CN106496424A - A kind of preparation method of maleic anhydride melt grafting polyolefine material - Google Patents
A kind of preparation method of maleic anhydride melt grafting polyolefine material Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F255/04—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 on to ethene-propene copolymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The present invention discloses a kind of preparation method of maleic anhydride melt grafting polyolefine material.It is prepared from by polyolefin, initiator, maleic anhydride, second comonomer styrene, auxiliary packing graphene oxide melt blending.The present invention can effectively suppress the crosslinking of the degraded of polypropylene tertiary carbon segment free radical, polyethylene secondary carbon segment free radical due to the addition of graphene oxide, higher initiator content can't cause larger degraded or crosslinking, can achieve effective control or the regulation of degraded and crosslinking.Maleic anhydride stem grafting polyolefin percent grafting height, the molecular weight height for obtaining is prepared by the method for the present invention, such as percent grafting is 3.1%, and melting means is 3.0g/10min (230 DEG C, 2.16kg).
Description
Technical field
The invention belongs to polymeric material field, and in particular to high percent grafting, high molecular or high percent grafting, low crosslinking degree
Maleic anhydride melt grafting polyolefine material preparation method.
Background technology
Polyolefin (PO, polyolefin) is a kind of general-purpose plastics with Good All-around Property, be widely used in automobile,
The fields such as electrical equipment, packaging.But as polyolefin is non-polar polymer, fill out with polar polymer (nylon, polylactic acid etc.), polarity
Material (glass, carbon fibre etc.) is incompatible.In order to improve polyolefinic polarity, it is usually added into peroxide initiator and vinyl is unsaturated
Polar monomer.
In commercial production, in order to obtain higher percent grafting, generally to add the peroxidating two of high-load in polyolefin
Isopropylbenzene (DCP) and maleic anhydride (MAH), such as add the peroxidating of 0.5phr (hundred number of weight, polyene hydrocarbon content are 100 parts)
Diisopropylbenzene (DIPB) and the maleic anhydride of 5phr, although now percent grafting improves, but as cumyl peroxide content is higher, gather
Alkene occurs in that serious side reaction：There is degraded (such as polypropylene PP) in propylene type polyolefin, and crosslinking occur in ethylene-based polyolefins
(such as polythene PE).In order to suppress side reaction, and improve percent grafting simultaneously, be usually added into styrene (St) this electron rich type
Second comonomer, i.e. PO/DCP/MAH/St systems.But the system there is also certain limitation, such as polypropylene (PP,
Polypropylene) maleic anhydride content is fixed at 190 DEG C in system for 5phr, when initiator content is relatively low (≤0.3phr),
The effect of styrene suppression degraded is limited, and when initiator content is higher (>=0.5phr), instead cinnamic addition increased drop
Solution, but the such as main side reaction of polyethylene (PE, polyethylene) system PE/DCP/MAH/St system is the friendship of polyethylene
Connection, and styrene is equally limited to the inhibitory action of polyethylene crosslinking.Therefore, it is difficult to obtaining while having high percent grafting, macromolecule
Amount or high percent grafting, maleic anhydride stem grafting polyolefin PO-g- (MAH-co-St) material of low crosslinking degree.
In order to suppress the degraded or crosslinking of PO/DCP/MAH/St systems, the present invention adds graphene oxide (GO), and this is new
Type filler.During melt blending, due to π-π effect (class phenyl ring sp2 on the carbon-carbon double bond and graphene oxide on maleic anhydride
The big pi-electron conjugated system of hybrid structure composition) and hydrogen bond action (the highly polar carbonyl group on maleic anhydride and oxidation stone
Carboxyl, hydroxyl isopolarity group on black alkene), maleic anhydride is inserted into graphene oxide interlayer so as to which interlamellar spacing becomes big, from
And form graphene oxide-maleic anhydride complex.The complex can be quenched polypropylene tertiary carbon segment free radical (PP3·)、
Polyethylene secondary carbon segment free radical (PE2), that is, suppress the former that β-fracture occurs, also may refrain from polyacrylic degraded, suppress
The latter crosslinks, and also may refrain from the crosslinking of polyethylene.But due to the electron cloud enriched in styrene conjugated system, PP3~
St and PE2～St activity is higher, and the complex can not effectively be quenched both cinnamic segment free radicals of connection,
Thus both free radicals can effectively carry out graft reaction.
