CN104130287A - Toughening flame retardant, preparation method thereof, and composition prepared from toughening flame retardant - Google Patents
Toughening flame retardant, preparation method thereof, and composition prepared from toughening flame retardant Download PDFInfo
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- CN104130287A CN104130287A CN201410283212.5A CN201410283212A CN104130287A CN 104130287 A CN104130287 A CN 104130287A CN 201410283212 A CN201410283212 A CN 201410283212A CN 104130287 A CN104130287 A CN 104130287A
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Abstract
The invention discloses a toughening flame retardant, a preparation method thereof, and a composition prepared from the toughening flame retardant. The preparation method of the toughening flame retardant comprises the steps of adding 150 parts of 40% formaldehyde solution in a reactor; adding 210 parts of melt diethanol amine with stirring; reacting for 1-1.5 h; distilling at a reduced pressure; adding 276 parts of diethyl phosphite; reacting for 3.5-4.5 h at a temperature of 70-80 DEG C; cooling a reaction system to a room temperature; adding 100-350 parts of acetonitrile, 190-390 parts of an epoxy chloride and 10-150 parts of K2CO3 into the reaction system; reacting for 2.5-3.5 h at a temperature of 55-65 DEG C under protection of N2 and with stirring; and finally distilling at a normal pressure. By adding an epoxy type phosphoric acid flame retardant prepared by an in-situ method into a certain epoxy system, the epoxy system has dual functions of flame retardance and toughening property.
Description
Technical field
The present invention relates to preimpregnation composition epoxy resin, be specifically related to a kind of toughness reinforcing-fire retardant and preparation method thereof and the composition that prepared by this toughness reinforcing-fire retardant.
Background technology
Epoxy resin is since earlier 1900s comes out, cause worldwide extensive concern, each large chemical company falls over each other to drop into great manpower financial capacity in the development of epoxy resin, makes epoxy resin be able to fast development and in nineteen forty-seven, has completed for the first time the manufacture with industrial value.
Why can be within short period of time so fast-developing appearance of getting up and constantly having product innovation of epoxy resin, trace it to its cause and be that epoxy resin is the thermosetting polymer synthetic materials that a class has the performances such as bonds well, corrosion-resistant, insulation, high strength, can be used as coating, sizing agent, casting material, laminating material etc. and is applied to daily living article or high-technology field.In electronics, electric, machinofacture, chemical anticorrosion, aerospace, ship, chemical building material, water conservancy and hydropower and other many industrial circles, play an important role, become indispensable important materials in each industrial circle.
Why epoxy resin can have above-mentioned performance, is widely used in each industrial circle, and key is solidifying of it.The epoxy resin of uncured is the monomer of some small molecules amounts or the oligopolymer of certain molecular weight, does not have actual use value.Epoxy resin after solidifying agent solidifies, can solidifying agent be that bridge is linked each epoxide group, forms stable build reticulated structure.
For example, notification number is that the patent application of CN 102341426A discloses a kind of composition epoxy resin, its viscosity that contains at 25 ℃ is epoxy resin and epoxy compounds more than 1000mPas, the content of described epoxy compounds is more than 1 weight part and below 90 weight parts with respect to described epoxy resin 100 weight parts, in formula, G representative ring oxygen groups, R represents hydrogen or alkyl, n represents 2～4 integer.
Epoxy resin between curing and its uncured state is also in B-stage state, the epoxy resin of B scalariform state refers to that epoxy carries out through solidifying agent the prepolymer that primary solidification forms certain consolidated structures, but do not have complete curing molding, part is solvable fusible, there is good solubility energy and shelf characteric, can apply to sizing agent, glass fiber reinforced plastics product, carbon-fibre composite, coating and rigid foamed plastics etc.
