CN118290616A - Halogenated copolymers and methods of making the same - Google Patents
Halogenated copolymers and methods of making the same Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 32
- 230000002140 halogenating effect Effects 0.000 claims abstract description 31
- 238000005286 illumination Methods 0.000 claims abstract description 20
- 238000002604 ultrasonography Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 30
- 230000026030 halogenation Effects 0.000 claims description 21
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 19
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 18
- 239000003999 initiator Substances 0.000 abstract description 12
- 239000007800 oxidant agent Substances 0.000 abstract description 11
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 239000004434 industrial solvent Substances 0.000 abstract description 2
- 238000005893 bromination reaction Methods 0.000 description 23
- 229910052794 bromium Inorganic materials 0.000 description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 18
- 230000031709 bromination Effects 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 10
- 150000003254 radicals Chemical group 0.000 description 9
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 8
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 8
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 8
- -1 methyl hydrogen Chemical compound 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical group BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007256 debromination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of rubber preparation, and discloses a halogenated copolymer and a preparation method thereof, wherein the preparation method of the halogenated copolymer comprises the following steps: under the conditions of illumination and ultrasound, the copolymer and a halogenating agent are subjected to contact reaction in a solvent to obtain the halogenated copolymer. When the method is used for preparing the halogenated copolymer, the selectivity of the halogenation reaction can be effectively controlled, the occurrence of side reactions in the copolymer and the solvent can be restrained, the requirement on the purity of the solvent in industrial production is reduced, the production requirement can be met by using a conventional industrial solvent, and the production cost is reduced. Furthermore, the introduction of impurities such as an initiator, an oxidant and the like into the product can be avoided, and the pure halogenated copolymer can be obtained under simple and easy process conditions and steps.
Description
Technical Field
The invention relates to the field of rubber preparation, in particular to a halogenation method of a copolymer and a halogenated copolymer prepared by the halogenation method.
Background
The brominated copolymer of isomonoolefin and para-alkylstyrene, especially brominated copolymer of isobutylene and para-methylstyrene BIMS, is a new fully saturated elastomer material with vulcanization activity and better overall properties than brominated butyl rubber, and the bromination reaction mechanism is free radical bromination. Bromination reaction conditions of the isobutylene-p-methylstyrene copolymer are very severe, and are very sensitive to various impurities in a reaction system, such as water, alcohol, acid, alkali and the like. The copolymer is generally dissolved in alkane solvent and added with an organic free radical initiator or an oxidant such as peroxide to carry out solution bromination reaction, but various bromination side reactions exist. For example: a pair of competitive bromination reactions exist on the copolymer macromolecular backbone of isobutylene and para-methylstyrene, namely tertiary hydrocarbon (3 DEG H) and para-methyl hydrogen (1 DEG H) bromination on the benzene ring. The target reaction of the bromination of the copolymer is bromination of a methyl hydrogen (1 DEG H) structure to generate benzyl bromide, but tertiary carbon hydrogen (3 DEG H) is relatively active and is easily substituted by bromine to be converted into a-C-Br group, and tertiary carbon bromine is extremely active and easy to generate debromination reaction when being dried at high temperature such as above 100 ℃, so that the product is crosslinked and discolored.
In addition, a solvent is an essential reaction medium in the production of halogenated polymers from polymers and halogenating agents. Literature has demonstrated that hydrocarbon solvents can undergo free radical halogenation, especially chlorination and bromination, under conditions of light, heat, and free radical initiators. Wherein, the alkane containing tertiary carbon hydrogen (3 DEG H) structure has higher halogenation activity. Hydrocarbon solvents are generally used in industrial production, for example, industrial n-hexane has a purity of 65wt% to 85wt%, and the solvents generally contain other components, particularly, isomers of n-hexane, such as methylcyclopentane, 2-methylpentane, 3-methylpentane, and the like, which are difficult to separate.
