CN103183781A - Plasma-initiated method for preparing allyl monomer-polyolefin grafted copolymer - Google Patents
Plasma-initiated method for preparing allyl monomer-polyolefin grafted copolymer Download PDFInfo
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Abstract
The invention provides a plasma-initiated method for preparing an allyl monomer-polyolefin grafted copolymer. The method comprises the following steps of: ionizing gas to plasmas by a dielectric barrier discharge (DBD) method, and meanwhile, treating the surfaces of polymer solid particles through the plasmas; generating active free radicals such as peroxy radicals on the surface of the polymer treated in a short time; immediately transferring the treated polymer particles to a flask containing allyl monomers such as styrene; grafting under protection of nitrogen; under initiating effect of various active radicals on the surface of the polymer, on the one hand grafting the allyl monomers such as styrene on the surface of the polymer to form the grafted polymer and on the other hand, performing homopolymerization on the allyl monomers; and after a period of time, washing the homopolymer by a special washing liquid to obtain the residual product which is the targeted product polymer grafted copolymer. The method is free from extra initiator, short in reaction time, free from high vacuum and high voltage, mild in reaction condition and higher in grafting efficiency, the reaction period is shortened and the energy resources are saved.
Description
Technical field
The present invention relates to the Cement Composite Treated by Plasma solid polyolefin particles and cause vinyl monomers such as vinylbenzene at its surface grafting polymerization to prepare the method for polymer graft multipolymer.
Background technology
Plasma state is also referred to as the 4th attitude of material, and the most of materials of visible all exist with isoionic state in the universe, all exists with plasma state such as fixed star and all visible interplanetary materials.Plasma body is a kind of ionized gas, is made up of positive ion, negative ion, electronics and uncharged particle usually.Along with the research of article on plasma body deepens continuously, plasma body is constantly expanded in the application of every field, and in field of polymer technology, plasma technology has been used to aspects such as plasma surface modification, plasma polymerization and plasma initiated polymerization.
The plasma surface modification refers to using plasma and handles polymer surfaces, the modification mode that its surface group and other character are changed.The basic skills of plasma polymerization is to utilize discharge technology to make organic gas monomer generation ionization produce positive ion, negative ion, free radical isoreactivity particle, reacts between these active particles or between active particle and the monomer and generates polymkeric substance.The plasma initiated polymerization refers to earlier and with plasma body polymer monomer is carried out the short period of time processing, afterwards monomer transfer is carried out polymerization generation polymkeric substance in reactor under proper temperature.
Single polymer materials may be not enough to some extent at aspects such as winter hardiness, weathering resistance, photostabilization, dyeability, cementability, static resistance, wetting abilities, and differ with the consistency of materials such as other polymkeric substance, inorganic filling and strongthener also quality, these shortcomings have restricted the application of polymer materials.In order to improve its performance, enlarge its range of application, need carry out modification to it.The method of modification has a lot, graft modification is exactly wherein very important a kind of, concrete grammar has a variety of, and as chemical graft, mechanical grafting, photo-grafting etc., wherein chemical graft comprises solution graft copolymerization, solid phase grafting, fusion-grafting, gas phase grafting, suspension grafting etc. again.At present, traditional graft-modification method day by day embodies some limitation, can cause to a certain degree change as the traditional chemical grafting method to the character of mass polymer, and need the extra initiator of introducing usually, and technology is also comparatively complicated, and percentage of grafting is not high.The using plasma chemical process does not then need additionally to introduce initiator, can keep to the full extent introducing polar functional group at material surface under the prerequisite of the original performance of polymkeric substance, improve the polymer surfaces performance, this method has advantages such as temperature of reaction is low, product is clean, technology is simple.
