CN105859970A - Method for increasing polyolefin grafting efficiency - Google Patents
Method for increasing polyolefin grafting efficiency Download PDFInfo
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- CN105859970A CN105859970A CN201610179145.1A CN201610179145A CN105859970A CN 105859970 A CN105859970 A CN 105859970A CN 201610179145 A CN201610179145 A CN 201610179145A CN 105859970 A CN105859970 A CN 105859970A
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- antioxidant
- maleic anhydride
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/29—Feeding the extrusion material to the extruder in liquid form
-
- 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
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
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- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a method for increasing polyolefin grafting efficiency. The method comprises the steps of weighing the raw materials in parts by weight: 99.88-83.0 parts of polyolefin, 0.1-12.0 parts of polar monomer, 0.01-3.0 parts of initiator and 0.01-2.0 parts of antioxidant, dissolving the polar monomer in a solvent, dissolving the initiator in anhydrous ethanol, uniformly mixing the polyolefin, the antioxidant and the solution of the polar monomer in a high-speed mixer, adding the mixture into a hopper of an extruder after the solvent of the polar monomer is volatilized, pumping the anhydrous ethanol solution of the initiator into different heating sections of the extruder according to different speeds, and subjecting extrudate to drawing, cooling, drying and granulating, thereby obtaining polar monomer grafted modified polyolefin granules. According to the method, the number of local free radicals is effectively prevented from being too high, the occurrence of side reactions such as polyolefin bridging or degrading is remarkably lowered, and the polyolefin grafting efficiency is greatly increased.
Description
Technical field
The present invention relates to a kind of polyolefin modified method, a kind of side improving polyolefin graft efficiency
Method.
Background technology
Polyolefin is the class general-purpose plastics kind that yield is maximum, have the electrical insulating property of excellence, hydrophobicity,
Chemically-resistant solvent aggressivity, low temperature properties and ductility, it is with low cost simultaneously, processing characteristics good, mainly
Common including Low Density Polyethylene, high density polyethylene (HDPE), linear low density polyethylene, polypropylene, ethylene, propylene
Polymers, POE etc..But polyolefin is non-polar material, its dyeability, bad adhesion,
With the poor compatibility of other polar polymer, these shortcomings constrain its application in many fields.
By polar group, such as carboxyl, anhydride, hydroxyl, epoxy radicals, ester group etc., it is incorporated into polyolefin segment
In it is modified, its caking property and the compatibility with polar polymer can be significantly improved, thus expand
The range of application of this kind of material.In numerous method of modifying, reactive extrursion method is utilized to carry out in an extruder
Free radical grafting is modified, has that the response time is short, can be continuously produced, be easily achieved the advantages such as industrialization,
Become the polyolefin modified method that application is most.Can be used as the Functional Polyolefine (CN of metal adhesion promoters
102241797A) disclose a kind of with peroxide as initiator, use reaction extrusion process to prepare propylene
The method of acid graft polypropylene.
A kind of heat resistant type transparency polyolefin PUR and preparation method thereof (CN 102241797A) discloses one
Plant heat resistant type transparency polyolefin PUR and preparation method thereof, by polyolefin, peroxide initiator, polarity
Monomer uniformly mixes, and then carries out reactive extrursion in double screw extruder at 160～200 DEG C, obtains polarity
The polyolefin hot-melt of monomer graft modification.
A kind of Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof (CN 101781389A) is public
Open a kind of Itaconic Acid Grafted ethylene-alpha-octylene copolymers and preparation method thereof, by ethylene-alpha-octylene copolymerization
Thing, peroxide initiator, itaconic acid polar monomer mix homogeneously in high-speed mixer, then in extrusion
Machine carries out reactive extrursion under 160～200 DEG C, screw speed 100～400 revs/min, obtains Itaconic Acid Grafted
Ethylene-alpha-octylene copolymers, this copolymer grafted efficiency is between 0.8～1.0%.
The preparation method (CN 102766239 A) of Itaconic Acid Grafted ethylene-octene block copolymer particulate material
Disclose the preparation method of a kind of Itaconic Acid Grafted ethylene-octene block copolymer particulate material, by ethylene-octene
Block copolymer, peroxide initiator dibenzoyl peroxide, itaconic acid polar monomer, antioxidant stir
Mix homogeneously, then obtains Itaconic Acid Grafted second by double screw extruder reactive extrursion at 150～170 DEG C
Alkene-octene block copolymer, 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 and connects
Branch polyolefin elastic precursor copolymer, by polyolefin elastomer, peroxide initiator cumyl peroxide,
Itaconic acid polar monomer, Tissuemat E mix homogeneously in banbury, reactive extrursion the most in an extruder,
It is prepared as described copolymer.
