CN116023568A - Application of hypergravity reactor in copolymerization of isobutene and maleic anhydride and method for copolymerization of isobutene and maleic anhydride - Google Patents
Application of hypergravity reactor in copolymerization of isobutene and maleic anhydride and method for copolymerization of isobutene and maleic anhydride Download PDFInfo
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 168
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000007791 liquid phase Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 230000035484 reaction time Effects 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 57
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000012265 solid product Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010926 purge Methods 0.000 description 9
- 229940117955 isoamyl acetate Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- 239000003381 stabilizer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 150000003949 imides Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
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- 229920000126 latex Polymers 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention relates to an application of a hypergravity reactor in copolymerization of isobutene and maleic anhydride and a method for copolymerization of isobutene and maleic anhydride, wherein the method comprises the following steps: s1, introducing isobutene and a maleic anhydride solution containing an initiator into a hypergravity reactor, and blending and pre-reacting the isobutene and the maleic anhydride; s2, introducing the liquid-phase product obtained in the step S1 into a reaction kettle for continuous reaction. The invention provides a novel isobutene polar copolymerization method, which enables isobutene and maleic anhydride to be fully blended in a very short time in a supergravity reactor mode, shortens the polar copolymerization reaction time, reduces the polar reaction cost and improves the generation rate of reactants; provides a more feasible method for efficiently producing the isobutene polar copolymer.
Description
Technical Field
The invention relates to the field of polar polymerization, in particular to a method for preparing an isobutylene maleic anhydride polar copolymer.
Background
The isobutylene maleic anhydride copolymer has different molecular weights and different functional groups (derivative products such as amide-ammonia type, imide type, crosslinking type, hydrolysis type, ionic type and the like), and is a chemical product with wide application. The low molecular weight isobutylene maleic anhydride copolymer can be used as a scale inhibitor, a dispersing agent, a water reducing agent of cement paste, and the medium and high molecular weight isobutylene maleic anhydride copolymer can be used as an adhesive for wood and paper processing, an emulsion polymerization stabilizer and the like. The anhydride groups in the isobutylene maleic anhydride copolymer can undergo esterification reaction, amidation reaction, imidization reaction and ionization reaction, so that the application range of the isobutylene maleic anhydride copolymer is further widened, the isobutylene maleic anhydride copolymer can be used as an adhesive, a water-based paint and the like after being aminated, the isobutylene maleic anhydride copolymer can be used as a polymerization stabilizer and adhesive latex after being modified, and the isobutylene maleic anhydride copolymer can be used as a water-absorbent resin after being crosslinked, and the isobutylene maleic anhydride copolymer has excellent performance and wide application range, and has important application prospect, and no mature preparation technology of similar products at present in China.
According to three documents of research on the copolymerization reaction of isobutene-maleic anhydride in 11 th stage P739-744 in petrochemical engineering 1990, synthesis and characterization of IBMA resin in 2 nd stage P38-43 in high molecular material science and engineering 1992 and synthesis research of isobutene-maleic anhydride copolymer in 9 th stage P56-59 in industrial water treatment volume 33 in 2013, the isobutene maleic anhydride copolymer is mainly synthesized by adopting a precipitation polymerization method. Isobutene is a gas at normal temperature, and if the isobutene is subjected to polar copolymerization with maleic anhydride, the isobutene is directly introduced into a maleic anhydride solution in a mode of longer dissolution time and lower utilization efficiency; isobutene may also be liquefied and added to the maleic anhydride solution, but this approach is costly. Aiming at the problems of shortening the dissolution time of isobutene, improving the copolymerization reaction efficiency of isobutene and maleic anhydride and shortening the reaction time, no related reaction device and reaction method are disclosed in the prior art.
Disclosure of Invention
The invention aims to provide an application of a hypergravity reactor in copolymerization of isobutene and maleic anhydride, so as to solve the problems of low polar copolymerization efficiency and overlong copolymerization time in the polymerization production of isobutene polar copolymers prepared in the prior art.
The invention also aims to provide a method for copolymerizing isobutene and maleic anhydride.
In order to achieve the aim, the invention provides an application of a hypergravity reactor in copolymerization of isobutene and maleic anhydride.
