CN109320688B - High-temperature-resistant hyperbranched epoxy resin and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of epoxy resin, and particularly discloses high-temperature-resistant hyperbranched epoxy resin and a preparation method thereof, wherein the high-temperature-resistant hyperbranched epoxy resin comprises the following steps: dicarboxylic imide compound and trihydroxy compound are reacted to prepare carboxyl-terminated or hydroxyl-terminated hyperbranched polymer, then the carboxyl-terminated or hydroxyl-terminated hyperbranched polymer and epoxy chloropropane are reacted under the action of a ring-opening catalyst to obtain an addition product, and the obtained addition product is subjected to ring-closing reaction in an organic solvent and under the action of a basic catalyst to generate the high-temperature-resistant hyperbranched epoxy resin, the molecular weight of which is 1800 ion-crosslinked and 29000 g/mol. The invention has simple process, and the product has the functions of low viscosity, high temperature resistance and self-reinforcement and toughening, and is expected to be used in the fields of reinforcement and toughening of epoxy resin, electronic packaging, solvent-free high temperature resistant coating and the like.
Description
Technical Field
The invention relates to the technical field of hyperbranched epoxy resin and a preparation method thereof, in particular to high-temperature-resistant hyperbranched epoxy resin and a preparation method thereof.
Background
The research on the synthesis of hyperbranched epoxy resin originated from 1993, and PCT international application patent (WO9317060) discloses that aliphatic sulfur-containing hyperbranched epoxy resin with high viscosity can be synthesized by using dimethylolpropionic acid as a raw material and reacting trimethylolpropane with epichlorohydrin. The inventor of the application (Zhanghong) invents nitrogen heterocyclic hyperbranched epoxy resin, silicon skeleton hyperbranched epoxy resin and degradable hyperbranched epoxy resin (ZL200910029024.9, ZL200910029026.8, ZL200910062871.5, ZL201010224451.5 and ZL201510855381.6) with high heat resistance temperature. In addition, the reported preparation technology (esterification reaction, hydrosilylation reaction, grafting reaction and group transfer polymerization reaction) of the sulfur-containing hyperbranched epoxy resin has low efficiency, low yield, long reaction time, high energy consumption, high curing temperature and long curing time. Therefore, the inventor of the application finds a process technology for preparing the sulfur-containing epoxy resin (ZL201310091452.0) and the sulfur-containing hyperbranched epoxy resin (ZL201210566173.0) by using a thiol-olefin click reaction, and improves the preparation efficiency. The heat resistance of the epoxy resin prepared by all the prior art technologies is still not high, the glass transition temperature is not high, the requirement of aerospace high-temperature-resistant resin is difficult to meet, and the development of the epoxy resin in structural materials and aerospace composite materials is inhibited. Therefore, the development of a preparation technology of the high-temperature resistant hyperbranched epoxy resin with simple process is a fundamental way for solving the problems existing in the field at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel high-temperature-resistant hyperbranched epoxy resin, which has the following structural formula:
wherein R is4The structure of (1) is as follows:
R1and
oxygen at the left end;
R5the structure of (1) is as follows:
in the formula, R1The chemical structure of a trihydroxy compound after hydrogen atoms on three hydroxyl groups are removed;
in the formula, R2The structure of (1) is as follows:
wherein n is 1 or 2;
R3the structure of (1) is as follows: -CH2(CH2)j-、
Or
Wherein j is 1, 2, 3, 4 or 5.
Further, the trihydroxy compound is trimethylolpropane, tris (2-hydroxyethyl) isocyanurate or glycerol.
The invention also aims to provide a preparation method of the high-temperature-resistant hyperbranched epoxy resin with the structural formula, and the reaction formula of the whole process is as follows:
and m is 6, 12, 24 or 48.
In order to further illustrate the reaction formula of the whole process, the preparation method comprises the following specific steps:
(a) uniformly mixing bismaleimide, a sulfhydryl compound, a photoinitiator and an organic solvent chloroform, carrying out an ultraviolet illumination reaction for 10-20 minutes at room temperature, wherein the power of ultraviolet light is 800-1200W, and after the reaction is finished, vacuum-pumping out the organic solvent chloroform to obtain the dicarboxyimide compound (A)2Monomers);
the dosage ratio of the bismaleimide, the sulfhydryl compound and the photoinitiator is 1mol to 5mol, preferably 1mol to 2.5mol to 5 g.