Therefore, in chemical production, in order to avoid halogenation of isomers in solvents, it is generally necessary to select high purity normal paraffins. For example, bromination of a copolymer of isomonoolefin and para-alkylstyrene, particularly a copolymer of isobutylene and para-methylstyrene in an alkane solvent, the use of high purity n-hexane or cyclohexane of 99% by weight or more leads to a significant increase in production costs in order to avoid bromination of the solvent.
In addition, the reaction of the polymer with the halogenating agent in the prior art is usually carried out in the presence of an organic radical initiator (e.g. azo compound) and/or an oxidizing agent (e.g. peroxide), and has many impurities and side reactions.
Therefore, it is necessary to provide a halogenation method suitable for the copolymer of isomonoolefin and para-alkylstyrene, so that when the copolymer is halogenated in a solvent, the selectivity of the halogenation reaction can be effectively controlled, the occurrence of side reactions in the copolymer and the solvent can be restrained, the requirement on the purity of the solvent in industrial production can be reduced, the production requirement can be met by using a conventional industrial solvent, and the production cost can be reduced; can avoid introducing the impurities such as initiator, oxidant and the like into the product, and obtain the pure halogenated polymer with simple, feasible and mild process conditions and steps.
Disclosure of Invention
The invention aims to overcome the defects of high requirement on solvent purity and low effective bromine utilization rate in the bromination process of the copolymer of isomonoolefin and alkylstyrene in the prior art, and provides a halogenation method of the copolymer. Furthermore, the introduction of impurities such as an initiator, an oxidant and the like into the product can be avoided, and the pure halogenated copolymer can be obtained under simple and easy process conditions and steps.
In order to achieve the above object, a first aspect of the present invention provides a process for producing a halogenated copolymer, characterized in that the process comprises the steps of:
under the condition of ultrasound and illumination, the copolymer and the halogenating agent are subjected to contact reaction in a solvent to obtain the halogenated copolymer.
In a second aspect, the present invention provides a halogenated copolymer produced by the above-described production method.
Through the technical scheme, the halogenated copolymer and the preparation method thereof provided by the invention have the following beneficial effects:
In the invention, under the conditions of illumination and ultrasound, when the copolymer is halogenated in a solvent, for example, bromination, the free radical halogenation reaction is initiated by adopting illumination, and the copolymer can be performed in the absence of an organic free radical initiator and an oxidant, so that the introduction of impurities such as the initiator, the oxidant and the like into a final halogenated copolymer product is avoided; simultaneously, under the action of ultrasound, the selectivity of the halogenation reaction can be effectively controlled, the target reaction of halogenating a methyl hydrogen (1 DEG H) structure to generate benzyl halide is completed, the occurrence of side reactions of impurities in the copolymer and the solvent is restrained when the copolymer is subjected to the halogenation reaction, the requirement on the purity of the solvent when the copolymer is subjected to the halogenation is reduced, the energy consumption is saved, the production cost is reduced, and the effective utilization rate of the halogenating agent is improved. Can obtain pure halogenated copolymer with simple, easy and mild process conditions and steps.
Further, in the prior art, when the copolymer is contacted with a halogenating agent to conduct halogenation, the purity requirement for the solvent is high, and other substances such as methylcyclopentane, 2-methylpentane, 3-methylpentane and the like are inevitably mixed in the alkane solvent sold in the prior art, so that the separation is difficult. In the presence of the halogenating agent, the isomerisation impurity in the solvent reacts with the copolymer to form a competing reaction, greatly reducing the effective utilization of the halogenating agent. When the method is adopted to halogenate the copolymer, the method can still have higher effective utilization rate of the halogenating agent under the condition of lower solvent purity.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a process for producing a halogenated copolymer, characterized in that the process comprises the steps of:
under the condition of ultrasound and illumination, the copolymer and the halogenating agent are subjected to contact reaction in a solvent to obtain the halogenated copolymer.
