CN103790020B - Epoxy resin sizing agent emulsion that polyurethane structural is modified and preparation thereof and application - Google Patents
Epoxy resin sizing agent emulsion that polyurethane structural is modified and preparation thereof and application Download PDFInfo
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Abstract
The present invention relates to the epoxy resin sizing agent emulsion that a kind of polyurethane structural is modified, its component includes: the modified composition epoxy resin 55 ~ 78wt% of polyurethane structural, surfactant 20 ~ 40wt%, antioxidant 0.5 ~ 2wt%, levelling agent 1 ~ 2wt%, and antifreezing agent 0.5 ~ 1wt%；Its preparation includes: bisphenol A type epoxy resin evacuation dehydration to bubble-free produced, and adds isocyanates, prepare composition epoxy resin after cooling；By above-mentioned material mark, surfactant and antioxidant are mixed homogenizing in a kettle., be then gradually adding deionized water, levelling agent and antifreezing agent, to obtain final product.Carbon fiber obtained by the epoxy resin sizing agent emulsion of the present invention has good convergence, wearability and toughness, and its convergence and wearability freely regulate easily by the consumption of isocyanate component；And this carbon fiber sizing agent need not add collecting agent and on-the-spot secondary mixing in the later stage, application has good stability, and carbon fiber starching wellability is good, and the stabilization of industry being beneficial to carbon fiber produces.
Description
Technical field
The invention belongs to the preparation field of water-base epoxy sizing agent emulsion, the epoxy resin sizing agent emulsion modified particularly to a kind of polyurethane structural with good convergence and wearability and preparation thereof and application.
Background technology
It is the important foundation reinforcement material that fiber-reinforced resin matrix compound material is prepared in production with the high-performance fiber that carbon fiber, graphite fibre, glass fibre, aramid fiber etc. are representative.It is fabricated to example with the through engineering approaches of high-performance carbon fibre, graphite fibre, in its technological process of production, the chemical surface treatment of fiber and starching are research and the requisite link producing carbon fiber (" carbon fiber and graphite fibre " He Fuzhu, Chemical Industry Press, 2010).By surface treatment of carbon fibers and sizing process, the production convergence of gained carbon fiber, wearability, toughness, antistatic behaviour etc. can be improved on the one hand, simultaneously the fibrillation of gained carbon fiber and the balance regulation of expanding be can be realized by the adjustment of sizing agent performance, carbon fiber, graphite fibre met at the performance requirement of the composite material manufacturing technologies such as follow-up braiding, laying, winding.On the other hand, carbon fiber, the process on graphite fibre surface are mated with the application performance of sizing agent, different composite material resin system and shaping project process conditions can be simultaneous for what guarantee fiber manufacture and subsequent technique performance, improve the interface binding intensity of carbon fiber, the matrix resin wellability of graphite fibre and solidified forming gained fiber-reinforced resin matrix compound material.
Based on sizing agent importance 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, be also current high-performance carbon fibre and the important focus of graphite fibre industrialization technology research.Chinese invention patent application 200510063352.2,201010300131.3,201010234852.9,2009102158.33,201010202372.4 individually disclose with epoxy resin, aqueous epoxy resins, (+)-2,3-Epoxy-1-propanol ether-ether, polypropylene nitrile, epoxy vinyl composite resin be key component the preparation method of carbon fiber sizing agent and application.In addition, in order to improve emulsion property and the performance of starching carbon fiber further, Chinese invention patent application 201010217247.0,201110102007.0,201110085545.3,200410064587.9 individually discloses the preparation method and application of the emulsion pasting agent adopting polyhydric alcohol, Graphene, CNT, nano silicon etc. modified.Meanwhile, Chinese invention patent application 201010217240.9 and 201010125199.2 individually discloses the synthesis preparation method of two kinds of self-emulsifying type epoxy radicals carbon fiber sizing agents.But from current application feature, when the sizing agent adopting above-mentioned resin formula and preparation method gained is applied to carbon fiber, graphite fibre, exist under normal fiber starching amount (< 1.40%) condition convergence and wear no resistance, fibrillation and expanding performance shortcoming and the problem such as resilience toughness is not enough, particularly in ubiquity in the carbon fiber through engineering approaches application of 12K and above tow number, constrain the practical engineering application of above-mentioned sizing agent.
