.35 | 92.3 |
| Embodiment 32 | ○ | 2900 | 1.25 | 93.8 |
| Embodiment 33 | ○ | 3088 | 1.01 | 101.6 |
| Embodiment 34 | ○ | 2880 | 1.28 | 99.2 |
| Embodiment 35 | ● | 3102 | 0.99 | 99.6 |
| Embodiment 36 | ● | 3281 | 0.76 | 100.2 |
Note: convergence Index grading ●-fine zero-good △-bad ×-poor
Embodiment 37-48
One, the preparation of polyurethane-modified composition epoxy resin
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 condenser pipe.Under high pure nitrogen protection; quantitative toluene di-isocyanate(TDI) (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 composition epoxy resin of polyurethane structural modification.Epoxy resin composition kind used and consumption, toluene di-isocyanate(TDI) (TDI) consumption are in table 10.
Table 10. reacts uses material quality table
Two, 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 0.32g 2,6-BHT (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 stirred 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 rotation viscometer 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 average grain diameter adopts the ZetasizerNanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company of Britain to obtain, and prepared emulsion property indices is in table 11.
Table 11, emulsion property index test result
Three, the starching of carbon fiber
Embodiment 37-48 is prepared to gained emulsion pasting agent and carry out starching in self-control on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, 130 ℃ 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 emulsion sizing agent) method test obtains ABRASION 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 ocular estimate to starching, carbon fiber cluster performance is graded, and gained starching carbon fiber Evaluation results is in table 12.
Table 12, starching carbon fiber Evaluation results
| ? | Convergence | ABRASION RESISTANCE/time | Lousiness amount/mg | ILSS/Mpa |
| Comparative example | × | 1757 | 3.85 | 67.9 |
| Embodiment 37 | ○ | 2496 | 1.41 | 89.9 |
| Embodiment 37 | ○ | 2696 | 1.12 | 82.3 |
| Embodiment 39 | ● | 2905 | 0.82 | 81.7 |
| Embodiment 40 | ○ | 2709 | 1.10 | 91.6 |
| Embodiment 41 | ● | 2934 | 0.78 | 87.6 |
| Embodiment 42 | ● | 3177 | 0.39 | 85.0 |
| Embodiment 43 | ● | 2864 | 0.88 | 88.0 |
| Embodiment 44 | ● | 3128 | 0.40 | 81.2 |
| Embodiment 45 | ○ | 2508 | 1.39 | 89.2 |
| Embodiment 46 | ● | 3153 | 0.42 | 86.1 |
| Embodiment 47 | ○ | 2516 | 1.38 | 81.7 |
| Embodiment 48 | ○ | 2676 | 1.15 | 88.9 |
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; 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 (23)
1. an epoxy resin sizing agent emulsion for polyurethane structural modification, its component comprises:
The composition epoxy resin of described polyurethane structural modification, its component comprises:
Bisphenol A type epoxy resin 88 ~ 99wt%
Isocyanates 1 ~ 12wt%.
2. the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 1, is characterized in that: described bisphenol A type epoxy resin is selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51.
3. the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 1 and 2, is characterized in that: described bisphenol A type epoxy resin, its mean molecule quantity is 350 ~ 2500 grams/mol.
4. the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 1, is characterized in that: described isocyanates is aromatic series, aliphatic or alicyclic isocyanate.
5. according to the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification described in claim 1 or 4, it is characterized in that: described isocyanates is aromatic series toluene di-isocyanate(TDI) TDI, aromatic series methyl diphenylene diisocyanate MDI, six methylene diisocyanate HDI of aliphatic or alicyclic isophorone diisocyanate IPDI.
6. the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 1, is characterized in that: described surfactant is fatty alcohol-polyoxyethylene ether the carbochain that its hydrophobic fat alcohol moiety is C1 ~ C18; In fatty alcohol-polyoxyethylene ether, the degree of polymerization of oxirane is 5 ~ 100.
7. the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 6, is characterized in that: described fatty alcohol-polyoxyethylene ether is hexadecanol polyoxyethylene ether, polyoxyethylene octadecanol.
8. the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 1, it is characterized in that: described antioxidant is 2,6-BHT, described levelling agent is Siloxane-Oxyalkylene Copolymers BNK-LK380, described antifreezing agent is butyl glycol ether.
