CN113980186B - 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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- CN113980186B CN113980186B CN202010734589.3A CN202010734589A CN113980186B CN 113980186 B CN113980186 B CN 113980186B CN 202010734589 A CN202010734589 A CN 202010734589A CN 113980186 B CN113980186 B CN 113980186B
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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 73
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000007790 solid phase Substances 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000003860 storage Methods 0.000 claims description 63
- 238000005406 washing Methods 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 30
- 239000007787 solid Substances 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
- 239000003999 initiator Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000007789 gas 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
- 230000008569 process Effects 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- 239000002904 solvent Substances 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 14
- 229920001155 polypropylene Polymers 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 polypropylene Polymers 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 235000019645 odor Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 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
- 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 2
- 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
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 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
- 125000000524 functional group Chemical group 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
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 150000001412 amines Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000008064 anhydrides 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
- 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 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
- 238000002309 gasification 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 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
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 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
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 238000010998 test method Methods 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
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
Landscapes
- 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 application discloses a preparation method and a device of polyolefin solid-phase grafting maleic anhydride, wherein the device comprises a liquid preparation tank, a conical reactor and a reaction kettle; the conical reactor is internally provided with a sprayer and a heating device, and also comprises a discharge port, and the discharge port 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. The device and the preparation method can solve the problem of waste of unreacted monomers and interface agents, realize recycling of materials, and simultaneously realize higher grafting rate of the prepared polyolefin grafted MAH.
Description
Technical Field
The invention belongs to the field of polyolefin, and particularly relates to a preparation method and a device for solid-phase grafting maleic anhydride on polyolefin.
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, polyolefin materials have large shrinkage, strong water absorption, poor dimensional stability, and poor compatibility with other polymer materials or inorganic fillers, which limits the application field of polyolefin materials. By modifying the 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 can be improved.
Maleic Anhydride (MAH) is a polar compound containing various functional groups, unsaturated double bonds are contained in the molecular structure, and the Maleic Anhydride (MAH) is easy to carry out polymerization reaction with other polymers under the action of an initiator; the anhydride group can also react with functional groups such as hydroxyl, carboxyl, amine, etc. Thus, MAH functionalization of some non-polar polymers is beneficial to increasing compatibility with polar polymers, improving adhesion of materials, improving interactions 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 the post-treatment is complex due to the use of a large amount of solvent, 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 unreacted MAH and the like, so that the performance of a post-processing product is seriously influenced. The solid phase grafting is carried out under the melting temperature of the polymer, has the advantages of low reaction temperature, less polyolefin degradation, convenient operation, high grafting rate of the product, no or less use of solvent, no environmental pollution and the like, and is a grafting method with very good development prospect. The first two types are surface grafts of molded products, so-called powder grafts, which are classified into film grafts, fiber grafts and powder grafts according to the morphology of the grafted polyolefin.
Patent document CN1704436 discloses a continuous solid-phase grafting production method and device for polyolefin, and the document mentions that various raw materials are continuously added into a horizontal or vertical reactor with a stirrer for reaction, and the raw materials are subjected to washing, filtering, drying and other working procedures to obtain grafted modified polyolefin, wherein the stirrer adopted by the reactor with the stirrer is provided with two spiral belts with opposite inner and outer spiral directions, so that the material pushing directions in the reactor are opposite, and the reaction efficiency is improved. The grafting rate of the product obtained by carrying out solid phase grafting on the polyolefin by adopting the method can reach more than 1%, but a great amount of acid wastewater is generated in the washing process, and a great amount of unreacted MAH is dissolved in water, so that the environment is polluted and the resource is wasted.
