阅读说明：本技术 一种两亲性三嵌段聚合物及其制备方法和由其制备的压敏胶 (Amphiphilic triblock polymer, preparation method thereof and pressure-sensitive adhesive prepared from amphiphilic triblock polymer ) 是由 孙桃林 秦轩杰 陆孟泽 谭睿 于 2021-05-26 设计创作，主要内容包括：本发明公开了一种两亲性三嵌段聚合物及其制备方法和由其制备的压敏胶。本发明的两亲性三嵌段聚合物的结构式为：式中,m取60～370的整数,n取100～200的整数,p取60～370的整数。本发明的两亲性三嵌段聚合物的聚合度和嵌段比例可以灵活调节,将其制备成压敏胶适用于粘附铝板、钢板、硅橡胶、丙烯酸卞酯弹性体、PET板、聚四氟乙烯板、木材、离子凝胶等基材,可以实现多次剥离后的循环粘附,剥离后在基材表面几乎无残留,且无挥发性和腐蚀性,适合大面积推广应用。(The invention discloses an amphiphilic triblock polymer, a preparation method thereof and a pressure-sensitive adhesive prepared from the amphiphilic triblock polymer. The structural formula of the amphiphilic triblock polymer is as follows: wherein m is an integer of 60 to 370, n is an integer of 100 to 200, and p is an integer of 60 to 370. The polymerization degree and the block proportion of the amphiphilic triblock polymer can be flexibly adjusted, and the amphiphilic triblock polymer is prepared into pressure-sensitive adhesive suitable for adhering aluminum plates, steel plates and silicon rubberThe adhesive, the benzyl acrylate elastomer, the PET plate, the polytetrafluoroethylene plate, the wood, the ionic gel and other base materials can realize the cyclic adhesion after being peeled for many times, almost no residue is left on the surface of the base material after being peeled, and the adhesive has no volatility and corrosiveness, and is suitable for large-area popularization and application.)

1. An amphiphilic triblock polymer characterized by the structural formula:

wherein m is an integer of 60 to 370, n is an integer of 100 to 200, and p is an integer of 60 to 370And 60 to 370.

2. The method of preparing an amphiphilic triblock polymer of claim 1, comprising the steps of:

1) carrying out the reaction of 2-bromoisobutyryl bromide and ethylene glycol to obtainIs marked as a compound A;

2) carrying out the reaction of acrylic acid-2-hydroxyethyl ester and tert-butyldimethylsilyl chloride to obtainIs marked as compound B;

3) carrying out the reaction of the compound A and the compound B to obtainn₁Taking an integer of 50-100, n₂Taking an integer of 50-100, and marking as a compound C;

4) carrying out the reaction of benzyl acrylate and a compound C to obtainIs marked as a compound D;

5) carrying out the reaction of the compound D and tetrabutylammonium fluoride to obtain the amphiphilic triblock polymer

3. The method of preparing an amphiphilic triblock polymer according to claim 2, characterized in that: the molar ratio of the 2-bromoisobutyryl bromide to the ethylene glycol in the step 1) is 2: 1-2.5: 1; the reaction in the step 1) is carried out in a protective atmosphere, the reaction temperature is 0-4 ℃, and the reaction time is 12-24 h.

4. The method of preparing an amphiphilic triblock polymer according to claim 2 or 3, characterized in that: the mol ratio of the 2-hydroxyethyl acrylate to the tert-butyldimethylsilyl chloride in the step 2) is 1: 1-1: 1.5; the reaction in the step 2) is carried out in a protective atmosphere, the reaction temperature is 0-4 ℃, and the reaction time is 60-80 h.

5. The method of preparing an amphiphilic triblock polymer according to claim 2 or 3, characterized in that: the molar ratio of the compound A to the compound B in the step 3) is 1: 200-1: 300; the reaction in the step 3) is carried out under the condition of oxygen isolation, the reaction temperature is 80-100 ℃, and the reaction time is 2-12 h.

6. The method of preparing an amphiphilic triblock polymer according to claim 2 or 3, characterized in that: the molar ratio of the benzyl acrylate to the compound C in the step 4) is 200: 1-800: 1; the reaction in the step 4) is carried out under the condition of oxygen isolation, the reaction temperature is 80-100 ℃, and the reaction time is 12-24 hours.

