CN106995575B - One-step method chain extension mixes the preparation method of polyethylene Remanufacture plastic pipe PP Pipe Compound - Google Patents
One-step method chain extension mixes the preparation method of polyethylene Remanufacture plastic pipe PP Pipe Compound Download PDFInfo
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- CN106995575B CN106995575B CN201710244328.1A CN201710244328A CN106995575B CN 106995575 B CN106995575 B CN 106995575B CN 201710244328 A CN201710244328 A CN 201710244328A CN 106995575 B CN106995575 B CN 106995575B
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- polyethylene
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- -1 polyethylene Polymers 0.000 title claims abstract description 44
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 43
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229920003023 plastic Polymers 0.000 title claims abstract description 19
- 239000004033 plastic Substances 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 104
- 229920005989 resin Polymers 0.000 claims abstract description 104
- 238000004064 recycling Methods 0.000 claims abstract description 73
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000010721 machine oil Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 68
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 19
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 48
- 230000008569 process Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 16
- 238000005453 pelletization Methods 0.000 description 11
- 239000000498 cooling water Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229920001903 high density polyethylene Polymers 0.000 description 9
- 239000004700 high-density polyethylene Substances 0.000 description 9
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000007348 radical reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RNPXCFINMKSQPQ-UHFFFAOYSA-N dicetyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCC RNPXCFINMKSQPQ-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229940068921 polyethylenes Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
The invention discloses the preparation method that a kind of one-step method chain extension mixes polyethylene Remanufacture plastic pipe PP Pipe Compound, solve the problems, such as that regeneration cost height existing for existing polyethylene Remanufacture plastic pipe PP Pipe Compound, complex process, performance are bad.Technical solution floats polyethylene recycling resin, co-monomer, active dispersing agents, initiator, methyl propenoic acid glycidyl, regulator, antioxidant as raw material using machine oil pot recycling resin, drum recycling resin, film recycling resin, salt, is made using one-step method chain extension is modified.Present invention process is simple, it is at low cost, meet performance requirement, promote the recycling of low-quality reclaimed materials.
Description
Technical field
The present invention relates to environmental friendly regenerated field, specifically a kind of system of polyethylene Remanufacture plastic pipe PP Pipe Compound
Preparation Method.
Background technique
Polyethylene (PE) is used as most important general-purpose plastics, has extremely extensive purposes, consumption figure is huge at home.By
Many kinds of in polyethylene, various modified poly ethylenes enter market, and the polyethylene product that different performance requires is producing
Various auxiliary agents, such as antioxidant, colorant, filler, fire retardant can be added in the process, it is also possible to be mixed into some different types of
Resin, such as polypropylene, polystyrene, cost recovery is different when this results in different polyethylene products is discarded to recycle, and difference is come
Source reclaimed materials performance is different, is difficult to be blended between each other.When preparing plastic particles raw materials with different reclaimed materials, properties of product
Also different.
As CN103613835A discloses the side of a kind of multiple groups part technics of reclaim of plastic waste toughening compatilizer particle and its preparation
Method, the toughening compatilizer are matched by SBS, EVA, SEBS, Aluminate, silane coupling agent, DCP, calcium carbonate, stearic acid, calcium stearate
It makes, recycling resin is granulated with toughening compatilizer by one-step method blending extrusion, which realizes the re-using of resource,
Technics of reclaim of plastic waste rate is improved, environment is protected, increases economic efficiency, while the toughness for recycling resin is also improved, but is added
Enter the decline of its intensity of elastic body toughening, compatilizer can not adjust the relatively high problem of resin melting index.
For another example CN102585256A discloses a kind of Recycled HDPE plastic toughening method, and this method is by recycling
It is squeezed out after low-density polyethylene film crushing extruding pelletization with the high-density polyethylene plastics blended cross linking of recycling.The invention is realized
The cycling and reutilization of waste, has saved resource, reduces plastics cost, also help environmental protection, at low cost excellent
Point can significantly improve its toughness, but the melting of the invention sample under the premise of guaranteeing Recycled HDPE plastics rigidity
Index is higher, and pipe ring stiffness is insufficient, and blended cross linking extrusion is easy to that strand is made to form close network, adjusts melt index
While can make extruded product surface generate obvious shortcoming, be unable to satisfy the market demand of high quality tubing.
