CN112694567A - Microwave-assisted polypropylene grafting method - Google Patents
Microwave-assisted polypropylene grafting method Download PDFInfo
- Publication number
- CN112694567A CN112694567A CN202011640914.6A CN202011640914A CN112694567A CN 112694567 A CN112694567 A CN 112694567A CN 202011640914 A CN202011640914 A CN 202011640914A CN 112694567 A CN112694567 A CN 112694567A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- microwave
- grafting
- monomer
- assisted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 86
- -1 polypropylene Polymers 0.000 title claims abstract description 83
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 230000008961 swelling Effects 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 18
- 235000019400 benzoyl peroxide Nutrition 0.000 description 18
- 239000004342 Benzoyl peroxide Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 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 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 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 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
Abstract
The invention discloses a microwave-assisted polypropylene grafting method, and belongs to the technical field of polymer modification. The method provided is that initiator is added into organic solvent, certain amount of polypropylene and grafting monomer are added, swelling is carried out in inert gas environment, the system is irradiated for certain time in microwave condition, and polypropylene grafting product is obtained.
Description
Technical Field
The invention belongs to the field of polymer modification, and provides a microwave-assisted polypropylene grafting method which shortens the reaction time and has the same or higher grafting rate as that of the traditional solid-phase grafting method.
Background
Polypropylene is a colorless and semitransparent thermoplastic light general-purpose plastic, has chemical resistance, heat resistance, electrical insulation, high-strength mechanical property, good high-wear-resistance processing property and the like, and has wide development and application in a plurality of fields of machinery, automobiles, electronic and electric appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like.
However, polypropylene molecules are nonpolar crystalline polymers, and have poor compatibility with polar polymers and inorganic reinforced filling materials, and poor hydrophilicity, dyeing property, antistatic property, adhesion property, printability and the like, so that the application field of the polypropylene molecules is greatly limited.
The graft modification is used as a modification method of a high molecular material, and polar groups are introduced into a macromolecular chain of the high molecular material, so that the blending property, the compatibility and the cohesiveness of polypropylene are improved, and the defects of difficult blending, difficult compatibility and difficult bonding are overcome.
There are many methods of grafting, and a melt grafting method, a solution grafting method, a suspension grafting method, a solid phase grafting method, and the like are used in many cases.
The solvent method has high grafting rate and relatively low temperature in the reaction process. The solution grafting method has less side reaction and lower degradation degree of polypropylene, but the post-treatment of reaction products is more complicated, a large amount of organic solvent is needed, the cost is high, the technical requirement is high, and the environmental pollution is easily caused. The method is only suitable for small-batch production and is difficult to realize industrialization.
The melt grafting method is the most reasonable method at present and is suitable for industrial production. The method is the most studied method, and is characterized in that polypropylene, a monomer, an initiator and the like are melted and extruded together for grafting reaction, and the reaction temperature is higher than the melting point of the polypropylene and is generally 190-230 ℃. The boiling point of the grafting monomer selected by the melt grafting method is relatively high, and the monomers selected commonly comprise MAH and esters thereof, acrylic acid and esters thereof and the like. However, the beta-scission reaction in the melt grafting process is an unavoidable side reaction in the grafting process, so that the melt index of the maleic anhydride grafted polypropylene product prepared by the melt grafting method is usually very high, i.e., the molecular weight is greatly reduced, which can cause the mechanical property of the polypropylene product to be poor. The main problem faced by the melt grafting method is how to obtain a sufficiently high maleic anhydride grafting ratio while maintaining the mechanical properties of the polypropylene matrix, i.e. maintaining the molecular weight substantially unchanged, so that the final overall mechanical properties of the material are not affected when blended with other materials.
The solid phase grafting method includes dissolving monomer, initiator and other material in certain solvent to compound solution, grinding polypropylene into powder, reaction at temperature lower than the melting point of polypropylene and maintaining the system in inert gas atmosphere. The method has the advantages of proper reaction temperature, easy reaction process, less solvent consumption, simple post-treatment and less degradation of polypropylene, so that the product well keeps the mechanical property thereof, and the development is faster in recent years and general attention is paid. The solid phase grafting method is a local modification method, the reaction is mostly under the melting point of polypropylene, the solid phase grafting reaction of the polypropylene mainly occurs on the outer surface of polypropylene particles, reactants are easy to stick to the wall in the reaction process, the distribution of monomers is not uniform, and the grafting rate and the grafting efficiency of the monomers are relatively low.
