CN113980186A - Preparation method and device of polyolefin solid-phase grafted maleic anhydride - Google Patents
Preparation method and device of polyolefin solid-phase grafted maleic anhydride Download PDFInfo
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- CN113980186A CN113980186A CN202010734589.3A CN202010734589A CN113980186A CN 113980186 A CN113980186 A CN 113980186A CN 202010734589 A CN202010734589 A CN 202010734589A CN 113980186 A CN113980186 A CN 113980186A
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- polyolefin
- maleic anhydride
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000007790 solid phase Substances 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims description 61
- 238000005406 washing Methods 0.000 claims description 57
- 239000007787 solid Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 8
- 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 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 13
- 229920001155 polypropylene Polymers 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 polypropylene Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
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- 239000008096 xylene Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 5
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- 238000011156 evaluation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 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 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method and a device of polyolefin solid-phase grafted maleic anhydride, wherein the device comprises a liquid preparation tank, a conical reactor and a reaction kettle; a sprayer and a heating device are arranged in the conical reactor, the conical reactor also comprises a discharge hole, and the discharge hole of the conical reactor is connected with the reaction kettle; the liquid preparation tank comprises a discharge port, and the discharge port of the liquid preparation tank is connected with a sprayer of the conical reactor through a booster pump. By the device and the preparation method, the problem of waste of unreacted monomers and the interfacial agent can be solved, the materials can be recycled, and the grafting rate of the prepared polyolefin grafted MAH is high.
Description
Technical Field
The invention belongs to the field of polyolefin, and particularly relates to a preparation method and a device of polyolefin solid-phase grafted maleic anhydride.
Background
The polyolefin material has the advantages of small density, good physical and chemical comprehensive properties, good colorability, good price performance and the like, so that the polyolefin material is widely applied. However, the polyolefin material has large shrinkage, strong water absorption, poor dimensional stability and poor compatibility with other polymer materials or inorganic fillers, and limits the application field of the polyolefin material. By modifying polyolefin and introducing polar groups into the main chain, the interfacial bonding strength of the polymer and the inorganic filler can be enhanced, and the compatibility of the polymer blend alloy is improved.
Maleic Anhydride (MAH) is a polar compound containing multiple functional groups, contains unsaturated double bonds in a molecular structure, and is easy to generate polymerization reaction with other polymers under the action of an initiator; the acid anhydride group can also react with a functional group such as a hydroxyl group, a carboxyl group, or an amine group. Therefore, MAH functionalization of some non-polar polymers is beneficial to increase compatibility with polar polymers, improve adhesion of materials, and improve interaction between fillers and polymers.
MAH grafted polyolefin mainly comprises a solution grafting method, a melt grafting method, a solid phase grafting method and the like. The solution grafting method can obtain higher grafting rate, but because a large amount of solvent is used, the post-treatment is complex, the environmental pollution is serious, and the cost is high; the melt grafting process is simple, continuous production can be realized, but the grafting rate is relatively low, the polymer is seriously degraded, and the grafted product contains impurities such as MAH and the like which are not completely reacted, thereby seriously affecting the performance of a post-processing product. The solid phase grafting is carried out the grafting reaction under the melting temperature of the polymer, and has the advantages of low reaction temperature, less polyolefin degradation, convenient operation, high product grafting rate, no or little solvent, no environmental pollution and the like, thereby being a grafting method with great development prospect. The grafted polyolefins can be classified into film grafting, fiber grafting and powder grafting, the first two being surface grafting of the shaped product, the so-called grafting being powder grafting.
Patent document CN1704436 discloses a continuous solid phase grafting production method and device for polyolefin, wherein the document mentions that various raw materials are continuously added into a horizontal or vertical reactor with a stirrer for reaction, and the graft modified polyolefin is obtained after the processes of washing, filtering, drying and the like, and the stirrer adopted by the reactor with the stirrer is provided with an inner spiral belt and an outer spiral belt with opposite spiral directions, so that the material propelling directions in the reactor are opposite, and the reaction efficiency is improved. The product grafting rate of the polyolefin solid phase grafting by adopting the method can reach more than 1 percent, but a large amount of acid waste water is generated in the washing process, and a large amount of MAH which does not participate in the reaction is dissolved in water, thereby causing environmental pollution and resource waste.
