CN115724776A - Monofunctional epoxy compound modified diamino diphenyl sulfone and application thereof - Google Patents
Monofunctional epoxy compound modified diamino diphenyl sulfone and application thereof Download PDFInfo
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- CN115724776A CN115724776A CN202211583466.XA CN202211583466A CN115724776A CN 115724776 A CN115724776 A CN 115724776A CN 202211583466 A CN202211583466 A CN 202211583466A CN 115724776 A CN115724776 A CN 115724776A
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- diaminodiphenyl sulfone
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 79
- -1 compound modified diamino diphenyl sulfone Chemical class 0.000 title claims abstract description 48
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000012658 bimolecular nucleophilic substitution Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 6
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 5
- AYHLPQOWRMPEKH-UHFFFAOYSA-N 2-(6-methylheptoxymethyl)oxirane Chemical compound CC(C)CCCCCOCC1CO1 AYHLPQOWRMPEKH-UHFFFAOYSA-N 0.000 claims description 4
- NKVCYHYQKKNFJI-UHFFFAOYSA-N 2-(hexacosan-13-yloxymethyl)oxirane Chemical compound CCCCCCCCCCCCCC(CCCCCCCCCCCC)OCC1CO1 NKVCYHYQKKNFJI-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 5
- 230000000269 nucleophilic effect Effects 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 150000004982 aromatic amines Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NVKSMKFBUGBIGE-UHFFFAOYSA-N 2-(tetradecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCOCC1CO1 NVKSMKFBUGBIGE-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZDGWGNDTQZGISB-UHFFFAOYSA-N acetic acid;perchloric acid Chemical compound CC(O)=O.OCl(=O)(=O)=O ZDGWGNDTQZGISB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
The invention discloses a monofunctional epoxy compound modified diamino diphenyl sulfone and a preparation method and application thereof. The monofunctional epoxy compound modified diaminodiphenyl sulfone is obtained by carrying out bimolecular nucleophilic substitution reaction on a fatty chain monofunctional epoxy compound and 4,4' -diaminodiphenyl sulfone. The prepared monofunctional epoxy compound modified diaminodiphenyl sulfone contains amino active hydrogen, and the hydroxyl generated by nucleophilic attack of amino on the epoxy compound can enhance the curing reaction activity, so that the monofunctional epoxy compound modified diaminodiphenyl sulfone serving as a curing agent for epoxy resin can be dissolved and mixed in the resin at a lower preheating temperature, the use convenience is improved, the brittleness of a cured product is improved, and the toughness is increased.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a monofunctional epoxy compound modified diaminodiphenyl sulfone and application thereof.
Background
4,4' -diaminodiphenyl sulfone (DDS) is a pale yellow powder with a melting point of about 176 ℃ and low hygroscopicity, and is a commonly used epoxy resin curing agent.
The sulfonyl group has strong electron-withdrawing effect, and the sulfur atom has the highest valence, so that 4,4' -diaminodiphenyl sulfone has strong oxidation resistance. On the other hand, the sulfur-oxygen double bond shows certain stability due to higher bond energy, and an electron high-degree delocalization system formed between the amino group and the diphenyl sulfone group can enable the energy of the whole molecule to be lower and has good stability, so that when external energy is provided, the structure can be utilized for absorption, and the breakage of chemical bonds or the cross-linking of molecules is avoided.
Although 4,4' -diaminodiphenyl sulfone has excellent oxidation resistance and heat resistance, the nucleophilic property of amino group is strongly weakened by the conjugated structure formed by amino group and phenyl group, and this phenomenon is further aggravated by the presence of sulfone group. In addition to the electronic effect, the presence of sterically hindered groups in the molecule likewise leads to the problems described above. Therefore, 4,4' diaminodiphenyl sulfone is less reactive than the conventional amine curing agents and is slow to react, requiring either a large amount of addition or the addition of an additional accelerator. In addition, the high-conjugated diphenyl sulfone structure in the molecule has stronger rigidity and poorer toughness, and the higher melting point also causes the difficulty in mixing the diphenyl sulfone structure with the epoxy resin and the limitation in use, so that the application of 4,4' -diaminodiphenyl sulfone is limited to a certain extent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a monofunctional epoxy compound modified diamino diphenyl sulfone and a preparation method and application thereof.
