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    1 / 1 abstract “Benzoxazine blend, composition of curable resin, cured resin, monofunctional wet wool substitute benzoxazine, composite material, and methods for making a composite part Disclosed herein are monofunctional benzoxazine compounds with at least one electron leaving group. the monofunctional benzoxazine compounds can be combined with one or more multifunctional benzoxazine compounds to form a single benzoxazine mixture. this benzoxazine mixture can be combined with additional components such as catalysts and hardening agents to form a curable resin composition suitable for forming resin films or composite materials. The presence of monofunctional benzoxazine improves the processability of the benzoxazine-based resin composition, reducing the viscosity of the resin composition and results in improved adhesion and drape in composite films and materials, formed at from the composition without the loss of the modulus in the cured resin.
    公开号:BR112014019823B1
    申请号:R112014019823
    申请日:2013-03-19
    公开日:2020-01-28
    发明作者:edward harriman Mark；Richard Ward Steven
    申请人:Cytec Tech Corp；
    IPC主号:
    专利说明:

    “COMPOSITION OF CURABLE RESIN, CURED RESIN, COMPOSITE MATERIAL, AND, METHODS FOR MANUFACTURING A PART OF COMPOSITES AND FOR MANUFACTURING A PREPREG” FUNDAMENTALS [0001] The use of benzoxazins offers a number of advantages compared to other thermoset resins, including lifetime relatively long shelf, molecular design flexibility, low cost, high glass transition temperature (Tg), high modulus, relatively low viscosities, good flame retardant properties, low moisture absorption, no release of by-products during curing and very low shrinkage after curing. In addition, benzoxazines are capable of healing themselves after heating; that is, there is no need for an additional curing agent. This combination of properties means that benzoxazines are potentially attractive for use in aerospace applications. In particular, they can be useful as the thermosetting matrix in composite materials. However, the currently available multifunctional benzoxazines are glazed solids at temperatures below 120 ° C, making them difficult to process using standard aerospace techniques such as prepregging and infusion resin.
    [0002] “Prepregging” refers to the process of impregnating unidirectionally aligned reinforced fibers or fabric with a resin matrix to form prepregs in the form of ribbons or sheets. These prepregs are then stacked together in a particular orientation on a tool to form a laminate. The prepregs are then subjected to high temperature and pressure to cure and consolidate the composite part. The method of applying pressure is dependent on the part and configuration, but the use of the autoclave is more common for high-performance structural parts.
    Petition 870190081580, of 08/21/2019, p. 12/51 / 26
    Prepregs must have a certain amount of grip and trim in order to shape correctly. "Adherence" is the ability of the prepreg folds to come together, while "trim" is the prepreg's ability to conform to different contours.
    [0003] Resin infusion approach is different from conventional prepregging in that the dry structural reinforcement fibers are placed in a mold cavity or other modeling tool and a matrix resin is injected or infused into the structural reinforcement fibers. Resin infusion covers processing techniques such as Resin Transfer Molding (RTM), Liquid Resin Infusion (LRI), Resin Infusion under Flexible Tool (RIFT), Vacuum Assisted Resin Transfer Molding (VARTM), Film Infusion Resin (RFI) and the like. These conventional techniques require that resins have relatively low viscosity and are thermally stable at processing temperatures.
    SUMMARY [0004] A benzoxazine mixture containing one or more monofunctional benzoxazine compounds with at least one electron withdrawing group and one or more multifunctional benzoxazine compounds is disclosed herein. This benzoxazine mixture is combinable with additional components, such as catalysts and curing agents to form a curable resin composition suitable for forming resin films or composite materials. The presence of monofunctional benzoxazine improves the processing capacity of the benzoxazine-based resin composition, reducing the viscosity of the resin composition and results in improved adhesion and drop in films and composite materials, formed from the composition without losing the module in the resin healed. Through the addition of the electron withdrawal group, monofunctional benzoxazine compounds offer greater stability at the high temperatures that are normally used in aerospace curing cycles, compared to currently available benzoxazine systems. An additional benefit of the electron withdrawal group is a decrease in the temperature of the beginning of the cure, thus allowing any beneficial modifications to the cure cycles. BRIEF DESCRIPTION OF THE DRAWINGS [0005] FIG. 1 shows cured samples based on different mixtures of Bisphenol A-benzoxazine and fluorinated liquid benzoxazine formed from 3-fluorphenol and m-toluidine.
    [0006] FIG. 2 shows the Differential Scanning Calorimetry (DSC) curve and reactivity table for Bisphenol-A benzoxazine.
    [0007] FIG. 3A shows the DSC activation energy curves and reactivity table for certain fluorinated benzoxazines.
    [0008] FIG. 3B shows the DSC activation energy curves and reactivity table for certain chlorinated benzoxazines.
    [0009] FIG. 4 shows the DSC activation energy curves and reactivity table for an alkylated liquid benzoxazine.
    [00010] FIG. 5 shows mixtures of alkylated liquid benzoxazine and Bisphenol-A benzoxazine in different weight ratios.
    [00011] FIG. 6 shows the DSC activation energy curves and reactivity table for a commercially available liquid benzoxazine RD2009-008.
    [00012] FIG. 7 shows a sample of cured resin formed from a mixture of RD2009-008 (32%) and Bisphenol-A benzoxazine (68%).
    [00013] FIG. 8 shows the Gravimetric Thermal Analysis (TGA) curves for various liquid benzoxazines.