Disclosure of Invention
The invention provides a microwave-assisted polypropylene grafting method, which comprises the steps of adding an initiator into an organic solvent, adding a certain amount of polypropylene and a grafting monomer, swelling in an inert gas environment, and irradiating the system for a certain time under a microwave condition to obtain a polypropylene grafting product.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of microwave assisted polypropylene grafting, the method comprising the steps of:
1) dissolving an initiator in an interfacial agent until the initiator is completely dissolved, adding polypropylene into the interfacial agent for swelling, and continuously introducing nitrogen in the swelling process;
2) adding a first monomer and a second monomer into the reaction system in the step 1), and heating and irradiating by using microwaves to perform reaction;
3) and (3) after the reaction in the step 2) is finished, cooling to room temperature, and drying to constant weight.
In a preferred embodiment of the present invention, the initiator includes an azo initiator or a peroxide initiator.
Preferably, the initiator is selected from dibenzoyl peroxide BPO, tert-butyl benzoyl peroxide TBP, azobisisobutyronitrile AIBN or dicumyl peroxide DCP. Most preferably, the initiator of the present invention is Benzoyl Peroxide (BPO).
In a preferred embodiment of the present invention, the interfacial agent comprises benzene.
The interfacial agent can be dimethylbenzene or a mixed solution of dimethylbenzene and polyalcohol, and the volume ratio is 5: 1-3.
In a preferred embodiment of the present invention, the first monomer is Styrene (ST).
In a preferred embodiment of the present invention, the second monomer includes one or more of the group consisting of Maleic Anhydride (MAH), Acrylic Acid (AA), Acrylonitrile (AN), Glycidyl Methacrylate (GMA), Methyl Methacrylate (MMA), hydroxyethyl methacrylate (HEMA), vinyl acetate (Vac), and Acrylamide (AM).
In a preferable embodiment of the present invention, the mass ratio of the polypropylene to the first monomer is not less than 10: 1.
In a preferable embodiment of the present invention, the mass ratio of the polypropylene to the second monomer is greater than or equal to 10: 1.
As a preferable scheme of the invention, the power of the microwave heating irradiation is 0-1000W, and the time of the microwave heating irradiation is 0-60 min.
As a preferable mode of the present invention, the temperature for drying in the step 3) is 50 to 80 ℃.
Compared with the prior art, the invention has the following advantages:
the invention can obtain higher grafting rate than the traditional solid phase grafting under the same condition by microwave irradiation assisted polypropylene grafting, and can obtain the grafting rate close to the traditional solid phase grafting in a shorter time; meanwhile, the invention purifies the product while the microwave irradiation assists grafting, thereby avoiding the subsequent extraction step, saving the working procedure and improving the production efficiency.
Drawings
FIG. 1 is an infrared analysis spectrum of the PP-g-MAH/St graft of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is an improvement on the traditional solid phase grafting method, and can obtain higher grafting rate than the traditional solid phase grafting under the same condition by microwave irradiation assisted polypropylene grafting, and can obtain the grafting rate close to the traditional solid phase grafting in a shorter time.
In the preparation method of the functional monomer grafted polypropylene resin, the polypropylene resin used for grafting is various polypropylene resins in the prior art, and the polymerization process of the polypropylene resin is also available in the prior art. The polypropylene resin of the present invention comprises a solid form of powder, pellet or article, preferably polypropylene powder, which is preferably polypropylene powder obtained by polymerization using a spherical catalyst. The polypropylene powder obtained by polymerization with the spherical catalyst has spherical particles and a plurality of pores on the surface of the particles, so that the polypropylene powder has a large specific surface area and a large contact area with the monomer, and is beneficial to obtaining a grafted product with a higher grafting rate.
The polypropylene used for grafting is preferably a polypropylene free of antioxidants. Usually, the polypropylene resin raw materials in the prior art all contain certain antioxidant, and the antioxidant is added when the polypropylene powder obtained after polymerization reaction is melted, extruded and granulated. However, the antioxidant easily consumes free radicals in the subsequent graft modification, and the polypropylene graft effect without the antioxidant is better. The polypropylene of the invention is preferably a polypropylene obtained by polymerization and not yet melt-extruded and pelletized, in which case the polypropylene is free of antioxidant.
The polypropylene may be any of various types of polypropylene commonly used in the art, including but not limited to at least one of homopolypropylene, random copolymer polypropylene, and impact copolymer polypropylene. When the polypropylene powder is copolymerized polypropylene, random copolymerized polypropylene and impact copolymerized polypropylene are preferred.