Not enough in order to improve carbon fiber, the convergence of graphite fibre and anti-wear performance, to be typically employed in aqueous epoxy resins base emulsion sizing agent at present extra adds the auxiliary agents such as features penetrating agent, collecting agent.For carbon fiber collecting agent, the chemical conversion company CHEMITYLEN collection of filaments agent of presently commercially available product such as Sanyo, its active chemical is bisphenol type unsaturated polyester (UP).In practical engineering application, after water-based emulsion sizing agent adds the mixing of boundling function additive, there is the technical problems such as sizing agent stability of emulsion declines, easily layering, solid content are wayward.Simultaneously because the component of additional boundling function additive is easily caused the hardening of starching carbon fiber, lose elasticity and wearability that later stage fiber process molding needs, it is impossible to meet the application demand of final composite.
Summary of the invention
The technical problem to be solved is to provide the modified epoxy resin sizing agent emulsion of a kind of polyurethane structural and preparation thereof and application, carbon fiber obtained by this epoxy resin sizing agent emulsion has good convergence, wearability and toughness, the chemical stability of sizing agent resin is good simultaneously, is conducive to the long term storage of starching carbon fiber to guarantee the quality；And preparation technology simply, easily operate, reaction raw materials convenient sources, cost is low, it is possible to complete preparation process in common apparatus, and economic benefit is good, is advantageously implemented industrialized production.
The epoxy resin sizing agent emulsion that a kind of polyurethane structural of the present invention is modified, its component includes:
The composition epoxy resin that described polyurethane structural is modified, its component includes:
Bisphenol A type epoxy resin 88 ~ 99wt%
Isocyanates 1 ~ 12wt%
The described bisphenol A type epoxy resin mixture of one or more 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, it is preferable that 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 (HDI) of aliphatic or alicyclic isophorone diisocyanate (IPDI)；
Described surfactant is fatty alcohol-polyoxyethylene ether, and its hydrophobic fat alcohol moiety is the carbochain of C1 ~ C18；Preferred hexadecanol polyoxyethylene ether, polyoxyethylene octadecanol；
In described fatty alcohol-polyoxyethylene ether, the degree of polymerization of oxirane is 5 ~ 100, it is preferable that the degree of polymerization is 5 ~ 50；
Described antioxidant is 2,6 ditertiary butyl p cresol, 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%, and emulsion mean diameter is 100 ~ 350nm, surface tension 30 ~ 50mN/m, and emulsion room temperature rotary viscosity is 10 ~ 500cp.
The preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural of the present invention is modified, including:
(1) preparation of the composition epoxy resin that polyurethane structural is modified
Bisphenol A type epoxy resin reactant at high temperature evacuation dehydration to bubble-free is produced; then the dry epoxy resin of vacuum dehydration gained is cooled to 50 ~ 70 DEG C; isocyanate reaction thing is added under the drying nitrogen of purity 99.999% is protected; the mass ratio of its epoxy resin and isocyanates is 88 ~ 99:1 ~ 12; prior to 50 ~ 70 DEG C; stirring reaction 1 ~ 2 hour; then heat to 80 ~ 100 DEG C; continue reaction more than 2 hours; control isocyanate functional group's content of product less than 0.1% stopped reaction, prepare the composition epoxy resin that polyurethane structural is modified；
(2) preparation of the epoxy resin sizing agent emulsion that polyurethane structural is modified
The composition epoxy resin modified by above-mentioned polyurethane structural, mixes homogenizing by following quality of material number in a kettle. with surfactant, antioxidant, and intimate mixing temperature controls at 70 ~ 120 DEG C, and the intimate mixing time is 0.5 ~ 2 hour；Then, uniform homogeneous blend being cooled to 60 ~ 90 DEG C, is gradually added deionized water simultaneously high speed shear dispersion and emulsion, uniform homogeneous blend is 30 ~ 60:70 ~ 40 with deionized water quality ratio, add levelling agent and antifreezing agent after completing, prepare the epoxy resin sizing agent emulsion that polyurethane structural is modified；
In described step (1) the bisphenol A type epoxy resin mixture of one or more in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, the bisphenol A-type E51；
In described step (1) bisphenol A type epoxy resin, its mean molecule quantity is 350 ~ 2500 grams/mol, it is preferable that mean molecule quantity is 350 ~ 1500 grams/mol；
The temperature of the vacuum dehydration in described step (1) is 90 ~ 150 DEG C, 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 (HDI) of aliphatic or alicyclic isophorone diisocyanate (IPDI)；
Surfactant in described step (2) is fatty alcohol-polyoxyethylene ether, and its hydrophobic fat alcohol moiety is the carbochain of C1 ~ C18；Preferred hexadecanol polyoxyethylene ether, polyoxyethylene octadecanol；
In described fatty alcohol-polyoxyethylene ether, the degree of polymerization of oxirane is 5 ~ 100, it is preferable that the degree of polymerization is 5 ~ 50；
Described antioxidant is 2,6 ditertiary butyl p cresol, and described levelling agent is Siloxane-Oxyalkylene Copolymers BNK-LK380, and described antifreezing agent is butyl glycol ether；
Intimate mixing temperature in described step (2) controls at 70 ~ 120 DEG C, it is preferable that temperature 85 ~ 120 DEG C；
In described step (2), deionized water pH value is 6.0 ~ 8.0, and resistance is more than 1 megohm；Preferable ph is 6.0 ~ 7.5, and resistance is more than 10 megohms.