In the prior art, there have been some to utilize the patent of invention of plasma chemical method, feed in the reaction chamber with a kind of carbonization molecular gas with as the polyreaction gas that the helium of assist gas is formed as CN1412347, apply high-voltage at electrode then, make the gas generation plasma reaction that feeds polymerization reaction chamber, thereby form the polymerization plated film and the surface property of material is changed at material surface, gas condition is strict in the reaction required voltage height in this patent of invention, reaction chamber.CN1687149A under atmospheric pressure utilizes nitrogen gas plasma to synthesize the homopolymer of vinylformic acid and acrylamide monomer respectively, but need keep high vacuum to feed N in one minute then system with vacuum pump
2To normal pressure, three times with the O of displacement in the container repeatedly
2, reactions steps is comparatively complicated, and the post polymerization overlong time, needs more than 120～200 hours, and reactive behavior is lower, and reaction time is long, and energy dissipation is serious.CN1259173 sends into unsaturated aliphatic hydrocarbon monomer gas (or fluorochemical monomer gas) and non-polymeric gas with predetermined pressure in reaction chamber under high vacuum, utilize direct current (DC) discharge plasma the metallic surface to be handled the polymeric film that makes its surface deposition one deck hydrophilic or hydrophobic afterwards, need in reaction chamber, to install the anode electrode of cathode electrode and pending metal matrix in the process, and need the pressure in the reaction chamber is maintained under the predetermined vacuum tightness, the conditional request strictness, the process complexity wastes energy.
At problem described above, the invention provides vinyl monomers such as a kind of Cement Composite Treated by Plasma polymer solid particles surface and then initiation vinylbenzene and carry out the plasma modification method that graft polymerization prepares the polymer graft multipolymer on its surface.The method applied in the present invention can be classified as the method for solid phase grafting, compare with traditional graft-modification method, not only can under the situation that keeps the original performance of polymkeric substance, introduce polar functional group, and have low temperature, low pressure, low cost, advantages such as technology is simple, percentage of grafting is high, product cleaning; Compare with the relevant patent of existing plasma chemical method, method provided by the invention is mainly used in thermoplastic polymer graft modification by copolymerization, does not need harsh technology controlling and process such as high vacuum; Compare with the method for plasma initiated polymerization, the present invention carries out graft polymerization on the surface of activating after earlier polymer surfaces being activated, and method is obviously different.
Summary of the invention
The purpose of this invention is to provide a kind of Cement Composite Treated by Plasma polymer solid particles surface and cause vinyl monomer such as vinylbenzene at its surface grafting polymerization to prepare the method for polymer graft multipolymer.The method of working medium barrier discharge (DBD) makes ionization of gas become plasma body; utilize these plasma bodys that the polymer solid particles surface is handled simultaneously; short period of time handles post polymerization thing surface and generates peroxy isoreactivity free radical; be transferred to the polymer beads after handling in the flask that fills vinyl monomers such as vinylbenzene immediately; carry out graft reaction under the nitrogen protection; under the initiation of the various active groups of polymer surfaces; vinyl monomers such as vinylbenzene are grafted on polymer surfaces on the one hand and form graftomer, and homopolymerization also takes place for self on the other hand.Behind the certain hour, use the specific scavenging solution can be with the homopolymer flush away, a resultant product be target product polymer graft multipolymer.This method does not need additionally to add initiator, and the reaction times is short, does not need the high vacuum high voltage condition, the reaction conditions gentleness, and percentage of grafting is higher, has shortened reaction time, save energy.
Plasma body provided by the invention causes the method for preparing vinyl monomer-polyolefin graft copolymer, and the method at its surface grafting polymerization may further comprise the steps:
1) solid polyolefin particles that takes by weighing certain mass places beaker, adds a certain amount of ethanol, makes particle be immersed in wherein supersound process 30min fully.Clean repeatedly three times with distilled water afterwards, leach solid particulate and place baking oven, 50 ℃ of following oven dry stored for future use after 24 hours.
2) the step 1) polymer solid particles is placed plasma processing apparatus, connecting the carrier gas medium and make it be full of reactor, connect AC power, is the 1-100 volt at voltage, gas flow is 60 ml/min, and be to carry out surface treatment under the condition in 1～30 minute discharge time;
3) step 2) the gained material mixes with vinyl monomer, carries out graft reaction under 90～120 ℃ of conditions, logical nitrogen protection all the time in the reaction process, condensing reflux, 0.5～8 hour reaction times;
4) after the homopolymer of the product solubilizing agent flush away vinyl monomer that obtains of step 3), continue Soxhlet and extracted 48 hours, obtain polyolefin graft copolymer.