In order to achieve the above object, the present invention also provides a method for copolymerizing isobutylene and maleic anhydride, comprising the steps of:
s1, introducing isobutene and a maleic anhydride solution containing an initiator into a hypergravity reactor, and blending and pre-reacting the isobutene and the maleic anhydride;
s2, introducing the liquid-phase product obtained in the step S1 into a reaction kettle for continuous reaction.
The method for copolymerizing isobutene and maleic anhydride, disclosed by the invention, has the advantages that the pre-reaction time in the step S1 is 1-4S, the pressure is 0.1-0.8 MPa, and the reaction temperature is 55-100 ℃.
The method for copolymerizing isobutene and maleic anhydride, disclosed by the invention, has the advantages that the reaction time in the step S2 is 1-4 h, the pressure is 0.2-2 MPa, and the reaction temperature is 50-100 ℃.
The invention relates to a method for copolymerizing isobutene and maleic anhydride, wherein the rotating speed of a hypergravity reactor in the step S1 is 100 rpm-2000 rpm; preferably, the rotation speed is 300rpm to 2000rpm.
The invention relates to a method for copolymerizing isobutene and maleic anhydride, wherein in the step S1, the volume ratio of isobutene to a maleic anhydride solution containing an initiator is 50-500:1.
the invention relates to a method for copolymerizing isobutene and maleic anhydride, wherein the weight ratio of isobutene to maleic anhydride is 0.2-5:1, preferably, the weight ratio is 0.5-3:1.
the invention relates to a method for copolymerizing isobutene and maleic anhydride, wherein the dosage of an initiator is 1-20% of the weight of the maleic anhydride.
The method for copolymerizing isobutene and maleic anhydride comprises the following steps of enabling the concentration of maleic anhydride in a maleic anhydride solution containing an initiator to be 3-25 wt%, and enabling a solvent for dissolving the maleic anhydride and the initiator to be at least one of organic acid alkyl ester, alkane and aromatic hydrocarbon.
The invention relates to a method for copolymerizing isobutene and maleic anhydride, wherein the initiator is a thermal decomposition type initiator and comprises at least one of dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.
The method for copolymerizing isobutene and maleic anhydride comprises the steps of separating the liquid-solid blending product obtained in the step S2 after the step S2 is finished, and then washing and drying the solid-phase product.
The method for copolymerizing isobutene and maleic anhydride comprises the steps of filtering separation or centrifugal separation, recycling liquid phase products after separation, washing the liquid phase products, and drying the liquid phase products.
The beneficial effects of the invention are as follows:
aiming at the characteristic of the reaction of isobutene and maleic anhydride, a process strengthening device hypergravity reactor is introduced into the polar copolymerization reaction. Compared with a reaction kettle, the hypergravity reactor can enhance the mass transfer efficiency of isobutene, reduce the dissolution time of isobutene and improve the reaction efficiency of isobutene.
Through the technical scheme, the invention provides a novel isobutene polar copolymerization method, isobutene and maleic anhydride are fully blended in a very short time through the supergravity reactor, so that the efficiency of further copolymerization reaction is quickened, the reaction time of copolymerization is shortened, the reaction cost is reduced, and a more feasible method is provided for efficiently producing isobutene polar copolymers.
Drawings
FIG. 1 is a flow chart of the process for copolymerizing isobutylene and maleic anhydride according to the present invention;
FIG. 2 is an infrared spectrum of the polymer obtained in example 5 of the present invention.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
A process for the polar copolymerization of isobutylene comprising the steps of:
(1) After nitrogen purging, contacting isobutene heated to 55-100 ℃ with a maleic anhydride solution containing an initiator heated to 55-100 ℃ in a hypergravity reactor, so that the isobutene and the maleic anhydride are fully blended and subjected to preliminary polar copolymerization; the residence time of the reaction monomer passing through the hypergravity reactor is 1-4 s, and the outlet temperature is 50-100 ℃;
(2) After all the liquid-phase product obtained in the step (1) is introduced into a reaction kettle through a buffer tank and a metering pump, continuing the polar copolymerization reaction of isobutene and maleic anhydride; wherein the volatilized isobutene can be recycled;
(3) And (3) taking the liquid-solid blending product obtained in the step (2) out of the reaction kettle, separating, and washing and drying the solid product to obtain the solid product which is the isobutylene maleic anhydride copolymer.