The invention hopes to modify the molecular structure of 4,4 '-diaminodiphenyl sulfone from the expected performance, and prepare a modified 4,4' -diaminodiphenyl sulfone through the nucleophilic substitution reaction of aromatic amine and aliphatic chain monofunctional epoxy compound. On the basis of keeping original excellent heat resistance, the problem of curing reaction activity reduction caused by molecular weight increase is solved by hydroxyl generated by nucleophilic attack of amino on an epoxy compound, and molecular rigidity is alleviated, toughness is increased, and a melting point is reduced by introducing a fatty chain, so that the comprehensive performance and use convenience of 4,4' -diaminodiphenyl sulfone are improved, and the application and development prospects of the compound are expanded. The modified diamino diphenyl sulfone prepared by the invention is used as an epoxy resin curing agent, and the curing agent has the characteristics of simple and convenient synthesis process, good reaction activity, high heat resistance, good flexibility, good water resistance, low VOC (organic volatile component) and the like.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a monofunctional epoxy compound modified diaminodiphenyl sulfone is prepared from the aliphatic monofunctional epoxy compound and 4,4' -diaminodiphenyl sulfone through bimolecular nucleophilic substitution reaction.
Preferably, the aliphatic chain monofunctional epoxy compound is one or more of butyl glycidyl ether, isooctyl glycidyl ether, and dodecyl-tetradecyl glycidyl ether.
Preferably, the ratio of the amount of the aliphatic monofunctional epoxy compound to the amount of 4,4' -diaminodiphenyl sulfone is 1: (1-2).
The invention also provides a preparation method of the mono-functional group epoxy compound modified diamino diphenyl sulfone, which comprises the following steps:
adding a fatty chain monofunctional epoxy compound and 4,4' -diaminodiphenyl sulfone into a container, and stirring to obtain a reaction solution;
condensing and refluxing the obtained reaction liquid to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone.
Preferably, the temperature of the condensation reflux is 85-120 ℃, and the time of the condensation reflux is 3-5 h.
The invention also provides an application of the monofunctional epoxy compound modified diamino diphenyl sulfone as an epoxy resin curing agent.
Preferably, the application of the monofunctional epoxy compound modified diaminodiphenyl sulfone as the epoxy resin curing agent comprises the following steps: and stirring and mixing the monofunctional epoxy compound modified diamino diphenyl sulfone and the epoxy resin, and then quickly pouring the mixture after mixing and dissolving into a mold for curing for 2-3 h.
Preferably, the mass ratio of the monofunctional epoxy compound modified diaminodiphenyl sulfone to the epoxy resin is (0.89-3.39): 1.96.
preferably, the epoxy resin is one of epoxy resin E-51 and epoxy resin E-44.
Preferably, the mixing is carried out at a temperature of 90 to 100 ℃ and a stirring rate of 700 to 1100 rpm.
