CN103113544B - Phenolic aldehyde modified amine curing agent and preparation method thereof - Google Patents
Phenolic aldehyde modified amine curing agent and preparation method thereof Download PDFInfo
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- CN103113544B CN103113544B CN201310036101.XA CN201310036101A CN103113544B CN 103113544 B CN103113544 B CN 103113544B CN 201310036101 A CN201310036101 A CN 201310036101A CN 103113544 B CN103113544 B CN 103113544B
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Abstract
The invention discloses a phenolic aldehyde modified amine curing agent which is prepared by polycondensing mixed phenol, polyformaldehyde and mixed amine through Mannich reaction. The preparation method comprises the following steps: adding phenol, nonylphenol and m-cresol at 35-45 DEG C, and evenly mixing; sequentially adding hexamethylene diamine and triethylene tetramine, and adding polyformaldehyde for reaction in batches in the process of gradually heating to 70-80 DEG C; and after the addition of the polyformaldehyde is finished, further reacting at 70-80 DEG C to obtain the product after the reaction is finished. The curing agent can be directly cured in water, has certain toughness and is favorable in curing effect; an epoxy resin cured by the curing agent has high dry shear bonding strength and in-water cured shear bonding strength; and the preparation method of the curing agent is simple to operate and mild in reaction conditions, and industrial production can be realized.
Description
Technical field
The present invention relates to a kind of phenol aldehyde modified amine curing agent and preparation method thereof, belong to solidifying agent technical field.
Background technology
Epoxy resin adhesive has the advantages such as bonding force is large, cure shrinkage is little, good corrosion resistance, therefore building a bridge, electronic apparatus, historical relic reparation, waterproofing and leakage-stopping, the field such as underwater engineering be widely used.The curing system of epoxy resin mainly contains polyamine, the large class of acid anhydrides two.Polynary amine curing agent occupies very large point rate in the curing system of epoxy resin, but unmodified polynary amine curing agent itself has some shortcomings, as operation time toxicity large, volatile, easily absorb CO
2, cured article fragility is large, under the environment of band water, solidification effect is good enough etc.The quality of solidifying agent determines the quality of epoxy resin adhesive curing performance to a great extent.Therefore, modification must be carried out to polynary amine curing agent, expand its range of application.Emphasis and the focus that modification is still current research is carried out to polynary amine.
Summary of the invention
The object of the present invention is to provide a kind of can directly fast-curing epoxy resin and the good phenol aldehyde modified amine curing agent of good toughness, solidification effect in water, the epoxy resin of this solidifying agent solidification has in stronger dry state shear bond strength and water and solidifies shear bond strength.
Another object of the present invention is to provide the preparation method that a kind of above-mentioned solidifying agent is simple to operate, reaction conditions is gentle.
The invention provides a kind of phenol aldehyde modified amine curing agent, this solidifying agent reacts polycondensation by mixed phenol, paraformaldehyde and mixed amine by Mannich and obtains; Wherein, paraformaldehyde: mixed phenol: mixed amine mass component is than being 100:300 ~ 500:500 ~ 800; Described mixed phenol is made up of phenol, nonyl phenol and meta-cresol; Described mixed amine is made up of hexanediamine and triethylene tetramine; Wherein, the amine value of solidifying agent is 450 ~ 500mgKOH/g, and viscosity is 360 ~ 1500mPas.
Nonyl phenol in described mixed phenol: phenol: the mass component ratio of meta-cresol is 130 ~ 360:44 ~ 125:15 ~ 126.
In described mixed amine, hexanediamine is 200 ~ 370:300 ~ 430 with the mass component ratio of triethylene tetramine.
Present invention also offers a kind of preparation method of solidifying agent as above, the method is after adding the mixing of phenol, nonyl phenol and meta-cresol under the condition prior to 35 ~ 45 DEG C, add hexanediamine and triethylene tetramine successively, add polyformaldehyde reaction being progressively warming up in the process of 70 ~ 80 DEG C more in batches, at 70 ~ 80 DEG C, reaction is continued after paraformaldehyde adds, after having reacted, to obtain final product.
