CN106432614B - A method of promoting polyolefin graft reaction - Google Patents
A method of promoting polyolefin graft reaction Download PDFInfo
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- CN106432614B CN106432614B CN201610946608.2A CN201610946608A CN106432614B CN 106432614 B CN106432614 B CN 106432614B CN 201610946608 A CN201610946608 A CN 201610946608A CN 106432614 B CN106432614 B CN 106432614B
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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
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- Chemical Kinetics & Catalysis (AREA)
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- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of methods of promotion polyolefin graft reaction, comprising the following steps: polyolefin is carried out corona treatment first, obtains the modified polyolefin in surface；Then the modified polyolefin in surface, polar monomer, the solution containing initiator, antioxidant are uniformly mixed, are put into extruder and are reacted, extrudate obtains the polyolefin particles of polar compound graft modification by traction, cooling, dry, pelletizing.Polyolefin is modified first with plasma, on the one hand it can increase polyolefin surfaces polar group number, polyolefin polar can also be improved, be conducive to improve the compatibility with polar compound in an extruder, on the other hand, in an extruder in addition to the polar group introduced using plasma can carry out condensation reaction with polar compound, other than polar compound is grafted on polyolefin, utilize initiator, further polar compound can also be grafted on polyolefin, grafting efficiency can be greatly improved.
Description
Technical field
The present invention relates to a kind of polyolefin modified method, specifically a kind of method for promoting polyolefin graft reaction.
Background technique
Polyolefin is the maximum a kind of general-purpose plastics kind of yield, has excellent electrical insulating property, hydrophobicity, chemically-resistant molten
Agent aggressivity, low temperature properties and ductility, while its is low in cost, processing performance is good, mainly includes low density polyethylene (LDPE), highly dense
Spend polyethylene, linear low density polyethylene, polypropylene, ethylene propylene copolymer, ethylene octene copolymer etc..But polyolefin is equal
For non-polar material, dyeability, bad adhesion, the poor compatibility with other polar polymers, these disadvantages constrain it
The application in many fields.
By polar group, such as carboxyl, acid anhydrides, hydroxyl, epoxy group, ester group, it is introduced into polyolefin segment and it is carried out
It is modified, its caking property and the compatibility with polar polymer can be significantly improved, to expand the application range of this kind of material.?
In numerous method of modifying, it is most common for carrying out the reactive extrursion of polyolefin in an extruder, under the action of radical initiator
Method of modifying.
The Functional Polyolefine (CN102241797A) that can be used as metal adhesion promoters discloses one kind with peroxide
For initiator, the method that acrylic acid-grafted polypropylene is prepared using reaction extrusion process.
A kind of heat resistant type transparency polyolefin hot melt adhesive and preparation method thereof (CN103059785A) discloses a kind of heat resistant type
Polyolefin, peroxide initiator, polar monomer are uniformly mixed, are then existed by transparency polyolefin hot melt adhesive and preparation method thereof
Reactive extrursion is carried out in double screw extruder at 160~200 DEG C, obtains the modified polyolefin hot-melt of polar monomer graft.
A kind of Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof (CN101781389A) discloses a kind of clothing
Health acid grafted ethylene-α-octene copolymer and preparation method thereof, by ethylene-alpha-octylene copolymers, peroxide initiator, clothing health
Sour polar monomer in high-speed mixer be uniformly mixed, then in an extruder 160~200 DEG C, 100~400 turns of screw speed/
It is minute lower to carry out reactive extrursion, obtain Itaconic Acid Grafted ethylene-alpha-octylene copolymers, the copolymer grafted efficiency 0.8~
Between 1.0%.
The preparation method (CN102766239A) of Itaconic Acid Grafted ethylene-octene block copolymer particulate material discloses one kind
The preparation method of Itaconic Acid Grafted ethylene-octene block copolymer particulate material, by ethylene-octene block copolymer, peroxide
Initiator dibenzoyl peroxide, itaconic acid polar monomer, antioxidant are uniformly mixed, and are then existed by double screw extruder
Reactive extrursion obtains Itaconic Acid Grafted ethylene-octene block copolymer at 150~170 DEG C, and copolymer grafted efficiency is 1.35%
~1.65%.
