CN110204724A - A method of preparing carbonyl sulfide co-production sulfur-containing polymer - Google Patents
A method of preparing carbonyl sulfide co-production sulfur-containing polymer Download PDFInfo
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- CN110204724A CN110204724A CN201910376139.9A CN201910376139A CN110204724A CN 110204724 A CN110204724 A CN 110204724A CN 201910376139 A CN201910376139 A CN 201910376139A CN 110204724 A CN110204724 A CN 110204724A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
- C01B32/77—Carbon oxysulfide
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- 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
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- 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
- C08G75/28—Polythiocarbonates
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Abstract
The invention discloses a kind of methods for preparing carbonyl sulfide co-production sulfur-containing polymer, comprising steps of under lewis base M catalysis and initiation, obtaining COS through oxygen sulphur exchange reaction using carbon disulfide and oxygen-containing monomer A as raw material, aliphatic poly thioether is generated simultaneously, and reaction temperature is 60~180 DEG C；The COS of generation reacts to obtain Polythiocarbonate at lewis base N and/or Louis acid catalysis effect with oxygen-containing monomer B, and reaction temperature is 0~100 DEG C.Present invention utilizes oxygen sulphur exchange reactions existing for carbon disulfide and oxycompound, and carbonyl sulfide and a variety of sulfur-containing polymers is prepared.The problem of catalyst used is directly bought and be can be obtained, and there is no metal residual and color residuals.Universality of the present invention is good, adapts to large-scale industrial production, and obtain three kinds of high value-added products by two kinds of products, therefore the aliphatic poly thioether and Polythiocarbonate type being prepared are abundant, extend the type and application of sulfur-containing polymer.
Description
Technical field
The present invention relates to synthesis chemistry and polymer chemistry synthesis technical fields, and in particular to a kind of to prepare carbonyl sulfide
The method of co-production sulfur-containing polymer.
Background technique
Carbonyl sulfide (COS) can manufacture urea, carbonic ester, thiocarbamate and heterocyclic compound etc., be a kind of heavy
The basic chemical industry raw material wanted.In addition to this, COS is more used as soil fumigant and stores the stifling of crop products
Agent.COS was synthesized by Hungary scientist in 1867 for the first time, was realized first greatly in Yi Hala chemical industrial company, Japan in 1970
Technical scale metaplasia produces.
The synthetic method of COS is more, there is dry and wet two major classes.Dry synthesis is mainly used in the absence of a solvent
CO and sulphur steam reaction generate COS.The method process is simple, high income, considers from cost and raw material sources, and industrial production is generally adopted
With dry method, but there are more impurity, such as H2S、SO2And CO2Deng.Moist chemical synthesis includes urea method, potassium rhodanide, thiocyanic acid
Ammonium method etc. has the characteristics that synthesizer is simple, operation is easy, but due to the presence of aqueous solvent, is easy to keep products C OS further
Impurity is resolved into, increases purification difficulty, and the waste water that the method generates is difficult to handle, is not suitable for scale of mass production.
The Chinese patent literature of Publication No. CN102674349A discloses the method for dry process COS a kind of, is reacting
Carbon monoxide is passed through in melting sulphur in device, using calcium chloride as catalyst, carbon monoxide and sulfur reaction is made to generate oxygen sulphur
Change carbon；COS is set to pass sequentially through calcium chloride and molecular sieve two-stage adsorption column to remove impurity and moisture.
For another example the Chinese patent literature of Publication No. CN101973547A discloses a kind of method for preparing carbonyl sulfide, packet
It includes following steps: (1) synthetic reaction: the ammonium thiocyanate solution of saturation being reacted in reactor with sulfuric acid, generation contains
Impurity carbonyl sulfide gas；(2) alkali cleaning: the carbonyl sulfide gas containing impurity continuously enters a caustic wash tower and secondary caustic wash tower
It is middle to remove micro acid impurities；(3) primary drying；(4) redrying and (5) rectifying.
The preparation method process of patent documents above is relatively long, produces more by-product, it is therefore desirable to rectification flow,
It increases cost and also produces waste material, thus limit the application of carbonyl sulfide industrially.
Summary of the invention
For shortcoming existing for this field, carbonyl sulfide co-production sulfur-containing polymer is prepared the present invention provides a kind of
Method under lewis base catalytic action, obtained through oxygen sulphur exchange reaction first using carbon disulfide and oxygen-containing monomer as raw material
COS, while generating aliphatic poly thioether, the COS of generation in another reactor by oxygen-containing monomer absorption, in lewis base and road
The effect of Lewis acid co-catalysis is lower to generate Polythiocarbonate.
Inventor is on the basis of further investigation oxygenatedchemicals is reacted with carbon disulfide, it was found that oxygen sulphur exchanges phenomenon
In the presence of generating carbonyl sulfide and carbon dioxide in system, and in the polymerization based on sulfocarbonate chain link of generation
There are a small amount of thioether link configurations in object chain.And CS2Quickly with the oxygen sulphur exchange reaction of oxygenatedchemicals, it is difficult to inhibit,
COS or CO always can be generated2, thus inventor has sufficiently probed into the method how to prepare COS using oxygen sulphur exchange reaction, discovery
Carbonyl sulfide can be made under normal pressure, while obtaining polythiaether, then the carbonyl sulfide of generation is passed into another reactor,
Its oxygen-containing monomer therein is absorbed, under the effect of the co-catalysis of lewis acid and lewis base, is copolymerized
Polythiocarbonates is obtained, so as to form the present invention.
A method of carbonyl sulfide co-production sulfur-containing polymer is prepared, comprising steps of
(1) it using carbon disulfide and oxygen-containing monomer A as raw material, under lewis base M catalysis and initiation, is exchanged through oxygen sulphur
Reaction obtains carbonyl sulfide, while generating aliphatic poly thioether；Reaction temperature is 60~180 DEG C；
(2) carbonyl sulfide generated is reacted at lewis base N and/or Louis acid catalysis effect with oxygen-containing monomer B
To Polythiocarbonate；Reaction temperature is 60~100 DEG C.