So, the degraded or crosslinking under higher initiator content in (0.3phr～3phr) polyene hydrocarbons and their derivates system
It still is able to be effectively suppressed, but PP3～St or PE2～St can not be effective with the grafting process of maleic anhydride monomer
Suppress, thus can obtain while having high percent grafting, high molecular or high percent grafting, the maleic anhydride-benzene second of low crosslinking degree
Alkene cograft polyolefine material PO-g- (MAH-co-St).
Content of the invention
It is an object of the invention to provide a kind of preparation method of maleic anhydride melt grafting polyolefine material, its percent grafting
High, molecular weight is high or percent grafting height, the degree of cross linking are low.
To achieve these goals, the preparation method of maleic anhydride melt grafting polyolefine material of the present invention, concrete steps
As follows：
Step (1), it is 0.01～15 part of maleic anhydride, the oxidation stone that parts by weight are 0.01～10 part by parts by weight
Black alkene is added directly on the polyolefin pellets that parts by weight are 100 parts or powder, mix homogeneously under room temperature, by the physical mixed
Thing is added to consersion unit；
Step (2), it is 0.01～5 part of initiator, the styrene liquid that parts by weight are 0.01～10 part by parts by weight
Body mix homogeneously, adds the mixture to consersion unit, and melt blending is formed at a certain temperature；
Wherein described consersion unit is banbury, response type extruder etc., and it is 160～230 DEG C that reaction temperature is interval, its
Middle closed-smelting machine rotor rotating speed is 50～150rpm, and response type extruder screw rotating speed is 30～600rpm.
Described polyolefin is polypropylene, polyethylene and polypropylene derivatives and polythene derivative, wherein polypropylene
Derivant is Ethylene-Propylene Block Copolymer, ethylene-propylene random copolymer, and polyethylene is Low Density Polyethylene, and high density is gathered
Ethylene etc..
Described initiator be peroxide type initiators, i.e. cumyl peroxide, dual-tert-butyl peroxy isopropyl base benzene,
Double (the uncles of tert-butyl hydroperoxide, tert-butyl peroxide benzoate, two carbonic ester of tert-butyl peroxide, 2,5- dimethyl -2,5-
Butyl peroxy) hexane, the one kind or several in 2,5- dimethyl -2,5- bis(t-butylperoxy) hexins, benzoyl peroxide
Kind.
It is 80%～99% that described graphene oxide is single or multiple lift graphene oxide powder, i.e. purity, and thickness is
0.34～17nm, the number of plies are 1～50 layer, and lamella is a diameter of 5～100 μm, and specific surface area is 50～1000m2/ g, isabelline or black
Color powder, surface and edge be mainly carboxyl, hydroxyl, epoxide group, can tonne volume production single or multiple lift graphene oxide.
Compared with prior art, the advantages of the present invention are as follows：
(1) the maleic anhydride stem grafting polyolefin percent grafting height of present invention preparation, molecular weight are high, or percent grafting height, crosslinking
Degree is low；
(2) of the invention compared with maleic anhydride-styrene comonomer graft polyolefin system, due to adding for graphene oxide
Enter effectively to suppress degraded, the crosslinking of polyethylene secondary carbon segment free radical of polypropylene tertiary carbon segment free radical, higher initiation
Agent content can't cause larger degraded or crosslinking, can achieve effective control or the regulation of degraded and crosslinking；
(3) present invention first graphene oxide is applied in maleic anhydride melt grafting polyolefin system, different from
The range of application of graphene oxide has been expanded in application of the past graphene oxide in systems such as composite, drug loadings, the present invention,
Large-scale application for graphene oxide provides new possibility.