The beneficial effects of the invention are:
(1) Compared with other aromatic amines, the 4,4' -diaminodiphenyl sulfone used in the invention has lower volatility, irritation and toxicity, and the related synthetic reaction conditions are mild and green;
(2) The epoxy resin prepared by the invention uses a monofunctional epoxy compound to modify diamino diphenyl sulfone curing agent, wherein the curing agent contains amino active hydrogen, and the curing reaction activity can be enhanced by cooperating with hydroxyl generated by nucleophilic attack of amino on the epoxy compound;
(3) The monofunctional epoxy compound modified diamino diphenyl sulfone curing agent for the epoxy resin, which is prepared by the invention, has the advantages that the introduced fatty chain can relieve the molecular rigidity, increase the toughness and reduce the melting point, so that the monofunctional epoxy compound modified diamino diphenyl sulfone curing agent is dissolved and mixed in the resin at a lower preheating temperature, the use convenience is improved, and the brittleness of a cured product is improved;
(4) The monofunctional epoxy compound modified diaminodiphenyl sulfone curing agent for epoxy resin prepared by the invention has the characteristics of simple and convenient synthesis process, good reaction activity, high heat resistance, good flexibility, good water resistance, low VOC (volatile organic compound) and the like, and can be widely applied to the fields of high-performance thermosetting resin, composite materials thereof and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of mono-functional group epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amount of the aliphatic chain monofunctional epoxy compound to the amount of 4,4' -diaminodiphenyl sulfone is 1:1 feeding, namely adding 13.0g of butyl glycidyl ether and 24.8g of 4,4' -diaminodiphenyl sulfone into a four-neck flask provided with an electric stirrer, a spherical condenser and a thermometer for stirring;
(2) And heating the reaction system to 85 ℃, stirring and reacting for 3 hours to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
Respectively weighing 1.26g of monofunctional epoxy compound modified diaminodiphenyl sulfone prepared in the embodiment and 1.96g of epoxy resin E-51, putting into a flask, stirring, adjusting the temperature to 90 ℃ after all the materials are mixed, quickly stirring at the speed of 800rpm until the materials are uniformly mixed, then quickly pouring the mixture which is well mixed into a mold for curing for 2 hours, and testing the performance of a cured material after the curing is completely finished.
Example 2
A preparation method of mono-functional group epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amounts of the materials satisfies that the ratio of the aliphatic chain monofunctional epoxy compound to 4,4' -diaminodiphenyl sulfone is 1:1 feeding, namely adding 18.6g of isooctyl glycidyl ether and 24.8g of 4,4' -diaminodiphenyl sulfone into a four-neck flask provided with an electric stirrer, a spherical condenser and a thermometer for stirring;
(2) And heating the reaction system to 85 ℃, stirring and reacting for 3 hours to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
1.45g of monofunctional epoxy compound modified diaminodiphenyl sulfone prepared in example 2 and 1.96g of epoxy resin E-51 were weighed and placed in a flask for stirring, after all mixing, the temperature was adjusted to 90 ℃, and the mixture was rapidly stirred at 800rpm until uniform mixing, and then the mixture which was well mixed was poured into a mold for curing for 2 hours, and after complete curing, the properties of the cured product were tested.
Example 3
A preparation method of mono-functional group epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amounts of the materials satisfies that the ratio of the aliphatic chain monofunctional epoxy compound to 4,4' -diaminodiphenyl sulfone is 1:1 feeding, namely adding 76.9g of dodecyl-tetradecyl glycidyl ether and 24.8g of 4,4' -diaminodiphenyl sulfone into a four-neck flask provided with an electric stirrer, a spherical condenser and a thermometer for stirring;
(2) And (3) heating the reaction system to 90 ℃, stirring and reacting for 3 hours to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
3.39g of the monofunctional epoxy compound modified diaminodiphenyl sulfone prepared in example 3 and 1.96g of epoxy resin E-51 were weighed and placed in a flask and stirred, after all the components were mixed, the temperature was adjusted to 90 ℃, the mixture was rapidly stirred at 800rpm until the components were uniformly mixed, the mixture was rapidly poured into a mold and cured for 2 hours, and the properties of the cured product were tested after the curing was complete.
