CN107312174B - A kind of synthetic method of polythiaether - Google Patents
A kind of synthetic method of polythiaether Download PDFInfo
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- CN107312174B CN107312174B CN201710590167.1A CN201710590167A CN107312174B CN 107312174 B CN107312174 B CN 107312174B CN 201710590167 A CN201710590167 A CN 201710590167A CN 107312174 B CN107312174 B CN 107312174B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
Abstract
The invention discloses a kind of synthetic methods of polythiaether, and specially using benzaldehyde derivative as the sulfydryl of catalyst-alkene photopolymerization reaction system, by α, ω-dimercaptan and α, ω-divinyl ether are that monomer synthesizes polythiaether.The method have the advantages that using cheap benzaldehydes compound as catalyst, it is seen that light (such as household 23W energy-saving lamp) is light source, and sulfydryl-alkene gradually polyaddition reaction can be realized at room temperature.Moreover, α, ω-dimercapto sealing end telechelic polymer can be prepared by regulation reaction monomers ratio.In addition, the telechelic polymer still possesses the feature of living polymerization, can continue to carry out addition reaction with divinyl base class monomer under the action of catalyst.Reaction condition of the present invention is mild, applied widely, and colourless/tasteless (without post-processing to product), reaction speed is fast.
Description
Technical field
The present invention relates to a kind of sulfydryl under benzaldehyde derivative catalyst action-alkene visible light Photopolymer Systems, specifically
It is to be related at room temperature, using the Benzaldehyde derivatives containing substituent group as organic catalyst, promotes dimercapto monomer and two
The gradually addition polymerization of vinyl ether monomers, and prepare the polysulfide polymers with Yao Zhao functional group.
Background technique
Compared to the photopolymerization reaction of traditional vinyl monomer, sulfydryl-alkene polymerization reaction in polymerization process and
It has a clear superiority in terms of polymer performance.For example, sulfydryl-alkene polymerization reaction oligomerization shrinking percentage, raw material range is wide etc..It is more important
, sulfydryl-alkene polymerization reaction can combine effectively with click chemistry.Therefore, the type of polymerization in industrial circle and
Sphere of learning attracts wide attention.
Sulfydryl-alkene polymerization reaction of free radical regulation is gradually addition reaction mechanism (STEP 1 and STEP 2).It is reacting
In the process, mercaptan compound gradually adds on the carbon-carbon double bond of vinyl monomer.
Such reaction can be caused by the thermal decomposition of radical initiator.For example, 2007, Cook et al. (Cook W D,
Chen F, Pattison D W, et al.Polymer International, 2007,56 (12): 1572-1579) it reports
The polymerization reaction of four (3- mercaptopropionic acid) pentaerythritol esters and triethyleneglycol divinylether that heat causes.2010, Lluch and
Its partner (Lluch C, Ronda J C, Gali à M, et al.Biomacromolecules, 2010,11 (6): 1646-
1653) telechelic polymer with fine structure is prepared by continuous sulfydryl-alkene click-reaction twice with " one kettle way ".It is first
First, by undecenoic acid and 3, it is 1000 that the reaction of 6- dioxa -1,8- octanedithiol can prepare molecular weight respectively,
2000 and 3000gmol-1Ethenyl blocking linear polymer.It then, is forerunner with the polymer of ethenyl blocking
Body prepares block copolymer.But the above-mentioned sulfydryl referred to-alkene polymerization reaction is heat initiation or ultraviolet light-initiated mostly.So
And the polymerization reaction that heat causes usually requires higher reaction temperature, and cannot regulate and control simultaneously polymerization from the time and spatially
The progress of reaction.And ultraviolet light-initiated sulfydryl-alkene polymerization also tends to meeting along with side reaction product.
In the recent period, our seminars are with fac-Ir (ppy)3For catalyst, two are successfully realized under the conditions of visible light exposure
The gradually addition reaction of vinyl ethers monomer and dimercapto monomer is prepared for having the active linear polythiaether of high end reaction
Oligomer (Ma W, Chen D, Liu L, et al.J.Polym.Sci., Part A:Polym.Chem., 2016,54:740-
749).But the use of transition metal complex catalyst have the defects that it is certain.Such as the polymer material prepared may
Can due to metal residual and there are toxicity or cause polymer degradation reaction, limit it in the application in the fields such as biological medicine.
