CN110964176A - Preparation method of high-heat-resistance phosphorus-containing epoxy resin - Google Patents
Preparation method of high-heat-resistance phosphorus-containing epoxy resin Download PDFInfo
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Abstract
The invention discloses a preparation method of high heat-resistant phosphorus-containing epoxy resin, which is characterized by comprising the following steps: adding 50-70 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 35-50 parts by mass of diallyl dihydroxy compound and 8-15 parts by mass of bismaleimide into a reactor, heating to 80-110 ℃ under stirring to react for 1.5-3.5 h, adding 170-230 parts by mass of novolac epoxy resin, 85-105 parts by mass of bisphenol diglycidyl ether and 0.2-1 part by mass of catalyst, reacting at 120-150 ℃ for 2-5 h, heating to 160-190 ℃ to react for 4-7 h, and cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; adding 130-160 parts by mass of solvent and mixing uniformly to prepare the high heat-resistant phosphorus-containing epoxy resin solution. The high heat-resistant phosphorus-containing epoxy resin prepared by the invention is suitable for being used as matrix resin of a high heat-resistant electronic copper-clad plate, and has good performance.
Description
Technical Field
The invention belongs to the preparation of high molecular compounds, and relates to a preparation method of high heat-resistant phosphorus-containing epoxy resin. The high heat-resistant phosphorus-containing epoxy resin prepared by the invention is particularly suitable for being used as matrix resin of a high heat-resistant electronic copper-clad plate.
Background
In the flame-retardant copper-clad plate, brominated epoxy resin is generally adopted as main resin, and the product has a flame-retardant function under the action of bromine. Since the RoHS instruction and WEEE instruction issued by the European Union in 2003 formally take effect, environment-friendly products become a trend, and halogen-free flame retardance becomes the basic requirement of the copper-clad plate industry. The phosphorus-containing epoxy resin is used as an important modified halogen-free flame-retardant matrix resin, and is widely applied to the fields of electronic copper clad laminates, laminated plates, printing ink, adhesives, various composite materials and the like due to the halogen-free flame-retardant characteristic, so that the development of a preparation method of the halogen-free flame-retardant epoxy resin suitable for industrial production is of great significance.
In the prior art, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short) or a derivative thereof is mainly industrially adopted to react with quinone compounds (such as 1, 4-naphthoquinone, p-benzoquinone and the like) to generate a phosphorus-containing active hydroxyl intermediate, and then the generated intermediate and novolac epoxy resin are subjected to ring-opening reaction under the action of a catalyst to prepare the phosphorus-containing modified epoxy resin. However, quinone compounds, especially 1, 4-naphthoquinone, mainly come from import at present, domestic production is basically blank, meanwhile, along with the proposal of lead-free compatibility requirements, the eutectic point of lead-free solder is improved by more than 30 ℃, in order to ensure the welding quality, the heat resistance and reliability of the plate must be improved, and the heat resistance of the plate mainly depends on filling materials and bonding resin, so under the localization trend of key raw materials, phosphorus-containing epoxy resin without quinone structures is designed, high heat resistance halogen-free flame retardant matrix resin is developed, the requirements of no lead and no halogenation are met, and the high-temperature flame-retardant lead-free flame-retardant epoxy resin has important industrial application value.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of high-heat-resistance phosphorus-containing epoxy resin. The invention provides a preparation method of high heat-resistant phosphorus-containing epoxy resin with good product performance by redesigning the product structure, taking 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), diallyl dihydroxy compound, bismaleimide (BMI for short), novolac epoxy resin and bisphenol diglycidyl ether as raw materials, carrying out two-stage reaction under the action of a catalyst to prepare the high heat-resistant phosphorus-containing epoxy resin, and finally adding a solvent to obtain a high heat-resistant phosphorus-containing epoxy resin solution.