7. The method of preparing an amphiphilic triblock polymer according to claim 2 or 3, characterized in that: the molar ratio of the compound D to tetrabutylammonium fluoride in the step 5) is 1: 100-1: 200; the reaction in the step 5) is carried out at 15-25 ℃ for 12-24 h.

8. A pressure sensitive adhesive comprising the amphiphilic triblock polymer of claim 1.

9. The method of claim 8, comprising the steps of: the amphiphilic triblock polymer of claim 1 is soaked with petroleum ether and then placed at normal temperature to obtain the pressure-sensitive adhesive.

10. Use of the pressure sensitive adhesive of claim 8 for adhering aluminum panels, steel panels, silicone rubber, benzyl acrylate elastomer, PET panels, polytetrafluoroethylene panels, wood or ionic gels.

Technical Field

The invention relates to the technical field of adhesives, in particular to an amphiphilic triblock polymer, a preparation method thereof and a pressure-sensitive adhesive prepared from the amphiphilic triblock polymer.

Background

In the field of intelligent robots, in order to realize the coordination of different components, good connection among the components is a problem which cannot be ignored. The new soft materials are required to be relied on for the update and development of the future intelligent robot, and at present, good connection of different parts is required to be realized through adhesives between different soft materials.

The pressure-sensitive adhesive is a pressure-sensitive material, and can gradually reach adsorption balance with a bonded surface after being subjected to pressure, so that certain bonding force is generated. Currently, most commercially available pressure-sensitive adhesives are polymeric adhesives with a single structure, such as: cyanoacrylate quick-drying glue and acrylate pressure-sensitive glue. Cyanoacrylate quick-drying adhesives can be instantly adhered to most surfaces, but cannot be adhered for two or more times. The acrylate pressure-sensitive adhesive is divided into a solvent type and a hydrosol type, the solvent type acrylate pressure-sensitive adhesive can pollute the environment to a certain extent and can cause certain damage to the health of sizing personnel, and the hydrosol type acrylate pressure-sensitive adhesive is high in strength and can generate more residues when being stripped.

In conclusion, the existing pressure-sensitive adhesive products all have obvious defects, the actual application requirements are difficult to completely meet, and the development of pressure-sensitive adhesives with more excellent comprehensive properties is urgently needed.

Disclosure of Invention

The invention aims to provide an amphiphilic triblock polymer, a preparation method thereof and a pressure-sensitive adhesive prepared from the amphiphilic triblock polymer.

The technical scheme adopted by the invention is as follows:

an amphiphilic triblock polymer having the structural formula:wherein m is an integer of 60 to 370, n is an integer of 100 to 200, and p is an integer of 60 to 370.

The preparation method of the amphiphilic triblock polymer comprises the following steps:

1) carrying out the reaction of 2-bromoisobutyryl bromide and ethylene glycol to obtainIs marked as a compound A;

2) carrying out the reaction of acrylic acid-2-hydroxyethyl ester and tert-butyldimethylsilyl chloride to obtainIs marked as compound B;

3) carrying out the reaction of the compound A and the compound B to obtainn₁Taking an integer of 50-100, n₂Taking an integer of 50-100, and marking as a compound C;

4) carrying out the reaction of benzyl acrylate and a compound C to obtainIs marked as a compound D;

5) carrying out the reaction of the compound D and tetrabutylammonium fluoride to obtain the amphiphilic triblock polymer

Preferably, the preparation method of the amphiphilic triblock polymer comprises the following steps:

1) dispersing triethylamine and ethylene glycol in dichloromethane, adding dichloromethane solution of 2-bromoisobutyryl bromide for reaction, and separating and purifying to obtain the final productIs marked as a compound A;

2) dispersing 2-hydroxyethyl acrylate and triethylamine in dichloromethane, adding dichloromethane solution of tert-butyldimethylsilyl chloride for reaction, and separating productAnd purifying to obtainIs marked as compound B;

3) dispersing the compound A, the compound B and pentamethyldiethylenetriamine in toluene, adding cuprous bromide, reacting, and separating and purifying to obtain the final productn₁Taking an integer of 50-100, n₂Taking an integer of 50-100, and marking as a compound C;

4) dispersing pentamethyldiethylenetriamine, benzyl acrylate and compound C in solvent, adding cuprous bromide for reaction, separating and purifying to obtain the productIs marked as a compound D;

5) dispersing the D in tetrahydrofuran, adding a tetrahydrofuran solution of tetrabutylammonium fluoride, and reacting to obtain the amphiphilic triblock polymer

Preferably, the molar ratio of the 2-bromoisobutyryl bromide to the ethylene glycol in the step 1) is 2: 1-2.5: 1.