Example 4
A preparation method of mono-functional group epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amounts of the materials satisfies that the ratio of the aliphatic chain monofunctional epoxy compound to 4,4' -diaminodiphenyl sulfone is 1:1.5 charging, namely adding 13.0g of butyl glycidyl ether and 37.2g of 4,4' -diaminodiphenyl sulfone into a four-neck flask provided with an electric stirrer, a spherical condenser and a thermometer for stirring;
(2) And (3) heating the reaction system to 100 ℃, stirring and reacting for 4 hours to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
1.00g of the monofunctional epoxy compound modified diaminodiphenyl sulfone prepared in example 4 and 1.96g of epoxy resin E-51 were weighed and placed in a flask and stirred, after all the components were mixed, the temperature was adjusted to 90 ℃, the mixture was rapidly stirred at 800rpm until the components were uniformly mixed, the mixture was rapidly poured into a mold and cured for 2 hours, and the properties of the cured product were tested after the curing was complete.
Example 5
A preparation method of mono-functional group epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amounts of the materials satisfies that the ratio of the aliphatic chain monofunctional epoxy compound to 4,4' -diaminodiphenyl sulfone is 1:1.5 charge, namely, 18.6g of isooctyl glycidyl ether and 37.2g of 4,4' -diaminodiphenyl sulfone are added into a four-neck flask provided with an electric stirrer, a spherical condenser tube and a thermometer for stirring;
(2) And (3) heating the reaction system to 100 ℃, stirring and reacting for 4 hours to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
1.12g of monofunctional epoxy compound modified diaminodiphenyl sulfone prepared in example 5 and 1.96g of epoxy resin E-51 were weighed and placed in a flask for stirring, after all mixing, the temperature was adjusted to 90 ℃, and the mixture was rapidly stirred at 800rpm until uniform mixing, and then the mixture which was well mixed was poured into a mold for curing for 2 hours, and after complete curing, the properties of the cured product were tested.
Example 6
A preparation method of monofunctional epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amounts of the materials satisfies that the ratio of the aliphatic chain monofunctional epoxy compound to 4,4' -diaminodiphenyl sulfone is 1:1.5 charging, 76.9g of dodecyl to tetradecyl glycidyl ether and 37.2g of 4,4' -diaminodiphenyl sulfone were charged into a four-necked flask equipped with an electric stirrer, a spherical condenser and a thermometer and stirred;
(2) And heating the reaction system to 110 ℃, stirring and reacting for 4 hours to obtain the monofunctional group epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
2.28g of the monofunctional epoxy compound modified diaminodiphenyl sulfone prepared in example 6 and 1.96g of the epoxy resin E-51 were weighed and placed in a flask for stirring, after all mixing, the temperature was adjusted to 90 ℃, and the mixture was rapidly stirred at 800rpm until uniform mixing, and then the mixture which was well mixed was poured into a mold for curing for 2 hours, and after complete curing, the properties of the cured product were tested.
Example 7
A preparation method of mono-functional group epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amounts of the materials satisfies that the ratio of the aliphatic chain monofunctional epoxy compound to 4,4' -diaminodiphenyl sulfone is 1:2, feeding, namely adding 13.0g of butyl glycidyl ether and 49.6g of 4,4' -diaminodiphenyl sulfone into a four-neck flask with an electric stirrer, a spherical condenser and a thermometer for stirring;
(2) And (3) heating the reaction system to 110 ℃, stirring and reacting for 5 hours to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
0.89g of the monofunctional epoxy compound-modified diaminodiphenyl sulfone prepared in example 7 and 1.96g of epoxy resin E-51 were weighed out and placed in a flask and stirred, after all the components were mixed, the temperature was adjusted to 90 ℃, the mixture was rapidly stirred at 800rpm until the components were mixed uniformly, the mixture was rapidly poured into a mold to cure for 2 hours, and after the curing was completed, the properties of the cured product were tested.
Example 8
A preparation method of mono-functional group epoxy compound modified diamino diphenyl sulfone comprises the following steps:
(1) At room temperature, the ratio of the amounts of the materials satisfies that the ratio of the aliphatic chain monofunctional epoxy compound to 4,4' -diaminodiphenyl sulfone is 1:2 feeding, namely adding 76.9g of dodecyl-tetradecyl glycidyl ether and 49.6g of 4,4' -diaminodiphenyl sulfone into a four-neck flask provided with an electric stirrer, a spherical condenser and a thermometer for stirring;
(2) And heating the reaction system to 120 ℃, stirring and reacting for 5 hours to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone after the reaction is finished.
