CN105820281B - A kind of preparation method of halogen polymer - Google Patents
A kind of preparation method of halogen polymer Download PDFInfo
- Publication number
- CN105820281B CN105820281B CN201510012875.8A CN201510012875A CN105820281B CN 105820281 B CN105820281 B CN 105820281B CN 201510012875 A CN201510012875 A CN 201510012875A CN 105820281 B CN105820281 B CN 105820281B
- Authority
- CN
- China
- Prior art keywords
- polymer
- initiator
- halogen
- glue
- alkali lye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a kind of preparation method of halogen polymer, comprise the following steps：A) polymer is contacted in the presence of organic solvent and initiator with halogenating agent, so that the part hydrogen atom in the polymer is substituted with halogen atoms, obtains the halogenated polymer solution containing hydrogen halides and initiator；B) halogenated polymer solution for obtaining step a) is sufficiently mixed under ul-trasonic irradiation with alkali lye, to remove the hydrogen halides and initiator.The method according to the invention, it can effectively suppress halogen polymer product dehalogenation in follow-up drying process and change colour；And with simple and easy process conditions and step, there is provided halogen polymer product pure, not easy to change.
Description
Technical field
The present invention relates to the preparation field of halogen polymer.
Background technology
The isobutene and p-methylstyrene copolymer (BIMS) of bromination are a kind of because molecular backbone is full saturated structures
With sulfurate activity, the combination property elastomer new material more excellent than brombutyl.Prepared using solution polymerization process
During the halogenated rubbers such as the isobutene of halogenation/p-methylstyrene copolymer, produce the halogenation containing hydrogen halides and initiator and gather
Polymer solution.Generally neutralize, wash through aqueous alkali, after drying, obtain watered pellets and (contain<10-20wt% water).Grinding
Study carefully middle discovery halogen polymer product and (110 DEG C) either dried using mill, or do not heat in vacuum drying oven and only
It is dried in vacuo, as long as when the water content in glue declines to a certain extent, halogenation glue will change colour, and with bitterness
Dust smell.Contrast and find from test result, product halogen atom content is decreased obviously before and after drying, and shows that product changes colour
While occur with dehalogenation reaction.The main reason for finding out by analysis, causing product drying to change colour is the halogenation in product
Hydrogen is not fully neutralized.
The common method for improving the discoloration of halogen polymer product be halogenation, in and/or drying steps during add erosion acid
Agent, alkali or other additive/stabilizers.For example epoxy soybean is added into halogenated butyl rubber during arranging process is dried
Oily (ESBO) prevents its dehalogenation from changing colour.But ESBO is costly, and influence the curability of halogenated butyl rubber.
CN1370197A adds the weak base such as sodium acid carbonate to solve the halogen caused by containing ferric bromide during arranging process is dried
Change butyl rubber discoloration problem.Gardner et al. (US5087674) is before or during halogenation step in halogenated butyl polymer
Middle use loses sour agent, such as metal oxide, hydroxide and carboxylate, prevents product from changing colour.However, pass through letter in the prior art
Singly add the sour agent of erosion, alkali etc. to mix with halogenated polymer solution, hydrogen halides can not usually be neutralized completely, can not use up can
Initiator can be fully removed, therefore the effect of pre- Anti- tarnishing still has much room for improvement.Also, experiment proves that finding, add erosion acid
Agent can substantially suppress halogenation, and excessive impurity can be introduced in halogenation product, and then influence the performance of halogen polymer.
The content of the invention
It is an object of the invention to provide a kind of method for preparing halogen polymer, especially wherein processing comprising hydrogen halides and
The method of the halogenated polymer solution of initiator, both ensured that halogenation was smoothed out, and do not introduced other impurity, and can be effective
The generation of dehalogenation side reaction is prevented, finally prevents product drying from changing colour.
According to the present invention, there is provided a kind of preparation method of halogen polymer, comprise the following steps：A) by polymer and halogen
Agent contacts in the presence of organic solvent and initiator, so that the part hydrogen atom in the polymer is taken by halogen atom
In generation, obtain the halogenated polymer solution containing hydrogen halides and initiator；B) halogenated polymer solution for obtaining step a)
It is sufficiently mixed under ul-trasonic irradiation with alkali lye, to remove the hydrogen halides and initiator.Especially, the invention provides one kind
The processing method of halogenated polymer solution comprising hydrogen halides and initiator, including by the halogen comprising hydrogen halides and initiator
Fluidized polymer solution is sufficiently mixed under ul-trasonic irradiation with alkali lye, fully to remove hydrogen halides and initiator.
