CN104830262A - Heat-resistant epoxy adhesive for non-excavation rehabilitation technology and preparation method of heat-resistant epoxy adhesive - Google Patents
Heat-resistant epoxy adhesive for non-excavation rehabilitation technology and preparation method of heat-resistant epoxy adhesive Download PDFInfo
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Abstract
The invention discloses a heat-resistant epoxy adhesive for a non-excavation rehabilitation technology. The adhesive consists of a material A and a material B, wherein the material A comprises the following components in parts by weight: 65.0-90.0 parts of organic silicon modified epoxy resin, 20.0-30.0 parts of ethanol, 0.05-2.0 parts of a silane coupling agent and 1.0-3.0 parts of nanosilicon dioxide; the material B comprises 20.0-30.0 parts of blocked isocyanate. A preparation method comprises the following steps: modifying nanosilicon dioxide by using the silane coupling agent under a special process condition; then modifying epoxy resin by using organic silicon; mixing the modified nanosilicon dioxide with the modified epoxy resin; carrying out heating reflux; and finally adding the material B and filling to obtain a finished product. The adhesive has both excellent heat resistance and mechanical property and can be particularly applied to heat pipelines in the non-excavation rehabilitation technology.
Description
Technical field
The present invention relates to adhesive field, particularly a kind of heat-proof epoxy tackiness agent for non-excavation repairing technique and preparation method thereof.
Background technology
Heating pipe line is divided into by heating agent kind: 1, operating pressure is less than or equal to 1.6MPa, and medium temperature is less than or equal to the steam pipe system of 350 DEG C; And 2, operating pressure is less than or equal to 2.5MPa, medium temperature is less than or equal to the hot water pipe net of 200 DEG C.Find according to the study, pipeline fault is caused by corrosive pipeline to a great extent, and internal corrosion and outer corrosion normally simultaneous, and outer corrosion is more serious than internal corrosion, and the major cause that valve and loop expansion pipe damage also is corrosion failure in fact.As can be seen here, the corrosion failure of pipeline and annex thereof is the major cause affecting heating system reliability, cause pipeline fault.
The non-excavation repairing technique of hot duct can be avoided excavating completely the pipeline of seriously corroded, thoroughly changing, therefore advantage of lower cost, engineering time is short, reveals the problem that cannot change especially have also been obtained fine solution for the pipeline corrosion be embedded under high-lager building and the important main line of communication.No-dig technique pipe rehabilitation technology is divided into multiple, what such as last century 80, the nineties grew up turns over the reparation of lining method, it is exactly a kind of typical non-excavation repairing technique, its principle adopts textile fiber material to make tubing, anti seepage membrane coating and resin impregnation process are carried out to it, then adopt inversion method to utilize air pressure to make it to be close on old inner-walls of duct, the tubular textile of the shaping rear formation inner wall smooth of resin solidification, thus form the prevention and restoration to old pipeline.
But, in the middle of prior art, the epoxy resin binder that can be applied to hot water in trenchless technology/hot steam pipe network is considerably less, and this is that mechanical property because the tackiness agent of routine possesses and resistance toheat cannot meet the Working environment that in non-excavation rehabilitation, hot channel is severe.A kind of epoxyn disclosed in CN 104099051 A, containing epoxy resin 20 ~ 60 parts, acid anhydride type curing agent 20 ~ 50 parts, toughner 5 ~ 25 parts, supporting material 5 ~ 15 parts, thinner 10 ~ 20 parts, promotor 0.1 ~ 2 part.Wherein supporting material is ultra-fine or nanometer grade silica.According to the test result that above-mentioned patent documentation discloses, although add nanometer grade silica as strengthening agent and toughner to improve the mechanical property of tackiness agent, but effect is very limited, the shearing resistance of product is the highest can only reach 13.5MPa, in addition, the second-order transition temperature of the tackiness agent disclosed in document is about 130 DEG C, and such resistance toheat cannot be applied in the middle of the hot channel of more than 200 DEG C completely.Some other method of modifying are also disclosed in prior art, to improve the performance of epoxy resin binder, but often cannot take into account mechanical property and resistance toheat, especially thermotolerance promote limited, under environment more than 200 DEG C, thermosteresis is comparatively large, still cannot be applied in the middle of hot channel.Applicant, by lot of experiments, have employed specific compatibility and proportioning, is preparing a kind of epoxy resin binder with superior heat resistance performance and mechanical property, thus complete the present invention under specific processing condition.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of heat-proof epoxy tackiness agent for non-excavation repairing technique, this tackiness agent, with the thermotolerance of excellence and mechanical property, especially can be applied in no-dig technique pipe rehabilitation technology in hot channel.
