CN101597361B - Method for preparing segmented copolymer of polydimethylsiloxane-b-polystyrene - Google Patents
Method for preparing segmented copolymer of polydimethylsiloxane-b-polystyrene Download PDFInfo
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Abstract
The invention discloses a method for preparing a segmented copolymer of polydimethylsiloxane-b-polystyrene, and relates to a copolymer. The invention provides a method for preparing a segmented copolymer of polydimethylsiloxane-b-polystyrene, which has the advantages of mild reaction conditions, clear structure of reaction products, controllable molecular weight and molecular weight distribution and easy and convenient operation. The method comprises the following steps of: firstly synthesizing a chain transfer agent of polydimethylsiloxane macromolecule, of which the end is capped by an ethoxy-dithioformicacid group, and preparing the segmented copolymer of PDMS-b-PS. In the method, by using the polydimethylsiloxane macromolecule, of which the end is capped by the ethoxy-dithioformicacid group, as the chain transfer agent and azodiisobutyronitrile as an initiator, the styrene is initialized to carry out the reversible addition-fragmentation chain transfer polymerization to prepare the segmented copolymer of polydimethylsiloxane-b-polystyrene.
Description
Technical field
The present invention relates to a kind of multipolymer, especially relating to the end capped polydimethylsiloxane macromole of a kind of employing xanthogenic acid base (PDMS-macro RAFT agent) is chain-transfer agent, Diisopropyl azodicarboxylate (AIBN) is an initiator, and initiation vinylbenzene (St) carries out reversible addition-fracture chain transfer (RAFT) polymerization and prepares the method for segmented copolymer of polydimethylsiloxane--b-polystyrene.
Background technology
Polydimethylsiloxane (PDMS) has good thermostability, extremely low second-order transition temperature, low surface energy, good water repelling anti-fouling, electric insulation, scale resistance and physiology inertia etc., and these special performances make organosilicon be widely used in many special occasions.That polystyrene (PS) has is inexpensive, processibility good, transparent, advantage such as matter is hard, dimensional stability is good, and shock strength is relatively poor, inflammable, the uvioresistant ability is lower, temperature tolerance is relatively poor but exist, and shortcomings such as oil resistant, acid, alcohol not.Not only can improve the part shortcoming of PS with the PDMS modification, make it obtain the various excellent specific properties that organosilicon possessed, can strengthen the mechanical property of PS simultaneously.
The synthetic method of PDMS-b-PS segmented copolymer mainly contains anionic polymerization ([1] V.Bellas, H.Iatrou, N.Hadjichristidis.Controlled Anionic Polymerization of Hexamethylcyclotrisiloxane.Model Linearand Miktoarm Star Co-and Terpolymers of Dimethylsiloxane with Styrene and Isoprene[J] .Macromolecules, 2000,33 (19): 6993-6997), reaction between active function groups ([2] Nakagave Y, Miller P J, Matyjaszewski K.Development of novel attachable initiators for atom transfer radicalpolymerization.Synthesis of block and graft copolymers from poly (dimethylsiloxane) macroinitiators[J] .Polymer 1998,39 (21): 5163～5169), atom transfer radical polymerization ([3] Bajaj P, Varshney S K.Morphology and mechanical properties of poly (dimethyl siloxane-b-styrene-b-dimethyl siloxane) block copolymers[J] .Polymer, 1980,21 (2): 201-206) etc.Anionoid polymerization is had relatively high expectations to polymerization environment and reagent purity, and reaction is being carried out just obtaining product preferably under the low temperature very much usually.Utilizing the active function groups reaction to obtain block polymer needs polystep reaction usually, and actually operating is got up comparatively loaded down with trivial details, and can produce a large amount of homopolymer, and final reaction yield is often lower.Although atom transfer radical polymerization does not have anionic polymerisation condition harshness, because less its industrial application that limited of molecular weight of product.Compare with above-mentioned synthetic method, the RAFT polymerization has the clear and definite and molecular weight of reaction conditions gentleness, reaction product structure and controllable molecular weight distribution and advantage such as easy and simple to handle.
Summary of the invention
The purpose of this invention is to provide a kind of reaction conditions gentleness, the reaction product structure is clear and definite, and the preparation method of molecular weight and controllable molecular weight distribution and segmented copolymer of polydimethylsiloxane--b-polystyrene easy and simple to handle (following abbreviate segmented copolymer of polydimethylsiloxane--b-polystyrene as the PDMS-b-PS segmented copolymer).
The chemical structural formula of PDMS-b-PS segmented copolymer of the present invention is shown below:
Wherein, x is the polymerization degree of PDMS-OH, and y is the polymerization degree of PS.
