CN-122011293-A - Temperature-responsive emulsifier, preparation method, application and epoxy resin emulsifying equipment

CN122011293ACN 122011293 ACN122011293 ACN 122011293ACN-122011293-A

Abstract

The invention belongs to the technical field of emulsification of epoxy resin, and particularly relates to a temperature response type emulsifier, a preparation method, application and epoxy resin emulsification equipment. The preparation method of the temperature response type emulsifier comprises the following steps of (1) mixing polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer with water, dissolving, regulating pH to obtain a pre-polymerized solution, (2) adding N-isopropyl acrylamide monomer and an initiator into the pre-polymerized solution under the protection of nitrogen, heating to react to obtain a reaction solution, (3) adding a cross-linking agent into the reaction solution to carry out cross-linking modification to obtain a crude product, and (4) purifying the crude product obtained by the treatment of the step (3) to obtain the temperature response type emulsifier. The temperature response type emulsifier disclosed by the invention is favorable for realizing the regulation and control of the surface activity of the emulsifier, and the technical limitation of the traditional static emulsifier is broken through.

Inventors

PANG BO
CHEN YIDONG
LIU LIRONG
GAO JIANGUO
Jing Shuaikang
JIN ZUQUAN
ZHANG WEI
LIU YONG
SONG XIAOYUN
YUAN LIANWANG
MA JIHUA
WANG ZHIYONG

Assignees

青岛理工大学
江苏启青新型材料科技有限公司

Dates

Publication Date: 20260512
Application Date: 20260112

Claims (10)

1. The preparation method of the temperature-responsive emulsifier is characterized by comprising the following steps of: (1) Mixing polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer with water, dissolving, and regulating pH to obtain a prepolymerization solution; (2) Under the protection of nitrogen, adding an N-isopropyl acrylamide monomer and an initiator into the prepolymerization solution, and heating to react to obtain a reaction solution; (3) Adding a cross-linking agent into the reaction liquid to carry out cross-linking modification to obtain a crude product; (4) Purifying the crude product obtained by the treatment in the step (3) to obtain the temperature-responsive emulsifier.
2. The method for preparing the temperature-responsive emulsifier according to claim 1, wherein the mass ratio of the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer to the N-isopropylacrylamide monomer is 100 (15-25); The mass ratio of the initiator to the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer is (0.5-1.2) 100; the mass ratio of the cross-linking agent to the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer is (0.1-0.3) 100; Preferably, the initiator is potassium persulfate, and the cross-linking agent is N, N' -methylene bisacrylamide.
3. The method for producing a temperature-responsive emulsifier according to claim 1, wherein in the step (1), the dissolution is performed at 75 to 85 ℃, and the pH is adjusted to 6.5 to 7.5; in the step (2), the reaction temperature is controlled to be 68-72 ℃, the reaction time is controlled to be 4-6h, and the conversion rate is more than or equal to 95%; In the step (3), after adding the cross-linking agent, reacting for 2-3 hours at 55-65 ℃; In the step (4), the purification mode is dialysis, and dialysis is performed by using a dialysis membrane with molecular weight cutoff of 3500 Da.
4. A temperature responsive emulsifier prepared by the method of any one of claims 1 to 3.
5. The temperature-responsive emulsifier of claim 4 wherein the temperature-responsive emulsifier has a formula of ; Wherein a=20-45, b=15-35, and the grafting degree is 8wt% to 15wt%.
6. An epoxy resin emulsion, characterized in that the components of the epoxy resin emulsion comprise an epoxy resin, the temperature-responsive emulsifier according to claim 4 or 5 and water.
7. The method for preparing an epoxy resin emulsion according to claim 6, comprising the steps of: A. dissolving the temperature-responsive emulsifier in water to obtain an emulsifier solution; B. preheating epoxy resin to 35-45 ℃, and mixing with the emulsifier solution under stirring to obtain a mixed solution; C. Shearing and stirring the mixed solution; D. performing steam activated emulsification on the mixed solution; E. And D, performing ultrasonic dispersion on the mixed solution obtained by the treatment in the step D.
8. The method of preparing an epoxy resin emulsion according to claim 7, wherein in step a, the mass of the temperature responsive emulsifier is 2% -8% of the mass of the epoxy resin; In the step B, the mixing is carried out at the rotating speed of 800rpm, and the mixing time is 10-15min; in the step C, the shearing comprises first-stage shearing, second-stage shearing and third-stage shearing, and the rotating speeds of the first-stage shearing, the second-stage shearing and the third-stage shearing are gradually increased; in the step D, when the steam is activated and emulsified, the temperature of the steam is 100-120 ℃; In step E, the frequency of the ultrasonic wave is 28-40kHz.
9. An epoxy resin emulsifying device is characterized by comprising a shearing mechanism, a steam spraying mechanism, an ultrasonic mechanism and a bracket; The support is provided with a vertical rod, a motor is slidably assembled on the vertical rod, a spiral stirring head is arranged on a rotating shaft of the motor, a supporting rod which extends downwards along the bottom surface of the motor and is parallel to the rotating shaft is arranged in the circumferential direction of the motor, and the upper end of the supporting rod is connected with a shell of the motor; The steam injection mechanism comprises a steam collector, the steam collector is connected with the lower end of the supporting rod, the steam collector is in a hollow column shape, a plurality of steam spray holes are formed in the circumference of the steam collector, the rotating shaft penetrates through the steam collector, and the spiral stirring head is arranged above the steam collector; The shearing mechanism comprises a mechanical shearing head which is arranged on the rotating shaft at a position corresponding to the lower part of the steam collector; The ultrasonic mechanism comprises a transducer, and the transducer is arranged on the supporting rod.
10. The epoxy resin emulsifying device of claim 9, wherein the mechanical shearing head of the shearing mechanism is provided with a first-stage shearing head, a second-stage shearing head and a third-stage shearing head which are sequentially arranged from outside to inside; The plurality of transducers are arranged, and the transducers are symmetrically distributed in an upper layer and a lower layer in a hexagonal manner; the steam injection mechanism further comprises a steam generator in communication with the steam accumulator for delivering steam to the steam accumulator.