In the invention, the copolymer is halogenated in the solvent under the conditions of ultrasound and illumination, for example, during bromination, the occurrence of side reactions of the copolymer and impurities in the solvent during the halogenation reaction can be restrained, the requirement on the purity of the solvent during the halogenation of the copolymer is reduced, the introduction of the impurities such as an initiator, an oxidant and the like into the halogenated copolymer product is avoided, and the effective utilization rate of the halogenating agent (such as bromine) is improved.
Specifically, in the invention, the free radical halogenation reaction is initiated by adopting illumination, and can be carried out in the absence of an organic free radical initiator and an oxidant, so that the introduction of impurities such as the initiator, the oxidant and the like into the final halogenated copolymer product is avoided.
Further, the inventor researches the bromination reaction process of the model polymer molecules of paraxylene and liquid bromine, specifically, under the same illumination condition, main solvent impurities such as methylcyclopentane, 2-methylpentane, 3-methylpentane and the like and the model polymer molecules of paraxylene are respectively added with equal amounts of liquid bromine, and bromination reaction is carried out under the ultrasonic condition and the non-ultrasonic condition respectively, and orange fading in the solution indicates the end of the reaction. The time taken for the contact reaction of the different substances with the brominating agent under ultrasonic conditions and without ultrasonic conditions was determined, respectively.
Research results show that the photo-bromination contact reaction is carried out under the condition of no ultrasonic wave, the bromination reaction rate of the polymer molecule paraxylene and impurities is simulated to have smaller difference, which is unfavorable for bromination of the polymer molecule, namely the effective utilization rate of bromine is relatively reduced; and the photo-bromination contact reaction is carried out under the ultrasonic condition, the reaction of the polymer molecule paraxylene is rapid, the bromination reaction rate of the polymer molecule paraxylene and the impurity is greatly different, namely the impurity is not reacted yet, and the polymer molecule is simulated to be reacted possibly.
The inventor of the invention has found that under the action of ultrasound, the selectivity of halogenation reaction can be effectively controlled, the target reaction of halogenating methyl hydrogen (1 DEG H) structure to generate benzyl halide is completed, the occurrence of side reactions of impurities in the copolymer and the solvent is restrained when the copolymer is subjected to halogenation reaction, the requirement on the purity of the solvent when the copolymer is subjected to halogenation is reduced, the energy consumption is saved, the production cost is reduced, and the effective utilization rate of the halogenating agent is improved. Can obtain pure halogenated copolymer with simple, easy and mild process conditions and steps.
In the present invention, the effective utilization ratio of the halogenating agent means a ratio of the molar amount of the halogenating agent forming benzyl halide to the molar amount of the halogenating agent participating in the halogenation reaction, which is introduced at the para-methylhydrogen (1 DEG H) position of the copolymer.
According to the invention, the frequency of the ultrasound is 20KHz-400KHz.
In the present invention, the frequency of the ultrasonic wave can be selected within a wide range, for example, when the frequency of the ultrasonic wave is controlled to satisfy the above range, the purpose of suppressing the occurrence of side reactions in the copolymer and the solvent and improving the effective utilization ratio of the halogenating agent can be achieved, but the higher the frequency of the ultrasonic wave, the higher the energy consumption.
Further, in order to improve the effective utilization rate of the halogenating agent and reduce the power consumption, it is preferable that the frequency of the ultrasonic wave is 20KHz to 50KHz.
According to the invention, the purity of the solvent is not less than 50wt%.
In the prior art, when the copolymer is contacted with a halogenating agent to carry out halogenation reaction, the purity requirement on the solvent is high, and other substances such as methylcyclopentane, 2-methylpentane, 3-methylpentane and the like are inevitably mixed in alkane solvents sold in the prior art, so that the separation is difficult. In the presence of the halogenating agent, the isomerisation impurity in the solvent reacts with the copolymer to form a competing reaction, greatly reducing the effective utilization of the halogenating agent. When the method is adopted to halogenate the copolymer, the method can still have higher effective utilization rate of the halogenating agent under the condition of lower solvent purity.
