CN114907526B - Preparation method of high-performance maleic anhydride grafted POE - Google Patents
Preparation method of high-performance maleic anhydride grafted POE Download PDFInfo
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- CN114907526B CN114907526B CN202210500672.3A CN202210500672A CN114907526B CN 114907526 B CN114907526 B CN 114907526B CN 202210500672 A CN202210500672 A CN 202210500672A CN 114907526 B CN114907526 B CN 114907526B
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- maleic anhydride
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 238000001125 extrusion Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 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
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 xylenyl peroxide Chemical class 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000004677 Nylon Substances 0.000 description 11
- 229920001778 nylon Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000005086 pumping Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002978 peroxides Chemical class 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000010888 cage effect Methods 0.000 description 1
- 230000003047 cage effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 230000004580 weight loss Effects 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
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the field of preparation of maleic anhydride grafted POE, and discloses a preparation method of high-performance maleic anhydride grafted POE, which aims to solve the problems of long preparation time, low grafting rate and monomer and initiator residues of products in the prior art, and comprises the following steps: adding the dried POE, maleic anhydride monomer and initiator into a reaction kettle, and introducing carbon dioxide into the reaction kettle to enable the reaction kettle to react for a period of time after heating and pressurizing; raising the temperature in the reaction kettle, slowly releasing the pressure until the pressure in the reaction kettle is reduced to the atmospheric pressure, and obtaining POE particles with pre-dispersed maleic anhydride; adding POE particles with pre-dispersed maleic anhydride into an extruder for reactive extrusion, adding supercritical carbon dioxide in the extrusion process, and then vacuumizing, extruding, cooling and granulating at a machine head. The invention has high grafting efficiency, convenient process flow and high production efficiency, and the obtained product has less VOC residue and can improve the mechanical property and the ageing resistance of the plastic polymer.
Description
Technical Field
The invention relates to the technical field of preparation of maleic anhydride grafted POE, in particular to a preparation method of high-performance maleic anhydride grafted POE.
Background
The POE plastic is a thermoplastic elastomer which adopts metallocene catalyst to realize in-situ polymerization of ethylene and butene or octene, has good compatibility with polyolefin such as PE, PP and the like, has excellent toughness and good processability, and has excellent ageing resistance because unsaturated double bonds are not arranged in a molecular structure. The maleic anhydride grafted POE can become a bridge for improving the adhesion and compatibility of polar materials and nonpolar materials, and the most important application is in the field of nylon modification. The maleic anhydride grafted POE can be used as a compatilizer for filling nylon composite materials such as glass fiber, talcum powder, calcium carbonate and the like, so that the compatibility and the cohesiveness of a nylon base material and a filler interface are improved, and the mechanical property of the composite materials can be greatly improved; the modified nylon material has obviously improved toughness, high impact strength and notch impact strength. The preparation of maleic anhydride grafted POE generally adopts peroxide as an initiator, and maleic anhydride grafted monomer and POE matrix resin are blended and extruded in a double-screw extruder, and the process flow is characterized by simplicity, convenience and high yield, so that the method is widely applied. However, the defects of the process are obvious, namely, the grafting rate of maleic anhydride is low, the grafting efficiency is low, and if the content of an initiator or a monomer is increased, the problems of POE degradation, crosslinking and the like are caused; secondly, the residual of monomer maleic anhydride, which is impossible to completely react in a molten state, inevitably causes monomer residual, so that the product has a great odor problem, and the residual peroxide initiator can be slowly decomposed along with time, so that POE matrix resin is degraded, and the mechanical property is further influenced; thirdly, the traditional method generally distributes maleic anhydride grafting monomers and initiator on the surface of POE through solution or liquid such as silicone oil, the viscosity of POE is very high in the melt grafting process, and the monomers and initiator are difficult to diffuse, so that the reaction interface is small, and the result of low grafting rate is caused.
For example, in the "solvothermal synthesis preparation method of maleic anhydride grafted ethylene-octene copolymer" disclosed in chinese patent literature, its publication number is CN1807473a, ethylene-octene resin, maleic anhydride, initiator and comonomer are put in an autoclave and dissolved in a solvent, the reaction temperature is controlled above the boiling point of the solvent, the system is allowed to react in a state similar to supercritical, so that ethylene-octene can be fully contacted with the reactant, and then washed and dried, to obtain ethylene-octene-maleic anhydride grafted copolymer. The preparation process has high grafting rate but long time consumption, and overall grafting efficiency is low, which seriously hinders the industrial application of the preparation process, and the prepared product has monomer and initiator residues.