The content of the invention is as follows: a preparation method of high heat-resistant phosphorus-containing epoxy resin is characterized by comprising the following steps: adding 50-70 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 35-50 parts by mass of diallyl dihydroxy compound and 8-15 parts by mass of bismaleimide into a reactor, heating to 80-110 ℃ under stirring, keeping the temperature to react for 1.5-3.5 h, then adding 170-230 parts by mass of novolac epoxy resin, 85-105 parts by mass of bisphenol diglycidyl ether and 0.2-1 part by mass of catalyst, reacting for 2-5 h at 120-150 ℃ (heat preservation), heating to 160-190 ℃ (heat preservation) to react for 4-7 h, and then cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; dropwise adding 130-160 parts by mass of solvent and uniformly mixing to prepare high-heat-resistance phosphorus-containing epoxy resin solution;
the diallyl dihydroxy compound can be one or a mixture of two of diallyl bisphenol A, diallyl bisphenol F and 2, 2-diallyl bisphenol biphenyl;
the bismaleimide can be one or a mixture of two of 4, 4-diaminodiphenylmethane bismaleimide, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide;
the catalyst can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethyl benzyl ammonium chloride and tetrabutyl ammonium bromide.
The invention comprises the following steps: the novolac epoxy can be one or a mixture of more than two of phenol novolac epoxy, o-cresol novolac epoxy, DCPD (dicyclopentadiene) phenol novolac epoxy, bisphenol A novolac epoxy and trifunctional novolac epoxy. The provided production enterprises of the novolac epoxy include southern Asia Plastic industry Co., Ltd, Shandong Laiwu Runda New Material Co., Ltd, Shandong De Yuan epoxy technology Co., Ltd, and the like.
The invention comprises the following steps: the bisphenol type diglycidyl ether can be one or a mixture of two of bisphenol A type diglycidyl ether and bisphenol F type diglycidyl ether. The provided enterprises for producing bisphenol diglycidyl ether include southern Asia plastics industry Co., Ltd, Shandong Laiwu Runda New Material Co., Ltd, and Guo Du chemical industry (Kunshan) Co., Ltd.
The invention comprises the following steps: the solvent can be one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (a mixture in any proportion), and a mixture of acetone and propylene glycol methyl ether (a mixture in any proportion).
The invention comprises the following steps: the materialization data of the prepared high heat-resistant phosphorus-containing epoxy resin solution are as follows: the solid content is 74-76%, the viscosity is 1500-5000 mPa.s, the epoxy equivalent is 400-500 g/eq, the phosphorus content is 1.6-2.7%, the glass transition temperature is 148-155 ℃, and the liquid is a light orange yellow to light reddish brown transparent liquid.
The chemical structural general formula of the high heat-resistant phosphorus-containing epoxy resin is as follows:
in the formula: a is
And m is 1-15, wherein: r is CH2、C(CH3)2、
And n is 1 to 10 or
And z is 1 to 5, R1Is H or CH3，R2Is H or CH3；
A1is-CH ═ CH2、
Or
A2is-CH ═ CH2、
Or
The molecular weight of the high heat-resistant phosphorus-containing epoxy resin is 600-2000.
The definition of "amount of solids" as described herein in the present invention is: 1g of a sample (i.e., a high heat-resistant phosphorus-containing epoxy resin solution) was baked in an oven at 160 ℃ for 1 hour, and the mass of the non-volatile matter was calculated as a percentage of the total mass, and the amount of solid finally determined by the mass blending of the added solvent was calculated based on the mass of the non-volatile matter.
The definition of "phosphorus content" as described herein is: the content of the phosphorus element accounts for the percentage of the total solid mass of the high heat-resistant phosphorus-containing epoxy resin.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the invention adopts a prepolymer of a diallyl dihydroxy compound and bismaleimide reaction as a precursor, DOPO as a phosphorus source, prepares a phosphorus-containing intermediate through an addition reaction, introduces an aromatic heterocyclic rigid structure through the body, and greatly improves the glass transition temperature of the material;
(2) the invention adopts diallyl dihydroxy compounds to replace 1, 4-naphthoquinone, avoids introducing quinone chromogenic substances, and has the characteristic of light color under the condition of ensuring the excellent performances of high heat resistance, halogen-free flame retardance;
(3) the preparation process is simple, and the prepared high heat-resistant phosphorus-containing epoxy resin (solution) has good performance, excellent heat resistance, flame retardance and flexibility, is an environment-friendly flame retardant material, and has the characteristics of environmental friendliness, simplicity and convenience in operation, high reaction speed and strong practicability.