A kind of modifying agent and the preparation method and application thereof (CN101831131B) discloses a kind of Itaconic Acid Grafted polyolefin
Elastomer copolymer, by polyolefin elastomer, peroxide initiator cumyl peroxide, itaconic acid polar monomer, poly- second
Alkene wax is uniformly mixed in mixer, then reactive extrursion in an extruder, is prepared into the copolymer.
It can see from the patent about Graft Modification of Polyolefine, due to the apolar character of polyolefin, with polarity
The polarity and solubility parameters difference of monomer are huge, have the solubility parameters of document report itaconic acid and low density polyethylene (LDPE) to be respectively
24.6 and 16.1 (J cm-3)0.5(Polymer, 2001,42 (2): 469~475).When two kinds of substance solubility parameters differ by more than 2
(J cm-3)0.5When, which is thermodynamics Immiscible Polymer Blends (Polymer, 1990,31 (7): 1187~1203).It is positive because
Compatibility for polyolefin and polar monomer melt in reactive extrursion is very poor, and the reactive extrursion time is very short, and only 1~5 point
Clock, this results in polar monomer and is difficult to evenly spread in polyolefin, and lamination hair is had in some regions of extruder
Raw, this not only results in polyolefin graft reaction uniformity decline, can also because of the reactive extrursion time short, polar monomer and polyene
The contact of hydrocarbon macromolecular radical and reaction probability decline, significantly reduce this main reaction of polar monomer graft polyolefin, increase simultaneously
The probability for having added polyolefin macromolecular radical self-contact and reaction is conducive to the generation (crosslinking of such as polyethylene of side reaction
Or polyacrylic degradation side reaction), this will cause the variation of polyolefine material melt index and influence properties for follow.
It is a kind of improve polyolefin graft efficiency method (CN 105859970A) disclose single or several peroxidating
Object initiator solution is pumped into extruder different heating section according to friction speed in polyolefin extrusion process, with existing patent
Polyolefin, polar monomer are disposably mixed with whole peroxide initiators in document, then carry out reactive extrursion phase again
Than peroxide initiator is added in extruder along Cheng Butong section the present invention in several times, effectively prevents local freedom
Base excessive concentration significantly reduces the generation of the side reactions such as polyolefin crosslinking or degradation, greatly improves the initiation effect of initiator
Rate and polyolefin graft efficiency.But the disadvantage is that, it needs to be transformed extrusion equipment, multiple peroxide is being set along journey
Addition point and pumping equipment, increase equipment investment cost.
A kind of nylon toughener, preparation method and application (105693890A) are mainly to set out to prepare nylon toughener
Point, in the case where not introducing radical initiator, increases the work of polyolefin surfaces generation using lower temperature plasma technology
Property group (such as hydroxyl, carboxyl, carbonyl, amino) type and concentration, reaction mechanism in an extruder are the condensations of polar group
Reaction.But the disadvantage is that graft reaction is inefficient, polyolefin is modified just with plasma, polyolefin surfaces
Polar group number it is limited.To sum up, it needs at present a kind of while guaranteeing high grafting efficiency, moreover it is possible to significantly reduce polyene
The polyolefin modified method of the side reactions such as hydrocarbon crosslinking and degradation.
Summary of the invention
The present invention proposes a kind of binding plasma and reactive extrusion technology to promote polar monomer graft improved polyalkene
Method.Polyolefin is placed in plasma reaction device, the type of gas is passed through by control, ratio, gas pressure intensity, is put
Electrical power, discharge time, active group (such as hydroxyl, carboxyl, carbonyl, amino) type that adjustable polyolefin surfaces generate and
Concentration, to improve the polarity and solubility parameters of polyolefin.Then by the polyolefin and polar monomer, initiation after corona treatment
Agent and antioxidant mixing, obtain polar monomer graft improved polyalkene using the method for reactive extrursion.
The present invention is achieved through the following technical solutions:
A method of promoting polyolefin graft reaction, comprising the following steps:
Polyolefin is subjected to Low Temperature Plasma Treating first, obtains the modified polyolefin in surface；Then surface is modified
Polyolefin, polar monomer, the solution containing initiator, antioxidant afterwards is uniformly mixed, and is put into extruder and is reacted, extrudate
By traction, cooling, drying, pelletizing, the polyolefin particles of polar compound graft modification are obtained.