Liu Huayan et al studied the process of preparing maleic anhydride graft modified polypropylene by solid phase graft copolymerization in an internal circulation impinging stream reactor (Liu Huayan et al, research on modification of polypropylene by solid phase graft copolymerization in an internal circulation impinging stream reactor, university of Zhejiang industrial university, 2004, 32, 4:423-427), wherein the method is that solid particles can accelerate, impinge and react for a plurality of times in a central tube by adding a circulating annular chamber of the solid particles in the reactor in the internal circulation impinging stream reactor, thereby achieving forced mixing and prolonging the residence time of the particles in the reactor. The reactor is used for the solid-phase grafting modification of polypropylene (PP), so that PP particles are impacted with atomized solvent liquid drops accelerated by air flow after the air flow is accelerated by the central tube, and the PP particles and the solvent are fully contacted and mixed; while mixing, PP and comonomer are subjected to graft copolymerization under the action of an initiator and a surfactant (solvent). Although the use of the reactor can improve the conditions of uneven temperature and concentration distribution in the reactor, shorten the reaction time and improve the grafting rate or reduce the solvent consumption to a certain extent, the problems of incapability of effectively improving the grafting rate of polypropylene in the impinging stream reactor, high processing difficulty of the impinging stream reactor and the like limit the industrialization of the method.
Wang Liwei, and the like, adopts a double-blade stirring powder reactor to carry out continuous amplification production of polyolefin solid-phase grafting Maleic Anhydride (MAH) (Wang Liwei, and the like, research on polypropylene solid-phase grafting maleic anhydride, university of great company, university of Chinese scholars, 2008), the production process comprises three reactors, connecting the three reactors in series, keeping different constant temperature conditions in each reactor, adding a catalyst into a first reactor in a spraying manner after dissolving xylene in advance for a certain time, discharging to a second reactor, stirring in an inert gas atmosphere for a certain time, and finally discharging to a third reactor for a certain time, and washing and drying to obtain the grafting rate of the product of 1.6%. The reactor breaks through the limitation of the traditional intermittent production method and can realize semi-continuous production, but the production process needs to introduce the generated waste gas into the acetone solution, and the waste liquid needs to be separated and recycled for acetone, the acetone is a control reagent, and the waste liquid separation can cause high energy consumption and higher production cost.
Disclosure of Invention
The invention aims to solve the problems that the grafting rate is low, unreacted monomers cannot be completely removed and raw materials are wasted, and provides a preparation method and a device for polyolefin solid-phase grafting maleic anhydride.
Specifically, the invention firstly provides a device for solid-phase grafting of maleic anhydride on polyolefin, which comprises a liquid preparation tank, a conical reactor and a reaction kettle;
the conical reactor is internally provided with a sprayer and a heating device, and also comprises a discharge port, and the discharge port 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 further comprises a solid feed inlet, and the solid feed inlet is used for adding polyolefin solids.
According to the technical scheme of the invention, the reaction kettle further comprises a washing liquid feeding port for adding washing liquid.
Further, the reaction kettle also comprises an air inlet for introducing pressurized gas.
When the device is used, the interfacial agent, the organic initiator and the maleic anhydride are added into a liquid preparation tank and uniformly stirred to form uniform 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 by using a booster pump, and stirring at high temperature for reaction to obtain a crude grafting product; and adding the washing liquid and the crude grafting product into a reaction kettle, pressurizing and pressing to form a solid filter cake, and drying to obtain a final product, namely the MAH grafted polyolefin.
According to the technical scheme of the invention, the conical reactor is selected from vertical reactors, and because the state of the reacted substances is solid, if the conical reactor is unevenly stirred, the reactor is excessively heated, the materials are insufficiently mixed, and the problems of scorching or agglomeration of powder, lower grafting rate and the like are caused. Preferably, 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 further 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 to a chiller for providing a condensing medium of the first condenser.
Further, the reaction kettle comprises a solid discharge port and a liquid discharge port, wherein the solid discharge port is used for discharging a final product, and the liquid discharge port is used for discharging washing liquid.
Further, the device also comprises a washing liquid storage tank, wherein the washing liquid storage tank comprises a feed inlet and a discharge outlet; the liquid discharge port of the reaction kettle and the discharge port of the first condenser are connected with the feed inlet of the washing liquid storage tank.
Further, a washing liquid buffer tank is arranged between the 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.
Further, 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 is used for discharging gas in the condensate storage tank.
Further, the device also comprises 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.