Domestic and foreign literature about polar monomer graft improved polyalkene in an extruder has maleic anhydride to be grafted
Polypropylene (Polymer Engineering and Science, 2012,52 (4): 814～819), Malaysia
Acid anhydride-grafted linear low density polyethylene (Journal of Applied Polymer Science, 2009,113 (5):
3125～3129), itaconic acid and glycidyl methacrylate graft polypropylene (Journal of Applied
Polymer Scienc, 2002,86 (1): 64～72), Itaconic Acid Grafted Low Density Polyethylene (Polymer,
2001,42 (2): 469～475), maleic anhydride grafted ethene octene copolymer/polypropylene miser (is moulded
Material auxiliary agent, 2006,3:21～23), maleic anhydride inoculated polypropylene (plastics industry, 2010,38 (5):
15～18), Itaconic Acid Grafted POE (polymer material science and engineering, 2011,27 (10):
46～48), Itaconic Acid Grafted Low Density Polyethylene (plastics science and technology, 2007,35 (2): 40～43),
It is all that polyolefin is uniformly mixed with peroxide initiator, polar monomer, then carries out reactive extrursion, institute
The grafting efficiency of the graft copolymer of preparation is respectively less than 1.5%.
From above-mentioned patent and document it will be seen that described inventor and researcher carry out polyolefin in an extruder
It is all by peroxide initiators one whole in polyolefin, polar monomer and formula during polar monomer graft modification
Play mix homogeneously, under specific extrusion temperature and screw speed, then carry out reactive extrursion.Owing to drawing all
Send out agent and disposably join in extruder by extruder hopper, can cause in the extrusion reaction starting stage, draw
Sending out agent and decompose the free radical produced too much, these free radicals draw except forming grafting site on polyolefin segment
Send out outside this primary response of polar monomer graft, too much grafting site also can cause numerous side reaction generation (as
The crosslinking of polyethylene or polyacrylic degraded side reaction), this will significantly reduce per-compound and cause pole
The efficiency of property monomer graft polyolefin, so the grafting efficiency of graft copolymer described in above-mentioned patent and document
The highest, respectively less than 1.5%.
Summary of the invention
The present invention proposes a kind of method improving polyolefin graft efficiency.Anhydrous by one or more initiators
Ethanol solution is pumped into extruder different heating section according to friction speed, it is achieved pole in polyolefin extrusion
The graft modification of property monomer.When using a kind of initiator, it is 1～7 along extruder screw initiator addition point,
And add speed from hopper toward heading initiator and be gradually lowered；When using several initiator, along extrusion
Machine screw rod initiator addition point is 1～7, adds speed from hopper toward heading initiator and is gradually lowered,
And the short initiator addition point of half-life compared with the addition point of half-life length closer to machine
Head direction.The present invention by by the initiator of one or more different decomposition speed at extruder along journey not same district
The mode that territory adds, it is achieved that constantly produce the purpose of reasonable concentration free radical in polyolefin extrusion, i.e.
Ensure that polyolefin produces enough free radicals and is grafted with initiation polar monomer, make again number of free radical not
As for too high and cause polyolefin crosslinking or the generation of the side reaction such as degraded, greatly improve the initiation of initiator
Efficiency and polyolefin graft efficiency.
The present invention is achieved through the following technical solutions:
A kind of method improving polyolefin graft efficiency, by polyolefin, polar monomer, initiator, antioxidant
Weigh according to weight portion, wherein polyolefin 99.88～83.0 parts, polar monomer 0.1～12.0 parts, initiation
Agent 0.01～3.0 parts, antioxidant 0.01～2.0 parts, be dissolved in polar monomer in solvent, initiator be dissolved in nothing
In water-ethanol, polyolefin, antioxidant are mixed homogeneously with polar monomer solution in high-speed mixer, works as pole
Property monomer solvent volatilization after, said mixture is added in extruder hopper, extruder each district temperature exists
Between 140 DEG C～220 DEG C, driving screw rotating speed 60～400 revs/min, feed screw rotating speed 10～80 revs/min,
The ethanol solution of initiator is pumped into extruder different heating section according to friction speed, extrusion simultaneously
Thing through drawing, cool down, be dried, pelletizing, obtain polar monomer graft modified polyolefin particles.