Composition epoxy resin involved in the present invention is to be mainly applied to insulating composite material, it is the flexible insulation matrix material being formed by polyester film two sides bonded polyester fiber, when flood B rank epoxy resin on matrix material after, often there is the dust phenomenon that drops in made semicure material in the later stage in using.Dust can pollute Working environment, and the workers with long time disease that can bring out its occupational illness of working under such environment is sent out.Epoxy resin very easily fires, and epoxy resin time can produce toxic gas and follow a large amount of dense smoke in burning, and this has limited its Application Areas to a certain extent, especially the use on electrical apparatus industry.
For this reason, the epoxy type phosphoric acid fire retardant that the present invention adopts original position to prepare, adds in certain epoxy systems, and original epoxy systems is realized flame retardant properties, has again the double effects of toughness reinforcing performance.The method of epoxy type phosphoric acid fire retardant prepared by employing this patent original position has not yet to see open report.
Summary of the invention
The invention provides a kind of toughness reinforcing-fire retardant and preparation method thereof and the composition that prepared by this toughness reinforcing-fire retardant, composition of the present invention is coated in by polyester film and the prepared composite flexible material of polyester fiber non-woven fabric, after thermal treatment forms B rank epoxy resin, matrix material bending is dropped without dust, after matrix material system volume, epoxy layer is at room temperature without adhesion phenomenon, through regelate interlayer, there is good adhesive property, and matrix material has certain flame-retarding characteristic after regelate, can reach V-2 level.
An epoxidation N, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, comprises as following steps:
(1) in reactor, put into the formalin of 150 weight parts 40%, under stirring, add the 210 weight parts diethanolamine of melting, reaction 1～1.5h;
(2) after step (1) reaction finishes, after underpressure distillation, add 276 weight part diethyl phosphites, react 3.5～4.5h at 70～80 ℃, obtain N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-;
(3) reaction system of step (2) is cooled to after room temperature, in reaction system, adds 100-350 weight part acetonitrile, 190-390 weight part epoxy muriate and 10-150 weight part K
2cO
3, at N
2under the environment of protection, in 55～65 ℃ of stirring reaction 2.5～3.5h, finally by air distillation, obtain epoxidation N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-.
Temperature while stirring in step (1) is preferably 38～42 ℃, and more preferably 40 ℃, and remain at this temperature and react with the diethanolamine of melting; The time of reacting with the diethanolamine of melting is preferably 1h.
Temperature in step (2) during underpressure distillation remains on 80 ℃ of left and right, preferably 75～85 ℃, most preferably is 80 ℃; Adding preferred reaction conditions after diethyl phosphite is to react 4h at 75 ℃.
Temperature in step (3) during air distillation remains on 120 ℃ of left and right, preferably 115～125 ℃, most preferably is 120 ℃; N
2reaction conditions under protection is 60 ℃ of stirring reaction 3h more preferably.
Preferably, the muriatic structural formula of described epoxy is R-Cl, and wherein R is
Room temperature of the present invention refers to the temperature that normal experiment is indoor, is generally 10～30 ℃.
For convenience, by product called after ZK08 of the present invention, structural formula is:
Wherein R is
Its synthetic route is:
First preparation feedback intermediate N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters (BHAPE) of N-, then react and obtain final product ZK08 with epoxy muriate as reaction intermediate original position by BHAPE, specifically building-up process is as shown in Figure 1.
The epoxy type phosphoric acid fire retardant that the present invention adopts original position to prepare, adds in certain epoxy systems, and original epoxy systems is realized flame retardant properties, has again the double effects of toughness reinforcing performance.
