CN114262401B - Photoinduced reversible solid-liquid conversion azobenzene high polymer material and application thereof in trenchless pipeline repair - Google Patents
Photoinduced reversible solid-liquid conversion azobenzene high polymer material and application thereof in trenchless pipeline repair Download PDFInfo
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Abstract
The invention discloses a photo-induced reversible solid-liquid conversion azobenzene high polymer material and application thereof in trenchless pipeline repair, wherein the photo-induced reversible solid-liquid conversion azobenzene high polymer material has a trans-form configuration and a cis-form configuration, and is respectively shown as the following formula I- (E) and the following formula I- (Z):
the trans-configured polymer of formula I- (E) is solid at room temperature, and the cis-configured polymer of formula I- (Z) is liquid at room temperature. The azobenzene high polymer material can be used as a trenchless pipeline repairing lining material, and a pipeline lining layer is obtained by spraying or pouring azobenzene high polymer solution; when the pipeline is damaged, ultraviolet light is applied to the lining layer, so that the lining material can flow to fill the crack, and the pipeline repair is realized.
Description
Technical Field
The invention belongs to the technical field of pipeline repair, and particularly relates to a photoinduced reversible solid-liquid conversion azobenzene high polymer material and application thereof in trenchless pipeline repair.
Background
In 2020, the length of the urban drainage pipeline exceeds 80 kilometers, and the pipeline is damaged by aging, corrosion, cracking, collapse and the like after being used for a long time, and needs to be maintained in time. The pipeline non-excavation repairing technology is a new construction technology for laying, replacing and repairing various underground pipelines by utilizing various rock-soil drilling equipment and technical means and adopting the modes of guiding, directional drilling and the like under the condition of excavating a tiny part of the ground surface, does not obstruct traffic and damage vegetation, does not influence the normal operation of the society, and has higher social and economic values.
The existing trenchless pipeline repairing technology is an ultraviolet curing pipeline repairing technology from Germany, and is a mainstream technology for trenchless repairing of municipal pipelines. However, the inner liner tube of this repair technique cannot be repaired again because the conventional crosslinked polymer cannot be melted or dissolved after being damaged again. And the lining pipe can be flushed again or the pipeline can be directly replaced by excavating to prevent the water pipe from leaking.
Disclosure of Invention
In view of the above, the invention provides a photo-induced reversible solid-liquid conversion azobenzene polymer material and an application thereof in trenchless pipeline repair. The azobenzene high polymer material can be converted from a solid state to a liquid state under ultraviolet light for many times, and returns to the solid state after stopping illumination, so that the requirement of non-excavation repair of pipelines for many times is met.
The photo-induced reversible solid-liquid conversion azobenzene high polymer material has a trans-form configuration and a cis-form configuration, and is respectively shown as the following formula I- (E) and the following formula I- (Z):
the trans-configured polymer of formula I- (E) is solid at room temperature, and the cis-configured polymer of formula I- (Z) is liquid at room temperature.
The polymerization degree n = n of the azobenzene high polymer material 1 +n 2 N ranges from 14 to 200; the polydispersity index is 1.1-2.
The preparation method of the azobenzene high polymer material comprises the following steps:
step 1: putting a monomer 6- (4- ((4-decylphenyl) dinitrogen) phenoxy) hexyl methacrylate, cuprous bromide and an initiator into a pressure-resistant bottle, operating in a glove box, adding a ligand and anhydrous anisole into the bottle by using an injector, taking out the bottle after sealing, reacting at room temperature for 20-320min, passing through an alkaline alumina column, pouring into petroleum ether, carrying out suction filtration and drying, dissolving solid by using tetrahydrofuran, then carrying out multiple precipitation in diethyl ether to remove unreacted monomers, and carrying out vacuum overnight drying at 45 ℃ to prepare the azobenzene polymer with the structure shown in the formula I- (E).
Step 2: trans-configured azobenzene polymer I- (E) is 1-100mW/cm 2 The azobenzene molecules I- (Z) with cis-configuration are converted under the irradiation of 365nm ultraviolet light, and the phase state is converted from solid state to liquid state; the cis-configured azobenzene polymer I- (Z) is naturally placed at room temperature or at 1-100mW/cm 2 The azobenzene polymer I- (E) is converted into a trans-configuration azobenzene polymer I- (E) under the irradiation of visible light of 530nm, and the phase state is converted into a solid state from a liquid state.
