CN106432614A - Method of promoting polyolefin grafting reaction - Google Patents
Method of promoting polyolefin grafting reaction Download PDFInfo
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- CN106432614A CN106432614A CN201610946608.2A CN201610946608A CN106432614A CN 106432614 A CN106432614 A CN 106432614A CN 201610946608 A CN201610946608 A CN 201610946608A CN 106432614 A CN106432614 A CN 106432614A
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- Prior art keywords
- polyolefin
- antioxidant
- parts
- initiator
- butyl
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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
-
- 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
-
- 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
Abstract
The invention discloses a method of promoting polyolefin grafting reaction. The method includes following steps: performing plasma treatment on polyolefin to obtain surface-modified olefin; well mixing the surface-modified olefin, polar monomer, a solution containing an initiator and an antioxidant, putting into an extruder for reaction, and subjecting extrudate to traction, cooling, drying and cutting into particles to obtain polar compound graft modified polyolefin particles. Plasma is utilized to modify polyolefin, so that number of polar groups on the surface of polyolefin can be increased, polarity of polyolefin can be improved, and improving of compatibility with a polar compound in the extruder is facilitated; the polar groups introduced by the plasma can be utilized for condensation reaction with the polar compound in the extruder to graft the polar compound onto polyolefin, and the polar compound can be further grafted onto polyolefin by utilizing the initiator, so that grafting efficiency can be improved greatly.
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 technology
Polyolefin is a class general-purpose plastics kind of yield maximum, molten with excellent electrical insulating property, hydrophobicity, chemically-resistant
Agent aggressivity, low temperature properties and ductility, while which is with low cost, processing characteristics good, mainly include Low Density Polyethylene, highly dense
Degree polyethylene, linear low density polyethylene, polypropylene, ethylene propylene copolymer, POE etc..But polyolefin is equal
For non-polar material, its dyeability, bad adhesion, the poor compatibility with other polar polymers, these shortcomings constrain it
The application in many fields.
By polar group, such as carboxyl, anhydride, hydroxyl, epoxy radicals, ester group etc., being incorporated in polyolefin segment is carried out to which
Modification, can significantly improve its caking property and the compatibility with polar polymer, so as to expand the range of application of this kind of material.?
In numerous method of modifying, in an extruder, to carry out polyolefinic reactive extrursion in the presence of radical initiator be the most frequently used
Method of modifying.
The Functional Polyolefine (CN 102241797A) that can be used as metal adhesion promoters discloses one kind with peroxide
For initiator, the method for preparing acrylic acid-grafted polypropylene using reaction extrusion process.
A kind of heat resistant type transparency polyolefin PUR and preparation method thereof (CN103059785A) discloses a kind of heat resistant type
Transparency polyolefin PUR and preparation method thereof, polyolefin, peroxide initiator, polar monomer is uniformly mixed, Ran Hou
Reactive extrursion is carried out at 160～200 DEG C in double screw extruder, obtain the modified polyolefin hot-melt of polar monomer graft.
A kind of Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof (CN 101781389A) disclose one kind
Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof, by ethylene-alpha-octylene copolymers, peroxide initiator, clothing
Health acid polar monomer mix homogeneously in the high-speed mixer, then 160～200 DEG C, screw speed 100～400 in an extruder
Reactive extrursion is carried out under rev/min, obtains Itaconic Acid Grafted ethylene-alpha-octylene copolymers, the copolymer grafted efficiency 0.8～
Between 1.0%.
The preparation method (102766239 A of CN) of Itaconic Acid Grafted ethylene-octene block copolymer particulate material discloses one
The preparation method of Itaconic Acid Grafted ethylene-octene block copolymer particulate material is planted, by ethylene-octene block copolymer, peroxidating
Thing initiator dibenzoyl peroxide, itaconic acid polar monomer, antioxidant are uniformly mixed, and then pass through double screw extruder
At 150～170 DEG C, reactive extrursion obtains Itaconic Acid Grafted ethylene-octene block copolymer, and copolymer grafted efficiency is
1.35%～1.65%.
A kind of modifying agent and preparation method and application (CN 101831131B) 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 mix homogeneously in banbury, then reactive extrursion in an extruder, is prepared into the copolymer.