Described polyolefin is Low Density Polyethylene (LDPE), high density polyethylene (HDPE) (HDPE), the lowest
Density polyethylene (LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), ethylene octene
One or more polyolefinic mixture in copolymer (POE), ethylene propylene diene rubber (EPDM).
Described polar monomer be maleic acid, fumaric acid, itaconic acid, citraconic acid .beta.-methylacrylic acid, maleic anhydride,
Itaconic anhydride, citraconic anhydride, crotonic anhydride, acrylic acid, methacrylic acid, acrylic acid methyl ester., acrylic acid
One in ethyl ester, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate or
Several mixture.
Described initiator is cumyl peroxide, benzoyl peroxide, dilauroyl peroxide, di-t-butyl
Peroxide, tert-butyl hydroperoxide, tert butyl peroxy benzoate, Isosorbide-5-Nitrae-bis-(tert-butyl hydroperoxides
Isopropyl) benzene, methyl ethyl ketone peroxide, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, 2,2-bis-(uncle
Butyl peroxy)-5,5,6-trimethyl bicyclo-[2.2.1] heptane, 2,2-bis-(3-methyl isophthalic acid-butynyl-3-yllperoxy)
5,5,6-trimethyl bicyclo-[2.2.1] heptane, 2,5-dimethyl-2-hydroxyl-5-t-butylperoxy-3-hexin, peroxide
Change di-t-butyl, 2, the 2-diperoxy tert-butyl group-5, one or more in 5,6-trimethyl bicyclo-(2,2,1) heptane
Mixture.
Described antioxidant 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 '-bis--(3-(3,5-
Di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), BHT be (anti-
Oxygen agent 264), 2,4,6-tri-butyl-phenols (antioxidant 246), (2,4-di-tert-butyl-phenyl) tricresyl phosphite
The mixture of one or more in ester (irgasfos 168).
Extruder each district temperature between 140 DEG C～220 DEG C, driving screw rotating speed 60～400 revs/min, feeding
Screw speed 10～80 revs/min.
According to friction speed, the ethanol solution of one or more initiators is pumped into extruder difference add
Hot-section；When using a kind of initiator, it is 1～7 along extruder screw initiator addition point, and from material
Bucket adds speed toward heading initiator and is gradually lowered；When using several initiator, draw along extruder screw
Sending out agent addition point is 1～7, adds speed from hopper toward heading initiator and is gradually lowered, and partly declines
Time phase short initiator addition point compared with the addition point of half-life length closer to heading.
The invention has the beneficial effects as follows:
By single or several peroxide initiator solution in polyolefin extrusion according to friction speed
Be pumped into extruder different heating section, with existing patent and document in by polyolefin, polar monomer with all
Peroxide initiator disposably mixes, and carries out reactive extrursion the most again and compares, and peroxide is drawn by the present invention
Send out agent to add along Cheng Butong section mark time at extruder, be effectively prevented local number of free radical too high,
Significantly reduce the generation of the side reactions such as polyolefin crosslinking or degraded, greatly improve the efficiency of initiation of initiator
With polyolefin graft efficiency.
Accompanying drawing explanation
Fig. 1: use a kind of initiator to carry out the device schematic diagram of reactive extrursion for the present invention；
In figure: initiator 1: dibenzoyl peroxide
Fig. 2: use two kinds of initiators to carry out the device schematic diagram of reactive extrursion for the present invention.
In figure: initiator 1: dibenzoyl peroxide；Initiator 2: cumyl peroxide
Detailed description of the invention
Below in conjunction with the accompanying drawing of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground describes.
A kind of method improving polyolefin graft efficiency, by polyolefin, polar monomer, initiator, antioxidant
Weigh according to weight portion, wherein polyolefin 99.88～83.0 parts, polar monomer 0.1～12.0 parts, initiation
Agent 0.01～3.0 parts, antioxidant 0.01～2.0 parts, be dissolved in polar monomer in solvent, initiator be dissolved in nothing
In water-ethanol, polyolefin, antioxidant are mixed homogeneously with polar monomer solution in high-speed mixer, works as pole
Property monomer solvent volatilization after, said mixture is added in extruder hopper, extruder each district temperature exists
Between 140 DEG C～220 DEG C, driving screw rotating speed 60～400 revs/min, feed screw rotating speed 10～80 revs/min,
The ethanol solution of initiator is pumped into extruder different heating section according to friction speed, extrusion simultaneously
Thing through drawing, cool down, be dried, pelletizing, obtain polar monomer graft modified polyolefin particles.