The preparation of maleic anhydride graft modified polypropylene by means of solid-phase graft copolymerization in internal circulation impinging stream reactor is studied by means of Liuhua Yan, etc. (the study on the modification of polypropylene solid-phase graft copolymerization in internal circulation impinging stream reactor, Zhejiang university of industry, 2004, 32, 4: 423) and the method is characterized by that in the internal circulation impinging stream reactor the circulating chamber of solid particles is added, so that the solid particles can be accelerated, impacted and reacted several times in the central tube, therefore it not only can obtain forced mixing, but also can prolong the retention time of particles in the reactor. The reactor is used for solid-phase grafting modification of polypropylene (PP), so that PP particles are accelerated by airflow in a central pipe and then collide with atomized solvent droplets accelerated by the airflow, and the PP particles and the solvent are fully contacted and mixed; while mixing, the PP and the comonomer are subjected to graft copolymerization reaction under the action of an initiator and a surfactant (solvent). Although the use of the reactor may improve the condition of uneven temperature and concentration distribution in the reactor, shorten the reaction time, and increase the grafting rate or reduce the solvent consumption to a certain extent, the problems that the polypropylene grafting rate in the impinging stream reactor cannot be effectively increased, the processing difficulty of the impinging stream reactor is high, and the like all restrict the industrialization of the method.
The production process comprises three reactors, wherein the three reactors are connected in series, different constant temperature conditions are required to be kept in each reactor, a catalyst is dissolved in xylene in advance, then the catalyst is added into the first reactor in a spraying mode for keeping for a certain time, then the mixture is discharged to the second reactor to be stirred and kept for a certain time under an inert gas atmosphere, and finally the mixture is discharged to the third reactor for keeping for a certain time, and then the discharged mixture is washed and dried to obtain the product with the grafting rate of 1.6%. Although the reactor breaks through the limitation of the traditional intermittent production method and can realize semi-continuous production, the production process needs to introduce the generated waste gas into an acetone solution and separate and recycle acetone from the waste liquid, the acetone is a control reagent, and the waste liquid separation causes high energy consumption and high production cost.
Disclosure of Invention
The invention aims to solve the problems of low grafting rate, incomplete removal of unreacted monomers and waste of raw materials, and provides a preparation method and a device for polyolefin solid-phase grafted maleic anhydride.
Specifically, the invention firstly provides a device for grafting maleic anhydride on a polyolefin solid phase, which comprises a liquid preparation tank, a conical reactor and a reaction kettle;
a sprayer and a heating device are arranged in the conical reactor, the conical reactor also comprises a discharge hole, and the discharge hole of the conical reactor is connected with the reaction kettle;
the liquid preparation tank comprises a discharge port, and the discharge port of the liquid preparation tank is connected with a sprayer of the conical reactor through a booster pump.
According to the technical scheme of the invention, the conical reactor also comprises a solid feeding hole, and the solid feeding hole is used for adding polyolefin solid.
According to the technical scheme of the invention, the reaction kettle further comprises a washing liquid feeding hole for feeding washing liquid.
Further, the reaction kettle also comprises a gas inlet for introducing pressurized gas.
When the device is used, the interfacial agent, the organic initiator and the maleic anhydride are added into the liquid preparation tank and are uniformly stirred to form a uniform and transparent solution; simultaneously adding polyolefin solid powder into a conical reactor (the conical reactor is a liquid mixer commonly used in the prior art), spraying the transparent solution into the conical reactor in the form of liquid drops through a sprayer by utilizing a booster pump, and stirring at high temperature for reaction to obtain a crude grafting product; and adding a washing solution and the coarse grafted product into the reaction kettle, pressurizing and pressing the mixture into a solid filter cake, and drying the solid filter cake to obtain a final product, namely the MAH grafted polyolefin.
According to the technical scheme of the invention, the conical reactor is selected from a vertical reactor, and the reaction substance is solid, so that if the conical reactor is not uniformly stirred, the inside of the reactor is excessively heated, the materials are not sufficiently mixed, and the problems of powder scorching or agglomeration, low grafting ratio and the like are caused. Preferably, in order to avoid the above problems, the conical reactor is a vertical reactor with strong stirring; for example, the conical reactor is selected from an anchor stirred tank reactor, a ribbon reactor or a vacuum rake reactor. Wherein, the conical reactor is not only used for mixing materials but also can be used as a reactor for grafting reaction, and the stirring mode is superior to the traditional common stirring mode.
Further, the device also comprises a first condenser, wherein the first condenser comprises an air inlet and a discharge hole; the conical reactor also comprises an air outlet, and the air outlet of the conical reactor is connected with the air inlet of the first condenser.
Further, the reaction kettle further comprises an air outlet, and the air outlet of the reaction kettle is connected with the air inlet of the first condenser.