The reaction condition of corona treatment polyolefin of the present invention is the mixture for being passed through one or several kinds of gases, gas
1~100Pa of body pressure, 4~120W of discharge power, 0.1~100min of discharge time.From the point of view of improving polyolefin graft efficiency,
Preferably, the gas pressure intensity is 1~50Pa, and 10~30W of discharge power, discharge time is 0.5~20min；Most preferably, gas
Body pressure is 50Pa, discharge power 30W, discharge time 20min.Processing polymerization is carried out using suitable low-temperature plasma concrete conditions in the establishment of a specific crime
Object can generate active group in polymer surfaces, improve the polarity of polymer；The setting of low-temperature plasma concrete conditions in the establishment of a specific crime simultaneously is also
It need to be conducive to subsequent extrusion reaction.
Corona treatment polyolefin equipment therefor of the present invention is reaction of low temperature plasma device, and discharge mode can be
One of glow discharge, corona discharge, dielectric barrier discharge, radio frequency discharge and microwave discharge.
Plasma reaction gas of the present invention is air, oxygen, nitrogen, carbon dioxide, argon gas, helium, ammonia
A kind of several mixture.Preferably, gas is argon gas, the mixed gas of argon gas and oxygen, air, carbon dioxide.
Preferably, in terms of mass parts, 93.999~68 parts of polyolefin, 5~20 parts of polar monomer, initiator 0.001~7
Part, 1~5 part of antioxidant.It is further preferred that in terms of mass parts, 86.999~68 parts of polyolefin, 10~20 parts of polar monomer,
0.001~0.009 part of initiator, 1~3 part of antioxidant；Most preferably, in terms of mass parts, 86.999 parts of polyolefin, polar monomer
10 parts, 0.001 part of initiator, 3 parts of antioxidant.The type and proportional quantity of raw material have significant impact for graft reaction effect,
The graft reaction efficiency that inappropriate raw material type and proportional quantity will lead to polymer reduces, and can also have showing for polyolefin crosslinking
As the side reaction more with generation.
Initiator of the invention is added in the form of a solution, and initiator is dissolved in acetone and the acetone containing initiator is prepared
Solution.
Polyolefin of the present invention is low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) (HDPE), linea low density gather
Ethylene (LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), ethylene octene copolymer (POE), ethylene propylene diene rubber
One or more of (EPDM) mixture of polyolefin.Preferably, the polyolefin is low density polyethylene (LDPE) (LDPE) or gathers
Propylene (PP).
Polar monomer of the present invention is maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, clothing health
Acid anhydrides, citraconic anhydride, crotonic anhydride, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate
The mixture of one or more of ester, ethyl methacrylate, glycidyl methacrylate.Preferably, the polarity
Monomer is maleic anhydride.
Initiator of the present invention is cumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl
The mixture of one or more of bis- (t-butylperoxyisopropyl) benzene of peroxide benzoate, 1,4-.Preferably, described
Initiator is dibenzoyl peroxide.From reducing side reaction and reducing the generation of the cross-linking reaction between polyolefin, polyene is improved
Hydrocarbon reaction efficiency selects suitable initiator type, wherein, the effect that generates the most suitable using dibenzoyl peroxide
It is most prominent.
Antioxidant of the present invention is [four (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant
1010), 3- (3,5- di-t-butyl -4- hydroxyl) propylene octadecyl ester (antioxidant 1076), N, N'- is bis--(3- (3,5- di-t-butyl -
4- hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), 2,6- di-t-butyl -4- cresols (antioxidant 264), 2,4,6- tri-
One or more of tert-butyl phenol (antioxidant 246), (2,4- di-tert-butyl-phenyl) tris phosphite (irgasfos 168)
Mixture.Preferably, the antioxidant is [four (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Preferably, for grafting efficiency and melt index, the polyolefin is low density polyethylene (LDPE) (LDPE) or poly- third
Alkene (PP), the polar monomer are maleic anhydride, and the initiator is dibenzoyl peroxide, and antioxidant is [four (3,5- bis- uncles
Butyl -4- hydroxy phenyl) propionic acid] pentaerythritol ester.
