CN1884309A - Polyolefin material melted extrusion functionalization stress induction method - Google Patents
Polyolefin material melted extrusion functionalization stress induction method Download PDFInfo
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- CN1884309A CN1884309A CNA2006100407117A CN200610040711A CN1884309A CN 1884309 A CN1884309 A CN 1884309A CN A2006100407117 A CNA2006100407117 A CN A2006100407117A CN 200610040711 A CN200610040711 A CN 200610040711A CN 1884309 A CN1884309 A CN 1884309A
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 33
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 26
- 238000001125 extrusion Methods 0.000 title claims abstract description 24
- 230000006698 induction Effects 0.000 title claims description 7
- 239000000047 product Substances 0.000 claims abstract description 106
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 60
- 239000003999 initiator Substances 0.000 claims description 50
- 230000000977 initiatory effect Effects 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 238000007086 side reaction Methods 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 8
- -1 polyethylene, Ethylene-Propylene Polymers 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims description 6
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
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- 229910000077 silane Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 7
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/55—Screws having reverse-feeding elements
Abstract
The invention relates to a new technology for functionalization reaction by fusing ANF squeezing polyolefin material, belonging to field of modifying polymer material. It comprises following steps: dissolving ethylene monomer into solvent and mixing it with polyolefin material, stewing, adding lubricant after solvent volatilization, filling them into parallel spin reverse-flighted screw extrusion machine with high rotation speed and high cutting, the squeezing temperature is between 160 to 350 Deg. C, the rotation speed of main bolt is between 350 to 1200 rmp, cooling, grain cutting and drying and getting final product. The method can inhibit or avoid cross bonding secondary reaction during functionalization reaction, increase grafting rate for function product and flux flowing speed, and is characterized by simple, high effective and easiness for industrialization.
Description
Technical field:
The present invention relates to a kind of new technology of polyolefin material melted extrusion functionalization, belong to the modification field of polymer materials.
Background technology:
Polyolefine material is owing to lack polar group, surface energy is low, be difficult to carry out surface printing, application or use as tackiness agent, poor with other polymer phase capacitives, with a little less than the interaction force of fiber and inorganic filler surface etc., these all to polyolefine material toughness reinforcing, strengthen or brought bigger difficulty with the blending and modifying of other polymkeric substance etc.Therefore polyolefine material being carried out functionalization and modification, is research focus and the key problem in technology that further improves polyolefine material performance and broadened application field.
At present polyolefine material is carried out nearly three kinds of the approach of functionalization and modification: functionizing method behind process for copolymerization, reactive group functionizing method and the polymkeric substance.Wherein process for copolymerization is owing to needing to select appropriate catalyst and copolymerization monomer, for the research bigger breakthrough of acquisition as yet at present in this respect.The reactions steps of reactive group functionizing method is many, and the functionalization transformation efficiency in second step is low, is difficult to obtain the polyolefin product of complete functionalized structure.The back functionizing method of polymkeric substance has then that reactions steps is simple, efficient is high, can serialization carry out, and the functional group's form in the multipolymer can be various, and implementation method also can have characteristics such as multiple choices.It is the chemical modification method of the present a kind of polyolefine material that adopts usually.But at present the back functionizing method of polyolefine material is generally in the presence of organic peroxide evocating agent the functionalization with maleic anhydride, and reaction method can be divided into solution method, scorification and solid phase method etc.Wherein in the reaction process that melt extrudes functionizing method that is easy to industrializing implementation, often be attended by comparatively serious crosslinked, degraded, oxidation or all side reactions such as polymerization, the structure of products therefrom is also comparatively complicated, is difficult to control.Particularly for polyethylene, ethylene-propylene copolymer or segmented copolymer, often be attended by comparatively serious crosslinking side reaction in its functionalized process, cause the serious decline of product melt flow rate (MFR) and the formation of partial gel material, influence the effect of functionalized products.Therefore seek a kind of suitable, can avoid or suppress the new technology that polyolefine material melt extrudes crosslinking side reaction in the functionalized process, significant.
Calendar year 2001 Chinese patent 01107332.2 once report adopt ultrasonic wave to induce the mechanochemical method that causes polyolefine material fusion-grafting vinyl monomer, this method has overcome the crosslinking side reaction in the functionalized process of polyolefine material, improve grafting (block) rate and the melt flow rate (MFR) of functionalized products, improved material modified result of use.But because the power of ultrasonic transducer in the ultrasonic wave fusion extrusion device is less, be difficult for amplifying, and for more powerful ultrasonic radiation need be isolated, technical barrier such as protection, carry out fairly large industrialization modification so this kind method is difficult.Therefore on the basis of former studies work, continue to seek and a kind ofly can overcome crosslinking side reaction and polyolefine material convenient, efficient, easily industrializing implementation melt extrudes the functionalization and modification new technology, have important practical usage.
Summary of the invention:
A kind of polyolefine material that the objective of the invention is to provide at the deficiencies in the prior art melt extrudes the new technology of functionalization and modification, this method can be avoided the crosslinking side reaction in the functionalized process of polyolefine material equally, improve grafting (block) rate and the melt flow rate (MFR) of functionalized products, and have simple and directly, efficient, be easy to the characteristics of industrializing implementation.