As shown in figure 1, heated isobutene and a maleic anhydride solution containing an initiator are added into a hypergravity reactor through a metering pump, the isobutene enters the hypergravity reactor from a gas phase inlet, the maleic anhydride solution containing the initiator enters the hypergravity reactor from a liquid phase inlet for full mixing and preliminary polar copolymerization reaction, unreacted gas-phase isobutene circulates to the gas phase inlet of the hypergravity reactor, an obtained liquid-phase product enters a reaction kettle through a buffer tank and the metering pump for continuous reaction, the gas-phase isobutene which cannot participate in the reaction process circulates to the gas phase inlet of the hypergravity reactor for recycling, separation is carried out after the reaction is finished, the liquid-phase product circulates to the liquid phase inlet of the hypergravity reactor for recycling, and the solid-phase product is washed and dried to finally obtain the isobutene maleic anhydride polar copolymer.
The isobutene and the maleic anhydride solution containing the initiator can be mixed and subjected to preliminary reaction in a hypergravity reactor in a mode of gas-liquid countercurrent, gas-liquid cocurrent or gas-liquid baffling. The used hypergravity reactor can make the isobutene gas fully and quickly mutually dissolve with the maleic anhydride solution containing the initiator, and complete the preliminary polar copolymerization reaction.
Example 1
After purging the hypergravity reactor with nitrogen, heat-exchanging 1.4L of isoamyl acetate solution containing 3.1g of azobisisobutyronitrile and 196g of maleic anhydride to 60 ℃, entering a liquid phase inlet of the hypergravity reactor through a metering pump, heat-exchanging isobutene to 60 ℃, entering a gas phase inlet through the metering pump, and fully mixing gas and liquid in the hypergravity reactor to perform primary reaction; wherein, the gas-liquid ratio in the hypergravity reactor is 400: 1 (v/v), and the operating pressure was 0.6MPa.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, and the reaction time is 3 hours;
filtering and separating the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 1 shows the residence time of the gas and liquid in the hypergravity reactor, and the yield of the copolymer, by varying the rotation speed of the hypergravity reactor.
TABLE 1
| Sequence number | Super gravity rotating speed | Residence time | Copolymer mass | Copolymer number average molecular weight |
| 1 | 500 | 4 | 244g | 56000 |
| 2 | 1000 | 2.5 | 276g | 77000 |
| 3 | 1500 | 2 | 263g | 71000 |
| 4 | 2000 | 1 | 252g | 61000 |
Example 2
After purging the hypergravity reactor with nitrogen, heat-exchanging 1.4L of isoamyl acetate solution containing 3.1g of azobisisobutyronitrile and 196g of maleic anhydride to 60 ℃, entering a liquid phase inlet of the hypergravity reactor through a metering pump, heat-exchanging isobutene to 60 ℃, entering a gas phase inlet through the metering pump, and fully mixing gas and liquid in the hypergravity reactor to perform primary reaction; wherein the rotating speed in the hypergravity reactor is 1000rpm, the operating pressure is 0.6Mpa, and the gas-liquid residence time is 2.5 seconds.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, and the reaction time is 3 hours;
filtering and separating the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 2 shows the gas-liquid ratio of the hypergravity reactor, and the yield of the copolymer.
TABLE 2
| Sequence number | Ratio of gas to liquid | Copolymer mass | Copolymer number average molecular weight |
| 1 | 100 | 247g | 63000 |
| 2 | 300 | 288g | 84000 |
| 3 | 400 | 276g | 77000 |
| 4 | 500 | 263g | 70000 |
Example 3
After purging the supergravity reactor by nitrogen, 1.4L of butyl acetate solution containing 3.1g of benzoyl peroxide and 196g of maleic anhydride is subjected to heat exchange to 60 ℃, and enters a liquid phase inlet of the supergravity reactor through a metering pump, isobutene is subjected to heat exchange to 60 ℃, enters a gas phase inlet through the metering pump, and the gas and the liquid are fully mixed in the supergravity reactor and undergo preliminary reaction; wherein, the gas-liquid ratio in the hypergravity reactor is 300:1 (v/v), the rotation speed is 1000rpm, and the gas-liquid residence time is 2.5s.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out polar copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, and the reaction time is 3 hours;
filtering and separating the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 3 shows the operating pressure of the hypergravity reactor, and the yield of the copolymer.