Further, the first condenser is connected with a refrigerator, and the refrigerator is used for providing a condensing medium of the first condenser.
Further, reation kettle includes solid discharge gate and liquid discharge gate, and the solid discharge gate is used for the discharge of final product, and the liquid discharge gate is used for the discharge of washing liquid.
Further, the device also comprises a washing liquid storage tank, wherein the washing liquid storage tank comprises a feeding hole and a discharging hole; and the liquid discharge port of the reaction kettle and the discharge port of the first condenser are connected with the feed port of the washing liquid storage tank.
Further, a washing liquid buffer tank is arranged between a liquid discharge port of the reaction kettle and the washing liquid storage tank, and a third pump is arranged between the washing liquid buffer tank and the washing liquid storage tank.
Furthermore, a condensate storage tank is arranged between the first condenser and the washing liquid storage tank, and a fourth pump is arranged between the condensate storage tank and the washing liquid storage tank.
Further, a vacuum pump is arranged on the condensate storage tank and used for discharging gas in the condensate storage tank.
Further, the device still includes rectifying column and a plurality of holding vessel, the discharge gate and the rectifying column of washing liquid storage tank link to each other, the rectifying column links to each other with a plurality of holding vessels.
Further, the discharge gate of washing liquid storage tank with be equipped with the pre-heater between the rectifying column, set up a discharge gate and two at least pan feeding mouths on the rectifying column, the pre-heater includes the discharge gate, the discharge gate of pre-heater is connected with the first pan feeding mouth of rectifying column.
Further, the discharge hole of the rectifying tower is arranged at the upper part of the rectifying tower, for example, at the top of the rectifying tower.
Further, the plurality of storage tanks comprise an interface agent storage tank and a solvent storage tank; a discharge hole of the rectifying tower is sequentially connected with a second condenser, a reflux tank and the interfacial agent storage tank, and the discharge hole of the interfacial agent storage tank is connected with a feed inlet of the liquid preparation tank; the reflux tank is also connected with a material inlet of the solvent storage tank, and the material inlet of the solvent storage tank is also connected with a second material inlet of the rectifying tower through a sixth pump.
Further, a filter is arranged between the liquid preparation tank and the booster pump.
Further, a first screw conveyor is arranged between the conical reactor and the reaction kettle.
Further, the solid discharge port of the reaction kettle is connected with the hydraulic station and the second screw conveyor.
This application device obtains after the final product in reation kettle, the final product is followed reation kettle's solid discharge gate discharges, adds remaining filtrating in reation kettle again to the washing liquid storage tank in, simultaneously will, the waste gas in toper reactor and the reation kettle passes through first condenser condensation, lets in the condensate to the washing liquid storage tank in, mixes, obtains mixed liquid, will mixed liquid is leading-in to the rectifying column, and mixed liquid separates in the rectifying column, obtains interfacial agent, washing liquid and MAH to save respectively to a plurality of holding tanks in, retrieve reuse. The reaction kettle can complete reaction, washing, filtering and drying in sequence, and further reaction and product purification are realized. And the interfacial agent and the washing liquid enter a solvent recovery system, so that the interfacial agent and the washing liquid are reused.
The invention also aims to provide a preparation method of the polyolefin solid-phase grafted maleic anhydride, which specifically comprises the following steps:
s1: adding the interfacial agent, the organic initiator and the maleic anhydride into a liquid preparation tank, and uniformly stirring to form a uniform and transparent solution;
s2: adding polyolefin solid powder into a conical reactor, and heating and stirring uniformly under the protection of inert gas;
s3: spraying the transparent solution obtained in the step S1 in the form of liquid drops into the conical reactor, heating and stirring for reaction to obtain a crude grafting product;
s4: and (4) adding a washing solution and the crude grafting product obtained in the step S3 into the reaction kettle, and reacting to obtain a final product, namely the grafted MAH polyolefin.
According to the technical scheme of the invention, the method further comprises the following steps:
s5: adding the residual filtrate in the step S4 into a washing liquid storage tank, simultaneously condensing waste gas in the liquid preparation tank, the conical reactor and the reaction kettle through a first condenser, introducing the condensate into the washing liquid storage tank, and mixing to obtain a mixed liquid;
s6: and (4) introducing the mixed liquid obtained in the step (S5) into a rectifying tower, separating the mixed liquid in the rectifying tower, and recycling the separated interfacial agent, the washing liquid and the MAH.