Preferably, the reaction temperature of the step (1) is 80~180 DEG C, the reaction time is 0.5~12h.
Oxygen sulphur exchange reaction needs higher temperature conditions.Therefore, COS and fat are selectively produced in step (1)
Adoption thioether is preferably carried out at 80 DEG C or more.And as temperature increases, reaction rate is also increased accordingly, and is conducive to improve this conjunction
At the efficiency of method.
Preferably, carbon disulfide (the CS2) it with the molar ratio of oxygen-containing monomer A is 1~10:1, further preferably
1~5:1, using slightly excessive CS2The quick progress for being conducive to reaction, is also beneficial to the complete conversion of oxygen-containing monomer A.
Preferably, the molar ratio of the lewis base M and oxygen-containing monomer A is 1:10~5000, further preferably
1:50~500, in preferred range, oxygen sulphur exchange reaction sufficiently occurs, and selectively produces COS and aliphatic poly thioether.
Preferably, the reaction temperature of the step (2) is 0~80 DEG C, the reaction time is 0.5~12h.It is preferred that reaction temperature
The generation of avoidable side reaction under degree, so as to obtain the specific Polythiocarbonate of structure.
Preferably, the molar ratio of the lewis base N or lewis acid and oxygen-containing monomer B is 1:10~5000, into
One step is preferably 1:50~500, and in preferred range, COS and oxygen-containing monomer copolyreaction can be rapidly completed, and is generated poly- single
Sulfocarbonate.
Preferably, the molar ratio of the lewis acid and lewis base N are 0.1~10:1, further preferably 1~
5:1, in preferred range, COS and the copolymerization of oxygen-containing monomer selectively produce Polythiocarbonate, reduce cyclic annular thio carbon
The content of acid esters.
Preferably, the aliphatic poly thioether and Polythiocarbonate obtain after purifying, drying.
The number-average molecular weight of the aliphatic poly thioether is 1~100kg/mol, and molecular weight distribution is 1.1~2.0.
The number-average molecular weight of the Polythiocarbonate is 1~100kg/mol, and molecular weight distribution is 1.1~2.0.
The oxygen-containing monomer A and oxygen-containing monomer B is respectively and independently selected from epoxide, oxetanes and 3- and replaces oxygen
At least one of azetidine.
Preferably, the epoxide is selected from ethylene oxide, propylene oxide, 1,2- epoxy butane, C5~C20's
Alpha-oxidation alkene, phenyl glycidyl ether, benzyl glycidyl ether, epoxy methyl undecylenate, allyl glycidyl ether, epoxy
Chloropropane, epoxy iso-butane, 7-oxa-bicyclo[4.1.0,4 vinyl epoxy cyclohexane, glycidyl methacrylate, oxidation lemon
At least one of alkene, cyclopentane epoxide and styrene oxide.
Preferably, the 3- replaces oxetanes to be selected from 3,3- dimethyl oxygen azetidine, 3- methyl -3- benzyloxy
Ylmethyl oxetanes, 3- chloromethyl -3- methy oxetane, 3- methyl -3- oxetane methanol, 3- oxa- ring fourth
At least one of ketone, 3- (allyloxy) oxetanes and 3- bromine oxetanes.
Further preferably, the oxygen-containing monomer A and oxygen-containing monomer B are respectively and independently selected from ethylene oxide, propylene oxide, ring
Oxygen hexamethylene, phenyl glycidyl ether, benzyl glycidyl ether, styrene oxide, oxetanes and 3- chloromethyl -3- methyl
At least one of oxetanes.These preferred oxygen-containing monomers are cheap and easily-available industrial products, and storage and transportation is convenient.Especially
It is important that these preferred oxygen-containing monomers and carbon disulfide have the effect of it is reactive and excellent well.Obtained polysulfide
Ether is the market demand, and other methods are difficult to the product obtained.
The lewis base M and lewis base N is respectively and independently selected from quaternary ammonium salt, quaternary alkylphosphonium salt, organic base and alkali metal alcohol
At least one of salt.
Preferably, the quaternary ammonium salt be selected from bis- (dihalotriphenylphosphoranes base) ammonium chlorides, cetyl trimethyl ammonium halide,
Tetrabutylammonium hydroxide, trimethyl ammonium halide, ten alkylpolyoxyethylenes, benzyl triethyl ammonium ammonium halide, benzyl
Tripropyl ammonium halide, benzyl tributyl ammonium halide, benzyl triethyl ammonium ammonium acetate, benzyl tripropyl ammonium acetate, benzyl tributyl vinegar
In sour ammonium, tetraethyl ammonium acetate, tetrabutylammonium iodide, tetrabutyl ammonium nitrate, tetrapropyl ammonium acetate and tetra-alkyl-phosphonium halide ammonium salt
It is at least one.
Preferably, the quaternary alkylphosphonium salt is selected from tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, tetraalkyl halogenation phosphonium salt, benzyl
At least one of base triphenylphosphinebromide, butyl triphenyl phosphonium iodide and propyl triphenylphosphinebromide.
Preferably, the organic base be selected from 1,8- diazabicyclo [5.4.0] 11-7- carbene, 7- methyl-1,5,
At least one of 11-7- carbene of tri- azabicyclo of 7- [4.4.0] decyl- 5- alkene and 1,5,7- diazabicyclo [5.4.0].
Preferably, the alkali metal alcoholates are selected from sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, ethyl alcohol
At least one in lithium, potassium tert-butoxide, tert-butyl alcohol lithium, sodium tert-butoxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and lithium hydroxide
Kind.