(4) maleic anhydride stem grafting polyolefin prepared by the present invention is different from common bulking agent, there is oxygen in the bulking agent
Graphite alkene, with higher heat stability, gas barrier property etc.；
(5) present invention is not related to the use of solvent, institute in maleic anhydride stem grafting polyolefin bulking agent preparation process completely
There is component and further need not process, physical mixed is carried out by blender directly；
(6) by banbury or the required bulking agent of extruder melt blending preparation, the method has the big rule of industry to the present invention
The possibility of mould production.
Description of the drawings
Infared spectrums of the Fig. 1 for GO, GO-MAH, MAH；
X ray diffracting spectrums of the Fig. 2 for GO, GO-MAH, MAH；
Weight-temperature collection of illustrative plates of the Fig. 3 for the thermal weight loss curve of stability of GO, GO-MAH, MAH；
Weight loss rate-temperature collection of illustrative plates of the Fig. 4 for the thermal weight loss curve of stability of GO, GO-MAH, MAH；
Fig. 5 is the 1 sample photo of embodiment 1 and comparative example for preparing.
Specific embodiment
Next step in conjunction with the embodiments, further illustrates the present invention:
In order to determine the percent grafting of maleic anhydride stem grafting polyolefin in embodiment, first PO-g-MAH grafts are carried out pure
Change, the assay method for then being combined using infrared spectrum and acid base titration is characterizing percent grafting.
PO-g-MAH purification is comprised the following steps that：First, take 1.5g samples to add in 50ml dimethylbenzene, 140 DEG C of oil baths
30min, sample are completely dissolved, and pour solution in 100ml acetone into while hot, then by the filtrate sucking filtration, 70 DEG C of vacuum of sucking filtration thing
Dry 3h；Secondly, dried sucking filtration thing filter paper is wrapped up and is put into acetone extraction device, under 90 DEG C of oil baths, extract 24h；
Finally, by 70 DEG C of vacuum drying 8h of extract, dry purification of samples is obtained.
FTIR spectrum method (FT-IR) is comprised the following steps that：First, take 0.3g or so purification of samples and be placed in poly- four
On fluoride film, 5min in compression molding instrument, at 190 DEG C, is preheated, hot pressing 2min under 60MPa, water flowing are cooled to room temperature taking-up, gently
Gently ironed for an institute film is uncovered；Secondly, the thin film of 100 μ m thicks or so is selected to carry out infrared test：Through pattern TR, absorbance
Absorbance, resolution 1cm-1, sweep limitss：4000-400cm-1, scanning times 64scans；Finally, soft using omnic
Part is respectively to 1780cm-1、2721cm-1、1470cm-1Peak is integrated, and obtains peak area A1780、A2721And A1470, A1780/A2721、
A1780/A1470The ratio Ra of as absorbance, can quantitatively characterize the size of percent grafting.Wherein 1780cm-1Carbonyl in for anhydride
Peak, 2721cm-1For polypropylene segment skeleton peak, 1470cm-1For polyethyleneimine methyl characteristic peak, i.e. internal standard peak.
Acid base titration purification of samples is comprised the following steps that：First, take 0.5g or so purification of samples to be put into equipped with 50ml bis-
In the three-neck flask (volume 250ml) of toluene, 150 DEG C of oil bath temperature is heated to reflux 20min, and sample fully dissolves；Secondly, will
Oil bath temperature is adjusted to 100 DEG C, and makes three-neck flask be suspended on oil bath device, treats that xylene solution is cooled to 70 in three-neck flask
DEG C, 10ml potassium hydroxide-isopropanol solution is slowly dropped into while magneton agitating solution, and now three-neck flask is placed in oil bath
100 DEG C are heated to reflux 1.5h, carboxylated maleic anhydride is fully reacted with potassium hydroxide；Then, oil bath is cooled down to 80 DEG C, this
When 70 DEG C of solution temperature, while hot Deca 5 drop phenolphthalein solution, solution pinkiness；Finally titrated with hydrochloric acid-aqueous isopropanol while hot
To colourless, as the hydrochloric acid-aqueous isopropanol of instillation is room temperature during being somebody's turn to do, so the xylene solution temperature in titration process
Degree can reduce, and can suitably raise oil bath temperature to keep xylene solution temperature for 70 DEG C in titration process.