Described be progressively warming up in the process of 70 ~ 80 DEG C that to add paraformaldehyde be by following operation in batches: at 40 ~ 50 DEG C, add 35 ~ 45% of paraformaldehyde quality, be warmed up to 50 ~ 60 DEG C, add 25 ~ 35% of paraformaldehyde quality again, continue to be warmed up to 60 ~ 70 DEG C, add 15 ~ 25% of paraformaldehyde quality, be finally warmed up to the paraformaldehyde that 70 ~ 80 DEG C add surplus.
Add paraformaldehyde under the described condition progressively heated up is progressively heat up in 40 ~ 80 DEG C of temperature ranges in batches, and added by being no less than 3 batches by paraformaldehyde, the present invention preferably adds by 4 batches.
In above-mentioned preparation method, paraformaldehyde reacts 1.5 ~ 3 hours after adding at 70 ~ 80 DEG C.
The concrete preparation method of phenol aldehyde modified amine curing agent of the present invention: 1. connect reaction unit, and whole reaction unit is incubated at 35 ~ 45 DEG C; 2. in mass ratio nonyl phenol, phenol, meta-cresol are added reactor and start to be uniformly mixed; 3. hexanediamine and triethylene tetramine is added in mass ratio successively; 4. in the process of stirring that heats up, add paraformaldehyde in batches, paraformaldehyde divides four times and adds (also can divide more batches to add): 40 ~ 50 DEG C add 35 ~ 45% of paraformaldehyde quality, 50 ~ 60 DEG C add 25 ~ 35% of paraformaldehyde quality, 60 ~ 70 DEG C add 15 ~ 25% of paraformaldehyde quality, 70 ~ 80 DEG C add remaining paraformaldehyde (if temperature of reaction is 70 DEG C, after 70 DEG C of constant temperature 5min, then add the paraformaldehyde of surplus), temperature-stable isothermal reaction 1.5 ~ 3 hours after 70 ~ 80 DEG C; 5. cool to room temperature obtains reddish tan thick liquid.
Beneficial effect of the present invention:
1, phenol aldehyde modified amine curing agent of the present invention has toughness, water tolerance and moisture resistance, and solidification value is low, and the speed solidified in water, condensate performance is good;
2, the reaction process that the present invention relates to is simple, easy to operate, not high to equipment requirements, is easy to suitability for industrialized production;
3, using E-44 epoxy resin as sizing (matrix resin), phenol aldehyde modified amine curing agent of the present invention (or claiming new T31 solidifying agent) self-vulcanizing 24h dry state shear tension intensity 7.0 ~ 10.0MPa is added; Add a certain amount of compounded mix, coupling agent self-vulcanizing 24h dry state shear tension intensity 10.0 ~ 20.0MPa in E-44/ new T31 solidifying agent again, in water, after bonding solidification 24h, shear bond strength is 6.0 ~ 13.2MPa.
Embodiment
Following examples further illustrate of the present invention, instead of restriction the present invention.
Embodiment 1
In about 40 DEG C thermostat water baths, to agitator is housed, nonyl phenol 33g is added in the there-necked flask of 250 milliliters of prolong, phenol 14.1g, meta-cresol 16.2g mixes, insulation is at about 40 DEG C, add hexanediamine 31.3g successively, triethylene tetramine 39.5g, stir 5 minutes under constant temperature, start heat temperature raising, and add paraformaldehyde (altogether 13.5g), repeatedly add in batches and (when temperature is raised to 50 DEG C from 40 DEG C, add 40% of paraformaldehyde quality total amount, temperature adds 30% of paraformaldehyde total amount when being raised to 60 DEG C from 50 DEG C, 20% of paraformaldehyde total amount is added when 60 DEG C to 70 DEG C, 10% of paraformaldehyde total amount is added) when 70 DEG C to 80 DEG C, after being warming up to 80 DEG C, be incubated 2 hours.Cool to room temperature obtains flaxen viscous liquid, and amine value is 470mg KOH/g, and viscosity is 1325mPa ﹒ s.Adopt E-44 epoxy resin as base-material, the amount of solidifying agent is 20/100, does not add any auxiliary self-vulcanizing 24h dry state shear tension intensity 7.5MPa; As added CaO(160 order) 5/100, gas phase SiO
20.5/100, KH-5502/100 self-vulcanizing 24h dry state shear tension intensity 15.7Mpa, hygrometric state is bonding, solidify 24h shear tension intensity 13.2Mpa in water.