Further, a preheater is arranged between the discharge port of the washing liquid storage tank and the rectifying tower, a discharge port and at least two feed ports are arranged on the rectifying tower, the preheater comprises a discharge port, and the discharge port of the preheater is connected with the first feed port of the rectifying tower.
Further, the discharge port of the rectifying tower is arranged at the upper part of the rectifying tower, for example, at the top of the tower.
Further, the plurality of storage tanks include an interfacial agent storage tank and a solvent storage tank; the discharge port of the rectifying tower is sequentially connected with a second condenser, a reflux tank and the interfacial agent storage tank, and the discharge port of the interfacial agent storage tank is connected with the feed port of the liquid preparation tank; the reflux tank is also connected with the feed inlet of the solvent storage tank, and the feed inlet of the solvent storage tank is also connected with the second feed 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 conveyer is arranged between the conical reactor and the reaction kettle.
Further, a solid discharge port of the reaction kettle is connected with a hydraulic station and a second screw conveyor.
After the device obtains a final product in a reaction kettle, the final product is discharged from a solid discharge port of the reaction kettle, residual filtrate in the reaction kettle is added into a washing liquid storage tank, waste gas in a conical reactor and the reaction kettle is condensed through a first condenser, condensate is introduced into the washing liquid storage tank and mixed to obtain mixed liquid, the mixed liquid is introduced into a rectifying tower, the mixed liquid is separated in the rectifying tower to obtain an interface agent, the washing liquid and MAH, and the interface agent, the washing liquid and the MAH are respectively stored into a plurality of storage tanks for recycling. The reaction kettle can sequentially complete the reaction, washing, filtering and drying, and further realize the reaction and the purification of the product. The interfacial agent and the cleaning solution enter a solvent recovery system, so that the interfacial agent and the cleaning solution 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 an interfacial agent, an organic initiator and maleic anhydride into a liquid preparation tank, and uniformly stirring to form a uniform 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 in the step S1 into the conical reactor in the form of liquid drops, and heating and stirring to react to obtain a crude grafting product;
s4: and (3) adding the washing liquid and the crude grafting product obtained in the step (S3) into a 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, condensing waste gas in a liquid preparation tank, a conical reactor and a reaction kettle through a first condenser, introducing condensate into the washing liquid storage tank, and mixing to obtain mixed liquid;
S6: and (3) introducing the mixed solution in the step (S5) into a rectifying tower, separating the mixed solution in the rectifying tower, and recycling the separated interfacial agent, washing solution and MAH.
According to the present invention, the interfacial agent in step S1 is an organic solvent having a solubility or swelling for 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 a C 1-8 alkyl substituted benzene, the substitution may be mono-or poly-substituted; 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 30wt%, preferably 10 to 25wt%, and illustratively 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, 30wt% of the polyolefin mass.
According to the technical scheme of the invention, the organic initiator in the step S1 is 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 to 40 minutes at 80 to 140 ℃; illustratively, the initiator is t-butyl peroxybenzoate. Wherein the initiator is added in an amount of 0.1 to 10wt%, preferably 1 to 9wt%, more preferably 4 to 7.5wt% based on the mass of the polyolefin; illustratively, the initiator is added in an amount of 0.5wt%, 2wt%, 5wt%, 6.4wt%, 8wt%, 10wt%.
According to the technical scheme of the invention, the Maleic Anhydride (MAH) in the step S1 is a commercial product. Wherein the MAH is added in an amount of 0.2 to 15wt%, preferably 2 to 12wt%, more preferably 3 to 10wt% based on the mass of the polyolefin; illustratively, the MAH is added in an amount of 2wt%, 4wt%, 5wt%, 6wt%, 8wt% or 10wt%.
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 normal pressure, preferably 40-60 ℃, more preferably 45-55 ℃, for example 50 ℃.