Disclosure of Invention
The invention provides a preparation method of high-performance maleic anhydride grafted POE, which aims to solve the problems of long preparation time, low grafting rate, monomer and initiator residues of products in the prior art, and has the advantages of high grafting efficiency, less VOC residues of the obtained product and good mechanical property and ageing resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of high-performance maleic anhydride grafted POE comprises the following steps:
A. adding the dried POE, maleic anhydride monomer and initiator into a reaction kettle, and introducing carbon dioxide into the reaction kettle to enable the reaction kettle to react for a period of time after heating and pressurizing;
B. raising the temperature in the reaction kettle, slowly releasing the pressure until the pressure in the reaction kettle is reduced to the atmospheric pressure, and obtaining POE particles with pre-dispersed maleic anhydride;
C. adding POE particles with pre-dispersed maleic anhydride into an extruder for reactive extrusion, adding supercritical carbon dioxide in the extrusion process, and then vacuumizing, extruding, cooling and granulating at a machine head.
According to the method, the supercritical fluid dissolution characteristic is utilized, the grafting monomer and the initiator are dissolved in the supercritical fluid by controlling the pressure and the temperature, and as the vitrification temperature of POE is very low and is generally about-30 ℃, POE can be swelled by the supercritical fluid at a mild temperature, then the process parameters are controlled, the temperature is increased, the supercritical fluid is removed by slowly releasing the pressure, so that the monomer and the initiator can be uniformly distributed in POE molecules, and the reaction interface is increased; and then the particles are subjected to reactive extrusion granulation at high temperature by a double-screw extruder, in the extrusion process, supercritical carbon dioxide fluid is added, and the supercritical fluid has the general diffusion coefficient of gas and the general dissolving capacity of liquid, so that a micro-fluid phase is formed in a melt, the mass transfer of grafted monomers is promoted, the 'cage effect' caused by high viscosity of a high polymer melt is overcome, the grafting efficiency is improved, and meanwhile, vacuum extraction can be arranged at the rear end of the extruder, and low VOC molecules such as unreacted grafted monomers or initiators dissolved in the supercritical fluid are removed, so that the odor level and ageing resistance of the product are improved.
Preferably, in the step A, the mass ratio of the maleic anhydride monomer to POE is (1-4): 100.
Preferably, in the step a, the initiator is one of xylenyl peroxide, dicumyl peroxide, and 2, 5-dimethyl-2 ',5' -bis (t-butylperoxy) hexane.
Preferably, in the step A, the mass ratio of the initiator to the maleic anhydride monomer is 1 (10-20).
Preferably, in the step A, the temperature of the reaction kettle is 35-45 ℃, the pressure is 8-12 MPa, and the reaction time is 1-2 h after the reaction kettle is heated and pressurized.
In the step A, the temperature of the reaction kettle is raised to 35-40 ℃, so that the injected carbon dioxide is changed into a supercritical state, and the grafting monomer maleic anhydride is dissolved as much as possible, so that the grafting monomer maleic anhydride permeates into POE particles, and the dispersibility of the grafting monomer maleic anhydride and the initiator in the POE particles is improved.
Preferably, in the step B, the temperature in the reaction kettle is raised to 75-85 ℃.
The higher the temperature, the lower the density of the supercritical fluid, which reduces the solubility of the grafting monomer maleic anhydride, thus leaving the grafting monomer in the POE particles without redissolving in the supercritical carbon dioxide.
Preferably, in the step B, the pressure release time of the reaction kettle is 20 to 30 minutes.
The expansion ratio of the swelling POE particles can be reduced as much as possible by slow pressure release.
Preferably, in the step C, the temperature of each section of the extruder is 160-210 ℃ and the rotation speed is 200-250 rpm.
Preferably, in the step C, the mass ratio of the supercritical carbon dioxide to the swollen POE particles is (1-3) 100, and the injection pressure is 12-18 MPa.
