2-aminoethyl sulfonic acid modified aqueous epoxy resin and preparation method thereof and the aqueous epoxy emulsion for preparing by this aqueous epoxy resins
Technical field
The present invention relates to a kind of aqueous epoxy resins, particularly a kind of 2-aminoethyl sulfonic acid modified aqueous epoxy resin and preparation method thereof and the aqueous epoxy emulsion for preparing by this aqueous epoxy resins.
Background technology
Resins, epoxy has excellent performance, as advantages such as sticking power height, hardness height, wear resistance are good, used widely in industrial acquisition, but Resins, epoxy often needs to use solvent when using, and this understands cause severe contamination to environment.Along with the enhancing of people's environmental protection consciousness, aqueous epoxy resins more and more is subjected to the attention of this field researcher, has become popular research direction in recent years, obtains widespread use in a plurality of fields such as coating, tackiness agent, fine chemistry industry auxiliary agent.
At present, the method for preparing aqueous epoxy resins both at home and abroad mainly contains two kinds, promptly direct outer emulsion process and chemical modification reemulsification method.Directly outer emulsion process refers to Resins, epoxy under admixture emulsifying agent situation, be prepared from by direct emulsification or phase reversion method.Chemical modification reemulsification method refers to Resins, epoxy earlier through the chemical reaction modification, introduces the water-based group, and then is prepared from by direct emulsification or phase reversion method.The aqueous epoxy resins particle diameter that direct outer emulsion process makes is bigger, is generally micron order, because particle diameter is bigger, makes that the emulsion that forms is stable inadequately.And the prepared particle of chemic modified method is thinner, is generally nano level, and the stability of emulsion height has bigger research and development meaning and practical value.At present, introduce aqueous substance by chemic modified method both at home and abroad and comprise introduction contraposition methyl hydroxybenzoate, Thiovanic acid or contraposition benzaminic acid etc., they react with Resins, epoxy earlier, and product is prepared the stabilized aqueous epoxy emulsion by direct emulsification or phase reversion method again.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of 2-aminoethyl sulfonic acid modified aqueous epoxy resin.
Another object of the present invention is to provide above-mentioned preparation method of water-dilutable epoxide resin.
A further object of the present invention is to provide the aqueous epoxy emulsion by above-mentioned aqueous epoxy resins preparation.
The present invention relates to a kind of aqueous epoxy resins, adopt the chemical reaction of 2-aminoethyl sulfonic acid (taurine) and Resins, epoxy, polar group is introduced Resins, epoxy, in and salify, make its possess hydrophilic property, and further prepared the stabilized aqueous epoxy emulsion.
Purpose of the present invention is achieved through the following technical solutions: a kind of 2-aminoethyl sulfonic acid modified aqueous epoxy resin, and the compound of structure such as general formula (1) expression, described general formula (1) is:
Formula (1)
2-aminoethyl sulfonic acid modified aqueous epoxy resin of the present invention, wherein the related chemical equation of 2-aminoethyl sulfonic acid modified epoxy is as follows:
A kind of preparation method of 2-aminoethyl sulfonic acid modified aqueous epoxy resin, comprise the steps: raw material epoxy resin, 2-aminoethyl sulfonic acid, water and tensio-active agent are mixed, in temperature is 80~85 ℃ of reactions 3~9 hours, obtains the 2-aminoethyl sulfonic acid modified aqueous epoxy resin.Wherein each chemical composition is counted by weight: Resins, epoxy: 100 parts; 2-aminoethyl sulfonic acid: 3~50 parts; Water: 10~50 parts; Tensio-active agent: 0.3~5 part.
Particularly preferred scope is: Resins, epoxy: 100 parts; 2-aminoethyl sulfonic acid: 15~20 parts; Water: 10~25 parts; Tensio-active agent: 1~2 part.
Also can add silane coupling agent in the described raw material, silane coupling agent is counted 3~6 parts by weight.
Described Resins, epoxy is bisphenol A type epoxy resin, and its oxirane value is 0.03~0.54mol/100g.
The optional polyoxyethylene octylphenol ether type of described tensio-active agent tensio-active agent, polyoxyethylene nonylphenol ether type tensio-active agent, polyoxyethylene carboxylate type tensio-active agent or any two kinds of mixtures between them.