A kind of heat-proof epoxy tackiness agent for non-excavation repairing technique provided by the invention, expected to form by A material and B, described A material comprises following component by weight: modifying epoxy resin by organosilicon 65.0-90.0 part, ethanol 20.0-30.0 part, silane coupling agent 0.05-2.0 part, nano silicon 1.0-3.0 part;
Described B material is the blocked isocyanate of 20.0-30.0 part.
Preferably, above-mentioned modifying epoxy resin by organosilicon is the epoxy resin with Diphenylsilanediol modification.
More preferably, described modifying epoxy resin by organosilicon is the epoxy resin E-44 with Diphenylsilanediol modification.
Most preferably, be prepared by a method comprising the following steps with the epoxy resin E-44 of Diphenylsilanediol modification and obtain: by epoxy resin E-44: the mass ratio of Diphenylsilanediol=4:1 is got the raw materials ready, epoxy resin E-44 is placed in reaction vessel, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, stannous octoate accounts for the 1-2% of reactant total mass (i.e. the total mass of epoxy resin E-44 and Diphenylsilanediol), and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours.
Preferably, described blocked isocyanate is blocked isocyanate YG-75F (purchased from Donghai County according to high resin production company limited).
Preferably, described silane coupling agent is silane coupling agent KH-560.
Preferably, the particle diameter of described nano silicon is 20 ~ 100nm.
The above-mentioned heat-proof epoxy tackiness agent for non-excavation repairing technique, by thermogravimetic analysis (TGA) method, the heat-proof epoxy tackiness agent for non-excavation repairing technique is detected, in air atmosphere, when temperature rise rate is 10 DEG C/min, outlet temperature is 200 ~ 300 DEG C, thermal weight loss ratio for the heat-proof epoxy tackiness agent of non-excavation repairing technique is less than 2.1%, can reach 0% under most preferably embodiment.
For the preparation method of the heat-proof epoxy tackiness agent of non-excavation repairing technique, comprise the steps:
(1) getting ethanol pours in container, drips silane coupling agent, and concussion shakes up rear standing 10 minutes wiring solution-formings; Then being poured into by the solution that this configures is equipped with in the container of nano silicon, ultrasonic disperse 10-20 minute, and ultrasonic frequency is 20-50KHz, obtains transparent modified manometer silicon dioxide solution;
(2) epoxy resin E-44 is placed in reaction vessel, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, the mass ratio of epoxy resin E-44 and Diphenylsilanediol is 4:1, stannous octoate accounts for the 1-2% of reactant total mass, and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours;
(3) under room temperature, the surface modified nano silicon solution that step (1) obtains is poured in modified epoxy product, reflux at 90 DEG C, stirs pressure reducing and steaming ethanol after 1 hour, obtains nano-silicon dioxide modified epoxy resin;
(4) under the middling speed dispersion state of 500-800r/min, in nano-silicon dioxide modified epoxy resin, cyclohexanone resin and B material is added successively, the filling heat-proof epoxy tackiness agent namely obtained for non-excavation repairing technique after dispersion stirs.
Each component in the present invention all can commercially directly be buied.