Described polyolefin is Low Density Polyethylene (LDPE), high density polyethylene (HDPE) (HDPE), the lowest
Density polyethylene (LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), ethylene octene
One or more polyolefinic mixture in copolymer (POE), ethylene propylene diene rubber (EPDM).
Described polar monomer be maleic acid, fumaric acid, itaconic acid, citraconic acid .beta.-methylacrylic acid, maleic anhydride,
Itaconic anhydride, citraconic anhydride, crotonic anhydride, acrylic acid, methacrylic acid, acrylic acid methyl ester., acrylic acid
One in ethyl ester, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate or
Several mixture.
Described initiator is cumyl peroxide, benzoyl peroxide, dilauroyl peroxide, di-t-butyl
Peroxide, tert-butyl hydroperoxide, tert butyl peroxy benzoate, Isosorbide-5-Nitrae-bis-(tert-butyl hydroperoxides
Isopropyl) benzene, methyl ethyl ketone peroxide, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, 2,2-bis-(uncle
Butyl peroxy)-5,5,6-trimethyl bicyclo-[2.2.1] heptane, 2,2-bis-(3-methyl isophthalic acid-butynyl-3-yllperoxy)
5,5,6-trimethyl bicyclo-[2.2.1] heptane, 2,5-dimethyl-2-hydroxyl-5-t-butylperoxy-3-hexin, peroxide
Change di-t-butyl, 2, the 2-diperoxy tert-butyl group-5, one or more in 5,6-trimethyl bicyclo-(2,2,1) heptane
Mixture.
Described antioxidant 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 '-bis--(3-(3,5-
Di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), BHT be (anti-
Oxygen agent 264), 2,4,6-tri-butyl-phenols (antioxidant 246), (2,4-di-tert-butyl-phenyl) tricresyl phosphite
The mixture of one or more in ester (irgasfos 168).
Extruder each district temperature between 140 DEG C～220 DEG C, driving screw rotating speed 60～400 revs/min, feeding
Screw speed 10～80 revs/min.
According to friction speed, the ethanol solution of one or more initiators is pumped into extruder difference add
Hot-section；When using a kind of initiator, it is 1～7 along extruder screw initiator addition point, and from material
Bucket adds speed toward heading initiator and is gradually lowered；When using several initiator, draw along extruder screw
Sending out agent addition point is 1～7, adds speed from hopper toward heading initiator and is gradually lowered, and partly declines
Time phase short initiator addition point compared with the addition point of half-life length closer to heading.
Embodiment 1: comparative example
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by Low Density Polyethylene, diphenyl peroxide
Formyl solution, maleic anhydride solution, antioxidant 1010 mix homogeneously in high-speed mixer, by above-mentioned mixed
Compound adds in extruder hopper, extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70
Rev/min, feed screw rotating speed 60 revs/min, extrudate through draw, cool down, be dried, pelletizing, must
To polar monomer graft modified polyolefin particles.
Embodiment 2:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution being pumped into extruder I and II district respectively, rate of pumping divides
Be not 1 part/minute and 0.8 part/minute, by extrudate through drawing, cool down, be dried, pelletizing, obtain
Polar monomer graft modified polyolefin particles.
Embodiment 3:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution is pumped into respectively extruder I, II, III district, rate of pumping
Be respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, by extrudate through drawing, cool down, be dried,
Pelletizing, obtains polar monomer graft modified polyolefin particles.
Embodiment 4:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution is pumped into respectively extruder I, II, III, IV district, pumping
Speed is respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, 0.4 part/minute, is passed through by extrudate
Draw, cool down, be dried, pelletizing, obtain polar monomer graft modified polyolefin particles.
Embodiment 5:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution is pumped into respectively extruder I, II, III, IV, V district,
Rate of pumping is respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, 0.4 part/minute, 0.2 part/point
Clock, by extrudate through drawing, cool down, be dried, pelletizing, obtain polar monomer graft improved polyalkene
Grain.