Described polyoxyethylene octylphenol ether type tensio-active agent comprises tensio-active agent OP-10, tensio-active agent OP-10 or tensio-active agent OP-10 etc.; Described polyoxyethylene nonylphenol ether type tensio-active agent comprises tensio-active agent NP-5 etc.; Described polyoxyethylene carboxylate type tensio-active agent comprises hard ester acid polyoxyethylene ester, lauric acid polyoxyethylene ester or polyoxyethylene oleic acid ester etc.
Aqueous epoxy emulsion (being the emulsifying water thing of aqueous epoxy resins) by above-mentioned aqueous epoxy resins preparation, be prepared from as follows: the 2-aminoethyl sulfonic acid modified aqueous epoxy resin is neutralized to meta-alkalescence (PH=7~8) with alkaline aqueous solution earlier, then with its emulsification, make solid content and be 20~40% stabilized aqueous epoxy emulsion.
Described alkaline aqueous solution is mineral alkali such as sodium hydroxide, potassium hydroxide, yellow soda ash; The aqueous solution such as organic bases such as triethylamine, the mol ratio of described alkaline aqueous solution and 2-aminoethyl sulfonic acid are 1: 1.
The present invention compared with prior art has following advantage and beneficial effect: chemic modified method of the present invention prepares the water-base epoxy method, and to have reactions steps few, enforcement easy to operate; Aqueous epoxy emulsion has particle thin (being generally nano level), stable performance, and characteristics such as cured product hardness and resistance to impact shock excellent property can obtain widespread use in fields such as coating, tackiness agent, fine chemistry industry auxiliary agents.
Stability of emulsion is an important indicator of estimating the aqueous epoxy resins performance.Be that the 2-aminoethyl sulfonic acid consumption is as shown in table 1 to the influence of stability of emulsion under 25% the situation at emulsion solid content.
The stability test of table 1 aqueous epoxy emulsion
Resins, epoxy: 2-aminoethyl sulfonic acid (weight ratio) |
100∶0 |
100∶5 |
100∶15 |
100∶25 |
100∶35 |
One month |
Layering |
Not stratified |
Not stratified |
Not stratified |
Layering |
Three months |
Layering |
Layering |
Not stratified |
Not stratified |
Layering |
Six months |
Layering |
Layering |
Not stratified |
Not stratified |
Layering |
Resins, epoxy is E-44 Resins, epoxy in the table 1.
As shown in Table 1, compare with the Resins, epoxy that does not adopt chemical modification, Resins, epoxy is after passing through the 2-aminoethyl sulfonic acid chemical modification, corresponding stability of emulsion obviously improves, shown that fully technology of the present invention improves effect, wherein Resins, epoxy and 2-aminoethyl sulfonic acid amount ratio are that 100: 15~25 o'clock stability of emulsion are best, and it is the highest that technology improves effect.
Aqueous epoxy resins provided by the invention also has good curing performance.
The excellent properties of Resins, epoxy is mainly reflected on the performance of its cured product, Resins, epoxy be a kind of with liquid state to solid-state material.It does not almost have independent use value, generally has only with the cancellated insoluble not cladding polymer of solidifying agent reaction generation three-dimensional using value is just arranged.The curing reaction of Resins, epoxy mainly occurs on the epoxy group(ing), and its oxirane ring is opened in the oxirane ring reaction in solidifying agent and the Resins, epoxy, makes it ring-opening polymerization.Because the reaction principle of this aqueous epoxy resins is to introduce hydrophilic radical by using 2-aminoethyl sulfonic acid to open oxirane ring, so the consumption of 2-aminoethyl sulfonic acid influences to some extent to the performance of aqueous epoxy resins cured article.Table 2 has been listed the performance of aqueous epoxy resins cured article under the situation that the 2-aminoethyl sulfonic acid consumption changes.
The test of table 2 aqueous epoxy resins condensate performance
Resins, epoxy: 2-taurine (weight ratio) |
100∶0 |
100∶5 |
100∶15 |
100∶25 |
100∶35 |
Oxirane value mol/100g |
0.42 |
0.38 |
0.34 |
0.30 |
0.14 |
Curing situation/hardness |
Can not solidify |
6H |
7H |
7H |
5H |
Curing situation/resistance to impact shock/Mpa |
Can not solidify |
7.2 |
8.6 |
8.2 |
6.5 |
1, the Resins, epoxy that uses in the table 2 is E-42 Resins, epoxy.
2, its oxirane value is measured with hydrochloric acid-acetone method.