In the prior art, usually halogenation, in and/or drying steps in add alkali lye and handle reaction product, to prevent
Or alleviate product discoloration problem.Handled, can not always be obtained it has been found, however, that adding alkali lye by simple mode
Good effect.Also, now it has furthermore been found that if the initiator containing residual, initiator can also have a strong impact on that halogenation gathers
The performance of compound, being dried even in room temperature in vacuo can also change colour.
Unexpectedly, it was found by the inventors of the present invention that under ul-trasonic irradiation, by the halogen containing hydrogen halides and initiator
Fluidized polymer solution mixes with alkali lye (such as sodium hydrate aqueous solution), enables to hydrogen halides in mixture and initiator by more
Remove well, so as to which in follow-up drying process, halogen polymer will not change colour after drying.This result be probably by
In, on the one hand, using ultrasonic wave peptizaiton, halogenated polymer solution and alkali lye mixing can be made more uniform, so that
Reaction is more fully and completely；On the other hand, the neutralization of hydrogen halides and alkali lye is accelerated using " cavitation effect " of ultrasonic wave；Meanwhile
One as the present invention it is prominent the advantages of, by using ul-trasonic irradiation, promoting residual initiation in halogenated polymer solution
The decomposition of agent.Therefore, using the halogen polymer preparation method of the present invention, by gathering to the halogenation containing hydrogen halides and initiator
Polymer solution is handled, and can effectively be suppressed halogen polymer product dehalogenation in follow-up drying process and be changed colour, product is pure
It is and simple for process.
In the present invention, the polymer is preferably C4-C12At least one of isomonoolefin is total to ring-alkylated styrenes
Polymers, also preferably C4-C7The copolymer of at least one of isomonoolefin and ring-alkylated styrenes, more preferably isobutene
And/or the copolymer of iso-amylene and p-methylstyrene.
In a preferred embodiment, the polymer is the copolymer of isobutene and p-methylstyrene.
According to the present invention, the halogenating agent is preferably halogen, also preferably Br2；The organic solvent is selected from C5-C10Fat
At least one of fat race or cyclic aliphatic alkane, preferably n-hexane and/or hexamethylene；The initiator is preferably that free radical draws
Agent, for example, biradical compound of azo are sent out, is selected from ABVN, azodiisobutyronitrile, AMBN, azo
At least one of isobutyl itrile group formamide, azo-bis-iso-dimethyl and azo diisopropyl imidazoline hydrochloride, and preferably azo
Two different heptonitriles.
According to the present invention, the alkali lye can be selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate
At least one of with wet chemical.The concentration and dosage of alkali lye are not particularly limited, as long as its dosage can be whole
Only chlorination reaction, and fully reacted with hydrogen chloride therein, reach the purpose for removing the hydrogen halides.It is preferred at some
In embodiment, the concentration of alkali lye can be 0.1-1wt%.In some preferred embodiments, alkali lye dosage can be alkali lye
The mol ratio of solute and halogenating agent is 1.2-1.5：1.In order to reduce the introducing of impurity, the higher halogen polymer of purity is obtained,
In the preferred case, the water in the alkali lye is deionized water.
According to method provided by the invention, the ultrasonic frequency selectable range hands over width, for example, the ultrasonic frequency
Can be 50KHz-1MHz, under the ul-trasonic irradiation of this range frequencies, it is possible to achieve by the halogen containing hydrogen halides and initiator
Fluidized polymer solution carries out the purpose of good contact with alkali lye.Generally, ultrasonic frequency is higher, and contact effect is better, but frequency
Rate more highly energy-consuming is bigger, and therefore, combined factors consider from every side, and it is preferably 80KHz- that the ultrasonic frequency, which is preferably,
200KHz。
The mixing temperature of the method according to the invention, the halogenated polymer solution and the alkali lye is preferably 0-80 DEG C,
Also preferably 30-60 DEG C, more preferably 50-60 DEG C.Incorporation time is preferably 5-60min, more preferably 10-
20min.It is of the present invention as above in the range for the treatment of temperature and processing time, halogen polymer can be avoided the occurrence of
Degraded, while the efficiency for removing hydrogen halides and initiator can also be improved.