In an extruder reaction temperature be 10~500 DEG C, 10~100 revs/min of driving screw revolving speed, feed screw revolving speed 50
~300 revs/min.Preferably, the reaction temperature be 10~100 DEG C, 10~50 revs/min of driving screw revolving speed, feed screw
60~100 revs/min of revolving speed.Most preferably, 50 revs/min of the driving screw revolving speed, 70 revs/min of feed screw revolving speed.
The present invention also protects the polyolefin particles for the polar compound graft modification being prepared by above method.
A technical solution in above-mentioned technical proposal has the following beneficial effects:
Prominent improve of the invention is to be modified first with low temperature plasma to polyolefin, on the one hand can be increased
Polyolefin surfaces polar group number can also improve polyolefin polar, be conducive to improve in an extruder and polar compound
Compatibility, on the other hand, in an extruder in addition to using plasma introduce polar group can with polar compound into
Row condensation reaction, can also be further by polar compound using initiator other than polar compound is grafted on polyolefin
It is grafted on polyolefin, grafting efficiency can be greatly improved.And it has been surprisingly found that, the addition of the initiator can inhibit polyolefin
Generation (crosslinking of such as polyethylene or polyacrylic degradation side reaction), it may not be necessary to draw as described in patent CN105859970A
The addition needs of hair agent are pumped into extruder different heating section according to friction speed in polyolefin extrusion process；Moreover, phase
Than in patent CN105693890A, grafting efficiency of the invention is significantly improved.In addition, invention also reduces initiators
Dosage, avoid the generation for increasing the cross-linking reaction between side reaction and polyolefin using initiator.
Graft polyolefin material prepared by the present invention has good machinability, may be used as polyolefin and polar polymeric
Compatilizer, toughener when object, the mixing of various fillers.
Detailed description of the invention
Fig. 1 is the schematic device of corona treatment polyolefin.
Specific embodiment
Embodiment 1:
Comparative example weigh LDPE86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min),
10.0 parts of maleic anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, are dissolved in 5.0 for dibenzoyl peroxide
In part acetone, in a high speed mixer by low density polyethylene (LDPE), dibenzoyl peroxide solution, maleic anhydride, antioxidant 1010
Said mixture is added in extruder hopper for mixing 60 minutes, and at 150 DEG C -180 DEG C, driving screw turns each area's temperature of extruder
60 revs/min of speed, 70 revs/min of feed screw revolving speed, extrudate obtains polar monomer by traction, cooling, dry, pelletizing
Graft-modified polyolefin particle.
Embodiment 2:
Weigh LDPE86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
Dibenzoyl peroxide is dissolved in 5.0 parts of acetone by 10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010
In.LDPE is placed in reaction of low temperature plasma device, as shown in Figure 1, first vacuumize, is passed through argon gas, gas pressure intensity 50Pa,
Radio frequency discharge power 30W, discharge time 20min, then by the modified LDPE in surface, maleic anhydride, dibenzoyl peroxide solution,
Antioxidant 1010 mixes 60 minutes in a high speed mixer, and mixture is put into extruder hopper, and at 180 DEG C, driving screw turns
It is reacted under the conditions of 50 revs/min, 70 revs/min of feed screw revolving speed of speed, extrudate passes through traction, cooling, drying, cuts
Grain, obtains the polyolefin particles of polar compound graft modification.Wherein, reaction of low temperature plasma device and extruder are ability
The commonly used equipment in domain, it is available by commercial sources.
Embodiment 3:
Weigh LDPE86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
Dibenzoyl peroxide is dissolved in 5.0 parts of acetone by 10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010
In.LDPE is placed in reaction of low temperature plasma device, argon gas/oxygen (volume ratio 4/1) mixed gas, gas pressure intensity are passed through
50Pa, radio frequency discharge power 30W, discharge time 20min, then by surface modified LDPE, maleic anhydride, dibenzoyl peroxide
Solution, antioxidant 1010 mix 60 minutes in a high speed mixer, and mixture is put into extruder hopper, at 180 DEG C, main spiral shell
Reacted under the conditions of 50 revs/min of bar revolving speed, 70 revs/min of feed screw revolving speed, extrudate by traction, it is cooling, dry,
Pelletizing obtains the polyolefin particles of polar compound graft modification.