Repeat the experiment 3 times, calculate percent grafting G1.
The titration process of blank sample (being not added with purification of samples) ibid, calculates percent grafting G2.
Finally, the percent grafting of the purification of samples that acid-base titrations are obtained is, G=G1-G2.
Melt index determination
Tested on high ferro fusion index instrument according to GB3682-83 standards：230 DEG C, 2.16kg.
With reference to embodiment, the present invention is described in detail.However, these embodiments are only used as exemplary purpose, this
The scope not limited to this of invention.
Embodiment 1：PP/DCP/MAH/St/GO
PP/DCP/MAH/GO is carried out mixing and manual than 100/0.5/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 190 DEG C
5min.
The test result of sample is shown in Table 1.
Comparative example 1：PP/DCP/MAH/St
PP/DCP/MAH is mixed and is mixed simultaneously than 100/0.5/5 (wherein polypropylene weighs 46g) according to weight
Hand operated mixing is uniform, adds in banbury, then adds the liquid St of 2.5phr, is kneaded with the speed of 50rpm at 190 DEG C
5min.
The test result of sample is shown in Table 1.
Comparative example 2：PP/DCP/MAH/GO
PP/DCP/MAH/GO is carried out mixing and manual than 100/0.5/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 1.
Comparative example 3：PP/DCP/St/GO
PP/DCP/GO is carried out mixing than 100/0.5/0.1 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is equal
Even, add in banbury, then add the liquid St of 2.5phr, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 1.
Comparative example 4：PP/DCP/MAH
PP/DCP/MAH is carried out mixing than 100/0.5/5 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is equal
Even, add in banbury, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 1.
Comparative example 5：PP/DCP/St
PP/DCP is carried out mixing than 100/0.5 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is uniform, adds
In banbury, the liquid St of 2.5phr is then added, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 1.
Comparative example 6：PP/DCP/GO
PP/DCP/GO is carried out mixing than 100/0.5/0.1 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is equal
Even, add in banbury, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 1.
Comparative example 7：PP/DCP
PP/DCP is carried out mixing than 100/0.5 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is uniform, adds
In banbury, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 1.
Comparative example 8：Pure PP
Add in banbury according to 46g polypropylene solids granule, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 1.
Embodiment 2：PP/DCP/MAH/St/GO (it is 1.0phr to change DCP contents)
PP/DCP/MAH is carried out mixing and manual than GO/100/1.0/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 190 DEG C
5min.
The test result of sample is shown in Table 1.
Comparative example 9：PP/DCP/MAH/GO/100/0.5/5/0.1
PP/DCP/MAH/GO is carried out mixing and manual than 100/0.5/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 190 DEG C
5min.
The test result of sample is shown in Table 1.
Embodiment 3：PP/DCP/MAH/St/GO (it is 180 DEG C to change temperature)
PP/DCP/MAH/GO is carried out mixing and manual than 100/0.5/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 180 DEG C
5min.
The test result of sample is shown in Table 1.
Comparative example 10：PP/DCP/MAH/100/0.5/5,180 DEG C
PP/DCP/MAH is carried out mixing than 100/0.5/5 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is equal
Even, add in banbury, then add the liquid St of 2.5phr, with the speed mixing 5min of 50rpm at 180 DEG C.
The test result of sample is shown in Table 1.
Comparative example 11：PP/DCP/MAH/GO/100/0.5/5/0.1
PP/DCP/MAH/GO is carried out mixing and manual than 100/0.5/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 190 DEG C
5min.
The test result of sample is shown in Table 1.
Embodiment 4：PP/DCP/MAH/St/GO, 180 DEG C
PP/DCP/MAH/GO is carried out mixing and manual than 100/3.0/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 180 DEG C
5min.