The mass ratio of described polyolefine solid grain and vinyl monomer is 1:1～1:40.
Described polymer solid particles is a kind of in the pellets such as isotatic polypropylene, Atactic Polypropelene, syndiotactic polypropylene and Low Density Polyethylene.
Described styrene monomer can be selected from one or more the mixture in p-methylstyrene, alpha-methyl styrene, vinylbenzene or the right-chloro-styrene.
Described solvent can be selected from one or more the mixture in chloroform, tetrahydrofuran (THF), ethyl acetate or the n-butyl acetate.
Described gaseous media is one or more the mixing in argon gas, air, nitrogen or the carbonic acid gas.
The present invention has following outstanding feature:
1) plasma treated polymeric aggregate can cause the graft reaction of vinyl monomer fast, and efficiency of initiation height, product use the situation of initiator purer.
2) under temperature of reaction, polymkeric substance is solid, and the pellet after the plasma treatment can cause the polymerization of vinyl monomer fast, just can react completely in the very short time.Separated product can not contained the graft product of homopolymer impurity, and can calculate the percentage of grafting of grafts, efficiency of initiation height, percentage of grafting height.
Description of drawings
Fig. 1 is the infrared spectra of example 1 polymer graft multipolymer.
Fig. 2 is the infrared spectra of example 2 polymer graft multipolymers.
Fig. 3 is the infrared spectra of example 3 polymer graft multipolymers.
Specific implementation method
Below by real case the present invention is described specifically; this example is only for the present invention will be further described; can not be interpreted as limiting the scope of the invention, those skilled in the art makes improvement and the adjustment of some non-intrinsically safes according to the described content of preamble, all belongs to protection domain of the present invention.
Example 1
The polypropylene granules that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that argon gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 2 hours down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 7.4%.For characterizing the grafting situation, the gained final product carries out compressing tablet and send infrared test, and its infrared spectra spectrogram is seen accompanying drawing 1,698cm
-1The place is the characteristic peak of tangible polystyrene segment.
Example 2
The polypropylene granules that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that nitrogen, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 26 minutes under the condition of 35V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 1 hour down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, it is following dry 12 hours afterwards product to be put into 50 ℃ of vacuum drying ovens, pure products after the drying is accurately weighed, calculating percentage of grafting is 3%, the gained final product carries out compressing tablet and send infrared test, and its infrared spectra spectrogram is seen accompanying drawing 2,698cm
-1The place is the characteristic peak of tangible polystyrene segment.
Example 3
The polypropylene granules that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 16 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 5 hours down at 110 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, it is following dry 12 hours afterwards product to be put into 50 ℃ of vacuum drying ovens, pure products after the drying is accurately weighed, calculating percentage of grafting and be 6.6% gained final product carries out compressing tablet and send infrared test, its infrared spectra spectrogram is seen accompanying drawing 3,698cm
-1The place is the characteristic peak of tangible polystyrene segment.
Example 4
The polypropylene granules that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 13 minutes under the condition of 35V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 8 hours down at 110 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, obtain pure products after the drying, weighing and calculating percentage of grafting is 5.4%.
Example 5
The polypropylene granules that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that argon gas and Air mixing gas (volume ratio 2:1), air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 20 minutes under the condition of 45V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 2 hours down at 100 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, obtain dry back pure products, accurately weighing and calculating percentage of grafting is 6.5%.
Example 6
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that nitrogen, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 6 minutes under the condition of 28V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 7 hours down at 120 ℃, with the styrene homopolymers in the n-butyl acetate lysate, extract the solid particulate crude product after reaction is finished.Be solvent with the n-butyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 4.3%.
Example 7
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that nitrogen, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 2 minutes under the condition of 50V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:10 with styrene monomer, reacted 3.5 hours down at 115 ℃, with the styrene homopolymers in the tetrahydrofuran (THF) lysate, extract the solid particulate crude product after reaction is finished.Be solvent with the tetrahydrofuran (THF), crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3.2%.