Its reaction formula of the preparation method of PDMS-b-PS segmented copolymer of the present invention is as follows:
Wherein, PDMS-OH is hydroxy-end capped polydimethylsiloxane, PDMS-Br is the end capped polydimethylsiloxane of bromine, PDMS-macro RAFT agent is the end capped polydimethylsiloxane macromolecular chain of an xanthogenic acid base transfer agent, and PDMS-b-PS is a segmented copolymer of polydimethylsiloxane--b-polystyrene.X is the polymerization degree of PDMS-OH, and y is the polymerization degree of PS.
The preparation method of PDMS-b-PS segmented copolymer of the present invention may further comprise the steps:
(1) the end capped polydimethylsiloxane macromolecular chain of xanthogenic acid base transfer agent (PDMS-macro RAFT agent) is synthetic:
1) PDMS-OH is dissolved with inert organic solvents and the adding stirrer, sealing is stirred and is vacuumized-the filling with inert gas operation, add triethylamine, after the ice bath cooling 2-bromine isobutyl acylbromide is splashed in the reaction flask, reaction finishes after-filtration, after filtrate decompression distillation removed inert organic solvents, be dissolved in the methylene dichloride, wash with sodium hydrogen carbonate solution, separatory, organic layer siccative drying refilters, and at last the end capped polydimethylsiloxane macromole of bromine (PDMS-Br) that methylene dichloride obtains yellow oily is removed in the filtrate decompression distillation;
2) will contain the compound organic solvent dissolution of xanthogen, and add the PDMS-Br for preparing in the step 1) and also add stirrer and stir, reaction finishes after-filtration, precipitation CH
2Cl
2Wash, remove organic solvent, obtain the end capped polydimethylsiloxane macromolecular chain of the xanthogenic acid base transfer agent (PDMS-macro RAFT agent) of faint yellow oily;
(2) preparation of PDMS-b-PS segmented copolymer:
In PDMS-macro RAFT agent, add radical initiator, add inert solvent again, through freezing-vacuumize-thaw cycles after, add vinylbenzene, reversible addition-fracture chain transfer (reversible addition-fracture chain transfer abbreviates RAFT as) polyreaction is carried out in heating, and cool to room temperature is with termination reaction, after the polymerization system dilution, with the precipitation agent precipitation, dissolving-post precipitation with the product vacuum-drying that obtains, obtains the PDMS-b-PS segmented copolymer more repeatedly.
Step (1) 1) in, described inert organic solvents is preferably tetrahydrofuran (THF) or methylene dichloride etc., described rare gas element is preferably nitrogen or argon gas etc., described sealing stirs and vacuumizes-and filling with inert gas operates best repetitive operation 3 times, in molar ratio, PDMS-OH: triethylamine: 2-bromine isobutyl acylbromide is preferably 1: (3～6): (1.5～3); The temperature of described reaction is preferably 20～40 ℃, and the time of reaction is preferably 15～24h; Described sodium hydrogen carbonate solution is preferably saturated solution, and described underpressure distillation can be adopted Rotary Evaporators; Described siccative can adopt anhydrous magnesium sulfate or anhydrous sodium sulphate etc.
Step (1) 2) in, the described compound that contains xanthogen is preferably potassium ethyl xanthonate etc., described organic solvent is preferably ethanol etc., in molar ratio, PDMS-Br: the compound that contains xanthogen: ethanol is preferably 1: (1.5～3): (50～100); The temperature of described reaction is preferably 20～40 ℃, and the time of reaction is preferably 10～20h, described precipitation CH
2Cl
2Wash and preferably wash repeatedly 3 times, the described organic solvent of removing is preferably removed organic solvent by underpressure distillation.
In step (2), described radical initiator is preferably Diisopropyl azodicarboxylate etc., described inert solvent is preferably toluene etc., described the most handy freezing liquid nitrogen freezing, described reversible addition-fracture chain transfer polymerization reaction is preferably under the protection of inert gas and carries out, described rare gas element is preferably nitrogen or argon gas etc., in molar ratio, vinylbenzene: PDMS-macro RAFT agent: Diisopropyl azodicarboxylate is preferably (100～500): 1: (0.1～1), described freezing-vacuumize-thaw cycles is preferably freezing-vacuumize-thaw cycles at least 3 times, the temperature of described polyreaction is preferably 60～80 ℃, and the time of polyreaction is preferably 5～16h; The most handy thinner tetrahydrofuran (THF) of described dilution dilutes, described precipitation agent is preferably sherwood oil or methyl alcohol etc., described vacuum drying temperature is preferably 40～50 ℃, vacuum drying vacuum tightness is preferably 0.08～-0.1MPa, described dissolving-precipitation repeatedly is dissolving-precipitation at least 3 times repeatedly preferably.