A kind of heat-proof epoxy tackiness agent for non-excavation repairing technique provided by the invention, has following beneficial effect:
(1) specific surface area due to nanometer SiO 2 particle is large, filler and substrate contact area increase, strong interaction is there is between nanoparticle and epoxy resin, nanoparticle after surface treatment, the actual effect playing cross-linking set in the base, is conducive to the entanglement of epoxy resin chain, forms physical crosslinking; Its surface treatment agent and matrix bonding simultaneously, forms interface cohesion good between particle filled composite and matrix, plays the effect of chemically crosslinked point.Therefore, along with adding of nanoparticle, cross-linking density increases, and then improves the thermotolerance of system.
(2) by ultrasonic technology dispersing nanometer silicon-dioxide.During ultrasonication, hole or bubble can be produced in mixed solution, hole or bubble vibrate under the effect of sound field, when acoustic pressure reaches certain value, hole or bubble increase rapidly, then close suddenly, high pressure is produced at the regional area of liquid, cause fluid molecule strenuous exercise, the strenuous exercise of this pressure or fluid molecule makes the nanometer silicon dioxide particle aggregate that can be separated be dispersed into less aggregate or single particle, the surface of nanometer silicon dioxide particle is fully contacted with silane coupling agent KH-560, improve the dispersiveness of nano material.
(3) the main body starting material Diphenylsilanediol modified epoxy E-44 of patent use of the present invention, be rolled into a ball by substrate ring epoxy resins epoxy group to obtain with the hydroxyl generation opening in Diphenylsilanediol, this opening makes hydroxyl quantity increase.Thus the cross-linking density of the epoxy resin of modification and the isocyanate curing agent of end-blocking is increased, improve binder performance.Diphenylsilanediol modified epoxy introduces phenyl ring in substrate ring epoxy resins, because phenyl ring has special construction and better stability, is rigidity, thermotolerance that modified epoxy provides.The introducing of contraposition phenyl ring makes the good heat resistance of modifying epoxy resin by organosilicon in the modifying epoxy resin by organosilicon containing other groups such as methyl, methoxyl group.
(4) application is also surprised to find, under specific component compatibility and proportioning, by the considered critical to production craft step and parameter, can obtain thermal weight loss at 250 DEG C is the tackiness agent of 0%, namely thermosteresis phenomenon is not had to occur, meanwhile this tackiness agent also has excellent mechanical property concurrently, and this tackiness agent there is no method by routine techniques means of the prior art and obtains.
Embodiment
In order to make those skilled in the art person understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Tackiness agent in the present embodiment adopts the component of following weight part to prepare:
A expects:
B expects:
Blocked isocyanate YG-75F 30.0 parts
Preparation method is: (1) is got ethanol and poured in Erlenmeyer flask, drips silane coupling agent KH-560, and dropping limit, limit is shaken, and dropwises rear continuation concussion and shakes up until system is uniformly dispersed, and then leaves standstill 10 minutes wiring solution-formings stand-by; Then the solution that this configures is poured into particle diameter is housed is in the Erlenmeyer flask of the nano silicon of 20 ~ 100nm, with ultrasonic disperser ultrasonic disperse 15 minutes, ultrasonic frequency was 30KHz, obtains transparent modified manometer silicon dioxide solution;
(2) modifying epoxy resin by organosilicon is prepared as follows: by epoxy resin E-44: the mass ratio of Diphenylsilanediol=4:1 is got the raw materials ready, epoxy resin E-44 is loaded in three neck round-bottomed flasks, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, stannous octoate accounts for 1% of reactant total mass, and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours;
(3) under room temperature, the surface modified nano silicon solution that step (1) obtains is poured in modifying epoxy resin by organosilicon product, reflux at 90 DEG C, stirs pressure reducing and steaming ethanol after 1 hour, obtains nano-silicon dioxide modified epoxy resin;
(4) under the middling speed dispersion state of 500r/min, in nano-silicon dioxide modified epoxy resin, B material is added, the filling heat-proof epoxy tackiness agent namely obtained for non-excavation repairing technique after dispersion stirs.