Embodiment 6:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.05 part, initiator 2 cumyl peroxide 0.05 part, antioxidant 1010 1.0
Part, maleic anhydride is dissolved in 5.0 parts of dehydrated alcohol, by dibenzoyl peroxide and cumyl peroxide
It is dissolved in respectively in 2.5 parts of dehydrated alcohol, by Low Density Polyethylene, maleic anhydride solution, antioxidant 1010
Mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture, extruder each district temperature
Between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed 60 revs/min, will
Cumyl peroxide and dibenzoyl peroxide solution are pumped into extruder I, IV district, rate of pumping respectively
Be 1 part/minute, by extrudate through drawing, cool down, be dried, pelletizing, obtain polar monomer graft and change
Property polyolefin particles.
Embodiment 7:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.05 part, initiator 2 cumyl peroxide 0.05 part, antioxidant 1010 1.0
Part, maleic anhydride is dissolved in 5.0 parts of dehydrated alcohol, by dibenzoyl peroxide and cumyl peroxide
It is dissolved in respectively in 2.5 parts of dehydrated alcohol, by Low Density Polyethylene, maleic anhydride solution, antioxidant 1010
Mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture, extruder each district temperature
Between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed 60 revs/min, will
Cumyl peroxide solution is pumped into extruder I and II district respectively, and rate of pumping is respectively 1 part/minute
With 0.8 part/minute, dibenzoyl peroxide is pumped into extruder IV and V district respectively, and rate of pumping is respectively
Be 1 part/minute and 0.8 part/minute, by extrudate through drawing, cool down, be dried, pelletizing, obtain pole
Property monomer graft modification polyolefin particles.
Embodiment 8:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.05 part, initiator 2 cumyl peroxide 0.05 part, antioxidant 1010 1.0
Part, maleic anhydride is dissolved in 5.0 parts of dehydrated alcohol, by dibenzoyl peroxide and cumyl peroxide
It is dissolved in respectively in 2.5 parts of dehydrated alcohol, by Low Density Polyethylene, maleic anhydride solution, antioxidant 1010
Mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture, extruder each district temperature
Between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed 60 revs/min, will
Cumyl peroxide solution is pumped into extruder I, II, III district respectively, and rate of pumping is respectively 1 part/point
Clock, 0.8 part/minute, 0.6 part/minute, dibenzoyl peroxide is pumped into extruder IV, V, VI respectively
District, rate of pumping is respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, extrudate process is drawn,
Cooling, dry, pelletizing, obtain polar monomer graft modified polyolefin particles.
Embodiment 1～8 polar monomer graft grafted low density polyethylene efficiencies is as shown in the table:
In sum, employing a kind of method improving polyolefin graft efficiency of the present invention, embodiment 2-8, all
All being greatly improved than embodiment 1 (reference examples) grafting efficiency, optimal preference is embodiment 8, efficiency
Increase rate is 5.2%, and efficiency is 10.4 times of matched group.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art, can be easily in the technical scope that the invention discloses
The change expected or replacement, all should contain within protection scope of the present invention.
Claims (8)
1. the method improving polyolefin graft efficiency, by polyolefin, polar monomer, initiator, resists
Oxygen agent weighs according to weight portion, wherein polyolefin 99.88～83.0 parts, polar monomer 0.1～12.0 parts,
Initiator 0.01～3.0 parts, antioxidant 0.01～2.0 parts, be dissolved in polar monomer in solvent, and initiator is molten
In dehydrated alcohol, polyolefin, antioxidant are mixed homogeneously in high-speed mixer with polar monomer solution,
After the solvent of polar monomer volatilizees, said mixture is added in extruder hopper, extruder each district temperature
Between 140 DEG C～220 DEG C, driving screw rotating speed 60～400 revs/min, feed screw rotating speed 10～80 turns/
Minute, the ethanol solution of initiator is pumped into extruder different heating district according to friction speed simultaneously
Section, extrudate through drawing, cool down, be dried, pelletizing, obtain polar monomer graft modified polyolefin particles.
A kind of method improving polyolefin graft efficiency the most according to claim 1, is characterized in that institute
State polyolefin be Low Density Polyethylene (LDPE), high density polyethylene (HDPE) (HDPE), linea low density gather
Ethylene (LLDPE), polypropylene (PP), ethylene propylene copolymer (EPR), POE
(POE), one or more polyolefinic mixture in ethylene propylene diene rubber (EPDM).