According to the technical scheme of the invention, the stirring time in the step S1 is not excessively long, for example, 3min-60min, more preferably 10min-30min and 15min-25min; illustratively, the stirring time is 3min, 5min, 10min, 15min, 18min, 20min, 25min, 30min, 35min, 50min. When the heating and stirring time is short, the maleic anhydride, the interfacial agent and the initiator are unevenly mixed, and undissolved maleic anhydride still remains, so that the problems of spray blockage and the like are caused; when the heating and stirring time is long, the initiator is decomposed, so that the adding amount is uncontrollable and the like.
According to an aspect of the present invention, the polyolefin solid powder described in step S2 is selected from one, two or more of ethylene homo-or copolymer, propylene homo-or copolymer, butene homo-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 multiplied by 10 3)-(1×107), preferably (1 multiplied by 10 4)-(6×106); illustratively, the viscosity average molecular weight is 5X 10 3、1×105、5×105、1×106、5×106.
According to the solution of the present invention, the stirring speed in step S2 is 100-160rpm, for example 110-130rpm, and exemplary stirring speeds are 110rpm or 120rpm;
According to the solution of the present invention, the inert gas in step S2 may be selected from nitrogen and/or argon, preferably nitrogen.
According to the technical scheme of the invention, in the step S3, the transparent solution in the step S1 is sprayed and added into the conical reactor in the form of liquid drops by using a booster pump, and the raw grafting product is obtained through high-temperature stirring reaction.
According to the solution of the present invention, in step S3, the transparent solution is filtered through a filter (preferably a Y-filter) before being fed 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, for example 15-25min, and the spraying time is 10min, 15min, 20min and 25min. Further, stirring is carried out during spraying, 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 rotating speed is kept consistent with that in 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, and steam heating is preferred. Wherein the reaction temperature is 80-140 ℃, e.g., 90-130 ℃, illustratively 105 ℃, 120 ℃, 125 ℃, 130 ℃; the reaction time is 5 to 300min, preferably 8 to 260min, more preferably 10 to 240min. Illustratively, the reaction time is 5min, 20min, 40min, 60min, 100min, 120min, 150min, 180min, 200min, 240min; the stirring speed in step S3 is 60 to 200rpm, preferably 80 to 150rpm, more preferably 100 to 120rpm; exemplary stirring speeds are 80rpm, 100rpm, 105rpm, 110rpm, 115rpm, 120rpm.
According to the technical scheme of the invention, the washing liquid in the step S3 is selected from solvents which have good solubility to maleic anhydride and do not react with maleic anhydride, for example, the washing liquid is selected from one, two or more of ketones, ethers and esters, preferably acetone and/or ethyl acetate, and more preferably ethyl acetate. Further, the number of times of the 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 in the step S3 are added into a reaction kettle, and are pressed into a solid filter cake by pressurization, and are dried to obtain a final product, namely the grafted MAH polyolefin.
According to the technical scheme of the invention, the grafting rate of the grafted MAH polyolefin is 0.5-10.5wt%; for example 2.0-8.0wt%, 3.0-6.0wt%; illustratively, the grafting ratio is 3.0wt% or 5.0wt%.
The technical scheme of the invention has the beneficial effects that:
(1) On one hand, the invention utilizes the characteristics of easy rising of MAH and easy gasification of the interfacial agent at high temperature, and removes most of unreacted MAH and interfacial agent by vacuumizing the reactor; on the other hand, the MAH has good solubility in ethyl acetate, and the residual unreacted MAH can be removed by washing the grafted product after the first step with ethyl acetate for 1 time. The method overcomes the defect that a large amount of acetone or water is used for repeatedly washing the crude grafted product to remove ungrafted MAH and interfacial agent in the traditional method. The use of acetone and high boiling water is avoided, a large amount of energy is prevented from being consumed in the later stage when separating water and MAH is consumed, and a large amount of acidic water is generated to pollute the environment.
(2) The invention solves the problems that the residual MAH monomer and the smell thereof can not be completely removed in the industrial application of the grafted product, and a large amount of unreacted MAH and interface agent can be recovered after being cooled, thereby realizing the recycling of materials, reducing the material cost, solving the problems of environmental pollution and resource waste caused by MAH emission, and the like.