Traditional special material for tube generally adds other auxiliary agents by HDPE and is prepared, which is maintained at
1g/10min or so, tensile strength 20MPa or so, but the new HDPE resin huge market demand, price are higher.It is special to meet tubing
Under the premise of materials performance requirement, cost is controlled, preparing special material for tube using reclaimed materials is an important research direction, but
The reclaimed materials type that can be used in preparing materials in the tube PP Pipe Compound at present is limited, and cost recovery is higher.And as previously mentioned, conduct in the market
The polyethylene product of reclaimed materials is many kinds of, as machine oil pot recycling resin, film recycling resin, salt float polyethylene recycling resin,
Drum recycles resin, and drainpipe recycles resin, and waste and old machine casing recycles resin, is packed for recycling resin etc..Different returns
Since its material resin and additive are different, molecular weight, strand, melt index and mechanical property etc. are all different for rewinding,
The performance that different reclaimed materials can be used for regenerating the particulate material of preparation is not also identical.Reclaimed materials (such as drum recycling tree of high quality
Rouge) cost recovery is high, source is less, and it is renewable to be used to prepare the high products material of performance requirement, such as special material for tube.And low-quality
The reclaimed materials of amount, although cost recovery is low, often performance from a wealth of sources is bad, the field used for regeneration is few, Bu Nengyong
Premium quality product is prepared in regeneration.There is consideration to use the two with, but compatibility is poor if being directly blended to use, mechanical property with
Melt index is all unable to reach the requirement of special material for tube, especially Recycled HDPE (HDPE) resin and passes through cleaning
The salt that sorting process obtains is floated with salt and floats polyvinyl resin, these different types of recycling resin compatibles are poor, to reclaiming
The performance of material can have a significant impact.Currently, during recycling resin regeneration utilization, anxious at low cost, performance a kind of out to be developed
Excellent, simple process special material for tube.
Summary of the invention
The purpose of the present invention is to solve above-mentioned technical problem, provide a kind of simple process, it is at low cost, meet performance and want
The preparation method asked, the one-step method chain extension of low-quality reclaimed materials recycling is promoted to mix polyethylene Remanufacture plastic pipe PP Pipe Compound.
Technical solution of the present invention material component parts by weight proportion are as follows:
The preparation method comprises the following steps:
(1) methyl propenoic acid glycidyl and co-monomer are sufficiently mixed uniformly spare；
(2) active dispersing agents lauryl acrylate, initiator, regulator and antioxidant are sufficiently mixed uniformly spare.
(3) step (1) and (2) obtained blend are dispersed with stirring uniformly, obtain chain extension solution；
(4) machine oil pot resin, drum recycling resin, film recycling resin and the floating polyethylene recycling resin of salt is recycled to be put into
Blend composition is uniformly mixing to obtain in high-speed mixer；
(5) blend composition of the chain extension solution of step (3) and step (4) is put into stir evenly in high-speed mixer and is re-fed into
Extruder melting extrusion, drying, is made and is expected to obtain the final product at cooling, and the melting temperature is preferably controlled in 180~190 DEG C.
The co-monomer is the mixture of acrylic acid (AAc) and epoxy acrylate (EA).
The acrylic acid is 0.3~0.6 part, and epoxy acrylate is 0.1~0.3 part.
The regulator is caprolactam.
The active dispersing agents are lauryl acrylate.
The initiator is cumyl peroxide (DCP).
The extruder is single screw rod or double screw extruder.
The setting temperature of single screw rod or the double screw extruder are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas,
Four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head.The screw speed of the single screw rod or double screw extruder is set as 30r/
min。
The problem of for background technique, inventor carefully analyze existing various types of resins reclaimed materials,
Therefrom select raw material of four kinds of reclaimed materials as the application special material for tube, comprising:
Machine oil pot recycles resin (HDPE): its main feature is that strand is short, molecular weight is lower, is compounded with other polyolefin
Resin, it is mainly derived from oil pipkin material, which uses through reprocessabilty, different degrees of degradation has occurred,
Its melt index is caused to be greater than 3g/10min, elongation at break is lower than 100%, and comprehensive performance performance is poor, and price is lower；
Salt floats polyethylene and recycles resin: being the bigger recycling of the more other polyethylene of density that are flotated according to saline solution
Resin, this resin may be mixed with the resins such as a small amount of PET, PP, PS when recycling, containing a small amount of carboxyl, hydroxyl and amide group,
Impurity is more, and ash content is very big, and molecular weight distribution is wider, and performance is poor, but cheap；
Drum recycles resin: from the industry carrying big wood material of greater weight, the material molecule amount narrowly distributing, melting
Index (<0.8g/10min) is low, and mechanical property (>22MPa) is good, is fully able to reach the requirement of high quality special material for tube, but
The recycling resin material price is high；
Film recycling resin (low density polyethylene (LDPE) (LDPE) recycles resin): being film recycling resin from a wealth of sources, but
LDPE melt index is higher (>6g/10min), and tensile strength is low (<17MPa).