The mercapto compound is thioglycolic acid or mercaptopropionic acid, preferably thioglycolic acid or 3-mercaptopropionic acid;
(b) reacting a dicarboxylic imide compound (A)2Monomer), trihydroxy compound (B)3Uniformly mixing the monomer), the organic solvent A and the esterification reaction catalyst, stirring and reacting for 10-16h at 140-180 ℃, and then vacuumizing to remove the organic solvent to obtain a carboxyl-terminated or hydroxyl-terminated hyperbranched polymer;
the bismaleimide is N, N '- (4,4' -methylene diphenyl) bismaleimide, diaminodiphenyl ether bismaleimide or 1, 6-bismaleimidohexane;
the chemical structure of the dicarboxyimide compound is:
wherein R is3The structure of (1) is as follows: -CH2(CH2)j-、
Wherein j is 1, 2, 3, 4 or 5, and n is 1 or 2;
the trihydroxy compound is trimethylolpropane, tris (2-hydroxyethyl) isocyanurate or glycerol;
the esterification reaction catalyst is one or more than two of p-methyl benzene sulfonic acid, methanesulfonic acid, phosphoric acid, tetrabutyl titanate, zinc acetate and tetrapropyl titanate.
(c) Stirring and reacting carboxyl-terminated or hydroxyl-terminated hyperbranched polymer and epoxy chloropropane at 120-140 ℃ for 3-5 hours in the presence of an open-loop reaction catalyst, then vacuumizing excess epoxy chloropropane, adding an organic solvent B and an alkaline catalyst, stirring and reacting at-5-30 ℃ for 6-10 hours, stopping the reaction, layering, washing an organic layer to be neutral, and distilling to remove the organic solvent B to obtain the high-temperature-resistant hyperbranched epoxy resin with the molecular weight of about 1800 plus 29000 g/mol;
the ring-opening reaction catalyst is one or more than two of tetrabutylammonium bromide, hexadecyltrimethylammonium bromide, hexadecyltriethylammonium bromide, sodium hydroxide and potassium hydroxide.
Further, in the step (a), the photoinitiator is (2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone).
Further, the molar ratio of the dicarboximide compound, the trihydroxy compound and the organic solvent A in the step (b) is 1: (0.40-2.0): (0.5 to 4.0), preferably 1: (0.40-1.5): (0.5 to 3.1).
Further, in the step (b), the organic solvent A is one or more than two of xylene, N-methylpyrrolidone, dimethylformamide and dimethylacetamide.
Furthermore, the mass of the esterification reaction catalyst is 0.2 to 1.5 percent of the total mass of the dicarboxyimide compound and the trihydroxy compound.
Furthermore, the molar ratio of the carboxyl or hydroxyl in the carboxyl-terminated or hydroxyl-terminated hyperbranched polymer in the step (c), epichlorohydrin to the ring-opening reaction catalyst is 1 (2-10) to (0.005-0.1).
Further, the basic catalyst in the step (c) is sodium hydroxide and/or potassium hydroxide, and the molar ratio of the carboxyl or hydroxyl in the carboxyl-terminated or hydroxyl-terminated hyperbranched polymer to the basic catalyst is 1 (0.1-10), preferably 1 (0.2-8).
Further, in the step (c), the organic solvent B is one or more than two of tetrahydrofuran, ethyl acetate, dioxane and butyl acetate, and the using amount of the organic solvent B is 0.5-1.5 times of the mole number of the epoxy chloropropane.
The high-temperature resistant hyperbranched epoxy resin prepared by the invention has the advantages of lower viscosity, high temperature resistance and the like, and is expected to be applied to the fields of environment-friendly adhesives, environment-friendly low-volatility coatings, low-volatility resins, reinforcing and toughening of epoxy resins and the like.