Drawings
FIG. 1 is a schematic diagram of the structure of the present application;
Reference numerals: 1. a first pump; 2. a liquid preparation 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 drum; 29. a vacuum pump; 30. an interface agent storage tank; 31. a solvent storage tank; 32. a seventh pump; 33. and an eighth pump.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Unless otherwise specified, percentages in the present invention are mass percentages.
The "first", "second", and the like in the present invention are used only for distinction, and do not indicate the order of precedence.
Example 1
As shown in FIG. 1, the device for solid-phase grafting of the maleic anhydride on the polyolefin 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 inlet (for introducing materials in a liquid preparation tank), a discharge port, an air outlet and an air inlet are arranged on the conical reactor 5, and the discharge port of the conical reactor 5 is connected with the reaction kettle 10;
the conical reactor also comprises a solid feed inlet, wherein the solid feed inlet is used for adding polyolefin solids;
A discharge port and a feed port are arranged on the liquid preparation tank 2, and preferably, a first pump 1 is arranged at the feed port of the liquid preparation tank 2; the discharge port of the liquid preparation tank 2 is connected with the sprayer of the conical reactor 5 through a liquid inlet 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 of the liquid preparation tank 2;
The reaction kettle 10 comprises an air inlet, an air outlet, a feed inlet, a washing liquid feed inlet, a liquid discharge outlet and a solid discharge outlet, 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, the washing liquid feeding port of the reaction kettle 10 is also provided with a second pump 6; preferably, a first screw conveyer 7 is arranged between the discharge port of the conical reactor 5 and the feed port 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 port; the air outlet of the conical reactor and the air outlet of the reaction kettle are connected with the air 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 reservoir 18; the washing liquid storage tank comprises a feed inlet and a discharge outlet;
Preferably, the liquid outlet of the reaction kettle 10 and the outlet of the first condenser 15 are connected with a washing liquid storage tank 18;
The device also comprises a rectifying tower and a plurality of storage tanks, wherein the discharge port 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 interface agent storage tank 30 and a solvent storage tank 31.
Specifically, the reaction kettle further comprises an air inlet for introducing pressurized gas; the washing liquid feed inlet is used for adding washing liquid.
In one embodiment of the application, the solid discharge port of the reaction kettle 10 is connected with a hydraulic station 11 and a second screw conveyor 12.
In one embodiment of the present application, a washing solution buffer tank 13 is disposed between the reaction kettle 10 and the washing solution storage tank 18, and a third pump 14 is disposed between the washing solution buffer tank 13 and the washing solution 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, and a vacuum pump 20 is disposed on the condensate storage tank 16, and the vacuum pump 20 is used for discharging gas in the condensate storage tank.
In one embodiment of the application, a preheater 23 and a fifth pump 21 are arranged between the outlet of the washing liquid storage tank 18 and the rectifying column 24.
In one embodiment of the present application, the rectifying tower 24 is provided with at least two feed inlets and at least two discharge outlets, i.e. at least comprises a first feed inlet, a second feed inlet, a first discharge outlet and a second discharge outlet; the preheater 23 comprises a discharge hole, the discharge hole of the preheater 23 is connected with a first feed hole of the rectifying tower 24, and the solid discharge hole of the preheater 23 is connected with the heavy component collecting tank 22. Preferably, the first discharge port of the rectifying tower is arranged at the upper part of the rectifying tower, and the second discharge port is arranged at the lower part of the rectifying tower. Preferably, the first feed inlet of the rectifying tower is arranged in the middle of the rectifying tower, and the second feed inlet is arranged at the upper part of the rectifying tower. Preferably, the second outlet of the rectifying tower 24 is connected to the heavy component collecting tank 22 through the solid outlet of the preheater 23.
In one embodiment of the present application, the first outlet of the rectifying tower 24 is sequentially connected with a second condenser 27, a reflux tank 28 and an interfacial agent storage tank 30, the reflux tank 28 is further connected with the inlet of the solvent storage tank 31, and a vacuum pump 29 is disposed on the reflux tank 28 to discharge the gas in the reflux tank 28.