According to the present invention, the interfacial agent in step S1 is an organic solvent having a function of dissolving or swelling polyolefin. For example, the organic solvent is selected from at least one of benzene, alkyl-substituted benzene, and decalin; the alkyl-substituted benzene may be C1-8Alkyl substituted benzene, the substitution can be mono-substitution or multi-substitution; example (b)For example, the alkyl-substituted benzene is at least one of toluene, xylene, and the like; the organic solvent is preferably benzene, toluene and/or xylene; toluene and xylene are more preferable. Wherein the interfacial agent is added in an amount of 0.1 to 30 wt%, preferably 10 to 25 wt%, illustratively 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt% of the mass of the polyolefin.
According to the technical scheme of the invention, the organic initiator in the step S1 is a peroxide or azo initiator; for example, the initiator is selected from one, two or more of lauroyl peroxide, benzoyl peroxide, cumene peroxide, benzoyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxide and azobisisobutyronitrile; further preferably the initiator has a half-life of 4-40min at 80-140 ℃; illustratively, the initiator is tert-butyl peroxybenzoate. Wherein the addition amount of the initiator is 0.1-10 wt%, preferably 1-9 wt%, and more preferably 4-7.5 wt% of the polyolefin; illustratively, the initiator is added in an amount of 0.5 wt%, 2 wt%, 5 wt%, 6.4 wt%, 8 wt%, 10 wt%.
According to the technical scheme of the invention, the Maleic Anhydride (MAH) in the step S1 is a commercial product. Wherein the addition amount of the MAH is 0.2-15 wt%, preferably 2-12 wt%, and more preferably 3-10 wt% of the polyolefin; illustratively, the MAH is added in an amount of 2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, or 10 wt%.
According to the technical scheme of the invention, a steam heating mode is selected when the interfacial agent, the initiator and the maleic anhydride are mixed in the step S1. Wherein the heating steam temperature is selected to be lower than the sublimation temperature of maleic anhydride at atmospheric pressure, preferably from 40 to 60 ℃, more preferably from 45 to 55 ℃, for example 50 ℃.
According to the technical scheme of the invention, the stirring time in the step S1 is not longer, for example, 3min-60min, more preferably 10min-30min, 15min-25 min; illustratively, the stirring time is 3min, 5min, 10min, 15min, 18min, 20min, 25min, 30min, 35min, 50 min. When the heating and stirring time is short, the maleic anhydride, the interfacial agent and the initiator are not uniformly mixed, and undissolved maleic anhydride still remains, which causes problems of spraying blockage and the like; when the heating and stirring time is longer, the initiator is decomposed to cause the problem of uncontrollable addition amount and the like.
According to the technical scheme of the invention, the polyolefin solid powder in the step S2 is selected from one, two or more of ethylene homopolymer or copolymer, propylene homopolymer or copolymer and butylene homopolymer or copolymer. For example, the comonomer of the copolymer is selected from one, two or more of alpha-olefins, such as one, two or more of ethylene, 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. Illustratively, the copolymer may be an ethylene-propylene copolymer, a propylene-butylene copolymer, an ethylene-butylene copolymer, or an ethylene-propylene-butylene terpolymer.
According to the technical scheme of the invention, the polyolefin in the step S2 is in a granular shape, and the viscosity-average molecular weight of the polyolefin is (1 x 10)3)-(1×107) Preferably (1X 10)4)-(6×106) (ii) a Illustratively, it has a viscosity average molecular weight of 5X 103、1×105、5×105、1×106、5×106。
According to the technical solution of the present invention, the stirring speed in step S2 is 100-160rpm, for example, 110-130rpm, and exemplarily, the stirring speed is 110rpm or 120 rpm;
according to the technical scheme of the invention, the inert gas in the step S2 can be selected from nitrogen and/or argon, and preferably is nitrogen.
According to the technical scheme of the invention, in step S3, the transparent solution in step S1 is sprayed into the conical reactor in the form of liquid drops by using a booster pump, and the mixture is stirred at high temperature for reaction to obtain a crude grafting product.
According to the technical scheme of the invention, in the step S3, the transparent solution needs to be filtered by a filter (preferably a Y-shaped filter) before being added into the reactor.
According to the technical scheme of the invention, the spraying time of the liquid drops in the step S3 is 10-30min, such as 15-25min, and exemplarily, the spraying time is 10min, 15min, 20min, and 25 min. Further, the spraying is accompanied with stirring, and stirring is continued for 0.5-1h after the spraying is finished, for example, stirring is continued for 0.5h, 0.6h, 0.8h and 1h, and the stirring rotation speed is consistent with that of the step S2.