In the extrusion reaction process, the injected supercritical carbon dioxide fluid can effectively improve the grafting rate and the product performance in a certain range, and if the injected fluid exceeds a certain limit, maleic anhydride tends to self-polymerize in the micro-fluid phase, but can reduce the grafting rate of POE.
Therefore, the invention has the following beneficial effects: (1) The grafting efficiency is high, the product with high grafting rate can be obtained in a short time, the process flow is convenient, the production efficiency is high, and compared with a supercritical kettle method, the time for producing 1 ton of product is shortened by 60-80%; (2) Unreacted grafting monomers and initiator can be effectively removed in the preparation process, and the VOC residue of the obtained product is less and only 0.2-0.5%; (3) When the product prepared by the invention is used as a compatilizer, the mechanical property and the ageing resistance of the plastic polymer can be improved.
Detailed Description
The invention is further described below in connection with specific embodiments.
In the invention, sabic C1070D POE is selected as POE.
Example 1
A preparation method of high-performance maleic anhydride grafted POE comprises the following steps:
A. POE, MAH and DCP are added into a stainless steel high-pressure reaction kettle provided with a stirring and pressure sensor according to the mass ratio of 100:1.5:0.1, then carbon dioxide is introduced, the temperature of the reaction kettle is controlled at 45 ℃ and the pressure is controlled at 12MPa, and the reaction kettle is kept for 1h;
B. then the temperature in the reaction kettle is increased to 80 ℃ and the pressure is slowly released, the pressure release time is 30min, and POE particles with pre-dispersed maleic anhydride are obtained;
C. adding POE particles pre-dispersed with maleic anhydride into an extruder by using a weightless scale, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 2:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by using a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
Example 2
A preparation method of high-performance maleic anhydride grafted POE comprises the following steps:
A. adding POE, MAH and DCP into a stainless steel high-pressure reaction kettle provided with stirring and pressure sensors according to the mass ratio of 300:6:0.4, then introducing carbon dioxide, controlling the temperature of the reaction kettle at 45 ℃ and the pressure at 12MPa, and keeping for 1h;
B. then the temperature in the reaction kettle is increased to 80 ℃ and the pressure is slowly released, the pressure release time is 30min, and POE particles with pre-dispersed maleic anhydride are obtained;
C. adding POE particles pre-dispersed with maleic anhydride into an extruder by using a weightless scale, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 2:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by using a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
Example 3
A preparation method of high-performance maleic anhydride grafted POE comprises the following steps:
A. adding POE, MAH and DCP into a stainless steel high-pressure reaction kettle provided with stirring and pressure sensors according to the mass ratio of 300:6:0.4, then introducing carbon dioxide, controlling the temperature of the reaction kettle at 45 ℃ and the pressure at 12MPa, and keeping for 1h;
B. then the temperature in the reaction kettle is increased to 80 ℃ and the pressure is slowly released, the pressure release time is 30min, and POE particles with pre-dispersed maleic anhydride are obtained;
C. adding POE particles pre-dispersed with maleic anhydride into an extruder by using a weightless scale, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 3:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by using a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
Example 4
A preparation method of high-performance maleic anhydride grafted POE comprises the following steps:
A. adding POE, MAH and DCP into a stainless steel high-pressure reaction kettle provided with stirring and pressure sensors according to the mass ratio of 300:6:0.4, then introducing carbon dioxide, controlling the temperature of the reaction kettle at 35 ℃ and the pressure at 12MPa, and keeping for 1h;
B. then the temperature in the reaction kettle is increased to 85 ℃ and the pressure is slowly released for 20min, so as to obtain POE particles with pre-dispersed maleic anhydride;
C. adding POE particles pre-dispersed with maleic anhydride into an extruder by using a weightless scale, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 2:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by using a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
Comparative example 1
The preparation method of maleic anhydride grafted POE comprises the following steps:
A. dissolving MAH and DCP in butanone at a mass ratio of 15:1, wherein the mass ratio of MAH to butanone is 1:3, adding POE into the solution after the MAH and DCP are completely dissolved, wherein the mass ratio of POE to MAH is 100:2, then blending in a homogenizing barrel, setting the rotating speed to 30rpm, setting the temperature to 45 ℃, extracting and absorbing the butanone of the solution by using a vacuum pump, and blending for 20min to obtain maleic anhydride pre-dispersed POE particles;
B. adding POE particles pre-dispersed with maleic anhydride into an extruder by using a weightless scale, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 2:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by using a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
Comparative example 2
The preparation method of maleic anhydride grafted POE comprises the following steps:
A. adding POE, MAH and DCP into a stainless steel high-pressure reaction kettle provided with stirring and pressure sensors according to the mass ratio of 300:6:0.4, then introducing carbon dioxide, controlling the temperature of the reaction kettle at 45 ℃ and the pressure at 12MPa, and keeping for 1h;
B. then the temperature in the reaction kettle is increased to 145 ℃, at this time, the pressure of the supercritical fluid in the kettle is controlled to be kept at 16MPa by a pressure reducing valve and a supercritical fluid injection device, the reaction is carried out for 4 hours under the condition, and finally the temperature in the kettle is reduced and exhausted, so that the maleic anhydride grafted POE product is obtained.
