CN112279946A - Method for preparing chlorinated polypropylene through microchannel reaction and product - Google Patents
Method for preparing chlorinated polypropylene through microchannel reaction and product Download PDFInfo
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- CN112279946A CN112279946A CN202011110820.8A CN202011110820A CN112279946A CN 112279946 A CN112279946 A CN 112279946A CN 202011110820 A CN202011110820 A CN 202011110820A CN 112279946 A CN112279946 A CN 112279946A
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- polypropylene
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- microchannel
- chlorinated polypropylene
- chlorine
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 156
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 153
- -1 polypropylene Polymers 0.000 title claims abstract description 153
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 57
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- 239000006185 dispersion Substances 0.000 claims abstract description 41
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 25
- 230000000694 effects Effects 0.000 claims abstract description 18
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 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 8
- RINWGRJHXCCLOV-UHFFFAOYSA-N BPO Chemical compound BPO RINWGRJHXCCLOV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 abstract description 43
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 239000000976 ink Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000006467 substitution reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XJHDWSFEGCYSFP-UHFFFAOYSA-N C=C.ClC(Cl)=O Chemical compound C=C.ClC(Cl)=O XJHDWSFEGCYSFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005502 phase rule Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing chlorinated polypropylene through microchannel reaction and the chlorinated polypropylene, wherein the activity ratio of primary hydrogen, secondary hydrogen and tertiary hydrogen to chlorine atoms in the chlorination process of the polypropylene is 1: 0.8-1.5: 0.6-1.8. The preparation method comprises the following steps: (1) respectively injecting the polypropylene dispersion liquid and the liquid chlorine into a micro-channel reaction system at a certain flow rate and uniformly mixing; (2) controlling the reaction temperature and the residence time of the polypropylene dispersion liquid and the liquid chlorine in the microchannel reaction system until the reaction is finished; (3) and filtering the reaction product, collecting the separated powder, and washing and drying to obtain the chlorinated polypropylene. The invention effectively solves the problems in the preparation of chlorinated polypropylene in the prior art, so that the prepared chlorinated polypropylene has excellent chlorination uniformity, and the formed product has higher whiteness and adhesion fastness, thereby having wide application prospect in the fields of high-grade ink, adhesive, coating and the like.
Description
Technical Field
The invention belongs to the field of polypropylene, and particularly relates to a method for preparing chlorinated polypropylene through microchannel reaction and a product.
Background
Chlorinated polypropylene (CPP) is an important chemical modified product of polypropylene, has excellent wear resistance, aging resistance, acid and alkali resistance and other properties, has excellent adhesion characteristics to polyolefin, and is widely applied to the fields of high-grade ink, adhesive, coating and the like.
The CPP production method mainly comprises a solution chlorination method, an aqueous suspension chlorination method and a solid phase chlorination method. At present, most domestic enterprises mostly adopt the traditional solution method production process for technical reasons, a large amount of carbon tetrachloride solvent is used in the production process, the pollution is serious, and the solvent contained in the product is not easy to remove, so that the product quality is influenced. As the carbon tetrachloride solvent method needs to recover a large amount of carbon tetrachloride solvent and the product is easy to have carbon tetrachloride residue, the stipulation of Montreal protocol on ozone layer consuming substances strengthens the control of the carbon tetrachloride, so developed areas and countries close a plurality of carbon tetrachloride method chlorinated polymer production devices in 1995 and turn to the aqueous suspension method, and the foreign countries put forward very strict requirements on the carbon tetrachloride residue in chlorinated polypropylene products, so the solution method is only a reasonable measure and is inevitably eliminated in the future.