3, used solidifying agent is a diethylenetriamine, and according to the oxirane value of aqueous epoxy resins, the mass ratio of aqueous epoxy resins and diethylenetriamine is 100: 2~10, and condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time).
4, resistance to impact shock adopts standard GB1040-79.
5, hardness adopts standard GB6739-86.
By above data as can be seen, the Resins, epoxy through the 2-aminoethyl sulfonic acid modification can not form emulsion after shearing dispersion, so can not solidify; Resins, epoxy and 2-aminoethyl sulfonic acid mass ratio are 100: 5 o'clock, the emulsion instability of formation, and solidifying the after fixing rerum natura can be bad; Resins, epoxy and 2-aminoethyl sulfonic acid mass ratio are that the emulsion that formed in 100: 15,100: 25 o'clock is more stable, and condensate performance is also better; When Resins, epoxy and 2-aminoethyl sulfonic acid mass ratio are 100: 35, because the 2-aminoethyl sulfonic acid consumption is excessive, the emulsion instability of formation, solidifying the after fixing rerum natura can be also bad.By above result as can be seen, Resins, epoxy and 2-aminoethyl sulfonic acid mass ratio are 100: 15~100: 25 o'clock, and the aqueous epoxy resins performance that obtains is best.
Aqueous epoxy resins of the present invention can adopt solidifying agent such as diethylenetriamine, triethylene tetramine, polymeric amide to be cured, and table 3 has been listed the hardness and the resistance to impact shock of corresponding cured article.
The performance that the different solidifying agent of table 3 solidify the after fixing thing
Sequence number |
Solidifying agent |
Hardness |
Resistance to impact shock/MPa |
Consumption (the epoxy mass fraction is 100) |
1 |
Diethylenetriamine |
6H |
7.2 |
10 |
2 |
Triethylene tetramine |
7H |
8.3 |
8 |
3 |
Polymeric amide |
6H |
6.9 |
12 |
1, the aqueous epoxy resin emulsion that uses in the table 3 is that E-51 Resins, epoxy and 2-aminoethyl sulfonic acid mass ratio are to obtain under 100: 20 the situation, and the concentration of this aqueous epoxy emulsion is 30%.
2, solidified aqueous epoxy resins in the table 3, the oxirane value that records by hydrochloric acid-acetone method is 0.32mol/100g.
3, the condition of cure of diethylenetriamine is ambient cure (25 ℃ of a temperature, be 5 hours set time), and the condition of cure of triethylene tetramine and polymeric amide is 100 ℃ of following 2h.
4, resistance to impact shock adopts standard GB1040-79.
5, hardness adopts standard GB6739-86.
As shown in Table 3, diethylenetriamine, triethylene tetramine, polymeric amide all can be used as the solidifying agent of this aqueous epoxy resins, so aqueous epoxy resins has the stronger adaptability of technology, have shown that fully technology of the present invention improves effect.
Silane coupling agent can be used as auxiliary agent to be added in preparation process in the aqueous epoxy resins, because silane coupling agent has the crosslinked function of coupling, can improve hardness and resistance to impact shock that aqueous epoxy resins solidifies the cured article of back formation greatly.Table 4 is the performance of having added the aqueous epoxy resins cured article of silane coupling agent.
Table 4 aqueous epoxy resins condensate performance test (adding silane coupling agent) as auxiliary agent
Sequence number |
Silane coupling agent |
Hardness |
Resistance to impact shock |
Consumption (epoxy mass fraction |
|
|
|
/MPa |
Be 100) |
1 |
Do not have |
5H |
6.4 |
0 |
2 |
KH-550 |
7H |
8.5 |
2 |
3 |
A-1110 |
8H |
8.8 |
4 |
4 |
A-1120 |
8H |
8.9 |
3 |
5 |
KBM-602 |
9H |
9.5 |
5 |
6 |
Y-7162 |
9H |
9.7 |
3 |
1, the aqueous epoxy resins that uses in the table 4 is that E-54 Resins, epoxy and 2-aminoethyl sulfonic acid mass ratio are to obtain under 100: 20 the situation, and the concentration of this aqueous epoxy emulsion is 30%.
2, solidified aqueous epoxy resins in the table 4, the oxirane value that records by hydrochloric acid-acetone method is 0.33mol/100g.
3, solidifying agent is a diethylenetriamine, and condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time).
4, resistance to impact shock adopts standard GB1040-79.
5, hardness adopts standard GB6739-86.