    [00014] FIG. 9 shows examples of resins formed from 100% Bisphenol-A benzoxazine (a), 80:20 Bisphenol-A: 3-fluor benzoxazine (b), and 50:50 Bisphenol-A: 3-fluor benzoxazine (c), after being heated to 300 ° C.
    / 26
    DETAILED DESCRIPTION [00015] One aspect of the present disclosure is to provide a benzoxazine mixture that maintains all the beneficial properties of pure multifunctional benzoxazines and, at the same time, has thermal mechanical properties suitable for high performance aerospace applications. Currently available multifunctional benzoxazines are latent until heat is applied and usually require curing temperatures of 180 ° C or more. Several benzoxazine hybrid systems based on benzoxazine-epoxy mixtures are commercially available, but the addition of epoxy as a correagent overrides some of the benefits of pure benzoxazins. Liquid monofunctional benzoxazines are also available, but suffer from being very unstable at temperatures normally used for curing cycles in aerospace applications. It has been found that certain substituted monofunctional benzoxazines can be mixed with multifunctional benzoxazines to improve the processability of the multifunctional benzoxazine systems, which are usually solid or semi-solid at room temperature. The benzoxazine mixture is combined with additional components, such as curing agents and catalysts, to form a curable resin composition, which is suitable for forming resinous films (for example, surfactant films, adhesive films) or advanced composite materials (for example, prepregs) using conventional techniques such as prepregging and resin infusion. The presence of monofunctional liquid benzoxazine improves the processing capacity of the benzoxazine based resin composition, reducing the viscosity of the uncured composition, making it suitable for impregnation / infusion of reinforcement fibers. In addition, the presence of multifunctional liquid benzoxazine improves the handling characteristics (eg adhesion and trim) of the uncured (or partially cured) composite material (eg prepreg) made from the benzoxazine-based resin composition without loss of modulus in the cured resin. Two desired physical properties of film adhesives and prepregs are adhesion and drop at their intended use temperatures. Adhesion is necessary to ensure correct prepreg placement when stacking parts of the composite. The trim is necessary so that parts of the composite with different planar shapes can be easily manufactured. In this way, benzoxazine based resins with greater adherence and trim allow the manufacture of complex composite parts.
    [00016] As used here, "monofunctional benzoxazine" refers to a compound in which there is a single benzoxazine fraction, and "multifunctional benzoxazine" refers to a compound in which there are two or more benzoxazine fractions, enabling the formation of reticulated network.
    [00017] The substituted monofunctional benzoxazines from the present disclosure are based on substituted electron withdrawing derivatives and could be in liquid form at room temperature (20 ° C-25 ° C). Through the addition of electron withdrawal groups, these substituted monofunctional benzoxazins offer greater stability at elevated temperatures, typically used in aerospace curing cycles (for example, 180 ° C or more) compared to the currently available liquid benzoxazines. An additional benefit of the electron withdrawal group is a decrease in the temperature of the beginning of the cure, allowing beneficial changes to the cure cycles. Thus, these monofunctional benzoxazins are particularly suitable for use in aerospace applications, due to the increase in thermal stability compared to liquid benzoxazins currently available, thus allowing the mixture of monofunctional benzoxazins with multifunctional benzoxazins and subsequent high temperature cure without degradation. In addition, the presence of monofunctional benzoxazines with electron withdrawal groups in the / 26 benzoxazine systems containing multifunctional benzoxazines has been shown to decrease activation energy, which decreases the temperature at which they react. Without being bound by any particular theory, it is believed that the decrease in the onset of cure is a consequence of the intermediate or transition state of the monofunctional benzoxazine structure being more stable, thus less energy is needed to initiate polymerization. In addition, a decrease in the curing initiation temperature may allow for the use of lower temperature curing cycles, the elimination of post-curing time, or curing with a shorter curing time compared to benzoxazine systems without withdrawal substituents electron. These benefits are observed without loss of the glass transition temperature (Tg) or modulus in the cured resin. The “module” of the cured resin, as discussed here, includes the bending module and the tension module.
    [00018] The substituted monofunctional benzoxazine discussed above is a compound represented by the following Formula I:
    on what:
    at least one of Xi, X2, X3, X4 is an electron withdrawal group selected from halogen (such as F, Cl, Br, I), -COH, -COCH3, -COOCH3, SO3H, NO2, CF3, or CQ3, and the others are independently selected from hydrogen (H), alkyl (preferably C1-8 alkyl), cycloalkyl (preferably C5-7 cycloalkyl, more preferably C6 cycloalkyl), and aryl, in which the cycloalkyl and aryl groups are optionally substituted by example, by C1-8 alkyl, halogen and amine groups, and preferably by
    C1-8 alkyl;
    / 26 [00019] Ri, R2, R3, R4, R5 are independently selected from: H;
    alkyl (preferably C1-8 alkyl); cycloalkyl (preferably C5-7 cycloalkyl, more preferably C6 cycloalkyl); aryl; wherein the cycloalkyl and aryl groups are optionally substituted, for example, by C1-8 alkyl, halogen and amine groups, and preferably by C1-8 alkyl; an electron donation group such as alkoxy (for example, methoxy -OCH 3 ), -CH3, phenyl, NHCOR, OCOR, NH2, and OH.