The epoxy resin sizing agent emulsion applications that a kind of polyurethane structural of the present invention modifiies is in the sizing technique of T300 ~ T1000 grade carbon fiber.
By online for T300 ~ T1000 grade carbon fiber impregnation, impregnation time 10 ~ 50s, the temperature of hot air drying is 100 ~ 170 DEG C, 1 ~ 5 minute online dry time, can complete starching；
Described online impregnation time preferably 10 ~ 30s, the temperature of hot air drying preferably 120 ~ 160 DEG C, preferably 1 ~ 3 minute online dry time.
Beneficial effect
(1) the epoxy resin sizing agent emulsion that polyurethane structural provided by the invention is modified, its resin structure contains active epoxy group and Polar Amides formic acid ester bond, carbon fiber obtained by sizing agent has good convergence, wearability and toughness, and its convergence and wearability freely regulate easily by the consumption of isocyanate component；The chemical stability of above-mentioned sizing agent resin is good simultaneously, is conducive to the long term storage of starching carbon fiber to guarantee the quality；
(2) this carbon fiber sizing agent need not add collecting agent and on-the-spot secondary mixing in the later stage, and the application of water-based emulsion sizing agent has good stability, and carbon fiber starching wellability is good, and the stabilization of industry being beneficial to carbon fiber produces；
(3) this preparation technology simply, easily operate, reaction raw materials convenient sources, cost is low, it is possible to complete preparation process in common apparatus, and economic benefit is good, is advantageously implemented industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1-12
One, the preparation of polyurethane-modified composition epoxy resin
Being placed in the 250ml four-hole boiling flask with mechanical stirring device by quantitative epoxy resin composition, heating, to 110 DEG C, controls vacuum pressure 100-0.1mmHg, and evacuation dehydration produces for 2 hours to bubble-free.It is cooled to 70 DEG C, removes vacuum extractor, insert condensing tube.Under high pure nitrogen is protected; six times quantitative methylene diisocyanates (HDI) are added drop-wise in flask with Micro-metering Pumps very lentamente; first react 1 hour at 70 DEG C after dropwising; it is warming up to 95 DEG C again to react more than 2 hours; sampling carries out infrared analysis; during result display nothing-NCO group, prepare the composition epoxy resin that polyurethane structural is modified.Epoxy resin composition kind used and consumption, six methylene diisocyanate (HDI) consumptions are in Table 1.
Raw materials quality table is used in table 1, reaction
Two, the preparation of epoxy radicals carbon fiber sizing agent
Take 60g above-described embodiment and prepare the composition epoxy resin that the polyurethane structural of gained modifiies, add 0.32g2,6-ditertbutylparacresol (group produces by traditional Chinese medicines), 21.30g octadecanol polyoxyethylene ether surface active agent (ethylene oxide polymerization degree 20) (is produced by Hai'an, Jiangsu petrochemical plant), stir 1 hour at 90 DEG C.Then 80 DEG C it are cooled to, it is slowly added dropwise the high-speed stirred emulsifying simultaneously of 100g deionized water, after completing add 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(by BNK company of the U.S. produce), 0.32g butyl glycol ether (group produces by traditional Chinese medicines), prepare water-based emulsion.