According to the technical scheme of the invention, the heating mode in the step S3 can be steam or heat-conducting oil heating, and preferably steam heating. Wherein the reaction temperature is 80-140 ℃, such as 90-130 ℃, illustratively 105 ℃, 120 ℃, 125 ℃, 130 ℃; the reaction time is 5-300min, preferably 8-260min, more preferably 10-240 min. Illustratively, the reaction time is 5min, 20min, 40min, 60min, 100min, 120min, 150min, 180min, 200min, 240 min; the stirring speed in step S3 is 60-200rpm, preferably 80-150rpm, more preferably 100-120 rpm; illustratively, the stirring rotation speed is 80rpm, 100rpm, 105rpm, 110rpm, 115rpm, 120 rpm.
According to the technical scheme of the invention, the washing liquid in the step S3 is selected from a solvent which has good solubility for maleic anhydride and does not react with maleic anhydride, for example, the washing liquid is selected from one or two or more of ketones, ethers and esters, preferably acetone and/or ethyl acetate, and more preferably ethyl acetate. Further, the number of washing is not limited, and may be, for example, 1 time, 2 times or more, preferably 1 time.
According to the technical scheme of the invention, in the step S4, a washing solution and the crude grafting product obtained in the step S3 are added into a reaction kettle, pressed into a solid filter cake under pressure, and dried to obtain a final product, namely the grafted MAH polyolefin.
According to the technical scheme of the invention, the grafting ratio of the grafted MAH polyolefin is 0.5-10.5 wt%; for example, 2.0 to 8.0 wt%, 3.0 to 6.0 wt%; illustratively, the grafting yield is 3.0 wt% or 5.0 wt%.
The technical scheme of the invention has the beneficial effects that:
(1) on one hand, the characteristic that MAH is easy to be upgraded and the interfacial agent is easy to be gasified at high temperature is utilized, and most of the unreacted MAH and the interfacial agent are removed by vacuumizing the reactor; on the other hand, the grafting product after the first step is washed for 1 time by using ethyl acetate to remove the residual unreacted MAH by utilizing the good solubility of the MAH in the ethyl acetate. The method overcomes the defect that the crude grafting product is repeatedly washed by a large amount of acetone or water to remove the non-grafted MAH and the interfacial agent in the traditional method. Avoiding the use of acetone and high boiling point water, preventing the consumption of a large amount of energy in the later period when the separated water and the MAH are consumed, and preventing the environment from being polluted by a large amount of acid water.
(2) The method solves the problems that the residual MAH monomer and the odor thereof in the grafting product in industrial application can not be completely removed, a large amount of unreacted MAH and the interfacial agent can be recovered after being cooled, thereby realizing the recycling of materials, reducing the material cost, and solving the problems of environmental pollution, resource waste and the like caused by the emission of the MAH.
Drawings
FIG. 1 is a schematic structural diagram of the present application;
reference numerals: 1. a first pump; 2. preparing a liquid tank; 3. a filter; 4. a booster pump; 5. a conical reactor; 6. a second pump; 7. a first screw conveyor; 8. an air compressor; 9. a gas storage tank; 10. a reaction kettle; 11. a hydraulic station; 12. a second screw conveyor; 13. a washing liquid buffer tank; 14. a third pump; 15. a first condenser; 16. a condensate storage tank; 17. a fourth pump; 18. a washing liquid storage tank; 19. a freezer; 20. a vacuum pump; 21. a fifth pump; 22. a heavy component collection tank; 23. a preheater; 24. a rectifying tower; 25. a reboiler; 26. a sixth pump; 27. a second condenser; 28. a reflux tank; 29. a vacuum pump; 30. an interfacial agent storage tank; 31. a solvent storage tank; 32. a seventh pump; 33. and an eighth pump.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Unless otherwise specified, the percentages in the present invention are mass percentages.
The terms "first", "second", and the like in the present invention are used for distinction only and do not indicate a sequential order.