    [00020] Examples of substituted multifunctional benzoxazine include the following structures:
    (1) (2) (3) (4)

    / 26 (5) [00021]
    Cl
    CH3
    It was found that the effect of the halogen group in the target position (Structures 2 and 4) is the greatest in reactivity, since this position is more preferable.
    [00022] The substituted monofunctional benzoxazine compound discussed above is a reaction product of a phenol (represented by Formula II), an aromatic amine (represented by Formula III) and an aldehyde.

    X 15 X 2 , X 3 , X 4 in Formula II and R 15 R 2 , R3, R4, R 5 in Formula III are as defined above in reference to Formula I. Although several aldehydes can be used, the preferred aldehyde is formaldehyde (H-CHO).
    [00023] Substituted monofunctional benzoxazine compounds can be formed by ring formation in a compatible solvent or in a solvent-free system. The synthesis of monofunctional benzoxazine monomers using phenol, amine and aldehyde as reagents is well known in the art. Generally, the reagents are mixed at a temperature that causes the reagents to combine chemically, and the reagents are held at this temperature for a period of time sufficient to form the benzoxazine compounds.
    [00024] In some embodiments, monofunctional benzoxazine compounds with halogen substituents can be formed by reacting
    9/26 halogenated phenol reacts with an aromatic amine in the presence of formaldehyde or paraformaldehyde, as represented by the following exemplary reaction:
    [00025] For the type of reaction above, it should be noted that when the electron withdrawing substituent in the phenol compound is in the meta position as shown, the benzoxazine product formed will be a mixture of isomers represented by the following structures:

    where X is a halogen such as fluorine (F) or chlorine (Cl).
    [00026] When synthesized, this isomer mixture can exist as a mixture with the ratio of compound (IV) to compound (V) in the range of 70:30 to 80:20.
    [00027] In one embodiment, the substituted monofunctional benzoxazine contains an electron withdrawing substituent and an electron donating substituent. It has been found that the presence of the electron donation substituent further increases reactivity during polymerization. As an example, a halogenated phenol can be reacted with an amine with -OCH 3 as an electron donation and formaldehyde substituent to form a substituted monofunctional benzoxazine as follows:
    / 26

    where X is a halogen such as fluorine (F) or chlorine (Cl).
    [00028] As discussed earlier, one or more of the substituted monofunctional benzoxazine compounds discussed above can be mixed with one or more multifunctional benzoxazine compounds to form a benzoxazine mixture that is combinable with additional components such as hardeners and catalysts to form a composition of curable resin. The total amount of monofunctional and multifunctional benzoxazines in the resin composition can be adjusted to obtain the desired properties for the uncured composition (such as reactivity, viscosity, adhesion and trim) and in the cured composition (such as Tg, modulus, hardness etc.). The viscosity of the curable resin composition can be adjusted by the appropriate proportions of monofunctional and multifunctional benzoxazines to achieve certain Tg for the uncured resin and to give the necessary adhesion and trim for the uncured composite material (eg prepreg) formed from the resin composition. The weight ratio of the multifunctional benzoxazines to substituted monofunctional benzoxazines can vary within the range of 99.9: 0.1 to 0.1: 99.9. In some embodiments, the weight ratio of multifunctional benzoxazines to substituted monofunctional benzoxazine can be 99.9: 0.1 to 50:50. Even with a high concentration of substituted monofunctional benzoxazine, the composition remains thermally stable (that is, it is not degraded) during curing at a temperature of 180 ° C or higher, for example, 180 ° C / 26
    - 200 ° C.
    [00029] As used here, a "switchable resin composition" refers to a composition before curing. After curing, benzoxazine multifunctional and monofunctional compounds quickly polymerize through ring opening polymerization. This polymerization can be initiated by cation (using cationic initiators) or thermally.
    [00030] The multifunctional benzoxazine can be a compound (monomer or oligomer) in which there are two or more benzoxazine fractions, allowing the formation of a cross-linked polymer matrix. Any conventional multifunctional benzoxazine compounds, including difunctional, trifunctional and tetrafunctional benzoxazines, can be combined with the substituted monofunctional benzoxazine compounds described above to form a benzoxazine mixture.
    [00031] In one embodiment, the multifunctional benzoxazine can be represented by the following formula (VI):
    (SAW)
    on what:
    [00032] Z 1 is selected from a direct link, -C (R 3 ) (R 4 ) -, C (R 3 ) (aryl) -, -C (O) -, -S-, -O-, - S (O) -, -S (O) 2-, a divalent heterocycle and [C (R 3 ) (R 4 )] x-arylene- [C (R5) (R 6 )] y-, or the two rings benzyl from the benzoxazine fractions can be fused; and [00033] R 1 and R 2 are independently selected from alkyl (preferably C 1-8 alkyl), cycloalkyl (preferably C5-7 cycloalkyl, preferably C6 cycloalkyl) and aryl, wherein the cycloalkyl and aryl groups are optionally substituted, for example , by C1-8 alkyl, halogen and amine groups, and preferably by C1-8 alkyl, and when substituted, one or more substituent groups (preferably a substituent group) may be present in or in each cycloalkyl and aryl group;
    [00034] R 3 , R 4 , R5 and R 6 are independently selected from H, C 1-8 alkyl (preferably C 1-4 alkyl, and preferably methyl), and halogenated alkyl (wherein the halogen is usually chlorine or fluorine (preferably fluorine) and wherein the halogenated alkyl is preferably CF3); exey are independently 0 or 1.