The method according to the invention, the content of the hydrogen halides in the halogenated polymer solution that step a) is obtained is 0.1-
0.5mol%.
In some embodiments of the present invention, methods described can further include step c)：It will be obtained through step b)
To mixture washed, dry.Wherein, water-washing step and drying steps can be using modes well known in the art come real
Apply.For example, in water-washing step, suitable quantity of water can be added into the mixture that step b) is obtained, and certain temperature (such as
80-100 DEG C) under in water bath with thermostatic control boiling condense, deviate from organic solvent.Then the glue group that washing obtains is dried, example
Dry glue is such as dried under certain temperature (such as 100-120 DEG C) using mill.
In a preferred embodiment of the invention, step c) is being passed through before and after the processing through the mixture that step b) is obtained, its
In halogen polymer in the change of halogen element molar content be less than 0.05%, such as 0-0.03%.Specifically, through step b)
After step c) processing, the halogen element molar content decrement in halogen polymer therein is less than obtained mixture
0.05%.The halogen element molar content can be former containing halogen in terms of the total amount of construction unit for being based upon halogen polymer
The mode of the molar content of the construction unit of son represents.
Present invention also offers the halogen polymer that a kind of basis method as described above is prepared, especially halogenation
The copolymer of isobutene and p-methylstyrene.The halogen polymer has good anti-tarnishing ability.
The preparation method of halogen polymer provided by the invention, by the halogen polymer containing hydrogen halides and initiator
Solution is handled, and in particular by ul-trasonic irradiation, promotes the mixing between halogenated polymer solution and alkali lye, and
Promote the neutralization reaction between hydrogen halides and alkali lye, the decomposition of residual initiator is especially further promoted, so as to restrained effectively
Halogen polymer product dehalogenation in follow-up drying process changes colour.Therefore, the present invention can with simple and easy process conditions and
Step, there is provided halogen polymer product pure, not easy to change.
Embodiment
The present invention is described in detail with comparative example, but these embodiments are not considered as to model of the present invention with reference to embodiments
The limitation enclosed.
In following examples and comparative example, using the AVANCE400 type NMRs purchased from Bruker companies of Switzerland, with
CDC13Make solvent, TMS is internal standard, determines the composition of the polymer and its halide and the content of hydrogen halides.Wherein, bromine
Content refers to that on the basis of the total amount of the construction unit in halide the Mole percent of the construction unit containing halogen atom contains
Amount.
In following examples and comparative example, using the content of initiator in Speeord71IR determination of infrared spectroscopy glues,
Liquid cell light path is 0.1mm.
Solvent and monomer used in following examples and comparative example if not otherwise specified, the analysis being commercially available
Pure reagent, refined using preceding using method commonly used in the art.
Isobutene/p-methylstyrene the copolymer for being used to carry out halogenation in following examples and comparative example is in halogenation
Preceding first to be refined, through analysis, its p-methylstyrene content is in 5wt%, and Mooney viscosity [125 DEG C of ML (1+8)] is 40, and weight is equal
Molecular weight MwFor 453100, Mw/MnFor 5.24.
Iso-amylene/p -ethyl-styrene the copolymer for being used to carry out halogenation in following examples and comparative example is in halogenation
Preceding first to be refined, through analysis, its p -ethyl-styrene content is in 5wt%, and Mooney viscosity [125 DEG C of ML (1+8)] is 41, and weight is equal
Molecular weight MwFor 448700, Mw/MnFor 5.19.
In following examples and comparative example, halogenation is carried out in draughty darkroom.
Embodiment 1
(1) the 1000mL glass three-necked flasks that will be configured with strength constant speed agitating device are fixed in ultrasonic cleaner,
Isobutene/p-methylstyrene copolymer prepared by 40g is added in three-necked flask, n-hexane is then added and is configured to concentration and is
10wt% glue.1.5mol% bromines are added, 0.08g ABVNs are added after mixing 1 minute, in 56 DEG C of progress
Bromination.Glue red is taken off after 12 minutes, and bromination reaction terminates.It is sampled using glass probe tube rapidly, with core to be passed through
Bromination hydrogen content in magnetic resonance spectroscopy analysis glue, and the content using initiator in determination of infrared spectroscopy glue.
