CN102030960B - Preparation method of high-melt-strength polyolefine comprising hybrid long branch-chain structure - Google Patents
Preparation method of high-melt-strength polyolefine comprising hybrid long branch-chain structure Download PDFInfo
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 polypropylene Polymers 0.000 claims abstract description 82
- 239000004743 Polypropylene Substances 0.000 claims abstract description 54
- 229920001155 polypropylene Polymers 0.000 claims abstract description 54
- 239000004698 Polyethylene Substances 0.000 claims abstract description 11
- 229920000573 polyethylene Polymers 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- 150000002576 ketones Chemical class 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims description 44
- 238000001125 extrusion Methods 0.000 claims description 40
- 238000005303 weighing Methods 0.000 claims description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 28
- 229920001903 high density polyethylene Polymers 0.000 claims description 27
- 239000004700 high-density polyethylene Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 13
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 11
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- XHLCCKLLXUAKCM-UHFFFAOYSA-N octadecyl 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XHLCCKLLXUAKCM-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 8
- 150000001412 amines Chemical class 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 238000005187 foaming Methods 0.000 abstract description 3
- 238000010096 film blowing Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 229920005672 polyolefin resin Polymers 0.000 description 15
- 238000005453 pelletization Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229920001684 low density polyethylene Polymers 0.000 description 10
- 239000004702 low-density polyethylene Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of high-melt-strength polyolefine comprising a hybrid long branch-chain structure, comprising the following steps of: (1) weighting 100 parts by weight of polar monomer grafted polypropylene (a component A) with a grafting rate which is greater than or equal to 0.3 percent by weight, 5-30 parts by weight of polar monomer grafted polyethylene (a component B) with a grafting rate which is greater than or equal to 0.3 percent by weight, 1-10 parts by weight of amine or alcohol compound, 0-0.5 part by weight of antioxidant and 0-0.5 part by weight of light and heat stabilizing agent; (2) diluting the amine or alcohol compound into 20-80 percent by weight of solution by alcohol and/or ketone; (3) adding the component A, the component B, the antioxidant and the heat stabilizing agent into an extruder through a feeding hole, respectively adding the solution obtained in the step (2) and supercritical carbon dioxide from a first side line and a second side line, and melting and extruding to prepare the high-melt-strength polyolefine comprising the hybrid long branch-chain structure. The high-melt-strength polyolefine comprising the hybrid long branch-chain structure has good color, good mechanical property and good processing property and is suitable for the application fields of foaming, hot forming, film blowing and moulding, extruding, coating, and the like.
Description
Technical field
The present invention relates to a kind of high melt strength polyolefin that contains the hydridization long branched chain structure and preparation method thereof, relate in particular to supercritical reaction and extrude the method that preparation contains the high melt strength polyolefin of hydridization long branched chain structure, belong to technical field of polymer materials.
Background technology
Polypropylene (PP) industrial development is rapid, but mainly adopt at present the high isotactic PP (iPP) of Ziegler-Natta and metallocene catalyst catalytic production, generally can not produce the secondary activity center, only have the linear chain structure, cause its narrow molecular weight distribution, the shortcoming such as melt strength is low and Sag Resistance is poor.And PP does not have strain hardening effect under molten state, has therefore greatly limited the range of application of PP.In addition, PP or a kind of partially crystalline polymer, softening temperature and fusing point are very approaching, melt strength descends rapidly after surpassing fusing point, cause when adopting thermoforming container wall thickness inhomogeneous, occur edge curl, contraction during extrusion coated calendering, the abscess problem such as subside during extrusion foaming.Generally believe the melt strength that increases PP be its in plastics market more rapid growth, obtain the important factor of broader applications.
The preparation high melt strength, propylene, can be by improving polyacrylic relative molecular mass, increasing the methods such as relative molecular weight distribution, long-branched, concrete implementation method has the methods such as x ray irradiation x, blending and modifying, chemically crosslinked, solution graft copolymerization, fusion-grafting and in-situ polymerization.
Japanese Patent JP5531807 discloses a kind of PP, HDPE, LDPE and EPR blend, has improved melt strength, and the producing foamed material.US Patent No. 4365004 improves melt strength by the LDPE blend of CPP and high fondant-strength.Chinese patent CN1775851A discloses polypropylene, graft polypropylene, polyethylene and aminated compounds blending extrusion and has prepared high melt strength, propylene.But owing to only adopt the extremely difficult Uniform Dispersion that reaches molecular level of the method for simple blend, the product mechanical property is undesirable.