Embodiment 2
Tackiness agent in the present embodiment adopts the component of following weight part to prepare:
A expects:
B expects:
Blocked isocyanate YG-75F 25.0 parts
Preparation method is: (1) is got ethanol and poured in Erlenmeyer flask, drips silane coupling agent KH-560, and dropping limit, limit is shaken, and dropwises rear continuation concussion and shakes up until system is uniformly dispersed, and then leaves standstill 10 minutes wiring solution-formings stand-by; Then the solution that this configures is poured into particle diameter is housed is in the Erlenmeyer flask of the nano silicon of 20 ~ 100nm, with ultrasonic disperser ultrasonic disperse 10 minutes, ultrasonic frequency was 50KHz, obtains transparent modified manometer silicon dioxide solution;
(2) modifying epoxy resin by organosilicon is prepared as follows: by epoxy resin E-44: the mass ratio of Diphenylsilanediol=4:1 is got the raw materials ready, epoxy resin E-44 is loaded in three neck round-bottomed flasks, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, stannous octoate accounts for 1.5% of reactant total mass, and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours;
(3) under room temperature, the surface modified nano silicon solution that step (1) obtains is poured in modifying epoxy resin by organosilicon product, reflux at 90 DEG C, stirs pressure reducing and steaming ethanol after 1 hour, obtains nano-silicon dioxide modified epoxy resin;
(4) under the middling speed dispersion state of 800r/min, in nano-silicon dioxide modified epoxy resin, B material is added, the filling heat-proof epoxy tackiness agent namely obtained for non-excavation repairing technique after dispersion stirs.
Embodiment 3
Tackiness agent in the present embodiment adopts the component of following weight part to prepare:
A expects:
B expects:
Blocked isocyanate YG-75F 25.0 parts
Preparation method is: (1) is got ethanol and poured in Erlenmeyer flask, drips silane coupling agent KH-560, and dropping limit, limit is shaken, and dropwises rear continuation concussion and shakes up until system is uniformly dispersed, and then leaves standstill 10 minutes wiring solution-formings stand-by; Then the solution that this configures is poured into particle diameter is housed is in the Erlenmeyer flask of the nano silicon of 20 ~ 100nm, with ultrasonic disperser ultrasonic disperse 20 minutes, ultrasonic frequency was 20KHz, obtains transparent modified manometer silicon dioxide solution;
(2) modifying epoxy resin by organosilicon is prepared as follows: by epoxy resin E-44: the mass ratio of Diphenylsilanediol=4:1 is got the raw materials ready, epoxy resin E-44 is loaded in three neck round-bottomed flasks, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, stannous octoate accounts for 2% of reactant total mass, and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours;
(3) under room temperature, the surface modified nano silicon solution that step (1) obtains is poured in modifying epoxy resin by organosilicon product, reflux at 90 DEG C, stirs pressure reducing and steaming ethanol after 1 hour, obtains nano-silicon dioxide modified epoxy resin;
(4) under the middling speed dispersion state of 600r/min, in nano-silicon dioxide modified epoxy resin, B material is added, the filling heat-proof epoxy tackiness agent namely obtained for non-excavation repairing technique after dispersion stirs.
Embodiment 4
Tackiness agent in the present embodiment adopts the component of following weight part to prepare:
A expects:
B expects:
Blocked isocyanate YG-75F 20.0 parts
Preparation method is: (1) is got ethanol and poured in Erlenmeyer flask, drips silane coupling agent KH-560, and dropping limit, limit is shaken, and dropwises rear continuation concussion and shakes up until system is uniformly dispersed, and then leaves standstill 10 minutes wiring solution-formings stand-by; Then the solution that this configures is poured into particle diameter is housed is in the Erlenmeyer flask of the nano silicon of 20 ~ 100nm, with ultrasonic disperser ultrasonic disperse 10 minutes, ultrasonic frequency was 20KHz, obtains transparent modified manometer silicon dioxide solution;
(2) modifying epoxy resin by organosilicon is prepared as follows: by epoxy resin E-44: the mass ratio of Diphenylsilanediol=4:1 is got the raw materials ready, epoxy resin E-44 is loaded in three neck round-bottomed flasks, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, stannous octoate accounts for 2% of reactant total mass, and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours;
(3) under room temperature, the surface modified nano silicon solution that step (1) obtains is poured in modifying epoxy resin by organosilicon product, reflux at 90 DEG C, stirs pressure reducing and steaming ethanol after 1 hour, obtains nano-silicon dioxide modified epoxy resin;
(4) under the middling speed dispersion state of 600r/min, in nano-silicon dioxide modified epoxy resin, B material is added, the filling heat-proof epoxy tackiness agent namely obtained for non-excavation repairing technique after dispersion stirs.