And (3) repeating the step (2) to realize reversible circulation of solid-liquid conversion.
In step 1, the structure of the monomer is shown as the following formula II:
the monomer shown in the formula II has a trans-configuration and a cis-configuration, and when the trans-azobenzene polymer with the structure shown in the formula I- (E) is prepared, the trans-configuration content in the monomer shown in the formula II is ensured to be more than or equal to 85 percent, and the monomer can be directly used for preparing the azobenzene polymer material in the step 1 under the condition.
In step 1, the initiator is 1,8-diacylbis (2-bromo-2-methylpropionate) octane. Compared with the initiator for the conventional polymerization of the azobenzene, the initiator at two ends can improve the polymerization efficiency by at least one time, and is suitable for industrial production.
The initiator 1,8-diacylbis (2-bromo-2-methylpropionate) octane is prepared by a method comprising the following steps:
dissolving 1,8-octanediol (1.65g, 11.3mmol) in a dichloromethane solvent, adding triethylamine (8.2mL, 58.9 mmol) thereto, stirring well, and cooling to below 5 ℃ in an ice-water bath; dropwise adding 2-bromoisobutyryl bromide (7 ml,56.5 mmol) into the system at the speed of 3 s/drop, wherein white smoke is generated in the dropwise adding process, and the temperature is slightly increased; after the dropwise addition, sealing the bottle mouth with a sealing film, and continuously stirring overnight for reaction for 12 hours; after the reaction is finished, dichloromethane (lower layer) and saturated aqueous solution of sodium chloride are used for extraction for three times, organic phase is collected, anhydrous sodium sulfate is used for drying and dewatering, filtration is carried out, solvent is removed by rotary evaporation at 40 ℃, silica gel column is carried out, and eluent is petroleum ether: methylene chloride 100, 0-4:1 (v/v), dried at 45 ℃ for 4h under vacuum, yielded 1.8g of initiator.
According to the invention, an azobenzene high polymer material with a photoinduced reversible solid-liquid conversion characteristic at room temperature is obtained by an ATRP polymerization method, and can be used as a lining material for repairing a trenchless pipeline. In particular to a pipeline lining layer obtained by spraying or infusing azobenzene high molecular solution. When the pipeline is damaged, ultraviolet light is applied to the lining layer, so that the lining material can flow to fill the crack, and the pipeline repair is realized.
The thickness of the lining layer is 0.1-1mm.
The organic solvent of the azobenzene polymer solution can adopt any one of chloroform, tetrahydrofuran, anisole or dioxane.
The concentration of the azobenzene polymer solution is 20-50wt%.
In the azobenzene polymer solution, because the cis-configuration azobenzene polymer I- (Z) has fluidity and can be washed away by liquid in a pipeline, the content of the trans-configuration azobenzene polymer I- (E) needs to exceed 80%, and a lining layer with better mechanical property can be formed after the solvent is volatilized, so that the function of protecting the pipeline is achieved.
Compared with the existing lining material for repairing the trenchless pipeline, the invention has the following advantages:
the photoliquefaction lining material for repairing the trenchless pipeline is of a linear structure, can be heated to a melting point or above to enable the liner to flow, and can also utilize the photocis-trans isomerism characteristic to generate the photosolid-liquid conversion. Once the pipeline is damaged, azobenzene macromolecules can flow through heating or illumination, and the pipeline can be repaired in a non-excavation mode for many times. And due to the flowability of the cis-azobenzene polymer material, under the action of pressurization and gravity, cis-azobenzene polymers can be sucked into the crack by capillary force, so that the whole crack is completely filled, and a better repairing effect is achieved.
Drawings
FIG. 1 shows the NMR spectrum of polymerized monomers.
Figure 2 shows the nmr hydrogen spectrum of the azobenzene polymer.
FIG. 3 shows a photomicrograph (50 μm on scale) of a solid sample of trans-azobenzene that liquefies under UV light (365 nm LED light).
FIG. 4 shows the results of computerized tomography (6 mm on scale) of PVC-U tubes coated with azobenzene macromolecule before and after repair.
Detailed Description
In order to further illustrate the present invention, the following will describe in detail the synthesis method of the azobenzene polymer material with photo-reversible solid-liquid transition property and its application as a pipe repairing lining, with reference to the following examples.