A kind of method improving polyolefin graft efficiency the most according to claim 1, is characterized in that institute
Stating polar monomer is maleic acid, fumaric acid, itaconic acid, citraconic acid .beta.-methylacrylic acid, maleic anhydride, itaconic acid
Acid anhydride, citraconic anhydride, crotonic anhydride, acrylic acid, methacrylic acid, acrylic acid methyl ester., ethyl acrylate,
One or more in methyl methacrylate, ethyl methacrylate, glycidyl methacrylate
Mixture.
A kind of method improving polyolefin graft efficiency the most according to claim 1, is characterized in that institute
Stating initiator is cumyl peroxide, benzoyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide
Thing, tert-butyl hydroperoxide, tert butyl peroxy benzoate, Isosorbide-5-Nitrae-bis-(t-butylperoxyisopropyl)
Benzene, methyl ethyl ketone peroxide, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, 2,2-bis-(t-butyl peroxy
Base)-5,5,6-trimethyl bicyclo-[2.2.1] heptane, 2,2-bis-(3-methyl isophthalic acid-butynyl-3-yllperoxy) 5,5,6-tri-
Methyl bicyclic [2.2.1] heptane, 2,5-dimethyl-2-hydroxyl-5-t-butylperoxy-3-hexin, peroxidating two uncle
Butyl, 2, the 2-diperoxy tert-butyl group-5, the mixing of one or more in 5,6-trimethyl bicyclo-(2,2,1) heptane
Thing.
A kind of method improving polyolefin graft efficiency the most according to claim 1, is characterized in that institute
State antioxidant for [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 '-bis--(3-(3,5-bis-tertiary fourths
Base-4-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), BHT (antioxidant
264), 2,4,6-tri-butyl-phenols (antioxidant 246), (2,4-di-tert-butyl-phenyl) tris phosphite (resist
Oxygen agent 168) in the mixture of one or more.
A kind of method improving polyolefin graft efficiency the most according to claim 1, is characterized in that squeezing
Chu Jige district temperature is between 140 DEG C～220 DEG C, and driving screw rotating speed 60～400 revs/min, feed screw turns
Speed 10～80 revs/min.
A kind of method improving polyolefin graft efficiency the most according to claim 1, it is characterized in that by
The ethanol solution of one or more initiators is pumped into extruder different heating section according to friction speed.
When using a kind of initiator, it is 1～7 along extruder screw initiator addition point, and from hopper toward head
Direction initiator adds speed and is gradually lowered；When using several initiator, add along extruder screw initiator
Point is 1～7, adds speed from hopper toward heading initiator and is gradually lowered, and half-life is short
Initiator addition point compared with the addition point of half-life length closer to heading.
8., according to a kind of method improving polyolefin graft efficiency described in claim 1-7, use following real
Execute example:
Embodiment 1: comparative example
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by Low Density Polyethylene, diphenyl peroxide
Formyl solution, maleic anhydride solution, antioxidant 1010 mix homogeneously in high-speed mixer, by above-mentioned mixed
Compound adds in extruder hopper, extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70
Rev/min, feed screw rotating speed 60 revs/min, extrudate through draw, cool down, be dried, pelletizing, must
To polar monomer graft modified polyolefin particles.
Embodiment 2:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution being pumped into extruder I and II district respectively, rate of pumping divides
Be not 1 part/minute and 0.8 part/minute, by extrudate through drawing, cool down, be dried, pelletizing, obtain
Polar monomer graft modified polyolefin particles.
Embodiment 3:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution is pumped into respectively extruder I, II, III district, rate of pumping
Be respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, by extrudate through drawing, cool down, be dried,
Pelletizing, obtains polar monomer graft modified polyolefin particles.
Embodiment 4:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution is pumped into respectively extruder I, II, III, IV district, pumping
Speed is respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, 0.4 part/minute, is passed through by extrudate
Draw, cool down, be dried, pelletizing, obtain polar monomer graft modified polyolefin particles.
Embodiment 5:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.1 part, antioxidant 1010 1.0 parts, be dissolved in 5.0 parts of dehydrated alcohol by maleic anhydride
In, dibenzoyl peroxide is dissolved in 5.0 parts of dehydrated alcohol, by molten to Low Density Polyethylene, maleic anhydride
Liquid, antioxidant 1010 mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture,
Extruder each district temperature between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed
60 revs/min, dibenzoyl peroxide solution is pumped into respectively extruder I, II, III, IV, V district,
Rate of pumping is respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, 0.4 part/minute, 0.2 part/point
Clock, by extrudate through drawing, cool down, be dried, pelletizing, obtain polar monomer graft improved polyalkene
Grain.