Compare with the preparation method of existing segmented copolymer of polydimethylsiloxane--b-polystyrene, the present invention has following outstanding advantage:
1) adopts reversible addition-fracture chain transfer polymerization, reaction conditions gentleness, reaction product structure clear and definite and molecular weight and controllable molecular weight distribution and easy and simple to handle.
2) adopt the end capped polydimethylsiloxane macromole of xanthogenic acid base as chain-transfer agent, can be used as a block in the multipolymer, avoided adopting the shortcoming of small molecules siloxanyl monomers and styrene monomer copolyreaction condition harshness.
3) adopt conventional radical initiator Diisopropyl azodicarboxylate, cheap, do not need to add catalyzer and part.
4) be compared to polymerization such as negatively charged ion, have still less side reaction and gentle more reaction conditions, much lower relatively to the requirement of series reaction things such as reaction monomers, solvent.
The molecular weight of segmented copolymer of polydimethylsiloxane--b-polystyrene of the present invention and molecular weight distribution can be passed through gel permeation chromatography (GPC) and measure, the GPC experiment is at room temperature carried out, used leacheate is a tetrahydrofuran (THF), and the leacheate flow velocity is 1ml/min, uses polystyrene as calibration standard.The molecular weight distribution that records is 1.1～1.4.
Embodiment
In order to be easy to further understand the present invention, the following example will the invention will be further elaborated.
Embodiment 1
(1) PDMS-macro RAFT agent macromolecular chain transfer agent is synthetic:
1) in a 250ml exsiccant single port bottle, add 1 part of PDMS-OH with toluene dissolving and add stirrer, sealing stirs and vacuumizes-inflated with nitrogen repetitive operation 3 times, add 3 parts of triethylamines with syringe.Ice bath cooling back slowly splashes into 1.5 parts of 2-bromine isobutyl acylbromides in the reaction flask with syringe, mixed solution is at 20 ℃ of following stirring reaction 15h, reaction finishes after-filtration, inert organic solvents is removed in the filtrate decompression distillation, again it is dissolved in the methylene dichloride, wash with sodium hydrogen carbonate solution, separatory, organic layer siccative drying refilters, and at last the PDMS-Br macromole that dichloromethane solvent obtains yellow oily is removed in the filtrate decompression distillation.
2) in the round-bottomed flask of 100ml, add 1 part 1) in the PDMS-Br macromole for preparing, 1.5 parts of potassium ethyl xanthonates are used dissolve with ethanol, mixed solution is at 20 ℃ of following stirring reaction 10h, reaction finishes after-filtration, precipitation CH
2Cl
2Wash repeatedly 3 times, solvent is removed by underpressure distillation, obtains the PDMS-macro RAFT agent macromolecular chain transfer agent of faint yellow oily.
(2) preparation of PDMS-b-PS segmented copolymer:
The RAFT of St is aggregated under the inert atmosphere protection and carries out; add 1 part of PDMS-macro RAFT agent as the macromolecular chain transfer agent; 0.1 part AIBN is as the conventional free radical initiator; 100 parts of St and 100 parts of toluene; through freezing-vacuumize-thaw cycles at least 3 times after, stirring reaction 5h in 60 ℃ of constant temperature oil baths.Along with reaction is carried out, system viscosity increases gradually, and cool to room temperature is with termination reaction, with after the polymerization system dilution, with the precipitation agent precipitation, repeatedly after the dissolving-precipitation at least 3 times again with the product vacuum-drying that obtains, obtain the PDMS-b-PS segmented copolymer, the molecular weight (M of segmented copolymer
n) and molecular weight distribution (PDI) record by gel permeation chromatography (GPC), GPC experiment is at room temperature carried out, used leacheate is a tetrahydrofuran (THF), the leacheate flow velocity is 1ml/min, with polystyrene as calibration standard.Test result is: M
n=8310, PDI=1.12.
Embodiment 2
(1) PDMS-macro RAFT agent macromolecular chain transfer agent is synthetic:
1) in a 250ml exsiccant single port bottle, adding 1 part of PDMS-OH dissolves with toluene and the adding stirrer, sealing stirs and to vacuumize-inflated with nitrogen repetitive operation 3 times, add 3 parts of triethylamines with syringe, and ice bath cooling back slowly splashes into 1.5 parts of 2-bromine isobutyl acylbromides in the reaction flask with syringe.Mixed solution is at 25 ℃ of following stirring reaction 18h.Reaction finishes after-filtration, inert organic solvents is removed in the filtrate decompression distillation, again it is dissolved in the methylene dichloride, wash with sodium hydrogen carbonate solution, separatory, organic layer siccative drying refilters, and at last the PDMS-Br macromole that dichloromethane solvent obtains yellow oily is removed in the filtrate decompression distillation.