Drawings
FIG. 1 is an IR spectrum of a high heat-resistant phosphorus-containing epoxy resin solution prepared in example 1: 3375cm-1Is absorption peak of O-H, 3060cm-12922cm is the absorption peak of C-H on the benzene ring-1Absorption peak of methylene, 1710cm-1Is the absorption peak of C ═ O on the maleimide ring, 1607cm-1、1509cm-1Is the absorption peak of C ═ C，1451cm-1Is the absorption peak of P-Ph, 1241cm-1Is the absorption peak of P ═ O, 1181cm-1Is the absorption peak of P-O-Ph, 1033cm-1An absorption peak of C-O, 912cm-1Is the absorption peak of the chain-end epoxy group; the figure shows that the molecular chain of the prepared high heat-resistant phosphorus-containing epoxy resin introduces a bismaleimide structure and a DOPO structure.
FIG. 2 is a DSC (differential scanning calorimeter in Chinese meaning of DSC) spectrum of the highly thermostable phosphorous epoxy resin solution obtained in example 1: 152.9 ℃ is the glass transition temperature (Tg) of the cured resin, and the glue blending mode of the cured resin is as follows: resin: dicyandiamide: 2-methylimidazole (100: 3: 0.3) in mass ratio, and the curing procedure is 120 ℃ for 1h, 140 ℃ for 1h and 160 ℃ for 2 h; the figure shows that the Tg of the cured product of the prepared high heat-resistant phosphorus-containing epoxy resin is as high as 152.9 ℃ after the curing, and the cured product has higher glass transition temperature.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 50kg of DOPO, 38kg of diallyl bisphenol A and 8.5kg of 4, 4-diaminodiphenylmethane bismaleimide into a reactor, heating to 100 ℃ under stirring, keeping the temperature for reaction for 2 hours, then adding 170kg of novolac epoxy 638S, 85kg of bisphenol diglycidyl ether E54 and 0.2kg of catalyst triethylbenzyl ammonium chloride, carrying out heat preservation reaction for 3 hours at 130 ℃, heating to 170 ℃ for heat preservation reaction for 6 hours, cooling, and dropwise adding 130kg of butanone to prepare the high-heat-resistance phosphorus-containing epoxy resin solution. Phosphorus content 1.93%, glass transition temperature 154 ℃.
Example 2:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: 69kg of DOPO, 49kg of 2, 2-diallyl bisphenol biphenyl and 10.5kg of 4, 4-diaminodiphenylmethane bismaleimide are added into a reactor, the temperature is raised to 100 ℃ under stirring, the temperature is maintained, the reaction is carried out for 3 hours, then 190kg of novolac epoxy resin F51, 90kg of bisphenol diglycidyl ether E51 and 0.3kg of catalyst triphenylphosphine are added, after the reaction is carried out for 4 hours at the temperature of 120 ℃, the temperature is raised to 175 ℃, the reaction is carried out for 5 hours at the temperature, then the cooling is carried out, and 135kg of butanone is dropwise added, thus obtaining the high heat-resistant phosphorus-containing epoxy resin solution. Phosphorus content 2.42%, glass transition temperature 152 ℃.
Example 3:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: 70kg of DOPO, 49kg of diallyl bisphenol F, 15kg of 3, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide are added into a reactor, the temperature is raised to 100 ℃ under stirring, the temperature is maintained, the reaction is carried out for 2.5 hours, then 190kg of novolac epoxy resin NPCN704, 94kg of bisphenol diglycidyl ether NPEF170 and 0.4kg of catalyst imidazole are added, the temperature is raised to 165 ℃ after the reaction is carried out for 2 hours under the condition of heat preservation at 140 ℃, the reaction is carried out for 8 hours under the condition of heat preservation, then the cooling is carried out, and 140kg of butanone is dropwise added, thus obtaining the high heat-resistant phosphorus-containing epoxy resin solution. Phosphorus content 2.42%, glass transition temperature 155 ℃.