According to the invention, by utilizing the characteristic of microwave selective heating, the first monomer, the second monomer and the polypropylene are subjected to grafting reaction under the condition of adding an initiator by microwave irradiation, so that the grafted polypropylene with the molecular weight not remarkably reduced is prepared. Without being bound by any theory, it is believed that: polypropylene resins are microwave transparent in a microwave environment (little or no microwave absorption under microwave irradiation and therefore no heat generation under microwave irradiation). The invention utilizes the selective heating of microwave, controls the temperature at about 140 ℃, and the polypropylene is not subjected to chain scission at the temperature, but the tertiary carbon atom of the polypropylene can be dehydrogenated, so that the grafting reaction can be carried out, but the chain scission reaction can not be caused. The grafting method can greatly avoid the side reaction of the polypropylene during the grafting by the melting method during the microwave grafting reaction, does not reduce the molecular weight of the polypropylene and ensures that the product keeps excellent mechanical property.
Example 1
Dissolving 0.0691g of benzoyl peroxide in 35mL of xylene, performing ultrasonic treatment until the benzoyl peroxide is completely dissolved, weighing 5.0154g of polypropylene, adding the weighed polypropylene into the xylene to swell, continuously introducing nitrogen during the swelling process, adding 0.5105g of styrene and 0.5046g of maleic anhydride, and heating for 30min by 480W microwaves. After the reaction was completed and cooled to room temperature, the obtained product was extracted with acetone for 3 hours and dried at 60 ℃ to constant weight. The graft ratio was calculated to be 0.3555%.
Example 2
Dissolving 0.0645g of benzoyl peroxide in 25mL of dimethylbenzene and 10mL of ethylene glycol, carrying out ultrasonic treatment until the benzoyl peroxide is completely dissolved, weighing 5.0259g of polypropylene, adding the polypropylene into the dimethylbenzene for swelling, continuously introducing nitrogen during the swelling process, adding 0.5154g of styrene and 0.5059g of maleic anhydride, and heating for 30min by using 560W microwaves. After the reaction was cooled to room temperature, the reaction was dried at 60 ℃ to constant weight, and the graft ratio was calculated to be 1.3449%.
Example 3
0.0642g of benzoyl peroxide is dissolved in 29.2mL of dimethylbenzene and 5.8mL of 1, 4-butanediol, ultrasonic treatment is carried out until the benzoyl peroxide is completely dissolved, 5.0083g of polypropylene is weighed and added into the dimethylbenzene for swelling, nitrogen is continuously introduced during the swelling process, 0.5130g of styrene and 0.5135g of maleic anhydride are added, and microwave heating is carried out for 30min under 640W. After the reaction was cooled to room temperature, the reaction was dried at 60 ℃ to constant weight, and the graft ratio was calculated to be 1.6306%.
Example 4
0.0607g of benzoyl peroxide is dissolved in 35mL of xylene, ultrasonic treatment is carried out until the benzoyl peroxide is completely dissolved, 5.0725g of polypropylene is weighed and added into the xylene for swelling, nitrogen is continuously introduced during the swelling process, 0.5104g of styrene and 0.5040g of maleic anhydride are added, and the mixture is heated for 30min by 720W microwaves. After the reaction was completed and cooled to room temperature, the obtained product was extracted with acetone for 3 hours and dried at 60 ℃ to constant weight, and the grafting rate was calculated to be 1.0257%.
Example 5
0.0617g of benzoyl peroxide is dissolved in 35mL of xylene, ultrasonic treatment is carried out until the benzoyl peroxide is completely dissolved, 5.0094g of polypropylene is weighed and added into the xylene for swelling, nitrogen is continuously introduced during the swelling process, 0.5160g of styrene and 0.5049g of maleic anhydride are added, and microwave heating is carried out for 30min under 800W. After the reaction was completed and cooled to room temperature, the obtained product was extracted with acetone for 3 hours and dried at 60 ℃ to constant weight, and the grafting rate was calculated to be 0.8203%.
Example 6
Dissolving 0.0678g of benzoyl peroxide in 50mL of xylene, performing ultrasonic treatment until the benzoyl peroxide is completely dissolved, weighing 5.0931g of polypropylene, adding the weighed polypropylene into the xylene to swell, continuously introducing nitrogen during the swelling process, adding 0.5132g of styrene and 0.5057g of maleic anhydride, and heating for 30min by using 800W microwaves. After the reaction was completed and cooled to room temperature, the obtained product was extracted with acetone for 3 hours and dried at 60 ℃ to constant weight, and the grafting rate was calculated to be 1.4322%.