2) in the round-bottomed flask of 100ml, add the PDMS-Br macromole for preparing in 1 part (1), 2 parts of potassium ethyl xanthonates.Mixed solution is at 20 ℃ of following stirring reaction 10h.Reaction finishes after-filtration, and precipitation is washed 3 times repeatedly with methylene dichloride, and solvent is removed by underpressure distillation, obtains the PDMS-macro RAFT agent macromolecular chain transfer agent of faint yellow oily.
(2) preparation of PDMS-b-PS segmented copolymer:
The RAFT of St is aggregated under the inert atmosphere protection; in inert solvent toluene, carry out; add 1 part of PDMS-macro RAFTagent as the macromolecular chain transfer agent; 0.1 part AIBN is as the conventional free radical initiator; 200 parts of St; through freezing-vacuumize-thaw cycles at least 3 times after; stirring reaction 8h in 60 ℃ of constant temperature oil baths; along with reaction is carried out, system viscosity increases gradually, and cool to room temperature is with termination reaction; after the polymerization system dilution; with precipitation agent precipitation, repeatedly after the dissolving-precipitation at least 3 times again with the product vacuum-drying that obtains, obtain the PDMS-b-PS segmented copolymer.
The GPC test condition is the same, and test result is: M
n=13510, PDI=1.15.
Embodiment 3
(1) the 2-bromine isobutyl acylbromide that removes in the step 1) is 2 parts, step 2) in temperature of reaction be that 25 ℃, reaction times are outside the 15h, other is with the step among the embodiment 1 (1).
(2) removing temperature of reaction is 70 ℃, and other is with the step among the embodiment 2 (2).
The GPC test condition is the same, and test result is: M
n=14550, PDI=1.17.
Embodiment 4
(1) triethylamine in step 1) is that 4 parts, temperature of reaction are that 30 ℃, reaction times are the 20h, step 2) in potassium ethyl xanthonate be 2 especially, other is with the step among the embodiment 1 (1).
(2) be the 10h except that the reaction times, other is with the step among the embodiment 3 (2).
The GPC test condition is the same, and test result is: M
n=15170, PDI=1.19.
Embodiment 5
(1) reaction times of removing in the step 1) is 22h, step 2) in potassium ethyl xanthonate be that 2.5 parts, temperature of reaction are outside 30 ℃, other is with the step among the embodiment 4 (1).
(2) removing St is 300 parts, and AIBN is 0.2 especially, and other is with the step among the embodiment 4 (2).
The GPC test condition is the same, and test result is: M
n=20790, PDI=1.21.
Embodiment 6
(1) triethylamine in step 1) is that 6 parts, temperature of reaction are 40 ℃, step 2) in reaction times be outside the 20h, other is with the step among the embodiment 5 (1).
(2) removing temperature of reaction is 80 ℃, and the reaction times is outside the 12h, and other is with the step among the embodiment 5 (2).
The GPC test condition is the same, and test result is: M
n=25470, PDI=1.26.
Embodiment 7
(1) the 2-bromine isobutyl acylbromide that removes in the step 1) is 3 parts, step 2) in potassium ethyl xanthonate be that 3 parts, temperature of reaction are outside 40 ℃, other is with the step among the embodiment 6 (1).
(2) removing St is 500 parts, and AIBN is 0.5 especially, and other is with the step among the embodiment 5 (2).
The GPC test condition is the same, and test result is: M
n=36390, PDI=1.30.
Embodiment 8
(1) be the 24h except that the reaction times, other is with the step among the embodiment 6 (1).
(2) removing AIBN is 1 part, and the reaction times is outside the 16h, and other is with the step among the embodiment 7 (2).
The GPC test condition is the same, and test result is: M
n=38990, PDI=1.32.