    [00035] In one mode, Z 1 is selected from a direct link, C (R 3 ) (R 4 ) -, -C (R 3 ) (aryl) -, -C (O) -, -S-, - O-, a divalent heterocycle and [C (R 3 ) (R 4 )] x-arylene- [C (R 5 ) (R 6 )] y-, or the two benzyl rings of the benzoxazine fractions can be fused.
    [00036] When Z 1 is selected from a divalent heterocycle, it is preferably 3, 3-isobenzofuran-1 (3h) -one, ie. wherein the compound of formula (VI) is derived from phenolphthalein.
    [00037] When Z 1 is selected from - [C (R 3 ) (R 4 )] x-arylene [C (R 5 ) (R 6 )] y-, then the chain linking the two benzoxazine groups may still comprise , or be optionally interrupted by, one or more arylene groups and / or one or more groups -C (R 7 ) (R 8 ) - (where R 7 and R 8 are independently selected from the groups defined above for R 3 ), provided that the or each of the substituted or unsubstituted methylene groups is not adjacent to another substituted or unsubstituted methylene group.
    [00038] In a preferred embodiment, the arylene group is phenylene. In one embodiment, the groups linked to the phenylene group can be configured in the goal positions and in relation to each other. In a preferred embodiment, the aryl group is phenyl.
    [00039] The Z1 group can be linear or non-linear, and is generally linear. The Z1 group is preferably linked to the benzyl group of each of the benzoxazine fractions in the para position in relation to the oxygen atom of the / 26 benzoxazine fractions, as shown in formula (VI), and this is the preferred isomeric configuration. However, the Z1 group can also be attached at either the meta or ortho position, at one or both of the benzyl group in the bis-benzoxazine compound. Thus, the group that Z1 can be attached to the benzyl rings in a to / from configuration; for / goal; for / ortho, goal / goal or ortho / goal. In one embodiment, the thermosetting benzoxazine resin component (A) is composed of a mixture of isomers, preferably where most of the mixture is the para / para isomer shown in formula (VI), and preferably this is present in at least at least 75 mol%, preferably at least 90 mol%, and preferably at least 99 mol%, of the total isomeric mixture.
    [00040] In a preferred embodiment, the multifunctional benzoxazine is selected from compounds in which Z 1 is selected from C (CH3) 2-, -CH2- and 3,3-isobenzofuran-1 (3H) -one, that is, derivatives benzoxazine of bisphenol A, bisphenol F and phenolphthalein.
    [00041] In another embodiment, the multifunctional benzoxazine is selected from compounds in which R 1 and R 2 are independently selected from aryl, preferably phenyl. In one embodiment, the aryl group can be substituted, preferably in which the substituents are selected from C1-8 alkyl, and preferably in which there is a single substituent present in at least one aryl group. C1-8 alkyl includes straight and branched alkyl chains. Preferably, R 1 and R 2 are independently selected from substituted aryl, preferably unsubstituted phenyl.
    [00042] The benzyl ring in each benzoxazine group of the multifunctional benzoxazine compounds defined here can be substituted independently in any of the three available positions of each ring, and normally any optional substituent is present in the ortho position for the group Z bonding position 1 . Preferably, however, the / 26 benzyl ring remains unsubstituted.
    Curable resin composition and applications thereof [00043] The substituted monofunctional benzoxazine disclosed here, either alone or in a mixture with one or more multifunctional benzoxazines, can be combined with additional components to form a curable resin composition suitable for the manufacture of resin (eg adhesive films, surfactant films) or fiber reinforced composites (eg prepregs). The addition of catalyst is optional, but the use of this can increase the cure rate and / or reduce the cure temperatures. Suitable catalysts for the benzoxazine-based resin composition include, among others, Lewis acids, such as phenols and derivatives thereof, strong acids, such as alkylenic acids, methyl tosylate, cyanate esters, p-toluenesulfonic acid, 2-ethyl- 4-methylimidazole (EMI), 2,4-ditherc-butylphenol, BF3O (Et) 2, adipic acid, organic acids, phosphorus pentachloride (PCl ·).
    [00044] Hardening agents (or hardeners) can be added to produce a matrix of hard resin suitable for manufacturing advanced composite structures. Suitable curing agents include, but are not limited to, thermoplastic curing agents such as polyethersulfone (PES), PES copolymer and polyetherethersulfone (PEES) (e.g. KM 180 KM from Cytec Industries Inc.), elastomers, including liquid rubbers with reactive groups, particulate hardening agents such as thermoplastic particles, glass granules, rubber particles and core-shell rubber particles.
    [00045] Functional additives can also be included to influence one or more of the mechanical, rheological, electrical, optical, chemical, flame-resistant and / or thermal properties of the cured or uncured resin composition. Examples of such functional additives include, but are not limited to, diluents, color pigments, rheology control agents, adhesion promoters, conductive additives, flame retardants, ultraviolet (UV) protectors and the like. These additives can take the form of several geometries including, among others, particles, flakes, rods and the like.
    [00046] In one embodiment, the curable resin composition contains substituted monofunctional benzoxazine in combination with difunctional benzoxazine and trifunctional benzoxazine, and one or more additives discussed above.