The 4-n-decylaniline used in the following examples was purchased from TCL, concentrated hydrochloric acid, tetrahydrofuran, sodium nitrite, phenol, sodium hydroxide, sodium bicarbonate, anhydrous potassium carbonate, anhydrous sodium sulfate, chloroform, and methanol from national medicine, petroleum ether and methylene chloride from corm chemical, and 6-chloro-1-hexanol from ann naiji, methacryloyl chloride from mclin.
Example 1: synthesis of polymerized monomers
1. 4-n-decylaniline (10g, 42.8mmol) was added to a mixed solution of dilute hydrochloric acid (11.0 ml,. Rho =1.18g/ml,128.8 mmol) and tetrahydrofuran (40 ml), followed by placing in an ice-water bath. After stirring uniformly, an aqueous solution of sodium nitrite (2.950 g,42.8 mmol) was slowly added thereto and mixed for 20min. Phenol (4.6mL, 1.071g/ml,49.5 mmol) was dissolved in an aqueous solution of sodium hydroxide (1.7g, 43.0mmol) and potassium carbonate (6.0g, 43.4mmol) and stirred for 20min. The mixed solution containing the 4-n-decylaniline is slowly dripped into the mixed solution containing the phenol for reaction, the solution gradually changes from yellow to brown, and the solution is stirred for 4 hours at room temperature. Neutralized with dilute hydrochloric acid to pH =6, filtered with suction, and washed three times with water to give a yellowish brown solid. Vacuum drying overnight at 45 deg.C, thermal recrystallization from petroleum ether, filtration, and vacuum drying again gave 13.8g of product. Yield: 95 percent.
2. The product 4- (4-decylphenylazo) phenol (13.5g, 39.8mmol) of step 1 was weighed out and dissolved in 300ml of N, N-dimethylformamide, and potassium carbonate (6.0g, 43.4mmol) was added thereto and stirred for 20min. 6-chloro-1-hexanol (8 ml,. Rho =1.024g/ml,60.0 mmol) and several grains of potassium iodide were added thereto and reacted at 110 ℃ for 22h. After cooling, extraction is carried out with ethyl acetate and sodium bicarbonate aqueous solution, an organic phase is obtained by separation, dried by anhydrous sodium sulfate, filtered, and ethyl acetate is removed by rotary evaporation at 45 ℃ to obtain a crude product. The crude product was recrystallized twice using dichloromethane and petroleum ether as good and poor solvents, respectively. Drying overnight at 45 ℃ under vacuum gave 17.0g of product. Yield: 90 percent.
3. The product of step 2, 6- (4- ((4-decylphenylazo) phenoxy) hexan-1-ol (10.2g, 23.1mmol), triethylamine (3.6 mL,. Rho =0.73g/mL,25.5 mmol) and 150mL of dichloromethane were weighed into a 250mL single-neck flask, placed in an ice-water bath, stirred uniformly, and a mixed solution of methacryloyl chloride (2.7 mL,. Rho =1.1g/mL,28.5 mmol) and 30mL of dichloromethane was added thereto through a dropping funnel at a rate of 3 to 4 sec/drop, reacted overnight for 14h, the plate starting material was all reacted, a saturated aqueous solution of sodium bicarbonate was added to the solution with stirring to neutralize the remaining methacryloyl chloride, followed by extraction with dichloromethane three times, the organic phase was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated, and then recrystallized twice with tetrahydrofuran and methanol, dried under vacuum at 40 ℃ overnight to give 9.6g of a polymerized monomer at a yield of 80%.
FIG. 1 shows a nuclear magnetic hydrogen spectrum of the polymerized monomer prepared.
Example 2: polymerization of azobenzene Polymer
Dissolving 1,8-octanediol (1.65g, 11.3mmol) in 80mml dichloromethane solvent, adding triethylamine (8.2 mL,58.9 mmol), stirring well, and cooling to below 5 ℃ in an ice-water bath; 2-bromoisobutyryl bromide (7 ml,56.5 mmol) was added to the solution via a dropping funnel at a rate of 3 s/drop, and white smoke was generated during the dropping, and the temperature was slightly increased. After the dropwise addition, the bottle mouth is sealed by a sealing film, and the stirring is continued overnight for 12 hours. The mixture was extracted three times with dichloromethane (lower layer) and saturated aqueous solution of sodium chloride, and the organic phase was collected. Drying with anhydrous sodium sulfate to remove water, filtering, and rotary evaporating at 40 deg.C to remove solvent. Passing through a silica gel column, and eluting with petroleum ether: dichloromethane 100: 0-4:1. Vacuum drying at 45 ℃ for 4h gave 1.8g of initiator.