Example 4:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 54kg of DOPO, 35kg of 2, 2-diallyl bisphenol biphenyl, 8kg of 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide into a reactor, heating to 110 ℃ under stirring, keeping the temperature for reaction for 2 hours, then adding 90kg of novolac epoxy resin 638S, 95kg of novolac epoxy resin F51, 105kg of bisphenol diglycidyl ether E51 and 1kg of catalyst triphenyl phosphate, heating to 180 ℃ for reaction for 7 hours after reaction for 2 hours at 120 ℃, then cooling, and dropwise adding 130kg of acetone and propylene glycol methyl ether mixed solvent to prepare the high heat-resistant phosphorus-containing epoxy resin solution. Phosphorus content 2.00% and glass transition temperature 152 ℃.
Example 5:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: 66kg of DOPO, 22kg of diallyl bisphenol F, 25kg of 2, 2-diallyl bisphenol biphenyl, 11kg of 3, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide are added into a reactor, the temperature is raised to 90 ℃ under stirring, the temperature is maintained, reaction is carried out for 3.5h, then 185kg of novolac epoxy resin NPCN704, 80kg of bisphenol diglycidyl ether E51 and 20kg of bisphenol diglycidyl ether E54 are added, 0.4kg of catalyst triphenylphosphine and 0.1kg of catalyst tetrabutylammonium bromide are added, after the reaction is carried out for 3h under the condition of 140 ℃, the temperature is raised to 170 ℃ for the reaction under the condition of 5h under the condition of heat preservation, then cooling is carried out, 135kg of acetone solvent is dripped, and the high-heat-resistant phosphorus-containing epoxy resin solution is prepared. Phosphorus content 2.32%, glass transition temperature 148 ℃.
Example 6:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: 58kg of DOPO, 50kg of diallyl bisphenol F, 5kg of 3, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 8kg of 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide are added into a reactor, the temperature is raised to 110 ℃ under stirring, the temperature is maintained, the reaction is carried out for 2.5h, then 120kg of novolac epoxy resin F51, 75kg of novolac epoxy resin NPCN704, 95kg of bisphenol diglycidyl ether NPEF170, 0.2-1 kg of catalyst tetrabutylammonium bromide imidazole and 0.1kg of catalyst triphenyl phosphate are added, the temperature is raised to 185 ℃ after the reaction is carried out for 4.5h at 150 ℃, the reaction is carried out for 6h at the temperature, then the cooling is carried out, and 135kg of acetone solvent is dripped, so that the high-heat-resistant phosphorus-containing epoxy resin solution is prepared. Phosphorus content 2.03%, glass transition temperature 149 ℃.
Example 7:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 62kg of DOPO, 25kg of diallyl bisphenol A, 21kg of diallyl bisphenol F and 15kg of 4, 4-diaminodiphenylmethane bismaleimide into a reactor, heating to 95 ℃ under stirring, keeping the temperature for reaction for 2 hours, then adding 160kg of novolac epoxy 638S, 45kg of novolac epoxy NPCN704, 100kg of bisphenol diglycidyl ether E51, 0.2kg of catalyst imidazole and 0.3kg of catalyst triphenylphosphine, heating to 177 ℃ after carrying out heat preservation reaction for 4 hours at 125 ℃, carrying out heat preservation reaction for 4.5 hours, then cooling, and dropwise adding 142kg of butanone and propylene glycol methyl ether mixed solvent to prepare the high-heat-resistance phosphorus-containing epoxy resin solution. Phosphorus content 2.08%, glass transition temperature 150 ℃.