The patent CN86100791 of Himont company adopts electronic cathode x ray irradiation x straight chain PP, make it to produce long chain branching, produce the HMSPP of higher weight average molecular mass and higher branch degree, but because PP is semi-crystalline polymer, unformed part has produced grafting, and crystal region is then difficult, although can take some measures as reducing degree of crystallinity etc., but form easily a large amount of inhomogeneous gels, therefore exist the problem of product performance stability.Chinese patent CN1986589A and CN1432596A disclose and have adopted esters of acrylic acid fusion-grafting polypropylene with the method for raising melt strength, but traditional frit reaction is extruded owing to high temperature causes the serious product over-all properties that affects of polypropylene backbone degraded.
And solution graft copolymerization is not only wasted resource owing to need a large amount of solvents in the process of producing, and the more important thing is that solvent produces harm to surrounding environment and individual.Fusion-grafting is then because there are the problems such as the easy oxidative degradation of polypropylene at high temperature operation.
Summary of the invention
The purpose of this invention is to provide high melt strength polyolefin that contains the hydridization long branched chain structure of a kind of melt flow rate (MFR) wide ranges, gel-free and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: this preparation method who contains the high melt strength polyolefin of hydridization long branched chain structure comprises the steps:
(1) take by weighing each raw material by following prescription:
Described A component is the polar monomer graft polypropylene of percentage of grafting 〉=0.3% (weight), and the B component is the polar monomer fusion-grafting polyethylene of percentage of grafting 〉=0.3%, described polar monomer be in acid anhydrides, acid, the ester any or appoint several combinations; The C component is amine or alcohol compound;
(2) the C component being diluted to mass percent concentration with alcohol and/or ketone is 20%～80% solution;
(3) solution that step (2) is obtained from the first side line to join the screw extrusion press, supercritical fluid CO 2 adds the screw extrusion press from the second side line, and A component and B component and antioxidant and thermo-stabilizer added the screw extrusion press from spout, melt extrude the high melt strength polyolefin that obtains containing the hydridization long branched chain structure; Described supercritical CO
2The mass rate of fluid is 0.1～20% of A component and B constituent mass flow total amount; Screw speed is 100～300 rev/mins, and extrusion temperature is 140～220 ℃.
Further, the percentage of grafting of A component of the present invention is 0.5%～5%.
Further, A component of the present invention be in maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene, the glycidyl methacrylate graft polypropylene any or appoint several mixtures.
Further, B component of the present invention be in maleic anhydride grafted polyethylene, acrylic acid-grafted polyethylene, methacrylic acid grafted polyethylene and the glycidyl methacrylate graft polyethylene any or appoint several compounds or compound grafts.
Further, the component of B described in the present invention be in polar monomer graft high density polyethylene(HDPE), polar monomer graft linear low density polyethylene, the polar monomer graft Low Density Polyethylene any or appoint several mixtures.
Further, the percentage of grafting of B component of the present invention is 0.5%～5% (weight).
Among the present invention, described aminated compounds is thanomin, triethyl diamines, quadrol, Ursol D, Putriscine, 1, any in the diamine of 6-hexanediamine, Amino Terminated polyether(ATPE) and the Amino Terminated polyether(ATPE) tertiary amine compound or several mixture; Alcohol compound be ethylene glycol, polyoxyethylene glycol any or appoint several mixtures.
In the present invention, mainly utilize the specific functional groups on amino in amine, the alcohol compound or hydroxyl and Graft Polypropylene, the polycthylene grafted thing to react, thereby produce long branched chain structure, reach the final purpose that improves melt strength.
Antioxidant described in the present invention can adopt 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 2,6-tert-butyl-4-methyl-Phenol, 2, in amino p-cresol, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of the 6-tertiary butyl-alpha, alpha-dimethyl and the Tyox B any or several mixture.
Light and thermally stable agent described in the present invention is two (2,2,6,6-tetramethyl-piperidyl) any in SA ester, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole and the calcium stearate or several mixture.