Embodiment 2
In about 40 DEG C thermostatical oil water-baths, to agitator is housed, nonyl phenol 44g is added in the there-necked flask of 250 milliliters of prolong, phenol 18.8g, meta-cresol 10.8g, insulation is at about 40 DEG C, add hexanediamine 55.7g successively, triethylene tetramine 46.7g, stir 5 minutes under constant temperature, start heat temperature raising, and add paraformaldehyde (altogether 15g), repeatedly add in batches and (when temperature is raised to 50 DEG C from 40 DEG C, add 40% of paraformaldehyde quality total amount, temperature adds 25% of paraformaldehyde total amount when being raised to 60 DEG C from 50 DEG C, 25% of paraformaldehyde total amount is added when 60 DEG C to 70 DEG C, 10% of paraformaldehyde total amount is added) when 70 DEG C to 80 DEG C, after being warming up to 80 DEG C, be incubated 2.5 hours.Cool to room temperature obtains flaxen viscous liquid, and amine value is 485mgKOH/g, and viscosity is 360mPa ﹒ s.Adopt E-44 epoxy resin as base-material, the amount of solidifying agent is 20/100, does not add any auxiliary self-vulcanizing 24h dry state shear tension intensity 9.0MPa; As added CaO(160 order again) 6/100, gas phase SiO
20.5/100, KH-5504/100 self-vulcanizing 24h dry state shear tension intensity 11MPa, hygrometric state is bonding, solidify 24h shear tension intensity 10.1MPa in water.
Embodiment 3
In about 40 DEG C thermostatical oil water-baths, to agitator is housed, nonyl phenol 19.3g is added in the there-necked flask of 250 milliliters of prolong, phenol 16.5g, meta-cresol 9.5g, insulation is at about 40 DEG C, add hexanediamine 30.9g successively, triethylene tetramine 77.9g, stir 5 minutes under constant temperature, start heat temperature raising, and add paraformaldehyde (altogether 15g), repeatedly add in batches and (when temperature is raised to 50 DEG C from 40 DEG C, add 45% of paraformaldehyde quality total amount, temperature adds 30% of paraformaldehyde total amount when being raised to 60 DEG C from 50 DEG C, 15% of paraformaldehyde total amount is added when 60 DEG C to 70 DEG C, 10% of paraformaldehyde total amount is added) when 70 DEG C to 80 DEG C, after being warming up to 80 DEG C, be incubated 3 hours.Cool to room temperature obtains flaxen viscous liquid, and amine value is 480mg KOH/g, and viscosity is 760mPa ﹒ s.Adopt E-44 epoxy resin as base-material, the amount of solidifying agent is 20/100, does not add any auxiliary self-vulcanizing 24h dry state shear tension intensity 9.5MPa; As added CaO(160 order again) 5/100, gas phase SiO
21.0./100, KH-5502/100 self-vulcanizing 24h dry state shear tension intensity 11MPa, hygrometric state is bonding, solidify 24h shear tension intensity 7.1MPa in water.
Embodiment 4
In about 40 DEG C thermostatical oil water-baths, to agitator is housed, nonyl phenol 33g is added in the there-necked flask of 250 milliliters of prolong, phenol 22.6g, meta-cresol 6.5g, insulation is at about 40 DEG C, add hexanediamine 31.3g successively, triethylene tetramine 39.5g, stir 5 minutes under constant temperature, start heat temperature raising, and add paraformaldehyde (altogether 9g), repeatedly add in batches and (when temperature is raised to 50 DEG C from 40 DEG C, add 35% of paraformaldehyde quality total amount, temperature adds 35% of paraformaldehyde total amount when being raised to 60 DEG C from 50 DEG C, 25% of paraformaldehyde total amount is added when 60 DEG C to 70 DEG C, 5% of paraformaldehyde total amount is added) when 70 DEG C, after temperature keeps 70 DEG C, be incubated 2 hours.Cool to room temperature obtains flaxen viscous liquid, and amine value is 467mg KOH/g, and viscosity is 600mPa ﹒ s.Adopt E-44 epoxy resin as base-material, the amount of solidifying agent is 20/100, does not add any auxiliary self-vulcanizing 24h dry state shear tension intensity 8.0MPa; As added CaO(160 order again) 5/100, gas phase SiO
20.5/100, KH-5503/100 self-vulcanizing 24h dry state shear tension intensity 10MPa, hygrometric state is bonding, solidify 24h shear tension intensity 9.4MPa in water.