Further, the purity of the solvent is more than or equal to 60wt%.
According to the present invention, the solvent is selected from at least one of a linear n-alkane of C 4-C8 and a cycloalkane of C 4-C8; preferably, the solvent is selected from at least one of cyclohexane, n-hexane and n-heptane.
According to the invention, the illumination is provided by a light source of at least one of a visible light source and/or an ultraviolet light source, preferably a visible light source.
In the present invention, the type of the light source is not particularly limited, and various light sources commonly used in the prior art can be used, including but not limited to fluorescent lamps, tungsten lamps, LED light sources, solar light sources, xenon lamps, household energy-saving lamps, and the like.
According to the invention, the wavelength of the light source is 360-780nm.
According to the invention, the conditions of the contact reaction include: the illumination power is 10-500mW, the reaction temperature is 5-30 ℃, and the reaction time is 0.2-6min.
Further, in order to further suppress occurrence of side reactions in the copolymer and the solvent and to improve the effective utilization rate of the halogenating agent, preferably, the conditions of the contact reaction include: the power of illumination is 50-300mW, the reaction temperature is 8-25 ℃, the reaction time is 0.5-5min, and more preferably, the conditions of the contact reaction comprise: the illumination power is 100-250mW, the reaction temperature is 10-20 ℃, and the reaction time is 1-3min.
According to the invention, the copolymer is a copolymer of a C 4-C12 isomonoolefin and an alkylstyrene, preferably a copolymer of a C 4-C7 isomonoolefin and an alkylstyrene, more preferably a copolymer of isobutylene and/or isoamylene and p-methylstyrene.
According to the invention, the content of structural units derived from alkylstyrenes in the copolymer is from 0.5 to 90% by weight, preferably from 1 to 50% by weight, based on the total weight of the copolymer.
In one embodiment of the present invention, the copolymer is a copolymer of isobutylene and para-methylstyrene, wherein the content of structural units derived from para-methylstyrene in the copolymer is 3 to 20% by weight, based on the total weight of the copolymer. When the copolymer is halogenated according to the halogenation method provided by the invention, the effective utilization rate of the halogenating agent is further improved.
According to the invention, the weight average molecular weight of the copolymer is from 10 to 100 tens of thousands.
According to the invention, the halogenating agent is halogen, preferably liquid bromine.
In the present invention, in order to further improve the effective utilization rate of the halogenating agent, it is preferable that the copolymer is used in an amount of 1 to 20 parts by weight and the halogenating agent is used in an amount of 0.08 to 1.2 parts by weight with respect to 100 parts by weight of the solvent.
In the present invention, the parts by weight of the solvent are the weight of the solvent in terms of a solution.
More preferably, the copolymer is used in an amount of 5 to 15 parts by weight and the halogenating agent is used in an amount of 0.2 to 0.5 parts by weight with respect to 100 parts by weight of the solvent.
In a second aspect, the present invention provides a halogenated copolymer produced by the above-described halogenation process.
The present invention will be described in detail by examples.
In the examples below, the starting materials are all commercially available without specific description;
The effective utilization of bromine was determined by the following method: the bromination degree of the copolymer is measured by adopting a Bruker AVANCE400 nuclear magnetic resonance apparatus (400 Hz) with the magnetic field strength of 9.40 Tesla and CDCl 3 as a solvent and TMS as an internal standard;
Effective utilization of bromine% = mole amount of bromine in target product/mole amount of bromine participating in reaction x 100%, density of liquid bromine is 3.119g/mL.