The water phase method is a main synthetic route at home and abroad at present, and is also a synthetic technology which is urgently to be developed and popularized in China. The technological process includes adding crushed polypropylene powder, catalyst, surfactant and softened water in certain proportion into chlorination reactor and stirring until polypropylene is suspended. And (3) heating the polypropylene suspension to about 40-50 ℃ under stirring, keeping the temperature, introducing chlorine, stopping introducing chlorine after about 2 hours of reaction, and stopping the reaction to obtain the low-chlorinated polypropylene. If a high chlorinated product is expected to be obtained, adding a proper amount of maleic anhydride into the suspension after the chlorination in the previous step is finished, raising the temperature to 80-90 ℃ to continue chlorination reaction, stopping the reaction when the required chlorination degree is reached, replacing hydrogen chloride gas generated in the reaction and unreacted chlorine gas with nitrogen, absorbing the hydrogen chloride gas and the unreacted chlorine gas into byproducts such as dilute hydrochloric acid, sodium hypochlorite and the like by using water and caustic soda solution, cooling the reaction material to about 30 ℃, and performing deacidification, dehydration, washing, drying, molding and granulation to obtain a chlorinated polypropylene finished product. Because the aqueous phase method uses water to replace a solvent, the difficulty of pretreatment of the reaction is high, the viscosity of reaction materials is high, and how to completely and uniformly carry out the chlorination reaction is very critical, so that the method not only relates to the technical problem of the process, but also more importantly relates to a plurality of engineering factors such as the configuration of a chlorination kettle, the power of a stirrer and the like, wherein the stirring strength which cannot meet the reaction requirement is a key for restricting the chlorinated polypropylene aqueous phase method in China, and is also a key for restricting the modeling production of other chlorinated high polymer aqueous phase rules.
Chinese patent application No. CN01121781.2 discloses an industrial production method and product for producing chlorinated polypropylene by aqueous suspension, which comprises an industrial production process of introducing chlorine gas into isotactic or atactic polypropylene in a suspension state in an aqueous solution containing an emulsion accelerator, a dispersion separant and an activation initiator in the same reaction kettle for chlorination reaction, and injection molding and granulation to obtain a chlorinated polypropylene product with a chlorine content of 15-70%. The method completely gets rid of the phenomenon that the experiment can be carried out in a test tube, a flask and the like, but the experiment is difficult to realize in large-scale production. Has the characteristics of short reaction time, convenient operation, no environmental pollution and lower cost. Is a raw material used in the industries of flame retardants, anticorrosive coatings, chlorinated rubber substitutes, printing inks, adhesives, blown film additives and the like. Although the scheme of the invention avoids using carbon tetrachloride as a solvent, the defect of nonuniform chlorination caused by overlarge viscosity of reaction materials cannot be solved.
Chinese patent with application number 201710012100.X discloses a method for preparing chloroethylene carbonate by microchannel reaction, which comprises the following steps: (1) the used equipment comprises an enhanced mass transfer type micro-channel reactor, a first metering pump and a second metering pump, wherein the enhanced mass transfer type micro-channel reactor comprises a preheater, a second preheater, a heat exchanger and micro-channel modules, and each micro-channel module comprises a micro-channel, an exhaust valve and a nitrogen replacement valve; (2) heating ethylene carbonate from a solid to liquid, adding an initiator and a catalyst to obtain a mixed solution, inputting the liquid into a preheater through a first metering pump for preheating, inputting liquid chlorine into a storage tank through a second metering pump for synchronous input into a microchannel in a microchannel module, carrying out mixed reaction after heating, enabling a product to flow out of a discharge valve after the reaction is finished, and rectifying after cooling to obtain the chloroethylene carbonate. The method is simple, convenient and safe to operate, the byproduct ethylene dichlorocarbonate is less, and the purity and yield of the product are higher. It can be seen that the object of the present invention is to reduce the reaction by-products to improve purity and yield without solving the problem of non-uniform chlorination of chlorinated polypropylene.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a method and a product for preparing chlorinated polypropylene by microchannel reaction.
In order to solve the technical problems, the invention adopts the technical scheme that:
the invention provides a method for preparing chlorinated polypropylene through microchannel reaction, wherein the activity ratio of primary hydrogen, secondary hydrogen and tertiary hydrogen to chlorine atoms in the chlorination process of polypropylene is 1: 0.8-1.5: 0.6-1.8.
In the preparation method, in the preparation process of chlorinated polypropylene, the primary hydrogen bond energy in the raw material polypropylene is 95kcal/mol, the secondary hydrogen bond energy is 89kcal/mol, the tertiary hydrogen bond energy is 85kcal/mol, and the number ratio of tertiary hydrogen, secondary hydrogen and primary hydrogen is 1:2:3, generally, the activity of replacing the secondary hydrogen on a polypropylene molecular chain by chlorine atoms is relatively strong, and the steric hindrance effect of methyl on the molecular chain makes the activity of replacing the tertiary hydrogen by the chlorine atoms stronger than that of the primary hydrogen on the methyl, so that the chlorine atoms, the secondary hydrogen and the tertiary hydrogen of the chlorinated polypropylene are more, and the chlorination uniformity is poor. Compared with the chemical synthesis reaction carried out in a conventional reaction vessel, the microchannel reactor used in the method has the characteristics of large specific surface area, high mass and heat transfer efficiency, short reaction time, easily controlled reaction conditions and the like.