In one embodiment of the present application, the outlet of the interface agent storage tank 30 is connected to the inlet of the liquid preparation tank 2 by a seventh pump 32 (the connection is in the prior art, for example, a pipe connection, and the connection 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 column 24 by a sixth pump 26; the discharge port of the solvent storage tank 31 is connected to the feed port of the reaction kettle 10 by an eighth pump 33 (the connection mode is a prior art, for example, a pipe connection, and the connection mode is not shown in fig. 1).
In one embodiment of the present application, the rectifying tower 24 is further provided with a reboiler 25, and an air outlet of the reboiler 25 is connected to an air inlet of the rectifying tower 24 (for example, disposed at a lower portion of the rectifying tower 24); the second outlet of the rectifying tower 24 is connected to the inlet of the reboiler 25, while the solid outlet of the preheater 23 is connected to the heavy component collecting tank 22. The outlet of reboiler 25 is also connected to the inlet of preheater 23 (this connection is conventional, for example by means of a pipe connection, not shown).
Example 2
A method for preparing polyolefin solid-phase grafted maleic anhydride by adopting the device of the embodiment 1, which specifically comprises the following steps:
s1: adding an interfacial agent of dimethylbenzene, an organic initiator of azobisisobutyronitrile and Maleic Anhydride (MAH) into a liquid preparation tank, heating by steam at 50 ℃, and stirring for 30min to form a uniform and transparent solution; the addition amount of toluene is 10wt% of the mass of polyolefin, and the addition amount of the initiator is 0.5wt% of the mass of polyolefin; the MAH is added in an amount of 5wt% based on the mass of the polyolefin;
S2: adding polyolefin solid powder such as polyethylene (viscosity average molecular weight of 1×10 5) into a conical reactor, heating under inert gas protection, stirring uniformly at 110rpm;
S3: spraying the transparent solution in the step S1 into the conical reactor in the form of liquid drops by using a booster pump, wherein the spraying time of the liquid drops is 20min, stirring is carried out while spraying, and after spraying is finished, the stirring is continued for 60min at 90 ℃, and the stirring speed is 100rpm, so that a crude grafting product is obtained;
s4: adding washing liquid ethyl acetate and the crude grafting product obtained in the step S3 into a reaction kettle, pressurizing and pressing to form a solid filter cake, and drying to obtain a final product, namely the polyolefin grafting MAH;
s5: adding the residual filtrate in the step S4 into a washing liquid storage tank, condensing waste gas in a liquid preparation tank, a conical reactor and a reaction kettle through a first condenser, introducing condensate into the washing liquid storage tank, and mixing to obtain mixed liquid;
S6: and (5) introducing the mixed solution in the step (S5) into a rectifying tower, separating the mixed solution in the rectifying tower, and recycling and reutilizing the dimethylbenzene, the ethyl acetate and the MAH.
The grafting rate test method of the prepared polypropylene grafted maleic anhydride comprises the following steps:
1. And (3) testing the grafting rate:
(1) 1g of dried refined polypropylene grafted maleic anhydride sample is accurately weighed, placed in a 250mL flask, 80mL of xylene is added, and heated and refluxed until dissolved.
(2) After dissolution, an excess of 0.1mol/L KOH-ethanol solution was added, and the mixture was refluxed for 2 hours, followed by titration with 0.1mol/L HCl-isopropanol solution using phenolphthalein as an indicator.
(3) The amount of the added alkali and the amount of the acid consumed for neutralization were recorded, and the grafting ratio of the solid-phase grafting reaction product was calculated as follows.
MAH(％)＝9.806*[C1V1-C2V2)]/2m，
Wherein: c 1 is the concentration of KOH-ethanol solution and mol/L; v 1 is the volume of the KOH-ethanol solution added in excess, mL; c 2 is the concentration of HCl-isopropanol solution and mol/L; v 2 is the volume of HCl-isopropanol solution consumed by 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 invention is 0.5-10.5wt%.