Comparative example 3
The preparation method of maleic anhydride grafted POE comprises the following steps:
A. dissolving MAH and DCP in butanone at a mass ratio of 15:1, wherein the mass ratio of MAH to butanone is 1:3, adding POE into the solution after the MAH and DCP are completely dissolved, wherein the mass ratio of POE to MAH is 100:2, then blending in a homogenizing barrel, setting the rotating speed to 30rpm, setting the temperature to 45 ℃, extracting and absorbing the butanone of the solution by using a vacuum pump, and blending for 20min to obtain maleic anhydride pre-dispersed POE particles;
B. adding POE particles with pre-dispersed maleic anhydride into an extruder, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 2:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by utilizing a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
Comparative example 4
The preparation method of maleic anhydride grafted POE comprises the following steps:
A. adding POE, MAH and DCP into a stainless steel high-pressure reaction kettle provided with a stirring and pressure sensor according to the mass ratio of 100:1.5:0.1, then introducing carbon dioxide, controlling the temperature of the reaction kettle at 45 ℃ and the pressure at 12MP, and keeping for 1h;
B. then slowly decompressing the reaction kettle for 30min to obtain POE particles with pre-dispersed maleic anhydride;
C. adding POE particles pre-dispersed with maleic anhydride into an extruder by using a weightless scale, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 2:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by using a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
Comparative example 5
The preparation method of maleic anhydride grafted POE comprises the following steps:
A. POE, MAH and DCP are added into a stainless steel high-pressure reaction kettle provided with a stirring and pressure sensor according to the mass ratio of 100:1.5:0.1, then carbon dioxide is introduced, the temperature of the reaction kettle is controlled at 45 ℃ and the pressure is controlled at 12MPa, and the reaction kettle is kept for 1h;
B. then the temperature in the reaction kettle is increased to 80 ℃ and the pressure is released, the pressure release time is 5min, and POE particles with pre-dispersed maleic anhydride are obtained;
C. adding POE particles pre-dispersed with maleic anhydride into an extruder by using a weightless scale, setting the temperature of each area of the extruder to be 150 ℃ -160 ℃ -170 ℃ -180 ℃ -190 ℃ -200 ℃ -205 ℃ -185 ℃ -190 ℃, controlling the rotating speed of a screw at 240rpm, injecting supercritical carbon dioxide into the 3 rd area of the extruder, setting the injection pressure to be 16MPa, setting the mass ratio of supercritical carbon dioxide fluid to extruded melt to be 2:100, setting vacuum ports in the 10 and 11 areas of the extruder, pumping away small molecular components in the processed materials by using a vacuum pump, keeping the vacuum degree to be more than 0.08MPa, and extruding and granulating grafted POE at a machine head.
The VOC content of the maleic anhydride grafted POE particles prepared in the examples and the comparative examples is measured by DSC thermogravimetry, and the specific steps are as follows: and (3) drying the used crucible at 100 ℃ for more than 2 hours for later use, then taking about 15mg of a compatilizer sample, putting the crucible with the sample into a DSC thermogravimetry, heating from room temperature to 180 ℃, then keeping the temperature for 1 hour, wherein the heating rate is 5 ℃/min, and finally obtaining the weight loss rate of the sample, namely the VOC content.