The present invention develops a class formation is simple, at low cost fragrant aldehyde derivatives (including but not limited to methoxybenzene
Formaldehyde, to cyanobenzaldehyde and 2,4- dimethoxy benzaldehyde) non-metallic organocatalyst, with visible light (such as household 23W save
Energy lamp) it is light source, the gradually addition reaction of sulfydryl-alkene is realized at room temperature.By regulating and controlling reaction monomers ratio, preparation contains α,
ω-dimercapto functional group telechelic polymer.
Summary of the invention
The object of the present invention is to provide a kind of sulfydryl under benzaldehyde derivative catalyst action-alkene Photopolymer System and
High efficiency, inexpensive and easy-operating novel living radical polymerization and green reaction technique.Tool of the present invention
Body technique scheme are as follows: first under room temperature, using visible light as light source (compact type energy-saving lamp of such as 23W), aldehyde radical catalyst is (right
Methoxybenzaldehyde, to cyanobenzaldehyde and 2,4- dimethoxy benzaldehyde) it is non-metallic organocatalyst, realize two mercaptos
The gradually addition reaction of base-divinyl ether monomer.Particular functional group can be prepared by adjusting the ratio between amount of substance of two reaction monomers
The telechelic polymer of sealing end.When dimercapto monomer excess, α, ω-dimercapto sealing end can be successfully prepared using the catalyst system
Telechelic polymer.In addition, the telechelic polymer still possesses the feature of living polymerization, can continue under the action of catalyst and two
Vinyl monomer carries out addition reaction.
Polymerization reaction needs to exclude the oxygen in reactant and reactor.Method of deoxidation is common in polymerization reaction, for example,
Before polymerization, after monomer, aldehyde radical catalyst, solvent are mixed, it is placed in single branch mouth round-bottomed flask, seals.Freeze pump drainage three times, most
After be passed through inert gas (argon gas or nitrogen), carry out polymerization reaction in an inert atmosphere.Wherein, the concentration of monomer in a solvent
For 10%-50%, catalyst and two monomer total moles ratios are 10:1-20:1, and reaction temperature is room temperature, and light source is that two 23W are tight
Gather type energy-saving lamp.Wherein for light source at 420nm wave-length coverage, intensity of illumination is 600~1000 μ W cm-2。
Wherein, above-mentioned di-vinyl monomers include but is not limited to diethylene glycol divinyl ether and glycol divinyl
Base ether.Dimercapto monomer includes but is not limited to Isosorbide-5-Nitrae-benzene dimethanethiol, 1,6- ethanthiol and two (thioacetic acid)-Isosorbide-5-Nitraes-
Fourth diester.Aldehyde radical catalyst is preferably P-methoxybenzal-dehyde, in cyanobenzaldehyde and 2,4- dimethoxy benzaldehyde
Any one.
Preparation method provided by the invention is simple and easy to do, clean and environmental protection, has stronger practicability.
Detailed description of the invention
Fig. 1 is the relational graph of polymer molecular weight and reaction time in embodiment one
Fig. 2 is α, the linear polythioether oligomeric object of ω-dimercapto sealing end1H-NMR phenogram
Specific embodiment
It is specifically described the present invention below by way of some examples, but the present invention is not limited by these examples.Implement below
The concentration being not particularly illustrated in example is mass concentration.
Embodiment one, the Isosorbide-5-Nitrae-benzene dimethanethiol and diethylene glycol divinyl ether of P-methoxybenzal-dehyde catalysis are gradually
Addition reaction (wherein two monomer mole ratios are 1:1)
Diethylene glycol divinyl ether (1.44g), Isosorbide-5-Nitrae-benzene dimethanethiol are sequentially added in 25mL round-bottomed flask
(1.56g), methyl phenyl ethers anisole solution (3g), P-methoxybenzal-dehyde (0.249g) are filled with argon gas after freezing pump drainage deoxygenation, stir at room temperature
It mixes, making reaction in the compact type energy-saving lamp of two 23W, (i.e. at light source 420nm wave-length coverage, intensity of illumination is 600~1000 μ W
cm-2) carry out under irradiation condition.The extension of polymer molecular weight at any time is linearly increasing (Fig. 1).4h is reacted, monomer conversion reaches
89%, polymerizate Mn=9600g/mol, PDI=1.78.