    [00047] The curable resin composition, as discussed above, can be combined with the reinforcement fibers to form a composite material or structure. Reinforcement fibers can take the form of whiskers, short fibers, filaments, tow, bundles, sheets, folds and combinations thereof. Continuous fibers can also adopt a unidirectional, multidirectional, non-woven, woven, sewn, sewn and braided configuration, as well as swirling mat, carpet and chopped fiber structures. The composition of the fibers can be varied to achieve the properties necessary for the structure of the final composite. Exemplary fiber materials may include, but are not limited to, glass, carbon, graphite, aramid, quartz, polyethylene, polyester, poly-p-phenylene-polyphenol (PBO), boron, polyamide, graphite, silicon carbide, silicon nitride and combinations of the same.
    [00048] It is possible, although not necessary, to add a solvent, for example, a halogenated hydrocarbon or an alcohol, or a combination thereof, to assist in mixing the components. The solvent and its proportion are chosen so that the mixture of the components forms at least one stable emulsion, preferably a stable single-phase solution. Subsequently, the solvent is removed by evaporation to generate the resin composition.
    [00049] To form composite materials, the reinforcement fibers are / 26 impregnated or infused with the curable resin composition using conventional processing techniques such as prepregging and resin infusion. After resin impregnation or infusion, appropriate curing is carried out at an elevated temperature up to 200 ° C, preferably in the range of 160 to 200 ° C, more preferably at about 170-190 ° C and using high pressure to restrict the effects of deformation of the exhaust gases, or to restrict the formation of voids, appropriately at a pressure of up to 10 bar, preferably in the range of 3 to 7 bar abs. Appropriately, the curing temperature is reached with heating up to 5 ° C / min. For example, 2 ° C to 3 ° C / min and is maintained for the necessary period of up to 9 hours, preferably up to 6 hours, for example, 3 to 4 hours. The pressure is released during the process and the temperature is reduced by cooling down to 5 ° C / min. For example, up to 3 ° C / min. Post-curing at temperatures in the range of 190 ° C to 200 ° C can be performed, at atmospheric pressure, using appropriate heating rates to improve the glass transition temperature of the product or otherwise.
    [00050] To manufacture prepregs, a resin film can be formed from the curable resin composition by, for example, compression molding, extrusion, melting-casting-belt-casting, followed by laminating that film to one or both surfaces opposite sides of a reinforcement fiber fold in the form of, for example, a relatively short fiber non-woven mat, a continuous fiber fabric or a unilaterally aligned fiber fold (ie fibers aligned along the same direction), in sufficient temperature and pressure to allow the resin film to flow and impregnate the fibers. Alternatively, the prepreg can be manufactured by supplying the curable resin composition in liquid form and passing the fiber fold through the liquid resin composition to infuse the fiber fold with the heat curable composition, and removing excess resin from the fibrous fold. infused. The presence of substituted monofunctional benzoxazine / 26 results in prepreg with improved adhesion and drop compared to those formed from the same resin composition without the substituted monofunctional benzoxazine.
    [00051] To manufacture a composite part from prepregs, the folds of reinforcement fibers are stacked on a tool and laminated together by heat and pressure, for example, by molding with autoclave, vacuum or compression, or by rolls heated to a temperature above the curing temperature of the resin composition or, if curing has already occurred, above the glass transition temperature of the resin, normally at least 180 ° C and up to 200 ° C, and at a pressure, in particular, at excess of 1 bar, preferably in the range of 1-10 bar.
    [00052] The resulting multi-fold laminate can be anisotropic in which the fibers are continuous and unidirectional, oriented essentially parallel to each other, or almost isotropic in which the fibers in a fold are oriented at an angle, for example, 45 °, 30 ° , 60 ° or 90 ° in relation to the folds above and below. Intermediate guidelines between anisotropic and quasi-isotropic, and combinations thereof, can also be provided. Fabrics are an example of an almost isotropic or intermediate between anisotropic and almost isotropic. Suitable laminates contain at least 4, preferably at least 8, folds. The number of folds depends on the application for the laminate, for example, the required strength, and laminates containing 32 or even more, for example, several hundred, of folds may be desirable to form large composite parts. Interfold hardening particles can be supplied, in the interlaminate regions between the folds.
    [00053] To manufacture a composite part by means of resin infusion, for example, RTM or VaRTM processes, the first step is to form a dry fiber preform in the form of the desired structural part. The preform generally includes a number of folds or layers of fabric / 26 prepared from dry reinforcement fibers that give them the desired reinforcement properties for a resulting composite part. After the fiber preform has been formed, the preform is placed in a mold. The curable resin composition is injected / infused directly into the fiber preform, and then the resin-infused preform is cured. EXAMPLES
    Example 1 [00054] Liquid multifunctional benzoxazines were prepared by the following method:
    1. 18.68 phenol, 20.94 g amine and 20.76 g paraformaldehyde were weighed and then mixed in a glass jar at room temperature (~ 20.0 ° C) for 20 minutes.
    2. The mixed material was stirred while the glass bottle was placed in an oil bath heated to 115 ° C for 40 minutes.
    3. The temperature of the oil bath was raised to 120 ° C and mixing continued for another 20 minutes.
    4. The glass bottle was removed from the oil bath and cooled for approximately 5 minutes. The mixed material was slowly added to 10 ml of diethyl ether with stirring. This mixture was then stirred for another 20 minutes at room temperature (~ 20.0 ° C).
    5. Once stirred, the benzoxazine-ether mixture was washed 3 times with 2.0 M NaOH solution in water, in 100 ml portions, in a separating funnel.