In the method for the present invention, especially select machine oil pot recycling resin, drum recycling resin, film recycling resin and salt floating
Four kinds of recycling resin alloys of polyethylene are enhanced product performance simultaneously in order to solve the consistency problem of these four recycling resins, right
These recycling resins carry out chain extension and are modified, and do chain extender, co-monomer epoxy acrylic with glycidyl methacrylate (GMA)
Ester (EA) and acrylic acid (AAc) make adjuvant, and caprolactam (CPL) is used as regulator, and it is dilute that lauryl acrylate (LA) does activity
Release agent.Chain extension is completed in two steps, and the first step is graft reaction, since GMA, AAc and EA are with carbon-carbon double bond isoreactivity
The monomer of functional group, has very high reactivity, and three is easy to occur with polyethylene molecular chain under the initiation of initiator
Radical reaction forms the active macromolecules chain that end group is carboxyl or epoxy group.Based on the above basis, the invention by GMA, EA and
AAc is dispersed in LA, is made in the initiation and control of initiator cumyl peroxide (DCP) and regulator caprolactam (CPL)
Under, EA and AAc double bond is opened, and radical reaction occurs with carbochain, is preferentially grafted in the carbochain for mixing polyvinyl resin, so
Afterwards GMA further with grafting EA and AAc base macromolecular occur radical reaction, formation mix polyvinyl resin band GMA-EA or
The macromolecular chain of GMA-AAc active end group, and limit and mix the graft reaction or quick that polyvinyl resin forms highly branched chain
Cross-linking reaction.Second step is chain extending reaction, and end group is with carboxyl or is expanded between polyvinyl resin carbochain mixing for epoxy group
Chain reaction, recycling resin of the end group with epoxy group are opened in heating and epoxy bond under shear action, with the molecule for having carboxyl
Macromolecular reaction occurs for the polyethylene recycling resin of chain, and four kinds of structure differences, strand different in size are connected together, formed
The long-chain polymer of high molecular weight.
Co-monomer is compound using epoxy acrylate and acrylic acid in the present invention, and the effect of epoxy acrylic is collaboration GMA
More stable macromolecular radical is formed with macromolecular chain, prevents GMA that autohemagglutination occurs in the reaction, improves grafting efficiency.Third
The effect of diluted acid is primarily to provide double bond and polarity carboxylic group, and different resins are after the first step is grafted, end group band
There is the free radical that esterification or reactive group and macromolecular chain occur between carboxyl and epoxy group that radical reaction occurs,
Further improve chain extension efficiency.The two collective effect reduces compared with one pack system co-monomer compared with short molecular chain number, and molecular weight becomes larger,
And molecular weight distribution sharp, chain extension efficiency is improved, so that meeting variety classes resin reclaimed materials is blended preparation high quality tubing
PP Pipe Compound eutectic refers to, high-intensitive, high tenacity performance requirement., wherein the acrylic acid is 0.3~0.6 part, epoxy acrylic
Ester is 0.1~0.3 part, excessively not only results in acrylic acid and epoxy acrylic autohemagglutination, molecular weight distribution is caused to broaden, under performance
Drop, also wastes raw material, and improves cost；Very few to make the reduction of GMA grafting rate, homopolymerization occurs for the part GMA, and chain extension effect is deteriorated, property
It can not be up to standard；The addition of regulator caprolactam, which can be reduced, even inhibits PE macromolecular self-crosslinking during chain extension,
The generation of activated monomer and excitation state dimer is prevented, the chain extension regulator of suitable concentration has certain catch to macromolecular radical
Effect is obtained, to reduce the crosslinking of macromolecular.Its additive amount should be strictly limited at 0.05~0.1 part, excessively then can be single together
Side reaction occurs between body, consumes the amount of co-monomer, further reduced chain extension efficiency；It is very few to cause to be crosslinked inhibition not to PE
Foot, can not prevent the generation of activated monomer and excitation state dimer, the crosslinking for eventually leading to macromolecular chain is excessive, and strand is submissive
Property be deteriorated.