Further preferably, the lewis base M and lewis base N is respectively and independently selected from bis- (dihalotriphenylphosphoranes base) chlorinations
Ammonium ([PPN] Cl), dodecyl trimethyl ammonium bromide (DTMeAB), tetraphenyl phosphonium chloride (PPh4Cl), 1,8- diazabicyclo
[5.4.0] 11-7- carbene (DBU), sodium methoxide (CH3) and at least one of potassium tert-butoxide (t-BuOK) ONa.These are preferably
Lewis base alkalinity it is suitable, and dissolubility is preferable, all achieves finally for catalytic step (1) and (2) satisfactory
Result.
The lewis acid in boron triethyl, tri butyl boron, triphenyl borine, chromium complex and zinc complex at least
It is a kind of.
Preferably, the reaction in step (1) and step (2) uses solvent respectively.The use of solvent reduces reactant
The viscosity of system is conducive to stirring with heat transfer.
Reaction dissolvent in step (1) and step (2) is separately selected from methylene chloride, chloroform, tetrahydrofuran, first
At least one of benzene, trichloro-benzenes, o-dichlorohenzene, m-dichlorobenzene, paracide and dimethylformamide.By comparative test number
According to still further preferably, the reaction dissolvent in step (1) is selected from toluene and/or trichloro-benzenes；Reaction dissolvent choosing in step (2)
From tetrahydrofuran and/or dimethylformamide.These preferred solvents all have preferable dissolution for reactant and product
Property, and boiling point is suitable.
As a preference, the specific steps of the method for preparing carbonyl sulfide co-production sulfur-containing polymer are as follows:
(1) in reactor I, use the method for Multistep feeding using carbon disulfide and oxygen-containing monomer A as raw material, in anhydrous nothing
Under the conditions of oxygen, by lewis base M catalysis, initiation reaction, COS is released, and generate aliphatic poly thioether；Reaction temperature be 60~
180℃；
(2) COS released is introduced in reactor II, is absorbed by the oxygen-containing monomer B in reactor II, and in reactor
Under lewis base N and/or Louis acid catalysis effect in II, oxygen-containing monomer B and COS is copolymerized, and obtains poly- single sulphur
For carbonic ester；Reaction temperature is 60~100 DEG C.
Compared with prior art, the present invention major advantage includes:
(1) present invention is to propose on the basis of lot of experiments and a kind of completely new prepare carbonyl sulfide co-production
The method of sulfur-containing polymer, reactant are made of carbon disulfide and oxycompound, and monomer source is very extensive, cheap and easily-available；Make
Catalyst is directly bought and be can be obtained, and metal residual problem is not present.
(2) co-production used by, the COS of generation directly takes part in be polymerize in next step, avoids the purifying step of COS
Suddenly, the sulfur-containing polymer of high added value has been obtained, and entire reaction is completed in closed system, greatly reduces the shadow to environment
It rings.
(3) using the synthetic method in the present invention, since there are many oxygen-containing monomeric species, and synthetic method universality is good, fits
Large-scale industrial production is answered, and obtains three kinds of high value-added products, therefore the aliphatic polysulfide being prepared by two kinds of products
Ether and Polythiocarbonate type are abundant, extend the type and application of sulfur-containing polymer.
Detailed description of the invention
Fig. 1 is the polymerizate of 1 reactor I of embodiment preparation1H NMR spectra；
Fig. 2 is the polymerizate of 1 reactor I of embodiment preparation13C NMR spectra；
Fig. 3 is the co-polymeric product of 1 reactor II of embodiment preparation1H NMR spectra；
Fig. 4 is the co-polymeric product of 1 reactor II of embodiment preparation13C NMR spectra.
Specific embodiment
With reference to the accompanying drawing and specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate
The present invention rather than limit the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to
Normal condition, or according to the normal condition proposed by manufacturer.
In following embodiments, used lewis base is respectively with flowering structure, and serial number is as shown in following formula:
1 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and passes through valve, pipeline connection；Initial stage valve is closed, if being successively added into reactor I
1 1,8- diazabicyclo [5.4.0] of Louis (Lewis) alkali, the 11-7- carbene (DBU) of dry mass；Lewis alkali 1 and epoxy
The molar ratio of propane (PO) is 1:10；Add CS2、PO(CS2With PO molar ratio 1:1) and 1mL toluene.Then reactor I is sealed
It closes, is placed in 80 DEG C of oil baths and reacts 0.5h under self-generated pressure.Reactor I is cooled to room temperature after reaction.To reactor II
If the middle PO that dry mass is added, Lewis alkali 11,11-7- carbene (DBU) of 8- diazabicyclo [5.4.0] and Lewis triethylenetetraminehexaacetic acid
Base boron and 1mL THF；The molar ratio of Lewis alkali 1 and propylene oxide (PO) are 1:60, and the molar ratio with Lewis acid is 1:1, will
Reactor II closing.Valve between reactor I and reactor II is opened, reactor II is placed in Yu Zisheng in 80 DEG C of oil baths
1.5h is reacted under pressure.Reactor II is likewise cooled to room temperature after reaction.First use tetrahydrofuran dissolution reactor I and reaction
Crude product in device II, then polymer is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture, repetition is washed three times, and vacuum is dry
It is dry to constant weight.The molecular weight and molecular weight distribution of polymer is measured by gel chromatography, test result is shown in Tables 1 and 2.
The polythiaether that the present embodiment is prepared1H NMR spectra is as shown in Figure 1,13C NMR spectra is as shown in Figure 2；It is poly-
Single sulfocarbonate1H NMR spectra as shown in figure 3,13C NMR spectra is as shown in Figure 4.Fig. 1 and Fig. 2 is observed it is found that successfully closing
At polythiaether；Peak position and integral area corresponding to each hydrogen atom on thioether chain link are given in Fig. 1.Observe Fig. 3
With Fig. 4 it is found that successfully synthesizing Polythiocarbonate；Each hydrogen atom institute on sulfocarbonate chain link is given in Fig. 1
Corresponding peak position and integral area.