According to the above preparation method, the preparation method comprises the following steps:
(1) preparing polypropylene dispersion liquid, injecting the polypropylene dispersion liquid and liquid chlorine into a fluid channel of a micro-channel reaction system at certain flow rates respectively, and uniformly mixing;
(2) controlling the reaction temperature and the residence time of the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) in a microchannel reaction system until the reaction is finished;
(3) and (3) filtering the reaction product in the step (2), collecting the separated powder, and washing and drying to obtain the chlorinated polypropylene.
According to the preparation method, the microchannel reaction system comprises a plurality of single-chip microchannel reactors which are arranged in series according to the material flowing direction, each single-chip microchannel reactor comprises a reaction layer and a heat transfer layer which are arranged in a stacked mode, and the reaction layer is clamped between the two heat transfer layers; the reaction layers of the plurality of single-chip microchannel reactors are connected in series; preferably, the microchannel reaction system preferably comprises 1-10 monolithic microchannel reactors.
According to the preparation method, the polypropylene dispersion liquid in the step (1) comprises the following components in parts by weight: 100 parts of polypropylene powder, 0.01-1 part of emulsifier, 0.01-1 part of initiator and 400-900 parts of water.
In the preparation method, the polypropylene used as the starting material is isotactic polypropylene or atactic polypropylene, and the melt flow rate is 18-49 g/10 min.
According to the preparation method, the flow rate ratio of the polypropylene dispersion liquid to the liquid chlorine in the step (1) is 2-100: 1, preferably 20-80: 1, and more preferably 40-70: 1; the inner diameter of a fluid channel in the micro-channel reaction system is 0.3-1.0 mm, and preferably 0.4-0.8 mm.
According to the preparation method, the reaction temperature of the polypropylene dispersion liquid and the liquid chlorine in the step (2) is 60-120 ℃, and preferably 80-100 ℃.
According to the preparation method, the residence time of the reaction between the polypropylene dispersion liquid and the liquid chlorine in the step (2) is 10-600 s, preferably 30-480 s, and more preferably 60-300 s.
According to the preparation method, the particle size of the polypropylene powder is not more than 100 microns, and preferably the particle size is 10-80 microns.
According to the preparation method, the emulsifier is selected from one or two of OP-10, sodium methyl benzene sulfonate or Tween-80, and the initiator is selected from one or two of BPO, AIBN or ammonium persulfate.
According to the preparation method, the preparation method specifically comprises the following steps:
(1) mixing polypropylene powder with the particle size of 1-100 microns, an emulsifier, an initiator and water according to a certain mass ratio to prepare a polypropylene dispersion liquid serving as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 2-100: 1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) feeding the polypropylene dispersion liquid and liquid chlorine which are uniformly mixed in the step (1) into a microchannel reaction system, setting the reaction temperature to be 60-120 ℃, and setting the retention time to be 10-600 s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
The invention also provides chlorinated polypropylene prepared by using the microchannel reaction system, wherein the chlorine content of the chlorinated polypropylene is 18-65%, the whiteness is 60-80%, and the adhesion fastness on the polypropylene reaches 0-3 grade.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the invention effectively solves the defects of long reaction period, low reaction controllable degree, uneven particle chlorination and the like in the process of preparing chlorinated polypropylene by the traditional solution method and the aqueous phase chlorination method, and the preparation of the chlorinated polypropylene by adopting the microchannel reaction also has the advantages of simple equipment, continuous production, high production efficiency and the like;
2. the chlorinated polypropylene produced by the preparation method provided by the invention is uniformly chlorinated, can be completely dissolved in solvents such as dimethylbenzene, methylbenzene and ketones and ester solvents such as environment-friendly butyl acetate, is clear in solution, has no suspended matters and precipitates, and can meet the use requirements of environment-friendly ink and paint;
3. the chlorinated polypropylene produced by the preparation method provided by the invention keeps stable chlorination uniformity under different levels of chlorination degrees, so that the product has better whiteness and adhesion fastness.
The following describes in further detail embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below, and the following embodiments are used for illustrating the present invention and are not used for limiting the scope of the present invention.