Comparative example one
Referring to the reaction ratio in embodiment one, react polymerization system under dark condition, for 24 hours rear non-polymer
It generates, illustrates that the presence of visible light is particularly significant to the carry out of polymerization reaction.
Embodiment two, Isosorbide-5-Nitrae-benzene dimethanethiol of P-methoxybenzal-dehyde catalysis and the light of diethylene glycol divinyl ether are poly-
Close reaction (wherein 1,4- benzene dimethanethiol is excessive)
Diethylene glycol divinyl ether (1.10g), Isosorbide-5-Nitrae-benzene dimethanethiol are sequentially added in 25mL round-bottomed flask
(1.90g), methyl phenyl ethers anisole solvent (3g), P-methoxybenzal-dehyde (0.124g).Other operations are referring to (the i.e. freezing pump drainage of embodiment one
Be filled with argon gas after deoxygenation, stir at room temperature, make reaction the compact type energy-saving lamp of two 23W (at light source 420nm wave-length coverage, light
It is 600~1000 μ W cm according to intensity-2) carry out under irradiation condition, it is all the same that following embodiment omits description place).7h is reacted,
Monomer conversion is up to 71%, polymerizate Mn=4200g/mol, PDI=1.20.Hydrogen nuclear magnetic resonance spectrogram (Fig. 2) shows to react
The α of narrow distribution, ω-dimercapto sealing end telechelic polymer has been made.
Embodiment three, the telechelic polymer and diethylene glycol divinyl ether of the sulfydryl sealing end of P-methoxybenzal-dehyde catalysis
Photopolymerization reaction
α, ω-dimercapto sealing end oligomer (M are sequentially added in 25mL round-bottomed flaskn=4200g/mol, PDI=
1.20), diethylene glycol divinyl ether, P-methoxybenzal-dehyde (0.249g), methyl phenyl ethers anisole solvent (3g).Wherein telechelic polymer
It is 1:1 with diethylene glycol divinyl ether monomer mole ratio, the total concentration of two monomers in a solvent is 50%.Other operation references
Embodiment one.12h is reacted, monomer conversion is up to 87%, polymerizate Mn=16200g/mol, PDI=1.79.Prove the distant pawl
Polymer is still active, can continue to carry out addition reaction with divinyl base class monomer under the action of catalyst.
Example IV, Isosorbide-5-Nitrae-benzene dimethanethiol of P-methoxybenzal-dehyde catalysis and the light of triethyleneglycol divinylether are poly-
Close reaction
The molar ratio of Isosorbide-5-Nitrae-benzene dimethanethiol and triethyleneglycol divinylether is respectively 1:1 and 1.5:1, i.e. the present embodiment
Practical includes two groups of experiments, and total concentration of two monomers in methyl phenyl ethers anisole solvent (3g) is 50% in two groups of experiments, wherein to first
The additional amount of oxygroup benzaldehyde catalyst is 0.124g.Other operations are referring to embodiment one.When two monomer mole ratios are 1:1
When, 8h is reacted, monomer conversion is up to 89%, polymerizate Mn=9000g/mol, PDI=1.72.When two monomer mole ratios are
When 1.5:1,8h is reacted, the linear polythioether oligomeric object of sulfydryl sealing end can be obtained, monomer conversion is up to 75% at this time, polymerizate
Mn=4500g/mol, PDI=1.32.
Embodiment five, the photopolymerization to the Isosorbide-5-Nitrae-benzene dimethanethiol and diethylene glycol divinyl ether of cyanobenzaldehyde catalysis
Reaction
Diethylene glycol divinyl ether (1.45g), Isosorbide-5-Nitrae-benzene dimethanethiol are sequentially added in 25mL round-bottomed flask
(1.55g), methyl phenyl ethers anisole solution (3g), to cyanobenzaldehyde (0.119g).Other operations are referring to embodiment one.Polymer molecular weight
Extension at any time is linearly increasing.3h is reacted, monomer conversion is up to 98%, polymerizate Mn=7600g/mol, PDI=1.57.