Comparative example 1
Dissolving 0.0678g of benzoyl peroxide in 50mL of dimethylbenzene, carrying out ultrasonic treatment until the benzoyl peroxide is completely dissolved, weighing 5.0931g of polypropylene, adding the weighed polypropylene into the dimethylbenzene for swelling, continuously introducing nitrogen during the swelling process, adding 0.5132g of styrene and 0.5057g of maleic anhydride, and heating for 2 hours at 140 ℃ in an oil bath. After the reaction was completed and cooled to room temperature, the obtained product was extracted with acetone for 3 hours and dried at 60 ℃ to constant weight, and the grafting rate was calculated to be 1.1483%.
FIG. 1 is an infrared spectrum of PP-g-MAH/St graft of example 1 of the present invention, graft-modified PP is 1858cm-1And 1786cm-1There is an absorption peak, which indicates the grafting of MAH to PP by microwave irradiation; at the same time 1604cm-1、762cm-1、704cm-1The absorption peak indicates that styrene is grafted to PP.
As can be seen from comparative example 1 and example 6, under the condition that the process steps and raw materials are the same, the only difference is that the microwave heating irradiation assisted polypropylene grafting is adopted in example 6, the reaction time is 30min which is greatly shorter than the reaction time of 120min in comparative example 1, the production efficiency is improved, and meanwhile, the grafting rate is correspondingly improved.
Therefore, the invention can obtain higher grafting rate than the traditional solid phase grafting under the same condition by microwave irradiation assisted polypropylene grafting, and can obtain the grafting rate close to the traditional solid phase grafting in a shorter time; meanwhile, the invention purifies the product while the microwave irradiation assists grafting, thereby avoiding the subsequent extraction step, saving the working procedure and improving the production efficiency.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A microwave-assisted polypropylene grafting process, characterized in that it comprises the steps of:
1) dissolving an initiator in an interfacial agent until the initiator is completely dissolved, adding polypropylene into the interfacial agent for swelling, and continuously introducing nitrogen in the swelling process;
2) adding a first monomer and a second monomer into the reaction system in the step 1), and heating and irradiating by using microwaves to perform reaction;
3) and (3) after the reaction in the step 2) is finished, cooling to room temperature, and drying to constant weight.
2. The method of claim 1, wherein the initiator comprises azo initiator or peroxide initiator.
3. The method of claim 1, wherein the interfacial agent comprises benzene.
4. The microwave-assisted polypropylene grafting method according to claim 3, wherein the interfacial agent is a mixed solution of xylene and polyols in a volume ratio of 5: 1-2.
5. The method of claim 1, wherein the first monomer is styrene.
6. The method of claim 1, wherein the second monomer comprises one or more of the group consisting of maleic anhydride, acrylic acid, acrylonitrile, glycidyl methacrylate, methyl methacrylate, hydroxyethyl methacrylate, vinyl acetate, and acrylamide.
7. The microwave-assisted polypropylene grafting method according to claim 1, wherein the mass ratio of the polypropylene to the first monomer is not less than 10: 1.
8. The microwave-assisted polypropylene grafting method according to claim 1, wherein the mass ratio of the polypropylene to the second monomer is not less than 10: 1.
9. The microwave-assisted polypropylene grafting method according to claim 1, wherein the power of the microwave heating irradiation is 0-1000W, and the time of the microwave heating irradiation is 0-60 min.