The utility model has the advantages that
(1) in the resin that especially selection is blended, based on the lower machine oil pot recycling resin of cost recovery, cooperation is added big
Bucket recycling resin, then the film recycling resin and the floating polyethylene recycling resin of salt of low price are mixed, by various types of resins additive ratio
Strict control and suitable modified, the advantages of learning from other's strong points to offset one's weaknesses, give full play to all kinds of recycling resins, play the work of performance complement
With low price low performance rouge tree reclaimed materials of overcoming over cannot regenerate the technical problem for being used to prepare special material for tube, expand
The application field of this resinoid, while being greatly reduced the production cost that regenerating resin prepares special material for tube, compared in the past may be used
Reduction by 15%, it is environmentally friendly.
(2) active dispersing agents LA, chain extension co-monomer GMA, AAc are added into different types of recycling resin by one-step method
With EA, regulator, initiator DCP and antioxidant, compared with traditional graft crosslinking modification technology, the addition of EA and AAc have
Effect ground inhibits GMA autohemagglutination, greatly improves GMA to the chain extension efficiency for recycling resin, and the addition of LA, it is suppressed that free radical
The degradation for acting on lower PE is realized to improve the chain extension efficiency of the more LDPE of branch Yu the less HDPE of branch a variety of
The compatible blending of resin reclaimed materials also reduces the melt index of material while improving intensity and toughness.
(3) present invention process is extremely simple, easily controllable, and the melt index of the special material for tube of preparation can be down to 1.0g/
10min, tensile strength > 20MPa and elongation > 500%, properties are excellent.
Detailed description of the invention
Fig. 1 is the microstructure schematic diagram of special material for tube prepared by the present invention.
Specific embodiment
Comparative example 1
Weigh 5 parts of film recycling resins, 5 portions of salt float polyethylene recycling resin, 60 parts of machine oil pots recycle resins and 30 parts big
Bucket recycling resin, puts it into high-speed mixer and stirs 5 minutes, obtain uniform blend composition.Add mixture into twin-screw
It is granulated in extruder, double screw extruder each section temperature is respectively set are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas,
Four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed 30r/min.The lines of extrusion are cooling through cooling water, using air blast
Drying machine dries pelletizing, weighing and bagging.Obtain the mechanical property such as table 1 of material.
Comparative example 2
Weigh 10 parts of film recycling resins, 10 portions of salt float polyethylene recycling resin, 40 parts of machine oil pots recycle resins and 40 parts
Drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition.Add mixture into double spiral shells
It is granulated in bar extruder, double screw extruder each section temperature is respectively set are as follows: 180 DEG C of an area, two 185 DEG C of areas, three areas 185
DEG C, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed 30r/min.The lines of extrusion are cooling through cooling water, use
Blast drier dries pelletizing, weighing and bagging.Obtain the mechanical property such as table 1 of material.
Comparative example 3
(1) 1 part of active dispersing agents LA, 0.2 part of initiator DCP, 0.05 part of regulator CPL, 0.3 part of antioxidant are weighed
1010, it is sufficiently mixed uniformly；
(2) 10 parts of film recycling resins are weighed, 10 portions of salt float polyethylene recycling resin, 40 parts of machine oil pot recycling resins and 40
Part drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(3) blend of the solution of step (1) and step (2) is put into high-speed mixer and is stirred 5 minutes, obtained final
Blend.