Example 8
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that nitrogen, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 25 minutes under the condition of 60V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:10 with styrene monomer, reacted 1.5 hours down at 95 ℃, with the styrene homopolymers in the chloroform lysate, extract the solid particulate crude product after reaction is finished.Be solvent with the chloroform, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 2.9%.
Example 9
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that nitrogen, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 15 minutes under the condition of 55V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:10 with styrene monomer, reacted 4 hours down at 110 ℃, after finishing, reaction with the styrene homopolymers in mixing solutions (volume ratio 1:1) lysate of n-butyl acetate and ethyl acetate, extracts the solid particulate crude product.Mixing solutions with n-butyl acetate and ethyl acetate is solvent, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of following dryings of vacuum drying oven 12 hours, pure products after the drying is accurately weighed, calculating percentage of grafting is 4%.
Example 10
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that nitrogen, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 3 minutes under the condition of 35V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:10 with the vinyl toluene monomer, reacted 5 hours down at 110 ℃, with the vinyl toluene homopolymer in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 5.1%.
Example 11
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 3 minutes under the condition of 20V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with α-Jia Jibenyixidanti, reacted 2 hours down at 110 ℃, with the alpha-methyl styrene homopolymer in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3.2%.
Example 12
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 5 minutes under the condition of 60V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with right-chloro-styrene monomer, reacted 2 hours down at 100 ℃, with the right-chloro-styrene homopolymer in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3.8%.
Example 13
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 5 minutes under the condition of 80V.After finishing dealing with product right with vinylbenzene-chloro-styrene mix monomer (volume ratio 1:1) by by mass ratio 1:20 mix the input there-necked flask in, reacted 1 hour down at 100 ℃, after finishing, reaction with the non-graftomer in the acetic acid ethyl dissolution product, extracts the solid particulate crude product.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3.8%.
Example 14
The Atactic Polypropelene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 5 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 4 hours down at 100 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 7.1%.
Example 15
The syndiotactic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 5 minutes under the condition of 50V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:5 with styrene monomer, reacted 3 hours down at 100 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 5.8%.
Example 16
The Low Density Polyethylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 18 minutes under the condition of 50V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:5 with styrene monomer, reacted 7 hours down at 100 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3.3%.
Example 17
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that carbonic acid gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 13 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:5 with styrene monomer, reacted 3 hours down at 100 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 4.5%.
Example 18
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that argon gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 60V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:40 with styrene monomer, reacted 2 hours down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3.7%.
Example 19
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that argon gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 30V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:28 with styrene monomer, reacted 0.5 hour down at 110 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3%.
Example 20
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that argon gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 3 hours down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 6.4%.
Example 21
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 10V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:38 with styrene monomer, reacted 6 hours down at 90 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 1.0%.
Example 22
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 100V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:25 with styrene monomer, reacted 3.5 hours down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 7.1%.
Example 23
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 1 minute under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:30 with styrene monomer, reacted 8 hours down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 3.5%.
Example 24
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 30 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:2 with styrene monomer, reacted 5 hours down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 5.4%.
Example 25
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 0.5 hour down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 0.8%.
Example 26
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:5 with styrene monomer, reacted 4 hours down at 120 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 4.4%.
Example 27
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:35 with styrene monomer, reacted 2 hours down at 110 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 6.2%.
Example 28
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that argon gas, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:15 with styrene monomer, reacted 2 hours down at 100 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 6%.
Example 29
The isotatic polypropylene pellet that accurately takes by weighing after the 4.0g cleaning places the plasma reaction device, and selecting the carrier gas medium is that air, air-flow size are that 60 milliliters of per minutes, sparking voltage are to carry out plasma treatment 10 minutes under the condition of 40V.After finishing dealing with product is dropped in the there-necked flask by mixing by mass ratio 1:20 with styrene monomer, reacted 2 hours down at 90 ℃, with the styrene homopolymers in the acetic acid ethyl dissolution product, extract the solid particulate crude product after reaction is finished.Be solvent with the ethyl acetate, crude product dropped into carry out Soxhlet in the apparatus,Soxhlet's and extracted 48 hours, afterwards product was put into 50 ℃ of vacuum drying ovens dry 12 hours down, pure products after the drying is accurately weighed, calculating percentage of grafting is 2%.
