CN102875831A - Method for preparing surface temperature sensitive polyester film - Google Patents
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Abstract
The invention relates to a method for preparing a surface temperature sensitive polyester film and belongs to the field of polymer thin film material surface modification. The method is characterized in that a polyester film material is subjected to a series of surface treatment, a bromo-ester initiator is fixed on the surface of the polyester film material, and then a thermosensitive polymer poly(N-isopropylacrylamide) is grafted on the surface of the polyester film through a surface trigger atom transfer radical polymerization method. The method is simple in process and good in modification effect. By means of the method, the poly (N-isopropylacrylamide) is grafted on the surface of the polyester film to subject the polyester film to modification, the modified polyester film surface shows a stimulus responsiveness to temperature, the thermosensitive functionalization for polyester film surface is achieved, and the method has a certain application prospect in terms of preparation of a biological intelligence material.
Description
Technical field
The present invention relates to a kind of preparation method of surface temperature susceptibility polyester film, belong to polymer thin-film material surface modification field.
Background technology
Polyester refers to contain the abbreviation of the thermoplastic polymer of ester group, and the polyester film that relates among the present invention is that employing is extruded take polyethylene terephthalate (PET) as raw material, the thin-film material that two-way stretch is made; It is a kind of water white transparency, and glossiness polymeric film has good mechanical property, electrical insulating property, and creep resistance, resistance to fatigue, rub resistance, therefore dimensional stability is widely used in the fields such as medical science, electrician, electronics and packing; In various practical applications, the surface property of material will play vital effect, biological example affinity material, organism embedded material and microorganism surface cultivated material etc., in order to develop the PET thin-film material with specific functionality, need under the condition that keeps its original performance, make it surface-functionalized, and then widen Application Areas and the scope of polyester film material.
The treatment process that obtains at present surface-functional PET film mainly comprises: corona method, Cement Composite Treated by Plasma, chemical Treatment, uv photopolymerization grafting, surperficial Atom Transfer Radical Polymerization grafting etc.; And in these method of modifying, surperficial initiated polymerization especially surface causes radical polymerization owing to can obtain higher percentage of grafting, narrow molecular weight distributions and can design and control the material surface composition and performance and receiving much attention.
Poly N-isopropyl acrylamide (PNIPAM) owing to have simultaneously hydrophilic amide group and hydrophobic sec.-propyl on its molecular chain, therefore the aqueous solution of linear PNIPAM and crosslinked after the PNIPAM hydrogel present susceptibility to temperature; At room temperature, the uniform solution of linear PNIPAM formation soluble in water, in the time of near temperature is elevated to 32 ℃, because high temperature has destroyed the hydrogen bond of water and amide group, and occuring, separates solution phase, lower critical solution temperature (LCST) occurs, be also referred to as cloud point temperature (Cloud Point Temperature) or cloud point temperature; Because PNIPAM is very high to the responsive responsiveness of temperature, and its LCST is about 32 ℃, close with body temperature, when the hydrophilic or hydrophobic component in the telomerized polymer skeleton, LCST can rise or descend, the field such as separates in preparation biological intelligence material, bio-medical material and intelligence and have great potential, so become one of temperature sensing polymer of greatest concern.
By surperficial Atom Transfer Radical Polymerization PNIPAM is grafted on the polyester film surface, the polymer materials on specific functionality surface will be obtained having, and effectively comprehensively the two-part advantage of base material and graft modification surface prepares a series of novel materials with temperature-sensing property surface.
Chinese patent (201110357744.5) discloses a kind of preparation method of surface-grafted polyacrylic acid lead polyester film, it makes the polyester film surface hydrolysis at first successively, oxidation, chloride produces acid chloride group, make film surface produce the hydroxyl of higher density with the diethanolamine reaction with branched structure subsequently, then the hydroxyl reaction with 2-bromo isobutyl acylbromide and film surface prepares the atom transfer radical polymerization external dopant, utilize at last surperficial Atom Transfer Radical Polymerization technology that propylene lead plumbate initiation grafting is arrived polyester film surface, obtain the polyester film of surface-grafted polyacrylic acid lead.
Summary of the invention
The object of the invention is to disclose a kind of preparation method of surface temperature susceptibility polyester film, it is characterized in that using the method for surperficial Atom Transfer Radical Polymerization, adopt N-isopropylacrylamide as monomer, from through the surperficial fixedly polyester film surface initiated polymerization of initiator, prepare the functional polyalkylene ester film that surface grafting evenly has surperficial temperature-sensing property.