Compared with prior art, beneficial effect of the present invention is:
The present invention prepares hydridization high melt strength polyolefin resin by the continuous extrusion molding of response type twin screw extruder melting, and uses supercritical CO
2Auxiliary extruding strengthened the diffusion of molecule greatly when effectively having suppressed degradation of polypropylene, further promote the generation of reaction.In the reaction process, amine, alcohol compound (C component) react as specific function group in chainextender and the Graft Polyolefin, linear polypropylene molecule, sub polyethylene subchain are coupled together, thereby can generate the adjustable novel hybride polyolefine of melt flow rate (MFR) that each grafting site contains two long branched chain structures, have gel-free, Thermo-sensitive is good and the strain hardening characteristic.This product has all embodied its superiority in all many-sides such as color and luster, mechanical property and processing characteristicies, and preparation technology is simple, and product is transparent, is applicable to the Application Areass such as foaming, thermoforming, film blowing and Extrusion Coating.
Embodiment
Further specify the present invention below in conjunction with embodiment.Following example only is in order to illustrate, rather than limitation of the present invention.
Comparative Examples 1:
Taking by weighing maleic anhydride inoculated polypropylene, the 20kg percentage of grafting that the 100kg percentage of grafting is 0.3% (weight) is maleic anhydride graft Low Density Polyethylene, 0.3kg oxidation inhibitor four (the 4-hydroxyl-3 of 0.3% (weight), 5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 0.2kg three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.5kg stablizer calcium stearate, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 48: 1 twin screw extruder adds, and rate of feeding is 200g/min; Other takes by weighing the 5kg quadrol, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Do not add supercritical CO
2Fluid, the control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 220 ℃, and the extrusion temperature of other heating zone is 200 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 1:
Taking by weighing maleic anhydride inoculated polypropylene, the 20kg percentage of grafting that the 100kg percentage of grafting is 0.3% (weight) is maleic anhydride graft Low Density Polyethylene, 0.3kg oxidation inhibitor four (the 4-hydroxyl-3 of 0.3% (weight), 5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 0.2kg three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.5kg stablizer calcium stearate, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 48: 1 twin screw extruder adds, and rate of feeding is 200g/min; Other takes by weighing the 5kg quadrol, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 4g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride inoculated polypropylene and maleic anhydride graft Low Density Polyethylene the mass rate total amount 2%.The control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 160 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 2:
The methacrylic acid graft polypropylene, the 5kg percentage of grafting that take by weighing the 100kg percentage of grafting and be 0.5% (weight) are methacrylic acid grafted high density polyethylene, the 0.5kg oxidation inhibitor 3 of 0.5% (weight), 5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester and 0.5kg stablizer two (2,2,6, the 6-tetramethyl-piperidyl) SA ester, after stirring abundant mixing, be the spout adding of 36: 1 twin screw extruder from length-to-diameter ratio L/D, rate of feeding is 60g/min; Other takes by weighing the 10kg thanomin, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 7.5g/min the first side line from forcing machine behind 80% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 12g/min, at this moment supercritical CO
2The mass rate of fluid be about methacrylic acid graft polypropylene and methacrylic acid grafted high density polyethylene the mass rate total amount 20%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 140 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 3:
Taking by weighing acrylic acid-grafted polypropylene, the 30kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) is acrylic acid-grafted Low Density Polyethylene, the 0.3kg 2 of 0.5% (weight), 6-tert-butyl-4-methyl-Phenol and 0.3kg stablizer 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 24: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing 1kg triethyl diamines, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 0.5g/min, at this moment supercritical CO
2The mass rate of fluid be about acrylic acid-grafted polypropylene and acrylic acid-grafted Low Density Polyethylene the mass rate total amount 0.5%.The control screw speed is: 100 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 160 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 4:
The glycidyl methacrylate graft polypropylene and the 20kg percentage of grafting that take by weighing the 100kg percentage of grafting and be 0.5% (weight) are the glycidyl methacrylate graft Low Density Polyethylene of 0.5% (weight), 0.3kg2, the amino p-cresol of the 6-tertiary butyl-alpha, alpha-dimethyl and 0.3kg stablizer two (2,2,6, the 6-tetramethyl-piperidyl) SA is the spout adding of 36: 1 twin screw extruder from length-to-diameter ratio L/D, and rate of feeding is 100g/min; Other takes by weighing the 8kg Ursol D, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 10g/min the first side line from forcing machine behind 80% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 5g/min, at this moment supercritical CO