Compared with the prior art, the technical scheme of the invention has the following advantages and beneficial effects:
1. according to the invention, an imide structure is introduced into a hyperbranched epoxy resin structure, so that the high-temperature resistance function of the epoxy resin can be realized;
2. the dicarboxyimide compound is prepared by a mercapto compound-olefin click ultraviolet reaction technology, and has the advantages of simple preparation process, high yield, short reaction time, little pollution and low cost;
3. the high-temperature-resistant hyperbranched epoxy resin has the characteristic of high temperature resistance, has the function of remarkably improving the glass transition temperature for common epoxy resin, and is expected to be widely applied to the field of aerospace high-temperature-resistant composite materials;
4. the high-temperature-resistant hyperbranched epoxy resin has the advantages of hyperbranched polymers, has the functions of strengthening and toughening common epoxy resin, and is expected to be widely applied to the field of strengthening and toughening of epoxy resin;
5. the high-temperature resistant hyperbranched epoxy resin has simple preparation process and low raw material cost, and is suitable for industrial production;
6. the high-temperature resistant hyperbranched epoxy resin disclosed by the invention is low in viscosity, can be obviously reduced when being added into bisphenol A type epoxy resin, plays a role of an active diluent, and is expected to be applied to the field of solvent-free and low-volatility epoxy resin coatings.
Detailed Description
The present invention is described in detail below with reference to specific examples, but these examples should not be construed as limiting the scope of the present invention in any way.
The molecular weight of the product was determined by GPC from PL, UK, the epoxy value was determined by the national standard acetone hydrochloride method, and the viscosity was determined by Brookfield viscometer at 25 ℃.
The following examples 1, 6-bismaleimidohexane were prepared according to the methods in the literature (insulating material, 2014,47(3):8-12), and diaminodiphenylether bismaleimide was prepared according to the methods in the literature (insulating material, 2008,41(2): 19-21).
Dicarboxyimide compound (A)2The monomer is prepared by the following steps of,
) The preparation method is self-made by the inventor of the application and comprises the following specific preparation processes:
0.1mol of N, N '- (4,4' -methylenediphenyl) Bismaleimide (BMI), 0.25mol of thioglycolic acid and 0.5g of photoinitiator 2-methyl-1- [4- (methylthio) phenyl]Uniformly mixing (E) -2- (4-morpholinyl) -1-acetone and 100mL of chloroform, carrying out ultraviolet illumination reaction for 15 minutes at room temperature, wherein the power of ultraviolet light is 1000W, and after the reaction is finished, carrying out rotary evaporation and vacuum extraction on organic solvent chloroform and excessive mercaptoacetic acid under the conditions that the vacuum degree is 2-3mmHg and the temperature is 80-100 ℃ to obtain the dicarboximide compound (A)2Monomer) powder(s) of a monomer,the yield was about 80%. The monomer is marked A2-01, the remaining dicarboximide compounds are obtained in the same way, with yields of between 70 and 90%, by simply replacing the starting materials, the corresponding compounds are marked A2-02(0.1mol BMI and 0.25mol 3-mercaptopropionic acid starting materials), A2-03(0.1mol 1, 6-bismaleimidohexane and 0.25mol 3-mercaptopropionic acid starting materials), A2-04(0.1mol diaminodiphenyl ether bismaleimide and 0.25mol 3-mercaptopropionic acid starting materials).
Embodiment 1 a high temperature resistant hyperbranched epoxy resin, the preparation method steps are as follows:
(a) 0.20mol of Trimethylolpropane (TMP), 0.15mol of dicarboximide compound (A2-01), 0.15mol of xylene and zinc acetate (the mass of the zinc acetate is 0.5 percent of the total mass of the TMP and the A2-01 percent) are uniformly mixed, stirred and reacted for 10 hours at 180 ℃, and then the xylene is removed by vacuumizing at 110 ℃ to obtain hydroxyl-terminated hyperbranched polymer (HHBP-06, containing 6mol of hydroxyl per mol of HHBP-06) with the number average molecular weight of about 1500 g/mol.