TABLE 3 Table 3
| Sequence number | Supergravity pressure | Copolymer mass | Copolymer number average molecular weight |
| 1 | 0.2Mpa | 246g | 78000 |
| 2 | 0.6Mpa | 288g | 84000 |
| 3 | 1Mpa | 290g | 88000 |
| 4 | 2Mpa | 287g | 87000 |
Example 4
After purging the hypergravity reactor by nitrogen, carrying out heat exchange on 1.4L butyl acetate solution containing 3.1g of benzoyl peroxide and 196g of maleic anhydride, then, entering a liquid phase inlet of the hypergravity reactor by a metering pump, and entering a gas phase inlet by a flow meter after the heat exchange of isobutene, and fully mixing gas and liquid in the hypergravity reactor and carrying out primary reaction; wherein, the gas-liquid ratio in the hypergravity reactor is 300:1 (v/v), a rotational speed of 1000rpm, an operating pressure of 0.6MPa and a residence time of 2.5s.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out polar copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, and the reaction time is 3 hours;
filtering and separating the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 4 shows the variation of the inlet temperature of the hypergravity reactor and the yield of the copolymer.
TABLE 4 Table 4
| Sequence number | Super gravity inlet temperature | Copolymer mass | Copolymer number average molecular weight |
| 1 | 55℃ | 268g | 93000 |
| 2 | 75℃ | 290g | 80000 |
| 3 | 90℃ | 289g | 64000 |
Example 5
After purging the hypergravity reactor with nitrogen, heat-exchanging 1.4L of isoamyl acetate solution containing 3.1g of dicyclohexyl peroxydicarbonate and 196g of maleic anhydride to 75 ℃, feeding the solution into a liquid phase inlet of the hypergravity reactor through a metering pump, feeding isobutene to 75 ℃ through heat exchange, feeding the solution into a gas phase inlet through the metering pump, fully mixing gas and liquid in the hypergravity reactor, and carrying out primary reaction; wherein, the gas-liquid ratio in the hypergravity reactor is 300:1 (v/v), a rotational speed of 1000rpm, an operating pressure of 0.6MPa and a residence time of 2.5s.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out copolymerization reaction of isobutene and maleic anhydride, wherein the reaction pressure is 0.6MPa, and the reaction time is 2 hours;
and (3) carrying out centrifugal separation on the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 5 shows the change in the operating temperature of the reactor and the yield of the copolymer.
TABLE 5
| Sequence number | Reaction kettle temperature | Copolymer mass | Copolymer number average molecular weight |
| 1 | 55℃ | 209g | 86000 |
| 2 | 70℃ | 290g | 70000 |
| 3 | 90℃ | 291g | 54000 |
FIG. 2 is an infrared spectrum of a copolymer obtained under the condition of SEQ ID NO. 1 of example 5, 1773cm -1 And 1853 cm -1 C=O stretching vibration absorption peak of acid anhydride, 3000cm -1 Nearby are the stretching vibration absorption peaks of methyl and methylene.
Example 6
After purging the hypergravity reactor with nitrogen, exchanging heat between 1.4L butyl acetate solution containing 3.1g of azodiisobutyronitrile and 196g of maleic anhydride and then entering a liquid phase inlet of the hypergravity reactor through a metering pump, exchanging heat between isobutene and then entering a gas phase inlet through the metering pump, fully mixing gas and liquid in the hypergravity reactor and performing primary reaction; wherein, the gas-liquid ratio in the hypergravity reactor is 300:1 (v/v), a rotational speed of 1000rpm, an operating pressure of 0.6MPa and a residence time of 2.5s.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out polar copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours;
and (3) carrying out centrifugal separation on the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 6 shows the operating pressure of the reaction vessel, and the yield of the copolymer.
