CN103790019B - A kind of epoxy radicals carbon fiber sizing agent emulsion and preparation and application - Google Patents
A kind of epoxy radicals carbon fiber sizing agent emulsion and preparation and application Download PDFInfo
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- CN103790019B CN103790019B CN201210417873.3A CN201210417873A CN103790019B CN 103790019 B CN103790019 B CN 103790019B CN 201210417873 A CN201210417873 A CN 201210417873A CN 103790019 B CN103790019 B CN 103790019B
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Abstract
The present invention relates to a kind of epoxy radicals carbon fiber sizing agent emulsion, its component comprises: composition epoxy resin 55 ~ 78wt%, the surfactant 20 ~ 40wt% of polyurethane structural modification, antioxidant 0.5 ~ 2wt%, levelling agent 1 ~ 2wt%, and antifreezing agent 0.5 ~ 1wt%; Its preparation comprises: bisphenol f type epoxy resin reactant is vacuumized to dehydration to without Bubble formation, add isocyanate reaction thing, make composition epoxy resin; By above-mentioned material mark, surfactant and antioxidant are mixed to homogeneous in reactor, then progressively add deionized water, levelling agent and antifreezing agent, make sizing agent emulsion. Epoxy radicals carbon fiber sizing agent emulsion gained carbon fiber of the present invention has good convergence, wearability and toughness, and 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, is conducive to realize suitability for industrialized production.
Description
Technical field
The invention belongs to the preparation field of water-base epoxy sizing agent emulsion, particularly one has good convergence and wearabilityEpoxy radicals carbon fiber sizing agent emulsion and preparation and application.
Background technology
It is manufacture fiber reinforcement tree taking carbon fiber, graphite fibre, glass fibre, aramid fiber etc. as the high-performance fiber of representativeThe important foundation reinforcement material of resin-based composite. Through engineering approaches with high-performance carbon fibre, graphite fibre is fabricated to example, itsIn the technological process of production, the chemical surface treatment of fiber and starching are requisite links of research and production carbon fiber(" carbon fiber and graphite fibre " He Fuzhu, Chemical Industry Press, 2010). By surface treatment of carbon fibers and starching workOrder, can improve on the one hand the convergence, wearability, toughness, antistatic behaviour etc. of producing gained carbon fiber, can pass through simultaneouslyThe adjusting of sizing agent performance realizes the balance regulation of opening fibre and expanding of gained carbon fiber, meets carbon fiber, graphite fibreAt the performance requirement of the composite material manufacturing technologies such as follow-up braiding, laying, winding. On the other hand, carbon fiber, graphite fibreThe processing on surface is mated with the application performance of sizing agent, can be in guaranteeing fiber manufacture and subsequent technique performance for notWith composite resin system and shaping project process conditions, the matrix resin wellability of raising carbon fiber, graphite fibre and solidChange into the interface binding intensity of shape gained fiber-reinforced resin matrix compound material.