Claims (2)
1. a preparation method for phenol aldehyde modified amine curing agent, is characterized in that, reacts polycondensation obtain by mixed phenol, paraformaldehyde and mixed amine by Mannich, wherein, paraformaldehyde: mixed phenol: mixed amine mass component is than being 100:300 ~ 500:500 ~ 800, described mixed phenol is made up of nonyl phenol, phenol and meta-cresol 130 ~ 360:44 in mass ratio ~ 125:15 ~ 126, described mixed amine is made up of 200 ~ 370:300 ~ 430 in mass ratio hexanediamine and triethylene tetramine, described solidifying agent amine value is 450 ~ 500mgKOH/g, and viscosity is 360 ~ 1500mPas, described phenol aldehyde modified amine curing agent is prepared by following methods: add phenol under the condition prior to 35 ~ 45 DEG C, after nonyl phenol and meta-cresol mix, add hexanediamine and triethylene tetramine successively, at 40 ~ 50 DEG C, add 35 ~ 45% of paraformaldehyde quality, be warmed up to 50 ~ 60 DEG C, add 25 ~ 35% of paraformaldehyde quality again, continue to be warmed up to 60 ~ 70 DEG C, add 15 ~ 25% of paraformaldehyde quality, finally be warmed up to the paraformaldehyde that 70 ~ 80 DEG C add surplus, at 70 ~ 80 DEG C, reaction is continued after paraformaldehyde adds, after having reacted, obtain.
2. the preparation method of phenol aldehyde modified amine curing agent as claimed in claim 1, is characterized in that, reacts 1.5 ~ 3 hours after paraformaldehyde adds at 70 ~ 80 DEG C.
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| CN104945600B (en) * | 2015-07-17 | 2017-08-29 | 史铁钧 | A kind of epoxy curing agent of the benzoxazine of list containing aliphatic cyclic amine type and preparation method thereof |
| CN106046324B (en) * | 2016-06-28 | 2018-05-15 | 湖北绿色家园材料技术股份有限公司 | Utilize the curing agent and its synthesis technique of Ergol leftover bits and pieces modified aromatic amine system epoxy primary coat |
| CN109439253A (en) * | 2018-10-30 | 2019-03-08 | 湖南神力铃胶粘剂制造有限公司 | A kind of hydrophilic cured two-component epoxy face glue and preparation method thereof |
| CN109320690A (en) * | 2018-10-30 | 2019-02-12 | 湖南神力铃胶粘剂制造有限公司 | A kind of epoxy resin quick-setting pnenolic aldehyde amine hardener and preparation method thereof |
| CN112442159B (en) * | 2019-09-03 | 2022-10-04 | 彤程化学（中国）有限公司 | Vulcanized resin and preparation method and application thereof |
| CN112898516B (en) * | 2019-12-03 | 2023-05-12 | 南通星辰合成材料有限公司 | Phenolic aldehyde modified amine and preparation method thereof |
| CN113307948A (en) * | 2021-07-15 | 2021-08-27 | 中国工程物理研究院化工材料研究所 | Mussel bionic phenolic aldehyde amine curing agent capable of being bonded underwater and preparation method thereof |
| CN117511130A (en) * | 2023-11-07 | 2024-02-06 | 中国人民解放军陆军工程大学 | Quick-curing high-strength high-toughness epoxy resin system and preparation method thereof |
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| CN102532449B (en) * | 2010-12-24 | 2013-09-25 | 上海美东生物材料有限公司 | Preparation method of mixed cresol modified meta-xylylene diamine epoxy resin curing agent |
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