Can see from the patent for being related to Graft Modification of Polyolefine, due to polyolefinic apolar character, with polarity
The polarity of monomer and solubility parameters difference are huge, have document report itaconic acid and the solubility parameters of Low Density Polyethylene to be respectively
24.6 and 16.1 (J cm-3)0.5(Polymer, 2001,42 (2)：469～475).When two kinds of material solubility parameters differ by more than 2
(J cm-3)0.5When, the mixed system be thermodynamics Immiscible Polymer Blends (Polymer, 1990,31 (7)：1187～1203).Just because
It is that polyolefin is very poor with the compatibility of polar monomer melt in reactive extrursion, and the reactive extrursion time is very short, only 1～5 point
Clock, this results in polar monomer and is difficult to evenly spread in polyolefin, has lamination and send out in some regions of extruder
Raw, this not only results in polyolefin graft reaction uniformity decline, can also, polar monomer short because of the reactive extrursion time and polyene
The contact of hydrocarbon macromolecular radical and response probability decline, and significantly reduce this primary response of polar monomer graft polyolefin, while increasing
Add the probability of polyolefin macromolecular radical self-contact and reaction, be conducive to the generation (crosslinking as polyethylene of side reaction
Or polyacrylic degraded side reaction), this will cause the change of polyolefine material melt index and affect properties for follow.
A kind of method (CN 105859970A) for improving polyolefin graft efficiency is disclosed single or several peroxidating
Thing initiator solution is pumped into extruder different heating section according to friction speed in polyolefin extrusion, with existing patent
With in document, polyolefin, polar monomer are disposably mixed with whole peroxide initiators, then carry out reactive extrursion phase again
Than peroxide initiator is added along Cheng Butong section fraction time by the present invention in extruder, is effectively prevented local freely
Base excessive concentration, significantly reduces the generation of the side reactions such as polyolefin crosslinking or degraded, greatly improves the initiation effect of initiator
Rate and polyolefin graft efficiency.But which has the disadvantage, need extrusion equipment is transformed, multiple peroxide are being set along journey
Addition point and pumping equipment, increased equipment investment cost.
A kind of nylon toughener, preparation method and application (105693890A) are mainly to prepare nylon toughener as setting out
Point, using lower temperature plasma technology, in the case of radical initiator is not introduced, increased the work of polyolefin surfaces generation
Property group (as hydroxyl, carboxyl, carbonyl, amino) type and concentration, reaction mechanism in an extruder is the condensation of polar group
Reaction.But which has the disadvantage that graft reaction is inefficient, just with plasma, polyolefin is modified, polyolefin surfaces
Polar group number limited.
To sum up, need badly at present a kind of while high grafting efficiency is ensured, moreover it is possible to significantly reduce polyolefin crosslinking and drop
The polyolefin modified method of the side reactions such as solution.
Content 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, by controlling the type for being passed through gas, ratio, gas pressure intensity, putting
Electrical power, discharge time, can adjust polyolefin surfaces generation active group (as hydroxyl, carboxyl, carbonyl, amino) type and
Concentration, to improve polyolefinic polarity and solubility parameters.Then by the polyolefin after corona treatment and polar monomer, initiation
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 kind of method for promoting polyolefin graft reaction, comprises the following steps：
First polyolefin is carried out Low Temperature Plasma Treating, obtain the polyolefin of surface modification；
Then by the polyolefin after surface modification, polar monomer, the solution containing initiator, antioxidant mix homogeneously, it is put into
Reacted in extruder, extrudate obtains the polyolefin of polar compound graft modification through traction, cooling, dry, pelletizing
Granule.
The polyolefinic reaction condition of corona treatment of the present invention is to be passed through the mixture of one or several gases, gas
Body 1～100Pa of pressure, 4～120W of discharge power, 0.1～100min of discharge time.From the point of view of polyolefin graft efficiency is improved,
Preferably, the gas pressure intensity is 1～50Pa, 10～30W of discharge power, and discharge time is 0.5～20min；Most preferably, gas
Body pressure is 50Pa, discharge power 30W, discharge time 20min.Process polymerization is carried out using suitable low-temperature plasma concrete conditions in the establishment of a specific crime
Thing, can produce active group in polymer surfaces, improve the polarity of polymer；While the setting of low-temperature plasma concrete conditions in the establishment of a specific crime is also
Follow-up extrusion reaction need to be beneficial to.