Embodiment 4:
Weigh LDPE86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
Dibenzoyl peroxide is dissolved in 5.0 parts of acetone by 10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010
In.LDPE is placed in reaction of low temperature plasma device, air, gas pressure intensity 50Pa are passed through, radio frequency discharge power 30W is put
Electric time 20min, it is then that the modified LDPE in surface, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010 is mixed in high speed
It is mixed 60 minutes in conjunction machine, mixture is put into extruder hopper, at 180 DEG C, 50 revs/min of driving screw revolving speed, feeding spiral shell
It is reacted under the conditions of 70 revs/min of bar revolving speed, extrudate obtains polar compound and connect by traction, cooling, dry, pelletizing
The modified polyolefin particles of branch.
Embodiment 5:
Weigh LDPE86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
Dibenzoyl peroxide is dissolved in 5.0 parts of acetone by 10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010
In.LDPE is placed in reaction of low temperature plasma device, carbon dioxide, gas pressure intensity 50Pa, radio frequency discharge power are passed through
Then 30W, discharge time 20min exist the modified LDPE in surface, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010
It is mixed 60 minutes in high-speed mixer, mixture is put into extruder hopper, at 180 DEG C, 50 revs/min of driving screw revolving speed,
It is reacted under the conditions of 70 revs/min of feed screw revolving speed, extrudate obtains polarity by traction, cooling, dry, pelletizing
Close the polyolefin particles of object graft modification.
Embodiment 6:
Weigh PP86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical 1396D, melt index 4.2g/10min), maleic anhydride
10.0 parts, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone.
PP is placed in reaction of low temperature plasma device, argon gas, gas pressure intensity 50Pa, radio frequency discharge power 30W, discharge time are passed through
Then 20min mixes surface MODIFIED PP, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010 in a high speed mixer
It closes 60 minutes, mixture is put into extruder hopper, at 180 DEG C, 50 revs/min of driving screw revolving speed, feed screw revolving speed 70
It is reacted under the conditions of rev/min, extrudate obtains polar compound graft modification by traction, cooling, dry, pelletizing
Polyolefin particles.
Embodiment 7:
Weigh PP86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical 1396D, melt index 4.2g/10min), maleic anhydride
10.0 parts, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone.
PP is placed in reaction of low temperature plasma device, is passed through argon gas/oxygen (volume ratio 4/1) mixed gas, gas pressure intensity 50Pa,
Radio frequency discharge power 30W, discharge time 20min, then by surface MODIFIED PP, maleic anhydride, dibenzoyl peroxide solution, anti-
Oxygen agent 1010 mixes 60 minutes in a high speed mixer, and mixture is put into extruder hopper, at 180 DEG C, driving screw revolving speed
It being reacted under the conditions of 50 revs/min, 70 revs/min of feed screw revolving speed, extrudate passes through traction, cooling, dry, pelletizing,
Obtain the polyolefin particles of polar compound graft modification.
Embodiment 8:
Weigh PP86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical 1396D, melt index 4.2g/10min), maleic anhydride
10.0 parts, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone.
PP is placed in reaction of low temperature plasma device, air, gas pressure intensity 50Pa, radio frequency discharge power 30W, discharge time are passed through
Then 20min mixes surface MODIFIED PP, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010 in a high speed mixer
It closes 60 minutes, mixture is put into extruder hopper, at 180 DEG C, 50 revs/min of driving screw revolving speed, feed screw revolving speed 70
It is reacted under the conditions of rev/min, extrudate obtains polar compound graft modification by traction, cooling, dry, pelletizing
Polyolefin particles.
Embodiment 9:
Weigh PP86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical 1396D, melt index 4.2g/10min), maleic anhydride
10.0 parts, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone.
PP is placed in reaction of low temperature plasma device, carbon dioxide, gas pressure intensity 50Pa, radio frequency discharge power 30W, electric discharge are passed through
Time 20min, then by surface MODIFIED PP, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010 in high-speed mixer
Middle mixing 60 minutes, mixture is put into extruder hopper, and at 180 DEG C, 50 revs/min of driving screw revolving speed, feed screw turns
It is reacted under the conditions of 70 revs/min of speed, extrudate obtains polar compound grafting and change by traction, cooling, dry, pelletizing
The polyolefin particles of property.