Example 1
As shown in figure 1, a device for polyolefin solid phase grafting maleic anhydride comprises a liquid preparation tank 2, a conical reactor 5 and a reaction kettle 10;
a sprayer and a heating device are arranged in the conical reactor 5, a liquid feeding port (used for introducing materials in the liquid preparation tank), a discharging port, an air outlet and an air inlet are arranged on the conical reactor 5, and the discharging port of the conical reactor 5 is connected with the reaction kettle 10;
the conical reactor further comprises a solids feed inlet for the addition of polyolefin solids;
the liquid preparation tank 2 is provided with a discharge port and a feed port, and preferably, the feed port of the liquid preparation tank 2 is provided with a first pump 1; the discharge hole of the liquid preparation tank 2 is connected with the sprayer of the conical reactor 5 through a liquid feeding hole by a booster pump 4, preferably, a filter 3 is arranged between the liquid preparation tank 2 and the booster pump 4, and the filter 3 is used for filtering solid impurities in the liquid preparation tank 2;
the reaction kettle 10 comprises an air inlet, an air outlet, a feeding port, a washing liquid feeding port, a liquid discharging port and a solid discharging port, and preferably, the air inlet of the reaction kettle 10 is sequentially provided with an air compressor 8 and an air storage tank 9 from left to right; preferably, a second pump 6 is further arranged at a washing liquid feed inlet of the reaction kettle 10; preferably, a first screw conveyor 7 is arranged between the discharge hole of the conical reactor 5 and the feed inlet of the reaction kettle 10;
the device also comprises a first condenser 15, wherein the first condenser 15 comprises an air inlet and a discharge hole; the gas outlet of the conical reactor and the gas outlet of the reaction kettle are both connected with the gas inlet of the first condenser 15; the first condenser 15 is connected with a refrigerator 19, and the refrigerator 19 is used for providing a condensing medium of the first condenser;
the apparatus further comprises a washing liquid storage tank 18; the washing liquid storage tank comprises a feeding hole and a discharging hole;
preferably, a liquid discharge port of the reaction kettle 10 and a discharge port of the first condenser 15 are both connected with a washing liquid storage tank 18;
the device also comprises a rectifying tower and a plurality of storage tanks, wherein a discharge hole of the washing liquid storage tank 18 is connected with the rectifying tower 24, and the rectifying tower 24 is connected with the plurality of storage tanks; preferably, the plurality of storage tanks includes an interfacial agent storage tank 30 and a solvent storage tank 31.
Specifically, the reaction kettle further comprises a gas inlet for introducing pressurized gas; the washing liquid feed inlet is used for the interpolation of washing liquid.
In one embodiment of the present application, the solids outlet of the reaction vessel 10 is connected to a hydraulic station 11 and a second screw conveyor 12.
In one embodiment of the present application, a washing liquid buffer tank 13 is disposed between the reaction kettle 10 and the washing liquid storage tank 18, and a third pump 14 is disposed between the washing liquid buffer tank 13 and the washing liquid storage tank 18.
In one embodiment of the present application, a condensate storage tank 16 and a fourth pump 17 are disposed between the first condenser 15 and the washing liquid storage tank 18, a vacuum pump 20 is disposed on the condensate storage tank 16, and the vacuum pump 20 is used for exhausting gas in the condensate storage tank.
In one embodiment of the present application, a preheater 23 and a fifth pump 21 are provided between the outlet of the scrubbing liquid storage tank 18 and the rectifying tower 24.
In one embodiment of the present application, the rectifying tower 24 is provided with at least two feeding ports and at least two discharging ports, that is, at least a first feeding port, a second feeding port, a first discharging port and a second discharging port; the preheater 23 comprises a discharge port, the discharge port of the preheater 23 is connected with a first feeding port of the rectifying tower 24, and a solid discharge port of the preheater 23 is connected with the heavy component collecting tank 22. Preferably, the first discharge hole of the rectifying tower is arranged at the upper part of the rectifying tower, and the second discharge hole is arranged at the lower part of the rectifying tower. Preferably, the first feeding port of the rectifying tower is arranged in the middle of the rectifying tower, and the second feeding port is arranged at the upper part of the rectifying tower. Preferably, the second discharge port of the rectifying tower 24 is connected to the heavy component collecting tank 22 through the solid discharge port of the preheater 23.
In an embodiment of this application, the first discharge gate of rectifying column 24 connects gradually and is equipped with second condenser 27, backflow tank 28 and interfacial agent storage tank 30, backflow tank 28 still with solvent storage tank 31 pan feeding mouth is connected, set up vacuum pump 29 on the backflow tank 28, will gaseous the discharging in the backflow tank 28.
In one embodiment of the present application, the outlet of the interfacial agent storage tank 30 is connected to the inlet of the dispensing tank 2 by a seventh pump 32 (the connection is prior art, e.g., a pipe connection, which is not shown in fig. 1).
In one embodiment of the present application, the inlet of the solvent storage tank 31 is further connected to the second inlet of the rectifying tower 24 through a sixth pump 26; the outlet of the solvent storage tank 31 is connected to the inlet of the reaction kettle 10 by an eighth pump 33 (the connection is prior art, for example, a pipe connection, which is not shown in fig. 1).