Corona treatment polyolefin equipment therefor of the present invention is reaction of low temperature plasma device, and discharge mode can be
One kind in glow discharge, corona discharge, dielectric barrier discharge, radio-frequency discharge and microwave discharge.
Plasma reaction gas of the present invention are air, oxygen, nitrogen, carbon dioxide, argon, helium, ammonia
A kind of several mixture.Preferably, gas is argon, the mixed gas of argon 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 species of raw material and proportional quantity have significant impact for graft reaction effect,
Inappropriate raw material type and proportional quantity can cause the graft reaction efficiency of polymer to reduce, and can also there is showing for polyolefin crosslinking
As the side reaction more with generation.
The initiator of the present invention is added in the form of a solution, and initiator is dissolved in acetone and prepares the acetone containing initiator
Solution.
Polyolefin of the present invention is Low Density Polyethylene (LDPE), high density polyethylene (HDPE) (HDPE), linea low density gather
Ethylene (LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), POE (POE), ethylene propylene diene rubber
(EPDM) one or more the polyolefinic mixture in.Preferably, the polyolefin is Low Density Polyethylene (LDPE) or poly-
Propylene (PP).
Polar monomer of the present invention is maleic acid, fumaric acid, itaconic acid, citraconic acid .beta.-methylacrylic acid, maleic anhydride, clothing health
Anhydride, citraconic anhydride, crotonic anhydride, acrylic acid, methacrylic acid, acrylic acid methyl ester., ethyl acrylate, methyl methacrylate
The mixture of one or more in 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, the tert-butyl group
The mixture of one or more in double (t-butylperoxyisopropyl) benzene of peroxide benzoate, 1,4-.Preferably, described
Initiator is dibenzoyl peroxide.From the generation of the cross-linking reaction for reducing between side reaction and reduction polyolefin, polyene is improved
Hydrocarbon reaction efficiency, selects suitable initiator type, wherein, suitable using dibenzoyl peroxide, its effect for producing
Most prominent.
Antioxidant of the present invention is [four (3,5- di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant
1010), 3- (3,5- di-t-butyl -4- hydroxyl) propylene octadecyl ester (antioxidant 1076), N, N'- pair-(3- (3,5- di-t-butyl -
4- hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), 2,6- di-t-butyl -4- cresol (antioxidant 264), 2,4,6- tri-
One or more in 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) propanoic acid] pentaerythritol ester.
Preferably, from for grafting efficiency and melt index, described polyolefin is Low Density Polyethylene (LDPE) or poly- third
Alkene (PP), it is dibenzoyl peroxide that the polar monomer is maleic anhydride, the initiator, and antioxidant is [four (3,5- bis- uncles
Butyl -4- hydroxy phenyl) propanoic acid] pentaerythritol ester.
Reaction temperature is 10～500 DEG C, 10～100 revs/min of driving screw rotating speed in an extruder, feed screw rotating speed 50
～300 revs/min.Preferably, the reaction temperature is 10～100 DEG C, 10～50 revs/min of driving screw rotating speed, feed screw
60～100 revs/min of rotating speed.Most preferably, 50 revs/min of the driving screw rotating speed, 70 revs/min of feed screw rotating speed.
The present invention also protects the polyolefin particles of the polar compound graft modification for preparing by above method.
A technical scheme in technique scheme has the advantages that：
The prominent improvement of the present invention is first with low temperature plasma, polyolefin to be modified, and on the one hand can increase
Polyolefin surfaces polar group number, can also improve polyolefin polar, be conducive to improving in an extruder and polar compound
The compatibility, on the other hand, the polar group except being introduced using plasma can be entered with polar compound in an extruder
Row condensation reaction, beyond polar compound is grafted on polyolefin, using initiator, can also be further by polar compound
It is grafted on polyolefin, grafting efficiency can be greatly improved.And have been surprisingly found that, the addition of the initiator can suppress polyolefin
Generation (as crosslinking or the polyacrylic degraded side reaction of polyethylene), it may not be necessary to as described in patent CN 105859970A
The addition of initiator needs to be pumped into extruder different heating section according to friction speed in polyolefin extrusion；And,
Compared to patent CN105693890A, the grafting efficiency of the present invention is significantly improved.In addition, invention also reduces causing
The consumption of agent, it is to avoid increase the generation of the cross-linking reaction between side reaction and polyolefin using initiator.