(b) Adding 0.01mol of HHBP-06, 0.12mol of epoxy chloropropane and 0.006mol of tetrabutylammonium bromide into a three-neck flask, stirring and reacting at about 120 ℃ for 5 hours, then vacuum-pumping out excessive epoxy chloropropane, adding 0.06mol of tetrahydrofuran and 0.012mol of sodium hydroxide into the three-neck flask, stirring and reacting at-5-0 ℃ for 8 hours, stopping the reaction, standing and layering, washing an organic layer to be neutral by water, and distilling to remove the tetrahydrofuran which is an organic solvent to obtain the hyperbranched epoxy resin (the 1 st structure in claim 1, EP HH-06), wherein the number average molecular weight is about 1800g/mol, the viscosity is 6000cp and the epoxy value is 0.30mol/100 g.
Embodiment 2a high temperature resistant hyperbranched epoxy resin, which is prepared by the following steps:
(a) 0.23mol of tris (2-hydroxyethyl) isocyanurate (THEIC), 0.225mol of dicarboximide compound (A2-02), 0.69mol of xylene and tetrapropyl titanate (the mass of tetrapropyl titanate is 1.0% of the total mass of THEIC and A2-02) are mixed uniformly, stirred and reacted at 140 ℃ for 16h, and then xylene is removed by vacuum pumping at 100 ℃ to obtain hydroxyl-terminated hyperbranched polymer (HHBP-48 containing 48mol of hydroxyl groups per mol of HHBP-48) with the number average molecular weight of about 27000 g/mol.
(b) Adding 0.01mol of HHBP-48, 1.92mol of epoxy chloropropane and 0.0024mol of hexadecyl triethyl ammonium bromide into a three-neck flask, stirring and reacting for 4 hours at about 130 ℃, then extracting excessive epoxy chloropropane in vacuum, adding 1.92mol of ethyl acetate and 0.096mol of potassium hydroxide into the three-neck flask, stirring and reacting for 6 hours at 5-10 ℃, stopping the reaction, standing and layering, washing an organic layer to be neutral, distilling to remove the organic solvent of the ethyl acetate to obtain the hyperbranched epoxy resin (HHEP-48, the 4 th structure in claim 1), wherein the number average molecular weight is about 29000g/mol, the viscosity is 12000cp, and the epoxy value is 0.14mol/100 g.
Embodiment 3 a high temperature resistant hyperbranched epoxy resin, which is prepared by the following steps:
(a) 0.04mol of tris (2-hydroxyethyl) isocyanurate (THEIC), 0.09mol of dicarboximide compound (A2-03), 0.06mol of xylene, 0.02mol of N-methylpyrrolidone and tetrabutyl titanate (the mass of tetrabutyl titanate is 1.5 percent of the total mass of THEIC and A2-03) are uniformly mixed, stirred and reacted at 160 ℃ for 14 hours, and then the xylene and the N-methylpyrrolidone are removed by vacuum pumping at 120 ℃ to obtain carboxyl-terminated hyperbranched polymer (CHBP-06, containing 6mol of carboxyl groups per mol of CHBP-06) with the number average molecular weight of about 3200 g/mol.
(b) Adding 0.01mol of CHBP-06, 0.6mol of epoxy chloropropane and 0.006mol of hexadecyl trimethyl ammonium bromide into a three-neck flask, stirring and reacting for 3 hours at about 140 ℃, then vacuum-pumping out excessive epoxy chloropropane, adding 0.5mol of dioxane, 0.4mol of butyl acetate and 0.48mol of sodium hydroxide into the three-neck flask, stirring and reacting for 10 hours at 10-20 ℃, stopping the reaction, standing and layering, washing an organic layer to be neutral, distilling and removing organic solvents of butyl acetate and dioxane to obtain the hyperbranched epoxy resin (CHEP-06, the 1 st structure in claim 1), wherein the number average molecular weight is about 3500g/mol, the viscosity is 8000cp, and the epoxy value is 0.16mol/100 g.
Embodiment 4 a high temperature resistant hyperbranched epoxy resin, which is prepared by the following steps:
(a) 0.10mol of glycerol, 0.21mol of dicarboxyimide compound (A2-04), 0.1mol of xylene, 0.2mol of dimethylformamide and p-methylbenzenesulfonic acid (the mass of the p-methylbenzenesulfonic acid is 0.2 percent of the total mass of the glycerol and the A2-04) are uniformly mixed, stirred and reacted for 12 hours at 170 ℃, and then the xylene and the dimethylformamide are removed by vacuumizing at 120 ℃ to obtain carboxyl-terminated hyperbranched polymer (CHBP-12, containing 12mol of carboxyl groups per mol of CHBP-12) with the number average molecular weight of about 8100 g/mol.