2The mass rate of fluid be about vest base glycidyl acrylate graft polypropylene and glycidyl methacrylate graft Low Density Polyethylene the mass rate total amount 5%.The control screw speed is 200 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 5:
Taking by weighing maleic anhydride inoculated polypropylene and the 20kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) is the maleic anhydride grafted linear low density polyethylene of 0.5% (weight), do not add oxidation inhibitor and stablizer, the spout that from length-to-diameter ratio L/D is 48: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing the 10kg Putriscine, and being diluted to mass concentration with ethanol (50%) and acetone (50%) mixing solutions is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 1g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride inoculated polypropylene and maleic anhydride grafted linear low density polyethylene the mass rate total amount 1%.The control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein the first heating zone is 180 ℃, and other heating zone are 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 6:
Taking by weighing maleic anhydride inoculated polypropylene and the 20kg percentage of grafting that the 100kg percentage of grafting is 0.5% (weight) is the acrylic acid-grafted linear low density polyethylene of 0.5% (weight), 0.2kg 2, the amino p-cresol of the 6-tertiary butyl-alpha, alpha-dimethyl and 0.2kg 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester and stablizer 0.1kg two (2,2,6, the 6-tetramethyl-piperidyl) SA and 0.2kg 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, the spout that from length-to-diameter ratio L/D is 36: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing the diamine of 8kg Amino Terminated polyether(ATPE), and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 10g/min the first side line from forcing machine behind 80% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 5g/min, at this moment supercritical CO
2The mass rate of fluid be about the acrylic acid-grafted linear low density polyethylene of maleic anhydride inoculated polypropylene the mass rate total amount 5%.The control screw speed is 200 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the first heating zone is 180 ℃ extrusion temperature, and other heating zone are 150 ℃ extrusion temperature; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 7:
Taking by weighing maleic anhydride inoculated polypropylene and the 20kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) is the methacrylic acid grafted linear low-density polyethylene of 0.5% (weight), do not add oxidation inhibitor and stablizer, the spout that from length-to-diameter ratio L/D is 48: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing 10kg Amino Terminated polyether(ATPE) tertiary amine, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 1g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride inoculated polypropylene and methacrylic acid grafted linear low-density polyethylene the mass rate total amount 1%.The control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 8:
Take by weighing the maleic anhydride inoculated polypropylene that the 80kg percentage of grafting is 5% (weight), acrylic acid-grafted polypropylene, the 20kg percentage of grafting that the 20kg percentage of grafting is 3% (weight) is the glycidyl methacrylate grafted linear low-density polyethylene of 0.5% (weight), do not add oxidation inhibitor and stablizer, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 36: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing 10 parts of ethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 20g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, glycidyl methacrylate grafted linear low-density polyethylene the mass rate total amount 20%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 140 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 9:
Taking by weighing maleic anhydride inoculated polypropylene, the 20kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) is the maleic anhydride graft high density polyethylene(HDPE) of 0.5% (weight), do not add oxidation inhibitor and stablizer, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 36: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 10g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride inoculated polypropylene, maleic anhydride graft high density polyethylene(HDPE) the mass rate total amount 10%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 10:
Taking by weighing maleic anhydride inoculated polypropylene, the 20kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) is the acrylic acid-grafted high density polyethylene(HDPE) of 0.5% (weight), do not add oxidation inhibitor and stablizer, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 36: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 0.2g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride inoculated polypropylene, acrylic acid-grafted high density polyethylene(HDPE) the mass rate total amount 0.2%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 160 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.
