CN111440420B - Preparation method of high-performance epoxy toughening material - Google Patents
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Abstract
The invention discloses a preparation method of a high-performance epoxy toughening material, which relates to the field of modified epoxy resin materials and comprises the following steps: (1) Putting the raw material A into a reaction kettle, heating for the first time, preserving heat, and introducing nitrogen; (2) a reaction stage: cooling for the first time, adding the raw material B, heating for the second time, and introducing nitrogen; (3) secondary reaction: adding a catalyst C, heating for the third time, adding a raw material B, heating for the fourth time, and introducing nitrogen; (4) three-stage reaction: dropwise adding the rest raw material B, controlling the temperature, preserving the temperature and introducing nitrogen; (5) four-stage reaction: adding the raw material D and the raw material E, preserving heat and introducing nitrogen; (6) dissolving and diluting: adding a solvent F, cooling for the second time, and adding an auxiliary agent G; (7) Filtering and packaging to obtain the required high-performance epoxy toughening material. According to the invention, the IPN interpenetrating structure is formed by modifying the epoxy resin, and the phenoxy resin with large molecular weight is introduced to obtain the IPN epoxy resin with ultrahigh crosslinking density.
Description
Technical Field
The invention relates to the field of modified epoxy resin materials, in particular to a preparation method of a high-performance epoxy toughening material.
Background
Epoxy resins are a generic term for a class of polymers containing more than two epoxy groups in the molecule. It is a polycondensation product of epichlorohydrin and a polyol. Epoxy resin is an important thermosetting resin, is one of the most widely applied matrix materials in polymer composite materials, has excellent properties of adhesion, wear resistance, electrical insulation, chemical stability and the like, but has the defects of brittle quality, poor fatigue resistance, poor impact toughness and the like due to high crosslinking density after pure epoxy resin is cured, and is difficult to meet the requirements of engineering. The traditional toughening method is to modify the epoxy resin by adding a toughening agent or an elastomer, but the result is that the impact strength is improved and the heat resistance and the modulus of the corresponding cured product are reduced, so that the method is not satisfactory. The elastic body refers to a material which can recover after an external force is removed, but the elastic material is not necessarily an elastic body; the elastic modulus can be regarded as an index for measuring the difficulty of the material in elastic deformation, and the larger the value of the elastic modulus, the larger the stress for causing the material to generate certain elastic deformation, that is, the higher the rigidity of the material, that is, the smaller the elastic deformation generated under the action of certain stress. The elastic body is obviously deformed only under weak stress, and can be quickly recovered to a high polymer material close to the original state and size after the stress is relaxed. The commonly used toughening methods are: a rubber elastomer toughening method, a thermoplastic resin toughening method, a rigid particle toughening method, a core-shell structure polymer toughening method, a liquid crystal polymer toughening method, a nanoparticle toughening method, a hyperbranched molecule toughening method and the like.
At present, the research on toughening of epoxy resin is greatly developed at home and abroad, but some problems still exist. Although the toughening effect of the rubber elastomer toughened epoxy resin is obvious, the heat resistance and the modulus of the system are reduced. Although the modulus and heat resistance of the material are not reduced by the thermoplastic resin toughened epoxy resin, the dosage of the thermoplastic resin is large, and the solubility and the fluidity are poor. The liquid crystal polymer toughened epoxy resin can obviously improve the toughness with less dosage, but has higher cost and difficult processing. Among them, a Liquid Crystal Polymer (LCP) is an intermediate state polymer between a solid crystal and a liquid, and its molecular arrangement is not three-dimensionally ordered as in the solid crystal but is not disordered as in the liquid but has a certain order. It is a novel polymeric material which generally exhibits liquid crystallinity in the molten state. The hyperbranched polymer has a unique structure, is used for toughening resin, has good manufacturability, can effectively improve the toughness of the material, but can reduce the heat resistance of the material to a certain extent.