TABLE 6
| Sequence number | Pressure of reaction kettle | Copolymer mass | Copolymer number average molecular weight |
| 1 | 0.2Mpa | 274g | 65000 |
| 2 | 0.6Mpa | 290g | 70000 |
| 3 | 2Mpa | 289g | 72000 |
Example 7
After purging the hypergravity reactor with nitrogen, heat-exchanging 1.4L of isoamyl acetate solution containing 3.1g of azobisisobutyronitrile and 196g of maleic anhydride to 75 ℃, feeding the solution into a liquid phase inlet of the hypergravity reactor through a metering pump, feeding isobutene into a gas phase inlet through the metering pump to 75 ℃ after heat-exchanging, and fully mixing gas and liquid in the hypergravity reactor to perform primary reaction; wherein, the gas-liquid ratio in the hypergravity reactor is 300:1 (v/v), a rotational speed of 1000rpm, an operating pressure of 0.6MPa and a residence time of 2.5s.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out polar copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 70 ℃, the reaction pressure is 0.6MPa, and the reaction time is 2 hours;
and (3) carrying out centrifugal separation on the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 7 shows the amounts of initiator used in the system and the yields of the copolymers.
TABLE 7
| Sequence number | Mass of initiator | Copolymer mass | Copolymer number average molecular weight |
| 1 | 3.1g | 290g | 70000 |
| 2 | 15.4g | 291g | 53000 |
| 3 | 31g | 289g | 34000 |
Example 8
After purging the hypergravity reactor with nitrogen, heat-exchanging 1.4L of isoamyl acetate solution containing 3.1g of azobisisobutyronitrile and a certain amount of maleic anhydride to 75 ℃, then entering a liquid phase inlet of the hypergravity reactor through a metering pump, heat-exchanging isobutene to 75 ℃, entering a gas phase inlet through the metering pump, and fully mixing gas and liquid in the hypergravity reactor to perform primary reaction; wherein, the gas-liquid ratio in the hypergravity reactor is 300:1 (v/v), a rotational speed of 1000rpm, an operating pressure of 0.6MPa and a residence time of 2.5s.
Introducing a liquid-phase product obtained by the hypergravity reactor into a reaction kettle through a buffer tank and a metering pump to continuously carry out polar copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 70 ℃, the reaction pressure is 0.6MPa, and the reaction time is 2 hours;
filtering and separating the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 8 shows the ratios of maleic anhydride to solvent in the system, and the yields of the copolymers.
TABLE 8
| Sequence number | Maleic anhydride to solution ratio | Copolymer mass | Copolymer number average molecular weight |
| 1 | 5％ | 228g | 59000 |
| 2 | 14％ | 290g | 70000 |
| 3 | 22％ | 287g | 78000 |
Comparative example 1
The comparative example is carried out under the experimental condition that the hypergravity rotating speed is 0, namely, 1.4L of isoamyl acetate solution containing 3.1g of azodiisobutyronitrile and 196g of maleic anhydride is subjected to heat exchange to 60 ℃, isobutene is directly introduced into a reaction tube through a buffer tank and a metering pump to carry out polar copolymerization reaction of the isobutene and the maleic anhydride after being subjected to heat exchange to the temperature of 60 ℃, the reaction pressure is 0.6MPa, and the reaction time is 3 hours;
and filtering and separating the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain 180g of white isobutylene maleic anhydride copolymer powder.
Compared with the powder yield of the isobutylene maleic anhydride copolymer under the condition of super gravity (gas-liquid ratio of 300:1 (v/v), operating pressure of 0.6Mpa and rotating speed of 1000 rpm), the powder yield of the isobutylene maleic anhydride copolymer is reduced under the same reaction time.
Comparative example 2
The comparative example is carried out under the experimental condition that the hypergravity rotating speed is 0, namely, 1.4L of isoamyl acetate solution containing 3.1g of azodiisobutyronitrile and 196g of maleic anhydride is subjected to heat exchange to 60 ℃, isobutene is directly introduced into a reaction kettle through a buffer tank and a metering pump to carry out polar copolymerization reaction of the isobutene and the maleic anhydride after being subjected to heat exchange to the temperature of 60 ℃, and the reaction pressure is 0.6MPa;
filtering and separating the obtained liquid-solid blending product, and then washing and drying the solid product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 9 shows the reaction times of the reaction tubes, and the yields of the copolymers.
TABLE 9
| Sequence number | Reaction time of the reaction tube | Copolymer mass |
| 1 | 5h | 252g |
| 2 | 6h | 271g |
| 3 | 7h | 290g |
Compared with the method under the condition of supergravity (gas-liquid ratio is 300:1 (v/v), operating pressure is 0.6Mpa, rotating speed is 1000 rpm), if the isobutylene maleic anhydride copolymer powder with the same mass is obtained, the reaction time is increased by more than 1 time.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. The application of the hypergravity reactor in the copolymerization of isobutene and maleic anhydride.