The 60mL 1wt% NaOH aqueous solution is added into there-necked flask immediately, opening ultrasonic cleaner, (frequency is
60KHz) switch, ultrasonic cleaner heating-up temperature adjusting knob is adjusted to 60 DEG C, ultrasonic disperse 20min, neutralizes and terminates bromination
Reaction.It is sampled using glass probe tube, the degree of bromination reaction is analyzed using nuclear magnetic resonance spectroscopy.
After tested, the bromination hydrogen content in bromination reaction and before terminating in glue be 0.49mol%, in bromination reaction and end
Only the weight content of initiator is 50ppm in preceding glue.Bromination reaction terminates in the bromide of rear resulting polymers, and bromine atoms take
For the hydrogen atom on the methyl in the construction unit formed by methyl styrene, wherein, bromine content 0.93mol%, bromination rate
(percent value of practical measurement bromine content and theoretical bromine content) is 62.0%.
(2) glue neutralized after terminating is poured into 2L beaker, adds the water bath with thermostatic control that appropriate water is placed in 90 DEG C
Middle boiling cohesion, removes hexane solvent, obtains the glue group of white, then using drying 10min into dry glue at 110 DEG C of mill.
Tested through nuclear magnetic resonance spectroscopy, the bromine content of dry glue is 0.92mol%, and bromination rate is 61.5%, dry glue bromination
Hydrogen content is 0.018mol%.The content of initiator is 0 in infrared test dry glue.Dry glue outward appearance is still white, not existing red.
Embodiment 2
(1) the 1000mL glass three-necked flasks that will be configured with strength constant speed agitating device are fixed in ultrasonic cleaner,
Isobutene/p-methylstyrene copolymer prepared by 40g is added in three-necked flask, n-hexane is then added and is configured to concentration and is
10wt% glue.1.7mol% bromines are added, 0.10g ABVNs are added after mixing 1 minute, in 56 DEG C of progress
Bromination.Glue red is taken off after 12 minutes, and bromination reaction terminates.It is sampled using glass probe tube rapidly, with core to be passed through
Bromination hydrogen content in magnetic resonance spectroscopy analysis glue, and the content using initiator in determination of infrared spectroscopy glue.
40mL 1wt% Na is added into there-necked flask immediately2CO3The aqueous solution, opening ultrasonic cleaner, (frequency is
80KHz) switch, ultrasonic cleaner heating-up temperature adjusting knob is adjusted to 50 DEG C, ultrasonic disperse 20min, neutralizes and terminates bromination
Reaction.It is sampled using glass probe tube, the degree of bromination reaction is analyzed using nuclear magnetic resonance spectroscopy.
After tested, the bromination hydrogen content in bromination reaction and before terminating in glue be 0.48mol%, in bromination reaction and end
Only the weight content of initiator is 80ppm in preceding glue.Bromination reaction terminates in the bromide of rear resulting polymers, and bromine atoms take
For the hydrogen atom on the methyl in the construction unit formed by methyl styrene, wherein, bromine content 0.96mol%, bromination rate
For 64.0%.
(2) glue neutralized after terminating is poured into 2L beaker, adds the water bath with thermostatic control that appropriate water is placed in 90 DEG C
Middle boiling cohesion, removes hexane solvent, obtains the glue group of white, then using drying 10min into dry glue at 110 DEG C of mill.
Tested through nuclear magnetic resonance spectroscopy, the bromine content of dry glue is 0.96mol%, and bromination rate is 64.0%, dry glue bromination
Hydrogen content is 0.015mol%.The content of initiator is 0 in infrared test dry glue.Dry glue outward appearance is still white, not existing red.
Embodiment 3
(1) the 1000mL glass three-necked flasks that will be configured with strength constant speed agitating device are fixed in ultrasonic cleaner,
Isobutene/p-methylstyrene copolymer prepared by 40g is added in three-necked flask, hexamethylene is then added and is configured to concentration and is
10wt% glue.2.0mol% bromines are added, 0.12g ABVNs are added after mixing 1 minute, in 56 DEG C of progress
Bromination.Glue red is taken off after 12 minutes, and bromination reaction terminates.It is sampled using glass probe tube rapidly, with core to be passed through
Bromination hydrogen content in magnetic resonance spectroscopy analysis glue, and the content using initiator in determination of infrared spectroscopy glue.