The technical solution adopted in the present invention is: utilize the shearing force effect of the high rotating speed twin screw extruder that is occurred in recent years, in melt extruding process, induce the chain-breaking reaction of polyolefine material, cause and produce macromolecular radical, cause polyolefinic grafting, block reaction, polyolefine material is carried out functionalization and modification.Under the shearing force action condition of twin screw extruder, because the relative movement between the macromolecular radical increases, crosslinking side reaction between the macromolecular radical is subjected to suppressing significantly, and grafting between macromolecular radical and the small molecule monomer or block reaction are not subjected to obviously to influence, so using or do not using under the condition of initiator, all can suppress or avoid the crosslinking side reaction in the functionalized process by the method for control screw speed, improve grafting (block) rate and the melt flow rate (MFR) of product.
The concrete technical scheme that invention is adopted is: a kind of stress induction method of polyolefin material melted extrusion functionalization, it is characterized in that accounting for the reaction-ure mixture weight percentage is 0.1%～5.0% vinyl monomer, be dissolved in that to account for the reaction-ure mixture weight percentage be in 0.5%～4% solvent, and be that 88%～99.3% polyolefine material mixes with accounting for the reaction-ure mixture weight percentage, place, after treating solvent evaporates, with accounting for the reaction-ure mixture weight percentage is that 0～2% lubricant adds high rotating speed in the lump, in the high-shear type co-rotating twin screw extruder, extrusion temperature is at 160～350 ℃, the driving screw rotating speed carries out grafting with melt extrusion or block reaction in 350～1200rpm scope, reaction product is through water-cooled, after pelletizing and the drying, obtain the functionalized polyolefin product.
Wherein said polyolefine material is the blend of any one or 2 to 3 kinds in polyethylene, Ethylene-Propylene Block Copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-dienes terpolymer or the ethylene-vinyl acetate copolymer.
Wherein said vinyl monomer is the mixture of any one or 2 to 3 kinds in toxilic acid, maleic anhydride, fumaric acid anhydride, ethyl maleate, the single ester of fumaric acid, glycidyl methacrylate, vinyl acetate, vinylbenzene, acrylonitrile, γ-(methacryloxy) propyl trimethoxy silicane or vinyl three (Beta-methyl oxyethyl group) silane.
Wherein even for monomer and mixed with polymers, material preferably is dissolved in monomer an amount of solvent before mixing; Described solvent is at least a kind of in acetone, ethanol or the whiteruss.
For the stability of extrusion, before compound adds forcing machine, preferably add the moderate lubrication agent; Wherein said lubricant is at least a kind of in calcium stearate, Zinc Stearate or the hard esteramides.
The screwing element of twin screw extruder and kneading member can make up with multiple patterns such as preparation blend alloy type, filled plastics modified version or glass filament reinforced plastics types, to be used to adjust to the shear effect of material and to extrude flow rate.The screwing element of preferred twin screw extruder and the array configuration of kneading member are the array configuration of glass filament reinforced plastics type.Preferred extrusion temperature is 210～270 ℃, and preferred driving screw rotating speed is 600～1000rpm.
In the process of functionalization, account under the condition that the reaction-ure mixture weight percentage is 0.01% to 2.0% peroxide initiator in adding, present method can suppress by the method that improves screw speed or avoid crosslinking side reaction, and obviously improves grafting (block) rate and the melt flow rate (MFR) of product; Described peroxide initiator is at least dicumyl peroxide or 2,5-dimethyl-2, a kind of in 5-two (tert-butyl peroxy base) hexane.
Beneficial effect:
1. do not use initiator, do not have residual undecomposed initiator problem in the reaction product.
2. pass through the inducing action of twin screw extruder shearing force, cause polyolefine material molecule chain break, produce macromolecular radical, cause the grafting or the block reaction of vinyl monomer, have grafting or block reaction efficient height, homopolymer or by-products content are few in the product, purity is high, the measured characteristics of matter.
3. the process of functionalization is easy to control.Under the shearing force action condition of twin screw extruder, because the relative movement between the macromolecular radical increases, crosslinking side reaction between the macromolecular radical is subjected to suppressing significantly, and grafting between macromolecular radical and the small molecule monomer or block reaction are not subjected to obviously to influence, so using or do not using under the condition of initiator, all can suppress or avoid the crosslinking side reaction in the functionalized process by the method for control screw speed, improve grafting (block) rate and the melt flow rate (MFR) of product.
4. the temperature range of functionalization is wide, is not subjected to the restriction of decomposition of initiator temperature, can carry out multiple monomeric grafting or block copolymerization reaction, improves the polyolefine material performance.
5. even under the condition that adds a small amount of peroxide initiator, present method also can suppress by the method that improves screw speed or avoid crosslinking side reaction, obviously improves grafting (block) rate and the melt flow rate (MFR) of functionalized products.
6. convenient, efficient, be easy to amplify and be easy to industrializing implementation.Owing to adopted in being easy to the twin screw extruder of industrializing implementation and carried out, avoided in the ultrasonic wave extrusion device technical barriers such as the little difficult amplification of the power of ultrasonic transducer and more powerful ultrasonic radiation need be isolated, protection.
Embodiment:
Below by embodiment the present invention is specifically described, it is important to point out that following examples only are used for the present invention is further detailed, can not be interpreted as limiting the scope of the invention.The person skilled in the art of this area can carry out some nonessential improvement and adjustment according to the invention described above content.