Embodiment 10:
Weigh LDPE85.998 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), citraconic acid
Cumyl peroxide is dissolved in 5.0 parts of acetone by 12.0 parts of acid anhydride, 0.002 part of cumyl peroxide, 2.0 parts of antioxidant 1076
In.LDPE is placed in reaction of low temperature plasma device, argon gas, gas pressure intensity 80Pa are passed through, radio frequency discharge power 30W is put
Electric time 100min, then by the modified LDPE in surface, citraconic anhydride, cumyl peroxide solution, antioxidant 1076 in high speed
It is mixed 60 minutes in mixing machine, mixture is put into extruder hopper, at 180 DEG C, 40 revs/min of driving screw revolving speed, feeding
It is reacted under the conditions of 100 revs/min of screw speed, extrudate obtains polar compound by traction, cooling, dry, pelletizing
The polyolefin particles of graft modification.
Embodiment 11:
Weigh LDPE88 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), itaconic anhydride
8.0 parts, 2 parts of di-tert-butyl peroxide, 10982.0 parts of antioxidant, di-tert-butyl peroxide is dissolved in 5.0 parts of acetone.
LDPE is placed in reaction of low temperature plasma device, argon gas/oxygen (volume ratio 4/1) mixed gas, gas pressure intensity are passed through
100Pa, radio frequency discharge power 50W, discharge time 40min, then by surface modified LDPE, itaconic anhydride, di-t-butyl peroxide
Compound solution, antioxidant 1098 mix 60 minutes in a high speed mixer, and mixture is put into extruder hopper, at 170 DEG C,
Reacted under the conditions of 90 revs/min of driving screw revolving speed, 120 revs/min of feed screw revolving speed, extrudate by traction, it is cooling,
Dry, pelletizing, obtains the polyolefin particles of polar compound graft modification.
Embodiment 12:
Weigh LDPE86 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), methacrylic acid
0.5 part of ethylene oxidic ester, 0.5 part of tert butyl peroxy benzoate, 3.0 parts of irgasfos 168, by tert-butyl hydroperoxide benzoic acid
Ester is dissolved in 5.0 parts of acetone.LDPE is placed in reaction of low temperature plasma device, air, gas pressure intensity 50Pa, radio frequency are passed through
Discharge power 80W, discharge time 25min, then by surface modified LDPE, glycidyl methacrylate, t-butyl peroxy
Change benzoic ether, irgasfos 168 mix 60 minutes in a high speed mixer, mixture are put into extruder hopper, 160
DEG C, it is reacted under the conditions of 30 revs/min of driving screw revolving speed, 90 revs/min of feed screw revolving speed, extrudate, which passes through, to be drawn, is cold
But, dry, pelletizing, obtains the polyolefin particles of polar compound graft modification.
Embodiment 13:
Weigh PP86.999 parts (parts by weight, similarly hereinafter, Yanshan Petrochemical 1396D, melt index 4.2g/10min), metering system
Bis- 0.001 part of (t-butylperoxyisopropyl) benzene of 10.0 parts of acetoacetic ester, Isosorbide-5-Nitrae-, 3.0 parts of antioxidant 1010, by the bis- (uncles of Isosorbide-5-Nitrae-
Butyl peroxy isopropyl) benzene is dissolved in 5.0 parts of acetone.PP is placed in reaction of low temperature plasma device, argon gas, gas are passed through
Body pressure 190Pa, radio frequency discharge power 100W, discharge time 20min, then by surface MODIFIED PP, ethyl methacrylate, 1,
Bis- (t-butylperoxyisopropyl) benzole solns of 4-, antioxidant 1010 mix 60 minutes in a high speed mixer, and mixture is put
Enter in extruder hopper, is carried out under the conditions of 150 DEG C, 60 revs/min of driving screw revolving speed, 90 revs/min of feed screw revolving speed anti-
It answers, extrudate obtains the polyolefin particles of polar compound graft modification by traction, cooling, dry, pelletizing.
Embodiment 10~13 has made connecing divided by the polyolefin other than monomer maleic anhydride, initiator cumyl peroxide
Branch reaction, but the graft reaction effect of polyolefin is not so good as the effect in embodiment 2~9 and protrudes.