(4) mixture in step (3) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
Comparative example 4
(1) 1.2 parts of co-monomer GMA, 0.3 part of AAc and 0.3 part of EA are weighed, are sufficiently mixed uniformly；
(2) 1 part of active dispersing agents LA, 0.2 part of initiator DCP, 0.3 part of antioxidant 1010 are weighed, is sufficiently mixed uniformly；
(3) (1), (2) obtained blend are uniformly dispersed by manually stirring, obtain chain extension solution；
(4) 5 parts of film recycling resins are weighed, 5 portions of salt float polyethylene recycling resin, 60 parts of machine oil pots recycle resins and 30 parts
Drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(5) blend of the chain extension solution of step (3) and step (4) is put into high-speed mixer and is stirred 5 minutes, obtained
Final blend；
(6) mixture in step (5) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
Embodiment 1
(1) 1.2 parts of co-monomer GMA, 0.3 part of AAc and 0.3 part of EA are weighed, are sufficiently mixed uniformly；
(2) 1 part of active dispersing agents LA, 0.2 part of initiator DCP, 0.05 part of regulator CPL, 0.3 part of antioxidant are weighed
1010, it is sufficiently mixed uniformly；
(3) (1), (2) obtained blend are uniformly dispersed by manually stirring, obtain chain extension solution；
(4) 5 parts of film recycling resins are weighed, 5 portions of salt float polyethylene recycling resin, 60 parts of machine oil pots recycle resins and 30 parts
Drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(5) blend of the chain extension solution of step (3) and step (4) is put into high-speed mixer and is stirred 5 minutes, obtained
Final blend；
(6) mixture in step (5) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
Embodiment 2
(1) 1.3 parts of co-monomer methyl GMA, 0.45 part of AAc and 0.2 part of EA are weighed, are sufficiently mixed uniformly；
(2) 1 part of active dispersing agents LA, 0.3 part of initiator DCP, 0.07 part of regulator CPL, 0.4 part of antioxidant are weighed
1010, it is sufficiently mixed uniformly；
(3) (1), (2) obtained blend are uniformly dispersed by manually stirring, obtain chain extension solution；
(4) 5 parts of film recycling resins are weighed, 5 portions of salt float polyethylene recycling resin, 60 parts of machine oil pots recycle resins and 30 parts
Drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(5) blend of the chain extension solution of step (3) and step (4) is put into high-speed mixer and is stirred 5 minutes, obtained
Final blend；
(6) mixture in step (5) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
Embodiment 3
(1) 1.4 parts of co-monomer GMA, 0.6 part of AAc and 0.1 part of EA are weighed, are sufficiently mixed uniformly；
(2) 1.5 parts of active dispersing agents LA, 0.4 part of initiator DCP, 0.1 part of regulator CPL, 0.5 part of antioxidant are weighed
1010, it is sufficiently mixed uniformly；
(3) (1), (2) obtained blend are uniformly dispersed by manually stirring, obtain chain extension solution；
(4) 7 parts of film recycling resins are weighed, 8 portions of salt float polyethylene recycling resin, 50 parts of machine oil pots recycle resins and 35 parts
Drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(5) blend of the chain extension solution of step (3) and step (4) is put into high-speed mixer and is stirred 5 minutes, obtained
Final blend；
(6) mixture in step (5) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
Embodiment 4
(1) 1.2 parts of co-monomer GMA, 0.3 part of AAc and 0.3 part of EA are weighed, are sufficiently mixed uniformly；
(2) 1 part of active dispersing agents LA, 0.2 part of initiator DCP, 0.05 part of regulator CPL, 0.3 part of antioxidant are weighed
1010, it is sufficiently mixed uniformly；
(3) (1), (2) obtained blend are uniformly dispersed by manually stirring, obtain chain extension solution；
(4) 10 parts of film recycling resins are weighed, 10 portions of salt float polyethylene recycling resin, 40 parts of machine oil pot recycling resins and 40
Part drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(5) blend of the chain extension solution of step (3) and step (4) is put into high-speed mixer and is stirred 5 minutes, obtained
Final blend；
(6) mixture in step (5) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
Embodiment 5
(1) 1.3 parts of co-monomer GMA, 0.45 part of AAc and 0.2 part of EA are weighed, are sufficiently mixed uniformly；
(2) 1 part of active dispersing agents LA, 0.3 part of initiator DCP, 0.07 part of regulator CPL, 0.4 part of antioxidant are weighed
1010, it is sufficiently mixed uniformly；
(3) (1), (2) obtained blend are uniformly dispersed by manually stirring, obtain chain extension solution；
(4) 10 parts of film recycling resins are weighed, 10 portions of salt float polyethylene recycling resin, 40 parts of machine oil pot recycling resins and 40
Part drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(5) blend of the chain extension solution of step (3) and step (4) is put into high-speed mixer and is stirred 5 minutes, obtained
Final blend；
(6) mixture in step (5) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
Embodiment 6
(1) 1.4 parts of co-monomer GMA, 0.6 part of AAc and 0.1 part of EA are weighed, are sufficiently mixed uniformly；
(2) 1.5 parts of active dispersing agents LA, 0.4 part of initiator DCP, 0.1 part of regulator CPL, 0.5 part of antioxidant are weighed
1010, it is sufficiently mixed uniformly.