Example 8:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: 65kg of DOPO, 15kg of diallyl bisphenol A, 35kg of diallyl bisphenol F, 8kg of 4, 4-diaminodiphenylmethane bismaleimide and 5kg of 3, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide are added into a reactor, the temperature is raised to 100 ℃ under stirring, the temperature is maintained, reaction is carried out for 3.5h, then 200kg of novolac epoxy resin 638S and 30kg of novolac epoxy resin F51, 50kg of bisphenol diglycidyl ether E51, 50kg of bisphenol diglycidyl ether NPEF170 and 0.4kg of catalyst imidazole are added, after the temperature is kept at 135 ℃ for 5h, the temperature is raised to 190 ℃ for heat preservation reaction for 6.5h, then cooling is carried out, and 152kg of acetone and propylene glycol methyl ether mixed solvent is dripped to prepare the high-heat-resistant phosphorus-containing epoxy resin solution. Phosphorus content 2.04%, glass transition temperature 151 ℃.
Example 9:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 50 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 35 parts by mass of diallyl dihydroxy compound and 8 parts by mass of bismaleimide into a reactor, heating to 80 ℃ under stirring, keeping the temperature for reaction for 3.5 hours, then adding 170 parts by mass of novolac epoxy resin, 85 parts by mass of bisphenol diglycidyl ether and 0.2 part by mass of catalyst, reacting for 5 hours at 120 ℃ (heat preservation), heating to 160 ℃ (heat preservation for reaction for 7 hours, and then cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; then dripping 117 parts by mass of solvent and mixing uniformly to prepare high heat-resistant phosphorus-containing epoxy resin solution;
the diallyl dihydroxy compound is one or a mixture of two of diallyl bisphenol A, diallyl bisphenol F and 2, 2-diallyl bisphenol biphenyl;
the bismaleimide is one or a mixture of two of 4, 4-diaminodiphenylmethane bismaleimide, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide;
the catalyst is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethyl benzyl ammonium chloride and tetrabutyl ammonium bromide.
Example 10:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 70 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 50 parts by mass of diallyl dihydroxy compound and 15 parts by mass of bismaleimide into a reactor, heating to 110 ℃ under stirring, keeping the temperature for reaction for 1.5h, then adding 190 parts by mass of novolac epoxy resin, 95 parts by mass of bisphenol diglycidyl ether and 1 part by mass of catalyst, reacting for 2h at 150 ℃ (heat preservation), heating to 190 ℃ (heat preservation for reaction for 4h, and then cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; then dripping 160 parts by mass of solvent and mixing uniformly to prepare high heat-resistant phosphorus-containing epoxy resin solution;
the diallyl dihydroxy compound is one or a mixture of two of diallyl bisphenol A, diallyl bisphenol F and 2, 2-diallyl bisphenol biphenyl;
the bismaleimide is one or a mixture of two of 4, 4-diaminodiphenylmethane bismaleimide, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide;
the catalyst is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethyl benzyl ammonium chloride and tetrabutyl ammonium bromide.
Example 11:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 60 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 43 parts by mass of diallyl dihydroxy compound and 12 parts by mass of bismaleimide into a reactor, heating to 95 ℃ under stirring, keeping the temperature for reaction for 2.5 hours, then adding 200 parts by mass of novolac epoxy resin, 95 parts by mass of bisphenol diglycidyl ether and 0.6 part by mass of catalyst, reacting for 3.5 hours at 135 ℃ (heat preservation), heating to 175 ℃ (heat preservation) for reaction for 5.5 hours, and then cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; then dripping 136 parts by mass of solvent and mixing uniformly to prepare high heat-resistant phosphorus-containing epoxy resin solution;
the diallyl dihydroxy compound is one or a mixture of two of diallyl bisphenol A, diallyl bisphenol F and 2, 2-diallyl bisphenol biphenyl;
the bismaleimide is one or a mixture of two of 4, 4-diaminodiphenylmethane bismaleimide, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide;
the catalyst is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethyl benzyl ammonium chloride and tetrabutyl ammonium bromide.