Graft polyolefin material prepared by the present invention has good machinability, can serve as polyolefin with polar polymeric
Compatilizer, toughener when thing, the mixing of various fillers.
Description of the drawings
Fig. 1 is the polyolefinic schematic device of corona treatment.
Specific embodiment
Embodiment 1：Comparative example
Weigh LDPE86.999 part (weight portion, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone
In, Low Density Polyethylene, dibenzoyl peroxide solution, maleic anhydride, antioxidant 1010 are mixed 60 in high-speed mixer
Minute, said mixture is added in extruder hopper, each area's temperature of extruder between 150 DEG C～180 DEG C, driving screw rotating speed
60 revs/min, 70 revs/min of feed screw rotating speed, extrudate is obtained polar monomer and connects through traction, cooling, dry, pelletizing
Branch modified polyolefin particles.
Embodiment 2：
Weigh LDPE86.999 part (weight portion, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone
In.LDPE is placed in reaction of low temperature plasma device, as shown in figure 1, first evacuation, is passed through argon, gas pressure intensity 50Pa,
Radio-frequency discharge power 30W, discharge time 20min, then by surface modification LDPE, maleic anhydride, dibenzoyl peroxide solution,
Antioxidant 1010 mixes 60 minutes in high-speed mixer, and mixture is put in extruder hopper, between 80 DEG C, driving screw
50 revs/min of rotating speed, is reacted under the conditions of 70 revs/min of feed screw rotating speed, and extrudate is through drawing, cooling down, dry, cut
Grain, obtains the polyolefin particles of polar compound graft modification.Wherein, reaction of low temperature plasma device and extruder are ability
The common equipment in domain, can be obtained by commercial sources.
Embodiment 3：
Weigh LDPE86.999 part (weight portion, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone
In.LDPE is placed in reaction of low temperature plasma device, is passed through argon/oxygen (volume ratio 4/1) mixed gas, gas pressure intensity
50Pa, radio-frequency discharge power 30W, discharge time 20min, then by surface modification LDPE, maleic anhydride, dibenzoyl peroxide
Solution, antioxidant 1010 mix 60 minutes in high-speed mixer, and mixture is put in extruder hopper, at 80 DEG C, main spiral shell
50 revs/min of bar rotating speed, is reacted under the conditions of 70 revs/min of feed screw rotating speed, extrudate through traction, cooling, dry,
Pelletizing, obtains the polyolefin particles of polar compound graft modification.
Embodiment 4：
Weigh LDPE86.999 part (weight portion, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone
In.LDPE is placed in reaction of low temperature plasma device, is passed through air, gas pressure intensity 50Pa, radio-frequency discharge power 30W, put
Electric time 20min, then will be mixed in high speed to surface modification LDPE, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010
Mix 60 minutes in conjunction machine, mixture is put in extruder hopper, at 80 DEG C, 50 revs/min of driving screw rotating speed, feed screw
Reacted under the conditions of 70 revs/min of rotating speed, extrudate obtains polar compound grafting through traction, cooling, dry, pelletizing
Modified polyolefin particles.
Embodiment 5：
Weigh LDPE86.999 part (weight portion, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), maleic acid
10.0 parts of acid anhydride, 0.001 part of dibenzoyl peroxide, 3.0 parts of antioxidant 1010, dibenzoyl peroxide is dissolved in 5.0 parts of acetone
In.LDPE is placed in reaction of low temperature plasma device, is passed through carbon dioxide, gas pressure intensity 50Pa, radio-frequency discharge power
Then surface modification LDPE, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010 are existed by 30W, discharge time 20min
Mix 60 minutes in high-speed mixer, mixture is put in extruder hopper, at 80 DEG C, 50 revs/min of driving screw rotating speed, feed
Reacted under the conditions of 70 revs/min of screw speed of material, extrudate obtains polar compounds through traction, cooling, dry, pelletizing
The polyolefin particles of thing graft modification.