2 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and passes through valve, pipeline connection；Initial stage valve is closed, if being successively added into reactor I
2 1,5,7- of Lewis alkali tri- azabicyclo [4.4.0] decyl- 5- alkene (TBD) of dry mass；Lewis alkali 2 and propylene oxide (PO)
Molar ratio is 1/500；Add CS2、PO(CS2With PO molar ratio 3:1) and 1mL toluene.Then reactor I is closed, is placed in 80
6.0h is reacted under self-generated pressure in DEG C oil bath.Reactor I is cooled to room temperature after reaction.It is added into reactor II several
The PO of quality, Lewis alkali 21,5,7- tri- azabicyclo [4.4.0] decyl- 5- alkene (TBD) and Lewis triethylenetetraminehexaacetic acid base boron and 1mL
DMF；The molar ratio of Lewis alkali 2 and propylene oxide (PO) are 1/300, are 1/3 with lewis acidic molar ratio, by reactor II
Closing.Valve between reactor I and reactor II is opened, reactor II is placed in 60 DEG C of oil baths under self-generated pressure instead
Answer 3.0h.Reactor II is likewise cooled to room temperature after reaction.First in tetrahydrofuran dissolution reactor I and reactor II
Crude product, then polymer is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture, repetition is washed three times, and perseverance is dried under vacuum to
Weight.The molecular weight and molecular weight distribution of polymer is measured by gel chromatography, test result is shown in Tables 1 and 2.
3 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
First by the 2 reactor I and reactor II of 10mL, 2 hours or so removing moisture is simultaneously at 110 DEG C before polymerization reaction
It is cooled to room temperature in drier, and passes through valve, pipeline connection；Initial stage valve is closed, and is successively added into reactor I
If entering 3 sodium methoxide of Lewis alkali of dry mass；The molar ratio of Lewis alkali 3 and propylene oxide (PO) are 1/500；Add CS2、PO
(CS2With PO molar ratio 10:1) and 1mL toluene.Then reactor I is closed, is placed in 100 DEG C of oil baths under self-generated pressure anti-
Answer 0.5h.Reactor I is cooled to room temperature after reaction.If the PO of dry mass, 3 methanol of Lewis alkali are added into reactor II
Sodium and lewis acid tri butyl boron and 1mL THF；The molar ratio of Lewis alkali 3 and propylene oxide (PO) are 1/400, with Louis
The molar ratio of acid is 1/5, and reactor II is closed.Valve between reactor I and reactor II is opened, reactor II is set
2h is reacted under self-generated pressure in 30 DEG C of oil baths.Reactor II is likewise cooled to room temperature after reaction.First use tetrahydrofuran
Crude product in dissolution reactor I and reactor II, then it is settled out polymer in ethyl alcohol/deionized water/hydrochloric acid mixture,
Repetition is washed three times, and constant weight is dried under vacuum to.The molecular weight and molecular weight distribution of polymer, test result are measured by gel chromatography
See Tables 1 and 2.
4 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and passes through valve, piping connection；Initial stage valve is closed, if being successively added into reactor I
The Lewis alkali 4 of dry mass is bis- (dihalotriphenylphosphoranes base) ammonium chlorides ([PPN] Cl)；Lewis alkali 4 rubs with propylene oxide (PO's)
You are than being 1/100；Add CS2、PO(CS2With PO molar ratio 4:1) and 1mL trichloro-benzenes.Then reactor I is closed, is placed in
8h is reacted under self-generated pressure in 100 DEG C of oil baths.Reactor I is cooled to room temperature after reaction.If being added into reactor II
The PO of dry mass, Lewis alkali 4 is bis- (dihalotriphenylphosphoranes base) ammonium chlorides ([PPN] Cl) and Lewis triphenyl phosphate base boron and 1mL
DMF；The molar ratio of Lewis alkali 4 and propylene oxide (PO) are 1/100, and the molar ratio with Lewis acid is 1/0.1, by reactor II
Closing.Valve between reactor I and reactor II is opened, reactor II is placed in 80 DEG C of oil baths under self-generated pressure instead
Answer 8h.Reactor II is likewise cooled to room temperature after reaction.First with thick in tetrahydrofuran dissolution reactor I and reactor II
Product, then polymer is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture, repetition is washed three times, and constant weight is dried under vacuum to.
The molecular weight and molecular weight distribution of polymer is measured by gel chromatography, test result is shown in Tables 1 and 2.
5 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and passes through valve, piping connection；Initial stage valve is closed, if being successively added into reactor I
The 5 tetraphenyl phosphonium chloride (PPh of Lewis alkali of dry mass4Cl)；The molar ratio of Lewis alkali 5 and propylene oxide (PO) are 1/50；Again
CS is added2、PO(CS2With PO molar ratio 1:1).Then reactor I is closed, is placed in 180 DEG C of oil baths and is reacted under self-generated pressure
0.5h.Reactor I is cooled to room temperature after reaction.If the PO of dry mass, 5 tetraphenyl of Lewis alkali are added into reactor II
Phosphonium chloride (PPh4) and Lewis acid tri butyl boron Cl；The molar ratio of Lewis alkali 5 and propylene oxide (PO) are 1/10, with Lewis
The molar ratio of acid is 1/10, and reactor II is closed.Valve between reactor I and reactor II is opened, by reactor II
It is placed in 0 DEG C of oil bath and reacts 5.5h under self-generated pressure.Reactor II is likewise cooled to room temperature after reaction.First use tetrahydro furan
Crude product in dissolution reactor of muttering I and reactor II, then polymerization is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture
Object, repetition are washed three times, and constant weight is dried under vacuum to.The molecular weight and molecular weight distribution of polymer, test are measured by gel chromatography
It the results are shown in Table 1 and table 2.