    6. Another water wash was performed to neutralize the pH (pH7) after adding NaOH.
    7. This mixture rested overnight, and then the magnesium sulfate drying agent was added to the mixture for 4 hours.
    8. The residual ether was removed on a rotary evaporator under vacuum / 26 for 15 minutes at 50 ° C.
    9. The final product was dried under vacuum at 60 ° C in a vacuum oven for 2 hours.
    [00055] Table 1 reveals five substituted monofunctional benzoxazins that were prepared by this method using the phenol and amine reagents.
    / 26 difunctional benzoxazine) from Huntsman Specialty Chemicals in various weight ratios of Bisphenol-A benzoxazine: monofunctional benzoxazine. The following experimental method was performed:
    1. Monofunctional benzoxazine and benzoxazine Bisphenol-A were degassed separately in a vacuum oven at 110 ° C for 90 minutes.
    2. 1.5 g of degassed benzoxazine and 18.5 g of degassed bisphenol-A benzoxazine were added to a 250 ml glass vial
    3. The flask was immersed in an oil bath heated to 90 ° C for 30 minutes and then the material mixture was stirred at 90 ° C for 45 minutes
    4. The mixture was removed from the oil bath and poured into aluminum plates.
    5. The mixed benzoxazine plates were degassed in a vacuum oven at 110 ° C for 90 minutes.
    [00057] Degassed benzoxazine mixtures were cured using the following curing cycle: 25 ° C to 180 ° C at 1 ° C / min, maintained for 2 hours, 180 ° C to 200 ° C at 1 ° C / min, maintained for 2 hours, 200 ° C to 25 ° C to 2 ° C / min.
    [00058] It was found that when the substituted monofunctional benzoxazines (shown in Table 1) were mixed with Bisphenol-A benzoxazine, the cured samples were stable with increasing concentration of substituted monofunctional benzoxazine. As an illustration, FIG. 1 shows cured samples based on mixtures of Bisphenol Abenzoxazine and 3-fluorphenol, m-toluidine benzoxazine (Structure 2 in Table
    1), in different weight ratios of Bisphenol-A benzoxazine: fluorinated benzoxazine.
    [00059] An investigation was carried out to analyze the reactivity of the prepared / 26 halogenated monofunctional benzoxazine compounds revealed in Table 1 and compare them with standard Bisphenol-A benzoxazine using the Free Kinetics Model (MFK) method - Differential Scanning Calorimetry (DSC). This MFK method is based on the assumption that the activation energy, Ea, is dependent on the conversion (a). In a particular conversion, the activation energy, Ea, is independent of the heating rate. FIG. 2 shows the DSC curve for Bisphenol-A benzoxazine. FIG. 3A shows the DSC curves for fluorinated benzoxazines and FIG. 3B shows the DSC curves for chlorinated benzoxazines. It can be seen from FIGS. 2, 3A and 3B, that the effect of the halogen group on reactivity is greater when it is in the target position in relation to oxygen.
    Example 2 Comparison [00060] For comparison, an alkylated liquid benzoxazine, which does not contain an electron withdrawing group, was formed from the m-cresol, m-toluidine and paraformaldehyde using the method described in Example 1. The alkylated liquid benzoxazine has the following structure:
    [00061] FIG. 4 shows the DSC activation energy curves and reactivity table generated for this alkylated liquid benzoxazine. From FIG. 4, a higher activation energy and a lower conversion rate are seen compared to the data shown in FIGS. 3A-3B for halogenated liquid benzoxazines.
    [00062] Mixtures of alkylated liquid benzoxazine and Bisphenol-A benzoxazine were formed based on the weight ratio Bisphenol-A benzoxazine: alkylated liquid benzoxazine of 95: 5, 90:10, 80:20, and 50:50. The / 26 mixtures were then cured according to the curing cycle described in Example 1. The cured mixtures are shown in FIG. 5. FIG. 5 shows that the stability level of the alkylated liquid benzoxazine when cured with Bisphenol-A benzoxazine is decreased with the increased amount of alkylated benzoxazine.
    [00063] Also, for comparison, a commercially available liquid benzoxazine, Huntsman RD2009-008, with the following
    was analyzed using the MFK-DSC method. FIG. 6 shows the DSC activation energy curve and reactivity table for RD2009-008. From FIG. 6, again a higher activation energy and a lower conversion rate are seen compared to the data shown in FIGS. 3A-3B for halogenated liquid benzoxazines.
    [00064] A mixture of 68% Bisphenol-A benzoxazine and 32% RD2009008 was prepared and cured according to the curing cycle described in Example 1. An image of the cured resin is shown in FIG. 7. FIG. 7 shows that the level of stability of material RD2009-008 when cured with Bisphenol-A benzoxazine has also been decreased.
    [00065] FIG. 8 shows the Gravimetric Thermal Analysis (TGA) curves for RD2009-008, alkylated liquid benzoxazine and fluorinated liquid benzoxazine (Example 1, Structure 2). From FIG. 8, it can be seen that the stability of the commercial benzoxazine RD2009-008 and the alkylated liquid benzoxazine show greater weight loss in TGA than the fluorinated liquid benzoxazine. This corresponds well with the greater stability shown in the optical images of FIG. 1 for fluorinated / 26 benzoxazine mixtures.
    [00066] When cured, liquid halogenated benzoxazins also showed higher performance (Tg, torsion modulus) than benzoxazine RD2009-008 mixed with Bisphenol-A benzoxazine, see Table
    2.