Example 12:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 55 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 38 parts by mass of diallyl dihydroxy compound and 11 parts by mass of bismaleimide into a reactor, heating to 90 ℃ under stirring, keeping the temperature for reaction for 3 hours, then adding 180 parts by mass of novolac epoxy resin, 90 parts by mass of bisphenol diglycidyl ether and 0.4 part by mass of catalyst, reacting for 4 hours at 129 ℃ (heat preservation), heating to 170 ℃ (heat preservation for reaction for 6 hours, and then cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; dripping 125 parts by mass of solvent and mixing uniformly to prepare high heat-resistant phosphorus-containing epoxy resin solution;
the diallyl dihydroxy compound is one or a mixture of two of diallyl bisphenol A, diallyl bisphenol F and 2, 2-diallyl bisphenol biphenyl;
the bismaleimide is one or a mixture of two of 4, 4-diaminodiphenylmethane bismaleimide, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide;
the catalyst is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethyl benzyl ammonium chloride and tetrabutyl ammonium bromide.
Example 13:
a preparation method of high heat-resistant phosphorus-containing epoxy resin comprises the following steps: adding 65 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 46 parts by mass of diallyl dihydroxy compound and 13 parts by mass of bismaleimide into a reactor, heating to 105 ℃ under stirring, keeping the temperature for reaction for 2.5 hours, then adding 215 parts by mass of novolac epoxy resin, 100 parts by mass of bisphenol diglycidyl ether and 0.8 part by mass of catalyst, reacting for 3 hours at 145 ℃ (heat preservation), then heating to 180 ℃ (heat preservation) for reaction for 5 hours, and then cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; then dripping 147 parts by mass of solvent and mixing uniformly to prepare high heat-resistant phosphorus-containing epoxy resin solution;
the diallyl dihydroxy compound is one or a mixture of two of diallyl bisphenol A, diallyl bisphenol F and 2, 2-diallyl bisphenol biphenyl;
the bismaleimide is one or a mixture of two of 4, 4-diaminodiphenylmethane bismaleimide, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide;
the catalyst is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethyl benzyl ammonium chloride and tetrabutyl ammonium bromide.
In examples 9 to 13 above: the novolac epoxy is one or a mixture of more than two of phenol novolac epoxy, o-cresol novolac epoxy, DCPD phenol novolac epoxy, bisphenol A novolac epoxy and trifunctional novolac epoxy. The provided production enterprises of the novolac epoxy include southern Asia Plastic industry Co., Ltd, Shandong Laiwu Runda New Material Co., Ltd, Shandong De Yuan epoxy technology Co., Ltd, and the like.
In examples 9 to 13 above: the bisphenol type diglycidyl ether is one or a mixture of two of bisphenol A type diglycidyl ether and bisphenol F type diglycidyl ether. The provided enterprises for producing bisphenol diglycidyl ether include southern Asia plastics industry Co., Ltd, Shandong Laiwu Runda New Material Co., Ltd, and Guo Du chemical industry (Kunshan) Co., Ltd.
In examples 9 to 13 above: the solvent can be one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (a mixture in any proportion), and a mixture of acetone and propylene glycol methyl ether (a mixture in any proportion).
In examples 9 to 13 above: the materialization data of the prepared high-heat-resistance phosphorus-containing epoxy resin solution are in the following ranges: the solid content is 74-76%, the viscosity is 1500-5000 mPa.s, the epoxy equivalent is 400-500 g/eq, the phosphorus content is 1.6-2.7%, the glass transition temperature is 148-155 ℃, and the liquid is a light orange yellow to light reddish brown transparent liquid.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the mass (weight) parts are all grams or kilograms.
In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (6)
1. A preparation method of high heat-resistant phosphorus-containing epoxy resin is characterized by comprising the following steps: adding 50-70 parts by mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 35-50 parts by mass of diallyl dihydroxy compound and 8-15 parts by mass of bismaleimide into a reactor, heating to 80-110 ℃ under stirring, keeping the temperature to react for 1.5-3.5 h, then adding 170-230 parts by mass of novolac epoxy resin, 85-105 parts by mass of bisphenol diglycidyl ether and 0.2-1 part by mass of catalyst, reacting at 120-150 ℃ for 2-5 h, heating to 160-190 ℃ to react for 4-7 h, and then cooling to obtain the high heat-resistant phosphorus-containing epoxy resin; dropwise adding 130-160 parts by mass of solvent and uniformly mixing to prepare high-heat-resistance phosphorus-containing epoxy resin solution;
the diallyl dihydroxy compound is one or a mixture of two of diallyl bisphenol A, diallyl bisphenol F and 2, 2-diallyl bisphenol biphenyl;
the bismaleimide is one or a mixture of two of 4, 4-diaminodiphenylmethane bismaleimide, 3-diethyl-4, 4-diaminodiphenylmethane bismaleimide and 3, 3-dimethyl-4, 4-diaminodiphenylmethane bismaleimide;
the catalyst is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethyl benzyl ammonium chloride and tetrabutyl ammonium bromide.