Embodiment 1 (the functionalized HDPE of stress induced initiation maleic anhydride): (raising sub-petro-chemical corporation produces to get high density polyethylene 5000S, MFR=1.1 gram/10 minutes) 0.30 kilogram, (raise sub-petro-chemical corporation produces high density polyethylene 6070, MFR=7.0 gram/10 minutes) 0.63 kilogram, get maleic anhydride (MAH) 30 grams, be dissolved in the 30ml acetone solvent, and mix, place with above-mentioned HDPE.After treating that wherein acetone solvent fully volatilizees, add in high rotating speed, the high-shear type co-rotating twin screw extruder and carry out functionalization.The twin screw extruder screw diameter is φ 20mm, and length-to-diameter ratio is L/D=32, and the screw thread combination form is for being applicable to the combination of simple glass fibre reinforced plastics type.Driving screw rotating speed 800rpm, feed screw rotating speed 96rpm, extrusion temperature: 185 ℃ of leading portions, 175 ℃ in stage casing, 160 ℃ of feeding sections, extrusion reaction obtains the functionalized HDPE product about about 1000 grams after about 20 minutes.Grafting (block) rate that records product is 0.41%, and melt flow rate (MFR) is 2.18 grams/10 minutes, and product gel content is 0.28%.
The measuring method of wherein product grafting (block) rate is: sample carries out through the method for xylene soluble, potassium hydroxide/ethanolic soln neutralization, hydrochloric acid/aqueous isopropanol back titration after xylene soluble, acetone precipitating, extracting and exsiccant purification process again.
The product melt flow rate (MFR) is carried out with reference to GB GB3682-83,190 ℃ of probe temperatures, load 2.16kg.
The product gel assay carries out with reference to ASTM D2765.
Comparative example 1-1 (the functionalized HDPE of high shear stress induced initiation maleic anhydride): the driving screw rotating speed changes 1000rpm into, and other conditions are with embodiment 1.Grafting (block) rate that records product is 0.55%, and melt flow rate (MFR) is 2.45 grams/10 minutes, and product gel content is 0.21%.
Comparative example 1-2 (the functionalized HDPE of thermal initiation maleic anhydride): the driving screw rotating speed changes 100rpm into, and other conditions are with embodiment 1.Grafting (block) rate that records product is 0.06%, and melt flow rate (MFR) is 1.74 grams/10 minutes, and product gel content is 0.18%.
Comparative example 1-3 (initiator causes the functionalized HDPE of maleic anhydride): add initiator dicumyl peroxide (DCP) 2 grams and be dissolved in the acetone solvent in the lump with maleic anhydride, and get driving screw rotating speed 80rpm, other conditions are with embodiment 1.Grafting (block) rate that records product is 0.42%, and melt flow rate (MFR) is 0.17 gram/10 minutes, and product gel content is 0.28%.
Comparative example 1-4 (initiator and the functionalized HDPE of stress induced compound initiation maleic anhydride): add initiator 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane (AD) 0.6 gram is dissolved in the acetone solvent in the lump with maleic anhydride, and gets driving screw rotating speed 800rpm, and other conditions are with embodiment 1.Grafting (block) rate that records product is 0.86%, and melt flow rate (MFR) is 0.59 gram/10 minutes, and product gel content is 0.60%.
Embodiment 2 (the two functionalized HDPE of monomer of stress induced initiation): (raising sub-petro-chemical corporation produces to get high density polyethylene 5000S, MI=1.1 gram/10 minutes) 0.92 kilogram, get maleic anhydride 20 grams, γ-(methacryloxy) propyl trimethoxy silicane (A174, dawn chemical plant, Compton, Nanjing) 20 grams, be dissolved in the 30ml acetone solvent, and mix, place with above-mentioned HDPE.After treating that wherein acetone solvent fully volatilizees, add in high rotating speed, the high-shear type co-rotating twin screw extruder and carry out functionalization.Extrusion temperature: 230 ℃ of leading portions, driving screw rotating speed 840rpm, other is with embodiment 1.Grafting (block) rate that records product is 0.59%, and melt flow rate (MFR) is 0.53 gram/10 minutes, and the infrared spectra detection shows at 1727cm
-1And 1121cm
-1The place has the carbonyl of stronger A174 and the infrared signature absorption peak of silicon-oxygen key.
The two functionalized HDPE of monomer of comparative example 2-1:(thermal initiation) get driving screw rotating speed 100rpm, other is with embodiment 2.Grafting (block) rate that records product is 0.36%, and melt flow rate (MFR) is 0.50 gram/10 minutes, and the infrared spectra detection shows at 1727cm
-1And 1121cm
-1The A174 infrared signature absorption peak strength at place has obviously and weakens.
Embodiment 3 (the functionalized LLDPE of stress induced initiation maleic anhydride): (raise sub-petro-chemical corporation produces line taking new LDPE (film grade) LLDPE7042, MFR=2.0 gram/10 minutes) 0.95 kilogram, get maleic anhydride 30 grams, miscible in 10 gram whiterusss, and after mixing with above-mentioned LLDPE, add in high rotating speed, the high-shear type co-rotating twin screw extruder and carry out functionalization.Extrusion temperature: 270 ℃ of leading portions, driving screw rotating speed 800rpm, other is with embodiment 1.Grafting (block) rate that records product is 0.44%, and melt flow rate (MFR) is 3.34 grams/10 minutes, and product gel content is 0.16%.
Comparative example 3-1 (the functionalized LLDPE of high shear stress induced initiation maleic anhydride): the driving screw rotating speed changes 1000rpm into, other is with embodiment 3, grafting (block) rate that records product is 0.58%, and melt flow rate (MFR) is 5.0 grams/10 minutes, and product gel content is 0.10%.
Comparative example 3-2 (the functionalized LLDPE of thermal initiation maleic anhydride): the driving screw rotating speed changes 200rpm into, and other is with embodiment 3, and grafting (block) rate that records product is 0.07%, and melt flow rate (MFR) is 1.76 grams/10 minutes, and product gel content is 0.38%.