10. The method of claim 1, wherein the drying temperature in step 3) is 50-80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011640914.6A CN112694567A (en) | 2020-12-31 | 2020-12-31 | Microwave-assisted polypropylene grafting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011640914.6A CN112694567A (en) | 2020-12-31 | 2020-12-31 | Microwave-assisted polypropylene grafting method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112694567A true CN112694567A (en) | 2021-04-23 |
Family
ID=75514012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011640914.6A Pending CN112694567A (en) | 2020-12-31 | 2020-12-31 | Microwave-assisted polypropylene grafting method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112694567A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478848A (en) * | 2021-12-28 | 2022-05-13 | 中化泉州石化有限公司 | Method for purifying and decontaminating polyolefin graft |
| CN115490904A (en) * | 2022-09-06 | 2022-12-20 | 浙江大学 | Method for grafting MAH on surface of PP (polypropylene) film through microwave induction, modified PP film and composite film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348772A (en) * | 1991-06-10 | 1994-09-20 | Institut Textile De France | Use of amino groups, obtained on a polymer material by an electric treatment under nitrogen atmosphere, for accelerating a grafting reaction |
| CN1670049A (en) * | 2005-03-15 | 2005-09-21 | 华南理工大学 | Process for preparing polyolefin and vinyl monomer graft copolymer |
| WO2019206288A1 (en) * | 2018-04-27 | 2019-10-31 | 中国石油化工股份有限公司 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| CN111848873A (en) * | 2019-04-26 | 2020-10-30 | 中国石油化工股份有限公司 | Functional monomer grafted polypropylene and preparation method thereof |
-
2020
- 2020-12-31 CN CN202011640914.6A patent/CN112694567A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348772A (en) * | 1991-06-10 | 1994-09-20 | Institut Textile De France | Use of amino groups, obtained on a polymer material by an electric treatment under nitrogen atmosphere, for accelerating a grafting reaction |
| CN1670049A (en) * | 2005-03-15 | 2005-09-21 | 华南理工大学 | Process for preparing polyolefin and vinyl monomer graft copolymer |
| WO2019206288A1 (en) * | 2018-04-27 | 2019-10-31 | 中国石油化工股份有限公司 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| CN111848873A (en) * | 2019-04-26 | 2020-10-30 | 中国石油化工股份有限公司 | Functional monomer grafted polypropylene and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SONGHE WANG,ET AL.: "Polymer Solid-Phase Grafting at Temperature Higher than the Polymer Melting Point through Selective Heating", 《MACROMOLECULES》 * |
| 陈宋辉等: "聚丙烯固相接枝马来酸酐改性研究", 《化学与生物工程》 * |
| 陈宋辉等: "聚丙烯微波辐照固相接枝改性研究", 《化学与生物工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478848A (en) * | 2021-12-28 | 2022-05-13 | 中化泉州石化有限公司 | Method for purifying and decontaminating polyolefin graft |
| CN114478848B (en) * | 2021-12-28 | 2023-06-30 | 中化泉州石化有限公司 | Method for purifying and removing impurities of polyolefin graft |
| CN115490904A (en) * | 2022-09-06 | 2022-12-20 | 浙江大学 | Method for grafting MAH on surface of PP (polypropylene) film through microwave induction, modified PP film and composite film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100443518C (en) | Method of palliating degradation degree in polypropylene fusion graft process | |
| EP3786202B1 (en) | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof | |
| CN101492517B (en) | Method of preparing polypropylene graft polymer | |
| CN112694567A (en) | Microwave-assisted polypropylene grafting method | |
| CN101880421B (en) | Polypropylene/ organic montmorillonite nano composite material and preparation method thereof | |
| CN111848873B (en) | Functional monomer grafted polypropylene and preparation method thereof | |
| CN101440145A (en) | Activated waste rubber powder and preparation thereof | |
| CN109054307B (en) | Impact-resistant weather-resistant PET/PC alloy material and preparation method thereof | |
| CN113265029A (en) | Long-chain branched polylactic acid with high melt strength and excellent processing fluidity and preparation method thereof | |
| KR20220056214A (en) | Solvent-free adhesion promoting chain extender and manufacturing method and application thereof | |
| CN101016361A (en) | Fusion preparation method for simultaneously reinforcing polarity and graft degree of polyolefin | |
| WO2023045268A1 (en) | Preparation method of hly-active tackifying chain extender without monomer residue and use thereof | |
| CN102199257A (en) | Preparation method of modified polylactic acid | |
| CN101418064B (en) | Method for preparing long-chain branch high fused mass strength polypropylene resin | |
| CN113402678B (en) | Method for preparing high-melt-strength polylactic resin through two-step reaction | |
| CN102532772A (en) | Method for improving performances of regenerated PE mulching film by using graft copolymerization | |
| CN106589868B (en) | A kind of polylactic acid/polypropylene/polybutadiene composite material and preparation method | |
| CN113292760B (en) | Cross-linked syndiotactic polypropylene foam and preparation method and application thereof | |
| US3567697A (en) | Method of producing articles of cross-linked polyethylene | |
| CN106519386A (en) | Preparing method of high-performance HDPE/PET microfiber strengthened blend | |
| CN106519123A (en) | High-impact polypropylene grafted polymer and preparation method thereof | |
| CN111378260A (en) | Modified polylactic acid and preparation method thereof | |
| CN1392169A (en) | Thermal synthesis process for preparing grafted polyvinyl-maleic anhydride copolymer in solvent | |
| CN109553724A (en) | A kind of high melt strength polypropylene material and preparation method thereof | |
| CN110818842A (en) | Reaction method of vinyl acetate monomer and grafted polyethylene matrix |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210423 |