2. A process for copolymerizing isobutylene and maleic anhydride comprising the steps of:
s1, introducing isobutene and a maleic anhydride solution containing an initiator into a hypergravity reactor, and blending and pre-reacting the isobutene and the maleic anhydride;
s2, introducing the liquid-phase product obtained in the step S1 into a reaction kettle for continuous reaction.
3. The method for copolymerizing isobutylene and maleic anhydride according to claim 2, wherein the pre-reaction time in step S1 is 1 to 4S, the pressure is 0.1 to 2MPa, and the reaction temperature is 55 to 100 ℃.
4. The method for copolymerizing isobutylene and maleic anhydride according to claim 2, wherein the reaction time in step S2 is 1 to 4 hours, the pressure is 0.2 to 2MPa, and the reaction temperature is 50 to 100 ℃.
5. The method for copolymerizing isobutylene and maleic anhydride according to claim 2, wherein the rotation speed of the supergravity reactor in step S1 is 100rpm to 2000rpm; preferably, the rotation speed is 300rpm to 2000rpm.
6. The method of copolymerizing isobutylene and maleic anhydride according to claim 2, wherein in step S1, the volume ratio of isobutylene to the maleic anhydride solution containing the initiator is 50 to 500:1.
7. the method for copolymerizing isobutylene and maleic anhydride according to claim 2, wherein the weight ratio of isobutylene to maleic anhydride is 0.2 to 5:1, preferably, the weight ratio is 0.5-3:1.
8. the method for copolymerizing isobutylene and maleic anhydride according to claim 2, wherein the amount of the initiator is 1 to 20% by weight of the maleic anhydride.
9. The method for copolymerizing isobutylene and maleic anhydride according to claim 2, wherein the concentration of maleic anhydride in the maleic anhydride solution containing the initiator is 3 to 25wt%, and the solvent in which maleic anhydride and the initiator are dissolved is at least one of an alkyl ester of an organic acid, an alkane and an aromatic hydrocarbon.
10. The method of copolymerizing isobutylene and maleic anhydride according to claim 2, wherein the initiator is a thermal decomposition type initiator comprising at least one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.
11. The method for copolymerizing isobutene and maleic anhydride according to claim 2, wherein after the step S2 is completed, further comprising a separation step of separating the liquid-solid blending product obtained in the step S2, and then washing and drying the solid-phase product.
12. The method for copolymerizing isobutene and maleic anhydride according to claim 11, wherein the separation mode is filtration separation or centrifugal separation, the separated liquid phase product is recycled, the washing liquid used for washing is alcohol liquid, and the drying mode is drying.
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|---|---|---|---|---|
| JPS6191208A (en) * | 1984-10-12 | 1986-05-09 | Idemitsu Petrochem Co Ltd | Production of isobutylene/maleic anhydride copolymer |
| JPS62235238A (en) * | 1986-04-03 | 1987-10-15 | 株式会社クラレ | Alpha-olefin-maleic anhydride copolymer composition |
| JP2005008801A (en) * | 2003-06-20 | 2005-01-13 | Tosoh Corp | Method for producing maleic anhydride/olefin copolymer |
| CN104028175A (en) * | 2014-06-20 | 2014-09-10 | 宋晓轩 | Improved continuous mixing and heat dissipating chemical production device |
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2021
- 2021-10-27 CN CN202111254126.8A patent/CN116023568A/en active Pending
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| JPS6191208A (en) * | 1984-10-12 | 1986-05-09 | Idemitsu Petrochem Co Ltd | Production of isobutylene/maleic anhydride copolymer |
| JPS62235238A (en) * | 1986-04-03 | 1987-10-15 | 株式会社クラレ | Alpha-olefin-maleic anhydride copolymer composition |
| JP2005008801A (en) * | 2003-06-20 | 2005-01-13 | Tosoh Corp | Method for producing maleic anhydride/olefin copolymer |
| CN104028175A (en) * | 2014-06-20 | 2014-09-10 | 宋晓轩 | Improved continuous mixing and heat dissipating chemical production device |
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