The interpenetrating polymer network is a crosslinked network-shaped multiphase system formed by two or more materials which are randomly penetrated and intertwined mutually through physical action. The structure is characterized in that different polymer molecules are mutually entangled to form a whole, thereby playing a role of 'forced inclusion'. In theory, the interpenetrating polymer system is completely compatible with the epoxy resin, but this results in a reduction in the toughness of the composite system. In addition, the modification of the epoxy resin with the interpenetrating polymer results in a decrease in the heat resistance of the system, and thus the resin cannot be used in a special place requiring high temperature.
The interpenetrating polymer network structure is actually the development of a method for modifying rubber elastomers, and polyurethane and epoxy resin form an interpenetrating polymer network, so that the epoxy resin is toughened. In the epoxy resin-polyurethane interpenetrating polymer grid, different acting forces (hydrogen bonds and chemical bonds) caused by the existence of various polar groups and reactive groups on two interfaces can effectively improve the compatibility and stability of two polymers.
The use of bisphenol a epoxy resins with the addition of polyurethane to form IPNs has been reported and has been found: no obvious phase separation phenomenon is generated in the curing process, and when the addition amount of the polyurethane reaches 5-10%, the impact strength and the bending property of the composite system are greatly increased. The same findings also include that in a bismaleimide and epoxy resin system, polyurethane is added, and an IPN structure is formed between two components through intermolecular force, and the research shows that: the addition of the polyurethane can effectively reduce the brittleness of the cured epoxy resin and improve the overall mechanical strength of the epoxy resin.
Professors of Hesieh and the like of Taiwan university study graft interpenetrating network polymers of polyurethane and epoxy resin, the polyurethane can enter an epoxy resin system for transition, and when the tensile strength of IPN entering the epoxy resin is maximum, the excessive polyurethane can cause the tensile strength of the whole composite system to be reduced. The research of the interpenetrating network method heat-insulating cargo adhesive uses epoxy resin and butyl acrylate semi-interpenetrating network toughening epoxy resin adhesive, and finds that the semi-interpenetrating network system using the polybutyl acrylate as the toughening modifier can improve the mechanical property of the epoxy resin adhesive. Different reaction conditions can have a certain influence on the adhesive strength. Part of special epoxy manufacturers try bifunctional epoxy resin and bisphenol A as polymerization monomers to prepare high-molecular dual-phenoxy resin, and the phenoxy resin is added into low-molecular-weight epoxy resin, so that the impact strength and the heat resistance of the cured epoxy resin can be improved. According to scanning electron microscope analysis, the toughened phenoxy resin continuously penetrates through a cross-linked network of the epoxy resin, and the entanglement results in that the fracture deformation of the system is improved when the system is impacted, so that the toughness is increased.
With the development of polymer materials, the research on toughening of epoxy resins has made great progress, but some problems still remain. The glass transition temperature, heat resistance and elastic modulus of the epoxy resin after partial toughening modification are reduced, and the application range of the epoxy resin is limited. The rigid ions can increase the modulus of the epoxy resin matrix and inhibit the expansion of cracks, but the inorganic particles have poor compatibility with organic materials. Some nano materials are easy to agglomerate and have poor dispersibility. The most important advantages of epoxy resin are convenient processing and simple process. The liquid crystal polymer is used for toughening the epoxy resin, and the biggest defects are that the raw material source is difficult, the synthesis process is complex, the cost is high, and the uniform dispersion is difficult.
The development of epoxy toughening materials still has many development directions: 1. find new toughening modifying materials with excellent mechanical properties and good compatibility and dispersion with epoxy resin. 2. The development of a new preparation process enables the molding processing of the modifier and the epoxy resin to be simpler and more convenient, widens the research and application field of epoxy resin materials, and enables the modified epoxy resin to be more widely applied.