Embodiment 6：
Weigh PP86.999 part (weight portion, 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
In.PP is placed in reaction of low temperature plasma device, is passed through argon, gas pressure intensity 50Pa, radio-frequency discharge power 30W, electric discharge
Time 20min, then by surface modification PP, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010 in high-speed mixer
Middle mixing 60 minutes, mixture is put in extruder hopper, at 80 DEG C, 50 revs/min of driving screw rotating speed, and feed screw rotating speed
Reacted under the conditions of 70 revs/min, extrudate obtains polar compound graft modification through traction, cooling, dry, pelletizing
Polyolefin particles.
Embodiment 7：
Weigh PP86.999 part (weight portion, 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
In.PP is placed in reaction of low temperature plasma device, is passed through argon/oxygen (volume ratio 4/1) mixed gas, gas pressure intensity
50Pa, radio-frequency discharge power 30W, discharge time 20min, then will be molten to surface modification PP, maleic anhydride, dibenzoyl peroxide
Liquid, antioxidant 1010 mix 60 minutes in high-speed mixer, and mixture is put in extruder hopper, at 80 DEG C, driving screw
50 revs/min of rotating speed, is reacted under the conditions of 70 revs/min of feed screw rotating speed, and extrudate is through drawing, cooling down, dry, cut
Grain, obtains the polyolefin particles of polar compound graft modification.
Embodiment 8：
Weigh PP86.999 part (weight portion, 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
In.PP is placed in reaction of low temperature plasma device, is passed through air, gas pressure intensity 50Pa, radio-frequency discharge power 30W, electric discharge
Time 20min, then by surface modification PP, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010 in high-speed mixer
Middle mixing 60 minutes, mixture is put in extruder hopper, at 80 DEG C, 50 revs/min of driving screw rotating speed, and feed screw rotating speed
Reacted under the conditions of 70 revs/min, extrudate obtains polar compound graft modification through traction, cooling, dry, pelletizing
Polyolefin particles.
Embodiment 9：
Weigh PP86.999 part (weight portion, 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
In.PP is placed in reaction of low temperature plasma device, is passed through carbon dioxide, gas pressure intensity 50Pa, radio-frequency discharge power 30W,
Discharge time 20min, then will be mixed in high speed to surface modification PP, maleic anhydride, dibenzoyl peroxide solution, antioxidant 1010
Mix 60 minutes in conjunction machine, mixture is put in extruder hopper, at 180 DEG C, 50 revs/min of driving screw rotating speed, feeding spiral shell
Reacted under the conditions of 70 revs/min of bar rotating speed, extrudate is obtained polar compound and connects through traction, cooling, dry, pelletizing
The modified polyolefin particles of branch.
Embodiment 10：
Weigh LDPE85.998 part (weight portion, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), citraconic acid
12.0 parts of acid anhydride, 0.002 part of cumyl peroxide, 2.0 parts of antioxidant 1076, cumyl peroxide is dissolved in 5.0 parts of acetone
In.LDPE is placed in reaction of low temperature plasma device, is passed through argon, gas pressure intensity 80Pa, radio-frequency discharge power 30W, put
Electric time 100min, then by surface modification LDPE, citraconic anhydride, cumyl peroxide solution, antioxidant 1076 at a high speed
Mix 60 minutes in mixer, mixture is put in extruder hopper, at 80 DEG C, 40 revs/min of driving screw rotating speed, feeding spiral shell
Reacted under the conditions of 100 revs/min of bar rotating speed, extrudate is obtained polar compound and connects through traction, cooling, dry, pelletizing
The modified polyolefin particles of branch.