The test result of sample is shown in Table 1.
Embodiment 5：PP/DCP/MAH/St/GO
PP/DCP/MAH/GO is carried out mixing and manual than 100/3.0/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 190 DEG C
5min.
The test result of sample is shown in Table 1.
Embodiment 6：The thermal weight loss stability of PP-g-MAH.
As can be seen that in PP/DCP/MAH/100/0.5/5 (190 DEG C) after the GO of addition 0.1phr, T5%Improve 11
DEG C, TmaxReduce 2.5 DEG C.
The test result of sample is shown in Table 2.
Embodiment 7：PE/DCP/MAH/St/GO
PE/DCP/MAH/GO is carried out mixing and manual than 100/0.5/5/0.1 (wherein polypropylene weighs 46g) according to weight
Stir, add in banbury, then add the liquid St of 2.5phr, kneaded with the speed of 50rpm at 190 DEG C
5min.
The test result of sample is shown in Table 3.
Comparative example 12：PE/DCP/MAH/St
PE/DCP/MAH is carried out mixing than 100/0.5/5 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is equal
Even, add in banbury, then add the liquid St of 2.5phr, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 3.
Comparative example 13：PE/DCP/MAH
PE/DCP/MAH is carried out mixing than 100/0.5/5 (wherein polypropylene weighs 46g) according to weight and hand operated mixing is equal
Even, add in banbury, with the speed mixing 5min of 50rpm at 190 DEG C.
The test result of sample is shown in Table 3.
Embodiment 8：The infared spectrum of GO, GO-MAH, MAH.Refer to Fig. 1.
Wherein GO-MAH is infrared, and sample preparation methods are as follows：Weigh GO powder, the block MAH of 28mg of 39mg respectively, make
With mortar grinder, the drop of Deca 3 acetone in process of lapping；After 40 DEG C of vacuum drying 12h, there is block in the complex, grinds again
Mill.
Two samples of GO, MAH and GO-MAH samples experienced identical preparation process, Deca acetone in process of lapping, so
After dry.
A small amount of drying sample is chosen, and using pellet technique tabletting, transmission mode, infrared survey is carried out to preparing sample
Examination (through contrast, unprocessed identical with the infared spectrum of GO, MAH sample of grinding-dried, eliminate grinding-do
Impact of the dry processing procedure to GO, MAH sample)
First, compared to GO, the change of GO/MAH is as follows,
(1) " " peak offsets OH hydroxyl in GO/MAH to lower wave number, and peak shape is passivated, and this is likely due to the presence of hydrogen bond
(between the carboxyl, hydroxyl on anhydride and GO)；
(2) there is big absworption peak in GO：3683-2814cm-1, the corresponding absworption peak scope in GO/MAH becomes much larger：
3683-1860cm-1, it is common with carbon-carbon double bond π-π in MAH that this is likely due to the unsaturated six-membered carbon ring π-pi-conjugated structure in GO
Yoke structure is conjugated, so that 1780cm-1、1860cm-1Disappear Deng carbonyl absorption peak, 3000-2000cm-1Scope hydrocarbon
Peak wave-length coverage becomes big；
(3) carbonyl peak is slightly to high wave-number migration, 1706cm-1Arrive 1717cm-1, and intensity dies down with respect to carbon-carbon double bond, may
Be due to anhydride in high wave number carbonyl absorption peak impact, i.e., there is hydrogen bond action with the carbonyl in GO, thus to high wave number
Skew, simultaneously because the conjugation between GO and MAH, carbonyl peak intensity relative carbon carbon double bond dies down；
(4) " C-OH " peak disappears, it may be possible to as MAH is reacted；
Secondly, compared to MAH, the change of GO/MAH is as follows,
1780-1860cm in GO-MAH-1Carbonylic stretching vibration peak disappear, only remaining 1717cm-1Carbonyl absorption peak,
This is likely due to the conjugation between GO and MAH, hydrogen bond effect so as to which cloud density is equalized.