The monomer, hexyl 6- (4- ((4-decylphenyl) azo) phenoxy) methacrylate (2.000g, 4 mmol), cuprous bromide (38.0 mg, 26.4. Mu. Mol), and the double-ended initiator 1,8-diacylbis (2-bromo-2-methylpropionate) octane (57.2 mg, 128.8. Mu. Mol) from example 1 were taken and placed in a 15mL thick-walled pressure-resistant bottle, followed by operation in a glovebox, ligand PMDETA (110. Mu.l, 529.0. Mu. Mol) was added to the bottle with a micro-syringe, followed by 4mL of anhydrous anisole, and the bottle was sealed and removed from the glovebox. Stirring in a water bath kettle at 31 ℃ for 40min, wherein the monomer conversion rate is 51.7%. Passing through alkaline alumina column, pouring into petroleum ether, filtering, and drying. Dissolving the solid with tetrahydrofuran, precipitating in diethyl ether to remove unreacted monomer, and vacuum drying at 45 deg.C overnight to obtain polymer shown in formula II- (E). Measurement of Polymer M by GPC n =15k, pdi =1.18. FIG. 2 shows a nuclear magnetic hydrogen spectrum of the prepared azobenzene polymer.
Example 3: photoinduced solid-liquid conversion of azobenzene macromolecules at micrometer scale
At room temperature, a small solid sample of azobenzene polymer (example 2) was placed on a smooth, clean glass slide on a microscope stage at 365nm (5.5 mW/cm) 2 ) And irradiating the surface of the solid sample by using ultraviolet light to cause the solid sample to generate photoisomerization, and after irradiating for 15min, realizing complete solid-liquid conversion. Figure 3 shows liquefaction of a trans-solid sample under uv light irradiation.
Example 4: repair result of PVC-U pipe with azobenzene macromolecule as lining
800mg of azobenzene polymer (example 2) was dissolved in 4ml of tetrahydrofuran at room temperature to prepare a 23wt% solution, which was spin-coated on a glass having an inner diameter of 28mm,PVC-U pipe with length of 10 cm. After standing at room temperature for 2h, the mixture was placed in a vacuum oven at 45 ℃ and dried overnight. Penetrating and damaging the PVC-U pipe by using a numerical control machine (the crack is 12mm long and 0.5mm wide), and then using 365nm (8 mW/cm) 2 ) The ultraviolet lamp tube irradiates the inside of the PVC-U tube to ensure that the azobenzene high-molecular lining is subjected to photoisomerization and generates fluidity, and the crack is repaired after about 4 hours. FIG. 4 shows the results of computerized tomography (6 mm on scale) of PVC-U tubes coated with azobenzene macromolecule before and after repair.
The embodiment shows that the azobenzene polymer provided by the invention has high synthesis efficiency and excellent photo-reversible solid-liquid conversion characteristics, and can be used for repairing pipelines.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. A photo-induced reversible solid-liquid conversion azobenzene high polymer material is characterized in that:
the photo-induced reversible solid-liquid conversion azobenzene high polymer material has a trans-configuration and a cis-configuration, and is respectively shown as the following formula I- (E) and the following formula I- (Z):
the trans-configuration type I- (E) polymer is solid at room temperature, and the cis-configuration type I- (Z) polymer is liquid at room temperature;
the polymerization degree n = n of the azobenzene high polymer material 1 +n 2 N ranges from 14 to 200; a polydispersity index of 1.1 to 2;
the photo-induced reversible solid-liquid conversion azobenzene high polymer material is prepared by a method comprising the following steps:
step 1: putting a monomer 6- (4- ((4-decylphenyl) dinitrogen) phenoxy) hexyl methacrylate, cuprous bromide and an initiator into a pressure-resistant bottle, operating in a glove box, adding a ligand and anhydrous anisole into the bottle by using an injector, taking out the bottle after sealing, reacting at room temperature for 20-320min, passing through an alkaline alumina column, pouring into petroleum ether, carrying out suction filtration and drying, dissolving a solid by using tetrahydrofuran, then carrying out multiple precipitation in diethyl ether to remove unreacted monomers, and carrying out vacuum drying to prepare an azobenzene polymer with the structure shown in the formula I- (E);
step 2: trans-configured azobenzene polymer I- (E) at 1-100mW/cm 2 The azobenzene molecule I- (Z) is converted into a cis-configuration azobenzene molecule under the irradiation of 365nm ultraviolet light, and the phase state is converted into a liquid state from a solid state; the cis-configured azobenzene polymer I- (Z) is naturally placed at room temperature or at 1-100mW/cm 2 The azobenzene polymer I- (E) is converted into a trans-configuration azobenzene polymer I- (E) under the irradiation of visible light of 530nm, and the phase state is converted into a solid state from a liquid state;
in step 1, the structure of the monomer is shown as formula II below:
in step 1, the initiator is 1,8-diacylbis (2-bromo-2-methylpropionate) octane.