A preferred preparation method, comprises the steps:
(1) in reactor, put into the formalin of 150 weight parts 40%, under 40 ℃ of stirrings, add the 210 weight parts diethanolamine of melting, reaction 1h;
(2) after step (1) reaction finishes, after underpressure distillation, add 276 weight part diethyl phosphites, react 4h at 75 ℃, obtain N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-;
(3) reaction system of step (2) is cooled to after room temperature, in reaction system, adds 100-350 weight part acetonitrile, 190-390 weight part epoxy muriate and 10-150 weight part K
2cO
3, at N
2under the environment of protection, in 60 ℃ of stirring reaction 3h, finally by air distillation, obtain epoxidation N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-; The muriatic structural formula of epoxy is R-Cl, and wherein R is
Most preferred preparation method's method, comprises the steps:
(1) in reactor, put into the formalin of 150 weight parts 40%, under 40 ℃ of stirrings, add the 210 weight parts diethanolamine of melting, reaction 1h;
(2) after step (1) reaction finishes, after underpressure distillation, add 276 weight part diethyl phosphites, react 4h at 75 ℃, obtain N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-;
(3) reaction system of step (2) is cooled to after room temperature, in reaction system, adds acetonitrile, epoxy muriate and K
2cO
3, at N
2under the environment of protection, in 60 ℃ of stirring reaction 3h, finally by air distillation, obtain epoxidation N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-; The muriatic structural formula of epoxy is R-Cl, and wherein R is
The acetonitrile, epoxy muriate and the K that wherein in step (3), add
2cO
3several groups of preferably combination be:
A: acetonitrile 108 weight parts; Epoxy muriate 196 weight parts; K
2cO
326 weight parts.
B: acetonitrile 154 weight parts; Epoxy muriate 248 weight parts; K
2cO
365 weight parts.
C: acetonitrile 213 weight parts; Epoxy muriate 327 weight parts; K
2cO
382 weight parts.
D: acetonitrile 339 weight parts; Epoxy muriate 383 weight parts; K
2cO
3141 weight parts.
The several prods that this optimum preparation method prepares is as shown in table 1:
The different synthesizing formulas of table 1:ZK08
The product purity being prepared by this most preferred preparation method is the highest, and during for epoxy composite system, performance is best.
The present invention also provide a kind of as described in the epoxidation N for preparing of preparation method, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-.
The thick product being prepared by the inventive method can be directly used in epoxy composite system, the present invention discloses original position preparation method to prepare epoxidation N first, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, and it is applied in preimpregnation epoxy composite as toughness reinforcing-fire retardant.
Therefore, it is a kind of by described epoxidation N that the present invention also provides, the composition epoxy resin that two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-prepare, and by weight, said composition is made by following component materials:
Preferably, by weight, said composition is made by following component materials:
ZK08 is preferably a kind of in ZK08-A, ZK08-B, ZK08-C and ZK08-D, most preferably is ZK08-C.
In the present invention, epoxy resin can be selected from one or more mixtures in E-51, E-44 in bisphenol A type epoxy resin, E-31, E-20, the conventional epoxy resin such as E-14, E-12; Solidifying agent is selected from one or more mixtures in the Common Curing Agents such as aromatic amine, aromatic anhydride, resol, Dyhard RU 100; Solvent orange 2 A is one or more mixtures in ethanol, ethylene glycol, DMF, acetone; Solvent B is one or more mixtures in Isosorbide-5-Nitrae butanediol diglycidyl ether, epoxy propane butyl ether, resorcinol diglycidyl ether, dimethylbenzene, toluene, acetone.
Further preferably, epoxy resin can be selected from a kind of in E-51, E-44 in bisphenol A type epoxy resin, E-31, E-20, the conventional epoxy resin such as E-14, E-12; Solidifying agent adopts the mixture of resol and Dyhard RU 100; Solvent orange 2 A is DMF; Solvent B is acetone.
Most preferably, by weight, said composition is made by following component materials:
100 parts of epoxy resin; 21.8 parts, solidifying agent; 5.4 parts of solvent orange 2 As; 100 parts of solvent B; ZK08-C12 part; And wherein epoxy resin is E-20, solidifying agent is the mixture of resol (20 parts) and Dyhard RU 100 (1.8 parts), and solvent orange 2 A is DMF, and solvent B is acetone.
Under this scheme, 20 dry linting amounts of gained preimpregnation matrix material bending are < 0.01g/m
2, fire-retardantly by UL94 V-2, to test, material extending shearing resistance is 5.4MPa, long-term placement occurs without adhesion situation.
The preparation method of the present composition is as follows:
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 1-6h (preferably 4h), and then the ZK08 that adds proportional quantity stirs 0-3h (preferably 2h), finally with copper wire gauze, filter and take out.