Disclosure of Invention
The invention provides a preparation method of a high-performance epoxy toughening material, which solves the problems that the glass transition temperature, the heat resistance and the elastic modulus of the existing toughened and modified epoxy resin are reduced and the application range of the epoxy resin is limited.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a high-performance epoxy toughening material comprises the following steps:
(1) Preparing materials: adding 495-505 parts of raw material A into a reaction kettle, heating for the first time, preserving heat, and introducing nitrogen;
(2) A first-stage reaction: cooling for the first time, adding 5-6 parts of raw material B, heating for the second time, and introducing nitrogen;
(3) And (3) secondary reaction: adding 0.88 part of catalyst C, heating for the third time, adding 10-11 parts of raw material B, heating for the fourth time, and introducing nitrogen;
(4) Three-stage reaction: dropwise adding the remaining 75-80 parts of the raw material B, controlling the temperature, preserving the temperature and introducing nitrogen;
(5) Four-stage reaction: adding 9-10 parts of raw material D and 40-42 parts of raw material E, preserving heat, and introducing nitrogen;
(6) Dissolving and diluting: 215-220 parts of solvent F are added, the temperature is reduced for the second time, and 6.4-6.5 parts of auxiliary agent G are added;
(7) Filtering and packaging to obtain the required high-performance epoxy toughening material.
Preferably, the reaction kettle in the step (1) is an ellipsoidal reaction device with the functions of heating and stirring.
Preferably, the raw material A is bisphenol A type epoxy resin; the raw material B is diphenylmethane diisocyanate; the catalyst C is quaternary ammonium salt; the raw material D is phenoxy resin; the raw material E is o-cresol novolac epoxy resin; the solvent F is butanone; the aid G is boric acid.
Preferably, the temperature is raised to 125-135 ℃ for the first time in the step (1), and the temperature is kept for 25-35min.
Preferably, the temperature is reduced to 115-125 ℃ for the first time in the step (2); in the step (2), the temperature is raised to 135-145 ℃ for the second time.
Preferably, the temperature in the third heating in the step (3) is raised to 135-145 ℃; in the step (3), the temperature is raised to 155-165 ℃ for the fourth time.
Preferably, the temperature of the residual raw material B dropwise added in the step (4) is controlled to be 155-165 ℃, and the dropwise addition is finished within 115-125 min; and (4) controlling the temperature to be 170-180 ℃, and keeping the temperature for 15-25min.
Preferably, the temperature in the step (6) is reduced to 45-55 ℃ for the second time.
Preferably, the phenoxy resin is a PKHH ultrahigh molecular epoxy phenoxy resin; the molecular weight reaches more than 50000.
By adopting the technical scheme, the invention modifies the epoxy resin to form an IPN interpenetrating structure, introduces the phenoxy resin with large molecular weight to obtain the IPN epoxy resin with ultrahigh crosslinking density, and then adjusts the integral cured performance by the formula combination of the resin. The defects in the aspects of heat resistance and peeling strength after the epoxy resin is toughened are overcome, and the manufactured finished product can keep a stable structure and is not easy to deform in the long-term running process. The ultra-high IPN interpenetrating cross-linking can ensure that the product has low shrinkage after being cured and can be stably used at low temperature. The formula improves the performance from the perspective of a matrix material, so that the resin material is not only used in the field of composite materials, but also has great application trend in the aspects of carbon fibers, electronics and electricians and the like.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an electron microscope image of the high performance epoxy toughening material prepared by the method of the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
As shown in fig. 1, a method for preparing a high-performance epoxy toughening material comprises the following steps:
(1) Preparing materials: putting 504g of bisphenol A epoxy resin into an ellipsoidal reaction kettle with heating and stirring functions, heating to 130 ℃, keeping the temperature for 30min, and introducing nitrogen;
(2) A first-stage reaction: cooling to 120 ℃, slowly adding 5g of diphenylmethane diisocyanate, heating to 140 ℃, and introducing nitrogen;
(3) And (3) secondary reaction: adding 0.88g of quaternary ammonium salt, heating to 140 ℃, adding 10g of diphenylmethane diisocyanate, heating to 160 ℃, and introducing nitrogen;
(4) Three-stage reaction: dripping 80g of diphenylmethane diisocyanate at 160 ℃, slowly dripping within 120min, controlling the temperature to 175 ℃, keeping the temperature for 20min, and introducing nitrogen;
(5) Four-stage reaction: adding 10g of PKHH super polymer epoxy phenoxy resin and 42g of o-cresol novolac epoxy resin, preserving heat, and introducing nitrogen;
(6) Dissolving and diluting: 217g of butanone is added, the temperature is reduced to 45-55 ℃ for the second time, and 6.5g of boric acid is added;
(7) Filtering and packaging to obtain the required high-performance epoxy toughening material.
