CN115894956A - Hyperbranched epoxy resin and application of flame-retardant and toughening modified epoxy resin thereof - Google Patents
Hyperbranched epoxy resin and application of flame-retardant and toughening modified epoxy resin thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched epoxy resin, which is prepared by the reaction of olefin-containing binary aromatic phenol, a phosphorus-containing compound and a trifunctional epoxy compound, and the preparation method comprises the following steps: (1) Stirring and reacting a binary aromatic phenol containing olefin and a phosphorus-containing compound at 80-180 ℃ for 12-36h to prepare an intermediate A; (2) And (3) stirring the intermediate A and a trifunctional epoxy compound for reaction for 5-15h at 90-130 ℃ in the presence of a catalyst to obtain the hyperbranched epoxy resin. The hyperbranched epoxy resin provided by the invention can improve the flame retardance of the epoxy resin and can also improve the toughness of the epoxy resin.
Description
Technical Field
The invention relates to the technical field of epoxy resin modification, in particular to hyperbranched epoxy resin and application of flame-retardant and toughening modified epoxy resin thereof.
Background
As a typical thermosetting resin, epoxy resin is widely applied to a plurality of fields of integrated circuits, aerospace, electronic telecommunications, traffic buildings and the like due to the advantages of good bonding property, high insulating property, low curing shrinkage, excellent processing property, low cost and the like. However, since the epoxy resin contains a large amount of epoxy groups, it has a high crosslinking density, and is liable to exhibit disadvantages such as poor toughness and brittleness, which limits the range of applications of engineering techniques. In addition, the epoxy resin has the defects of inflammability and poor flame retardant effect, and easily generates a large amount of heat and gas during combustion, thereby harming the safety of the society and the health of people. Therefore, the construction of a series of high-performance epoxy resins is very important for toughening and flame-retardant modification of the epoxy resins.
As is well known, halogen-containing flame retardants are a typical type of flame retardants, which have excellent flame retardant effect, but easily generate a large amount of corrosive gas and toxic smoke during the flame retardant process, and thus, the application of the halogen-containing flame retardants is limited. The halogen-free flame retardant also becomes an important research direction in the flame retardant field. Among them, phosphorus flame retardants are typically used, and have attracted much attention in recent years because of their strong designability of structure, and their non-toxicity and innocuity. In addition, the nitrogen flame retardant is used as another environment-friendly flame retardant, has the advantages of good flame retardant effect, good heat resistance and the like, and has a wide research range. Therefore, through reasonable construction of the two flame retardant elements, efficient flame retardance of the epoxy resin can be realized. In addition, the flame retardant has good smoke suppression effect, high designable structure performance, no toxicity and no harm, and has very wide research prospect in the aspect of flame retardant modification.
While hyperbranched epoxy resins mainly comprise a hyperbranched core and end groups with epoxy functional groups. The performance of the epoxy resin is mainly determined by the molecular structure, and a large number of cavity structures existing in the molecule are beneficial to improving the toughness of the epoxy resin. In addition, the hyperbranched epoxy resin has a highly branched structure, so that the viscosity and the solubility of the hyperbranched epoxy resin are low, the terminal group of the hyperbranched epoxy resin is also beneficial to modification of multiple functions, the designability performance is high, and the hyperbranched epoxy resin can be used for effectively toughening and flame-retardant modification of the epoxy resin. The preparation of the high-performance epoxy resin is especially necessary while the requirements on toughness and flame retardance of the epoxy resin are met.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides hyperbranched epoxy resin and application of flame-retardant, toughening and modifying epoxy resin thereof. The hyperbranched epoxy resin provided by the invention can improve the flame retardance of the epoxy resin and can also improve the toughness of the epoxy resin.
The technical scheme of the invention is as follows:
a hyperbranched epoxy resin is prepared by the reaction of olefin-containing binary aromatic phenol, a phosphorus-containing compound and a trifunctional epoxy compound, and the preparation method comprises the following steps:
(1) Stirring and reacting olefin-containing binary aromatic phenol and a phosphorus-containing compound at the temperature of 80-180 ℃ for 12-36h to prepare an intermediate A;
(2) And (3) stirring the intermediate A and a trifunctional epoxy compound to react for 5-15h at 90-130 ℃ in the presence of a catalyst to obtain the hyperbranched epoxy resin.