Based on sizing agent in high-performance carbon fibre and graphite fibre manufacturing engineering and fiber-reinforced resin matrix compound material applicationIn importance, sizing agent has become the important supplementary material of carbon fiber, graphite fibre through engineering approaches, its performance impact carbon fiberThe manufacturability of manufacturing engineering and the comprehensive mechanical property of composite are also current high-performance carbon fibre and graphite fibre industrializationThe important focus of 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 and preparation method instituteSizing agent while being applied to carbon fiber, graphite fibre, exist under normal fiber starching amount (< 1.40%) condition convergence andWear no resistance, open the problem such as fibre and expanding performance shortcoming and resilience toughness deficiency, especially at 12K and above tow numberCarbon fiber through engineering approaches application in ubiquity, 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 at aqueous epoxy resins at presentIn base emulsion sizing agent, additionally add the auxiliary agents such as features bleeding agent, collecting agent. Taking carbon fiber collecting agent as example, city at presentThe product of selling changes into the agent of the CHEMITYLEN of the company collection of filaments as Sanyo, and its active chemical is bisphenol type unsaturated polyesterEster. In practical engineering application, after adding boundling function additive to mix in water-based emulsion sizing agent, exist sizing agent emulsion steadyThe technical problems such as qualitative decline, easily layering, solid content are wayward. Simultaneously because the component of additional boundling function additive is heldEasily cause the sclerosis of starching carbon fiber, lose elasticity and wearability that later stage fiber process moulding needs, cannot meet finally compoundThe application demand of material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of epoxy radicals carbon fiber sizing agent emulsion and preparation and application, shouldThe obtained carbon fiber of epoxy radicals carbon fiber sizing agent emulsion has good convergence, wearability and toughness, simultaneously sizing agent treeThe chemical stability of fat is good, and the long term storage that is conducive to starching carbon fiber is guaranteed the quality; And preparation technology is simple, easy to operate, anti-Answer raw material sources convenient, cost is low, can in common apparatus, complete preparation process, and economic benefit is good, is conducive to realizeSuitability for industrialized production.
A kind of epoxy radicals carbon fiber sizing agent emulsion of the present invention, its component comprises:
The composition epoxy resin of described polyurethane structural modification, its component comprises:
Bisphenol f type epoxy resin 88 ~ 99wt%
Isocyanates 1 ~ 12wt%
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 isocyanate is aromatic series toluene twoIsocyanates (TDI), aromatic series methyl diphenylene diisocyanate (MDI), six methylene diisocyanates of aliphaticOr alicyclic IPDI (IPDI) (HDI);
Described surfactant is AEO, the carbochain that its hydrophobic fat alcohol moiety is C1 ~ C18; ExcellentSelect hexadecanol APEO, polyoxyethylene octadecanol;
In described AEO, 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 CopolymersBNK-LK380, described antifreezing agent is butyl glycol ether;
Described epoxy radicals carbon fiber 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 a kind of epoxy radicals carbon fiber sizing agent emulsion of the present invention, comprising:
(1) preparation of the composition epoxy resin of polyurethane structural modification
Bisphenol f type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, then by vacuum dehydration gainedDry epoxy resin be cooled to 50 ~ 70 DEG C, 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 DEG C, and stirring reaction 1 ~ 2 hour, soAfter be warming up to 80 ~ 100 DEG C, continue reaction more than 2 hours, control isocyanate functional group's content of product and be less than 0.1%Stopped reaction, makes the composition epoxy resin of polyurethane structural modification;
(2) preparation of epoxy radicals carbon fiber sizing agent emulsion
By the composition epoxy resin of above-mentioned polyurethane structural modification, by following quality of material umber and surfactant, antioxygenAgent is mixed homogeneous in reactor, and homogeneous mixing temperature is controlled at 70 ~ 120 DEG C, and homogeneous incorporation time is 0.5 ~ 2 hour;Then, uniform homogeneous blend is cooled to 60 ~ 90 DEG C, progressively adds deionized water while high speed shear dispersion and emulsion, homogeneousMixture is 30 ~ 60:70 ~ 40 with deionized water quality ratio, adds levelling agent and antifreezing agent after completing, and prepares epoxy radicalsCarbon fiber sizing agent emulsion;
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 ~ 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 virtueFragrant family's toluene di-isocyanate(TDI) (TDI), aromatic series methyl diphenylene diisocyanate (MDI), six methylene of aliphaticVulcabond (HDI) or alicyclic IPDI (IPDI);
Surfactant in described step (2) is AEO, and its hydrophobic fat alcohol moiety is C1 ~ C18Carbochain; Preferably hexadecanol APEO, polyoxyethylene octadecanol;
In described AEO, 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 CopolymersBNK-LK380, described antifreezing agent is butyl glycol ether;
Homogeneous mixing temperature in described step (2) is controlled at 70 ~ 120 DEG C, preferably 85 ~ 120 DEG C 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,Resistance is for being greater than 10 megohms.