(3) (1), (2) obtained blend are uniformly dispersed by manually stirring, obtain chain extension solution；
(4) 10 parts of film recycling resins are weighed, 10 portions of salt float polyethylene recycling resin, 40 parts of machine oil pot recycling resins and 40
Part drum recycles resin, puts it into high-speed mixer and stirs 5 minutes, obtains uniform blend composition；
(5) blend of the chain extension solution of step (3) and step (4) is put into high-speed mixer and is stirred 5 minutes, obtained
Final blend.
(6) mixture in step (5) is added twin-screw extrude into granulation, double screw extruder each section temperature point
It is not arranged are as follows: 180 DEG C of an area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head, screw speed
30r/min.The lines of extrusion are cooling through cooling water, using the dry pelletizing of blast drier, weighing and bagging.Obtain the mechanics of material
Performance such as table 1.
The Mechanics Performance Testing table of the different samples of table 1.
Mix polyethylene Remanufacture plastic pipe PP Pipe Compound according to one-step method chain extension prepared by embodiment, it is each to be detected it
Item physical property, which all has, significantly to be promoted, and elongation at break has been increased to 600% or so, and melt index values are reduced to 1.0 or so,
Meet the performance requirement of plastic pipe PP Pipe Compound.One-step method chain extension mixes polyethylene Remanufacture special material for tube and also possesses antioxygen
Change, the performance of the small and repeatable recycling of hygroscopicity, so that this PP Pipe Compound is suitable for the fields such as building materials and tubing.
Machine oil pot recycling resin, drum recycling resin, film recycling resin, salt float polyethylene recycling in the embodiment of the present invention
Resin is purchased from Hubei circumference green regenerating Science and Technology Ltd..
Claims (5)
1. the preparation method that a kind of one-step method chain extension mixes polyethylene Remanufacture plastic pipe PP Pipe Compound, which is characterized in that former
Expect component parts by weight proportion are as follows:
The preparation method comprises the following steps:
(1) by methyl propenoic acid glycidyl and co-monomer be sufficiently mixed uniformly it is spare, the co-monomer be acrylic acid and epoxy
The mixture of acrylate；
(2) active dispersing agents lauryl acrylate, initiator, regulator and antioxidant are sufficiently mixed to uniformly spare, wherein institute
The regulator stated is caprolactam；
(3) step (1) and (2) obtained blend are dispersed with stirring uniformly, obtain chain extension solution；
(4) machine oil pot is recycled into resin, drum recycling resin, film recycling resin and the floating polyethylene recycling resin of salt and is put into high speed
Blend composition is uniformly mixing to obtain in blender；
(5) blend composition of the chain extension solution of step (3) and step (4) is put into high-speed mixer to stir evenly and is re-fed into extrusion
Machine melting extrusion, drying, is granulated cooling to obtain the final product.
2. one-step method chain extension as described in claim 1 mixes the preparation method of polyethylene Remanufacture plastic pipe PP Pipe Compound,
It is characterized in that, the acrylic acid is 0.3~0.6 part, epoxy acrylate is 0.1~0.3 part.
3. one-step method chain extension as described in claim 1 mixes the preparation method of polyethylene Remanufacture plastic pipe PP Pipe Compound,
It is characterized in that, the initiator is cumyl peroxide (DCP).
4. one-step method chain extension as described in claim 1 mixes the preparation method of polyethylene Remanufacture plastic pipe PP Pipe Compound,
It is characterized in that, the extruder is single screw rod or double screw extruder.
5. one-step method chain extension as claimed in claim 4 mixes the preparation method of polyethylene Remanufacture plastic pipe PP Pipe Compound,
It is characterized in that, the setting temperature of single screw rod or the double screw extruder are as follows: 180 DEG C of an area, two 185 DEG C of areas, three areas 185
DEG C, four 190 DEG C of areas, five 185 DEG C of areas, 180 DEG C of head；The screw speed of the single screw rod or double screw extruder is set as
30r/min。
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| US20090069491A1 (en) * | 2007-09-06 | 2009-03-12 | Dow Global Technologies Inc. | Peroxide-free direct grafting of polar monomers onto unsaturated polyolefins |
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