Example 1
25G of a copolymer formed by isobutene monomer and p-methylstyrene monomer (the weight average molecular weight of the copolymer is 50 ten thousand, the content of structural units from the p-methylstyrene in the copolymer is 12 weight percent based on the total weight of the copolymer) is dissolved in 225g of 85 weight percent n-hexane, then 0.34mL of liquid bromine (1.06 g) is added, after the mixture is uniformly mixed, a tungsten lamp with the illumination power of 150W is adopted for irradiation, and the contact reaction is carried out under the ultrasonic action of 20KHz, wherein the reaction temperature is 10 ℃ and the reaction time is 2min.
Results: the effective utilization of bromine was calculated to be 81%.
Example 2
25G of a copolymer formed by isobutene monomer and p-methylstyrene monomer (the weight average molecular weight of the copolymer is 50 ten thousand, the content of structural units from the p-methylstyrene in the copolymer is 12 weight percent based on the total weight of the copolymer) is dissolved in 225g of 85 weight percent n-hexane, then 0.34mL of liquid bromine (1.06 g) is added, after the mixture is uniformly mixed, a tungsten lamp with the illumination power of 150W is adopted for irradiation, and the contact reaction is carried out under the ultrasonic action of 50KHz, wherein the reaction temperature is 10 ℃ and the reaction time is 2min.
Results: the effective utilization of bromine was calculated to be 78%.
Example 3
25G of a copolymer formed by isobutene monomer and p-methylstyrene monomer (the weight average molecular weight of the copolymer is 50 ten thousand, the content of structural units from the p-methylstyrene in the copolymer is 12 percent by weight based on the total weight of the copolymer) is dissolved in 225g of 85 percent by weight of n-hexane, then 0.34mL of liquid bromine (1.06 g) is added, after the mixture is uniformly mixed, the contact reaction is carried out under the ultrasonic action of 30KHz by adopting a tungsten lamp with the illumination power of 150W, the reaction temperature is 10 ℃, and the reaction time is 2min.
Results: the calculated effective bromine utilization was 80%.
Example 4
This example was conducted in a similar manner to example 1 except that:
In this example, the contact reaction was performed under 100KHz ultrasound.
Results: the calculated effective utilization of bromine was 76% respectively.
Example 5
This example was conducted in a similar manner to example 1 except that:
In this example, the contact reaction was performed under 200KHz ultrasound.
Results: the calculated effective utilization of bromine was 74% respectively.
Example 6
This example was conducted in a similar manner to example 1 except that:
In this example, the contact reaction was performed under 500KHz ultrasound.
Results: the calculated effective utilization of bromine was 73% respectively.
Example 7
This example was conducted in a similar manner to example 1 except that:
In this example, 85wt% of n-hexane was replaced with 60wt% of n-hexane of equal mass.
Results: the effective utilization of bromine was calculated to be 73%.
Comparative example 1
This example was conducted in a similar manner to example 1 except that:
25g of a copolymer (the weight average molecular weight of the copolymer is 50 ten thousand, the content of structural units from the p-methylstyrene in the copolymer is 12 wt% based on the total weight of the copolymer) formed by isobutene monomers and p-methylstyrene monomers is dissolved in 225g of 85wt% n-hexane, then 0.34mL of liquid bromine (1.06 g) is added, after uniform mixing, a contact reaction is carried out by adopting a tungsten lamp with illumination power of 150W under the condition of no ultrasonic effect, the reaction time is 2min, and the reaction temperature is 10 ℃.
Results: the copolymer was calculated to have an effective utilization of 47% bromine in 85wt% n-hexane.
Comparative example 2
This example was conducted in a similar manner to example 1 except that:
25g of a copolymer (the weight average molecular weight of the copolymer is 50 ten thousand, the content of structural units from the p-methylstyrene in the copolymer is 12 wt% based on the total weight of the copolymer) formed by isobutene monomers and p-methylstyrene monomers is dissolved in 225g of 97wt% n-hexane, then 0.34mL of liquid bromine (1.06 g) is added, after uniform mixing, a contact reaction is carried out by adopting a tungsten lamp with illumination power of 150W under the condition of no ultrasonic effect, the reaction time is 2min, and the reaction temperature is 10 ℃.