The grafting ratio of the maleic anhydride-grafted POE particles prepared in examples and comparative examples was measured as follows: 10g of the product was dissolved in 400ml of xylene at 100℃and 500ml of ethanol was added to give a polymer precipitate, unreacted maleic anhydride monomer was dissolved in the solvent, and the precipitate was dried under vacuum for 24h (60 ℃) for further use. 1g of the purified product was dissolved in 100ml of xylene at 100℃and titrated with 0.04mol/L KOH methanol solution, using phenolphthalein as an indicator, calculated on the amount of KOH methanol solution consumed:
wherein g is the grafting ratio, V 0 To titrate the volume of product consuming KOH methanol solution, V is the volume of ungrafted POE consuming KOH methanol solution, c is the molar concentration of KOH, and m is the mass of product added.
The maleic anhydride grafted POE particles prepared in the examples and the comparative examples are used as compatilizer and are prepared according to the following formula, wherein the compatilizer comprises the following components in mass percent: 5 parts of compatilizer, 70 parts of nylon (unit 1013B) and 30 parts of Glass Fiber (GF), and then measuring the tensile strength, elongation at break and notched impact strength by injection molding.
The test results of the above experiments are as follows:
as can be seen from the table, compared with the products obtained in examples 1 to 4, the comparative example 1 adopts the traditional melt extrusion grafting method, the grafting rate is the lowest, the VOC content is the highest, and the mechanical properties of the modified nylon prepared by using the modified nylon as the raw material are not as same as those of examples 1 to 4, which shows that the preparation method of the invention can not only improve the grafting rate of the maleic anhydride grafted POE particles and reduce the VOC content, but also improve the mechanical properties and the aging resistance of the modified nylon when the maleic anhydride grafted POE particles are used for nylon modification.
Compared with the products obtained by other examples, the kettle type grafting method and the supercritical fluid reaction extrusion method are adopted in the comparative example 2, the method has the advantages that the VOC content can be effectively removed, but under the same grafting reaction condition, the grafting rate is not as high as that of the other examples, and the mechanical properties such as tensile strength, elongation at break and notch impact strength of the product obtained by taking the prepared maleic anhydride grafted POE particles as a compatilizer are not as high as those of examples 1-4, and the production efficiency is lower when the preparation method of the comparative example 2 is far higher than that of the preparation method of the invention, so that the preparation method of the product by adopting supercritical fluid swelling dispersion and then supercritical fluid reaction extrusion injection is obviously superior to that of the kettle type supercritical grafting method.
Compared with the products obtained in examples 1-4, the product of comparative example 3 is not swelled and dispersed by supercritical fluid, but is directly injected into the supercritical fluid for reaction extrusion, so that the reaction interface is smaller, the grafting rate is better than that of the common melt extrusion method, but is far smaller than that of the product prepared by the invention, and therefore, the grafting rate of POE is greatly improved by adopting the supercritical swelled and dispersed grafting monomer and initiator.
Example 2 has a 33% increase in grafting monomer content and a 25% increase in grafting rate over example 1, with the injection pressure and flow rate unchanged. In example 3, the injection amount of the supercritical fluid during the reactive extrusion was increased without changing the grafting monomer, and it can be seen from the results that the grafting ratio was conversely decreased and the product performance was also decreased, because the injected supercritical fluid had the effect of enhancing mass transfer, but if the injection amount exceeded a certain range, the self-polymerization of the grafting monomer was caused, and the performance of the maleic anhydride-grafted POE particles was deteriorated.
The temperature of step a in example 4 is lower than that of example 2, and the temperature of step B is higher than that of example 2, so that the grafting rate of the obtained product is higher, the mechanical properties are strong, but the VOC residues are more, because lowering the temperature of supercritical carbon dioxide can increase the solubility of maleic anhydride monomer, and conversely, raising the temperature can leave as much maleic anhydride monomer as possible in POE particles, but too much maleic anhydride monomer can increase VOC residues. The comparative example 4 releases pressure at 45 ℃ without heating, so that the maleic anhydride grafted monomer which is dissolved in the supercritical carbon dioxide again is increased, most of the maleic anhydride monomer is discharged together with the supercritical carbon dioxide fluid, and only part of the maleic anhydride monomer remains in POE particles, so that the grafting rate is the lowest, and the obtained product has no toughening and compatibilizing effects on a nylon glass fiber system.