Preferably, the reaction in the step 1) is carried out in a protective atmosphere, the reaction temperature is 0-4 ℃, and the reaction time is 12-24 hours.

Preferably, the protective atmosphere in step 1) is a nitrogen atmosphere (the reaction under the nitrogen atmosphere is favorable for improving the reaction yield).

Preferably, the mol ratio of the 2-hydroxyethyl acrylate to the tert-butyldimethylsilyl chloride in the step 2) is 1: 1-1: 1.5.

Preferably, the reaction in the step 2) is carried out in a protective atmosphere, the reaction temperature is 0-4 ℃, and the reaction time is 60-80 h.

Preferably, the protective atmosphere in step 2) is a nitrogen atmosphere (the reaction under the nitrogen atmosphere is favorable for improving the reaction yield).

Preferably, the molar ratio of the compound A to the compound B in the step 3) is 1: 200-1: 300.

Preferably, the reaction in step 3) is carried out under oxygen-barrier conditions (a specific process of oxygen-removal operation: quickly freezing a reaction system by using liquid nitrogen, vacuumizing the reaction system, thawing at normal temperature, and circulating for multiple times; the system is kept in an oxygen-free state, which is beneficial to the ATRP polymerization reaction, and further can improve the reaction yield), the reaction temperature is 80-100 ℃, and the reaction time is 2-12 h.

Preferably, the molar ratio of benzyl acrylate to compound C in step 4) is 200: 1-300: 1.

Preferably, the reaction in step 4) is carried out under oxygen-barrier conditions (a specific process of oxygen-removal operation: quickly freezing a reaction system by using liquid nitrogen, vacuumizing the reaction system, thawing at normal temperature, and circulating for multiple times; the system is kept in an oxygen-free state, which is beneficial to the ATRP polymerization reaction, and further can improve the reaction yield), the reaction temperature is 80-100 ℃, and the reaction time is 12-24 h.

Preferably, the molar ratio of the compound D and tetrabutylammonium fluoride in the step 5) is 1: 100-1: 200.

Preferably, the reaction in the step 5) is carried out at 15-25 ℃ for 12-24 h.

The pressure-sensitive adhesive comprises the amphiphilic triblock polymer.

The preparation method of the pressure-sensitive adhesive comprises the following steps: and (3) soaking the amphiphilic triblock polymer in petroleum ether, and standing at normal temperature to obtain the pressure-sensitive adhesive.

The invention has the beneficial effects that: the polymerization degree and the block proportion of the amphiphilic triblock copolymer can be flexibly adjusted, the pressure-sensitive adhesive prepared from the amphiphilic triblock copolymer is suitable for adhering base materials such as aluminum plates, steel plates, silicon rubber, benzyl acrylate elastomers, PET plates, polytetrafluoroethylene plates, wood, ionic gel and the like, can realize cyclic adhesion after repeated stripping, almost has no residue on the surface of the base material after stripping, has no volatility and corrosivity, and is suitable for large-area popularization and application.

Drawings

FIG. 1 is a DSC chart of pressure-sensitive adhesives E1 to E3 in examples 1 to 3.

FIG. 2 is a graph showing the results of the probe adhesion test between the pressure-sensitive adhesives E1-E3 of examples 1-3 and the glass surface at different temperatures and at different peeling rates.

FIG. 3 is a graph showing the results of the probe adhesion test of the pressure-sensitive adhesive E1 of example 1 to various surfaces.

FIG. 4 is a graph showing the results of the adhesion property test in which the pressure-sensitive adhesive E1 in example 1 was adhered again after being peeled off at different time intervals.

FIG. 5 is a digital photograph of the pressure-sensitive adhesive E1 of example 1 before and after peeling off the glass surface.

Detailed Description

The invention will be further explained and illustrated with reference to specific examples.