2. The photo-reversible solid-liquid transition azobenzene polymer material according to claim 1, wherein said initiator 1,8-diacylbis (2-bromo-2-methylpropionate) octane is prepared by a method comprising the following steps:
dissolving 1,8-octanediol in dichloromethane solvent, adding triethylamine, stirring uniformly, and cooling to below 5 deg.C in ice water bath; dropwise adding 2-bromoisobutyryl bromide into the system, wherein white smoke is generated in the dropwise adding process, and the temperature is slightly increased; after the dropwise addition is finished, sealing the bottle mouth, and continuously stirring for reaction for 12 hours; and separating and purifying after the reaction is finished to obtain the initiator.
3. The application of the photo-induced reversible solid-liquid conversion azobenzene polymer material as claimed in claim 1, is characterized in that:
the azobenzene high polymer material is used as a trenchless pipeline repairing lining material, and a pipeline lining layer is obtained by spraying or infusing azobenzene high polymer solution; when the pipeline is damaged, ultraviolet light is applied to the lining layer, so that the lining material can flow to fill the crack, and the pipeline repair is realized.
4. Use according to claim 3, characterized in that:
the thickness of the lining layer is 0.1-1mm.
5. Use according to claim 3, characterized in that:
the organic solvent of the azobenzene polymer solution can adopt any one of chloroform, tetrahydrofuran, anisole or dioxane.
6. Use according to claim 3 or 5, characterized in that:
the concentration of the azobenzene high molecular solution is 20-50wt%.
7. Use according to claim 3, characterized in that:
in the azobenzene macromolecule solution, the content of the trans-configuration azobenzene macromolecule I- (E) is more than or equal to 80wt%.
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| CN104045754A (en) * | 2014-06-18 | 2014-09-17 | 北京科技大学 | Method for synthesizing visible-light response type azobenzene polymer |
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| CN109651545A (en) * | 2018-12-28 | 2019-04-19 | 中国科学技术大学 | A kind of azobenzene polymer material and its preparation method and application |
| JP2020144232A (en) * | 2019-03-06 | 2020-09-10 | コニカミノルタ株式会社 | Toner and image forming method |
| CN113402685A (en) * | 2021-05-26 | 2021-09-17 | 华南理工大学 | Amphiphilic triblock polymer, preparation method thereof and pressure-sensitive adhesive prepared from amphiphilic triblock polymer |
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Patent Citations (5)
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|---|---|---|---|---|
| CN104045754A (en) * | 2014-06-18 | 2014-09-17 | 北京科技大学 | Method for synthesizing visible-light response type azobenzene polymer |
| CN104892871A (en) * | 2015-06-16 | 2015-09-09 | 厦门大学 | Hydrogel with self-repairing function and preparation method of hydrogel |
| CN109651545A (en) * | 2018-12-28 | 2019-04-19 | 中国科学技术大学 | A kind of azobenzene polymer material and its preparation method and application |
| JP2020144232A (en) * | 2019-03-06 | 2020-09-10 | コニカミノルタ株式会社 | Toner and image forming method |
| CN113402685A (en) * | 2021-05-26 | 2021-09-17 | 华南理工大学 | Amphiphilic triblock polymer, preparation method thereof and pressure-sensitive adhesive prepared from amphiphilic triblock polymer |
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| Azobenzene-Containing Block Copolymers as Light-Induced Reworkable Adhesives: Effects of Molecular Weight, Composition, and Block Copolymer Architectures on the Adhesive Properties;Shotaro Ito et al.;《Journal of Polymer Science, Part A: Polymer Chemistry》;20190130;第57卷(第7期);第806-813页 * |
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