The epoxy composite that invention provides is applied on insulating composite material, and application art step and products obtained therefrom partial properties testing conditions are as follows:
(1) each component (except ZK08) in composition epoxy resin is added in reactor according to-epoxy composite weight part, mechanical stirring 1-5h under room temperature (preferably 3h), and then add toughner to stir 0-3h (preferably 2h), finally with copper wire gauze, filter and take out;
(2) insulating composite material is flooded on vertical dip coater to the epoxy composite preparing in (1);
(3) material after vertical dip coater divides four sections of regions to impregnation is heat-treated, and Heating temperature is respectively 40-60 ℃, 60-80 ℃, 80-100 ℃, 100-120 ℃;
(4) tensile shear strength of test products is made product to be cut out to the sample of 6 10*10mm specifications, stacks between two, covers up and down Copper Foil, and being placed in pressure is 0.1MPa, and temperature is 1h under the pressing machine of 150 ℃, then takes out and survey tensile shear strength;
(5) whether adhesion is products made thereby to be cut into the sample of 2 100*100mm specifications to test products, overlays in two blocks of rubber, and being placed in pressure is 0.1MPa, and temperature is 2h under the pressing machine of 45 ℃, takes out and checks whether adhesion of sample;
(6) flame retardant properties of product is carried out measuring according to UL94 standard testing.
Compared with prior art, beneficial effect of the present invention:
(1) the present invention adds after toughness reinforcing-fire retardant in preimpregnation epoxy composite, can play good toughening effect, gained preimpregnation matrix material arbitrarily bends without the epoxy dust phenomenon that drops and occurs, and this air quality problems to shop worker's Working environment has been made guarantee;
(2) the present invention adds after toughness reinforcing-fire retardant in preimpregnation epoxy composite, has increased the flame retardant properties that like product is never accomplished, can reach V-2 rank;
(3) utilize the preimpregnation matrix material tensile shear strength of preimpregnation epoxy composite gained of the present invention far above industry standard >=3MPa, but reached the standard of > 5MPa;
(4) toughness reinforcing-fire-retardant preimpregnation epoxy composite of the present invention is in practice, and production technique is simple, with low cost, and the preimpregnation composite material surface of gained is smooth, smooth, during uncoiling without adhesion phenomenon.
Accompanying drawing explanation
Fig. 1 is synthetic route chart of the present invention.
Embodiment
The preparation of toughness reinforcing-fire retardant ZK-08, comprises the steps;
(1) in reactor, put into the formalin of 150 weight parts 40%, under 40 ℃ of stirrings, add the 210 weight parts diethanolamine of melting, reaction 1h;
(2) after step (1) reaction finishes, after underpressure distillation, add 276 weight part diethyl phosphites, react 4h at 75 ℃, obtain N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-;
(3) reaction system of step (2) is cooled to after room temperature, in reaction system, adds acetonitrile, epoxy muriate and K
2cO
3, at N
2under the environment of protection, in 60 ℃ of stirring reaction 3h, finally by air distillation, obtain epoxidation N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-; The muriatic structural formula of epoxy is R-Cl, and wherein R is
The acetonitrile, epoxy muriate and the K that wherein in step (3), add
2cO
3several groups of preferably combination be:
A: acetonitrile 108 weight parts; Epoxy muriate 196 weight parts; K
2cO
326 weight parts.
B: acetonitrile 154 weight parts; Epoxy muriate 248 weight parts; K
2cO
365 weight parts.
C: acetonitrile 213 weight parts; Epoxy muriate 327 weight parts; K
2cO
382 weight parts.
D: acetonitrile 339 weight parts; Epoxy muriate 383 weight parts; K
2cO
3141 weight parts.
The several prods of preparing is as shown in the table:
The different synthesizing formulas of ZK08
The product preparing through conventional gas phase analysis, the purity of product is all in 95% left and right.
Embodiment 1
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 18 parts, solidifying agent; 1.4 parts of solvent orange 2 As; Solvent B100 part; 6 parts of ZK08-A.