The present embodiment is prepared the viscosity of gained water-based emulsion and is adopted the test of BrookfieldDV-IIPro rotating cylinder viscometer to obtain, emulsion PH adopts Mettler Toledo Inc. of U.S. DELTA320pH measurement examination to obtain, emulsion surface tension adopts the DCAT21 type dynamic contact angle of DataPhysics company of Germany to obtain with surface tension instrument test, emulsion mean diameter adopts the ZetasizerNanoZS90 type Dynamic laser scattering instrument test of Malvern 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 being prepared gained emulsion pasting agent and carries out starching making by oneself on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, baking temperature 130 DEG C, drying time 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341；Exercise question: temp, resisting type carbon fibre emulsion sizing agent) method test obtain wearability, lousiness figureofmerit；Shear strength ILSS between carbon fiber composite layer is tested according to GB3357-1982 unidirectional fibre reinforced plastics interlayer shear strength test method；Adopting feel ocular estimate that carbon fiber cluster performance after starching is graded, gained starching carbon fiber Evaluation results is in Table 3.
Table 3, starching carbon fiber Evaluation results
| Convergence | Wearability/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 5 --> |
| 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
Being placed in the 250ml four-hole boiling flask with mechanical stirring device by quantitative epoxy resin composition, heating, to 110 DEG C, controls vacuum pressure 100-0.1mmHg, and evacuation dehydration produces for 2 hours to bubble-free.It is cooled to 70 DEG C, removes vacuum extractor, insert condensing tube.Under high pure nitrogen is protected; quantitative isophorone diisocyanate (IPDI) is added drop-wise in flask with Micro-metering Pumps very lentamente; first react 1 hour at 70 DEG C after dropwising; it is warming up to 95 DEG C again to react more than 2 hours; sampling carries out infrared analysis; during result display nothing-NCO group, prepare the composition epoxy resin that polyurethane structural is modified.Epoxy resin composition kind used and consumption, isophorone diisocyanate (IPDI) consumption are in Table 4.
Raw materials quality table is used in table 4. reaction
Two, the preparation of epoxy radicals carbon fiber sizing agent
Take 60g above-described embodiment and prepare the composition epoxy resin that the polyurethane structural of gained modifiies, add 0.32g2,6-ditertbutylparacresol (group produces by traditional Chinese medicines), 21.30g octadecanol polyoxyethylene ether surface active agent (ethylene oxide polymerization degree 20) (is produced by Hai'an, Jiangsu petrochemical plant), stir 1 hour at 90 DEG C.Then 80 DEG C it are cooled to, it is slowly added dropwise the high-speed stirred emulsifying simultaneously of 100g deionized water, after completing add 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(by BNK company of the U.S. produce), 0.32g butyl glycol ether (group produces by traditional Chinese medicines), prepare water-based emulsion.
The present embodiment is prepared the viscosity of gained water-based emulsion and is adopted the test of BrookfieldDV-IIPro rotating cylinder viscometer to obtain, emulsion PH adopts Mettler Toledo Inc. of U.S. DELTA320pH measurement examination to obtain, emulsion surface tension adopts the DCAT21 type dynamic contact angle of DataPhysics company of Germany to obtain with surface tension instrument test, emulsion mean diameter adopts the ZetasizerNanoZS90 type Dynamic laser scattering instrument test of Malvern 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 being prepared gained emulsion pasting agent and carries out starching making by oneself on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, baking temperature 130 DEG C, drying time 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341；Exercise question: temp, resisting type carbon fibre emulsion sizing agent) method test obtain wearability, lousiness figureofmerit；Shear strength ILSS between carbon fiber composite layer is tested according to GB3357-1982 unidirectional fibre reinforced plastics interlayer shear strength test method；Adopting feel ocular estimate that carbon fiber cluster performance after starching is graded, 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 | × | 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
Being placed in the 250ml four-hole boiling flask with mechanical stirring device by quantitative epoxy resin composition, heating, to 110 DEG C, controls vacuum pressure 100-0.1mmHg, and evacuation dehydration produces for 2 hours to bubble-free.It is cooled to 50 DEG C, removes vacuum extractor, insert condensing tube.Under high pure nitrogen is protected; quantitative methyl diphenylene diisocyanate (MDI) is added drop-wise in flask with Micro-metering Pumps very lentamente; first react 1 hour at 50 DEG C after dropwising; it is warming up to 85 DEG C again to react more than 2 hours; sampling carries out infrared analysis; during result display nothing-NCO group, prepare the composition epoxy resin that polyurethane structural is modified.Epoxy resin composition kind used and consumption, methyl diphenylene diisocyanate (MDI) consumption are in Table 7.