A kind of epoxy radicals carbon fiber sizing agent emulsion applications 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 DEG C,1 ~ 5 minute online dry time, can complete starching;
Described preferably 10 ~ 30s of online impregnation time, preferably 120 ~ 160 DEG C of the temperature of heated-air drying, the online dry time is excellentSelect 1 ~ 3 minute.
Beneficial effect
(1) epoxy radicals carbon fiber sizing agent emulsion provided by the invention, its resin structure contains active epoxy group and the amino first of polarityAcid esters key, sizing agent gained carbon fiber has good convergence, wearability and toughness, and its convergence and wearability appearanceEasily by the consumption free adjustment of isocyanate component; The chemical stability of above-mentioned sizing agent resin is good simultaneously, is conducive toThe long term storage of slurry 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 is steadyQualitative good, carbon fiber starching wellability 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 systemStandby process, economic benefit is good, is 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
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 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 epoxy tree of polyurethane structural modificationOil/fat composition. Epoxy resin composition kind used and consumption, six methylene diisocyanates (HDI) consumption are in table 1.
Table 1. 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 0.32g2,6-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 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 on the small-sized starching instrument of self-control, carry out starching, selected fiber is 12KT300 grade carbon 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 plastic layerBetween shear strength test method test carbon fibre composite interlaminar shear strength ILSS; Carbon after adopting feel ocular estimate to starchingCollection of filaments performance is graded, and gained starching carbon fiber Evaluation results is in table 3.
Table 3, starching carbon fiber Evaluation results
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 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 epoxy tree of polyurethane structural modificationOil/fat composition. Epoxy resin composition kind used and consumption, IPDI (IPDI) consumption are in table 4.
Table 4, 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 0.32g2,6-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 EnglishThe ZetasizerNanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company of state obtains, and prepared emulsion is everyPerformance indications are 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 on the small-sized starching instrument of self-control, carry out starching, selected fiber is 12KT300 grade carbon 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 plastic layerBetween shear strength test method test carbon fibre composite interlaminar shear strength ILSS; Carbon after adopting feel ocular estimate to starchingCollection of filaments performance is graded, and gained starching carbon fiber Evaluation results is in table 6.
Table 6, starching carbon fiber Evaluation results
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 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 epoxy tree of polyurethane structural modificationOil/fat composition. 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 0.32g2,6-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 EnglishThe ZetasizerNanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company of state obtains, and prepared emulsion is everyPerformance indications are 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 on the small-sized starching instrument of self-control, carry out starching, selected fiber is 12KT300 grade carbon 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 plastic layerBetween shear strength test method test carbon fibre composite interlaminar shear strength ILSS; Carbon after adopting feel ocular estimate to starchingCollection of filaments performance is graded, and gained starching carbon fiber Evaluation results is in table 9.
Table 9, starching carbon fiber Evaluation results
Note: convergence Index grading ● fine zero good △ is 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 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 epoxy resin group of polyurethane structural modificationCompound. Epoxy resin composition kind used and consumption, toluene di-isocyanate(TDI) (TDI) consumption are in table 10.
Table 10, 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 0.32g2,6-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 EnglishThe ZetasizerNanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company of state obtains, and prepared emulsion is everyPerformance indications are 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 on the small-sized starching instrument of self-control, carry out starching, selected fiber is 12KT300 grade carbon 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 plastic layerBetween shear strength test method test carbon fibre composite interlaminar shear strength ILSS; Carbon after adopting feel ocular estimate to starchingCollection of filaments performance is graded, and gained starching carbon fiber Evaluation results is in table 12.