(b) Adding 0.01mol of CHBP-12, 0.24mol of epoxy chloropropane and 0.01mol of tetrabutylammonium bromide into a three-neck flask, stirring and reacting at about 120 ℃ for 5 hours, then vacuum-pumping out excessive epoxy chloropropane, adding 0.2mol of ethyl acetate, 0.1mol of butyl acetate and 0.1mol of sodium hydroxide into the three-neck flask, stirring and reacting at 5-10 ℃ for 8 hours, stopping the reaction, standing and layering, washing an organic layer to be neutral, distilling to remove organic solvents of butyl acetate and ethyl acetate to obtain the hyperbranched epoxy resin (CHEP-12, the 2 nd structure in claim 1), wherein the number average molecular weight is about 8600g/mol, the viscosity is 13000cp, and the epoxy value is 0.12mol/100 g.
Embodiment 5 a high temperature resistant hyperbranched epoxy resin, the preparation method steps are as follows:
(a) 0.22mol of Trimethylolpropane (TMP), 0.21mol of dicarboximide compound (A2-01), 0.20mol of xylene and zinc acetate (the mass of the zinc acetate is 0.5 percent of the total mass of the TMP and the A2-01 percent) are uniformly mixed, stirred and reacted for 10 hours at 180 ℃, and then the xylene is removed by vacuumizing at 110 ℃ to obtain hydroxyl-terminated hyperbranched polymer (HHBP-24, 24 contains 24mol of hydroxyl per mol of HHBP-24) with the number average molecular weight of about 9700 g/mol.
(b) Adding 0.01mol of HHBP-24, 0.48mol of epoxy chloropropane and 0.024mol of tetrabutylammonium bromide into a three-neck flask, stirring and reacting at about 120 ℃ for 5 hours, then vacuumizing excess epoxy chloropropane, adding 0.24mol of tetrahydrofuran and 0.048mol of sodium hydroxide into the three-neck flask, stirring and reacting at 0-5 ℃ for 8 hours, stopping the reaction, standing and layering, washing an organic layer to be neutral by water, and distilling to remove the tetrahydrofuran which is an organic solvent to obtain the hyperbranched epoxy resin (the 3 rd structure in claim 1, HHEP-24), wherein the number average molecular weight is 11200g/mol, the viscosity is 7700cp, and the epoxy value is 0.21mol/100 g.
According to the formula shown in Table 1, the curing agent 4,4' -diaminodiphenylmethane was uniformly mixed with the hyperbranched epoxy resin obtained in examples 1-5 and the bisphenol A type epoxy resin (E51, epoxy value 0.51mol/100g, viscosity 15600cp) by the same method, the mixture was poured into a mold, the temperature was raised to 160 ℃ for curing for 2 hours and 170 ℃ for 180 ℃ for curing for 6 hours, the sample was taken out, the mold was removed after cooling, and the properties of the material were respectively tested after being left at room temperature for 12 hours, with the results shown in Table 1. Wherein the tensile strength of the material is tested according to ASTM D638-82a, the bending property of the material is tested according to ASTM D790M-92 standard, the impact strength of the material is tested according to ASTM D256-81 standard, the thermal property (glass transition temperature) of the material is tested by DSC according to ASTM D3418-82, and the temperature rise rate of the test is 10 ℃/min.
TABLE 1 Properties of hyperbranched epoxy resin products obtained in examples 1 to 5
Claims (11)
1. A high-temperature resistant hyperbranched epoxy resin has the following structural formula:
wherein R is4The structure of (1) is as follows:
R1and
oxygen at the left end;
R5the structure of (1) is as follows:
in the formula, R1The chemical structure of a trihydroxy compound after hydrogen atoms on three hydroxyl groups are removed;
in the formula, R2The structure of (1) is as follows:
wherein n is 1 or 2;
R3the structure of (1) is as follows: -CH2(CH2)j-、
Or
Wherein j is 1, 2, 3, 4 or 5.