Raw materials quality table is used in table 7, reaction
Two, the preparation of epoxy radicals carbon fiber sizing agent
Take 60g above-described embodiment and prepare the composition epoxy resin that the polyurethane structural of gained modifiies, add 0.32g2,6-ditertbutylparacresol (group produces by traditional Chinese medicines), 21.30g octadecanol polyoxyethylene ether surface active agent (ethylene oxide polymerization degree 20) (is produced by Hai'an, Jiangsu petrochemical plant), stir 1 hour at 90 DEG C.Then 80 DEG C it are cooled to, it is slowly added dropwise the high-speed stirred emulsifying simultaneously of 100g deionized water, after completing add 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(by BNK company of the U.S. produce), 0.32g butyl glycol ether (group produces by traditional Chinese medicines), prepare water-based emulsion.
The present embodiment is prepared the viscosity of gained water-based emulsion and is adopted the test of BrookfieldDV-IIPro rotating cylinder viscometer to obtain, emulsion PH adopts Mettler Toledo Inc. of U.S. DELTA320pH measurement examination to obtain, emulsion surface tension adopts the DCAT21 type dynamic contact angle of DataPhysics company of Germany to obtain with surface tension instrument test, emulsion mean diameter adopts the ZetasizerNanoZS90 type Dynamic laser scattering instrument test of Malvern 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 being prepared gained emulsion pasting agent and carries out starching making by oneself on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, baking temperature 130 DEG C, drying time 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341；Exercise question: temp, resisting type carbon fibre emulsion sizing agent) method test obtain wearability, lousiness figureofmerit；Shear strength ILSS between carbon fiber composite layer is tested according to GB3357-1982 unidirectional fibre reinforced plastics interlayer shear strength test method；Adopting feel ocular estimate that carbon fiber cluster performance after starching is graded, gained starching carbon fiber Evaluation results is in Table 9.
Table 9, starching carbon fiber Evaluation results
| Convergence | Wearability/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
Being placed in the 250ml four-hole boiling flask with mechanical stirring device by quantitative epoxy resin composition, heating, to 110 DEG C, controls vacuum pressure 100-0.1mmHg, and evacuation dehydration produces for 2 hours to bubble-free.It is cooled to 50 DEG C, removes vacuum extractor, insert condensing tube.Under high pure nitrogen is protected; quantitative toluene di-isocyanate(TDI) (TDI) is added drop-wise in flask with Micro-metering Pumps very lentamente; first react 1 hour at 50 DEG C after dropwising; it is warming up to 85 DEG C again to react more than 2 hours; sampling carries out infrared analysis; during result display nothing-NCO group, prepare the composition epoxy resin that polyurethane structural is modified.Epoxy resin composition kind used and consumption, toluene di-isocyanate(TDI) (TDI) consumption are in Table 10.
Raw materials quality table is used in table 10. reaction
Two, the preparation of epoxy radicals carbon fiber sizing agent
Take 60g above-described embodiment and prepare the composition epoxy resin that the polyurethane structural of gained modifiies, add 0.32g2,6-ditertbutylparacresol (group produces by traditional Chinese medicines), 21.30g octadecanol polyoxyethylene ether surface active agent (ethylene oxide polymerization degree 20) (is produced by Hai'an, Jiangsu petrochemical plant), stir 1 hour at 90 DEG C.Then 80 DEG C it are cooled to, it is slowly added dropwise the high-speed stirred emulsifying simultaneously of 100g deionized water, after completing add 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(by BNK company of the U.S. produce), 0.32g butyl glycol ether (group produces by traditional Chinese medicines), prepare water-based emulsion.
The present embodiment is prepared the viscosity of gained water-based emulsion and is adopted the test of BrookfieldDV-IIPro rotating cylinder viscometer to obtain, emulsion PH adopts Mettler Toledo Inc. of U.S. DELTA320pH measurement examination to obtain, emulsion surface tension adopts the DCAT21 type dynamic contact angle of DataPhysics company of Germany to obtain with surface tension instrument test, emulsion mean diameter adopts the ZetasizerNanoZS90 type Dynamic laser scattering instrument test of Malvern 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 being prepared gained emulsion pasting agent and carries out starching making by oneself on small-sized starching instrument, selected fiber is 12KT300 grade carbon fiber, dipping time 30s, baking temperature 130 DEG C, drying time 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341；Exercise question: temp, resisting type carbon fibre emulsion sizing agent) method test obtain wearability, lousiness figureofmerit；Shear strength ILSS between carbon fiber composite layer is tested according to GB3357-1982 unidirectional fibre reinforced plastics interlayer shear strength test method；Adopting feel ocular estimate that carbon fiber cluster performance after starching is graded, gained starching carbon fiber Evaluation results is in Table 12.