6 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 6 potassium tert-butoxide of Lewis alkali of dry mass is added；The molar ratio of Lewis alkali 6 and propylene oxide (PO) are 1/5000；It adds
CS2、PO(CS2With PO molar ratio 2:1) and 1mL trichloro-benzenes.Then reactor I is closed, is placed in 80 DEG C of oil baths in self-generated pressure
Lower reaction 12h.Reactor I is cooled to room temperature after reaction.If the PO of dry mass, 6 uncle of Lewis alkali are added into reactor II
Butanol potassium and Lewis triphenyl phosphate base boron and 1mL THF；The molar ratio of Lewis alkali 6 and propylene oxide (PO) are 1/500, with
The molar ratio of Lewis acid is 1/4, and reactor II is closed.Valve between reactor I and reactor II is opened, will be reacted
Device II, which is placed in 80 DEG C of oil baths, reacts 7.0h under self-generated pressure.Reactor II is likewise cooled to room temperature after reaction.First use
Crude product in tetrahydrofuran dissolution reactor I and reactor II, then precipitated in ethyl alcohol/deionized water/hydrochloric acid mixture
Polymer out, repetition are washed three times, and constant weight is dried under vacuum to.The molecular weight and molecular weight point of polymer are measured by gel chromatography
Cloth, test result are shown in Tables 1 and 2.
7 CS of embodiment2/ CHO prepares carbonyl sulfide and prepares Polythiocarbonate with CHO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 3 sodium methoxide of Lewis alkali of dry mass is added；The molar ratio of Lewis alkali 3 and CHO are 1/1000；Add CS2、PO(CS2With
CHO molar ratio 5:1) and 1mL toluene.Then reactor I is closed, is placed in 100 DEG C of oil baths and reacts 8h under self-generated pressure.Instead
It should terminate post-reactor I to be cooled to room temperature.If the CHO of dry mass, 3 sodium methoxide of Lewis alkali and Lewis are added into reactor II
Sour tri butyl boron and 1mL DMF；The molar ratio of Lewis alkali 1 and CHO are 1/60, and the molar ratio with Lewis acid is 1/5000, will
Reactor II closing.Valve between reactor I and reactor II is opened, reactor II is placed in Yu Zisheng in 40 DEG C of oil baths
8.0h is reacted under pressure.Reactor II is likewise cooled to room temperature after reaction.First use tetrahydrofuran dissolution reactor I and reaction
Crude product in device II, then polymer is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture, repetition is washed three times, and vacuum is dry
It is dry to constant weight.The molecular weight and molecular weight distribution of polymer is measured by gel chromatography, test result is shown in Tables 1 and 2.
8 CS of embodiment2/ 3- chloromethyl -3- methy oxetane prepares carbonyl sulfide and prepares with PGE coproduction poly- single
Sulfocarbonate
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 1 1,8- diazabicyclo [5.4.0] of Lewis alkali, the 11-7- carbene (DBU) of dry mass is added；Lewis alkali 1 and 3- chloromethane
The molar ratio of base -3- methy oxetane is 1/1000；Add CS2, 3- chloromethyl -3- methy oxetane (CS2With
3- chloromethyl -3- methy oxetane molar ratio 3:1) and 1mL trichloro-benzenes.Then reactor I is closed, is placed in 90 DEG C of oil baths
In react 8.0h under self-generated pressure.Reactor I is cooled to room temperature after reaction.If dry mass is added into reactor II
Bis- (dihalotriphenylphosphoranes base) ammonium chlorides ([PPN] Cl) of PGE, Lewis alkali 4 and Lewis triphenyl phosphate base boron and 1mL THF；Lewis alkali
The molar ratio of 4 and PGE is 1/3000, and the molar ratio with Lewis acid is 1/3, and reactor II is closed.By reactor I and reaction
Valve between device II is opened, and reactor II is placed in 50 DEG C of oil baths and reacts 12h under self-generated pressure.It reacts after reaction
Device II is likewise cooled to room temperature.First with the crude product in tetrahydrofuran dissolution reactor I and reactor II, then ethyl alcohol/go from
Polymer is settled out in the mixture of sub- water/hydrochloric acid, repetition is washed three times, and constant weight is dried under vacuum to.It is poly- by gel chromatography measurement
The molecular weight and molecular weight distribution of object is closed, test result is shown in Tables 1 and 2.
9 CS of embodiment2/ benzyl glycidyl ether prepares carbonyl sulfide and prepares Polythiocarbonate with StO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If the Lewis alkali 4 that dry mass is added is bis- (dihalotriphenylphosphoranes base) ammonium chlorides ([PPN] Cl)；Lewis alkali 4 shrinks sweet with benzyl
The molar ratio of oily ether is 1/2000；Add CS2, benzyl glycidyl ether (CS2With benzyl glycidyl ether molar ratio 2:1) and
1mL toluene.Then reactor I is closed, is placed in 100 DEG C of oil baths and reacts 12h under self-generated pressure.Reactor after reaction
I is cooled to room temperature.If the StO of dry mass, Lewis alkali 11,8- diazabicyclo [5.4.0] 11-are added into reactor II
7- carbene (DBU) and Lewis acid tri butyl boron and 1mL DMF；The molar ratio of Lewis alkali 1 and StO are 1/200, with Lewis acid
Molar ratio be 1/4, reactor II is closed.Valve between reactor I and reactor II is opened, reactor II is placed in
10h is reacted under self-generated pressure in 70 DEG C of oil baths.Reactor II is likewise cooled to room temperature after reaction.It is first molten with tetrahydrofuran
The crude product in reactor I and reactor II is solved, then is settled out polymer in ethyl alcohol/deionized water/hydrochloric acid mixture, weight
After backwashing three times, is dried under vacuum to constant weight.The molecular weight and molecular weight distribution of polymer is measured by gel chromatography, test result is shown in
Tables 1 and 2.