Results: the copolymer was calculated to have an effective bromine utilization of 52% in 97wt% n-hexane.
Comparative example 3
25G of a copolymer of isobutylene monomer and p-methylstyrene monomer having a weight average molecular weight of 50 ten thousand and a content of structural units derived from p-methylstyrene of 12% by weight based on the total weight of the copolymer was dissolved in 225g of 85% by weight of n-hexane, followed by sequentially adding 10g of an n-hexane solution containing 0.4% by weight of azobisisoheptonitrile and 0.34mL of liquid bromine (1.06 g), and reacting for 2 minutes after uniformly mixing under no-light and no-ultrasonic conditions at a reaction temperature of 10 ℃.
Results: the effective utilization of bromine was calculated to be 40%.
The result shows that the method adopts the visible light source to irradiate, and simultaneously performs the contact reaction under the ultrasonic action, particularly under the ultrasonic action of 20KHz-400KHz, so that the requirement on the purity of the solvent when the copolymer is brominated can be obviously reduced, and when the purity of the solvent is 60wt%, the effective utilization rate of bromine can still reach 73%, thereby greatly reducing the requirement on the purity of the solvent, saving energy consumption and reducing the production cost. Meanwhile, the introduction of impurities such as an initiator, an oxidant and the like into the product can be avoided, and the target halogenated copolymer can be simply, easily, mildly and quickly obtained.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for preparing a halogenated copolymer, said process comprising the steps of:
under the condition of ultrasound and illumination, the copolymer and the halogenating agent are subjected to contact reaction in a solvent to obtain the halogenated copolymer.
2. The halogenation process according to claim 1, wherein the frequency of the ultrasound is 20KHz-400KHz, preferably 20KHz-50KHz.
3. The halogenation process according to claim 1 or 2, wherein the purity of the solvent is not less than 50wt%, preferably not less than 60wt%.
4. A halogenation process according to any one of claims 1-3, wherein the solvent is selected from at least one of a linear normal alkane of C 4-C8 and a cycloalkane of C 4-C8; preferably, the solvent is selected from at least one of cyclohexane, n-hexane and n-heptane.
5. The halogenation process according to any one of claims 1-4, wherein the illumination is provided by a light source of at least one of a visible light source and/or an ultraviolet light source, preferably a visible light source;
preferably, the wavelength of the light source is 360-780nm.
6. The halogenation process of any one of claims 1-5 wherein the conditions of the contact reaction comprise: the illumination power is 10-500mW, the reaction temperature is 5-30 ℃, and the reaction time is 0.2-6min.
7. The halogenation process according to any one of claims 1-6, wherein the copolymer is a copolymer of a C 4-C12 isomonoolefin and an alkylstyrene, preferably a copolymer of a C 4-C7 isomonoolefin and an alkylstyrene, more preferably a copolymer of isobutylene and/or isoamylene and p-methylstyrene;
preferably, the copolymer has a content of structural units derived from alkylstyrene of 0.5 to 90 wt%, preferably 1 to 50wt%, based on the total weight of the copolymer;
Preferably, the weight average molecular weight of the copolymer is from 10 to 100 tens of thousands.
8. The halogenation process according to any one of claims 1-7, wherein the halogenating agent is halogen, preferably liquid bromine.
9. The halogenation process according to any one of claims 1-8, wherein the copolymer is used in an amount of from 1 to 20 parts by weight and the brominating agent is used in an amount of from 0.08 to 1.2 parts by weight relative to 100 parts by weight of the solvent;
Preferably, the copolymer is used in an amount of 5 to 15 parts by weight and the brominating agent is used in an amount of 0.2 to 0.5 parts by weight with respect to 100 parts by weight of the solvent.
10. A halogenated copolymer produced by the production process according to any one of claims 1 to 9.
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