    TABLE 2
    Formulation DMTA tan delta Tg (° C) Twist module at 30 ° C (GPa) Bis-A benzoxazine 184 1.71 Bis-A benzoxazine 68:32Fluorinated benzoxazine 189 1.72 Bis-A benzoxazine 68:32Chlorinated benzoxazine 177 1.69 Bis-A benzoxazine 68:32Liquid benzoxazine RD2009-008 142 1.26
    Example 3
    Adhesion Test [00067] Samples based on the Bis-A Benzoxazine / Epoxy, Bis-A Benzoxazine / Fluorinated Liquid Benzoxazine Mixture, Bis-A Benzoxazine / Chlorinated Liquid Benzoxazine Mixture were prepared and degassed in a vacuum oven at 110 ° C ° C. Upon removal, they cooled to 80 ° C, at that time, a thumb adhesion test (thumb placed on the sample) was performed when the material cooled to 25 ° C. As a control, pure Bisphenol-A benzoxazine was also subjected to the same degassing conditions and thumb grip test. Table 3 shows the data collected in the tested samples.
    TABLE 3
    Components (weight%) Beginning of uncured Tg(° C) Midpoint ofUncured Tg (° C) Temp. minimum in which the adhesion was presented (° C) Bis-A Benzoxazine (100%) 43.97 45.69 > 80 Bis-A Benzoxazine (68%), CY179 epoxy (21%) 4,4’-thiodiphenol (11%) 46.15 58.78 > 80 Bis-A benzoxazine (68%) Fluorinated liquid benzoxazine (32%) 13.90 23.15 45 Bis-A benzoxazine (68%) Chlorinated liquid benzoxazine (32%) 12.86 18.29 45
    / 26 [00068] As can be seen in Table 3, the uncured Tg of halogenated benzoxazine systems is lower than pure Bisoxol-A benzoxazine and the Bisoxol-A benzoxazine / Epoxy mixture. This decrease in uncured Tg is related to the malleability of the uncured sample. For an uncured benzoxazine based material to have good trim characteristics, the uncured Tg should be approximately at or below room temperature.
    [00069] Adherence tests on halogenated benzoxazine systems demonstrated an increase in adherence when halogenated liquid benzoxazines were mixed with Bisphenol-A benzoxazine compared to pure Bisphenol-A benzoxazine or for Huntsman's commercial BisphenolA benzoxazine / epoxy mixture. The increased adherence and malleability shown by fluorinated and chlorinated benzoxazine mixtures should allow for easier processing capacity.
    Example 4 [00070] Three samples were prepared based on 100% BisphenolA benzoxazine, a mixture of Bisphenol-A benzoxazine and 3-fluor benzoxazine at a weight ratio of 80:20, and the same mixture at a weight ratio of 50: 50. The samples were then heated to 300 ° C. FIG.9 shows that there is an increase in thermal stability at elevated temperatures as a result of the addition of fluorinated liquid benzoxazine. In FIG. 9, the upper image (a) is the image for 100% Bisphenol-A benzoxazine, the middle image (b) is for 80:20 Bisphenol-A: 3-fluoro benzoxazine and the bottom image (c) is for 50 : 50 Bisphenol-A: 3-fluorobenzoxazine.
    [00071] The benefits described above were observed without compromise with the thermo-mechanical performance of the benzoxazine system. Cured samples based on pure Bisphenol-A benzoxazine and mixtures of Bisphenol-A benzoxazine and 3-fluor benzoxazine (fluorinated liquid benzoxazine) in different proportions were prepared.
    / 26
    TABLE 4
    Bis-A benzoxazine (%) 3-Fluor benzoxazine (%) DSC midpoint Tg (° C) DMTA Tan DeltaTg (° C) Module Fromtorsion (GPa) Flexural modulus (GPa) 100 0 169 184 1.71 5.36 95 5 169 184 1.83 - 90 10 170 185 1.75 - 80 20 166 186 1.75 - 68 32 167 189 1.69 5.28 50 50 165 184 1.83 -
    [00072] Table 4 shows that the cured samples benzoxazine mixtures bisphenol-A / 3-fluoro maintains Tg similar modules and torsion similar compared to pure Bisphenol A benzoxazine. The 68% / 32% mixture also shows a flexural modulus that is comparable to that of pure Bisphenol A benzoxazine.
    [00073] In the Examples above, flexural modulus measurements were performed by Intertek MSG in accordance with method ASTM 790-01 (procedure A) and the following conditions:
    • Instron 5544 (T21) • 2kN load cell series 53033 • Test speed 0.01mm / mm / min • Extensometer Series B • Micrometer R97 • Conditions 23 ° C ± 2 ° C r / h 50% ± 5% • Weights check cell loading nos. 1 & 2 (20N) = 40.03N [00074] The glass transition temperature (Tg) and torsion modulus of the cured resin samples were measured by Dynamic Mechanical Thermal Analysis (DMTA). The experiments were carried out in an ARES LS 2K / 2K FRT device in a rectangular torsion request mode and Dynamic Dynamic Temperature Test method, in accordance with the following experimental conditions: The Dynamic Mechanical Thermal Analysis (DMTA) measurements of the temperature of glass transition (Tg) and torsion module of the cured resin system were obtained in a / 26 appliance
    ARES LS 2K / 2K FRT in rectangular torsion request mode and increasing dynamic temperature test method, in accordance with the following experimental conditions:
    • frequency = 0.1 Hz • voltage = 0.1% • temperature ramp = 3 ° C / min.