Example 1:

an amphiphilic triblock polymer, the preparation method of which comprises the following steps:

1) adding 5.8mL of triethylamine, 1.24g of ethylene glycol and 50mL of dried dichloromethane into 250mL of three-neck flask, uniformly mixing, introducing nitrogen, placing the three-neck flask into an ice bath at 0 ℃, dropwise adding 50mL of dichloromethane solution of 2-bromoisobutyryl bromide (containing 13.8g of 2-bromoisobutyryl bromide), stirring for 12h after adding, filtering, washing the filtrate for 3 times by using 1mol/L hydrochloric acid solution, 5 mass percent sodium bicarbonate solution and deionized water in sequence, drying the organic phase by using anhydrous sodium sulfate, filtering, concentrating the filtrate by using a rotary evaporator, quickly separating the crude product by using a silica gel chromatographic column by using a mixed solution of petroleum ether and ethyl acetate (the volume ratio of the petroleum ether to the ethyl acetate is 20:1), dissolving by using methanol, and recrystallizing to obtain the product(4.22g, 58.6% yield), as compound A, according to the following reaction scheme:

2) adding 11.6g of 2-hydroxyethyl acrylate, 16.7g of triethylamine and 20mL of dry dichloromethane into a 100mL three-neck flask, uniformly mixing, introducing nitrogen, placing the three-neck flask in an ice bath at 0 ℃, adding 100mL of dichloromethane solution of tert-butyldimethylchlorosilane (containing 18.1g of tert-butyldimethylchlorosilane), stirring for 72h, carrying out suction filtration, taking the filtrate, diluting the filtrate with 30mL of ethyl acetate, sequentially washing with 50mL of deionized water, 50mL of saturated sodium chloride solution and 50mL of 5 mass percent sodium bicarbonate solution for 3 times, taking the organic phase, drying with anhydrous sodium sulfate, filtering, taking the filtrate, concentrating with a rotary evaporator, rapidly separating the crude product by using a mixed solution of petroleum ether and ethyl acetate (the volume ratio of the petroleum ether to the ethyl acetate is 10:1), distilling at 90 deg.C under reduced pressure to obtain(14.1g, 61.3% yield), as compound B, according to the following reaction scheme:

3) 135mg of the compound A, 21g of the compound B, 173mg of pentamethyldiethylenetriamine and 21g of dry toluene were put into a 125mL Schlenk bottle, mixed uniformly, and the reaction system was subjected to oxygen-removing treatment on a vacuum line (specific procedure: quickly freezing the reaction system by using liquid nitrogen, vacuumizing the reaction system, thawing at normal temperature) for 4 times, adding 53.6mg of cuprous bromide, reacting at 90 ℃ for 12 hours, quickly separating by using alumina to remove copper salt precipitate, concentrating the reaction solution, precipitating in glacial methanol for 3 times, placing the crude product in a vacuum oven at normal temperature for 7 days to obtain the product(13.5g, 64.3% yield), as compound C, according to the following reaction scheme:

4) 415mg of pentamethyldiethylenetriamine, 10g of benzyl acrylate, 6g of compound C and 10g of dry toluene are added into a 125mL Schlenk bottle, the mixture is uniformly mixed, and the reaction system is subjected to oxygen removal treatment on a vacuum line (specific process: quickly freezing the reaction system by using liquid nitrogen, vacuumizing the reaction system, thawing at normal temperature) for 5 times, adding 57.2g of cuprous bromide, reacting at 90 ℃ for 12 hours, quickly separating by using alumina to remove copper salt precipitate, concentrating the reaction solution, precipitating in glacial methanol for 3 times, placing the crude product in a vacuum oven at normal temperature for 2 days to obtain the product(6.2g), denoted Compound D, of the formula:

5) dispersing 1g of the compound D in 1mL of tetrahydrofuran, adding 3.47mL of tetrahydrofuran solution of tetrabutylammonium fluoride (containing 0.905g of tetrabutylammonium fluoride), mixing and oscillating for 10min, carefully paving the reaction solution on a tetrafluoroethylene plate with a groove, sealing a glass plate on the tetrafluoroethylene plate by using a double-sided adhesive tape, and standing for 12h to obtain the amphiphilic triblock polymerThe reaction formula is as follows:

a preparation method of the pressure-sensitive adhesive comprises the following steps:

combining amphiphilic triblock polymersSoaking in petroleum ether for 4 days, and standing at normal temperature for one week to obtain pressure-sensitive adhesive (E1).