A kind of surface temperature susceptibility polyester film and preparation thereof specifically may further comprise the steps:
(1) preparation of polyester film initiator
Polyester film is placed on first in the glacial acetic acid of sodium hydroxide solution 1 and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution 2 that diethanolamine concentration is 40g/L, reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
(2) polyester film of surface grafting PNIPAM is synthetic
Polyester film initiator, catalyzer, part and the polymerization single polymerization monomer NIPAM of preparation in the step (1) placed the drying deoxygenation and be full of the Kolle flask of argon gas, wherein the mol ratio of brominated esters class initiator and catalyzer is on the polyester film initiator: 1:780 ~ 820; Material molar ratio is: the n(catalyzer): the n(part): the n(monomer)=and 1:3:215 ~ 262), with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively solvent and free initiator 2-isobutyl ethyl bromide, the n(initiator that dissociates): the n(catalyzer)=1:50 ~ 148, the mass volume ratio of polymerization single polymerization monomer NIPAM and solvent is 0.5g/mL, place constant temperature oil bath under magnetic agitation, to react reaction flask, after the reaction, reaction system is exposed in the air, stop polymerization, the polyester film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, place vacuum drying oven to be dried to constant weight, namely obtain the Thermo-sensitive polyester film that surface grafting has PNIPAM.
The polyester material that adopts for the preparation of the polyester film of surface grafting PNIPAM among the present invention is PET.
Sodium hydroxide solution 1 concentration is 2mol/L in the described step (1), and dilute sulphuric acid concentration is 1.2mol/L, and sodium hydroxide 2 concentration are 1mol/L.
Polymerisation catalysts/the ligand combination that adopts for the preparation of the polyester film of surface grafting PNIPAM in the described step (2) is: cuprous bromide/2,2-dipyridyl, cuprous bromide/pentamethyl-diethylenetriamine, cuprous bromide/three-(N, the N-dimethylaminoethyl) amine, cuprous chloride/2,2-dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine or cuprous chloride/three-(N, N-dimethylaminoethyl) amine.
The solvent that adopts for the preparation of the polyester film of surface grafting PNIPAM in the described step (2) is acetone/deionized water mixed solvent, and the volume ratio of mixed solvent (v/v) is (9/1-7/3).
The polyreaction oil bath temperature that adopts for the preparation of the polyester film of surface grafting PNIPAM in the described step (2) is 4-50 ℃.
The polymerization reaction time that adopts for the preparation of the polyester film of surface grafting PNIPAM in the described step (2) is 6-16 hour.
Description of drawings
Fig. 1 is the surface infrared spectrum figure of PET film before and after the surface grafting PNIPAM modification, wherein (A) is the infrared spectrum of pure PET film, (B) be the infrared spectrum of the PET film of the fixing upper initiator in surface for preparing among the present invention, (C) be the infrared spectrum of the Thermo-sensitive PET film that utilizes the surface grafting PNIPAM that the present invention prepares; Shown in Fig. 1 (A), 1713cm
-1The absorption peak at place is the charateristic avsorption band of C=O group; 1340 cm
-1The place absorption peak be because-CH
2The formation vibration of-group causes; 1245cm
-1The strong absorption peak at place belongs to the stretching vibration peak of C-O key in the ester group; 1097cm
-1With 1018 cm
-1The absorption peak at place replaces owing to the Isosorbide-5-Nitrae of phenyl ring; At 875cm
-1The absorption peak at place can be classified as the flexural vibration of c h bond; Compare with the infrared spectrum of the pure PET film of Fig. 1 (A), the infrared spectrum of the surperficial fixedly polyester film of initiator of Fig. 1 (B) is almost without any variation, behind the surface grafting PNIPAM, shown in Fig. 1 (C), at 3500 ~ 3100 cm
1Occur an obvious broad peak in the scope, be attributed to the stretching vibration peak of secondary amide N-H key, at 1690 ~ 1630cm
-1The stretching vibration peak of secondary amide group C=O key appears in the place; 1550cm
-1The absorption peak at place is attributed to the flexural vibration peak of secondary amide group N-H key.