In one embodiment of the present application, the rectifying column 24 is further provided with a reboiler 25, and an outlet of the reboiler 25 is connected with an inlet of the rectifying column 24 (for example, arranged at a lower part of the rectifying column 24); a second discharge port of the rectifying tower 24 is connected to a feed port of the reboiler 25 while being connected to the heavy component collecting tank 22 through a solid discharge port of the preheater 23. The outlet of the reboiler 25 is also connected to the inlet of the preheater 23 (this connection is prior art, for example by means of a pipe connection, not shown in the figure).
Example 2
A preparation method of polyolefin solid-phase grafted maleic anhydride adopts the device of example 1, and specifically comprises the following steps:
s1: adding an interfacial agent xylene, an organic initiator azobisisobutyronitrile and Maleic Anhydride (MAH) into a liquid preparation tank, heating by steam at 50 ℃, and stirring for 30min to form a uniform transparent solution; the adding amount of the toluene is 10 wt% of the polyolefin, and the adding amount of the initiator is 0.5 wt% of the polyolefin; the adding amount of the MAH is 5 wt% of the polyolefin;
s2: mixing solid polyolefin powder, such as polyethylene (viscosity average molecular weight of 1 × 10)5) Adding the mixture into a conical reactor, and heating and uniformly stirring the mixture under the protection of inert gas at the stirring speed of 110 rpm;
s3: spraying the transparent solution obtained in the step S1 in the form of liquid drops into the conical reactor by using a booster pump, wherein the spraying time of the liquid drops is 20min, the stirring is carried out while spraying, and after the spraying is finished, the stirring is continued for 60min at 90 ℃ and the stirring speed is 100rpm, so as to obtain a crude grafting product;
s4: adding washing liquid ethyl acetate and the crude grafting product obtained in the step S3 into a reaction kettle, pressing the mixture into a solid filter cake under pressure, and drying the solid filter cake to obtain a final product, namely the polyolefin grafted MAH;
s5: adding the residual filtrate in the step S4 into a washing liquid storage tank, simultaneously condensing waste gas in the liquid preparation tank, the conical reactor and the reaction kettle through a first condenser, introducing the condensate into the washing liquid storage tank, and mixing to obtain a mixed liquid;
s6: and (4) introducing the mixed liquid obtained in the step (S5) into a rectifying tower, separating the mixed liquid in the rectifying tower, and recycling the xylene, the ethyl acetate and the MAH.
The method for testing the grafting rate of the polypropylene grafted maleic anhydride comprises the following steps:
firstly, testing the grafting ratio:
(1) 1g of dried refined polypropylene grafted maleic anhydride sample is accurately weighed, placed in a 250mL flask, added with 80mL of xylene, and heated and refluxed until being dissolved.
(2) After dissolution, an excess of 0.1mol/L KOH-ethanol solution was added, and the mixture was heated under reflux for 2 hours, followed by titration with 0.1mol/L HCl-isopropanol solution using phenolphthalein as an indicator.
(3) The amount of alkali added and the amount of acid consumed for neutralization were recorded, and the grafting ratio of the solid phase graft reaction product was calculated according to the following formula.
MAH(％)＝9.806*[C1V1-C2V2)]/2m，
In the formula: c. C1The concentration of KOH-ethanol solution is mol/L; v1The volume of the excess KOH-ethanol solution, mL; c. C2The concentration is HCl-isopropanol solution, mol/L; v2The volume of HCl-isopropanol solution consumed for titration of neutralizing base, mL; m is the mass of polypropylene grafted maleic anhydride, g.
The grafting rate of the polyolefin grafted MAH prepared by the method is 0.5-10.5 wt%.
Secondly, measuring the odor of the graft:
(1) weighing 20 +/-2 g of the polypropylene grafted maleic anhydride obtained in the embodiment, respectively putting the polypropylene grafted maleic anhydride into a smell bottle, tightly covering the smell bottle, putting the smell bottle into an oven with constant temperature of 80 +/-2 ℃ and forced ventilation, keeping the temperature of 80 +/-2 ℃ for 2 hours, and quickly opening the cover of the smell bottle when the temperature of the oven is cooled to 60 +/-5 ℃ for smell evaluation.
(2) In order to make the evaluation objective, the number of people to be evaluated is required to be at least 3, the distance between samples and people is 0.5m, and the test time of each person is 1 min.
(3) Detection result evaluation grading
Evaluation of odor all possible variables can be scored according to a rating scale (as shown in table 1) with scores of 1 to 4.