According to the determination standard of the epoxy equivalent of the epoxy compound of the GB/T4612-2008 plastic, the determination standard of the content of the non-volatile matter of the GB/T1725-2007 colored paint, varnish and plastic and the determination method standard of the viscosity of the GB/T22314-2008 plastic epoxy resin, the performance of the prepared high-performance epoxy toughening material is detected, and the detection results are as follows:
epoxy equivalent: 304g/eq
Hydrolyzing chlorine: 677ppm of
Viscosity: 2532cp.s
Solid content: 75.1 percent of
Gel test (curing with dicyandiamide): SG:280 seconds, tg156 degrees
Application test: tests were performed using dicyandiamide as curing agent and imidazole as accelerator; blending a resin curing agent and an accelerator together, and adjusting to a proper concentration; uniformly coating the adjusted glue solution on the prepared high-performance epoxy toughening material, baking, adjusting semi-solidification and manufacturing a prepreg; 5 made prepregs are stacked together in a group, the high-temperature high-pressure vacuum pressing is carried out through a press, after cooling, the performance of the plate is tested, and the detection result is as follows:
the shearing strength is 27Mpa; peel strength 175N/25mm; impact strength 140KJ/m 2 (ii) a Bending strength 402N/cm.
Example 2
As shown in fig. 1, a method for preparing a high-performance epoxy toughening material comprises the following steps:
(1) Preparing materials: putting 495g of bisphenol A epoxy resin into an ellipsoidal reaction kettle with heating and stirring functions, heating to 125 ℃, keeping the temperature for 25min, and introducing nitrogen;
(2) A first-stage reaction: cooling to 115 ℃, slowly adding 6g of diphenylmethane diisocyanate, heating to 135 ℃, and introducing nitrogen;
(3) And (3) secondary reaction: adding 0.88g of quaternary ammonium salt, heating to 135 ℃, adding 11g of diphenylmethane diisocyanate, heating to 155 ℃, and introducing nitrogen;
(4) Three-stage reaction: dropwise adding 75g of diphenylmethane diisocyanate at 155 ℃, slowly dropwise adding within 115min, controlling the temperature to 170 ℃, keeping the temperature for 15min, and introducing nitrogen;
(5) Four-stage reaction: adding 9g of PKHH super polymer epoxy phenoxy resin and 40g of o-cresol novolac epoxy resin, preserving heat, and introducing nitrogen;
(6) Dissolving and diluting: 220g of butanone is added, the temperature is reduced to 45 ℃ for the second time, and 6.4g of boric acid is added;
(7) Filtering and packaging to obtain the required high-performance epoxy toughening material.
According to the determination standard of the epoxy equivalent of the epoxy compound of the GB/T4612-2008 plastic, the determination standard of the content of the non-volatile matter of the GB/T1725-2007 colored paint, varnish and plastic and the determination method standard of the viscosity of the GB/T22314-2008 plastic epoxy resin, the performance of the prepared high-performance epoxy toughening material is detected, and the detection results are as follows:
epoxy equivalent: 295g/eq
Hydrolyzing chlorine: 756ppm of a catalyst
Viscosity: 2232cp.s
Solid content: 75.3 percent of
Gel test (curing with dicyandiamide): SG:278 seconds, tg152 degrees
Application test: tests were performed using dicyandiamide as curing agent and imidazole as accelerator; blending a resin curing agent and an accelerator together, and adjusting to a proper concentration; uniformly coating the adjusted glue solution on the prepared high-performance epoxy toughening material, baking, adjusting semi-solidification, and manufacturing a prepreg; 5 prepared prepregs are stacked together in a group, are pressed together in a high-temperature high-pressure vacuum manner through a press, and are cooled, and then the performance of the plate is tested, wherein the test result is as follows:
the shear strength is 26.3Mpa; peel strength 169N/25mm; impact strength 136KJ/m 2 (ii) a Bending strength was 407N/cm.