1.81g of monofunctional epoxy compound modified diaminodiphenyl sulfone prepared in the example 8 and 1.96g of epoxy resin E-51 were weighed and placed in a flask for stirring, after all mixing, the temperature was adjusted to 90 ℃, and the mixture was rapidly stirred at 800rpm until uniform mixing, and then the mixture which was well mixed was poured into a mold for curing for 2 hours, and after complete curing, the properties of the cured product were tested.
Comparative example 1
Comparative example 1 is a commercial unmodified diaminodiphenyl sulfone curing agent (available from Wuhana white pharmaceutical chemical Co., ltd., CAS No. 80-08-0, with 4,4' -diaminodiphenyl sulfone as the major component).
Respectively weighing 0.62g of diamino diphenyl sulfone curing agent and 1.96g of epoxy resin E-51, putting into a flask, stirring, adjusting the temperature to 120 ℃ after all the materials are mixed, quickly stirring until the materials are uniformly mixed, then quickly pouring the mixture into a mold for curing for 2 hours, and testing the performance of a cured product after the curing is completely finished.
Performance testing
The properties of the monofunctional epoxy compound-modified diaminodiphenyl sulfone prepared in examples 1 to 8 and the diaminodiphenyl sulfone of comparative example 1 were measured, and the results are shown in table 1.
The results of the performance tests of the cured products obtained using the monofunctional epoxy compound-modified diaminodiphenyl sulfone prepared in examples 1 to 8 and the diaminodiphenyl sulfone of comparative example 1 as the epoxy resin curing agents are shown in Table 2.
Table 1 examples and comparative examples the results of performance testing of modified and unmodified diaminodiphenyl sulfone curing agents
| Sample (I) | Amine number (mg KOH/g) | Melting Point (. Degree.C.) |
| Comparative example 1 | 452 | 176 |
| Example 1 | 298 | 86 |
| Example 2 | 259 | 81 |
| Example 3 | 112 | 72 |
| Example 4 | 281 | 98 |
| Example 5 | 252 | 92 |
| Example 6 | 125 | 83 |
| Example 7 | 270 | 101 |
| Example 8 | 135 | 92 |
Note: the amine value is measured according to a perchloric acid-acetic acid titration method, and the melting point is measured according to the national standard GB/T617-2006.
TABLE 2 results of property test of cured products obtained in examples 1 to 8 and comparative example 1
| Sample (I) | Impact Strength (kJ/m) 2 ) | Tensile modulus (GPa) | Elongation at Break (%) |
| Comparative example 1 | 26.4 | 3.04 | 3.35 |
| Example 1 | 41.5 | 2.69 | 4.89 |
| Example 2 | 42.6 | 2.64 | 5.01 |
| Example 3 | 45.3 | 2.58 | 5.24 |
| Example 4 | 38.4 | 2.77 | 4.62 |
| Example 5 | 39.1 | 2.74 | 4.73 |
| Example 6 | 41.9 | 2.67 | 4.93 |
| Example 7 | 36.8 | 2.82 | 4.48 |
| Example 8 | 38.7 | 2.76 | 4.66 |
Note: the impact strength is measured according to the national standard GB/T1043-1993, and the tensile modulus is measured according to the national standard GB/T2568-1995.
From the results in tables 1 and 2, it can be seen that, compared with diaminodiphenyl sulfone, the monofunctional epoxy compound modified diaminodiphenyl sulfone prepared by the present invention has a lower melting point, and the cured product formed by curing the compound with epoxy resin has stronger toughness, thereby improving the comprehensive performance and the convenience of use.