Preferably, the olefin-containing dihydric aromatic phenol in the step (1) is one or more of o-diallyl bisphenol A, 3 '-diallyl-4, 4' -biphenol and magnolol; the phosphorus-containing compound is one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diphenyl phosphine oxide, diethyl phosphite, diphenyl phosphite and dimethyl phosphite.
Preferably, in the step (1), the molar ratio of the olefin-containing dihydric aromatic phenol to the phosphorus-containing compound is 1.
Preferably, in the step (2), the trifunctional epoxy compound is one or more of triglycidyl isocyanurate and triglycidyl p-aminophenol; the catalyst is one or more of triphenylphosphine, tetrabutylammonium bromide and tetrabutylammonium chloride.
Preferably, in step (2), the molar ratio of the intermediate A to the trifunctional epoxy compound is 0.8-1.
The application of the hyperbranched epoxy resin is used for preparing an epoxy resin composition by using flame retardant, toughened and modified epoxy resin.
An epoxy resin composition containing the hyperbranched epoxy resin comprises the following raw materials in parts by weight: 1-20 parts of the hyperbranched epoxy resin, 80-100 parts of bisphenol A epoxy resin and 15-30 parts of a curing agent.
Preferably, the double-part A epoxy resin is one or more of bisphenol A epoxy resin E-51, E-44 and E-42.
Preferably, the curing agent is one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, diaminodiphenyl ether, diphenylenediamine, o-phenylenediamine, p-xylylenediamine, and o-tolidine.
A cured product prepared from the epoxy resin composition is prepared by the following method: preheating 80-100 parts of bisphenol A type epoxy resin at 90-140 ℃, then adding 1-20 parts of the hyperbranched epoxy resin for stirring, and cooling to 70-90 ℃ after the hyperbranched epoxy resin is completely dissolved; continuously adding 15-30 parts of curing agent and uniformly stirring to obtain a resin prepolymer;
pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at the temperature of 70-120 ℃ for 0.5-2h; placing in a forced air drying oven for stage heating, wherein the curing process is 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; after cooling and demoulding, the epoxy resin condensate with strong flame retardance and good toughness is prepared.
The beneficial technical effects of the invention are as follows:
the invention provides hyperbranched epoxy resin and application of the flame-retardant and toughening modified epoxy resin. Firstly, the epoxy resin is prepared from A containing phosphorus element on a side chain 2 Monomer and main chain nitrogen element-containing B 3 The monomer is formed, has better flame retardant effect in gas phase and condensed phase, and has excellent thermal performance; secondly, the end epoxy group further improves the compatibility of the epoxy resin in an epoxy matrix, and the toughness of an epoxy system is further improved through a flexible chain in the structure; in addition, various functional groups can be introduced into the terminal epoxy groups of the epoxy resin, so that the epoxy resin has more performances and has better performances in the fields of aerospace, electronic industry and the likeAnd (4) application prospect.
Description of the drawings:
FIG. 1 is a schematic structural view of a hyperbranched epoxy resin;
FIG. 2 is the nuclear magnetic hydrogen spectrum of the hyperbranched epoxy resin obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 108g DOPO was placed in a flask, the temperature was raised to 140 ℃ to melt DOPO completely, then 77g o-diallyl bisphenol A was added and stirred mechanically, N 2 Protecting, heating to 180 ℃, stirring at constant temperature for reaction for 16h, and obtaining a crude product after the reaction is finished; dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 33.3g of intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of tetrabutylammonium bromide are weighed out and dissolved in 100mL of DMF, the temperature is raised to 115 ℃ and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin.
The nuclear magnetic resonance hydrogen spectrum of the hyperbranched epoxy resin of the example is shown in FIG. 2. As can be seen from FIG. 2, 5.0 to 5.5ppm are ascribed to the proton signal peak of-OH after ring opening; 2.65ppm and 2.78ppm are assigned to the proton signal peaks of the terminal epoxy, respectively. The hyperbranched epoxy resin had a number average molecular weight of 9640 and an epoxy value of 0.24mol/100g as measured by the epoxyacetone method.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24.5 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 2
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 101g of diphenylphosphine oxide were placed in a flask and heated to 80 ℃ to completely melt it, then 77g of o-diallylbisphenol A were added and mechanically stirred, N 2 Protecting, stirring at constant temperature, reacting for 24h, and obtaining a crude product after the reaction is finished; and dissolving the intermediate crude product in 200mL of methanol, precipitating in 1L of n-hexane, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 32g of intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of triphenylphosphine are weighed out and dissolved in 100mL of DMSO, the temperature is raised to 115 ℃, and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the prepared hyperbranched epoxy resin is 8756, and the epoxy value measured by an epoxy acetone method is 0.18mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24.1 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 3
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 69g of diethyl phosphite were placed in a flask, 77g of o-diallylbisphenol A were then added, and the machine was operatedStirring, N 2 Protecting, heating to 120 ℃, stirring at constant temperature for reaction for 24 hours, and obtaining a crude product after the reaction is finished; and dissolving the intermediate crude product in 200mL of ethanol, precipitating in 1L of n-hexane, and repeatedly dissolving and precipitating for 3 times to obtain an intermediate A.