Embodiment six, to two (thioacetic acid)-Isosorbide-5-Nitrae-fourth diester and diethylene glycol divinyl base of cyanobenzaldehyde catalysis
The photopolymerization reaction of ether
The molar ratio of two (thioacetic acid)-Isosorbide-5-Nitrae-fourth diester and diethylene glycol divinyl ether is 1:1, and two monomers are in benzene first
Total concentration in ether solvents (3g) is 50%, wherein being 0.119g to the additional amount of cyanobenzaldehyde catalyst.Other operation ginsengs
According to embodiment one.5h is reacted, monomer conversion is up to 94%, polymerizate Mn=8200g/mol, PDI=1.51.
Embodiment seven, it is anti-to the photopolymerization of 1, the 6- ethanthiol and diethylene glycol divinyl ether of cyanobenzaldehyde catalysis
It answers
The molar ratio of 1,6- ethanthiol and diethylene glycol divinyl ether is 1:1, and two monomers are at methyl phenyl ethers anisole solvent (3g)
In total concentration be 50%, wherein being 0.119g to the additional amount of cyanobenzaldehyde catalyst.Other operations are referring to embodiment one.
8h is reacted, monomer conversion is up to 95%, polymerizate Mn=7900g/mol, PDI=1.48.
Embodiment eight, 2, the Isosorbide-5-Nitrae-benzene dimethanethiol and diethylene glycol divinyl ether of the catalysis of 4- dimethoxy benzaldehyde
Photopolymerization reaction
The molar ratio of 1,4- benzene dimethanethiol and diethylene glycol divinyl ether is respectively 1:1 and 1.5:1.That is the present embodiment
Practical includes two groups of experiments, and total concentration of two monomers in methyl phenyl ethers anisole solvent (3g) is 25% in two groups of experiments, wherein 2,4-
The additional amount of dimethoxy benzaldehyde catalyst is 0.151g.Other operations are referring to embodiment one.When two monomer mole ratios are
When 1:1,8h is reacted, monomer conversion is up to 92%, polymerizate Mn=9500g/mol, PDI=1.78.When two monomer mole ratios
When for 1.5:1,8h is reacted, the linear polythioether oligomeric object of sulfydryl sealing end can be obtained, up to 78%, polymerization produces monomer conversion at this time
Object Mn=3900g/mol, PDI=1.22.
Claims (5)
1. a kind of synthetic method of polythiaether, it is characterized in that using the derivative of benzaldehyde as catalyst, with divinyl ether and two
Sulfhydryl compound is monomer, and polymerization reaction carries out 2-10h under the irradiation of visible light, and reaction temperature is room temperature；Wherein, monomer exists
Mass concentration in solvent is 10%-50%, and catalyst and two monomer total moles ratios are 10:1-20:1, it is seen that light is in 420nm wave
At long range, intensity of illumination is 600~1000 μ W cm-2；The benzaldehyde derivative catalyst structure formula used is as follows:
Wherein Y group appears in 1,2,3,4,5 any one or more positions, Y group H, methoxyl group or cyano；
Catalyst is P-methoxybenzal-dehyde, to cyanobenzaldehyde or 2,4- dimethoxy benzaldehyde.
2. synthetic method according to claim 1, which is characterized in that divinyl ethers monomer is α, ω-divinyl
Compound.
3. synthetic method according to claim 2, which is characterized in that divinyl ethers monomer is diethylene glycol divinyl
Base ether or triethyleneglycol divinylether.
4. synthetic method according to claim 1, which is characterized in that dimercapto monomer is α, ω-dimercaptan.
5. synthetic method according to claim 4, which is characterized in that dimercapto monomer be Isosorbide-5-Nitrae-benzene dimethanethiol, 1,6-
Ethanthiol or two (thioacetic acid) -1,4- fourth diester.
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| US20050010003A1 (en) * | 2003-07-11 | 2005-01-13 | Prc-Desoto International, Inc. | Epoxy-capped polythioethers |
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