Table 12, starching carbon fiber Evaluation results
| Convergence | Wearability/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 preferred embodiment is disclosed as above by the present invention; so it is not limited to present disclosure; any it is familiar with this those skilled in the art; without departing from the main spirits of the present invention and context; when doing various change and retouching, the protection domain therefore invented should be as the criterion with the basic right claimed range applied for a patent.
Claims (11)
1. a preparation method for the epoxy resin sizing agent emulsion that polyurethane structural is modified, including:
(1) preparation of the composition epoxy resin that polyurethane structural is modified
Bisphenol A type epoxy resin at high temperature evacuation dehydration to bubble-free is produced; then the dry epoxy resin of vacuum dehydration gained is cooled to 50～70 DEG C; isocyanates is added under the drying nitrogen of purity 99.999% is protected; the mass ratio of its epoxy resin and isocyanates is 88～99:1～12; prior to 50～70 DEG C; stirring reaction 1～2 hour; then heat to 80～100 DEG C; continue reaction more than 2 hours; control isocyanate functional group's content of product less than 0.1% stopped reaction, prepare the composition epoxy resin that polyurethane structural is modified；
(2) preparation of the epoxy resin sizing agent emulsion that polyurethane structural is modified
The composition epoxy resin modified by above-mentioned polyurethane structural, mixes homogenizing by following quality of material percentage ratio in a kettle. with surfactant, antioxidant, and intimate mixing temperature controls at 70～120 DEG C, and the intimate mixing time is 0.5～2 hour；Then, uniform homogeneous blend is cooled to 60～90 DEG C, it is gradually added deionized water simultaneously high speed shear dispersion and emulsion, the mass ratio of uniform homogeneous blend and deionized water is 30～60:70～40, add levelling agent and antifreezing agent after completing, prepare the epoxy resin sizing agent emulsion that polyurethane structural is modified；
2. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 1 is modified, it is characterised in that: the mixture of one or more in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51 of the bisphenol A type epoxy resin in described step (1).
3. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 1 and 2 is modified, it is characterised in that: the bisphenol A type epoxy resin in described step (1), its mean molecule quantity is 350～2500 grams/mol.
4. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 1 is modified, it is characterized in that: the temperature of the vacuum dehydration in described step (1) is 90～150 DEG C, the vacuum pressure of dehydration is 100～0.1mmHg.
5. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 1 is modified, it is characterised in that: the isocyanates in described step (1) is aromatic series, aliphatic or alicyclic isocyanate.
6. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural is modified according to claim 1 or 5, it is characterised in that: described isocyanates is aromatic series toluene di-isocyanate(TDI) TDI, aromatic series methyl diphenylene diisocyanate MDI, aliphatic hexamethylene diisocyanate HDI or alicyclic isophorone diisocyanate IPDI.
7. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 1 is modified, it is characterized in that: the surfactant in described step (2) is fatty alcohol-polyoxyethylene ether, its hydrophobic fat alcohol moiety is the carbochain of C1～C18；In fatty alcohol-polyoxyethylene ether, the degree of polymerization of oxirane is 5～100.
8. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 7 is modified, it is characterised in that: described fatty alcohol-polyoxyethylene ether is hexadecanol polyoxyethylene ether, polyoxyethylene octadecanol.
9. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 1 is modified, it is characterized in that: described antioxidant is 2,6-ditertbutylparacresol, described levelling agent is Siloxane-Oxyalkylene Copolymers BNK-LK380, and described antifreezing agent is butyl glycol ether.
10. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 1 is modified, it is characterised in that: in described step (2), deionized water pH value is 6.0～8.0, and resistance is more than 1 megohm.
11. the preparation method of the epoxy resin sizing agent emulsion that a kind of polyurethane structural according to claim 10 is modified, it is characterised in that: described deionized water pH value is 6.0～7.5, and resistance is more than 10 megohms.
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| 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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| CN113969504A (en) * | 2021-11-24 | 2022-01-25 | 中复神鹰碳纤维股份有限公司 | Carbon fiber sizing agent with high heat resistance and wear resistance and preparation method thereof |
| CN114369225A (en) * | 2022-02-08 | 2022-04-19 | 山西钢科碳材料有限公司 | Polyurethane prepolymer modified epoxy resin emulsion and preparation method and application thereof |
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