Step two: 25.9g of the intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of tetrabutyl ammonium bromide are weighed and dissolved in 100mL of DMF, the temperature is raised to 115 ℃, and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the prepared hyperbranched epoxy resin is 9016, and the epoxy value measured by an epoxy acetone method is 0.21mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24.3 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 4
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 55g of dimethyl phosphite were placed in a flask, 77g of o-diallylbisphenol A were added and stirred mechanically, N 2 Protecting, heating to 140 ℃, stirring at constant temperature for reaction for 20 hours, and obtaining a crude product after the reaction is finished; dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 23.8g of intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of tetrabutylammonium bromide are weighed out and dissolved in 100mL of DMF, the temperature is raised to 115 ℃ and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the prepared hyperbranched epoxy resin is 9406, and the epoxy value measured by an epoxy acetone method is 0.16mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for staged temperature rise, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 5
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 117g of diphenyl phosphite were placed in a flask, 77g of o-diallylbisphenol A were added thereto, and the mixture was mechanically stirred, N 2 Protecting, heating to 150 ℃, stirring at constant temperature for reacting for 18h, and obtaining a crude product after the reaction is finished; dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 35g of the intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of tetrabutyl ammonium bromide are weighed and dissolved in 100mL of DMF, the temperature is raised to 115 ℃, and the reaction is carried out for 6 hours. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the prepared hyperbranched epoxy resin is 8832, and the epoxy value measured by an epoxy acetone method is 0.20mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24.2 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for staged temperature rise, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 6
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 108g of DOPO was placed in a flask, the temperature was raised to 140 ℃ to completely melt the DOPO, 66g of 3,3 '-diallyl-4, 4' -biphenol was then added, the mechanical stirring was carried out, N 2 Protecting, heating to 170 ℃, stirring at constant temperature for reaction for 30 hours, and obtaining a crude product after the reaction is finished; dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 33.3g of intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of triphenylphosphine were weighed out and dissolved in 100mL of DMF, and the temperature was raised to 115 ℃ for reaction for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the hyperbranched epoxy resin prepared was 8457, and the epoxy value measured by the epoxyacetone method was 0.27mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24.7 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 7
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: putting 108g DOPO in a flask, heating to 140 ℃ to completely melt the DOPO, adding 66g magnolol, mechanically stirring, and adding N 2 Protecting, heating to 160 ℃, stirring at constant temperature for reaction for 32 hours, and obtaining a crude product after the reaction is finished; and dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving and precipitating for 3 times to obtain an intermediate A.
Step two: 33.3g of intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of tetrabutylammonium chloride are weighed out and dissolved in 100mL of DMF, the temperature is raised to 115 ℃ and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the hyperbranched epoxy resin prepared was 8055, and the epoxy value measured by the epoxyacetone method was 0.30mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24.9 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 8
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 116g of DOPO was placed in a flask, the temperature was raised to 140 ℃ to completely melt DOPO, 77g of o-diallylbisphenol A were added thereto, and mechanical stirring was carried out, N 2 Protecting, heating to 180 ℃, stirring at constant temperature for reaction for 20 hours, and obtaining a crude product after the reaction is finished; dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 33.3g of intermediate A, 13.9g of triglycidyl p-aminophenol and 0.1g of tetrabutylammonium bromide are weighed out and dissolved in 100mL of DMF, the temperature is raised to 115 ℃ and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the hyperbranched epoxy resin prepared was 9624, and the epoxy value measured by the epoxyacetone method was 0.24mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 24.5 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 9
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 122g of DOPO was placed in a flask, the temperature was raised to 140 ℃ to completely melt DOPO, 77g of o-diallylbisphenol A were added thereto, and mechanical stirring was carried out, N 2 Protecting, heating to 170 ℃, stirring at constant temperature for reaction for 20 hours, and obtaining a crude product after the reaction is finished; dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 31.5g of intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of tetrabutyl ammonium bromide are weighed and dissolved in 100mL of DMF, the temperature is raised to 115 ℃, and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The hyperbranched epoxy resin prepared had a number average molecular weight of 7820 and an epoxy value of 0.32mol/100g as determined by the epoxyacetone method.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E51 epoxy resin at 140 ℃, then adding 10 parts of hyperbranched epoxy resin, stirring and mixing uniformly, and cooling to 90 ℃; continuously adding 25.1 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Example 10
The preparation method of the hyperbranched epoxy resin comprises the following steps:
the method comprises the following steps: 108g of DOPO was placed in a flask, the temperature was raised to 140 ℃ to completely melt DOPO, 77g of o-diallylbisphenol A were added thereto, and mechanical stirring was carried out, N 2 Protecting, heating to 180 ℃, stirring at constant temperature for reaction for 16h, and obtaining a crude product after the reaction is finished; dissolving the crude intermediate product in 200mL of ethanol, precipitating in 1L of ethyl acetate, and repeatedly dissolving the precipitate for 3 times to obtain an intermediate A.