Fig. 2 is that the x-ray photoelectron of the PET film before and after the surface grafting PNIPAM modification can spectrogram, and wherein (a) be the XPS spectrum figure of pure PET film, (b) is the XPS spectrum figure that utilizes the PET film of the surface grafting PNIPAM that the present invention prepares; 531.7 eV places and 284.7 eV places are attributed to respectively the electron binding energy peak of O1s and C1s among Fig. 2 (a), compare with Fig. 2 (a), behind the grafting PNIPAM, the PET film feature of N1s occurs in conjunction with the energy peak at 400.1 eV places, and since the PNIPAM molecular chain on isopropyl group, introduced a large amount of C atoms to the surface, therefore as can be seen from the figure than the XPS of initiator, the peak area of the XPS figure C1s of the PET film after the modification obviously becomes large with the ratio of the peak area of O1s.
Fig. 3 is that PET film contact angle after the surface grafting PNIPAM modification is with the situation of temperature response.As can be seen from the figure, in 25 ~ 35 ℃ Range of measuring temp, the hop about 28 ° of having an appointment of the polyester film contact angle of grafting PNIPAM, then arrive gradually plateau, explanation has been prepared the thermo-sensitive surface polyester film that temperature is had stimulating responsive by the present invention, and the functional polyalkylene ester film prepared according to the embodiment of the invention all has surface temperature susceptibility.
Fig. 4 is the shape appearance figure of PET film surface before and after the grafting PNIPAM modification, and wherein (A) be the scanning electron microscope (SEM) photograph of pure PET film, (B) is the scanning electron microscope (SEM) photograph that utilizes the PET film of the surface grafting PNIPAM that the present invention prepares.As can be seen from the figure, the surface of pure PET film (A) is more smooth, the many aggregates of larger change surface appearance occur and are evenly distributed in whole film surface in graftomer rear surface pattern, shown in Fig. 4 (B), this shows the equally distributed polymer layer of PET film surface grafting last layer after the grafting PNIPAM modification.
Embodiment
Following embodiment is to further specify of the present invention, rather than limits the scope of the invention.
The present invention is described in detail below in conjunction with embodiment:
Embodiment 1:
(1) preparation of polyester film initiator: polyester film is placed on first in the glacial acetic acid of the sodium hydroxide solution of 2mol/L and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid (dilute sulphuric acid concentration is 1.2mol/L) of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution that diethanolamine concentration is 40g/L (concentration of sodium hydroxide solution is 1mol/L), reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
(2) polyester film of surface grafting PNIPAM is synthetic: with the PET film initiator of preparation in two load weighted steps (1), 0.01g CuCl, 0.047g the monomer NIPAM of bpy and 2.5g, place the drying deoxygenation and be full of the Kolle flask of argon gas, the mol ratio of brominated esters class initiator and Catalysts Cu Cl is on the PET film initiator: 1:780, with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively 4.5mL acetone, 0.5mL deionized water, the free initiator 2-isobutyl ethyl bromide of 1 μ L, reaction flask is placed 4 ℃ of constant temperature oil bath stirring reaction 10h, after reaction is finished, open bottle cap, reaction system is exposed in the air, stop polymerization, the PET film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, vacuum obtains the PET film of surface grafting PNIPAM modification to constant weight.
Embodiment 2:
(1) preparation of polyester film initiator: polyester film is placed on first in the glacial acetic acid of the sodium hydroxide solution of 2mol/L and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid (dilute sulphuric acid concentration is 1.2mol/L) of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution that diethanolamine concentration is 40g/L (concentration of sodium hydroxide solution is 1mol/L), reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
(2) polyester film of surface grafting PNIPAM is synthetic: with the PET film initiator of preparation in two load weighted steps (1), 0.0146g CuBr, 0.047g bpy and the monomer NIPAM of 2.5g, place the drying deoxygenation and be full of the Kolle flask of argon gas, the mol ratio of brominated esters class initiator and Catalysts Cu Br is on the PET film initiator: 1:820, with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively 3.5mL acetone, 1.5mL deionized water, the free initiator 2-isobutyl ethyl bromide of 2 μ L, reaction flask is placed 30 ℃ of constant temperature oil bath stirring reaction 6h, after reaction is finished, open bottle cap, reaction system is exposed in the air, stops polymerization.PET film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, vacuum-drying obtains the PET film of surface grafting PNIPAM modification to constant weight.