Comparative example 5 releases supercritical carbon dioxide in the reaction kettle at a higher rate, so that the foaming multiplying power of the swollen POE particles is higher, the discharging of the swollen POE particles in the extruder is not facilitated, the production efficiency is reduced, and meanwhile, partial maleic anhydride monomers can be carried out together due to too fast pressure release, the grafting rate of products is reduced, and the use effect of the modified POE particles in the modified nylon is further reduced.
Claims (7)
1. The preparation method of the high-performance maleic anhydride grafted POE is characterized by comprising the following steps of:
A. adding the dried POE, maleic anhydride monomer and initiator into a reaction kettle, introducing carbon dioxide into the reaction kettle, heating the reaction kettle to 35-45 ℃, pressurizing to 8-12 MPa, and reacting for a period of time;
B. raising the temperature in the reaction kettle to 75-85 ℃, slowly releasing the pressure until the pressure in the reaction kettle is reduced to the atmospheric pressure, and obtaining POE particles with pre-dispersed maleic anhydride, wherein the pressure release time is 20-30 min;
C. adding POE particles with pre-dispersed maleic anhydride into an extruder for reactive extrusion, adding supercritical carbon dioxide in the extrusion process, wherein the mass ratio of the supercritical carbon dioxide to the POE particles with pre-dispersed maleic anhydride is (1-3): 100, and then vacuumizing, extruding, cooling and granulating at a machine head.
2. The method for preparing the high-performance maleic anhydride grafted POE according to claim 1, wherein in the step A, the mass ratio of maleic anhydride monomer to POE is (1-4) 100.
3. The method for preparing high-performance maleic anhydride grafted POE according to claim 1, wherein in step a, the initiator is one of xylenyl peroxide, dicumyl peroxide, and 2, 5-dimethyl-2 ',5' -bis (t-butylperoxy) hexane.
4. The method for preparing the high-performance maleic anhydride grafted POE according to claim 1 or 3, wherein in the step A, the mass ratio of the initiator to the maleic anhydride monomer is 1 (10-20).
5. The method for preparing high-performance maleic anhydride grafted POE according to claim 1, wherein in the step A, the reaction time is 1-2 h.
6. The method for preparing high-performance maleic anhydride grafted POE according to claim 1, wherein in the step C, the temperature of each section of the extruder is 160-210 ℃ and the rotating speed is 200-250 rpm.
7. The method for preparing high-performance maleic anhydride grafted POE according to claim 1 or 6, wherein in the step C, the injection pressure is 12-18 MPa.
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| CN104292393A (en) * | 2014-09-26 | 2015-01-21 | 宁波能之光新材料科技有限公司 | Method for preparing grafted copolymer by adopting supercritical carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102863588A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | Method for modifying polypropylene by supercritical carbon dioxide assisted solid phase grafting |
| JP7466306B2 (en) * | 2016-08-19 | 2024-04-12 | 中国科学院化学研究所 | Ultra-high molecular weight, ultra-fine particle polyethylene and its manufacturing method and applications |
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| US4762890A (en) * | 1986-09-05 | 1988-08-09 | The Dow Chemical Company | Method of grafting maleic anhydride to polymers |
| CN1336390A (en) * | 2001-09-11 | 2002-02-20 | 上海氯碱化工股份有限公司 | Prepn. of maleic anhydride grafted ethylene-alpha-octylene copolymers |
| CN1807473A (en) * | 2006-02-23 | 2006-07-26 | 上海交通大学 | Heat synthesis preparation method for maleic anhydride grafted ethene-octylen copolymer |
| CN102127281A (en) * | 2010-12-31 | 2011-07-20 | 浙江大学 | Method for extruding and preparing high melt strength polypropylene with long branched chain structure through supercritical reaction |
| CN104292393A (en) * | 2014-09-26 | 2015-01-21 | 宁波能之光新材料科技有限公司 | Method for preparing grafted copolymer by adopting supercritical carbon dioxide |
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