As shown in Table 4, compare with the situation of not using silane coupling agent, use silane coupling agent to add in the aqueous epoxy resins as auxiliary agent, the performance of aqueous epoxy resins cured article improves a lot.
Embodiment
The present invention is further described in detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) 100g E-44 Resins, epoxy, 3g 2-aminoethyl sulfonic acid, 24g water and 2g tensio-active agent OP-10 (polyoxyethylene octylphenol ether type tensio-active agent) are mixed in the input three-necked bottle, reaction is 9 hours when temperature is 80 ℃, and reaction finishes, and can to obtain solid content be 75% aqueous epoxy resins.
(2) with the solid content that makes be 75% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium hydroxide solution 200g (wherein sodium hydroxide 1g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 5 minutes, rotating speed is 1000 rev/mins, makes solid content and be 25% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 1g diethylenetriamine, condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time), and cured article hardness is 5H, and resistance to impact shock is 6.2MPa.
Embodiment 2
(1) 100g E-42 Resins, epoxy, 10g 2-aminoethyl sulfonic acid, 33g water and 1g tensio-active agent NP-5 (polyoxyethylene nonylphenol ether type tensio-active agent), 2g tensio-active agent OP-10 (polyoxyethylene octylphenol ether type tensio-active agent) are mixed in the input three-necked bottle, reaction is 10 hours when temperature is 83 ℃, and reaction finishes, and can to obtain solid content be 70% aqueous epoxy resins.
(2) with the solid content that makes be 70% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium hydroxide solution 133g (wherein sodium hydroxide 3.2g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 7 minutes, rotating speed is 2000 rev/mins, makes solid content and be 30% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 1.2g polymeric amide, condition of cure be 95 ℃ 2 hours, cured article hardness is 6H, resistance to impact shock is 6.7MPa.
Embodiment 3
(1) the hard ester acid polyoxyethylene ester of 100g E-51 Resins, epoxy, 15g 2-aminoethyl sulfonic acid, 14g water and 4g tensio-active agent (polyoxyethylene carboxylate type tensio-active agent) is mixed in the input three-necked bottle, reaction is 7 hours when temperature is 85 ℃, and reaction finishes, and can to obtain solid content be 80% aqueous epoxy resins.
(2) with the solid content that makes be 80% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with hydroxide Potassium aqueous solution 300g (wherein hydroxide Potassium 6.7g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 10 minutes, rotating speed is 1000 rev/mins, makes solid content and be 20% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 0.8g triethylene tetramine, condition of cure be 80 ℃ 2 hours, cured article hardness is 7H, resistance to impact shock is 8.2MPa.
Embodiment 4
(1) 100g E-54 Resins, epoxy, 20g 2-aminoethyl sulfonic acid, 25g water, 3g silane resin acceptor kh-550 (γ-An Bingjisanyiyangjiguiwan), 2g tensio-active agent lauric acid polyoxyethylene ester (polyoxyethylene carboxylate type tensio-active agent), the hard ester acid polyoxyethylene ester of 2g tensio-active agent (polyoxyethylene carboxylate type tensio-active agent) are mixed in the input three-necked bottle, reaction is 11 hours when temperature is 82 ℃, and reaction finishes, and can to obtain solid content be 75% aqueous epoxy resins.
(2) with the solid content that makes be 75% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium carbonate 87.5g (wherein yellow soda ash 15.6g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 8 minutes, rotating speed is 1500 rev/mins, makes solid content and be 40% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 1g triethylene tetramine, condition of cure is 100 ℃ of following 2h, and cured article hardness is 7H, and resistance to impact shock is 8.5MPa.
Embodiment 5
(1) 100g E-44 Resins, epoxy, 35g 2-aminoethyl sulfonic acid, 47g water, 6g silane coupling A-1110 (γ-An Bingjisanjiayangjiguiwan) and 4g tensio-active agent polyoxyethylene oleic acid ester (polyoxyethylene carboxylate type tensio-active agent) are mixed in the input three-necked bottle, reaction is 10 hours when temperature is 84 ℃, and reaction finishes, and can to obtain solid content be 65% aqueous epoxy resins.
(2) with the solid content that makes be 65% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium hydroxide solution 160g (wherein sodium hydroxide 11g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 4 minutes, rotating speed is 2500 rev/mins, makes solid content and be 25% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 0.8g diethylenetriamine, condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time), and cured article hardness is 5H, and resistance to impact shock is 6.1MPa.