Comparative example 3-3 (initiator and the functionalized LLDPE of stress induced compound initiation maleic anhydride): it is miscible in the lump in whiteruss with maleic anhydride to add initiator dicumyl peroxide (DCP) 0.5 gram, and get driving screw rotating speed 800rpm, extrusion temperature: 185 ℃ of leading portions, 175 ℃ in stage casing, 160 ℃ of feeding sections, other conditions are with embodiment 3.Grafting (block) rate that records product is 0.63%, and melt flow rate (MFR) is 1.8 grams/10 minutes, and product gel content is 0.0%.
Comparative example 3-4 (initiator causes the functionalized LLDPE of maleic anhydride): the driving screw rotating speed changes 200rpm into, other is with comparative example 3-2, grafting (block) rate that records product is 0.33%, and melt flow rate (MFR) is 0.64 gram/10 minutes, and product gel content is 0.0%.
Comparative example 3-5 (the functionalized LLDPE/POE of stress induced initiation maleic anhydride): (raise sub-petro-chemical corporation produces line taking new LDPE (film grade) LLDPE7042, MFR=2.0 gram/10 minutes) 0.77 kilogram, get ethylene-octene copolymer POE (9998, Du Pont Dow, MFR=0.5 gram/10 minutes) 0.18 kilogram, get maleic anhydride 30 grams and calcium stearate 3.0 grams, miscible in 10 gram whiterusss, and after mixing with above-mentioned LLDPE and POE, add in high rotating speed, the high-shear type co-rotating twin screw extruder and carry out functionalization.The twin screw extruder screw diameter is φ 20mm, and length-to-diameter ratio is L/D=32, and the screw flight combination form is for being applicable to the combination of common fillers filling blend shaped plastics.Driving screw rotating speed 800rpm, feed screw rotating speed 96rpm, forcing machine front-end temperature are 185 ℃, other is with embodiment 3.Grafting (block) rate that records product is 0.40%, and melt flow rate (MFR) is 3.1 grams/10 minutes.
Embodiment 4 (the functionalized EPR of stress induced initiation maleic anhydride): learning from else's experience, (CO 034 for the block ethylene-propylene rubber(EPR) EPR that pulverizes granulation; Italy Wo Ni company) 0.95 kilogram; get maleic anhydride 30 grams; be dissolved in the 10 gram whiterusss; and after mixing with above-mentioned ethylene-propylene rubber(EPR) particle, add in high rotating speed, the high-shear type co-rotating twin screw extruder and carry out functionalization.Extrusion temperature: 230 ℃ of leading portions, driving screw rotating speed 800rpm, other is with embodiment 1.Grafting (block) rate that records product is 0.42%, and melt flow rate (MFR) is 4.13 grams/10 minutes, product gel content 0.17%.
Comparative example 4-1 (the functionalized EPR of high shear stress induced initiation maleic anhydride): the driving screw rotating speed changes 1000rpm into, and add 5 the gram calcium stearates, other is with embodiment 4, grafting (block) rate that records product is 0.45%, melt flow rate (MFR) is 5.0 grams/10 minutes, product gel content 0.12%.
Comparative example 4-2 (the functionalized EPR of thermal initiation maleic anhydride): the driving screw rotating speed changes 80rpm into, and other is with embodiment 4, and grafting (block) rate that records product is 0.18%, and melt flow rate (MFR) is 0.64 gram/10 minutes, product gel content 0.16%.
Comparative example 4-3 (initiator and the functionalized EPR of stress induced compound initiation maleic anhydride): add initiator 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane (AD) 1.0 grams are dissolved in the acetone solvent in the lump with maleic anhydride, and get driving screw rotating speed 800rpm, and other conditions are with embodiment 4.Grafting (block) rate that records product is 0.90%, and melt flow rate (MFR) is 1.77 grams/10 minutes, product gel content 0.00%.
Comparative example 4-4 (initiator causes the functionalized EPR of maleic anhydride): the driving screw rotating speed changes 80rpm into, and other is with embodiment 4, and grafting (block) rate that records product is 0.62%, and melt flow rate (MFR) is 0.07 gram/10 minutes, product gel content 0.59%.
Embodiment 5 (the functionalized EPDM of stress induced initiation maleic anhydride): get terpolymer EP rubber EPDM (C240, Du Pont Dow) 0.96 kilogram, get maleic anhydride 20 grams, miscible in 10 gram whiterusss, and after mixing with above-mentioned terpolymer EP rubber, add in high rotating speed, the high-shear type co-rotating twin screw extruder and carry out functionalization.Extrusion temperature: 230 ℃ of leading portions, driving screw rotating speed 800rpm, other is with embodiment 1.Grafting (block) rate that records product is 0.40%, and melt flow rate (MFR) is 1.17 grams/10 minutes.
Comparative example 5-1 (the functionalized EPDM of thermal initiation maleic anhydride): the driving screw rotating speed changes 80rpm into, and other is with embodiment 5, and grafting (block) rate that records product is 0.09%, and melt flow rate (MFR) is 0.33 gram/10 minutes.
Comparative example 5-2 (initiator and the functionalized EPDM of stress induced compound initiation maleic anhydride): add initiator 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane (AD) 1.0 grams are miscible in the lump in whiteruss with maleic anhydride, and get driving screw rotating speed 800rpm, other conditions are with embodiment 5.Grafting (block) rate that records product is 0.89%, and melt flow rate (MFR) is 1.58 grams/10 minutes, product gel content 0.40%.
Comparative example 5-3 (initiator causes the functionalized EPDM of maleic anhydride): the driving screw rotating speed changes 80rpm into, and other is with embodiment 5, and grafting (block) rate that records product is 0.65%, and melt flow rate (MFR) is 0.04 gram/10 minutes, product gel content 0.60%.
Comparative example 5-4 (initiator causes the functionalized EPDM of maleic anhydride): the driving screw rotating speed changes 80rpm into, add initiator 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane (AD) changes 2.0 grams into, other is with embodiment 5, grafting (block) rate that records product is 0.84%, and melt flow rate (MFR) is 0.00 gram/10 minutes, product gel content 7.45%.
Embodiment 6 (the functionalized POE of stress induced initiation glycidyl methacrylate): get ethylene-octene copolymer POE (9998, Du Pont Dow, MFR=0.5 gram/10 minutes) 0.96 kilogram, get glycidyl methacrylate (GMA) 20 grams, be dissolved in the 30ml acetone solvent, and mix with above-mentioned ethylene-octene copolymer POE, place.After treating that wherein acetone solvent fully volatilizees, add in high rotating speed, the high-shear type co-rotating twin screw extruder and carry out functionalization.Extrusion temperature: 230 ℃ of leading portions, driving screw rotating speed 600rpm, other is with embodiment 1.The melt flow rate (MFR) that records product is 2.43 grams/10 minutes, and the infrared spectra detection shows at 1744cm
-1And 1643cm
-1The place has the carbonyl charateristic avsorption band of strong GMA.
Comparative example 6-1 (the functionalized POE of thermal initiation glycidyl methacrylate): change the driving screw rotating speed into 200rpm, other is with embodiment 11, and the melt flow rate (MFR) that records product is 0.85 gram/10 minutes, and the infrared spectra detection shows at 1744cm
-1And 1643cm
-1The GMA carbonyl characteristic absorbance peak intensity at place is very weak.
Under differing temps and the different initiator content condition, the twin screw extruder screw speed to polyolefine material functionalized products Effect on Performance referring to the table 1-1 to showing 1-9.Therefrom as seen, the grafting of functionalized products (block) rate and melt flow rate (MFR) all obviously increase with the increase of screw speed under the various conditions, and the gel content of product reduces, the stress induction method that shows the polyolefine material functionalization has the advantages that to suppress and/or to avoid crosslinking side reaction in the functionalized process, can control make have higher grafting (block) rate, better melt flow rate (MFR) and than the functionalized products of low-gel content.
Table 1-1 screw speed influences the functionalized HDPE of maleic anhydride (6070/5000S=2/1) product property
| Initiator content 0.00% | Initiator DCP content 0.10% | ||||||||
| Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) | Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) |
| 1-1-1 1-1-2 1-1-3 1-1-4 1-1-5 | 100 200 400 600 800 | 0.06 0.02 0.18 0.24 0.41 | 1.74 2.23 1.89 2.02 2.18 | 0.18 0.46 0.56 0.00 0.28 | 1-1-6 1-1-7 1-1-8 1-1-9 1-1-10 | 100 200 400 600 800 | 0.36 0.33 0.44 0.57 0.74 | 0.34 0.55 0.44 0.20 0.29 | 0.28 0.62 0.18 0.34 0.59 |
Annotate: 185 ℃ of temperature of reaction, maleic anhydride content 3.0%
Table 1-2 screw speed influences the functionalized HDPE of maleic anhydride (6070/5000S=2/1) product property
| Initiator A D content 0.06% | Initiator A D content 0.12% | ||||||||
| Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) | Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) |
| 1-2-1 1-2-2 1-2-3 1-2-4 1-2-5 | 100 200 400 600 800 | 0.34 0.41 0.61 0.83 0.86 | 0.69 0.48 0.33 0.31 0.59 | 0.24 0.85 0.52 0.16 0.60 | 1-2-6 1-2-7 1-2-8 1-2-9 1-2-10 | 100 200 400 600 800 | 0.60 0.80 0.94 1.21 1.34 | 0.17 0.06 0.04 0.11 0.39 | 0.48 0.59 0.48 0.34 0.86 |
Annotate: 210 ℃ of temperature of reaction, maleic anhydride content 3.0%
Table 1-3 screw speed influences the functionalized LLDPE of maleic anhydride (7042) product property
| Screw speed (rpm) | 230 ℃ of temperature of reaction | 270 ℃ of temperature of reaction | 310 ℃ of temperature of reaction | |||
| Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | |
| 80 200 400 600 800 | 0.10 0.06 0.12 0.18 0.31 | 1.66 1.80 1.59 1.26 2.14 | 0.14 0.07 0.18 0.29 0.44 | 1.97 1.76 1.44 1.87 3.34 | 0.23 0.19 0.25 0.37 0.49 | 1.20 1.24 1.76 2.31 4.64 |
Annotate: maleic anhydride content 3.0%
Table 1-4 screw speed influences the functionalized LLDPE of maleic anhydride (7042) product property
| Initiator DCP content 0.05% a | Initiator A D content 0.05% b | ||||||||
| Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) | Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) |
| 1-4-1 1-4-2 1-4-3 1-4-4 1-4-5 | 80 200 400 600 800 | 0.32 0.33 0.44 0.61 0.63 | 0.51 0.64 0.79 1.29 1.82 | 0.39 0.00 0.19 0.19 0.00 | 1-4-6 1-4-7 1-4-8 1-4-9 1-4-10 | 80 200 400 600 800 | 0.36 0.47 0.48 0.49 0.49 | 0.20 0.20 0.29 0.58 0.89 | 0.00 0.00 0.00 0.19 0.00 |
Annotate: 185 ℃ of a-temperature of reaction, 210 ℃ of b-temperature of reaction, maleic anhydride content 3.0%
Table 1-5 screw speed influences the functionalized EPR of maleic anhydride (CO034) product property
| Screw speed (rpm) | 230 ℃ of temperature of reaction | 270 ℃ of temperature of reaction | 310 ℃ of temperature of reaction | |||
| Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | |
| 80 200 400 600 800 | 0.18 0.23 0.32 0.38 0.42 | 0.64 0.66 1.61 3.25 4.13 | 0.26 0.33 0.37 0.44 0.47 | 0.85 1.05 2.33 4.14 7.13 | 0.39 0.41 0.49 0.56 0.58 | 2.19 2.28 4.15 6.52 8.55 |
Annotate: maleic anhydride content 3.0%
Table 1-6 screw speed influences the functionalized EPR of maleic anhydride (CO034) product property
| Initiator A D content 0.05% a | Initiator A D content 0.10% b | ||||||||
| Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) | Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) |
| 1-6-1 1-6-2 1-6-3 1-6-4 1-6-5 | 80 200 400 600 800 | 0.51 0.54 0.59 0.65 0.66 | 0.12 0.18 0.37 0.90 1.94 | 0.00 0.00 0.21 0.00 0.20 | 1-6-6 1-6-7 1-6-8 1-6-9 1-6-10 | 80 200 400 600 800 | 0.63 0.65 0.75 0.86 0.90 | 0.07 0.10 0.21 0.88 1.77 | 0.59 0.39 0.40 0.20 0.00 |
Annotate: 210 ℃ of temperature of reaction, maleic anhydride content 3.0%
Table 1-7 screw speed influences the functionalized EPDM of maleic anhydride (C240) product property
| Screw speed (rpm) | 230 ℃ of temperature of reaction | 270 ℃ of temperature of reaction | 310 ℃ of temperature of reaction | |||
| Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | |
| 80 200 400 600 800 | 0.09 0.14 0.21 0.28 0.40 | 0.33 0.40 0.42 0.63 1.17 | 0.16 0.22 0.29 0.37 0.46 | 0.52 0.56 0.58 0.65 1.06 | 0.25 0.32 0.43 0.51 0.54 | 0.53 0.66 1.14 2.10 3.89 |
Annotate: maleic anhydride content 2.0%
Table 1-8 screw speed influences the functionalized EPDM of maleic anhydride (C240) product property
| Initiator A D content 0.05% b | Initiator A D content 0.10% b | ||||||||
| Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) | Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) |
| 1-8-1 1-8-2 1-8-3 1-8-4 1-8-5 | 80 200 400 600 800 | 0.40 0.51 0.60 0.67 0.69 | 0.07 0.22 0.64 0.73 2.78 | 0.60 0.40 0.20 0.60 0.60 | 1-8-6 1-8-7 1-8-8 1-8-9 1-8-10 | 80 200 400 600 800 | 0.65 0.80 0.88 0.89 0.89 | 0.04 0.04 0.21 0.54 1.58 | 0.60 0.60 0.40 0.40 0.40 |
Annotate: 210 ℃ of temperature of reaction, maleic anhydride content 2.0%
Table 1-9 screw speed influences the functionalized EPDM of maleic anhydride (C240) product property
| Initiator A D content 0.15% b | Initiator A D content 0.20% b | ||||||||
| Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) | Sequence number | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | Gel content (mass%) |
| 1-9-1 1-9-2 1-9-3 1-9-4 1-9-5 | 80 200 400 600 800 | 0.79 0.89 0.63 0.58 0.55 | 0.00 0.00 0.08 0.52 1.55 | 2.82 1.99 1.00 0.60 0.60 | 1-9-6 1-9-7 1-9-8 1-9-9 1-9-10 | 80 200 400 600 800 | 0.84 1.13 0.83 0.56 0.51 | 0.00 0.01 0.04 0.46 2.13 | 7.46 1.39 0.80 0.60 0.40 |
Annotate: 210 ℃ of temperature of reaction, maleic anhydride content 2.0%
The effect of product of the present invention
1.HDPE functionalized products strengthens the influence of HDPE material mechanical performance to glass
Table 2-1 classifies the mechanical performance data that adopts functionalized products HDPE-g-MAH modification HDPE/GF material as.By data in the table as seen: under the close condition of content of glass fiber, adopt stress induced initiating method products therefrom (under no initiator and the higher screw speed condition) all obviously to be better than causing by initiator merely the product (containing under initiator and the low screw speed condition sample 2-1-2,2-1-4) of gained with adopting compound initiating method products therefrom (containing under initiator and the higher screw speed condition) modification HDPE/GF material mechanical performance (sample 2-1-6,2-1-7 and sample 2-1-3,2-1-5).And all significantly greater than the mechanical property of sample 2-1-1 (not containing functionalized products) material.Illustrate that functionalized products HDPE-g-MAH can significantly improve the interface binding power between HDPE and the glass fibre, obviously improves the mechanical property of its matrix material; And the mechanical property of stress induced initiating method and compound initiating method gained functionalized products modification HDPE/GF material all obviously is better than causing products therefrom by initiator merely; And be optimum with the modified effect of stress induced initiating method products therefrom especially wherein.
Table 2-1 HDPE functionalized products (HDPE-g-MAH) performance strengthens the influence of HDPE material mechanical performance to glass
*
| Sequence number | Initiator content (mass%) | Screw speed (rpm) | Grafting (block) rate (mass%) | Glass fiber content (mass%) | Tensile strength (MPa) | Charpy notched Izod impact strength (kJ/m 2) | Flexural strength (MPa) |
| 2-1-1 2-1-2 2-1-3 2-1-4 2-1-5 2-1-6 2-1-7 | DCP，0.1 DCP，0.1 AD，0.12 AD，012 0(185℃) 0(210℃) | 100 800 100 800 800 800 | 0 0.35 0.79 0.56 1.24 0.45 0.50 | 28.9 26.8 26.6 26.5 26.1 26.9 27.0 | 41.8 48.6 54.4 53.8 54.9 61.0 62.2 | 7.5 16.3 17.7 18.9 18.9 22.5 20.5 | 55.8 78.3 80.9 83.5 84.6 89.8 95.0 |
*HDPE6070/HDPE-g(b)-MAH＝90/10
2.LLDPE functionalized products is to cohesive strength influence between plastic-aluminum combined thin film layer
With LLDPE functionalized products (LLDPE-g-MAH) as the tackiness agent gained laminated film adhint stripping strength of plastic-aluminum combined film referring to table 2-2.Therefrom as seen, along with the increase of screw speed and the increase of product grafting (block) rate, the stripping strength of plastic-aluminum combined film T-type adhint obviously increases, and under close grafting (block) rate condition, the adhint intensity of stress induced initiation functionalized products (sample 2-2-5 and 2-2-10) is obviously greater than the adhint intensity that is caused the functionalized products of (sample 2-2-11) or compound initiation (sample 2-2-15) gained by initiator.
3.EPR functionalized products influences toughened Nylon 66 intermingling material notch shock flexible
Table 2-3 classifies the influence of different initiation mode functionalized products (EPR-g-MAH) to PA66/EPR-g-MAH intermingling material mechanical property as.By data in the table as seen, under the condition that does not contain initiator, sample 2-3-2,2-3-4 and sample 2-3-1,2-3-3 are relatively, because stress induced initiation gained functionalized products (sample 2-3-2,2-3-4) has higher grafting (block) rate under the high screw speed condition, so the notched Izod impact strength of its intermingling material and tensile strength all obviously are better than under the low screw speed condition functionalized products (sample 2-3-1,2-3-3) by the thermal initiation gained.Relatively situation is then opposite but sample 2-3-5 is with sample 2-3-6, though the gained functionalized products has higher grafting (block) rate under the high screw speed condition of this explanation, but because the melt flow rate (MFR) of product is excessive at this moment, the relative molecular mass of product descends obviously, so also be unfavorable for the toughening effect to PA66.
Table 2-2 LLDPE functionalized products (LLDPE-g-MAH) performance is to cohesive strength influence between plastic-aluminum combined thin film layer
*
| Sequence number | Initiator content (mass%) | The extrusion reaction temperature (℃) | Screw speed (rpm) | Grafting (block) rate (mass%) | Melt flow rate (MFR) (g/10min) | T type stripping strength (N) |
| 2-2-1 2-2-2 2-2-3 2-2-4 2-2-5 2-2-6 2-2-7 2-2-8 2-2-9 2-2-10 2-2-11 2-2-12 2-2-13 2-2-14 2-2-15 | 0 0 0 0 0 0 0 0 0 0 AD，0.05 AD，0.05 AD，0.05 AD，0.05 AD，0.05 | 230 230 230 230 230 270 270 270 270 270 210 210 210 210 210 | 80 200 400 600 800 80 200 400 600 800 80 200 400 600 800 | 0.10 0.06 0.12 0.18 0.30 0.14 0.07 0.18 0.29 0.42 0.36 0.47 0.48 0.48 0.49 | 1.66 1.80 1.59 1.26 2.14 1.97 1.76 1.44 1.87 3.34 0.19 0.20 0.29 0.58 0.88 | 0.2 1.1 3.1 7.9 13.0 2.5 4.7 12.1 12.5 14.9 6.0 8.5 9.1 11.0 11.6 |
*With the tackiness agent of LLDPE functionalized products (LLDPE-g-MAH) as plastic-aluminum combined film
Under the condition that adds a small amount of initiator, sample 2-3-7, sample 2-3-8 are relatively, because compound initiating method products therefrom (sample 2-3-8) has higher grafting (block) rate and comparatively suitable melt flow rate (MFR) simultaneously than causing products therefrom (sample 2-3-7) by initiator merely, so the notched Izod impact strength of sample 2-3-8 obviously increases, and reaches 91.6kJ/m
2And sample 2-3-10 and sample 2-3-9 are relatively, though products therefrom has higher grafting (block) rate and comparatively suitable melt flow rate (MFR) under the high screw speed condition, its material modified notched Izod impact strength also further increases, but 2-8 compares with sample, obvious decline has but all appearred, this phenomenon explanation is for the toughening modifying of PA66, and best grafting (block) rate of its functionalized products (EPR-g-MAH) and best melt flow rate (MFR) should be respectively near 0.66% and 1.9 grams/10 minutes.
Table 2-3 functionalized products (EPR-g-MAH) performance influences PA66/EPR-g-MAH intermingling material mechanical property
| Sample | Initiator/% | Screw speed/rmin -1 | Temperature/℃ | Percentage of grafting/% | Melt flow rate (MFR)/g10min -1 | Shock strength/kJm 2 | Tensile strength/MPa |
| 2-3-1 2-3-2 2-3-3 2-3-4 2-3-5 2-3-6 2-3-7 2-3-8 2-3-9 2-3-10 | 0 0 0 0 0 0 0.05 0.05 0.1 0.1 | 80 800 80 800 80 800 200 800 200 800 | 230 230 270 270 310 310 210 210 210 210 | 0.19 0.42 0.27 0.47 0.39 0.58 0.54 0.66 0.65 0.90 | 0.68 4.13 1.05 7.13 2.28 8.55 0.18 1.94 0.10 1.77 | 12.8 64.1 33.0 68.8 71.3 46.3 69.7 91.6 61.3 72.7 | 37.4 41.4 40.4 43.7 42.1 37.2 44.4 44.3 43.5 43.4 |
*PA66/EPR-g-MAH＝80/20
Claims (10)
1, a kind of stress induced initiating method of polyolefin material melted extrusion functionalization, it is characterized in that accounting for the reaction-ure mixture weight percentage is 0.1%～5.0% vinyl monomer, be dissolved in that to account for the reaction-ure mixture weight percentage be in 0.5%～4% solvent, and be that 88%～99.3% polyolefine material mixes with accounting for the reaction-ure mixture weight percentage, place, after treating solvent evaporates, with accounting for the reaction-ure mixture weight percentage is that 0～2% lubricant adds high rotating speed in the lump, in the high-shear type co-rotating twin screw extruder, extrusion temperature is at 160～350 ℃, the driving screw rotating speed carries out grafting with melt extrusion or block reaction in 350～1200rpm scope, reaction product is through water-cooled, after pelletizing and the drying, obtain the functionalized polyolefin product.
2, stress induction method according to claim 1 is characterized in that polyolefine material is the blend of any one or 2 to 3 kinds in polyethylene, Ethylene-Propylene Block Copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-dienes terpolymer or the ethylene-vinyl acetate copolymer.
3, stress induction method according to claim 1 is characterized in that vinyl monomer is the mixture of any one or 2 to 3 kinds in toxilic acid, maleic anhydride, fumaric acid anhydride, ethyl maleate, the single ester of fumaric acid, glycidyl methacrylate, vinyl acetate, vinylbenzene, acrylonitrile, γ-(methacryloxy) propyl trimethoxy silicane or vinyl three (Beta-methyl oxyethyl group) silane.
4. stress induction method according to claim 1 is characterized in that solvent is at least a kind of in acetone, ethanol or the whiteruss.
5, stress induced initiating method according to claim 1 is characterized in that lubricant is at least a kind of in calcium stearate, Zinc Stearate or the hard esteramides.
6, stress induced initiating method according to claim 1, it is characterized in that the screwing element of twin screw extruder and kneading member make up with the pattern of preparation blend alloy type, filled plastics modified version or glass filament reinforced plastics type, to be used to adjust to the shear effect of material and to extrude flow rate.
7, stress induced initiating method according to claim 6, the array configuration that it is characterized in that the screwing element of twin screw extruder and kneading member makes up with the pattern of glass filament reinforced plastics type.
8, stress induced initiating method according to claim 1 is characterized in that extrusion temperature is 210～270 ℃, and the driving screw rotating speed is 600～1000rpm.
9, stress induced initiating method according to claim 1, it is characterized in that in the process of functionalization, add that to account for the reaction-ure mixture weight percentage be 0.01% to 2.0% peroxide initiator, and suppress or avoid crosslinking side reaction by the method that improves screw speed, obviously improve grafting (block) rate and the melt flow rate (MFR) of functionalized products.
10, stress induced initiating method according to claim 9 is characterized in that peroxide initiator is at least dicumyl peroxide or 2,5-dimethyl-2, a kind of in 5-two (tert-butyl peroxy base) hexane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103492480A (en) * | 2011-04-19 | 2014-01-01 | Lg化学株式会社 | Olefin-based ionomer resin composition |
| CN104558425A (en) * | 2015-01-04 | 2015-04-29 | 南通日之升高分子新材料科技有限公司 | Ultrasonic technology-induced grafted allyl elastomer polymer and preparation method thereof |
| CN111793315A (en) * | 2020-07-28 | 2020-10-20 | 泰州思睿新材料科技有限公司 | Polyolefin toughening modifier and preparation method thereof |
| CN115286752A (en) * | 2022-06-30 | 2022-11-04 | 合复新材料科技(无锡)有限公司 | Preparation method of polypropylene resin-EVA resin alloyed graft |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103492480A (en) * | 2011-04-19 | 2014-01-01 | Lg化学株式会社 | Olefin-based ionomer resin composition |
| CN103492480B (en) * | 2011-04-19 | 2015-04-22 | Lg化学株式会社 | Olefin-based ionomer resin composition |
| CN104558425A (en) * | 2015-01-04 | 2015-04-29 | 南通日之升高分子新材料科技有限公司 | Ultrasonic technology-induced grafted allyl elastomer polymer and preparation method thereof |
| CN104558425B (en) * | 2015-01-04 | 2018-07-27 | 南通日之升高分子新材料科技有限公司 | Propylene-based elastomeric polymer of ultrasonic technology initiation grafting and preparation method thereof |
| CN111793315A (en) * | 2020-07-28 | 2020-10-20 | 泰州思睿新材料科技有限公司 | Polyolefin toughening modifier and preparation method thereof |
| CN115286752A (en) * | 2022-06-30 | 2022-11-04 | 合复新材料科技(无锡)有限公司 | Preparation method of polypropylene resin-EVA resin alloyed graft |
| CN115286752B (en) * | 2022-06-30 | 2023-12-22 | 合复新材料科技(无锡)有限公司 | Preparation method of polypropylene resin-EVA resin alloying graft |
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