Example 2:

an amphiphilic triblock polymer, the preparation method of which comprises the following steps:

1) 415mg of pentamethyldiethylenetriamine, 10g of benzyl acrylate, 6g of the compound C of example 1 and 10g of dry toluene were charged into a 125mL Schlenk bottle, mixed uniformly, and the reaction system was subjected to oxygen removal treatment on a vacuum line (specific procedure: quickly freezing the reaction system by using liquid nitrogen, vacuumizing the reaction system, thawing at normal temperature) for 5 times, adding 57.2g of cuprous bromide, reacting at 90 ℃ for 24 hours, quickly separating by using alumina to remove copper salt precipitate, concentrating the reaction solution, precipitating in glacial methanol for 3 times, placing the crude product in a vacuum oven at normal temperature for 2 days to obtain the product(8.4g) as compound D;

2) dispersing 1g of the compound D in 1mL of tetrahydrofuran, adding 2.31mL of tetrahydrofuran solution of tetrabutylammonium fluoride (containing 0.603g of tetrabutylammonium fluoride), mixing and shaking for 7min, carefully spreading the reaction solution on a tetrafluoroethylene plate with a groove, sealing a glass plate on the tetrafluoroethylene plate by using a double-sided adhesive tape, and standing for 18h to obtain the amphiphilic triblock polymer

A preparation method of the pressure-sensitive adhesive comprises the following steps:

combining amphiphilic triblock polymersSoaking in petroleum ether for 3 days, and standing at normal temperature for one week to obtain pressure sensitive adhesive (E2).

Example 3:

an amphiphilic triblock polymer, the preparation method of which comprises the following steps:

1) 415mg of pentamethyldiethylenetriamine, 20g of benzyl acrylate, 6g of the compound C of example 1 and 20g of dry toluene were charged into a 125mL Schlenk bottle, mixed uniformly, and the reaction system was subjected to oxygen removal treatment on a vacuum line (specific procedure: quickly freezing the reaction system by using liquid nitrogen, vacuumizing the reaction system, thawing at normal temperature) 6 times, adding 57.2g of cuprous bromide, reacting at 90 ℃ for 24 hours, quickly separating by using alumina to remove copper salt precipitate, concentrating the reaction solution, precipitating in glacial methanol for 3 times, placing the crude product in a vacuum oven at normal temperature for 2 days to obtain the product(10.3g) as compound D;

2) dispersing 1g of compound D in 1mL of tetrahydrofuran, adding 1.52mL of tetrahydrofuran solution of tetrabutylammonium fluoride (containing 0.397g of tetrabutylammonium fluoride), mixing and shaking for 5min, carefully spreading the reaction solution on a tetrafluoroethylene plate with a groove, sealing the glass plate on the tetrafluoroethylene plate by using a double-sided adhesive, and standing for 24h to obtain the amphiphilic triblock polymer

A preparation method of the pressure-sensitive adhesive comprises the following steps:

combining amphiphilic triblock polymersSoaking in petroleum ether for 2 days, and standing at normal temperature for one week to obtain pressure-sensitive adhesive (E3).

And (3) performance testing:

1) the number average molecular weight and the weight average molecular weight of the synthesized compound were characterized by Gel Permeation Chromatography (GPC), the mobile phase used in the entire test procedure was tetrahydrofuran, the flow rate was 1.0mL/min, the column temperature was 40 ℃, and the weight average molecular weights of the narrow molecular weight distribution standard polystyrene were 3000(1.04), 4000(1.06), 6000(1.04), 12000(1.03), 30000(1.07), 60000(1.05), 150000(1.08), 400000(1.04), 600000(1.04), and 1200000(1.04) in this order, the sample required to be dissolved in tetrahydrofuran at a concentration of about 3mg/mL to 7mg/mL, and the molecular weights and the molecular weight distribution data of compound C in example 1, compound D in example 1 (D1), compound D in example 2 (D2), and compound D in example 3 (D3) are shown below:

TABLE 1 molecular weight and molecular weight distribution data

Name of product	Mn(g/mol)	Mw(g/mol)	PDI
				Compound C	30100	32809	1.09
Compound D1	39711	49244	1.24
				Compound D2	63646	75751	1.19
Compound D3	92509	117623	1.27

As can be seen from Table 1: the invention prepares amphiphilic block polymers with different polymerization degrees and different block ratios.