Wherein epoxy resin is E-44, and solidifying agent is the mixture of aromatic anhydride (17 parts) and Dyhard RU 100 (1 part), and solvent orange 2 A is DMF, and solvent B is toluene.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add the ZK08-A of proportional quantity to stir 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to insulating composite material, zone heating (40-60 ℃, 60-80 ℃, 80-100 ℃, 100-120 ℃) forms epoxy prepolymer and makes glue-line be evenly distributed on insulating composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 5.8g/m
2(spread of preimpregnation matrix material is 65g/m
2, lower with), fire-retardantly by UL94 V-2, test, tensile shear strength is 3.1MPa (industry standard for>=3MPa).
Embodiment 2
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 18 parts, solidifying agent; 1.4 parts of solvent orange 2 As; Solvent B100 part; 6 parts of ZK08-B.
Wherein epoxy resin is E-44, and solidifying agent is the mixture of aromatic anhydride (17 parts) and Dyhard RU 100 (1 part), and solvent orange 2 A is DMF, and solvent B is toluene.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add the ZK08-B of proportional quantity to stir 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 5.1g/m
2, flame retardant rating reaches V-2 level, and tensile shear strength is 3.2MPa.
Embodiment 3
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 18 parts, solidifying agent; 1.4 parts of solvent orange 2 As; Solvent B100 part; 6 parts of ZK08-C.
Wherein epoxy resin is E-44, and solidifying agent is the mixture of aromatic anhydride (17 parts) and Dyhard RU 100 (1 part), and solvent orange 2 A is DMF, and solvent B is toluene.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add the ZK08-C of proportional quantity to stir 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 3.8g/m
2, flame retardant rating reaches V-2 level, and tensile shear strength is 3.2MPa.
Embodiment 4
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 18 parts, solidifying agent; 1.4 parts of solvent orange 2 As; Solvent B100 part; 6 parts of ZK08-D.
Wherein epoxy resin is E-44, and solidifying agent is the mixture of aromatic anhydride (17 parts) and Dyhard RU 100 (1 part), and solvent orange 2 A is DMF, and solvent B is toluene.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add the ZK08 of proportional quantity to stir 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 4.7g/m
2, flame retardant rating reaches V-2 level, and tensile shear strength is 3.1MPa.
Through embodiment 1-4, relatively can find out, ZK08-C has more excellent toughening effect compared with ZK08-A, ZK08-B and ZK08-D, and in same system in the situation that addition is identical, add ZK08-C gained matrix material through UL94 test t2+t3 shortest time, in four, ZK08-C flame retardant effect is best.Thereby, in following embodiment, all with ZK08-C, make toughening flame-proof additive.
Comparative example 1
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 18 parts, solidifying agent; 1.4 parts of solvent orange 2 As; Solvent B100 part.
Wherein epoxy resin is E-44, and solidifying agent is the mixture of aromatic anhydride (17 parts) and Dyhard RU 100 (1 part), and solvent orange 2 A is DMF, and solvent B is toluene.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h to being uniformly dissolved, finally with copper wire gauze, filter and take out.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
Gained preimpregnation matrix material tensile shear strength is 3.8MPa, and 20 dry linting amounts of material bending are 12g/m
2, without flame-retarding characteristic.
Embodiment 5
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 30 parts, solidifying agent; 1.9 parts of solvent orange 2 As; Solvent B68 part; 6 parts of ZK08-C.
Wherein epoxy resin is E-31, and solidifying agent is the mixture of resol (28 parts) and Dyhard RU 100 (2 parts), and solvent orange 2 A is DMF, and solvent B is toluene.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add the ZK08-C of respective amount to stir 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 4g/m
2, flame retardant rating reaches V-2 level, and tensile shear strength is 3.8MPa.
Embodiment 6
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 26.4 parts, solidifying agent; 1.6 parts of solvent orange 2 As; Solvent B82 part; 6 parts of ZK08-C.
Wherein epoxy resin is E-12, and solidifying agent is the mixture of resol (25 parts) and Dyhard RU 100 (1.4 parts), and solvent orange 2 A is DMF, and solvent B is toluene.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add the ZK08-C of proportional quantity to stir 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 4g/m
2, flame retardant rating reaches V-2 level, and tensile shear strength is 3.4MPa.
Embodiment 7
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 26.4 parts, solidifying agent; 1.6 parts of solvent orange 2 As; Solvent B97 part; 8 parts of ZK08-C.
Wherein epoxy resin is E-20, and solidifying agent is the mixture of resol (25 parts) and Dyhard RU 100 (1.4 parts), and solvent orange 2 A is DMF, and solvent B is acetone.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add the ZK08-C of proportional quantity to stir 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 2g/m
2, flame retardant rating reaches V-2 level, and tensile shear strength is 3.1MPa.
Embodiment 8
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 24.8 parts, solidifying agent; 3.6 parts of solvent orange 2 As; Solvent B100 part; 8 parts of ZK08-C.
Wherein epoxy resin is E-20, and solidifying agent is the mixture of resol (24 parts) and Dyhard RU 100 (0.8 part), and solvent orange 2 A is DMF, and solvent B is acetone.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add proportional quantity toughness reinforcing-fire retardant ZK08-C stirs 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.20 dry linting amounts of gained preimpregnation matrix material bending are 0.5g/m
2, fire-retardantly by UL94 V-2, to test, material extending shearing resistance is 4.2MPa, but when rolling, has the phenomenon of slight adhesion.
Embodiment 9
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 21.8 parts, solidifying agent; 5.4 parts of solvent orange 2 As; Solvent B100 part; 10 parts of ZK08-C.
Wherein epoxy resin is E-20, and solidifying agent is the mixture of resol (20 parts) and Dyhard RU 100 (1.8 parts), and solvent orange 2 A is DMF, and solvent B is acetone.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add proportional quantity toughness reinforcing-fire retardant ZK08-C stirs 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.20 dry linting amounts of gained preimpregnation matrix material bending are 0.08g/m
2, fire-retardantly by UL94 V-2, to test, material extending shearing resistance is 5.9MPa, long-term placement occurs without adhesion situation.
Embodiment 10
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 21.8 parts, solidifying agent; 5.4 parts of solvent orange 2 As; 100 parts of solvent B; 12 parts of ZK08-C.
Wherein epoxy resin is E-20, and solidifying agent is the mixture of resol (20 parts) and Dyhard RU 100 (1.8 parts), and solvent orange 2 A is DMF, and solvent B is acetone.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h, and then add proportional quantity toughness reinforcing-fire retardant ZK08-C stirs 2h, finally with copper wire gauze, filter and take out, obtain composition glue.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.20 dry linting amounts of gained preimpregnation matrix material bending are < 0.01g/m
2, fire-retardantly by UL94 V-2, to test, material extending shearing resistance is 5.4MPa, long-term placement occurs without adhesion situation.
Comparative example 2
According to the composition epoxy resin of the present embodiment, in weight part, its component materials is: 100 parts of epoxy resin; 21.8 parts, solidifying agent; 5.4 parts of solvent orange 2 As; Solvent B100 part.
Wherein epoxy resin is E-20, and solidifying agent is the mixture of resol (20 parts) and Dyhard RU 100 (1.8 parts), and solvent orange 2 A is DMF, and solvent B is acetone.
First with solvent orange 2 A, partly solidified dose is dissolved completely, then epoxy resin, remaining solidifying agent and solvent B are taken according to weight ratio, together with the solidifying agent having dissolved before, join in reactor, under room temperature environment, stir 3h to being uniformly dissolved, finally with copper wire gauze, filter and take out.
By the glue configuring through vertical dip coater gluing to matrix material, zone heating forms epoxy prepolymer and makes glue-line be evenly distributed on composite material surface.
20 dry linting amounts of gained preimpregnation matrix material bending are 13g/m
2, material extending shearing resistance is 5.4MPa, without flame-retarding characteristic.
