CN112694567A - Microwave-assisted polypropylene grafting method - Google Patents
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- 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
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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 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 ℃.
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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 |
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| CN116377652A (en) * | 2023-04-18 | 2023-07-04 | 浙江京博聚烯烃新材料有限公司 | A kind of hydrophilic modified polypropylene non-woven fabric and its preparation method and application |
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| 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 |
| CN116377652A (en) * | 2023-04-18 | 2023-07-04 | 浙江京博聚烯烃新材料有限公司 | A kind of hydrophilic modified polypropylene non-woven fabric and its preparation method and application |
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