Embodiment 3:
(1) preparation of polyester film initiator: polyester film is placed on first in the glacial acetic acid of the sodium hydroxide solution of 2mol/L and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid (dilute sulphuric acid concentration is 1.2mol/L) of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution that diethanolamine concentration is 40g/L (concentration of sodium hydroxide solution is 1mol/L), reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
(2) polyester film of surface grafting PNIPAM is synthetic: with the PET film initiator of preparation in two load weighted steps (1), 0.01g CuCl, 0.047g the monomer NIPAM of bpy and 3.0g, place the drying deoxygenation and be full of the Kolle flask of argon gas, the mol ratio of brominated esters class initiator and Catalysts Cu Cl is on the PET film initiator: 1:800, with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively 4.5mL acetone, 0.5mL deionized water, the free initiator 2-isobutyl ethyl bromide of 1 μ L; Reaction flask is placed 50 ℃ of constant temperature oil bath stirring reaction 10h, after reaction is finished, open bottle cap, reaction system is exposed in the air, stop polymerization, the PET film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, vacuum-drying obtains the PET film of surface grafting PNIPAM modification to constant weight.
Embodiment 4:
(1) preparation of polyester film initiator: polyester film is placed on first in the glacial acetic acid of the sodium hydroxide solution of 2mol/L and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid (dilute sulphuric acid concentration is 1.2mol/L) of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution that diethanolamine concentration is 40g/L (concentration of sodium hydroxide solution is 1mol/L), reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
(2) polyester film of surface grafting PNIPAM is synthetic: with the PET film initiator of preparation in two load weighted steps (1), 0.0146g CuBr, 0.047g the monomer NIPAM of bpy and 3.0g, place the drying deoxygenation and be full of the Kolle flask of argon gas, the mol ratio of brominated esters class initiator and Catalysts Cu Br is on the PET film initiator: 1:790, with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively 3.5mL acetone, 1.5mL deionized water, the free initiator 2-isobutyl ethyl bromide of 3 μ L.Reaction flask is placed 4 ℃ of constant temperature oil bath stirring reaction 10h, after reaction is finished, open bottle cap, reaction system is exposed in the air, stop polymerization.PET film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, vacuum-drying obtains the PET film of surface grafting PNIPAM modification to constant weight.
Embodiment 5:
(1) preparation of polyester film initiator: polyester film is placed on first in the glacial acetic acid of the sodium hydroxide solution of 2mol/L and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid (dilute sulphuric acid concentration is 1.2mol/L) of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution that diethanolamine concentration is 40g/L (concentration of sodium hydroxide solution is 1mol/L), reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
(2) polyester film of surface grafting PNIPAM is synthetic: with the PET film initiator of preparation in two load weighted steps (1), 0.01g CuCl, 0.047g the monomer NIPAM of bpy and 3.0g, place the drying deoxygenation and be full of the Kolle flask of argon gas, the mol ratio of brominated esters class initiator and Catalysts Cu Cl is on the PET film initiator: 1:800, with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively 4.5mL acetone, 0.5mL deionized water, the free initiator 2-isobutyl ethyl bromide of 1 μ L; Reaction flask is placed 30 ℃ of constant temperature oil bath stirring reaction 16h, after reaction is finished, open bottle cap, reaction system is exposed in the air, stop polymerization.PET film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, vacuum-drying obtains the PET film of surface grafting PNIPAM modification to constant weight.
Embodiment 6:
(1) preparation of polyester film initiator: polyester film is placed on first in the glacial acetic acid of the sodium hydroxide solution of 2mol/L and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid (dilute sulphuric acid concentration is 1.2mol/L) of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution that diethanolamine concentration is 40g/L (concentration of sodium hydroxide solution is 1mol/L), reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
(2) polyester film of surface grafting PNIPAM is synthetic: with the PET film initiator of preparation in two load weighted steps (1), 0.01g CuCl, 0.047g the monomer NIPAM of bpy and 3.0g, place the drying deoxygenation and be full of the Kolle flask of argon gas, the mol ratio of brominated esters class initiator and Catalysts Cu Cl is on the PET film initiator: 1:800, with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively 3.5mL acetone, 1.5mL deionized water, the free initiator 2-isobutyl ethyl bromide of 1 μ L.Reaction flask is placed 50 ℃ of constant temperature oil bath stirring reaction 16h, after reaction is finished, open bottle cap, reaction system is exposed in the air, stop polymerization.PET film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, vacuum-drying obtains the PET film of surface grafting PNIPAM modification to constant weight.