The 80mL 1wt% KOH aqueous solution is added into there-necked flask immediately, opening ultrasonic cleaner, (frequency is
120KHz) switch, at 20 DEG C, ultrasonic disperse 20min, neutralize and terminate bromination reaction.It is sampled, is adopted using glass probe tube
With the degree of nuclear magnetic resonance spectroscopy analysis bromination reaction.
After tested, the bromination hydrogen content in bromination reaction and before terminating in glue be 0.50mol%, in bromination reaction and end
Only the weight content of initiator is 100ppm in preceding glue.Bromination reaction terminates in the bromide of rear resulting polymers, bromine atoms
Substitute the hydrogen atom on the methyl in the construction unit formed by methyl styrene, wherein, bromine content 0.98mol%, bromination
Rate is 65.5%.
(2) glue neutralized after terminating is poured into 2L beaker, adds the water bath with thermostatic control that appropriate water is placed in 90 DEG C
Middle boiling cohesion, removes hexane solvent, obtains the glue group of white, then using drying 10min into dry glue at 110 DEG C of mill.
Tested through nuclear magnetic resonance spectroscopy, the bromine content of dry glue is 0.98mol%, and bromination rate is 65.3%, dry glue bromination
Hydrogen content is 0.010mol%.The content of initiator is 0 in infrared test dry glue.Dry glue outward appearance is still white, not existing red.
Embodiment 4
(1) the 1000mL glass three-necked flasks that will be configured with strength constant speed agitating device are fixed in ultrasonic cleaner,
Isobutene/p-methylstyrene copolymer prepared by 40g is added in three-necked flask, n-hexane is then added and is configured to concentration and is
10wt% glue.1.5mol% bromines are added, 0.08g ABVNs are added after mixing 1 minute, in 56 DEG C of progress
Bromination.Glue red is taken off after 12 minutes, and bromination reaction terminates.It is sampled using glass probe tube rapidly, with core to be passed through
Bromination hydrogen content in magnetic resonance spectroscopy analysis glue, and the content using initiator in determination of infrared spectroscopy glue.
The 60mL 1wt% NaOH aqueous solution is added into there-necked flask immediately, opening ultrasonic cleaner, (frequency is
150KHz) switch, at 60 DEG C, ultrasonic disperse 20min, neutralize and terminate bromination reaction.It is sampled, is adopted using glass probe tube
With the degree of nuclear magnetic resonance spectroscopy analysis bromination reaction.
After tested, the bromination hydrogen content in bromination reaction and before terminating in glue be 0.49mol%, in bromination reaction and end
Only the weight content of initiator is 50ppm in preceding glue.Bromination reaction terminates in the bromide of rear resulting polymers, and bromine atoms take
For the hydrogen atom on the methyl in the construction unit formed by methyl styrene, wherein, bromine content 1.01mol%, bromination rate
For 67.4%.
(2) glue neutralized after terminating is poured into 2L beaker, adds the water bath with thermostatic control that appropriate water is placed in 90 DEG C
Middle boiling cohesion, removes hexane solvent, obtains the glue group of white, then using drying 10min into dry glue at 110 DEG C of mill.
Tested through nuclear magnetic resonance spectroscopy, the bromine content of dry glue is 1.00mol%, and bromination rate is 66.8%, dry glue bromination
Hydrogen content is 0.008mol%.The content of initiator is 0 in infrared test dry glue.Dry glue outward appearance is still white, not existing red.
Embodiment 5
(1) the 1000mL glass three-necked flasks that will be configured with strength constant speed agitating device are fixed in ultrasonic cleaner,
Iso-amylene/p -ethyl-styrene copolymer prepared by 48g is added in three-necked flask, n-hexane is then added and is configured to concentration and is
10wt% glue.1.5mol% bromines are added, 0.08g ABVNs are added after mixing 1 minute, in 56 DEG C of progress
Bromination.Glue red is taken off after 12 minutes, and bromination reaction terminates.It is sampled using glass probe tube rapidly, with core to be passed through
Bromination hydrogen content in magnetic resonance spectroscopy analysis glue, and the content using initiator in determination of infrared spectroscopy glue.
The 60mL 1wt% NaOH aqueous solution is added into there-necked flask immediately, opening ultrasonic cleaner, (frequency is
200KHz) switch, at 30 DEG C, ultrasonic disperse 20min, neutralize and terminate bromination reaction.It is sampled, is adopted using glass probe tube
With the degree of nuclear magnetic resonance spectroscopy analysis bromination reaction.