Description

Temperature-responsive emulsifier, preparation method, application and epoxy resin emulsifying equipment Technical Field The invention belongs to the technical field of emulsification of epoxy resin, and particularly relates to a temperature response type emulsifier, a preparation method, application and epoxy resin emulsification equipment. Background At present, the preparation technology of the waterborne epoxy emulsion faces multiple challenges, the traditional emulsification process mainly depends on a static surfactant, the hydrophilic-lipophilic balance value of the static surfactant is fixed, and the static surfactant cannot adapt to dynamic changes of technological parameters such as temperature, viscosity and the like in the emulsification process, so that the emulsification efficiency is low, and the stability of the product is insufficient. Particularly, under the cold environment condition, the viscosity of the epoxy resin is increased sharply (the viscosity of the oily epoxy resin can be increased by 8-25 times in the low-temperature environment of-20 ℃ to 0 ℃, and the traditional mechanical stirring is difficult to realize effective dispersion), the traditional emulsification process needs to heat the whole reaction system in a large scale, the energy consumption is high, the temperature control is difficult, and the problem of resin degradation caused by local overheating often occurs. Existing emulsifier technology has significant limitations. The existing emulsifier is sensitive to pH value and ionic strength, and is easy to generate hydrolysis reaction under high temperature condition, so that the long-term stability of emulsion is affected. In addition, the traditional polymeric emulsifier has wide molecular weight distribution and poor batch stability, and is difficult to realize accurate process control. The technical problem is further aggravated by the influence of cold environment (the surface activity of the traditional emulsifier is obviously reduced, the critical micelle concentration is increased, and the emulsification efficiency is greatly reduced in a low-temperature environment). The existing emulsification equipment technology also has obvious defects. Traditional high-speed shearing equipment mainly relies on mechanical shearing force to realize dispersion, and energy utilization efficiency is low, and local high temperature is produced easily, leads to the inhomogeneous product performance. Although the ultrasonic dispersing equipment has good dispersing effect, the treatment capacity is limited when the ultrasonic dispersing equipment is used alone, and the industrial production requirement is difficult to meet. The lack of accurate temperature control of the steam heating equipment easily causes overheating or uneven heating, and influences the quality stability of products. Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art. Disclosure of Invention The invention aims to provide a temperature-responsive emulsifier, a preparation method, application and epoxy resin emulsifying equipment, which are used for solving or improving the problem that uniform dispersion of oily epoxy resin in water is difficult to realize. The preparation method of the temperature-responsive emulsifier comprises the following steps of (1) mixing polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer with water, dissolving, regulating pH to obtain a pre-polymerized solution, (2) adding N-isopropyl acrylamide monomer and an initiator into the pre-polymerized solution under the protection of nitrogen, heating to react to obtain a reaction solution, (3) adding a cross-linking agent into the reaction solution to carry out cross-linking modification to obtain a crude product, and (4) purifying the crude product obtained by the treatment of the step (3) to obtain the temperature-responsive emulsifier. The invention also provides a temperature response type emulsifier, which adopts the following technical scheme: A temperature-responsive emulsifier is prepared by the method. The invention also provides an epoxy resin emulsion which adopts the following technical scheme that the components of the epoxy resin emulsion comprise epoxy resin, the temperature-responsive emulsifier and water. The invention also provides a preparation method of the epoxy resin emulsion, which adopts the following technical scheme that the preparation method of the epoxy resin emulsion comprises the following steps of A, dissolving the temperature-responsive emulsifier in water to obtain an emulsifier solution, B, preheating epoxy resin to 35-45 ℃, mixing the epoxy resin with the emulsifier solution under stirring to obtain a mixed solution, C, shearing and stirring the mixed solution, D, performing steam activated emulsification on the mixed solution, and E, performing ultrasonic dispersion on the mixed solution obtained through the treatment in the ste