10 CS of embodiment2/ OX prepares carbonyl sulfide and prepares Polythiocarbonate with EO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 2 1,5,7- of Lewis alkali tri- azabicyclo [4.4.0] decyl- 5- alkene (TBD) of dry mass is added；Mole of Lewis alkali 2 and OX
Than being 1/500；Add CS2、OX(CS2With OX molar ratio 5:1) and 1mL trichloro-benzenes.Then reactor I is closed, is placed in 80 DEG C
10h is reacted under self-generated pressure in oil bath.Reactor I is cooled to room temperature after reaction.Several matter are added into reactor II
The EO of amount, Lewis alkali 11,11-7- carbene (DBU) of 8- diazabicyclo [5.4.0] and Lewis triethylenetetraminehexaacetic acid base boron and 1mL
THF；The molar ratio of Lewis alkali 1 and EO are 1/500, and the molar ratio with Lewis acid is 1/1, and reactor II is closed.It will reaction
Valve between device I and reactor II is opened, and reactor II is placed in 80 DEG C of oil baths and reacts 10h under self-generated pressure.Reaction
Terminate post-reactor II and is likewise cooled to room temperature.First with the crude product in tetrahydrofuran dissolution reactor I and reactor II, then
Polymer is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture, repetition is washed three times, and constant weight is dried under vacuum to.Pass through gel color
The molecular weight and molecular weight distribution of spectrum measurement polymer, test result are shown in Tables 1 and 2.
11 CS of embodiment2/ StO prepares carbonyl sulfide and prepares Polythiocarbonate with benzyl glycidyl ether coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 3 sodium methoxide of Lewis alkali of dry mass is added；The molar ratio of Lewis alkali 3 and StO are 1/1000；Add CS2、StO(CS2With
StO molar ratio 2:1) and 1mL toluene.Then reactor I is closed, is placed in 150 DEG C of oil baths and reacts 7.0h under self-generated pressure.
Reactor I is cooled to room temperature after reaction.If the benzyl glycidyl ether of dry mass, Lewis alkali 5 are added into reactor II
Tetraphenyl phosphonium chloride (PPh4) and Lewis triethylenetetraminehexaacetic acid base boron and 1mL THF Cl；Mole of Lewis alkali 1 and benzyl glycidyl ether
Than being 1/200, the molar ratio with Lewis acid is 1/1, and reactor II is closed.By the valve between reactor I and reactor II
It opens, reactor II is placed in 60 DEG C of oil baths and reacts 5.0h under self-generated pressure.Reactor II is equally cooling after reaction
To room temperature.The crude product in tetrahydrofuran dissolution reactor I and reactor II is first used, then mixed in ethyl alcohol/deionized water/hydrochloric acid
It closes and is settled out polymer in object, repetition is washed three times, and constant weight is dried under vacuum to.By gel chromatography measure polymer molecular weight with
Molecular weight distribution, test result are shown in Tables 1 and 2.
12 CS of embodiment2/ EO prepares carbonyl sulfide and prepares Polythiocarbonate with OX coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 1 1,8- diazabicyclo [5.4.0] of Lewis alkali, the 11-7- carbene (DBU) of dry mass is added；Lewis alkali 1 and EO's rubs
You are than being 1/500；Add CS2、EO(CS2With EO molar ratio 1:1) and 1mL trichloro-benzenes.Then reactor I is closed, is placed in
6h is reacted under self-generated pressure in 100 DEG C of oil baths.Reactor I is cooled to room temperature after reaction.If being added into reactor II
6 potassium tert-butoxide of the OX of dry mass, Lewis alkali and Lewis acid tri butyl boron and 1mL THF；The molar ratio of Lewis alkali 6 and OX is
1/500, the molar ratio with Lewis acid is 1/3, and reactor II is closed.Valve between reactor I and reactor II is beaten
It opens, reactor II is placed in 10 DEG C of oil baths and reacts 7h under self-generated pressure.Reactor II is likewise cooled to room after reaction
Temperature.The crude product in tetrahydrofuran dissolution reactor I and reactor II is first used, then in ethyl alcohol/deionized water/hydrochloric acid mixture
In be settled out polymer, repetition is washed three times, and constant weight is dried under vacuum to.The molecular weight and molecule of polymer are measured by gel chromatography
Amount distribution, test result are shown in Tables 1 and 2.
13 CS of embodiment2/ PGE prepares carbonyl sulfide and prepares with 3- chloromethyl -3- methy oxetane coproduction poly- single
Sulfocarbonate
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 1 1,8- diazabicyclo [5.4.0] of Lewis alkali, the 11-7- carbene (DBU) of dry mass is added；Lewis alkali 1 and PGE's
Molar ratio is 1/10；Add CS2、PGE(CS2With PGE molar ratio 1:500) and 1mL toluene.Then reactor I is closed, is set
8h is reacted under self-generated pressure in 120 DEG C of oil baths.Reactor I is cooled to room temperature after reaction.It is added into reactor II
If the 3- chloromethyl -3- methy oxetane of dry mass, 5 tetraphenyl phosphonium chloride (PPh of Lewis alkali4) and sour three fourths of Lewis Cl
Base boron and 1mL DMF；The molar ratio of Lewis alkali 5 and 3- chloromethyl -3- methy oxetane is 1/500, with Lewis acid
Molar ratio is 1/2, and high-pressure reactor II is closed.Valve between reactor I and reactor II is opened, reactor II is set
5h is reacted under self-generated pressure in 20 DEG C of oil baths.Reactor II is likewise cooled to room temperature after reaction.First use tetrahydrofuran
Crude product in dissolution reactor I and reactor II, then it is settled out polymer in ethyl alcohol/deionized water/hydrochloric acid mixture,
Repetition is washed three times, and constant weight is dried under vacuum to.The molecular weight and molecular weight distribution of polymer, test result are measured by gel chromatography
See Tables 1 and 2.
14 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 3 sodium methoxide of Lewis alkali of dry mass is added；The molar ratio of Lewis alkali 3 and propylene oxide (PO) are 1/50；Add CS2、
PO(CS2With PO molar ratio 1:1) and 1mL toluene.Then reactor I is closed, is placed in 120 DEG C of oil baths under self-generated pressure anti-
Answer 4h.Reactor I is cooled to room temperature after reaction.If the PO, metallic catalyst Cr- of dry mass are added into reactor II
Salen and 1mL THF；The molar ratio of metallic catalyst Cr-Salen and propylene oxide (PO) are 1/10, and reactor II is closed.