Claims (8)
1. the preparation method of a surface temperature susceptibility polyester film
,The synthesis step that specifically comprises the polyester film of the preparation process of polyester film initiator and surface grafting PNIPAM, it is characterized in that: the synthesis step of the polyester film of described surface grafting PNIPAM is: polyester film initiator, catalyzer, part and polymerization single polymerization monomer NIPAM are placed the drying deoxygenation and be full of the Kolle flask of argon gas, wherein the mol ratio of brominated esters class initiator and catalyzer is on the polyester film initiator: 1:780 ~ 820; Material molar ratio is: the n(catalyzer): the n(part): the n(monomer)=and 1:3:215 ~ 262), with rubber plug that reaction flask is airtight, vacuumize logical argon gas, circulate 3 times, use again the syringe through argon gas was washed in reaction flask, to inject successively solvent and free initiator 2-isobutyl ethyl bromide, the n(initiator that dissociates): the n(catalyzer)=1:50 ~ 148, the mass volume ratio of polymerization single polymerization monomer NIPAM and solvent is 0.5g/mL, place constant temperature oil bath under magnetic agitation, to react reaction flask, after the reaction, reaction system is exposed in the air, stop polymerization, the polyester film after the modification is taken out from reaction flask, use respectively deionized water and acetone ultrasonic washing for several times, place vacuum drying oven to be dried to constant weight, namely obtain the Thermo-sensitive polyester film that surface grafting has PNIPAM.
2. the preparation method of a kind of surface temperature susceptibility polyester film as claimed in claim 1
,It is characterized in that: the preparation process of described polyester film initiator is: polyester film is placed on first in the glacial acetic acid of sodium hydroxide solution 1 and analytical pure level, under 70 ℃ of conditions, is hydrolyzed respectively 1 hour; Then film being placed potassium permanganate concentration is the dilution heat of sulfuric acid of 50g/L, and oxidation was taken out and used respectively dilute hydrochloric acid, water, washing with acetone for several times after 1 hour under 60 ℃ of conditions, placed 80 ℃ of dry 12h of baking oven; Use again afterwards mass volume ratio (w/v) for the dichloromethane solution of the phosphorus pentachloride of 30g/L with the polyester film chloride, behind the normal temperature confined reaction 18 hours, film is used respectively methylene dichloride, washing with acetone for several times, then polyester film is placed and contain the sodium hydroxide solution 2 that diethanolamine concentration is 40g/L, reaction is after 20 hours under the normal temperature condition, take out respectively water, washing with acetone for several times, place 80 ℃ of dry 12h of baking oven, then be immersed in polyester film in the dry toluene fully, and to wherein adding 1/100 the triethylamine that volume is the dry toluene volume, slowly dripping mass volume ratio (w/v) with constant pressure funnel in the flask again is the anhydrous toluene solution of the 2-bromo isobutyl acylbromide of 100g/L, the anhydrous toluene solution add-on of 2-bromo isobutyl acylbromide is 1/5 of dry toluene volume, lucifuge reaction 4h during cryosel is bathed, behind the normal-temperature reaction 20h toluene is used respectively in the film taking-up again, dehydrated alcohol, distilled water, washing with acetone for several times, after placing 60 ℃ of dry 12h of vacuum drying oven, airtight preservation namely obtains the fixing upward polyester film of brominated esters class initiator in surface.
3. the preparation method of a kind of surface temperature susceptibility polyester film as claimed in claim 1 or 2
,It is characterized in that: described polyester material is PET.
4. the preparation method of a kind of surface temperature susceptibility polyester film as claimed in claim 2
,It is characterized in that: described sodium hydroxide solution 1 concentration is 2mol/L, and dilute sulphuric acid concentration is 1.2mol/L, and sodium hydroxide 2 concentration are 1mol/L.
5. the preparation method of a kind of surface temperature susceptibility polyester film as claimed in claim 1
,It is characterized in that: described polymerisation catalysts/ligand combination is: cuprous bromide/2,2-dipyridyl, cuprous bromide/pentamethyl-diethylenetriamine, cuprous bromide/three-(N, the N-dimethylaminoethyl) amine, cuprous chloride/2,2-dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine or cuprous chloride/three-(N, N-dimethylaminoethyl) amine.
6. the preparation method of a kind of surface temperature susceptibility polyester film as claimed in claim 1
,It is characterized in that: described solvent is acetone/deionized water mixed solvent, and the volume ratio of mixed solvent (v/v) is (9/1-7/3).
7. the preparation method of a kind of surface temperature susceptibility polyester film as claimed in claim 1
,It is characterized in that: described polyreaction oil bath temperature is 4-50 ℃.
8. the preparation method of a kind of surface temperature susceptibility polyester film as claimed in claim 1
,It is characterized in that: described polymerization reaction time is 6-16 hour.
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| CN109620689A (en) * | 2019-01-10 | 2019-04-16 | 浙江大学 | A kind of flexible device and human body surface based on software composite membrane continues massage method |
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