After tested, the bromination hydrogen content in bromination reaction and before terminating in glue be 0.51mol%, in bromination reaction and end
Only the weight content of initiator is 60ppm in preceding glue.Bromination reaction terminates in the bromide of rear resulting polymers, and bromine atoms take
For the hydrogen atom on the methyl in the construction unit formed by methyl styrene, wherein, bromine content 0.97mol%, bromination rate
For 64.6%.
(2) glue neutralized after terminating is poured into 2L beaker, adds the water bath with thermostatic control that appropriate water is placed in 90 DEG C
Middle boiling cohesion, removes hexane solvent, obtains the glue group of white, then using drying 10min into dry glue at 110 DEG C of mill.
Tested through nuclear magnetic resonance spectroscopy, the bromine content of dry glue is 0.96mol%, and bromination rate is 63.9%, dry glue bromination
Hydrogen content is 0.005mol%.The content of initiator is 0 in infrared test dry glue.Dry glue outward appearance is still white, not existing red.
Comparative example 1
(1) the 1000mL glass three-necked flasks that will be configured with strength constant speed agitating device are fixed in ultrasonic cleaner,
Isobutene/p-methylstyrene copolymer prepared by 40g is added in three-necked flask, n-hexane is then added and is configured to concentration and is
10wt% glue.1.5mol% bromines are added, 0.08g ABVNs are added after mixing 1 minute, in 56 DEG C of progress
Bromination.Glue red is taken off after 12 minutes, and bromination reaction terminates.It is sampled using glass probe tube rapidly, with core to be passed through
Bromination hydrogen content in magnetic resonance spectroscopy analysis glue, and the content using initiator in determination of infrared spectroscopy glue.
The 60mL 1wt% NaOH aqueous solution is added into there-necked flask immediately, at 60 DEG C, rotating speed is 300r/min machine
Under tool stirring, neutralize and terminate bromination reaction.It is sampled using glass probe tube, it is anti-to analyze bromination using nuclear magnetic resonance spectroscopy
The degree answered.
After tested, the bromination hydrogen content in bromination reaction and before terminating in glue be 0.50mol%, in bromination reaction and end
Only the weight content of initiator is 50ppm in preceding glue.Bromination reaction terminates in the bromide of rear resulting polymers, and bromine atoms take
For the hydrogen atom on the methyl in the construction unit formed by methyl styrene, wherein, bromine content 0.89mol%, bromination rate
For 59.3%.
(2) glue neutralized after terminating is poured into 2L beaker, adds the water bath with thermostatic control that appropriate water is placed in 90 DEG C
Middle boiling cohesion, removes hexane solvent, obtains the glue group of white, then using drying 10min into dry glue at 110 DEG C of mill.
Tested through nuclear magnetic resonance spectroscopy, the bromine content of dry glue is 0.81mol%, and bromination rate is 54.0%, dry glue bromination
Hydrogen content is 0.3mol%.The content of initiator is 20ppm in infrared test dry glue.Pale red is presented in dry glue outward appearance.
By the result of above example and comparative example, it is apparent that compared to comparative example, provided using the present invention
Halogen polymer preparation method, by handling the halogenated polymer solution containing hydrogen halides and initiator, especially
The after-applied ul-trasonic irradiation of alkali lye is added, the initiation of the hydrogen halides and residual in polymer glue can be removed to the utmost
Agent, change colour so as to restrained effectively halogen polymer product dehalogenation in follow-up drying process.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that each side of the invention recorded, different embodiments
Each several part and the various features enumerated can be combined or all or part of exchange.In above-mentioned each embodiment, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, and this is by by this area skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that description above is only the mode of example, not purport
In the limitation present invention.
Claims (15)
1. a kind of preparation method of halogen polymer, comprises the following steps：
A) polymer is contacted in the presence of organic solvent and initiator with halogenating agent, so that the part hydrogen in the polymer
Atom is substituted with halogen atoms, and obtains the halogenated polymer solution containing hydrogen halides and initiator；
B) halogenated polymer solution for obtaining step a) is sufficiently mixed under ul-trasonic irradiation with alkali lye, with described in removing
Hydrogen halides and initiator.