Step two: 33.3g of intermediate A, 14.8g of triglycidyl isocyanurate and 0.1g of tetrabutylammonium bromide are weighed out and dissolved in 100mL of DMF, the temperature is raised to 115 ℃ and the reaction is carried out for 6h. After the reaction is finished, precipitating the hyperbranched epoxy resin in 1L of hot water, then dissolving the mixture in ethanol, precipitating the mixture with diethyl ether for three times, and drying the mixture to obtain the hyperbranched epoxy resin. The number average molecular weight of the hyperbranched epoxy resin prepared was 9521, and the epoxy value measured by the epoxyacetone method was 0.24mol/100g.
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 90 parts of E44 epoxy resin at 140 ℃, then adding 10 parts of the hyperbranched epoxy resin prepared in the embodiment 1, uniformly stirring and cooling to 90 ℃; continuously adding 20.8 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for staged temperature rise, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Comparative example 1
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 95 parts of E51 epoxy resin at 140 ℃, then adding 5 parts of the hyperbranched epoxy resin prepared in the embodiment 1, uniformly stirring, and cooling to 90 ℃; continuously adding 25 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Comparative example 2
A condensate prepared from an epoxy resin composition is prepared by the following steps:
preheating 85 parts of E51 epoxy resin at 140 ℃, then adding 15 parts of the hyperbranched epoxy resin prepared in the embodiment 1, uniformly stirring and cooling to 90 ℃; continuing to add 23.4 parts of diaminodiphenylmethane and stirring uniformly to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for staged temperature rise, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; cooling and demolding to obtain the cured product of the modified epoxy resin.
Comparative example 3
The preparation method of the pure epoxy E51 cured product comprises the following steps:
preheating 100 parts of E51 epoxy resin at 70 ℃, then adding 25.8 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; after cooling and demoulding, the cured product of the pure epoxy resin E51 can be obtained.
Comparative example 4
The preparation method of the pure epoxy E44 cured product comprises the following steps:
preheating 100 parts of E44 epoxy resin at 70 ℃, and then adding 21.8 parts of diaminodiphenylmethane and uniformly stirring to obtain a resin prepolymer; pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at 100 ℃ for 0.5h; placing in a forced air drying oven for stage heating, and curing according to the curing procedures of 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; after cooling and demoulding, the cured product of the pure epoxy resin E44 can be obtained.
Performance testing of cured epoxy resins
The epoxy resin condensate prepared in the embodiment 1-10 and the comparative example 1-4 is subjected to related performance tests, and the bending strength is measured according to the GB/T-9341-2000 method; the impact strength is determined according to a GB/T-1843-2008 method; the thermal decomposition temperature of the cured epoxy resin is tested in a nitrogen atmosphere, and the heating rate is 10 ℃/min; t is g Is measured by DMA and has a sample size of 60X 13X 4mm 3 The temperature rise rate was 3 ℃/min, and the results of the performance test are shown in Table 1.