Comparative example 1
Tackiness agent in this comparative example adopts the component of following weight part to prepare:
A expects:
Epoxy resin E-44 70.0 parts
B expects:
Blocked isocyanate YG-75F 25.0 parts
Preparation method is: under the middling speed dispersion state of 500-800r/min, adds cyclohexanone resin, B material in epoxy resin E-44 successively, filling after dispersion stirs, and obtains tackiness agent.
Test example 1
Mechanics performance determining is carried out to the tackiness agent of embodiment 1-4 and comparative example 1.Mechanics Performance Testing adopts universal testing machine (CMT-6105) and JB-30A shock-testing machine.Tensile shear strength test loads with the constant speed of 10 ± 2mm/min, maximum load when record sample destroys.Impact bending strength test adopts cylinder sample (Φ 10mm × 52mm) to sticky, and shock-testing machine carries out impact toughness test.Logging is in the middle of following table 1.
Table 1 mechanics properties testing result
Test example 2
Carry out resistance toheat test to the tackiness agent that embodiment 1-4 and comparative example provide, testing method adopts thermogravimetic analysis (TGA) method well known in the art, concrete test condition and result as follows:
Embodiment 1 tackiness agent thermal weight loss measures: in air atmosphere, temperature rise rate is set as 10 DEG C/min, and temperature range is 25-300 DEG C, and when temperature reaches 250 DEG C, thermal weight loss ratio is 0%.
Embodiment 2 tackiness agent thermal weight loss measures: in air atmosphere, temperature rise rate is set as 10 DEG C/min, and temperature range is 25-300 DEG C, and when temperature reaches 200 DEG C, thermal weight loss ratio is 0%.
Embodiment 3 tackiness agent thermal weight loss measures: in air atmosphere, temperature rise rate is set as 10 DEG C/min, and temperature range is 25-300 DEG C, and when temperature reaches 250 DEG C, thermal weight loss ratio is 1.3%.
Embodiment 4 tackiness agent thermal weight loss measures: in air atmosphere, temperature rise rate is set as 10 DEG C/min, and temperature range is 25-300 DEG C, and when temperature reaches 250 DEG C, thermal weight loss ratio is 2.1%.
Comparative example 1 tackiness agent thermal weight loss measures: in air atmosphere, temperature rise rate is set as 10 DEG C/min, and temperature range is 25-300 DEG C, and when temperature reaches 200 DEG C, thermal weight loss ratio is 6.3%.
Above a kind of heat-proof epoxy tackiness agent for non-excavation repairing technique provided by the present invention and preparation method thereof is described in detail.Apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands core concept of the present invention for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention.These improve and modify and also should fall in the protection domain of the claims in the present invention.
Claims (9)
1. the heat-proof epoxy tackiness agent for non-excavation repairing technique, it is characterized in that, expected to form by A material and B, described A material comprises following component by weight: modifying epoxy resin by organosilicon 65.0-90.0 part, ethanol 20.0-30.0 part, silane coupling agent 0.05-2.0 part, nano silicon 1.0-3.0 part;
Described B material is the blocked isocyanate of 20.0-30.0 part.
2. the heat-proof epoxy tackiness agent for non-excavation repairing technique according to claim 1, is characterized in that, described modifying epoxy resin by organosilicon is the epoxy resin with Diphenylsilanediol modification.