2. according to the method for claim 1, it is characterised in that the polymer is C4-C12Isomonoolefin and alkylbenzene second
The copolymer of alkene.
3. according to the method for claim 2, it is characterised in that the polymer is C4-C7Isomonoolefin and ring-alkylated styrenes
Copolymer.
4. according to the method for claim 2, it is characterised in that the polymer is for isobutene and/or iso-amylene and to first
The copolymer of base styrene.
5. according to the method for claim 1, it is characterised in that the halogenating agent is halogen；The organic solvent is selected from C5-
C10Aliphatic or at least one of cyclic aliphatic alkane；The initiator is selected from ABVN, azodiisobutyronitrile, idol
At least one in nitrogen diisoamyl nitrile, azo isobutyronitrile base formamide, azo-bis-iso-dimethyl and azo diisopropyl imidazoline hydrochloride
Kind.
6. according to the method for claim 5, it is characterised in that the halogenating agent is Br2；The organic solvent is n-hexane
And/or hexamethylene.
7. according to the method for claim 1, it is characterised in that the alkali lye is selected from sodium hydrate aqueous solution, potassium hydroxide
At least one of the aqueous solution, aqueous sodium carbonate and wet chemical；The concentration of the alkali lye is 0.1-1wt%；Alkali lye
Dosage is that the mol ratio of alkali lye solute and halogenating agent is 1.2-1.5：1.
8. according to the method for claim 1, it is characterised in that the frequency of the ultrasonic wave is 50KHz-1MHz.
9. according to the method for claim 8, it is characterised in that the frequency of the ultrasonic wave is 80KHz-200KHz.
10. according to the method for claim 1, it is characterised in that the mixing of the halogenated polymer solution and the alkali lye
Temperature is 0-80 DEG C.
11. according to the method for claim 10, it is characterised in that the mixing of the halogenated polymer solution and the alkali lye
Temperature is 30-60 DEG C.
12. according to the method for claim 1, it is characterised in that the halogenation in the halogenated polymer solution that step a) is obtained
The content of hydrogen is 0.1-0.5mol%.
13. according to the method described in any one in claim 1-12, it is characterised in that methods described also includes step c)：
The mixture obtained through step b) is washed, dried.
14. according to the method for claim 13, it is characterised in that through the mixture that step b) is obtained by step c) places
Before and after reason, the halogen element molar content change in halogen polymer therein is less than 0.05%.
15. halogen polymer made from a kind of method in 1-14 according to claim described in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510012875.8A CN105820281B (en) | 2015-01-09 | 2015-01-09 | A kind of preparation method of halogen polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510012875.8A CN105820281B (en) | 2015-01-09 | 2015-01-09 | A kind of preparation method of halogen polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105820281A CN105820281A (en) | 2016-08-03 |
| CN105820281B true CN105820281B (en) | 2018-03-02 |
Family
ID=56514279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510012875.8A Active CN105820281B (en) | 2015-01-09 | 2015-01-09 | A kind of preparation method of halogen polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105820281B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020152739A (en) * | 2017-07-13 | 2020-09-24 | 株式会社カネカ | Brominated polyisobutylene-based polymer and production method |
| CN112661878A (en) * | 2020-12-17 | 2021-04-16 | 宁波普力通化学有限公司 | High-activity synthetic rubber for single-coated rubber metal adhesive and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650832A (en) * | 1984-09-17 | 1987-03-17 | Exxon Research & Engineering Co. | Process for the manufacture of halogenated polymers |
| JPH05504594A (en) * | 1990-03-01 | 1993-07-15 | エクソン・ケミカル・パテンツ・インク | Halogenation of polymers with improved neutralization |
| CN1225649A (en) * | 1996-07-24 | 1999-08-11 | 埃克森化学专利公司 | Improved process for halogenating isomonoolefin copolymers |
| CN1903892A (en) * | 2006-08-03 | 2007-01-31 | 江苏圣杰实业有限公司 | Method of manufacturing halogenated rubber like polymer |