Example 1
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of a polypropylene powder having a particle size of 20 μm, 0.1 part by weight of OP-10, 0.5 part by weight of AIBN, and 400 parts by weight of water were mixed to prepare a polypropylene dispersion as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 20:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 80 ℃ and setting the retention time to be 60s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.2: 1.3.
Example 2
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder having a particle size of 80 μm, 0.1 part by weight of OP-10, 0.5 part by weight of AIBN, and 400 parts by weight of water were mixed to prepare a polypropylene dispersion as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 20:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 80 ℃ and setting the retention time to be 300s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.0: 0.8.
Example 3
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder having a particle size of 100 μm, 0.1 part by weight of OP-10, 0.5 part by weight of AIBN, and 400 parts by weight of water were mixed to prepare a polypropylene dispersion as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 20:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 80 ℃ and setting the retention time to be 600s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:0.8: 0.6.
Example 4
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder having a particle size of 1 μm, 0.2 part by weight of sodium methylbenzenesulfonate, 0.3 part by weight of BPO, and 400 parts by weight of water were mixed to prepare a polypropylene dispersion as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 20:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 100 ℃ and setting the retention time to be 60s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.1: 1.2.
Example 5
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder having a particle size of 20 μm, 0.2 part by weight of sodium methylbenzenesulfonate, 0.3 part by weight of BPO, and 400 parts by weight of water were mixed to prepare a polypropylene dispersion as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 20:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 130 ℃ and setting the retention time to be 60s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.3: 1.4.
Example 6
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder with the particle size of 40 mu m, 0.01 part by weight of Tween-80, 1 part by weight of ammonium persulfate and 500 parts by weight of water are mixed to prepare polypropylene dispersion liquid as first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 100:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 60 ℃ and the retention time to be 30s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:0.9: 0.9.
Example 7
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder with the particle size of 60 mu m, 0.01 part by weight of Tween-80, 1 part by weight of ammonium persulfate and 500 parts by weight of water are mixed to prepare polypropylene dispersion liquid as first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 60:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 60 ℃ and the retention time to be 30s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.1: 1.2.
Example 8
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of a polypropylene powder having a particle size of 80 μm, 0.01 part by weight of OP-10, 0.5 part by weight of Tween-80, 0.1 part by weight of AIBN, 0.2 part by weight of BPO, and 900 parts by weight of water were mixed to prepare a polypropylene dispersion as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 20:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 130 ℃ and setting the retention time to be 300s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.5: 1.8.
Example 9
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of a polypropylene powder having a particle size of 80 μm, 0.01 part by weight of OP-10, 0.5 part by weight of Tween-80, 0.1 part by weight of AIBN, 0.2 part by weight of BPO, and 900 parts by weight of water were mixed to prepare a polypropylene dispersion as a first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 20:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 130 ℃ and setting the retention time to be 120s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.2: 1.1.
Example 10
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder with the particle size of 10 mu m, 0.2 part by weight of OP-10, 0.8 part by weight of sodium methyl benzene sulfonate, 0.1 part by weight of BPO, 0.1 part by weight of ammonium persulfate and 700 parts by weight of water are mixed to prepare polypropylene dispersion liquid as first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 80:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 120 ℃ and the retention time to be 480s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:0.9: 1.4.
Example 11
In this embodiment, the preparation method includes the following steps:
(1) 100 parts by weight of polypropylene powder with the particle size of 90 mu m, 0.2 part by weight of OP-10, 0.8 part by weight of sodium methyl benzene sulfonate, 0.1 part by weight of BPO, 0.1 part by weight of ammonium persulfate and 700 parts by weight of water are mixed to prepare polypropylene dispersion liquid as first fluid; using liquid chlorine as a second fluid; controlling the flow rate ratio of the first fluid to the second fluid to be 40:1, and sending the first fluid and the second fluid into a microchannel reaction system after fully mixing;
(2) after the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) are sent into a microchannel reaction system, setting the reaction temperature to be 120 ℃ and the retention time to be 480s until the reaction is finished;
(3) and opening a tail gas valve of the microchannel reaction system, absorbing redundant chlorine gas by using alkaline water, placing a product obtained by the reaction in a distributed funnel, separating powder in the slurry product by using a filter flask, cleaning the powder to be neutral by using distilled water, and then placing the powder in an oven to be dried at the temperature of 60 ℃ to obtain white powdery chlorinated polypropylene.