Embodiment 6:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.05 part, initiator 2 cumyl peroxide 0.05 part, antioxidant 1010 1.0
Part, maleic anhydride is dissolved in 5.0 parts of dehydrated alcohol, by dibenzoyl peroxide and cumyl peroxide
It is dissolved in respectively in 2.5 parts of dehydrated alcohol, by Low Density Polyethylene, maleic anhydride solution, antioxidant 1010
Mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture, extruder each district temperature
Between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed 60 revs/min, will
Cumyl peroxide and dibenzoyl peroxide solution are pumped into extruder I, IV district, rate of pumping respectively
Be 1 part/minute, by extrudate through drawing, cool down, be dried, pelletizing, obtain polar monomer graft and change
Property polyolefin particles.
Embodiment 7:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.05 part, initiator 2 cumyl peroxide 0.05 part, antioxidant 1010 1.0
Part, maleic anhydride is dissolved in 5.0 parts of dehydrated alcohol, by dibenzoyl peroxide and cumyl peroxide
It is dissolved in respectively in 2.5 parts of dehydrated alcohol, by Low Density Polyethylene, maleic anhydride solution, antioxidant 1010
Mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture, extruder each district temperature
Between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed 60 revs/min, will
Cumyl peroxide solution is pumped into extruder I and II district respectively, and rate of pumping is respectively 1 part/minute
With 0.8 part/minute, dibenzoyl peroxide is pumped into extruder IV and V district respectively, and rate of pumping is respectively
Be 1 part/minute and 0.8 part/minute, by extrudate through drawing, cool down, be dried, pelletizing, obtain pole
Property monomer graft modification polyolefin particles.
Embodiment 8:
Weigh Low Density Polyethylene 93.9 parts (weight portion, lower same), maleic anhydride 5.0 parts, initiator 1
Dibenzoyl peroxide 0.05 part, initiator 2 cumyl peroxide 0.05 part, antioxidant 1010 1.0
Part, maleic anhydride is dissolved in 5.0 parts of dehydrated alcohol, by dibenzoyl peroxide and cumyl peroxide
It is dissolved in respectively in 2.5 parts of dehydrated alcohol, by Low Density Polyethylene, maleic anhydride solution, antioxidant 1010
Mix homogeneously in high-speed mixer, adds in extruder hopper by said mixture, extruder each district temperature
Between 140 DEG C～190 DEG C, driving screw rotating speed 70 revs/min, feed screw rotating speed 60 revs/min, will
Cumyl peroxide solution is pumped into extruder I, II, III district respectively, and rate of pumping is respectively 1 part/point
Clock, 0.8 part/minute, 0.6 part/minute, dibenzoyl peroxide is pumped into extruder IV, V, VI respectively
District, rate of pumping is respectively 1 part/minute, 0.8 part/minute, 0.6 part/minute, extrudate process is drawn,
Cooling, dry, pelletizing, obtain polar monomer graft modified polyolefin particles.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674431A (en) * | 2016-12-05 | 2017-05-17 | 彭州市运达知识产权服务有限公司 | Preparation method of high-density polyethylene grafted maleic anhydride polymer |
| CN107915806A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method of PP GRANULES grafting of polar monomers |
| WO2019214975A1 (en) * | 2018-05-08 | 2019-11-14 | Sabic Global Technologies B.V. | Process for the production of modified polyethylene materials. |
| CN110751986A (en) * | 2019-10-15 | 2020-02-04 | 山东省科学院能源研究所 | Calculation model and detection method of polyolefin grafting rate based on artificial neural network |
| CN113388072A (en) * | 2021-07-30 | 2021-09-14 | 赣州能之光新材料有限公司 | Preparation method of efficient compatilizer for reclaimed materials (PE/PP) |
| CN113970821A (en) * | 2021-11-17 | 2022-01-25 | 长飞光纤光缆股份有限公司 | Air-blowing micro cable capable of being used under large duty ratio, and preparation method and application of outer layer of air-blowing micro cable |