9. the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 1, it is characterized in that: described epoxy resin sizing agent emulsion, resin solid content is 30 ~ 60%, emulsion average grain diameter is 100 ~ 350nm, surface tension 30 ~ 50mN/m, emulsion room temperature rotary viscosity is 10 ~ 500cp.
10. a preparation method for the epoxy resin sizing agent emulsion of polyurethane structural modification, comprising:
(1) preparation of the composition epoxy resin of polyurethane structural modification
Bisphenol A type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, then the dry epoxy resin of vacuum dehydration 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 isocyanates 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 product is less than 0.1% stopped reaction, make the composition epoxy resin of polyurethane structural modification,
(2) preparation of the epoxy resin sizing agent emulsion of polyurethane structural modification
By the composition epoxy resin of above-mentioned polyurethane structural modification, in reactor, mix homogeneous by following quality of material umber with surfactant, antioxidant, homogeneous mixing temperature is controlled at 70～120 ℃, and homogeneous incorporation time is 0.5 ~ 2 hour; Then, uniform homogeneous blend is cooled to 60 ~ 90 ℃, progressively add deionized water while high speed shear dispersion and emulsion, the mass ratio of uniform homogeneous blend and deionized water is 30 ~ 60:70 ~ 40, after completing, add levelling agent and antifreezing agent, prepare the epoxy resin sizing agent emulsion of polyurethane structural modification;
11. the preparation method of the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification according to claim 10, is characterized in that: in described step (1) bisphenol A type epoxy resin be selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51.
12. according to the preparation method of the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification described in claim 10 or 11, it is characterized in that: in described step (1) bisphenol A type epoxy resin, its mean molecule quantity is 350 ~ 2500 grams/mol.
The preparation method of the epoxy resin sizing agent emulsion of 13. a kind of polyurethane structural modifications according to claim 10, is characterized in that: the temperature of the vacuum dehydration in described step (1) is 90 ~ 150 ℃, and the vacuum pressure of dehydration is 100 ~ 0.1mmHg.
The preparation method of the epoxy resin sizing agent emulsion of 14. a kind of polyurethane structural modifications according to claim 10, is characterized in that: the isocyanates in described step (1) is aromatic series, aliphatic or alicyclic isocyanate.
15. according to the preparation method of the epoxy resin sizing agent emulsion of a kind of polyurethane structural modification described in claim 10 or 14, it is characterized in that: described isocyanates is aromatic series toluene di-isocyanate(TDI) TDI, aromatic series methyl diphenylene diisocyanate MDI, six methylene diisocyanate HDI of aliphatic or alicyclic isophorone diisocyanate IPDI.
The preparation method of the epoxy resin sizing agent emulsion of 16. a kind of polyurethane structural modifications according to claim 10, it is characterized in that: the surfactant in described step (2) is fatty alcohol-polyoxyethylene ether the carbochain that its hydrophobic fat alcohol moiety is C1 ~ C18; In fatty alcohol-polyoxyethylene ether, the degree of polymerization of oxirane is 5 ~ 100.
The preparation method of the epoxy resin sizing agent emulsion of 17. a kind of polyurethane structural modifications according to claim 16, is characterized in that: described fatty alcohol-polyoxyethylene ether is hexadecanol polyoxyethylene ether, polyoxyethylene octadecanol.
The preparation method of the epoxy resin sizing agent emulsion of 18. a kind of polyurethane structural modifications according to claim 10, it is characterized in that: described antioxidant is 2,6-BHT, described levelling agent is Siloxane-Oxyalkylene Copolymers BNK-LK380, and described antifreezing agent is butyl glycol ether.
The preparation method of the epoxy resin sizing agent emulsion of 19. a kind of polyurethane structural modifications according to claim 10, is characterized in that: in described step (2), deionized water pH value is 6.0 ~ 8.0, and resistance is for being greater than 1 megohm.
The preparation method of the epoxy resin sizing agent emulsion of 20. a kind of polyurethane structural modifications according to claim 19, is characterized in that: described deionized water pH value is 6.0 ~ 7.5, and resistance is for being greater than 10 megohms.
The epoxy resin sizing agent emulsion applications of 21. 1 kinds of polyurethane structural modifications is in the sizing technique of T300 ~ T1000 grade carbon fiber.