Embodiment 11
Weigh 88 parts of LDPE (weight portion, similarly hereinafter, Yanshan Petrochemical LD160, melt index 5.0g/10min), itaconic anhydride
8.0 parts, 2 parts of di-tert-butyl peroxide, 1,098 2.0 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, is passed through argon/oxygen (volume ratio 4/1) mixed gas, gas pressure intensity
100Pa, radio-frequency discharge power 50W, discharge time 40min, then by surface modification LDPE, itaconic anhydride, di-t-butyl peroxide
Compound solution, antioxidant 1098 mix 60 minutes in high-speed mixer, and mixture is put in extruder hopper, at 70 DEG C,
90 revs/min of driving screw rotating speed, is reacted under the conditions of 120 revs/min of feed screw rotating speed, extrudate through traction, cooling,
Dry, pelletizing, obtains the polyolefin particles of polar compound graft modification.
Embodiment 12：
Weigh LDPE86 part (weight portion, 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 benzene first
Acid esters is dissolved in 5.0 parts of acetone.LDPE is placed in reaction of low temperature plasma device, is passed through air, gas pressure intensity 50Pa, penetrates
Frequency discharge power 80W, discharge time 25min, then by surface modification LDPE, glycidyl methacrylate, tert-butyl group mistake
Oxidation benzoate, irgasfos 168 mix 60 minutes in high-speed mixer, mixture are put in extruder hopper, 60
DEG C, 30 revs/min of driving screw rotating speed, reacted under the conditions of 90 revs/min of feed screw rotating speed, extrudate through traction, cold
But, dry, pelletizing, obtains the polyolefin particles of polar compound graft modification.
Embodiment 13
Weigh PP86.999 part (weight portion, similarly hereinafter, Yanshan Petrochemical 1396D, melt index 4.2g/10min), metering system
10.0 parts of acetoacetic ester, 0.001 part of Isosorbide-5-Nitrae-bis- (t-butylperoxyisopropyl) benzene, 3.0 parts of antioxidant 1010, by Isosorbide-5-Nitrae-bis- (uncles
Butyl peroxy isopropyl) benzene is dissolved in 5.0 parts of acetone.PP is placed in reaction of low temperature plasma device, is passed through argon, gas
Body pressure 190Pa, radio-frequency discharge power 100W, discharge time 20min, then by surface modification PP, ethyl methacrylate, 1,
4- double (t-butylperoxyisopropyl) benzole soln, antioxidant 1010s mix 60 minutes in high-speed mixer, and mixture is put
Enter in extruder hopper, at 50 DEG C, 60 revs/min of driving screw rotating speed, carry out under the conditions of 90 revs/min of feed screw rotating speed anti-
Should, extrudate obtains the polyolefin particles of polar compound graft modification through traction, cooling, dry, pelletizing.
Embodiment 10～13 made divided by monomer maleic anhydride, initiator cumyl peroxide beyond polyolefinic connect
Branch reaction, but polyolefinic graft reaction effect is all not as the effect in embodiment 2～9 is projected.
1～9 polar monomer graft improved polyalkene result of embodiment is as shown in the table：
Can see from the LDPE graft modification result of embodiment 2～5, through gathering that different plasma atmosphere was processed
Alkene, the efficiency for carrying out graft reaction with polar monomer in an extruder is 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 its 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 suppressed 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 high yet, same explanation
PP degraded side reaction is controlled preferably.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change that is made under principle, modification, replacement, combine, simplify,
Equivalent substitute mode is all should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of method for promoting polyolefin graft reaction, is characterized in that, comprise the following steps：
First polyolefin is carried out corona treatment, the polyolefin of surface modification is obtained, corona treatment is polyolefinic anti-
It is to be passed through the mixture of one or several gases, 1～100 Pa of gas pressure intensity, 4～120 W of discharge power, electric discharge to answer condition
0.1～100 min of time；
Then by the polyolefin after surface modification, polar monomer, the solution containing initiator, antioxidant mix homogeneously, extrusion is put into
Reacted in machine, extrudate obtains the polyolefin of polar compound graft modification through traction, cooling, dry, pelletizing
Grain；Wherein, raw material is in terms of mass parts, 93.999～68 parts of polyolefin, 5～20 parts of polar monomer, 0.001 ~ 7 part of initiator, resists
1～5 part of oxygen agent；The initiator is cumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl group mistake
Oxidation benzoate, 1,4- are double（T-butylperoxyisopropyl）The mixture of one or more in benzene.