Example 3
As shown in fig. 1, a method for preparing a high-performance epoxy toughening material comprises the following steps:
(1) Preparing materials: putting 501g of bisphenol A epoxy resin into an ellipsoidal reaction kettle with heating and stirring functions, heating to 135 ℃, keeping the temperature for 35min, and introducing nitrogen;
(2) A first-stage reaction: cooling to 125 ℃, slowly adding 5g of diphenylmethane diisocyanate, heating to 145 ℃, and introducing nitrogen;
(3) And (3) secondary reaction: adding 0.88g of quaternary ammonium salt, heating to 145 ℃, adding 10g of diphenylmethane diisocyanate, heating to 165 ℃, and introducing nitrogen;
(4) Three-stage reaction: dripping 80g of diphenylmethane diisocyanate at 165 ℃, slowly dripping within 125min, controlling the temperature to 180 ℃, keeping the temperature for 25min, and introducing nitrogen;
(5) Four-stage reaction: adding 9g of PKHH ultra-high molecular epoxy phenoxy resin and 40g of o-cresol novolac epoxy resin, preserving heat, and introducing nitrogen;
(6) Dissolving and diluting: 220g of butanone is added, the temperature is reduced to 55 ℃ for the second time, and 6.4g of boric acid is added;
(7) Filtering and packaging to obtain the required high-performance epoxy toughening material.
According to the determination standard of the epoxy equivalent of the epoxy compound of the GB/T4612-2008 plastic, the determination standard of the content of the non-volatile matter of the GB/T1725-2007 colored paint, varnish and plastic and the determination method standard of the viscosity of the GB/T22314-2008 plastic epoxy resin, the performance of the prepared high-performance epoxy toughening material is detected, and the detection results are as follows:
epoxy equivalent: 295g/eq
Hydrolyzing chlorine: 756ppm of a catalyst
Viscosity: 2232cp.s
Solid content: 75.3 percent of
Gel test (curing with dicyandiamide): SG:278 seconds, tg152 degrees
Application test: tests were performed using dicyandiamide as curing agent and imidazole as accelerator; blending a resin curing agent and an accelerator together, and adjusting to a proper concentration; uniformly coating the adjusted glue solution on the prepared high-performance epoxy toughening material, baking, adjusting semi-solidification and manufacturing a prepreg; 5 made prepregs are stacked together in a group, the high-temperature high-pressure vacuum pressing is carried out through a press, after cooling, the performance of the plate is tested, and the detection result is as follows:
the shear strength is 25Mpa; peel strength 172N/25mm; impact strength 139KJ/m 2 (ii) a The bending strength is 401N/cm.
Wherein, the bisphenol A type epoxy resin has an epoxy equivalent of 181g/eq, and is a low molecular weight bisphenol A type epoxy resin with very large yield in the current market; diphenylmethane diisocyanate, the trademark of MDI200, is easy to react with compounds containing active hydrogen atoms, can modify epoxy resin, increase the crosslinking density of the epoxy resin and improve the heat resistance; the quaternary ammonium salt is a catalyst frequently used in the ring-opening reaction of the epoxy resin; the phenoxy resin is obtained by reacting epoxy resin containing bifunctional groups with bisphenol A, has very large molecular weight, is PKHH ultrahigh molecular epoxy phenoxy resin used in the invention, has the molecular weight of 50000, increases an IPN structure, and can improve the crosslinking density and heat resistance of a finished product; the o-cresol novolac epoxy resin is an insulating material commonly used in electronic-grade products, can improve the heat resistance and weather resistance of the material, and has excellent insulating property; boric acid is a gel time modifier that can increase the handling time in downstream use.