It should be noted that the above embodiments belong to the same inventive concept, and the description of each embodiment has a different emphasis, and reference may be made to the description in other embodiments where the description in individual embodiments is not detailed.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The monofunctional epoxy compound modified diamino diphenyl sulfone is characterized in that a fatty chain monofunctional epoxy compound and 4,4' -diamino diphenyl sulfone are subjected to bimolecular nucleophilic substitution reaction to obtain the monofunctional epoxy compound modified diamino diphenyl sulfone.
2. The mono-functional epoxy compound modified diaminodiphenyl sulfone of claim 1, wherein the aliphatic chain mono-functional epoxy compound is one or more of butyl glycidyl ether, isooctyl glycidyl ether, and dodecyl-tetradecyl glycidyl ether.
3. The monofunctional epoxy compound-modified diaminodiphenyl sulfone of claim 1, wherein the ratio of the amount of said aliphatic monofunctional epoxy compound to the amount of 4,4' -diaminodiphenyl sulfone is 1: (1-2).
4. The method for preparing the monofunctional epoxy compound modified diaminodiphenyl sulfone of claim 1, comprising the steps of:
adding an epoxy compound with a single fatty chain functional group and 4,4' -diaminodiphenyl sulfone into a container, and stirring to obtain a reaction solution;
and condensing and refluxing the reaction liquid to obtain the monofunctional epoxy compound modified diaminodiphenyl sulfone.
5. The method for preparing the monofunctional epoxy compound-modified diaminodiphenyl sulfone of claim 4, wherein the condensation reflux temperature is 85-120 ℃ and the condensation reflux time is 3-5 h.
6. Use of a monofunctional epoxy compound-modified diaminodiphenyl sulfone according to any one of claims 1 to 3 as an epoxy resin curing agent.
7. Use according to claim 6, characterized in that it comprises the following steps: stirring and mixing the monofunctional epoxy compound modified diamino diphenyl sulfone and epoxy resin, and then quickly pouring the mixture after mixing and dissolving into a mould for curing for 2-3 h.
8. The use according to claim 7, wherein the monofunctional epoxy compound-modified diaminodiphenyl sulfone and the epoxy resin are present in a mass ratio of (0.89 to 3.39): 1.96.
9. the use of claim 7, wherein the epoxy resin is at least one of epoxy E-51 and epoxy E-44.
10. Use according to claim 7, wherein the mixing is carried out at a temperature of 90 to 100 ℃ and a stirring speed of 700 to 1100 rpm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096412A (en) * | 2006-06-30 | 2008-01-02 | 中国科学院理化技术研究所 | Curing agent for epoxy resin and low-temperature using epoxy adhesive |
| CN101914267A (en) * | 2010-08-12 | 2010-12-15 | 蓝星(北京)化工机械有限公司 | High-performance epoxy resin composition for pulling and extrusion and preparation method thereof |
| CN103694641A (en) * | 2013-12-26 | 2014-04-02 | 青岛海洋新材料科技有限公司 | Buoyance material for curing modified arylamine and preparation method of buoyance material |
-
2022
- 2022-12-10 CN CN202211583466.XA patent/CN115724776A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096412A (en) * | 2006-06-30 | 2008-01-02 | 中国科学院理化技术研究所 | Curing agent for epoxy resin and low-temperature using epoxy adhesive |
| CN101914267A (en) * | 2010-08-12 | 2010-12-15 | 蓝星(北京)化工机械有限公司 | High-performance epoxy resin composition for pulling and extrusion and preparation method thereof |
| CN103694641A (en) * | 2013-12-26 | 2014-04-02 | 青岛海洋新材料科技有限公司 | Buoyance material for curing modified arylamine and preparation method of buoyance material |
Non-Patent Citations (2)
| Title |
|---|
| SONG, JIAN CHENG 等: "Fluorescence studies of diaminodiphenyl sulfone curing agent for epoxy cure characterization", 《MACROMOLECULES》, 31 December 1993 (1993-12-31), pages 4818 - 4824 * |
| 倪礼忠 等: "《聚合物基复合材料 第2版》", 31 January 2022, pages: 31 - 107 * |
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