2. Determination of graft odor:
(1) Weighing 20+/-2 g of the polypropylene grafted maleic anhydride obtained in the example, respectively placing the polypropylene grafted maleic anhydride into an odor bottle, tightly placing the odor bottle cap into a oven which is subjected to constant temperature forced ventilation at 80+/-2 ℃, keeping the temperature at 80+/-2 ℃ for 2 hours, and rapidly opening the odor bottle cap to evaluate the odor when the temperature of the oven is cooled to 60+/-5 ℃.
(2) For more objective evaluation, the number of evaluation persons was required to be at least 3, the distance between the sample and the person was 0.5m, and the test time per person was 1min.
(3) Detection result evaluation ranking
Evaluation of odors all possible variables can be scored according to the evaluation scale (as shown in table 1) with scores 1 to 4.
Table 1.
The grade of the polyolefin grafted MAH prepared by the invention is 1 grade.
3. Determination of MAH and interfacial agent recovery:
(1) Samples were taken from the first condenser feed, and the ratio of interfacial agent to MAH in the condensate was analyzed by chromatography. And (3) accurately measuring the liquid level of the liquid preparation tank after the condensate is returned to the liquid preparation tank. Further, the MAH (m 1) and the interfacial agent content (m 2) in the first step were calculated.
(2) After MAH in the flash evaporation kettle is sent into the liquid preparation tank, the liquid level of the liquid preparation tank is accurately measured. Further, the MAH content (m 3) in the second step was calculated.
MAH recovery (%) = (M 1+m3)/M,
Wherein: m is the mass of MAH added initially, g.
Interfacial agent recovery (%) = m 2/N,
Wherein: n is the mass and g of the interfacial agent added initially.
The recovery rates of MAH and interfacial agent xylene in the present application were 80% and 95%, respectively.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The device for solid-phase grafting of the maleic anhydride on the polyolefin is characterized by comprising a liquid preparation tank, a conical reactor and a reaction kettle;
the conical reactor is internally provided with a sprayer and a heating device, and also comprises a discharge port, and the discharge port 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;
the device also comprises a first condenser, wherein the first condenser comprises an air inlet and a discharge hole;
the conical reactor further comprises an air outlet, and the reaction kettle further comprises an air outlet; 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;
the device also comprises a washing liquid storage tank, wherein the washing liquid storage tank comprises a feed inlet and a discharge outlet;
The reaction kettle comprises a liquid discharge port, and the liquid discharge port of the reaction kettle is connected with a feed port of a washing liquid storage tank; the discharge port of the first condenser is connected with the feed port of the washing liquid storage tank;
the device also comprises 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.
2. The apparatus for solid phase grafting of maleic anhydride onto a polyolefin according to claim 1, wherein the first condenser is connected to a freezer.
3. The device for solid-phase grafting of maleic anhydride onto polyolefin according to claim 1, wherein a preheater is arranged between the discharge port of the washing liquid storage tank and the rectifying tower, at least two feed ports and one discharge port are arranged on the rectifying tower, and the discharge port of the preheater is connected with the first feed port of the rectifying tower.
4. A process for the preparation of a polyolefin solid-phase grafted maleic anhydride, characterized in that it uses a device according to any of claims 1 to 3, said process comprising the steps of:
S1: adding an interfacial agent, an organic initiator and maleic anhydride into a liquid preparation tank, and uniformly stirring to form a uniform 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 in the step S1 into the conical reactor in the form of liquid drops, and heating and stirring to react to obtain a crude grafting product;
s4: and (3) adding the washing liquid and the crude grafting product obtained in the step (S3) into a reaction kettle, and reacting to obtain a final product, namely the grafted MAH polyolefin.
5. The method according to claim 4, 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, cumene peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide and azobisisobutyronitrile.
6. The process according to claim 4, wherein the polyolefin solid powder in step S2 is at least one selected from the group consisting of ethylene homo-or copolymer, propylene homo-or copolymer, butene homo-or copolymer.
7. The method according to claim 4, wherein the washing liquid in step S4 is selected from acetone and/or ethyl acetate.
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