As shown in figure 2, the invention uses epoxy resin to modify to form IPN interpenetrating structure, and introduces phenoxy resin with large molecular weight to obtain IPN epoxy resin with ultrahigh crosslinking density, and then uses the formula combination of the resin to adjust the whole cured performance. The defects in the aspects of heat resistance and peeling strength after the epoxy resin is toughened are overcome, and the manufactured finished product can keep a stable structure and is not easy to deform in the long-term running process. The ultra-high IPN interpenetrating cross-linking can ensure that the product has low shrinkage after being cured and can be stably used at low temperature. The formula improves the performance from the perspective of a matrix material, so that the resin material is not only used in the field of composite materials, but also has great application trend in the aspects of carbon fiber, electronics and electricians and the like.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principles and spirit of the invention, and these embodiments are still within the scope of the invention.
Claims (2)
1. A preparation method of a high-performance epoxy toughening material is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing materials: putting 495-505 parts of bisphenol A epoxy resin into a reaction kettle, heating for the first time, preserving heat, and introducing nitrogen;
(2) A first-stage reaction: cooling for the first time, adding 5-6 parts of diphenylmethane diisocyanate, heating for the second time, and introducing nitrogen;
(3) And (3) secondary reaction: adding 0.88 part of quaternary ammonium salt, heating for the third time, adding 10-11 parts of diphenylmethane diisocyanate, heating for the fourth time, and introducing nitrogen;
(4) Three-stage reaction: dropwise adding the remaining 75-80 parts of diphenylmethane diisocyanate, controlling the temperature, preserving the temperature and introducing nitrogen;
(5) Four-stage reaction: adding 9-10 parts of phenoxy resin and 40-42 parts of o-cresol novolac epoxy resin, preserving heat, and introducing nitrogen;
(6) Dissolving and diluting: 215 to 220 portions of butanone is added, the temperature is reduced for the second time, and 6.4 to 6.5 portions of boric acid are added;
(7) Filtering and packaging to obtain the required high-performance epoxy toughening material;
in the step (1), the temperature is raised to 125-135 ℃ for the first time, and the temperature is kept for 25-35min;
the temperature is reduced to 115-125 ℃ for the first time in the step (2); in the step (2), the temperature is raised to 135-145 ℃ for the second time;
in the step (3), the temperature is raised to 135-145 ℃ for the third time; in the step (3), the temperature is raised to 155-165 ℃ for the fourth time;
the temperature of the residual raw material B dropwise added in the step (4) is controlled to be 155-165 ℃, and the dropwise addition is finished within 115-125 min; controlling the temperature to be 170-180 ℃ in the step (4), and keeping the temperature for 15-25min;
in the step (6), the temperature is reduced to 45-55 ℃ for the second time;
the phenoxy resin is a PKHH ultrahigh molecular epoxy phenoxy resin; the molecular weight reaches more than 50000.
2. The method for preparing the high-performance epoxy toughening material according to claim 1, wherein: the reaction kettle in the step (1) is an ellipsoidal reaction device with heating and stirring functions.
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| CN110527255A (en) * | 2019-09-09 | 2019-12-03 | 东莞泰合复合材料有限公司 | A kind of epoxy resin-base, composite material, vehicle frame and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110294963A1 (en) * | 2010-05-27 | 2011-12-01 | Far East University | Method of toughening epoxy resin and toughened epoxy resin composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11172076A (en) * | 1997-12-08 | 1999-06-29 | Toray Ind Inc | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| CN105968321A (en) * | 2015-03-13 | 2016-09-28 | 新日铁住金化学株式会社 | Oxazolidone ring-containing epoxy resin, method for producing the thereof, epoxy resin composition, cured product and application thereof |
| CN106987013A (en) * | 2017-05-17 | 2017-07-28 | 中威北化科技有限公司 | The preparation method for the intermediate temperature setting epoxy prepreg that glass transition temperature is improved |
| CN110527255A (en) * | 2019-09-09 | 2019-12-03 | 东莞泰合复合材料有限公司 | A kind of epoxy resin-base, composite material, vehicle frame and preparation method thereof |
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