Valve between reactor I and reactor II is opened, reactor II is placed in 0 DEG C of oil bath and reacts 4h under self-generated pressure.
Reactor II is likewise cooled to room temperature after reaction.The crude product in tetrahydrofuran dissolution reactor I and reactor II is first used,
Polymer is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture again, repetition is washed three times, and constant weight is dried under vacuum to.By solidifying
The molecular weight and molecular weight distribution of glue chromatographic determination polymer, test result are shown in Tables 1 and 2.
15 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 1 1,8- diazabicyclo [5.4.0] of Lewis alkali, the 11-7- carbene (DBU) of dry mass is added；Lewis alkali 1 and epoxy third
The molar ratio of alkane (PO) is 1/500；Add CS2、PO(CS2With PO molar ratio 4:1) and 1mL trichloro-benzenes.Then by reactor I
Closing, is placed in 140 DEG C of oil baths and reacts 3h under self-generated pressure.Reactor I is cooled to room temperature after reaction.To reactor II
If the middle PO, metallic catalyst Cr-Salen and 1mL THF that dry mass is added；Metallic catalyst Cr-Salen and propylene oxide
(PO) molar ratio is 1/500, and reactor II is closed.Valve between reactor I and reactor II is opened, by reactor
II, which is placed in 60 DEG C of oil baths, reacts 2h under self-generated pressure.Reactor II is likewise cooled to room temperature after reaction.First use tetrahydro
Crude product in furans dissolution reactor I and reactor II, then be settled out in ethyl alcohol/deionized water/hydrochloric acid mixture poly-
Object is closed, repetition is washed three times, and constant weight is dried under vacuum to.The molecular weight and molecular weight distribution of polymer is measured by gel chromatography, is surveyed
Test result is shown in Tables 1 and 2.
16 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If 2 1,5,7- of Lewis alkali tri- azabicyclo [4.4.0] decyl- 5- alkene (TBD) of dry mass is added；Lewis alkali 2 and propylene oxide
(PO) molar ratio is 1/100；Add CS2、PO(CS2With PO molar ratio 3:1) and 1mL trichloro-benzenes.Then reactor I is sealed
It closes, is placed in 100 DEG C of oil baths and reacts 4h under self-generated pressure.Reactor I is cooled to room temperature after reaction.Into reactor II
If the PO of dry mass, metallic catalyst bimetallic cyaniding complex (DMCC) and 1mL THF is added；Metallic catalyst DMCC and ring
The molar ratio of Ethylene Oxide (PO) is 1/50, and reactor II is closed.Valve between reactor I and reactor II is opened, it will
Reactor II, which is placed in 40 DEG C of oil baths, reacts 4h under self-generated pressure.Reactor II is likewise cooled to room temperature after reaction.First
It sinks with the crude product in tetrahydrofuran dissolution reactor I and reactor II, then in ethyl alcohol/deionized water/hydrochloric acid mixture
Form sediment polymer out, and repetition is washed three times, is dried under vacuum to constant weight.The molecular weight and molecular weight point of polymer are measured by gel chromatography
Cloth, test result are shown in Tables 1 and 2.
17 CS of embodiment2/ PO prepares carbonyl sulfide and prepares Polythiocarbonate with PO coproduction
Before polymerization reaction first by the reactor I of 10mL and reactor II at 110 DEG C 2 hours or so removing moisture and dry
It is cooled to room temperature in dry device, and by valve, piping connection to together；Initial stage valve is closed, successively into reactor I
If the 5 tetraphenyl phosphonium chloride (PPh of Lewis alkali of dry mass is added4Cl)；The molar ratio of Lewis alkali 5 and propylene oxide (PO) are 1/
300；Add CS2、PO(CS2With PO molar ratio 2:1) and 1mL toluene.Then reactor I is closed, is placed in 120 DEG C of oil baths
1h is reacted under self-generated pressure.Reactor I is cooled to room temperature after reaction.If the PO of dry mass is added into reactor II,
Metallic catalyst DMCC and 1mL THF；The molar ratio of metallic catalyst DMCC and propylene oxide (PO) are 1/500, by reactor
II closing.Valve between reactor I and reactor II is opened, reactor II is placed in 20 DEG C of oil baths under self-generated pressure
React 8h.Reactor II is likewise cooled to room temperature after reaction.First in tetrahydrofuran dissolution reactor I and reactor II
Crude product, then polymer is settled out in ethyl alcohol/deionized water/hydrochloric acid mixture, repetition is washed three times, and perseverance is dried under vacuum to
Weight.The molecular weight and molecular weight distribution of polymer is measured by gel chromatography, test result is shown in Tables 1 and 2.
The test result of the polymerizate of 1 embodiment of table, 1~17 reactor I
1Oxycompound type；
2Lewis base type: 11-7- carbene (DBU) of 11,8- diazabicyclo [5.4.0], 21,5,7- tri- azepines
Bicyclic [4.4.0] decyl- 5- alkene, 3 sodium methoxide (CH3ONa), 4 be bis- (dihalotriphenylphosphoranes base) ammonium chlorides ([PPN] Cl), 5 tetraphenyls
Phosphonium chloride (PPh4Cl), 6 potassium tert-butoxides (t-BuOK)；
3Lewis base and oxidiferous molar ratio；
4Carbon disulfide and oxidiferous molar ratio；
5Solvent type；
6Mn: number-average molecular weight is measured by gel permeation chromatography；
7PDI: molecular weight distribution is measured by gel permeation chromatography.