In the present example, the activity ratio of the substitution reaction of primary hydrogen, secondary hydrogen and tertiary hydrogen with chlorine atoms in the chlorinated polypropylene during the reaction process is 1.0:1.2: 1.8.
Comparative example 1
In this comparative example, chlorinated polyvinyl chloride was prepared as follows:
dissolving polypropylene powder in a carbon tetrachloride solvent in a weight ratio of 1:10, adding the mixture into a reaction tank, heating to 90-110 ℃, increasing the pressure to 0.10-0.15 MPa, and dissolving for 3 hours; and then cooling to 80 ℃, reducing the pressure to 0.05-0.10 MPa, adding 0.008 part by weight of azodiisobutyronitrile initiator, introducing liquid chlorine, carrying out chlorination reaction for 105 minutes, then distilling out carbon tetrachloride, cooling chlorinated polypropylene material solution, discharging, drying, cutting and sampling.
Comparative example 2
In this comparative example, chlorinated polypropylene was prepared using the same kind and amount of polypropylene, emulsifier, initiator and water as in example 1, using the method described in chinese patent application No. CN 01121781.2.
Test example 1
The chlorinated polypropylenes obtained in examples 1 to 11 and comparative examples 1 to 2 were used to determine chlorine content, viscosity, pH, whiteness (measured in accordance with GB 2913-1982) and adhesion. The method for testing the chlorine content comprises the following steps: and (3) burning chlorinated polypropylene powder, absorbing chloride ions by using anhydrous sodium carbonate, titrating by using silver nitrate standard solution, and calculating the total chlorine content of the chlorinated polypropylene. The method for testing the viscosity of the chlorinated polypropylene comprises the following steps: a20 wt% toluene solution was prepared and tested by a conventional rotational viscometer at 25 ℃ and a rotational speed of 750 rpm.
The adhesion fastness was tested using the following method: a toluene solution with 20 wt% chlorinated polypropylene concentration is prepared, and after coating is carried out on the surface of a polypropylene film, the adhesion fastness is measured (refer to GB/T9286-:
the template was placed on a hard flat object surface to prevent any deformation of the template during the test.
Manual cutting was accomplished according to the following defined procedure:
(1) the cutting edge of the tool was inspected prior to testing and maintained in good condition by sharpening or replacing the blade.
(2) The cutting tool is held so that the tool applies a uniform force to the cutting tool perpendicular to the surface of the template and a specified number of cuts are made on the coating with a uniform cutting rate using a suitable spacing guide. All cuts should be made through to the substrate surface.
If it is not possible to cut through to the substrate because the coating is too hard, the test is invalid and is recorded as faithfully.
(3) Repeating the above operations, and making the same number of parallel cutting lines to intersect the original cutting lines at an angle of 90 DEG to form a grid pattern.
(4) The grid pattern is swept back gently several times and then forward several times along each diagonal of the grid pattern with a soft brush.
(5) The tape was applied, a length of tape was pulled at a uniform rate, the first length was removed, and then approximately 75mm long tape was cut.
The central point of the adhesive tape is placed above the grid in a direction parallel to the set of cutting lines, and the adhesive tape is then pressed flat with the fingers at the location above the grid area, the length of the adhesive tape exceeding at least 20mm of the grid.
To ensure good contact between the tape and the coating, the tape was rubbed vigorously with the fingertips. Full color contact of the coating as seen through the tape is effectively displayed.
And then the adhesive tape is attached for 5min, the suspended end of the adhesive tape is held, and the adhesive tape is stably torn off within 0.5-1.0 s at an angle as close to 60 degrees as possible.
(6) The tape can be fixed to the transparent film surface and retained for reference.
At least three different position tests were performed on the template. If the three results are inconsistent and the difference exceeds a unit scale, the test is repeated at three or more different locations, if necessary, using additional templates and recording all test results.
The test results are given in the following table:
from the results in table 1, it can be seen that the chlorinated polypropylene with higher chlorine content, better whiteness and adhesion fastness can be generated in the examples 1 to 11 at a lower reaction temperature and in a shorter retention time, and the reason for this is that the larger specific surface area of the microchannel reactor affects the contact degree of polypropylene and chlorine in the reaction, reduces the influence of bond energy and steric hindrance effect in the polypropylene raw material, and the higher heat transfer efficiency accelerates the reaction rate, so that the chlorination uniformity of the product is higher.