    [00075] The test samples were in the form of rectangular bars (40 x 1.4 x 4 mm), dried before analysis. Tg measurements were recorded at the delta tan peak, while modulus values were recorded at 30 ° C and Tg + 40 ° C.
    [00076] The ranges revealed here are inclusive and independently combinable and include the endpoints and all intermediate values within the ranges. For example, the “1% to 10%” range includes 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% as well as intermediate values such as 1, 1%, 1.2% and 1.3%, etc.
    [00077] Although various modalities are described here, it will be appreciated from the specification that various combinations of elements, variations in modalities disclosed here can be made by those skilled in the art and are within the scope of the present disclosure. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the modalities revealed here without departing from its essential scope. Therefore, it is intended that the claimed invention is not limited to the particular embodiments disclosed herein, but that the claimed invention includes all embodiments falling within the scope of the appended claims.
    权利要求:
    Claims (15)
    [1]
    1. Curable resin composition, characterized by the fact that it comprises
    a) at least one substituted monofunctional benzoxazine compound, which is in liquid form at room temperature, in the range between 20 ° C and 25 ° C, and is selected from the following structures:

    [2]
    2. Curable resin composition according to the claim
    1, characterized by the fact that the weight ratio of benzoxazine that has two or more bezoxazine portions to monofunctional benzoxazine
    Petition 870190131154, of 12/10/2019, p. 7/10
    2/4 substituted is in the range of 99.9: 0.1 to 50:50.
    [3]
    3. Curable resin composition according to claim 2, characterized in that the benzoxazine compound has two benzoxazine portions.
    [4]
    4. Curable resin composition according to claim
    2, characterized by the fact that the benzoxazine compound that has two or more bezoxazine moieties is a compound of Formula (II):

    [5]
    5. Curable resin composition according to claim 4, characterized by the fact that Z 1 is - [C (R 3 ) (R 4 )] x -arylene- [C (R 5 ) (R6)] y-.
    [6]
    6. Curable resin composition according to claim 4, characterized in that Z 1 is selected from -C (CH3) 2-, -CH2- and 3,3isobenzofuran-1 (3H) -one.
    [7]
    7. Curable resin composition according to claim
    Petition 870190131154, of 12/10/2019, p. 8/10
    3/4
    4, characterized by the fact that R 1 or R 2 are independently selected from aryl.
    [8]
    Curable resin composition according to claim 1, characterized in that it additionally comprises at least one thermoplastic or elastomeric curing agent.
    [9]
    9. Curable resin composition according to claim
    1, characterized by the fact that it also comprises:
    a catalyst to activate the curing of the benzoxazine mixture.
    [10]
    10. Cured resin, characterized by the fact that it is formed from the curing of the resin composition as defined in claim 1 within the range of 180 O C-200 O C.
    [11]
    11. Composite material, characterized by the fact that it comprises reinforcement fibers impregnated with a curable resin composition as defined in claim 1.
    [12]
    12. Method for making a prepeg, characterized by the fact that it comprises:
    provide a layer of reinforcement fibers; and impregnating said layer with a curable resin resin composition as defined in claim 1.
    [13]
    13. Method for making a composite part, characterized by the fact that it comprises:
    providing a dry fiber preform composed of a plurality of reinforcement fiber layers;
    infusing said dry fiber preform with a curable resin composition as defined in claim 1; and curing the infused fiber preform.
    [14]
    14. Curable resin composition according to claim
    1, characterized by the fact that the substituted monofunctional benzoxazine compound is represented by structure (B) and the composition further comprises an isomer represented by structure (D):
    Petition 870190131154, of 12/10/2019, p. 9/10
    4/4

    [15]
    15. Curable resin composition according to claim
    1, characterized by the fact that it does not contain any solvent.
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    同族专利:
    公开号 | 公开日
    GB201205574D0|2012-05-16|
    US20130267659A1|2013-10-10|
    TW201348218A|2013-12-01|
    KR20140138146A|2014-12-03|
    CN104105693B|2016-06-22|
    CA2868786C|2018-11-27|
    JP6153234B2|2017-06-28|
    US9499666B2|2016-11-22|
    EP2831052B1|2017-06-14|
    CN104105693A|2014-10-15|
    JP2015512459A|2015-04-27|
    EP2831052A1|2015-02-04|
    WO2013148408A1|2013-10-03|
    KR102043742B1|2019-11-12|
    AU2013240174A1|2014-08-14|
    AU2013240174B2|2017-05-04|
    MX349687B|2017-08-09|
    MY169339A|2019-03-21|
    CA2868786A1|2013-10-03|
    MX2014010321A|2015-03-10|
    RU2014135227A|2016-05-27|
    ES2639856T3|2017-10-30|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-28| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-09-17| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-12-24| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: C07D 265/14 , C08K 5/357 , C08J 5/24 , C07D 265/16 Ipc: C07D 265/16 (1974.07), C08G 14/06 (1974.07), C08G |
    2020-01-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-01-28| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1205574.5A|GB201205574D0|2012-03-29|2012-03-29|Benzoxazines and compositions containing the same|
    PCT/US2013/032897|WO2013148408A1|2012-03-29|2013-03-19|Benzoxazines and compositions containing the same|
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