2. the method for claim 1, is characterized in that：The polyolefinic reaction condition of corona treatment is, the gas
Pressure is 1 ~ 50Pa, 10 ~ 30W of discharge power, and discharge time is 0.5 ~ 20min；Most preferably, gas pressure intensity is 50Pa, electric discharge
Power 30W, discharge time 20min.
3. method as claimed in claim 2, is characterized in that：Plasma reaction gas are air, oxygen, nitrogen, titanium dioxide
Carbon, argon, helium, a kind of several mixture of ammonia；Preferably, gas is argon, the mixed gas of argon and oxygen, sky
Gas, carbon dioxide.
4. the method for claim 1, 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 part of antioxidant；Preferably, in terms of mass parts, 86.999 parts of polyolefin, polarity
10 parts of monomer, 0.001 part of initiator, 3 parts of antioxidant.
5. the method for claim 1, is characterized in that：The polyolefin is Low Density Polyethylene（LDPE）, high density gather
Ethylene（HDPE）, linear low density polyethylene（LLDPE）, polypropylene（PP）, ethylene propylene copolymer（EPR）, ethylene octene common
Polymers（POE）, ethylene propylene diene rubber（EPDM）In one or more polyolefinic mixture；Preferably, the polyolefin is
Low Density Polyethylene（LDPE）Or polypropylene（PP）.
6. the method for claim 1, is characterized in that：The polar monomer is maleic acid, fumaric acid, itaconic acid, lemon health
Acid .beta.-methylacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, crotonic anhydride, acrylic acid, methacrylic acid, acrylic acid methyl ester., third
One or more in olefin(e) acid ethyl ester, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate mixed
Compound；Preferably, the polar monomer is maleic anhydride.
7. the method for claim 1, is characterized in that：The initiator is dibenzoyl peroxide.
8. the method for claim 1, is characterized in that：The antioxidant is [four (3,5- di-t-butyl -4- hydroxy benzeness
Base) propanoic acid] pentaerythritol ester（Antioxidant 1010）, 3- (3,5- di-t-butyl -4- hydroxyl) propylene octadecyl ester（Antioxidant 1076）、
N, N'- pair-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine（Antioxidant 1098）, 2,6- di-t-butyl -4-
Cresol（Antioxidant 264）, 2,4,6- tri-butyl-phenol（Antioxidant 246）, (2,4- di-tert-butyl-phenyl) tris phosphite（Anti-
Oxygen agent 168）In the mixture of one or more；Preferably, the antioxidant is [four (3,5- di-t-butyl -4- hydroxy benzeness
Base) propanoic acid] pentaerythritol ester.
9. the method for claim 1, is characterized in that：Reaction temperature is 10 ~ 500 DEG C, driving screw rotating speed in an extruder
10 ~ 100 revs/min, 50 ~ 300 revs/min of feed screw rotating speed；Preferably, the reaction temperature is 10 ~ 100 DEG C, driving screw
10 ~ 50 revs/min of rotating speed, 60 ~ 100 revs/min of feed screw rotating speed；Most preferably, 50 revs/min of the driving screw rotating speed,
70 revs/min of feed screw rotating speed.
10. the polyolefin of the polar compound graft modification for being prepared using the method any one of claim 1 ~ 9
Granule.
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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 |
| CN111100412A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polar graft modified polyolefin material for coating type dripping fog dispersal greenhouse film, preparation method thereof and greenhouse film |
| CN112830997A (en) * | 2020-12-31 | 2021-05-25 | 石家庄联合石化有限公司 | Preparation method of graft modified polypropylene |
| CN113088029A (en) * | 2021-04-08 | 2021-07-09 | 四川潽鑫科技集团有限公司 | High-impact-resistance double-wall corrugated pipe and preparation method thereof |
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| CN111100412A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polar graft modified polyolefin material for coating type dripping fog dispersal greenhouse film, preparation method thereof and greenhouse film |
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| CN113088029A (en) * | 2021-04-08 | 2021-07-09 | 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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| CN106432614B (en) | 2019-07-05 |
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