Claims (9)
1. the preparation method of a segmented copolymer of polydimethylsiloxane--b-polystyrene is characterized in that may further comprise the steps:
(1) the end capped polydimethylsiloxane macromolecular chain of xanthogenic acid base transfer agent is synthetic:
1) hydroxy-end capped polydimethylsiloxane is dissolved with inert organic solvents and the adding stirrer, sealing is stirred and is vacuumized-the filling with inert gas operation, add triethylamine, after the ice bath cooling 2-bromine isobutyl acylbromide is splashed in the reaction flask, reaction finishes after-filtration, after filtrate decompression distillation removed inert organic solvents, be dissolved in the methylene dichloride, wash with sodium hydrogen carbonate solution, separatory, organic layer siccative drying refilters, and at last the end capped polydimethylsiloxane macromole of bromine that methylene dichloride obtains yellow oily is removed in the filtrate decompression distillation;
2) will contain the compound organic solvent dissolution of xanthogenic acid base, and add the end capped polydimethylsiloxane of bromine for preparing in the step 1) and also add stirrer and stir, reaction finishes after-filtration, precipitation CH
2Cl
2Wash, remove organic solvent, obtain the end capped polydimethylsiloxane macromolecular chain of the xanthogenic acid base transfer agent of faint yellow oily;
(2) preparation of PDMS-b-PS segmented copolymer:
In the end capped polydimethylsiloxane macromolecular chain of xanthogenic acid base transfer agent, add radical initiator, add inert solvent again, through freezing-vacuumize-thaw cycles after, add vinylbenzene, reversible addition-fracture chain transfer polymerization reaction is carried out in heating, and cool to room temperature is with termination reaction, after the polymerization system dilution, with the precipitation agent precipitation, dissolving-post precipitation with the product vacuum-drying that obtains, obtains the PDMS-b-PS segmented copolymer more repeatedly.
2. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 1, it is characterized in that step (1) 1) in, described inert organic solvents is tetrahydrofuran (THF) or methylene dichloride, described rare gas element is nitrogen or argon gas, described sealing stirs and vacuumizes-and filling with inert gas operation repetitive operation 3 times.
3. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 1, it is characterized in that step (1) 1) in, in molar ratio, hydroxy-end capped polydimethylsiloxane: triethylamine: 2-bromine isobutyl acylbromide is 1: (3～6): (1.5～3), the temperature of described reaction is 20～40 ℃, and the time of reaction is 15～24h.
4. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 1, it is characterized in that step (1) 1) in, described sodium hydrogen carbonate solution is a saturated solution, described underpressure distillation is to adopt Rotary Evaporators; Described siccative is anhydrous magnesium sulfate or anhydrous sodium sulphate.
5. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 1, it is characterized in that step (1) 2) in, the described compound that contains the xanthogenic acid base is a potassium ethyl xanthonate, described organic solvent is an ethanol.
6. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 5, it is characterized in that step (1) 2) in, in molar ratio, the end capped polydimethylsiloxane of bromine: the compound that contains the xanthogenic acid base: ethanol is 1: (1.5～3): (50～100); The temperature of described reaction is 20～40 ℃, and the time of reaction is 10～20h.
7. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 1, it is characterized in that step (1) 2) in, described precipitation CH
2Cl
2Wash and wash 3 times repeatedly, the described organic solvent of removing is to remove organic solvent by underpressure distillation.
8. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 1; it is characterized in that in step (2); described radical initiator is a Diisopropyl azodicarboxylate; described inert solvent is a toluene; the described freezing liquid nitrogen freezing of using; described reversible addition-fracture chain transfer polymerization is reflected under the protection of inert gas and carries out, and described rare gas element is nitrogen or argon gas.
9. the preparation method of a kind of segmented copolymer of polydimethylsiloxane--b-polystyrene as claimed in claim 8, it is characterized in that in step (2), in molar ratio, vinylbenzene: the end capped polydimethylsiloxane macromolecular chain of xanthogenic acid base transfer agent: Diisopropyl azodicarboxylate is (100～500): 1: (0.1～1).
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| CN103833944B (en) * | 2014-02-22 | 2015-12-30 | 湖南科技大学 | A kind of detect mercury ion amphipathic nature polyalcohol nanoparticle, preparation method and application |
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| CN105482011B (en) * | 2016-01-13 | 2018-03-27 | 苏州大学 | A kind of preparation method of cyclic macromolecular chain-transferring agent and its ring comb-shaped polymer |
| CN106496447B (en) * | 2016-11-21 | 2021-06-25 | 山东交通学院 | Star-shaped amphoteric polycarboxylate superplasticizer with efficient anti-mud effect and preparation method thereof |
| CN108047402B (en) * | 2017-12-18 | 2020-12-18 | 华东理工大学 | Triblock copolymer based on ATRP mechanism and preparation method thereof |
| CN112175154B (en) * | 2020-10-09 | 2022-04-29 | 杭州万观科技有限公司 | Particle size controllable silicon-fluorine polymer nano particle and preparation method and application thereof |
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