| CN114002794A (en) * | 2021-11-17 | 2022-02-01 | 长飞光纤光缆股份有限公司 | Layer-stranded air-blown micro-cable with high fiber core density, and preparation method and application of outer layer thereof |
| CN115322310A (en) * | 2022-08-29 | 2022-11-11 | 苏州海顺包装材料有限公司 | Method for preparing polyolefin resin by solid phase method and heat-sealing adhesive |
| CN115709555A (en) * | 2022-11-11 | 2023-02-24 | 宏岳塑胶集团股份有限公司 | Production process of crosslinked polyethylene PE-Xa (polyethylene-Xa) pipe and high-speed raw material mixer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002026879A1 (en) * | 2000-09-29 | 2002-04-04 | Compco Pty Ltd | Halogen-free polymeric compositions |
| EP1221463A1 (en) * | 2001-01-09 | 2002-07-10 | Sumitomo Wiring Systems, Ltd. | Resin composition, method of making it and electrical wire covered with it |
| CN101100497A (en) * | 2007-06-08 | 2008-01-09 | 深圳市科聚新材料有限公司 | All-purpose double-screw extruder one-time extracted graft and preparation method thereof |
| CN104804143A (en) * | 2015-05-14 | 2015-07-29 | 华东理工大学 | Preparation method of maleic anhydride grafted polypropylene |
-
2016
- 2016-03-28 CN CN201610179145.1A patent/CN105859970A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002026879A1 (en) * | 2000-09-29 | 2002-04-04 | Compco Pty Ltd | Halogen-free polymeric compositions |
| EP1221463A1 (en) * | 2001-01-09 | 2002-07-10 | Sumitomo Wiring Systems, Ltd. | Resin composition, method of making it and electrical wire covered with it |
| CN101100497A (en) * | 2007-06-08 | 2008-01-09 | 深圳市科聚新材料有限公司 | All-purpose double-screw extruder one-time extracted graft and preparation method thereof |
| CN104804143A (en) * | 2015-05-14 | 2015-07-29 | 华东理工大学 | Preparation method of maleic anhydride grafted polypropylene |
Non-Patent Citations (1)
| Title |
|---|
| 沈新元，等: "《高分子材料加工原理》", 31 December 2014, 中国纺织出版社 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915806A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method of PP GRANULES grafting of polar monomers |
| CN107915806B (en) * | 2016-10-10 | 2020-11-10 | 中国石油化工股份有限公司 | Method for grafting polar monomer onto polypropylene particles |
| CN106674431B (en) * | 2016-12-05 | 2019-01-01 | 厦门艾美森新材料科技股份有限公司 | A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer |
| CN106674431A (en) * | 2016-12-05 | 2017-05-17 | 彭州市运达知识产权服务有限公司 | Preparation method of high-density polyethylene grafted maleic anhydride polymer |
| US11421064B2 (en) | 2018-05-08 | 2022-08-23 | Sabic Global Technologies B.V. | Process for the production of modified polyethylene materials |
| WO2019214975A1 (en) * | 2018-05-08 | 2019-11-14 | Sabic Global Technologies B.V. | Process for the production of modified polyethylene materials. |
| CN110751986A (en) * | 2019-10-15 | 2020-02-04 | 山东省科学院能源研究所 | Calculation model and detection method of polyolefin grafting rate based on artificial neural network |
| CN113388072A (en) * | 2021-07-30 | 2021-09-14 | 赣州能之光新材料有限公司 | Preparation method of efficient compatilizer for reclaimed materials (PE/PP) |
| CN113388072B (en) * | 2021-07-30 | 2022-03-22 | 赣州能之光新材料有限公司 | Preparation method of efficient compatilizer for reclaimed materials (PE/PP) |
| CN114002794A (en) * | 2021-11-17 | 2022-02-01 | 长飞光纤光缆股份有限公司 | Layer-stranded air-blown micro-cable with high fiber core density, and preparation method and application of outer layer thereof |
| CN113970821A (en) * | 2021-11-17 | 2022-01-25 | 长飞光纤光缆股份有限公司 | Air-blowing micro cable capable of being used under large duty ratio, and preparation method and application of outer layer of air-blowing micro cable |
| CN115322310A (en) * | 2022-08-29 | 2022-11-11 | 苏州海顺包装材料有限公司 | Method for preparing polyolefin resin by solid phase method and heat-sealing adhesive |
| CN115709555A (en) * | 2022-11-11 | 2023-02-24 | 宏岳塑胶集团股份有限公司 | Production process of crosslinked polyethylene PE-Xa (polyethylene-Xa) pipe and high-speed raw material mixer |
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