Table 12, starching carbon fiber Evaluation results
Note: convergence Index grading ● fine zero good △ is 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 (11)
1. a preparation method for epoxy radicals carbon fiber sizing agent emulsion, comprising:
(1) preparation of the composition epoxy resin of polyurethane structural modification
Bisphenol f type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, then by vacuum dehydration gainedDry epoxy resin be cooled to 50～70 DEG C, 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 DEG C, and stirring reaction 1～2 hour, soAfter be warming up to 80～100 DEG C, continue reaction more than 2 hours, control isocyanate functional group's content of product and be less than 0.1%Stopped reaction, makes the composition epoxy resin of polyurethane structural modification;
(2) preparation of epoxy radicals carbon fiber sizing agent emulsion
By the composition epoxy resin of above-mentioned polyurethane structural modification, by following quality of material umber and surfactant, antioxygenAgent is mixed homogeneous in reactor, and homogeneous mixing temperature is controlled at 70～120 DEG C, and homogeneous incorporation time is 0.5～2 hour;Then, uniform homogeneous blend is cooled to 60～90 DEG C, progressively adds deionized water while high speed shear dispersion and emulsion, homogeneousMixture is 30～60:70～40 with deionized water quality ratio, adds levelling agent and antifreezing agent after completing, and prepares epoxy radicalsCarbon fiber sizing agent emulsion;
2. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 1, is characterized in that: described stepSuddenly the bisphenol f type epoxy resin in (1) 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.
3. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 1 and 2, is characterized in that: instituteState the bisphenol f type epoxy resin in step (1), its mean molecule quantity is 350～2500 grams/mol.
4. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 1, is characterized in that: described stepSuddenly the temperature of the vacuum dehydration in (1) is 90～150 DEG C, and the vacuum pressure of dehydration is 100～0.1mmHg.
5. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 1, is characterized in that: described stepSuddenly the isocyanates in (1) is aromatic series, aliphatic or alicyclic isocyanate.
6. a kind of preparation method of epoxy radicals carbon fiber sizing agent emulsion according to claim 1 or 5, is characterized in that: instituteThe isocyanates of stating is aromatic series toluene di-isocyanate(TDI) TDI, aromatic series methyl diphenylene diisocyanate MDI, aliphaticHexamethylene diisocyanate HDI or alicyclic IPDI IPDI.
7. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 1, is characterized in that: described stepSuddenly the surfactant in (2) is AEO, the carbochain that its hydrophobic fat alcohol moiety is C1～C18; FatIn fat alcohol APEO, the degree of polymerization of oxirane is 5～100.
8. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 7, is characterized in that: describedAEO is hexadecanol APEO, polyoxyethylene octadecanol.
9. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 1, is characterized in that: describedAntioxidant is BHT, and described levelling agent is Siloxane-Oxyalkylene Copolymers BNK-LK380, describedAntifreezing agent is butyl glycol ether.
10. the preparation method of a kind of epoxy radicals carbon fiber sizing agent emulsion according to claim 1, is characterized in that: described inIn step (2), deionized water pH value is 6.0～8.0, and resistance is for being greater than 1 megohm.
The preparation method of 11. a kind of epoxy radicals carbon fiber sizing agent emulsions according to claim 10, is characterized in that: described inDeionized water pH value be 6.0～7.5, resistance is for being greater than 10 megohms.
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| CN105586775B (en) * | 2014-10-22 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of high wear-resistance carbon fiber emulsion pasting agent and its preparation and application |
| CN109722894B (en) * | 2017-10-27 | 2022-01-21 | 中国石油化工股份有限公司 | Polyolefin resin-based carbon fiber suspension sizing agent and preparation method thereof |
| CN109957969B (en) * | 2017-12-25 | 2022-01-07 | 比亚迪股份有限公司 | Carbon fiber sizing agent, preparation method thereof, reinforced carbon fiber and carbon fiber composite material |
| EP3553132A1 (en) * | 2018-04-13 | 2019-10-16 | SABIC Global Technologies B.V. | Fiber reinforced composition with good impact performance and flame retardance |
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