3. the heat-proof epoxy tackiness agent for non-excavation repairing technique according to claim 2, is characterized in that, described modifying epoxy resin by organosilicon is the epoxy resin E-44 with Diphenylsilanediol modification.
4. the heat-proof epoxy tackiness agent for non-excavation repairing technique according to claim 3, it is characterized in that, described modifying epoxy resin by organosilicon is prepared by a method comprising the following steps and obtains: epoxy resin E-44 is placed in reaction vessel, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, the mass ratio of epoxy resin E-44 and Diphenylsilanediol is 4:1, stannous octoate accounts for the 1-2% of reactant total mass, and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours.
5. the heat-proof epoxy tackiness agent for non-excavation repairing technique according to claim 1, is characterized in that, described blocked isocyanate is blocked isocyanate YG-75F.
6. the heat-proof epoxy tackiness agent for non-excavation repairing technique according to claim 1, is characterized in that, described silane coupling agent is silane coupling agent KH-560.
7. the heat-proof epoxy tackiness agent for non-excavation repairing technique according to claim 1, it is characterized in that, by thermogravimetic analysis (TGA) method, the heat-proof epoxy tackiness agent for non-excavation repairing technique is detected, in air atmosphere, when temperature rise rate is 10 DEG C/min, outlet temperature is 200 ~ 300 DEG C, the thermal weight loss ratio for the heat-proof epoxy tackiness agent of non-excavation repairing technique is less than 2.1%.
8. the heat-proof epoxy tackiness agent for non-excavation repairing technique according to claim 1, is characterized in that, the particle diameter of described nano silicon is 20 ~ 100nm.
9. described in claim 1 for a preparation method for the heat-proof epoxy tackiness agent of non-excavation repairing technique, it is characterized in that, comprise the steps:
(1) getting ethanol pours in container, drips silane coupling agent, and concussion shakes up rear standing 10 minutes wiring solution-formings; Then being poured into by the solution that this configures is equipped with in the container of nano silicon, ultrasonic disperse 10-20 minute, and ultrasonic frequency is 20-50KHz, obtains transparent modified manometer silicon dioxide solution;
(2) epoxy resin is placed in reaction vessel, 0.5 hour is vacuumized at 120 DEG C, add Diphenylsilanediol and the sub-tin of octoate catalyst successively, the mass ratio of epoxy resin and Diphenylsilanediol is 4:1, stannous octoate accounts for the 1-2% of reactant total mass, and at 145 DEG C, reaction obtains modifying epoxy resin by organosilicon product in 2 hours;
(3) under room temperature, the surface modified nano silicon solution that step (1) obtains is poured in modified epoxy product, reflux at 90 DEG C, stirs pressure reducing and steaming ethanol after 1 hour, obtains nano-silicon dioxide modified epoxy resin;
(4) under the middling speed dispersion state of 500-800r/min, in nano-silicon dioxide modified epoxy resin, B material is added, the filling heat-proof epoxy tackiness agent namely obtained for non-excavation repairing technique after dispersion stirs.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479117A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of chemical pipeline binding agent |
| CN111234167A (en) * | 2020-04-03 | 2020-06-05 | 胡黎明 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
| CN113234208A (en) * | 2021-05-10 | 2021-08-10 | 广州高驰新材料科技有限公司 | Preparation method of solvent-free epoxy topcoat curing agent |
-
2015
- 2015-05-22 CN CN201510264694.4A patent/CN104830262A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479117A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of chemical pipeline binding agent |
| CN111234167A (en) * | 2020-04-03 | 2020-06-05 | 胡黎明 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
| CN111234167B (en) * | 2020-04-03 | 2021-02-19 | 赵牧青 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
| CN113234208A (en) * | 2021-05-10 | 2021-08-10 | 广州高驰新材料科技有限公司 | Preparation method of solvent-free epoxy topcoat curing agent |
| CN113234208B (en) * | 2021-05-10 | 2021-10-22 | 广州高驰新材料科技有限公司 | Preparation method of solvent-free epoxy topcoat curing agent |
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Application publication date: 20150812 |