Table 1.
The polyolefin grafted MAH prepared by the method is grade 1.
And thirdly, determination of the recovery rate of the MAH and the interfacial agent:
(1) samples were taken from the first condenser discharge and the condensate was chromatographed for the ratio of interfacial agent to MAH. And after the condensate liquid is returned to the liquid preparation tank, the liquid level of the liquid preparation tank is accurately measured. Further calculate MAH (m) in the first step1) And an interfaceContent of agent (m)2)。
(2) And (3) after the MAH in the flash evaporation kettle is sent into the liquid preparation tank, accurately metering the liquid level of the liquid preparation tank. Further calculating the MAH content (m) in the second step3)。
MAH recovery (%) ═ m1+m3)/M，
In the formula: m is the mass of MAH initially charged, g.
The recovery rate (%) of the interfacial agent is m2/N，
In the formula: n is the initial mass of the interfacial agent, g.
The recovery rates of MAH and the xylene as an interfacial agent in the present application are 80% and 95%, respectively.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The device for grafting maleic anhydride on the polyolefin solid phase is characterized by comprising a liquid preparation tank, a conical reactor and a reaction kettle;
a sprayer and a heating device are arranged in the conical reactor, the conical reactor also comprises a discharge hole, and the discharge hole of the conical reactor is connected with the reaction kettle;
the liquid preparation tank comprises a discharge port, and the discharge port of the liquid preparation tank is connected with a sprayer of the conical reactor through a booster pump.
2. The device for the solid-phase grafting of maleic anhydride on polyolefin according to claim 1, further comprising a first condenser, wherein the first condenser comprises a gas inlet and a discharge port;
the conical reactor also comprises an air outlet, and the reaction kettle also comprises an air outlet; and the gas outlet of the conical reactor and the gas outlet of the reaction kettle are connected with the gas inlet of the first condenser.
3. The apparatus for solid phase grafting maleic anhydride onto polyolefin according to claim 2, wherein the first condenser is connected to a refrigerator.
4. The device for the solid-phase grafting of maleic anhydride on polyolefin according to any one of claims 1 to 3, further comprising a washing liquid storage tank, wherein the washing liquid storage tank comprises a feeding port and a discharging port;
the reaction kettle comprises a liquid discharge port, and the liquid discharge port of the reaction kettle is connected with a feed port of the washing liquid storage tank; and/or the discharge hole of the first condenser is connected with the feed inlet of the washing liquid storage tank.
5. The device for the solid-phase grafting of maleic anhydride onto polyolefin according to claim 4, further comprising a rectifying tower and a plurality of storage tanks, wherein the discharge port of the washing liquid storage tank is connected with the rectifying tower, and the rectifying tower is connected with the plurality of storage tanks.
6. The device for grafting maleic anhydride onto polyolefin in a solid phase according to claim 5, wherein a preheater is disposed between the discharge port of the washing liquid storage tank and the rectifying tower, the rectifying tower is provided with at least two feeding ports and one discharge port, and the discharge port of the preheater is connected to the first feeding port of the rectifying tower.
7. A method for preparing polyolefin solid-phase grafted maleic anhydride, which is characterized by adopting the device of claim 5, and comprises the following steps:
s1: adding the interfacial agent, the organic initiator and the maleic anhydride into a liquid preparation tank, and uniformly stirring to form a uniform and transparent solution;
s2: adding polyolefin solid powder into a conical reactor, and heating and stirring uniformly under the protection of inert gas;
s3: spraying the transparent solution obtained in the step S1 in the form of liquid drops into the conical reactor, heating and stirring for reaction to obtain a crude grafting product;
s4: and (4) adding a washing solution and the crude grafting product obtained in the step S3 into the reaction kettle, and reacting to obtain a final product, namely the grafted MAH polyolefin.
8. The method according to claim 7, wherein the organic initiator in step S1 is a peroxide or azo initiator; the initiator is at least one selected from lauroyl peroxide, benzoyl peroxide, cumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide and azobisisobutyronitrile.
9. The method according to claim 8, wherein the solid polyolefin powder in step S2 is at least one selected from ethylene homo-or copolymer, propylene homo-or copolymer, and butene homo-or copolymer.
10. The method according to claim 8, wherein the washing solution in step S3 is selected from acetone and/or ethyl acetate.
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| CN115181200B (en) * | 2022-07-06 | 2023-11-07 | 中国石油天然气股份有限公司 | Preparation method of C4-C8 alpha-mono-olefin-maleic anhydride copolymer |
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