2) A differential scanning calorimeter (model: discovery 2500) is used for testing the thermodynamic property of the pressure-sensitive adhesive, the temperature testing range of DSC is-75-150 ℃, the heating and cooling rate is 2 ℃/min, the test is firstly carried out by rising from room temperature to 150 ℃ and staying for 3min, then cooling to-75 ℃ and staying for 3min, then heating to 150 ℃, the DSC curve is taken to be the last heating part at-75-150 ℃, the whole testing process is carried out under the protection of nitrogen, and the Differential Scanning Calorimetry (DSC) of the pressure-sensitive adhesives E1-E3 in examples 1-3 is shown in figure 1.

As can be seen from fig. 1: the pressure-sensitive adhesive has lower glass transition temperature and accords with the use characteristics of the pressure-sensitive adhesive.

3) The pressure-sensitive adhesive was contacted with the substrate glass to be bonded at 25 ℃ for 300 seconds with a force of 1.5N using a stretcher (model: instron 5965) and keeping the pressure between the two at 1.5N, heating the temperature to 70 ℃ through an environmental balance box and stabilizing for 10min, then respectively cooling to 60 ℃, 50 ℃, 40 ℃ and 25 ℃ and stabilizing for 10min, then respectively carrying out interface stripping at stripping rates of 1mm/min, 10mm/min and 100mm/min, and recording the maximum stress value in the stripping process, wherein the probe adhesion test results of the pressure-sensitive adhesives E1-E3 in the examples 1-3 and the glass surface at different temperatures and different stripping rates are shown in figure 2.

As can be seen from fig. 2: the pressure-sensitive adhesive disclosed by the invention has sensitivity to temperature, the stripping force of the pressure-sensitive adhesive is reduced along with the increase of the temperature, and the requirements of different occasions on adhesion can be met.

4) The pressure-sensitive adhesive was cut into a disk shape having a diameter of 8mm and coated with a strong ultra-thin double-sided adhesive (type: 3M 300LSE) is adhered to an upper fixture probe with the diameter of 15mm, different solid surfaces are respectively adhered to lower fixture probes, the pressure sensitive adhesive is controlled by a program to contact with the surfaces of various materials for 10s under the pressure of 20N, the materials are peeled from the interface at the speed of 10mm/min, the maximum stress in the peeling process is recorded, and a probe adhesion test result graph of the pressure sensitive adhesive E1 in the embodiment 1 and different surfaces (comprising an aluminum plate, a steel plate, silicon rubber (PDMS), benzyl acrylate elastomer (PBzA), a PET plate, a polytetrafluoroethylene Plate (PTFE), wood and ionic gel) under different peeling speeds is shown in FIG. 3.

As can be seen from fig. 3: the pressure-sensitive adhesive can realize adhesion to different surfaces.

5) The pressure-sensitive adhesive was brought into contact with the glass substrate with a force of 1.5N for 100s and peeled at a peeling rate of 10mm/min, and after unloading was waited for 25min, and then adhesion-peeled off was performed for a second time with the same parameters, and thereafter, the waiting time was 20min, so that adhesion-peeling-unloading was repeatedly performed for 15min, 10min, 5min, 3min and 1min, and the adhesion energy of the peeling process was recorded, and the pressure-sensitive adhesive E1 in example 1 was adhered again after the interval of different times (25min, 20min, 15min, 10min, 5min, 3min and 1min) after adhesion-peeling, and the result of the adhesion property test was shown in fig. 4.

As can be seen from fig. 4: the pressure-sensitive adhesive can realize cyclic adhesion after multiple stripping.

6) The digital photographs of the pressure-sensitive adhesive E1 of example 1 before and after peeling off the glass surface are shown in fig. 5.

As can be seen from fig. 5: the pressure-sensitive adhesive of the present invention has almost no residue on the surface of the substrate after peeling.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.