In contrast, the chlorinated polypropylene prepared in comparative example 1 by the solvent method has poor performances of total chlorine content, whiteness and adhesion fastness, and the reaction takes a long time. In contrast, the chlorinated polypropylene prepared by the conventional aqueous suspension method in comparative example 2 has a chlorine content close to that of the chlorinated polypropylene, but has poor whiteness and adhesion fastness, because the viscosity of the reaction material is very high, and when the stirring strength does not meet the reaction requirement, chlorination is not uniform, which causes product defects.
In summary, the invention uses the microchannel reactor to prepare the chlorinated polypropylene, which not only has short reaction period and low reaction temperature, but also can realize continuous preparation, and the chlorinated polypropylene prepared by the invention has better chlorination degree, and the formed product prepared by the chlorinated polypropylene has better whiteness and adhesion fastness, thus the invention can really achieve the purpose of the invention.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing chlorinated polypropylene through a microchannel reaction is characterized in that the activity ratio of primary hydrogen, secondary hydrogen and tertiary hydrogen to chlorine atoms in the chlorination process of polypropylene is 1: 0.8-1.5: 0.6-1.8.
2. The microchannel reaction process for preparing chlorinated polypropylene according to claim 1, wherein the preparation process comprises the steps of:
(1) preparing polypropylene dispersion liquid, injecting the polypropylene dispersion liquid and liquid chlorine into a fluid channel of a micro-channel reaction system at certain flow rates respectively, and uniformly mixing;
(2) controlling the reaction temperature and the residence time of the polypropylene dispersion liquid and the liquid chlorine which are uniformly mixed in the step (1) in a microchannel reaction system until the reaction is finished;
(3) and (3) filtering the reaction product in the step (2), collecting the separated powder, and washing and drying to obtain the chlorinated polypropylene.
3. The method for preparing chlorinated polypropylene by the microchannel reaction according to claim 1 or 2, wherein the microchannel reaction system comprises a plurality of monolithic microchannel reactors arranged in series according to the material flow direction, each monolithic microchannel reactor comprises a reaction layer and a heat transfer layer which are arranged in a stacked manner, and the reaction layer is sandwiched between the two heat transfer layers; the reaction layers of the plurality of single-chip microchannel reactors are connected in series;
preferably, the microchannel reaction system preferably comprises 1-10 monolithic microchannel reactors.
4. The method for preparing chlorinated polypropylene by the microchannel reaction according to claim 2, wherein the polypropylene dispersion in the step (1) comprises the following components in parts by weight:
5. the method for preparing chlorinated polypropylene through the microchannel reaction according to any one of claims 2 to 4, wherein the flow rate ratio of the polypropylene dispersion liquid to the liquid chlorine in the step (1) is 2-100: 1, preferably 20-80: 1, and more preferably 40-70: 1; the inner diameter of a fluid channel in the micro-channel reaction system is 0.3-1.0 mm, and preferably 0.4-0.8 mm.
6. The method for preparing chlorinated polypropylene by microchannel reaction according to claim 2 or 3, wherein the reaction temperature of the polypropylene dispersion liquid and the liquid chlorine in the step (2) is 60-120 ℃, preferably 80-100 ℃.
7. The method for preparing chlorinated polypropylene by the microchannel reaction according to claim 2 or 3, wherein the residence time of the polypropylene dispersion liquid and the liquid chlorine in the step (2) is 10-600 s, preferably 30-480 s, and more preferably 60-300 s.
8. The method for preparing chlorinated polypropylene through the microchannel reaction, according to claim 4, wherein the particle size of the polypropylene powder is not more than 100 μm, and preferably the particle size is 10-80 μm.
9. The method for preparing chlorinated polypropylene through the microchannel reaction, according to claim 4, wherein the emulsifier is one or two selected from OP-10, sodium methyl benzene sulfonate or Tween-80, and the initiator is one or two selected from BPO, AIBN or ammonium persulfate.
10. Chlorinated polypropylene prepared by the method for preparing chlorinated polypropylene through the microchannel reaction, wherein the chlorinated polypropylene has a chlorine content of 18-65%, a whiteness of 60-80% and an adhesion fastness on the polypropylene surface of 0-3 grade.
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Denomination of invention: A method and product for preparing chlorinated polypropylene through microchannel reaction Granted publication date: 20230908 Pledgee: Kunming Branch of China Minsheng Bank Co.,Ltd. Pledgor: YUNNAN ZHENGBANG TECHNOLOGY CO.,LTD. Registration number: Y2023530000069 |