The test result of sample is shown in Fig. 1.
Embodiment 9：X-ray diffraction, the XRD samples of GO, GO/MAH, MAH prepare sample using 8 mid-infrared of embodiment.In detail
See Fig. 2.
Calculated according to Bragg equation 2dsin θ=n λ and understood, after graphene oxide is ground with maleic anhydride, interlamellar spacing
0.94nm is changed into from 0.77nm, this shows maleic anhydride insertion graphene oxide interlayer, shows between the two by obvious phase interaction
With, corresponding with infrared results, show in polypropylene fusion graft process, to generate really GO/MAH complex, the exactly complex is inhibited
Which is degraded, grafting.
The test result of sample is shown in Fig. 2.
Embodiment 10：Thermal weight loss stability curve, the XRD samples of GO, GO/MAH, MAH are prepared using 8 mid-infrared of embodiment
Sample.
The heat stability of GO-MAH declines, and GO-MAH new T occurs near 100 DEG CmaxCharacteristic peak, this should be due to
MAH inserts GO interlayers, and inserts the heat stability of the MAH of GO interlayers less than pure MAH, and this shows maleic anhydride insertion oxygen
Graphite alkene interlayer, shows between the two by significantly interacting.
The test result of sample is shown in Table 1, Fig. 3 and Fig. 4.
Embodiment 11：The picture of PP-g-MAH (embodiment 1 and comparative example 1) sample and SEM figures.
As can be seen that 1 sample of comparative example of lamellar is milky in Fig. 5, and 1 sample of embodiment of lamellar is Lycoperdon polymorphum Vitt, though
So there is small amounts Graphene to agglomerate into little particle of black, but generally speaking graphene oxide is still dispersed in which
In.
The test result of sample is shown in Table 1 and Fig. 5.
The melting means of 1. maleic anhydride inoculated polypropylene system of table and the ratio of absorbance
| Sample | T5%(℃) | Tmax(℃) |
| Neat PP | 355 | 426.4 |
| PP/DCP/MAH/100/0.5/5(190℃) | 398 | 468.2 |
| PP/DCP/MAH/GO/100/0.5/5/0.1(190℃) | 409 | 465.7 |
| PP/DCP/MAH/GO/100/0.5/5/0.1(190℃) | 412 | 466.1 |
The thermal weight loss stability of table 2.PP-g-MAH
The melting means of 3. maleic anhydride grafted polyethylene system of table and the ratio of absorbance
Embodiment 12：
5g MAH, 0.05g GO are added directly in 50g Ethylene-Propylene Block Copolymer pellets, the mixture is stirred
Banbury is added to after mixing uniformly；It is added to after 0.005g dual-tert-butyl peroxy isopropyl base benzene, 0.005g St are mixed above-mentioned close
In mill, with the speed mixing 5min of 100rpm at 160 DEG C.
Embodiment 13：
0.005g MAH, 0.5g GO are added directly in 50g Ethylene-Propylene Block Copolymer pellets, by the mixture
It is stirring evenly and then adding into banbury；It is added in above-mentioned banbury after 2.5g tert-butyl hydroperoxide, 0.5g St are mixed,
With the speed mixing 5min of 60rpm at 230 DEG C.
Embodiment 14：
7.5g MAH, 1g GO are added directly in 50g isotactic polypropylene pellets, are added after the mixture is stirred
Enter to screw extruder；It is added in above-mentioned screw extruder after 1g tert-butyl peroxide benzoates, 2.5g St are mixed,
Extruded with the speed of 200rpm at 180 DEG C.
Embodiment 15：
0.05g MAH, 5g GO are added directly in 50g ethylene-propylene random copolymer pellets, the mixture is stirred
Screw extruder is added to after mixing uniformly；It is added to after two carbonic ester of 0.05g tert-butyl peroxides benzene, 5g St are mixed above-mentioned
In screw extruder, extruded with the speed of 400rpm at 170 DEG C.