TABLE 1
As can be seen from Table 1, the thermal properties, mechanical properties and flame retardant properties of examples 1-10 are compared with those of comparative examples 1-4, and in different epoxy systems, the cured product has better thermal properties due to the existence of a large number of rigid structures on the main chain of the hyperbranched flame retardant; in addition, the data of tensile strength, impact strength, bending strength and fracture toughness show that when the addition content is 10wt%, the hyperbranched epoxy resin has a very good mechanical property improving effect on an epoxy system, and the mechanical property of the hyperbranched epoxy resin is better mainly based on the existence of terminal epoxy in the hyperbranched flame retardant and a large amount of flexible chains in the hyperbranched flame retardant; on the other hand, the hyperbranched flame retardant has A of phosphorus element 2 Monomers and nitrogen-containing compounds B 3 Monomer, by A 2 +B 3 The method can carry out efficient structure on the two, and the isocyanurate structure is the same as the phosphorus-containing compound, can realize double optimization of a condensed phase and a gas phase, and has excellent synergistic flame retardant effect, so that the UL-94 and LOI performance of the epoxy resin is obviously improved. The data show that the flame-retardant hyperbranched epoxy resin can modify the epoxy resin to achieve the optimal flame-retardant property and toughness, and the prepared epoxy resin with excellent performance is expected to be used for packaging electronic materials.
Claims (10)
1. The hyperbranched epoxy resin is characterized by being prepared by reacting olefin-containing binary aromatic phenol, a phosphorus-containing compound and a trifunctional epoxy compound, and the preparation method comprises the following steps:
(1) Stirring and reacting olefin-containing binary aromatic phenol and a phosphorus-containing compound at the temperature of 80-180 ℃ for 12-36h to prepare an intermediate A;
(2) And (3) stirring the intermediate A and a trifunctional epoxy compound for reaction for 5-15h at 90-130 ℃ in the presence of a catalyst to obtain the hyperbranched epoxy resin.
2. The hyperbranched epoxy resin of claim 1, wherein in step (1), the olefin-containing dihydric aromatic phenol is one or more of ortho-diallyl bisphenol A, 3 '-diallyl-4, 4' -biphenol, and magnolol; the phosphorus-containing compound is one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenyl phosphine oxide, diethyl phosphite, diphenyl phosphite and dimethyl phosphite.
3. The hyperbranched epoxy resin of claim 1, wherein in step (1), the molar ratio of the ortho-diallyl aromatic phenol to the phosphorus-containing compound is 1.
4. The hyperbranched epoxy resin of claim 1, wherein in step (2), the trifunctional epoxy compound is one or more of triglycidyl isocyanurate and triglycidyl p-aminophenol; the catalyst is one or more of triphenylphosphine, tetrabutylammonium bromide and tetrabutylammonium chloride.
5. The hyperbranched epoxy resin of claim 1, wherein in step (2), the molar ratio of the intermediate A to the trifunctional epoxy compound is 0.8-1.
6. The application of the hyperbranched epoxy resin of claim 1, which is used for preparing an epoxy resin composition for flame retarding, toughening and modifying epoxy resin.
7. An epoxy resin composition containing the hyperbranched epoxy resin of claim 1, wherein the epoxy resin composition comprises the following raw materials in parts by weight: 1-20 parts of the hyperbranched epoxy resin, 80-100 parts of bisphenol A epoxy resin and 15-30 parts of a curing agent.
8. The epoxy resin composition of claim 7, wherein the double part a epoxy resin is one or more of the bisphenol a epoxy resins E-51, E-44, and E-42.
9. The epoxy resin composition of claim 7, wherein the curing agent is one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, diaminodiphenyl ether, diphenylenediamine, o-phenylenediamine, p-xylylenediamine, and o-tolidine.
10. A cured product produced from the epoxy resin composition according to claim 7, characterized in that the method for producing the cured product comprises: preheating 80-100 parts of bisphenol A type epoxy resin at 90-140 ℃, then adding 1-20 parts of the hyperbranched epoxy resin for stirring, and cooling to 70-90 ℃ after the hyperbranched epoxy resin is completely dissolved; continuously adding 15-30 parts of curing agent and uniformly stirring to obtain a resin prepolymer;
pouring the mixture into a preheated mold, and defoaming the mixture in a vacuum oven at the temperature of 70-120 ℃ for 0.5-2h; placing in a forced air drying oven for stage heating, wherein the curing process is 110 ℃ multiplied by 1h, 120 ℃ multiplied by 1h, 140 ℃ multiplied by 2h, 160 ℃ multiplied by 2h and 180 ℃ multiplied by 2h; after cooling and demoulding, the epoxy resin condensate with strong fire resistance and good toughness is prepared.
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