Claims (6)
1. a plasma body causes the method for preparing the single body ?of alkene class polyolefin graft copolymer, it is characterized in that may further comprise the steps and finishes:
1) solid polyolefin particles that takes by weighing certain mass places beaker, adds a certain amount of ethanol, makes particle be immersed in wherein supersound process 30min fully.Clean repeatedly three times with distilled water afterwards, leach solid particulate and place baking oven, 50 ℃ of following oven dry stored for future use after 24 hours.
2) the step 1) polymer solid particles is placed plasma processing apparatus, connecting the carrier gas medium and make it be full of reactor, connect AC power, is the 1-100 volt at voltage, gas flow is 60 ml/min, and be to carry out surface treatment under the condition in 1～30 minute discharge time;
3) step 2) the gained material mixes with vinyl monomer, carries out graft reaction under 90～120 ℃ of conditions, logical nitrogen protection all the time in the reaction process, condensing reflux, 0.5～8 hour reaction times;
4) after the homopolymer of the product solubilizing agent flush away vinyl monomer that obtains of step 3), continue Soxhlet and extracted 48 hours, obtain polyolefin graft copolymer.
2. in accordance with the method for claim 1, the mass ratio that it is characterized in that described polymer solids pellet and vinyl monomer is 1:1～40.
3. in accordance with the method for claim 1, it is characterized in that described polymer solids pellet is a kind of in isotatic polypropylene, Atactic Polypropelene, syndiotactic polypropylene or the Low Density Polyethylene pellet.
4. in accordance with the method for claim 1, it is characterized in that described styrene monomer is selected from one or more the mixture in p-methylstyrene, alpha-methyl styrene, vinylbenzene or the right-chloro-styrene.
5. in accordance with the method for claim 1, it is characterized in that described gaseous media is one or more the mixing in argon gas, air, nitrogen or the carbonic acid gas.
6. in accordance with the method for claim 1, it is characterized in that described solvent is selected from one or more the mixture in chloroform, tetrahydrofuran (THF), ethyl acetate or the n-butyl acetate.
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| CN107474256A (en) * | 2017-07-24 | 2017-12-15 | 天津大学 | A kind of method for triggering polypropylene and ethylene propylene diene rubber graft reaction by carbon dioxide plasma |
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| CN111548522A (en) * | 2020-06-08 | 2020-08-18 | 闽江学院 | Device for plasma-initiated surface graft polymerization modification of polymer material |
| CN112403282A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Amphiphilic polypropylene porous membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103696256A (en) * | 2013-08-30 | 2014-04-02 | 南京工业大学 | Method for improving benzene series adsorbability and regeneration adsorbability of PP fibers |
| CN106432614A (en) * | 2016-10-26 | 2017-02-22 | 山东省科学院能源研究所 | Method of promoting polyolefin grafting reaction |
| CN106432614B (en) * | 2016-10-26 | 2019-07-05 | 山东省科学院能源研究所 | A method of promoting polyolefin graft reaction |
| CN107474256A (en) * | 2017-07-24 | 2017-12-15 | 天津大学 | A kind of method for triggering polypropylene and ethylene propylene diene rubber graft reaction by carbon dioxide plasma |
| CN108588006A (en) * | 2018-05-10 | 2018-09-28 | 华东理工大学 | A kind of biological support and its preparation method and application for liver cell dimensional culture |
| CN112403282A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Amphiphilic polypropylene porous membrane and preparation method and application thereof |
| CN112403282B (en) * | 2019-08-23 | 2022-06-03 | 中国石油化工股份有限公司 | Amphiphilic polypropylene porous membrane and preparation method and application thereof |
| CN110698598A (en) * | 2019-09-17 | 2020-01-17 | 上海交通大学 | Polyolefin material with surface grafted with polymer, and preparation method and application thereof |
| WO2021052071A1 (en) * | 2019-09-17 | 2021-03-25 | 浙江伟星新型建材股份有限公司 | Polyolefin material having polymer grafted on surface, and preparation method and application thereof |
| CN111548522A (en) * | 2020-06-08 | 2020-08-18 | 闽江学院 | Device for plasma-initiated surface graft polymerization modification of polymer material |
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