| CN101671412A (en) * | 2009-10-10 | 2010-03-17 | 江苏圣杰实业有限公司 | 1-polyolefin halogenation production method |
| CN102382223A (en) * | 2011-09-08 | 2012-03-21 | 北京化工大学 | Method for preparing brominated butyl rubber |
| CN102786618A (en) * | 2012-07-23 | 2012-11-21 | 华东理工大学 | Preparation method for brominated and chlorinated butyl rubber |
| WO2013011017A1 (en) * | 2011-07-20 | 2013-01-24 | Lanxess International Sa | Process for producing brominated butyl rubber |
| CN105111347A (en) * | 2015-09-15 | 2015-12-02 | 黄河三角洲京博化工研究院有限公司 | Producing method for brominating butyl rubber |
-
2015
- 2015-01-09 CN CN201510012875.8A patent/CN105820281B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650832A (en) * | 1984-09-17 | 1987-03-17 | Exxon Research & Engineering Co. | Process for the manufacture of halogenated polymers |
| JPH05504594A (en) * | 1990-03-01 | 1993-07-15 | エクソン・ケミカル・パテンツ・インク | Halogenation of polymers with improved neutralization |
| CN1225649A (en) * | 1996-07-24 | 1999-08-11 | 埃克森化学专利公司 | Improved process for halogenating isomonoolefin copolymers |
| CN1903892A (en) * | 2006-08-03 | 2007-01-31 | 江苏圣杰实业有限公司 | Method of manufacturing halogenated rubber like polymer |
| CN101671412A (en) * | 2009-10-10 | 2010-03-17 | 江苏圣杰实业有限公司 | 1-polyolefin halogenation production method |
| WO2013011017A1 (en) * | 2011-07-20 | 2013-01-24 | Lanxess International Sa | Process for producing brominated butyl rubber |
| CN102382223A (en) * | 2011-09-08 | 2012-03-21 | 北京化工大学 | Method for preparing brominated butyl rubber |
| CN102786618A (en) * | 2012-07-23 | 2012-11-21 | 华东理工大学 | Preparation method for brominated and chlorinated butyl rubber |
| CN105111347A (en) * | 2015-09-15 | 2015-12-02 | 黄河三角洲京博化工研究院有限公司 | Producing method for brominating butyl rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105820281A (en) | 2016-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105820281B (en) | A kind of preparation method of halogen polymer | |
| US10703829B2 (en) | Aqueous polymerization of perfluoromonomer using hydrocarbon surfactant | |
| EP2891668B1 (en) | Glove having excellent chemical resistance and composition for said glove | |
| US8563670B2 (en) | Nucleation in aqueous polymerization of fluoromonomer | |
| JP3975249B2 (en) | Aqueous dehydrofluorination process | |
| KR101785126B1 (en) | Method for the production of homo- or copolymers | |
| US9676929B2 (en) | Employing polyalkylene oxides for nucleation in aqueous polymerization of fluoromonomer | |
| CN1290273A (en) | Fluorinated i onomers and their uses | |
| WO2006009761A1 (en) | Insulation for an improved high-speed data transmission cable | |
| CN1390643A (en) | Application method of heteropoly acid type catalyst | |
| EP2228428A1 (en) | Scale-reducing additive for automatic dishwashing systems | |
| CN104072751B (en) | Preparation method of vinylbenzyl-polyphenyl ether composition | |
| CN1355787A (en) | Fluorinated ionic polymers | |
| CN103694391B (en) | A kind of modified butyl rubber synthetic method | |
| CN109439455A (en) | A kind of use in dishwasher detergent block and preparation method thereof | |
| CN105601779A (en) | Process for direct halogenation of poly(p-methyl styrene-CO-isobutylene) prepared with solution method | |
| CN113930038B (en) | Soft polyvinyl formal sponge in dry state and preparation method thereof | |
| JP2003138003A (en) | Method for producing polyether-based polymer | |
| JP6638456B2 (en) | Vinyl chloride resin for paste processing and its production method | |
| CN112552509A (en) | Low-foaming antibacterial surfactant, dish-washing machine cleaning sheet containing low-foaming antibacterial surfactant and preparation method of dish-washing machine cleaning sheet | |
| TWI580695B (en) | Chlorinated polyvinyl chloride and the preparation thereof | |
| CN108822240A (en) | A kind of preparation method of isobutene and p-methylstyrene copolymer | |
| JPH01115933A (en) | Stabilization of tetrafluoroethylene copolymer | |
| CN112342002A (en) | Descaling agent for sandstone acidification and preparation method thereof | |
| JP3947831B2 (en) | Aggregation method of alkoxycarbonyl group-containing fluorine-containing polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |