CN101348563A - Tough mannich base curing agent and preparation thereof - Google Patents
Tough mannich base curing agent and preparation thereof Download PDFInfo
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- CN101348563A CN101348563A CNA2008102224938A CN200810222493A CN101348563A CN 101348563 A CN101348563 A CN 101348563A CN A2008102224938 A CNA2008102224938 A CN A2008102224938A CN 200810222493 A CN200810222493 A CN 200810222493A CN 101348563 A CN101348563 A CN 101348563A
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Abstract
The invention relates to a mannich alkali hardener with flexibility and a preparation method thereof. The method comprises the following steps of: under the action of an acidic catalyst, firstly carrying out the Friedel-Crafts reaction of tung oil and phenols; then under the conditions of certain temperature and time, adding gradually amine and aldehyde into the reaction system to complete a mannich condensation reaction; removing water content and matters with a low boiling point after the reaction is finished; finally adding additives of proper amount for dissolution to obtain a finished product. The mannich alkali hardener has a flexible long chain, an intramolecular toughening capability, abundant active hydrogen and phenolic aldehyde structures in the molecular structure, good reaction activity and low temperature solidification performance, and obviously improved heat tolerance, thereby belonging to an epoxy resin hardener with excellent performance. Simultaneously, the preparation method provided by the invention is simple and easily controlled; the product is actually nontoxic and has good industrialization prospects.
Description
Technical field
The present invention relates to a kind of solidifying agent, particularly relate to a kind of flexible mannich base solidification agent that has, simultaneously, the invention still further relates to the preparation method that this has the flexible mannich base solidification agent.
Background technology
General purpose epoxy resin has characteristics such as excellent bonding strength, chemical proofing, low-shrinkage, is widely used in the every field of national economy.Be used but have only, just can show above-mentioned characteristic after the curing with good epoxy curing agent.Because unmodified amine exists curing speed fast, and pungency is big, and cured article fragility is big, working life is short at present, and the ratio requirement strictness is easily with airborne CO
2Generate volatile salt, the whiting of cured article paint film, bellding solidifies defectives such as incomplete, has not re-used simple unmodified amine as solidifying agent.The epoxy resin modification amine curing agent is that purposes is maximum, the kind of consumption maximum, the modification approach is a lot, for example, epoxide modification, two key addition, Manny phaseization, ketoimineization, physics are composite etc., wherein mannich base solidification agent belongs to important a kind of modified amine curing agent, is widely used in various occasions such as low temperature, humidity, waits environment or bonding fast, antiseptic project, terrace paint etc. under water.
Initial typical mannich base solidification agent carries out modification by phenol, formaldehyde to quadrol, and the production trade mark is T31.The research of mannich base solidification agent focuses mostly on the synthetic of alkylphenol, many alcoxyls support diamines and formaldehyde and uses, and phenols, amine raw material develop towards diversity.Take various method of modifying simultaneously, increase molecular chain length, reduce reactive behavior.For example adopt alkylphenol, formaldehyde, the synthetic two interim mesosomes of alkylphenol Manny of many alcoxyls support diamines, further obtain two alkylphenol Mannich condensed products with formaldehyde and another kind of many alcoxyl support diamine reactants, intermediate and the finished product all can be used as curing agent for epoxy resin.
It is the synthetic cardanol of raw material that U.S. Ka Delai company develops with natural cashew nut shell oil, further synthetic mannich base solidification agent.Molecular structure contains the C that is with unsaturated double-bond
15Long-chain has been given the low special performance of viscosity under this solidifying agent low temperature, has good flowability; The existence of a large amount of phenolic hydroxyl groups has strengthened reactive behavior; C on the phenyl ring
15Long carbochain has reduced the surface tension of Resins, epoxy, has strengthened sticking power and hydrophobic nature.
There is the raw material sources difficulty equally in above-mentioned modification design, costs an arm and a leg, and the product cost height, work-ing life is still shorter, gentle elasticity deficiency, water-fast and sea water resistance can not be satisfactory, and technical process is long, and is numerous and diverse, produces a large amount of problems such as " three wastes ".
Summary of the invention
The object of the present invention is to provide a kind of flexible mannich base solidification agent that has, it has good toughness and shock resistance.
Another object of the present invention is to provide this to have the preparation method of flexible mannich base solidification agent, this method is started with from molecular designing, adopt in the molecular structure of chemic modified method with the two kinds of dual introducing phenolic aldehyde of long chain alkyl group amine curing agents, make mannich base solidification agent, can improve sticking power, resistance to impact shock with excellent toughness.
The invention provides a kind of flexible mannich base solidification agent that has, Fu-Ke reaction takes place by tung oil and phenols in it, carries out mannich reaction with aldehydes and amine then and is prepared from.
Described tung oil contains conjugated double bond, has good reaction activity, can substitution reaction take place with the adjacency pair position of the phenolic hydroxyl group of phenols.
Described phenols is selected from one or more in phenol, ortho-cresol, mixture cresol, nonyl phenol, p-tert-butylphenol, Resorcinol, the dihydroxyphenyl propane.Suitable for phenol, ortho-cresol, nonyl phenol or its miscellany etc.; More suitable phenols is phenol, nonyl phenol.
Described aldehydes is selected from one or more in the formalin of formaldehyde, acetaldehyde, butyraldehyde, phenyl aldehyde, methylal, solid paraformaldehyde, furfural and 37%.Suitable aldehydes is 37% formalin.
Described amine is selected from one or more in quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamine, m-xylene diamine, mphenylenediamine, different Buddhist diketone diamines, the dimethylamine.Suitable amine has quadrol, hexanediamine, diethylenetriamine, mphenylenediamine, m-xylene diamine or its mixture etc.; More suitable amine is quadrol, hexanediamine, m-xylene diamine.
Described tung oil: phenols: amine: the molar ratio of aldehyde is 1: 3～6: 6～15: 6～15.Phenols: molecular proportion of catalyst is 1: 0.01～0.10.Preferably, molar ratio is 1: 1.7～2.5: 3.4～6.25: 3.4～6.25, phenols: molecular proportion of catalyst is 1: 0.03～0.05.
The present invention has the flexible mannich base solidification agent, has following general structure:
Wherein, R
1Be H, methyl or nonyl, R
2Be C
2H
4, C
6H
12, C
8H
10Deng.
The present invention also provides a kind of described method with flexible mannich base solidification agent for preparing, and it is characterized in that, comprises the steps:
1) tung oil is mixed with phenols, under the katalysis of an acidic catalyst, Fu-Ke substitution reaction takes place, temperature of reaction is 70～130 ℃, and the reaction times is 1.0～1.5h;
2) in the step 1) reaction system, add amine, salt-forming reaction takes place, 40～60 ℃ of temperature, time 1.0～3.0h; Add aldehydes then and carry out mannich reaction in reaction system, temperature is 40～90 ℃, and the time is 1.0～5.0h;
3) with step 2) heating of the product of gained, heat up and finish polycondensation, 80～120 ℃ of temperature, time 1.0～3.0h;
4) the solidifying agent crude product of step 3) gained is continued heat temperature raising, normal pressure, underpressure distillation remove the low-boiling-point substance and the moisture of reaction system;
5) in the solidifying agent finished product of step 4) gained, add auxiliary agent, stir.
The described an acidic catalyst of step 1) comprises: mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid etc., organic acid such as formic acid, oxalic acid, tosic acid, methylsulphonic acid etc.Preferable acids is a tosic acid.
The described temperature of reaction of step 1) is 70～130 ℃, and the reaction times is 1.0～1.5h, and optimum condition is that temperature is 90～100 ℃, time 1.0h.
Described Fu of step 1)-Ke substitution reaction belongs to violent thermopositive reaction, in the reaction process, will emit a large amount of heat, and automatic intensification phenomenon appears in system, need take suitable cooling provision such as water coolant to remove heat.
Step 2) described salt-forming reaction condition is 40～60 ℃ of temperature, time 1.0～3h; The mannich reaction condition is that temperature is 40～90 ℃, and time 1.0～5.0h, optimum condition are that temperature is 40～60 ℃, time 2.0～4.0h.
Step 2) salt-forming reaction and the condensation reaction of Manny phase of described quadrol and phenols are violent thermopositive reaction, and the adding mode of quadrol and formaldehyde adopts the dropping mode, needs to take suitable cooling provision such as water coolant to remove heat in the reaction process.
The described polycondensation of step 3) (increasing chain reaction) condition is 80～120 ℃ of temperature, time 1.0～3h.Too high or the overlong time of temperature all will influence the quality of solidifying agent finished product, and molecular weight will obviously increase, and viscosity is bigger than normal.Optimum condition is that temperature is 90～100 ℃, time 2.0h.
The described distillation mode of step 4) mainly adopts normal pressure and underpressure distillation, removes raw material and brings water in the system into, the water that reaction generates, and the intact amine material of traces of unreacted and other minor by-products etc.
The auxiliary agent of the described employing of step 5) comprises alcohols, as methyl alcohol, ethanol, phenylcarbinol, propyl carbinol or its mixture etc., ketone such as methyl second butyl ketone, acetone, pimelinketone, methylethylketone etc.But the kind of auxiliary agent and consumption produce certain influence to the curing speed and the performance of solidifying agent.Proper auxiliary agent is ethanol and phenylcarbinol etc.
The auxiliary agent of the described employing of step 5) is 0.05～0.2 times (weight ratio) of phenols charging capacity, and suitable consumption is 0.15 times.
The preparation method that the present invention proposes, the technical indicator that gained has the flexible mannich base solidification agent is:
(1) amine value: 480～550mgKOH/g;
(2) viscosity (25 ℃): 1000～2000mPa.s;
(3) outward appearance: the transparent thick liquid of reddish-brown.
Tung oil is 18 carbon conjugated trienes-9,11, the glyceryl ester of 13 acid, and Fu-Ke easily takes place with the reactive hydrogen of the adjacency pair position of phenolic hydroxyl group and reacts in contained conjugated double bond, further with amine, aldehydes generation mannich reaction.The solidifying agent that obtains like this has the toughness reinforcing long flexible chain structure of intramolecularly, during with epoxy resin cure, the flexible chain of the length in the solidifying agent molecule participates in the cured article structure, has greatly improved the fragility and the snappiness of resin cured matter, has higher sticking power, cementability and shock resistance.
The present invention passes through Molecular Structure Design, directly adopt the tung oil that has flexible long carbochain, phenols such as phenol, ortho-cresol, nonyl phenol, cardanol etc., proper is nonyl phenol, carries out Fu-Ke reaction, introduces long flexible chain in molecular structure, molecular weight increases, reduction reaches the fragility of improving epoxy resin cured product and improves flexible purpose water, vapour susceptibility, improves sticking power and bonding force.
The invention provides that the direct modification of tung oil is synthetic to have the preparation method of flexible mannich base solidification agent, easy easy control, product reality is nontoxic.Of the present invention have an epoxy curing agent that the flexible mannich base solidification agent is an excellent combination property, and the deep processing that becomes more meticulous for natural tung oil simultaneously provides bright development prospect.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1 (lab scale synthesis example)
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 95 ℃.Hierarchy of control temperature begins to drip the 180g quadrol at 50 ℃, drips time 1.5h.Dropwise, hierarchy of control temperature is 50 ℃, begins to drip 380g formaldehyde, and the dropping time is 1.5h.Add thermal material, 100 ℃ of controlled temperature, reaction 2.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds 30g ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 500; Viscosity (25 ℃, mPa.s): 1400; Outward appearance: the transparent thick liquid of reddish-brown.
Application test:
A component: E-51; B component: above-mentioned made solidifying agent; C component: other auxiliary agent such as promotor etc.
Usage ratio is: A: B: C=1: 0.25: 0.02 (weight ratio).After the mixing, stir by hand, carry out film-making respectively and brush test and performance test according to standard.
The performance that table 1 gained is filmed
Embodiment 2
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 95 ℃.Hierarchy of control temperature begins to drip the 180g quadrol at 50 ℃, drips time 1.5h.Dropwise, hierarchy of control temperature is 50 ℃, begins to drip 380g formaldehyde, and the dropping time is 1.5h.Add thermal material, 100 ℃ of controlled temperature, reaction 2.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds 30g ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 490; Viscosity (25 ℃, mPa.s): 1600; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 3
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 95 ℃.Hierarchy of control temperature begins to drip the 180g quadrol at 50 ℃, drips time 1.5h.Dropwise, hierarchy of control temperature is 50 ℃, begins to drip 380g formaldehyde, and the dropping time is 1.5h.Add thermal material, 100 ℃ of controlled temperature, reaction 2.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds the 30g phenylcarbinol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 510; Viscosity (25 ℃, mPa.s): 1450; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 4
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 95 ℃.Hierarchy of control temperature begins to drip the 360g hexanediamine at 50 ℃, drips time 1.5h.Dropwise, hierarchy of control temperature is 50 ℃, begins to drip 380g formaldehyde, and the dropping time is 1.5h.Add thermal material, 100 ℃ of controlled temperature, reaction 2.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds 30g ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 490; Viscosity (25 ℃, mPa.s): 1800; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 5
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 95 ℃.Hierarchy of control temperature begins to drip the 400g m-xylene diamine at 50 ℃, drips time 1.5h.Dropwise, hierarchy of control temperature is 50 ℃, begins to drip 380g formaldehyde, and the dropping time is 1.5h.Add thermal material, 100 ℃ of controlled temperature, reaction 2.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds 30g ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 490; Viscosity (25 ℃, mPa.s): 1800; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 6
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 95 ℃.Hierarchy of control temperature begins to drip the 180g quadrol at 50 ℃, drips time 1.5h.Dropwise, hierarchy of control temperature is 50 ℃, and gradation adds 120g solid paraformaldehyde, and the dropping time is 1.5h.Add thermal material, 100 ℃ of controlled temperature, reaction 2.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds 30g ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 500; Viscosity (25 ℃, mPa.s): 1650; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 7
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 70 ℃.Hierarchy of control temperature begins to drip the 180g quadrol at 40 ℃, drips time 1.0h.Dropwise, hierarchy of control temperature is 40 ℃, begins to drip 380g formaldehyde, and the dropping time is 1.0h.Add thermal material, 80 ℃ of controlled temperature, reaction 3.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds 30g ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 500; Viscosity (25 ℃, mPa.s): 1450; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 8
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h at 130 ℃.Hierarchy of control temperature begins to drip the 180g quadrol at 60 ℃, drips time 3.0h.Dropwise, hierarchy of control temperature is 90 ℃, begins to drip 380g formaldehyde, and the dropping time is 5.0h.Add thermal material, 120 ℃ of controlled temperature, reaction 1.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds 30g ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 488; Viscosity (25 ℃, mPa.s): 1380; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 9
In the 2000ml four-hole boiling flask that agitator, electrically heated cover, Dropping feeder, condenser and thermometer are housed, add nonyl phenol 200g, 120g tung oil earlier, the 1.0g tosic acid, hierarchy of control temperature is kept reaction 1.0h 70.Hierarchy of control temperature begins to drip the 180g quadrol at 60 ℃, drips time 3.0h.Dropwise, hierarchy of control temperature is 90 ℃, begins to drip 380g formaldehyde, and the dropping time is 1.0h.Add thermal material, 120 ℃ of controlled temperature, reaction 1.0h.System heats up, and carries out normal pressure and decompression dehydration.The cooling material promptly adds the 30g phenylcarbinol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 478; Viscosity (25 ℃, mPa.s): 1200; Outward appearance: the transparent thick liquid of reddish-brown.
Embodiment 10 (pilot scale synthesis example)
In the 50L reactor that is equipped with agitator, steam jacket, high-order Dropping feeder, condenser and temperature regulator and other auxiliary facility, add the 5kg nonyl phenol earlier, 3kg tung oil, add catalyzer tosic acid 25g, hierarchy of control temperature is kept reaction 2.0h at 95 ℃.Cooling material to 55 ℃ begins to drip the 4.5kg quadrol, drips time 1.5h.Dropwise, hierarchy of control temperature is 50 ℃, begins to drip 9.5kg formaldehyde, and the dropping time is 1.5h.Add thermal material, 90 ℃ of controlled temperature, reaction 2.0h.System heats up, and dewaters under normal pressure and the condition of negative pressure and the low-boiling-point substance operation.The cooling material promptly adds ethanol, stirs, and obtains finished product.
The finished product technical indicator is: amine value (mgKOH/g): 520; Viscosity (25 ℃, mPa.s): 1500; Outward appearance: the transparent thick liquid of reddish-brown.
Application test:
A component: E-51; B component: above-mentioned made solidifying agent; C component: other auxiliary agent such as promotor etc.
Usage ratio is: A: B: C=1: 0.25: 0.02 (weight ratio).After the mixing, stir by hand, carry out film-making respectively and brush test and performance test according to testing standard.
The performance that table 2 gained is filmed
Claims (9)
1, a kind of have a flexible mannich base solidification agent, it is characterized in that, it by tung oil and phenols Fu-Ke reaction takes place, and carries out mannich reaction with aldehydes and amine then and is prepared from.
2, according to claim 1 have a flexible mannich base solidification agent, it is characterized in that described phenols is selected from one or more in phenol, ortho-cresol, mixture cresol, nonyl phenol, p-tert-butylphenol, Resorcinol, the dihydroxyphenyl propane.
3, according to claim 1 have a flexible mannich base solidification agent, it is characterized in that, described aldehydes is selected from one or more in the formalin of formaldehyde, acetaldehyde, butyraldehyde, phenyl aldehyde, methylal, solid paraformaldehyde, furfural and 37%.
4, according to claim 1 have a flexible mannich base solidification agent, it is characterized in that described amine is selected from one or more in quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamine, m-xylene diamine, mphenylenediamine and the different Buddhist diketone diamines.
5, have the flexible mannich base solidification agent according to claim 1, it is characterized in that, described tung oil: phenols: amine: the mol ratio of aldehyde is 1: 3～6: 6～15: 6～15.
6, according to claim 1 have a flexible mannich base solidification agent, it is characterized in that the technical indicator of described mannich base solidification agent is: amine value: 480～550mgKOH/g; Viscosity (25 ℃): 1000～2000mPa.s.
7, according to claim 1 have a flexible mannich base solidification agent, it is characterized in that having following general structure:
Wherein, R
1Be H, methyl or nonyl, R
2Be C
2H
4, C
6H
12Or C
8H
10
8, a kind of any described method with flexible mannich base solidification agent of claim 1～7 for preparing is characterized in that, comprises the steps:
1) tung oil is mixed with phenols, under the katalysis of an acidic catalyst, Fu-Ke substitution reaction takes place, temperature of reaction is 70～130 ℃, and the reaction times is 1.0～1.5h;
2) in the step 1) reaction system, add amine, salt-forming reaction takes place, 40～60 ℃ of temperature, time 1.0～3h; Add aldehydes then and carry out mannich reaction in reaction system, temperature is 40～90 ℃, and the time is 1.0～5.0h;
3) with step 2) heating of the product of gained, heat up and finish polycondensation, 80～120 ℃ of temperature, time 1.0～3.0h;
4) the solidifying agent crude product of step 3) gained is continued heat temperature raising, normal pressure, underpressure distillation remove the low-boiling-point substance and the moisture of reaction system;
5) in the solidifying agent finished product of step 4) gained, add auxiliary agent, stir.
9, the preparation method with flexible mannich base solidification agent according to claim 8 is characterized in that, the auxiliary agent that adopts in the described step 5) is selected from one or more in alcohol, the ketone, and consumption accounts for 5～20% of phenols charging capacity by weight.
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| CN1154981A (en) * | 1995-12-13 | 1997-07-23 | 国际壳牌研究有限公司 | Mannich base solidification agent |
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| CN106957241B (en) * | 2016-01-11 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of high hydroxyl value tung oil polyalcohol and preparation method thereof |
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| CN111732716A (en) * | 2020-06-22 | 2020-10-02 | 中国林科院林产化工研究所南京科技开发有限公司 | Mannich base curing agent for epoxy floor sealing primer and preparation method thereof |
| CN111732716B (en) * | 2020-06-22 | 2021-09-07 | 中国林业科学研究院林产化学工业研究所 | Mannich base curing agent for epoxy floor sealing primer and preparation method thereof |
| CN113265038A (en) * | 2021-04-08 | 2021-08-17 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based modified amine curing agent and preparation method and application thereof |
| CN113265038B (en) * | 2021-04-08 | 2022-03-25 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based modified amine curing agent and preparation method and application thereof |
| CN115340749A (en) * | 2022-08-05 | 2022-11-15 | 四川大学 | Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof |
| CN117534962A (en) * | 2023-09-27 | 2024-02-09 | 广东阿普邦新材料科技股份有限公司 | Wear-resistant antibacterial silica gel and preparation method thereof |
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