2. The high temperature resistant hyperbranched epoxy resin of claim 1, wherein: the trihydroxy compound is trimethylolpropane, tris (2-hydroxyethyl) isocyanurate or glycerol.
3. A preparation method of high-temperature resistant hyperbranched epoxy resin comprises the following steps:
(a) uniformly mixing bismaleimide, a sulfhydryl compound, a photoinitiator and an organic solvent chloroform, carrying out ultraviolet illumination reaction for 10-20 minutes at room temperature, wherein the power of ultraviolet light is 800-1200W, and after the reaction is finished, vacuum-pumping out the organic solvent chloroform to obtain a dicarboxyimide compound;
the dosage ratio of the bismaleimide to the mercapto compound to the photoinitiator is 1mol to 5g, wherein the molar ratio of the bismaleimide to the mercapto compound to the photoinitiator is 1mol to 5 mol;
the mercapto compound is thioglycolic acid or mercaptopropionic acid;
(b) uniformly mixing a dicarboxyimide compound, a trihydroxy compound, an organic solvent A and an esterification reaction catalyst, stirring and reacting for 10-16h at 140-180 ℃, and then vacuumizing to remove the organic solvent A to obtain a carboxyl-terminated or hydroxyl-terminated hyperbranched polymer;
the chemical structure of the dicarboxyimide compound is:
wherein n is 1 or 2, R3The structure of (1) is as follows: -CH2(CH2)j-、
Or
Wherein j is 1, 2, 3, 4 or 5;
the trihydroxy compound is trimethylolpropane, tris (2-hydroxyethyl) isocyanurate or glycerol;
the esterification reaction catalyst is one or more than two of p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, tetrabutyl titanate, zinc acetate and tetrapropyl titanate;
(c) stirring and reacting carboxyl-terminated or hydroxyl-terminated hyperbranched polymer and epoxy chloropropane at 120-140 ℃ for 3-5 hours in the presence of an open-loop reaction catalyst, then vacuumizing excess epoxy chloropropane, adding an organic solvent B and a basic catalyst, stirring and reacting at-5-30 ℃ for 6-10 hours, stopping the reaction, layering, washing an organic layer to be neutral, and distilling to remove the organic solvent B to obtain the high-temperature-resistant hyperbranched epoxy resin with the molecular weight of 1800 plus 29000 g/mol;
the ring-opening reaction catalyst is one or more than two of tetrabutylammonium bromide, hexadecyltrimethylammonium bromide, hexadecyltriethylammonium bromide, sodium hydroxide and potassium hydroxide.
4. The production method according to claim 3, characterized in that: the bismaleimide is N, N '- (4,4' -methylene diphenyl) bismaleimide, diaminodiphenyl ether bismaleimide or 1, 6-bismaleimide hexane.
5. The method of claim 4, wherein: the photoinitiator in the step (a) is (2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone).
6. The method of claim 5, wherein: the molar ratio of the dicarboxyimide compound to the trihydroxy compound to the organic solvent A in the step (b) is 1: (0.40-2.0): (0.5-4.0).
7. The method of claim 6, wherein: in the step (b), the organic solvent A is one or more than two of dimethylbenzene, N-methylpyrrolidone, dimethylformamide and dimethylacetamide.
8. The method of claim 7, wherein: the mass of the esterification reaction catalyst is 0.2-1.5% of the total mass of the dicarboxyiimide compound and the trihydroxy compound.
9. The method of claim 8, wherein: in the step (c), the molar ratio of the carboxyl or hydroxyl of the carboxyl-terminated or hydroxyl-terminated hyperbranched polymer, the epoxy chloropropane and the ring-opening reaction catalyst is 1 (2-10) to 0.005-0.1.
10. The method of claim 9, wherein: in the step (c), the basic catalyst is sodium hydroxide and/or potassium hydroxide, and the molar ratio of the carboxyl or hydroxyl of the carboxyl-terminated or hydroxyl-terminated hyperbranched polymer to the basic catalyst is 1 (0.1-10).
11. The method of manufacturing according to claim 10, wherein: in the step (c), the organic solvent B is one or more than two of tetrahydrofuran, ethyl acetate, dioxane and butyl acetate, and the using amount of the organic solvent B is 0.5-1.5 times of the mole number of the epoxy chloropropane.
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