Embodiment 11:
Taking by weighing maleic anhydride inoculated polypropylene, the 20kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) is the methacrylic acid grafted high density polyethylene of 0.5% (weight), do not add oxidation inhibitor and stablizer, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 36: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 0.1g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride inoculated polypropylene, methacrylic acid grafted high density polyethylene the mass rate total amount 0.1%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 170 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 12:
Taking by weighing maleic anhydride inoculated polypropylene, the 20kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) is the glycidyl methacrylate graft high density polyethylene(HDPE) of 0.5% (weight), do not add oxidation inhibitor and stablizer, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 36: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 10g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride grafted polypropylene, glycidyl methacrylate graft high density polyethylene(HDPE) the mass rate total amount 10%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 13:
The glycidyl methacrylate graft high density polyethylene(HDPE), the 10kg percentage of grafting that take by weighing maleic anhydride inoculated polypropylene, 10kg percentage of grafting that the 100kg percentage of grafting is 2% (weight) and be 0.5% (weight) are the methacrylic acid grafted high density polyethylene of 0.5% (weight), do not add oxidation inhibitor and stablizer, after stirring abundant mixing, the spout that from length-to-diameter ratio L/D is 36: 1 twin screw extruder adds, and rate of feeding is 100g/min; Other takes by weighing 10 parts of polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min the first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from the second side line of twin screw extruder
2The rate of feeding of fluid is 10g/min, at this moment supercritical CO
2The mass rate of fluid be about maleic anhydride grafted polypropylene, glycidyl methacrylate graft high density polyethylene(HDPE), methacrylic acid grafted high density polyethylene the mass rate total amount 10%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of the first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, the tests such as melt flow rate (MFR) the results are shown in Table 1.
Table 1
By as seen from Table 1, compare with Comparative Examples 1, embodiment 1-13 adds supercritical CO in extrusion
2After, extrusion temperature significantly descends, and the product mechanical property all improves a lot, and melting index descends.Proof the present invention uses supercritical CO
2Effectively suppress the generation of degraded, and be conducive to the diffusion of molecule, promoted the carrying out of graft reaction.Adopt present technique invention scheme, according to reaction mechanism, it is large to make the melting index scope by the variation component ratio, and regulatable hydridization long-chain branch polyolefine.Above-mentioned each scheme products obtained therefrom is carried out gel content determining, and gel content is zero.
Claims (6)
1. a preparation method who contains the high melt strength polyolefin of hydridization long branched chain structure is characterized in that comprising the steps:
1) take by weighing each raw material by following prescription:
A component 100 weight parts
B component 5 ~ 30 weight parts
C component 1 ~ 10 weight part
Antioxidant 0～0.5 weight part
Light and thermally stable agent 0～0.5 weight part
By weight percentage, any in the described A component maleic anhydride inoculated polypropylene that is percentage of grafting 〉=0.3%, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene, the glycidyl methacrylate graft polypropylene or appoint several mixtures; By weight percentage, the B component be in the maleic anhydride grafted polyethylene of percentage of grafting 〉=0.3%, acrylic acid-grafted polyethylene, methacrylic acid grafted polyethylene, the glycidyl methacrylate graft polyethylene any or appoint several mixtures; Described C component or thanomin, triethyl diamines, quadrol, Ursol D, 1,4-butanediamine, 1, in the diamine of 6-hexanediamine, Amino Terminated polyether(ATPE), the Amino Terminated polyether(ATPE) tertiary amine compound any or appoint several mixtures, or in the ethylene glycol, polyoxyethylene glycol any or appoint several mixtures;
(2) the C component being diluted to mass percent concentration with alcohol and/or ketone is 20%～80% solution;
(3) solution that step (2) is obtained from the first side line to join the screw extrusion press supercritical CO
2Fluid from the second side line adds screw extrusion press, and with A component and B component and antioxidant and thermo-stabilizer from spout adding screw extrusion press, melt extrude the high melt strength polyolefin that obtains containing the hydridization long branched chain structure; Described supercritical CO
2The mass rate of fluid be A component and B component the mass rate summation 0.1 ~ 20%; Screw speed is 100 ~ 300 rev/mins, and extrusion temperature is 140 ~ 220 ℃.
2. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, it is characterized in that: by weight percentage, the percentage of grafting of described A component is 0.5%～5%.
3. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, it is characterized in that: in described B component, described polyethylene is high density polyethylene(HDPE), linear low density polyethylene or Low Density Polyethylene.
4. according to claim 1 or the 3 described preparation methods that contain the high melt strength polyolefin of long branched chain structure, it is characterized in that: by weight percentage, the percentage of grafting of described B component is 0.5%～5%.
5. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, it is characterized in that: described antioxidant is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 2,6-tert-butyl-4-methyl-Phenol, 2, in amino p-cresol, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of the 6-tertiary butyl-alpha, alpha-dimethyl, the Tyox B any or several mixture.
6. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, it is characterized in that: described light and thermally stable agent is two (2,2,6,6-tetramethyl-piperidyl) SA ester, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-in the 5-chlorinated benzotriazole, calcium stearate any or appoint several mixtures.
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