The test result of the polymerizate of 2 embodiment of table, 1~17 reactor II
1Oxycompound type；
2Metallic catalyst type；
3Lewis base type: 11-7- carbene (DBU) of 11,8- diazabicyclo [5.4.0], 21,5,7- tri- azepines
Bicyclic [4.4.0] decyl- 5- alkene, 3 sodium methoxide (CH3ONa), 4 be bis- (dihalotriphenylphosphoranes base) ammonium chlorides ([PPN] Cl), 5 tetraphenyls
Phosphonium chloride (PPh4Cl), 6 potassium tert-butoxides (t-BuOK)；
4Lewis base or metallic catalyst and oxidiferous molar ratio；
5Solvent type, THF: tetrahydrofuran, DMF: dimethylformamide；
6Mn: number-average molecular weight is measured by gel permeation chromatography；
7PDI: molecular weight distribution is measured by gel permeation chromatography.
It can be seen from the above result that:
Embodiment 1~17 be different reaction conditions prepare carbonyl sulfide and coproduction sulfur-containing polymer as a result, can be with
Find out that this synthetic method has high activity and universality.
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (10)
1. a kind of method for preparing carbonyl sulfide co-production sulfur-containing polymer, comprising steps of
(1) using carbon disulfide and oxygen-containing monomer A as raw material, under lewis base M catalysis and initiation, through oxygen sulphur exchange reaction
Carbonyl sulfide is obtained, while generating aliphatic poly thioether；Reaction temperature is 60~180 DEG C；
(2) carbonyl sulfide generated reacts at lewis base N and/or Louis acid catalysis effect with oxygen-containing monomer B and is gathered
Single sulfocarbonate；Reaction temperature is 0~100 DEG C.
2. the method according to claim 1 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that described
The molar ratio of carbon disulfide and oxygen-containing monomer A are 1~10:1；
The molar ratio of the lewis base M and oxygen-containing monomer A are 1:10~5000.
3. the method according to claim 1 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that described
The molar ratio of lewis base N or lewis acid and oxygen-containing monomer B is 1:10~5000.
4. the method according to claim 1 or 3 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that institute
The molar ratio of the lewis acid and lewis base N stated is 0.1~10:1.
5. the method according to claim 1 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that described
Oxygen-containing monomer A and oxygen-containing monomer B is respectively and independently selected from epoxide, oxetanes and 3- and replaces in oxetanes extremely
Few one kind.
6. the method according to claim 5 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that described
Epoxide is selected from ethylene oxide, propylene oxide, 1,2- epoxy butane, C5~C20Alpha-oxidation alkene, phenyl glycidyl ether,
Benzyl glycidyl ether, epoxy methyl undecylenate, allyl glycidyl ether, epoxychloropropane, epoxy iso-butane, epoxide ring
Hexane, 4 vinyl epoxy cyclohexane, glycidyl methacrylate, limonene oxide, cyclopentane epoxide and Oxybenzene second
At least one of alkene；
The 3- replaces oxetanes to be selected from 3,3- dimethyl oxygen azetidine, 3- methyl -3- benzyloxymethyl oxa- ring
Butane, 3- chloromethyl -3- methy oxetane, 3- methyl -3- oxetane methanol, 3- oxetanone, 3- (allyl oxygen
Base) at least one of oxetanes and 3- bromine oxetanes.
7. the method according to claim 1 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that described
Lewis base M and lewis base N is respectively and independently selected from least one of quaternary ammonium salt, quaternary alkylphosphonium salt, organic base and alkali metal alcoholates.
8. the method according to claim 7 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that described
Quaternary ammonium salt is selected from bis- (dihalotriphenylphosphoranes base) ammonium chlorides, cetyl trimethyl ammonium halide, tetrabutylammonium hydroxide, dodecyl
Trimethyl-ammonium halide, ten alkylpolyoxyethylenes, benzyl triethyl ammonium ammonium halide, benzyl tripropyl ammonium halide, benzyl tributyl
Ammonium halide, benzyl triethyl ammonium ammonium acetate, benzyl tripropyl ammonium acetate, benzyl tributyl ammonium acetate, tetraethyl ammonium acetate, the tetrabutyl
At least one of ammonium iodide, tetrabutyl ammonium nitrate, tetrapropyl ammonium acetate and tetra-alkyl-phosphonium halide ammonium salt；
The quaternary alkylphosphonium salt is selected from tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, tetraalkyl halogenation phosphonium salt, benzyltriphenylphosphonium bromide
At least one of phosphine, butyl triphenyl phosphonium iodide and propyl triphenylphosphinebromide；
The organic base is selected from 1,8- diazabicyclo [5.4.0] 11-7- carbene, 7- methyl-1, tri- azabicyclo of 5,7-
At least one of 11-7- carbene of [4.4.0] decyl- 5- alkene and 1,5,7- diazabicyclo [5.4.0]；
The alkali metal alcoholates are selected from sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, potassium tert-butoxide, uncle
At least one of butanol lithium, sodium tert-butoxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and lithium hydroxide.
9. the method according to claim 1 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that the road
Lewis acid is selected from least one of boron triethyl, tri butyl boron, triphenyl borine, chromium complex and zinc complex.
10. the method according to claim 1 for preparing carbonyl sulfide co-production sulfur-containing polymer, which is characterized in that step
(1) and the reaction dissolvent in step (2) is separately selected from methylene chloride, chloroform, tetrahydrofuran, toluene, trichloro-benzenes, neighbour two
At least one of chlorobenzene, m-dichlorobenzene, paracide and dimethylformamide.
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| CN114874121A (en) * | 2022-04-28 | 2022-08-09 | 浙江大学 | Method for preparing material containing monothiocarbonate group and product |
| CN115197422A (en) * | 2022-07-27 | 2022-10-18 | 华东师范大学 | Preparation method of aliphatic polythioether |
| CN116355215A (en) * | 2023-03-23 | 2023-06-30 | 昆明理工大学 | Method for preparing polythiocarbonate by utilizing carbon dioxide and sulfur dioxide |
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| CN113372555A (en) * | 2021-06-25 | 2021-09-10 | 浙江大学 | Composite material with low dielectric constant and low dielectric loss as well as preparation method and application thereof |
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Application publication date: 20190906 |