Embodiment 16：
500g MAH, 5g GO are added directly in 5000g pellets of high density polyethylene, the mixture is stirred
After be added to screw extruder；Above-mentioned Screw Extrusion is added to after two carbonic ester of 5g tert-butyl peroxides benzene, 500g St are mixed
In machine, extruded with the speed of 400rpm at 170 DEG C.
Embodiment 17：
50g MAH, 1g GO are added directly in 5000g pellets of high density polyethylene, after the mixture is stirred
It is added to screw extruder；By two carbonic ester of 0.2g tert-butyl peroxides benzene, 0.3g tert-butyl peroxide benzoates, 50g St
It is added to after mixing in above-mentioned screw extruder, is extruded with the speed of 100rpm at 230 DEG C.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment, as long as meeting for the restriction of the present invention
Application claims, belong to protection scope of the present invention.
Claims (8)
1. a kind of preparation method of maleic anhydride melt grafting polyolefine material, it is characterised in that the method is comprised the following steps：
Step (1), it is 0.01～15 part of maleic anhydride, the graphene oxide that parts by weight are 0.01～10 part by parts by weight
It is added directly on the polyolefin pellets or powder that parts by weight are 100 parts, the physical mixture is added by mix homogeneously under room temperature
Enter to consersion unit；
Step (2), be 0.01～5 part of initiator by parts by weight, the styrene liquid that parts by weight are 0.01～10 part mixes
Close uniformly, add the mixture to consersion unit, blending at a certain temperature is formed.
2. a kind of preparation method of maleic anhydride melt grafting polyolefine material as claimed in claim 1, it is characterised in that institute
The polyolefin that states is polypropylene, polyethylene, polypropylene derivatives or polythene derivative.
3. a kind of preparation method of maleic anhydride melt grafting polyolefine material as claimed in claim 1, it is characterised in that poly-
Acryloyl derivative is propylene-ethylene block copolymer, Propylene-ethylene random copolymer, and polyethylene is Low Density Polyethylene, highly dense
Degree polyethylene.
4. a kind of preparation method of maleic anhydride melt grafting polyolefine material as claimed in claim 1, it is characterised in that institute
The initiator that states is peroxide type initiators.
5. a kind of preparation method of maleic anhydride melt grafting polyolefine material as claimed in claim 1, it is characterised in that institute
The initiator that states is cumyl peroxide, dual-tert-butyl peroxy isopropyl base benzene, tert-butyl hydroperoxide, tert-butyl peroxide benzene
Formic acid esters, two carbonic ester of tert-butyl peroxide, 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes, 2,5- dimethyl -2,
One or more in 5- bis(t-butylperoxy) hexins, benzoyl peroxide.
6. a kind of preparation method of maleic anhydride melt grafting polyolefine material as claimed in claim 1, it is characterised in that institute
It is 80%～99% that the graphene oxide that states is single or multiple lift graphene oxide powder, i.e. purity, and thickness is 0.34～17nm,
The number of plies is 1～50 layer, and lamella is a diameter of 5～100 μm, and specific surface area is 50～1000m2/ g, isabelline or black powder, surface
And edge be mainly carboxyl, hydroxyl, epoxide group, can tonne volume production single or multiple lift graphene oxide.
7. a kind of preparation method of maleic anhydride melt grafting polyolefine material as claimed in claim 1, it is characterised in that institute
The consersion unit that states be banbury, response type extruder, wherein closed-smelting machine rotor rotating speed be 50～150rpm, response type extruder
Screw speed is 30～600rpm.
8. a kind of preparation method of maleic anhydride melt grafting polyolefine material as claimed in claim 1, it is characterised in that step
Suddenly it is 160～230 DEG C that (2) reaction temperature is interval.
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| CN110684281A (en) * | 2019-10-17 | 2020-01-14 | 温州鑫泰新材料股份有限公司 | High-rigidity PP (polypropylene) plastic uptake cold-resistant material |
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| CN115057969A (en) * | 2022-07-29 | 2022-09-16 | 乐山职业技术学院 | Preparation method of graphene modified polyolefin |
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