Examples 1 to 9 polar monomer graft improved polyalkene result is as shown in the table:
It can see from the LDPE graft modification result of embodiment 2~5, it is processed poly- by different plasma atmosphere
Alkene, the efficiency for carrying out graft reaction with polar monomer in an extruder are above 5.4%, and grafting efficiency is apparently higher than free radical
Result (as described in Example 1) under initiation conditions, LDPE is after grafting, and melt index fall is again smaller than free radical
Result (as described in Example 1) under initiation conditions, illustrates that the crosslinking side reaction of LDPE is inhibited well；Embodiment 6~9
Grafting efficiency of the middle PP after corona treatment is above 5.5%, and the increasing degree of melt index is not also high, same explanation
PP degradation side reaction is controlled preferable.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of method for promoting polyolefin graft reaction, characterized in that the following steps are included:
Polyolefin is subjected to Low Temperature Plasma Treating first, obtains the modified polyolefin in surface, Low Temperature Plasma Treating is poly-
The reaction condition of alkene is to be passed through the mixture of one or several kinds of gases as plasma reaction gas, the gas pressure intensity
It is 4-120 W for 1-100 Pa, discharge power, discharge time 0.1-100min；
Then the modified polyolefin in surface, polar monomer, the solution containing initiator, antioxidant are uniformly mixed, are put into extrusion
It is reacted in machine, extrudate obtains the polyolefin of polar compound graft modification by traction, cooling, dry, pelletizing
Grain；Wherein, raw material is in terms of mass parts, additive amount are as follows: 93.999-68 parts of polyolefin, 5-20 parts of polar monomer, initiator
0.001~7 part, 1-5 parts of antioxidant；
The type of the plasma reaction gas are as follows: volume ratio be 4:1 argon gas and oxygen gaseous mixture or air, or
Person's carbon dioxide；
The initiator is dibenzoyl peroxide, and the polar monomer is maleic anhydride；
The polyolefin is that low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene, ethylene, propylene are total
The mixture of one or more of polymers, ethylene octene copolymer, ethylene propylene diene rubber polyolefin.
2. the method as described in claim 1, it is characterized in that: the gas pressure intensity is 50Pa, discharge power 30W, discharge time
20min。
3. the method as described in claim 1, it is characterized in that: in terms of mass parts, 86.999-68 parts of polyolefin, polar monomer 10-
20 parts, 0.001~0.009 part of initiator, 1-3 parts of antioxidant.
4. method as claimed in claim 3, it is characterized in that: in terms of mass parts, 86.999 parts of polyolefin, 10 parts of polar monomer,
0.001 part of initiator, 3 parts of antioxidant.
5. the method as described in claim 1, it is characterized in that: the polyolefin is low density polyethylene (LDPE) or polypropylene.
6. the method as described in claim 1, it is characterized in that: the antioxidant is [four (3,5- di-tert-butyl-hydroxy phenyls)
Propionic acid] pentaerythritol ester, 3- (3,5- di-t-butyl -4- hydroxyl) propylene octadecyl ester, N, N'- is bis--(3- (3,5- di-t-butyl -4-
Hydroxy phenyl) propiono) hexamethylene diamine, 2,6- di-t-butyl -4- cresols, 2,4,6- tri-butyl-phenol, (2,4- di-tert-butyl
Base) one or more of tris phosphite mixture.
7. method as claimed in claim 6, it is characterized in that: the antioxidant is [four (3,5- di-tert-butyl-hydroxy phenyls)
Propionic acid] pentaerythritol ester.
8. using the polyolefin for the polar compound graft modification that method of any of claims 1-7 is prepared
Grain.
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| 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 |
| CN112830997B (en) * | 2020-12-31 | 2022-08-09 | 石家庄联合石化有限公司 | Preparation method of graft modified polypropylene |
| CN113088029B (en) * | 2021-04-08 | 2022-09-16 | 四川潽鑫科技集团有限公司 | High-impact-resistance double-wall corrugated pipe and preparation method thereof |
| CN114133488A (en) * | 2021-12-13 | 2022-03-04 | 罗莱生活科技股份有限公司 | Hydrophilic modified polypropylene material, preparation method thereof and fiber |
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