Embodiment 6
(1) with 100g E-42 Resins, epoxy, 50g 2-aminoethyl sulfonic acid, 34g water, 5g silane coupling agent Y-7162 (N, N '-two (β-aminoethyl)-γ-aminopropyl-Trimethoxy silane) and 2g polyoxyethylene oleic acid ester (polyoxyethylene carboxylate type tensio-active agent), 2g tensio-active agent OP-10 (polyoxyethylene octylphenol ether type tensio-active agent) mix and drop in the three-necked bottle, reaction is 7 hours when temperature is 82 ℃, and reaction finishes, and can to obtain solid content be 70% aqueous epoxy resins.
(2) with the solid content that makes be 70% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with triethylamine aqueous solution 133g (wherein triethylamine 24.2g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 9 minutes, rotating speed is 1000 rev/mins, makes solid content and be 30% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 0.8g diethylenetriamine, condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time), and cured article hardness is 4H, and resistance to impact shock is 4.5MPa.
Embodiment 7
(1) 100g E-03 Resins, epoxy (oxirane value is 0.03mol/100g), 3g 2-aminoethyl sulfonic acid, 24g water and 0.3g tensio-active agent OP-10 (polyoxyethylene octylphenol ether type tensio-active agent) are mixed in the input three-necked bottle, reaction is 9 hours when temperature is 80 ℃, and reaction finishes, and can to obtain solid content be 75% aqueous epoxy resins.
(2) with the solid content that makes be 75% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium hydroxide solution 5g (wherein sodium hydroxide 1g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 5 minutes, rotating speed is 1000 rev/mins, makes solid content and be 50% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 1g diethylenetriamine, condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time), and cured article hardness is 5H, and resistance to impact shock is 6.3MPa.
Embodiment 8
(1) 100g E-03 Resins, epoxy (oxirane value is 0.03mol/100g), 3g 2-aminoethyl sulfonic acid, 24g water and 1g tensio-active agent OP-10 (polyoxyethylene octylphenol ether type tensio-active agent) are mixed in the input three-necked bottle, reaction is 9 hours when temperature is 80 ℃, and reaction finishes, and can to obtain solid content be 75% aqueous epoxy resins.
(2) with the solid content that makes be 75% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium hydroxide solution 10g (wherein sodium hydroxide 1g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 5 minutes, rotating speed is 1000 rev/mins, makes solid content and be 50% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 1g diethylenetriamine, condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time), and cured article hardness is 6H, and resistance to impact shock is 7.1MPa.
Embodiment 9
(1) 100g E-54 Resins, epoxy (oxirane value is 0.54mol/100g), 3g 2-aminoethyl sulfonic acid, 24g water and 5g tensio-active agent OP-10 (polyoxyethylene octylphenol ether type tensio-active agent) are mixed in the input three-necked bottle, reaction is 9 hours when temperature is 80 ℃, and reaction finishes, and can to obtain solid content be 75% aqueous epoxy resins.
(2) with the solid content that makes be 75% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium hydroxide solution 20g (wherein sodium hydroxide 1g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 5 minutes, rotating speed is 1000 rev/mins, makes solid content and be 50% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 1g diethylenetriamine, condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time), and cured article hardness is 6H, and resistance to impact shock is 6.8MPa.
Embodiment 10
(1) 100g E-54 Resins, epoxy (oxirane value is 0.54mol/100g), 3g 2-aminoethyl sulfonic acid, 24g water and 1g tensio-active agent OP-10 (polyoxyethylene octylphenol ether type tensio-active agent) are mixed in the input three-necked bottle, reaction is 9 hours when temperature is 80 ℃, and reaction finishes, and can to obtain solid content be 75% aqueous epoxy resins.
(2) with the solid content that makes be 75% aqueous epoxy resins 100g, be neutralized to meta-alkalescence (PH=7~8) with aqueous sodium hydroxide solution 100g (wherein sodium hydroxide 1g), again with high-shearing dispersion emulsifying machine with its emulsification, high-speed stirring 5 minutes, rotating speed is 1000 rev/mins, makes solid content and be 50% stabilized aqueous epoxy emulsion.Get this epoxy emulsion 10g, be cured with the 1g diethylenetriamine, condition of cure is ambient cure (25 ℃ of a temperature, be 5 hours set time), and cured article hardness is 7H, and resistance to impact shock is 8.2MPa.
As mentioned above, can realize the present invention preferably.