The application of the epoxy resin sizing agent emulsion of 22. a kind of polyurethane structural modifications according to claim 21, it is characterized in that: by T300 ~ T1000 grade carbon fiber online impregnation time 10 ~ 50s, the temperature of heated-air drying is 100 ~ 170 ℃, 1 ~ 5 minute online dry time, can complete starching.
The application of the epoxy resin sizing agent emulsion of 23. a kind of polyurethane structural modifications according to claim 22, is characterized in that: described online impregnation time 10 ~ 30s, 120 ~ 160 ℃ of the temperature of heated-air drying, 1 ~ 3 minute online dry time.
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Cited By (11)
| 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 |
| CN105484041A (en) * | 2016-01-21 | 2016-04-13 | 中复神鹰碳纤维有限责任公司 | Composite water-based emulsion sizing agent for carbon fibers, and preparation method for sizing agent |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551871A (en) * | 1991-08-16 | 1993-03-02 | Mitsubishi Rayon Co Ltd | Sizing agent for carbon fiber |
| CN1701148A (en) * | 2001-05-25 | 2005-11-23 | 三菱丽阳株式会社 | Sizing agent for carbon fiber, aqueous dispersion thereof, carbon fiber treated by sizing, sheet-form object comprising the carbon fiber, and carbon fiber-reinforced composite material |
| CN101045809A (en) * | 2007-04-20 | 2007-10-03 | 常熟佳发化学有限责任公司 | Epoxy resin composite, and preparation method thereof and using method thereof |
| CN101602915A (en) * | 2009-07-13 | 2009-12-16 | 天津开发区科泰化工新材料开发有限公司 | Polyurethane water-proof paint of environment-friendly and high-performance inierpeneirating network structure and preparation method thereof |
| CN101858038A (en) * | 2010-06-18 | 2010-10-13 | 济南大学 | Carbon fiber emulsion sizing agent and preparation method and application thereof |
| CN102459728A (en) * | 2009-06-10 | 2012-05-16 | 三菱丽阳株式会社 | Carbon fiber bundle that develops excellent mechanical performance |
-
2012
- 2012-10-26 CN CN201210417876.7A patent/CN103790020B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551871A (en) * | 1991-08-16 | 1993-03-02 | Mitsubishi Rayon Co Ltd | Sizing agent for carbon fiber |
| CN1701148A (en) * | 2001-05-25 | 2005-11-23 | 三菱丽阳株式会社 | Sizing agent for carbon fiber, aqueous dispersion thereof, carbon fiber treated by sizing, sheet-form object comprising the carbon fiber, and carbon fiber-reinforced composite material |
| CN101045809A (en) * | 2007-04-20 | 2007-10-03 | 常熟佳发化学有限责任公司 | Epoxy resin composite, and preparation method thereof and using method thereof |
| CN102459728A (en) * | 2009-06-10 | 2012-05-16 | 三菱丽阳株式会社 | Carbon fiber bundle that develops excellent mechanical performance |
| CN101602915A (en) * | 2009-07-13 | 2009-12-16 | 天津开发区科泰化工新材料开发有限公司 | Polyurethane water-proof paint of environment-friendly and high-performance inierpeneirating network structure and preparation method thereof |
| CN101858038A (en) * | 2010-06-18 | 2010-10-13 | 济南大学 | Carbon fiber emulsion sizing agent and preparation method and application thereof |
Cited By (15)
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|---|---|---|---|---|
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| CN110551372A (en) * | 2018-05-31 | 2019-12-10 | 比亚迪股份有限公司 | Sizing agent and preparation method thereof, chopped glass fiber and preparation method thereof, and sheet and preparation method thereof |
| CN111979775A (en) * | 2020-07-24 | 2020-11-24 | 福建创立佳科技有限公司 | Preparation method of surface sizing agent for aramid fiber composite material |
| CN111979775B (en) * | 2020-07-24 | 2022-05-27 | 福建创立佳科技有限公司 | Preparation method of surface sizing agent for aramid fiber composite material |
| CN112679110A (en) * | 2020-12-31 | 2021-04-20 | 江苏天龙玄武岩连续纤维股份有限公司 | Impregnating compound and treatment method of impregnating compound on basalt fiber |
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