Claims (9)
1. an epoxidation N, the preparation method of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-, is characterized in that, comprises as following steps:
(1) in reactor, put into the formalin of 150 weight parts 40%, under stirring, add the 210 weight parts diethanolamine of melting, reaction 1～1.5h;
(2) after step (1) reaction finishes, after underpressure distillation, add 276 weight part diethyl phosphites, react 3.5～4.5h at 70～80 ℃, obtain N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-;
(3) reaction system of step (2) is cooled to after room temperature, in reaction system, adds 100-350 weight part acetonitrile, 190-390 weight part epoxy muriate and 10-150 weight part K
2cO
3, at N
2under the environment of protection, in 55～65 ℃ of stirring reaction 2.5～3.5h, finally by air distillation, obtain epoxidation N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-;
Described epoxidation N, the structural formula of two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-is suc as formula shown in (1) or formula (2), called after ZK-08:
(1)；
(2)；
Wherein R is
2. preparation method according to claim 1, is characterized in that, the temperature while stirring in step (1) is 38～42 ℃.
3. preparation method according to claim 1, is characterized in that, the time of reacting with the diethanolamine of melting in step (1) is 1h, and temperature of reaction is 38～42 ℃.
4. preparation method according to claim 1, is characterized in that, the temperature in step (2) during underpressure distillation remains on 75～85 ℃.
5. preparation method according to claim 1, is characterized in that, in step (2), adding the reaction conditions after diethyl phosphite is to react 4h at 75 ℃.
6. preparation method according to claim 1, is characterized in that, the temperature in step (3) during air distillation remains on 115～125 ℃.
7. preparation method according to claim 1, is characterized in that, N in step (3)
2reaction conditions under protection is 60 ℃ of stirring reaction 3h.
8. the epoxidation N that as described in as arbitrary in claim 1～7, preparation method prepares, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl esters of N-.
9. by an epoxidation N described in claim 8, two (2-hydroxyethyl) composition epoxy resins that AminomethylphosphoniAcid Acid diethyl ester prepares of N-, is characterized in that, by weight, said composition is made by following component materials:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319765A (en) * | 2016-08-19 | 2017-01-11 | 马鞍山湖滨无纺布科技有限公司 | Nonwoven fabric with performances of toughening and retarding flame and capability of releasing negative oxygen ions and preparation method of nonwoven fabric |
| CN108383978A (en) * | 2018-02-25 | 2018-08-10 | 李嘉顺 | A kind of solvent-free phosphorous epoxy resin curing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03199229A (en) * | 1989-12-27 | 1991-08-30 | Chugoku Marine Paints Ltd | Epoxy resin composition of under water coating type |
| KR20100084091A (en) * | 2009-01-15 | 2010-07-23 | 풍림유화공업(주) | Flame-retardant semiconductor encapsulating epoxy resin composition |
| CN102276645A (en) * | 2011-05-18 | 2011-12-14 | 烟台万华聚氨酯股份有限公司 | Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate |
-
2014
- 2014-06-23 CN CN201410283212.5A patent/CN104130287A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03199229A (en) * | 1989-12-27 | 1991-08-30 | Chugoku Marine Paints Ltd | Epoxy resin composition of under water coating type |
| KR20100084091A (en) * | 2009-01-15 | 2010-07-23 | 풍림유화공업(주) | Flame-retardant semiconductor encapsulating epoxy resin composition |
| CN102276645A (en) * | 2011-05-18 | 2011-12-14 | 烟台万华聚氨酯股份有限公司 | Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319765A (en) * | 2016-08-19 | 2017-01-11 | 马鞍山湖滨无纺布科技有限公司 | Nonwoven fabric with performances of toughening and retarding flame and capability of releasing negative oxygen ions and preparation method of nonwoven fabric |
| CN108383978A (en) * | 2018-02-25 | 2018-08-10 | 李嘉顺 | A kind of solvent-free phosphorous epoxy resin curing agent and preparation method thereof |
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