2. The process for preparing phosphorus-containing epoxy resin with high heat resistance as claimed in claim 1, wherein: the novolac epoxy is one or a mixture of more than two of phenol novolac epoxy, o-cresol novolac epoxy, DCPD phenol novolac epoxy, bisphenol A novolac epoxy and trifunctional novolac epoxy.
3. The process for preparing a phosphorus-containing epoxy resin having high heat resistance as claimed in claim 1 or 2, wherein: the bisphenol type diglycidyl ether is one or a mixture of two of bisphenol A type diglycidyl ether and bisphenol F type diglycidyl ether.
4. The process for preparing a phosphorus-containing epoxy resin having high heat resistance as claimed in claim 1 or 2, wherein: the solvent is one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether, and a mixture of acetone and propylene glycol methyl ether.
5. The process for preparing phosphorus-containing epoxy resin with high heat resistance as claimed in claim 3, wherein: the solvent can be one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether, and a mixture of acetone and propylene glycol methyl ether.
6. The process for preparing a phosphorus-containing epoxy resin having high heat resistance as claimed in claim 1, 2 or 5, wherein: the materialization data of the prepared high heat-resistant phosphorus-containing epoxy resin solution are as follows: 74 to 76 percent of solid, 1500 to 5000 mPa.s of viscosity, 400 to 500g/eq of epoxy equivalent, 1.6 to 2.7 percent of phosphorus content and 148 to 155 percent of glass transition temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679700A (en) * | 2020-12-23 | 2021-04-20 | 江苏东材新材料有限责任公司 | Preparation method of high-heat-resistance brominated epoxy resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911345A (en) * | 2012-10-19 | 2013-02-06 | 株洲时代新材料科技股份有限公司 | Preparation method and application of epoxy resin adhesive |
| CN103627146A (en) * | 2013-11-08 | 2014-03-12 | 建滔（江苏）化工有限公司 | Preparation and application of high-flexibility phosphorus-containing halogen-free epoxy resin |
| CN107009651A (en) * | 2017-03-23 | 2017-08-04 | 苏州苏绝电工材料股份有限公司 | The technique that halogen-free flameproof span epoxy adhesive produces glass cloth laminated board |
| US20190202168A1 (en) * | 2018-01-02 | 2019-07-04 | Iteq Corporation | Laminated substrate |
-
2019
- 2019-12-18 CN CN201911305555.6A patent/CN110964176A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911345A (en) * | 2012-10-19 | 2013-02-06 | 株洲时代新材料科技股份有限公司 | Preparation method and application of epoxy resin adhesive |
| CN103627146A (en) * | 2013-11-08 | 2014-03-12 | 建滔（江苏）化工有限公司 | Preparation and application of high-flexibility phosphorus-containing halogen-free epoxy resin |
| CN107009651A (en) * | 2017-03-23 | 2017-08-04 | 苏州苏绝电工材料股份有限公司 | The technique that halogen-free flameproof span epoxy adhesive produces glass cloth laminated board |
| US20190202168A1 (en) * | 2018-01-02 | 2019-07-04 | Iteq Corporation | Laminated substrate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679700A (en) * | 2020-12-23 | 2021-04-20 | 江苏东材新材料有限责任公司 | Preparation method of high-heat-resistance brominated epoxy resin |
| CN112679700B (en) * | 2020-12-23 | 2023-01-20 | 江苏东材新材料有限责任公司 | Preparation method of high-heat-resistance brominated epoxy resin |
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