CN101125947A - High fused mass strength polypropylene containing long branched chain structure and preparing method thereof - Google Patents
High fused mass strength polypropylene containing long branched chain structure and preparing method thereof Download PDFInfo
- Publication number
- CN101125947A CN101125947A CNA2007100703702A CN200710070370A CN101125947A CN 101125947 A CN101125947 A CN 101125947A CN A2007100703702 A CNA2007100703702 A CN A2007100703702A CN 200710070370 A CN200710070370 A CN 200710070370A CN 101125947 A CN101125947 A CN 101125947A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- branched chain
- chain structure
- screw extruder
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 79
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 56
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000005303 weighing Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005453 pelletization Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- 239000000470 constituent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000011259 mixed solution 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
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000002253 acid Substances 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000005482 strain hardening Methods 0.000 abstract description 3
- 238000003856 thermoforming Methods 0.000 abstract description 3
- 239000004970 Chain extender Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 108010010803 Gelatin Proteins 0.000 abstract 1
- 238000007664 blowing Methods 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 229920000159 gelatin Polymers 0.000 abstract 1
- 239000008273 gelatin Substances 0.000 abstract 1
- 235000019322 gelatine Nutrition 0.000 abstract 1
- 235000011852 gelatine desserts Nutrition 0.000 abstract 1
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 238000005516 engineering process Methods 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
- 238000005187 foaming Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 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
- 241000024287 Areas Species 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 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
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000007787 solid Substances 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
- B29C48/25—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
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a high fused mass strength polypropylene contained long-chain branch and the preparation method thereof. The high fused mass strength polypropylene resin is prepared by polypropylene grafted object, amine or alcohols compound as well as antioxidant and heat stabilizer, etc. The invention adopts a melting and continuously extrusion method with a reaction-type double screw extruder to prepare the high fused mass strength polypropylene, and uses supercritical carbon dioxide to assist the extrusion, which can lower the extrusion temperature, reduce the degradation of polymer and meanwhile greatly strengthen the pervasion of molecule, so as to further promote the reaction. In the reaction process, as chain extender, amine and alcohols compound react with special functional group of polypropylene grafted object, link linearity polypropylene molecular chain, consequently produce novel polypropylene that each grafted point includes two long-chain branch structures and of which the melt flow rate is adjustable. The novel polypropylene is characterized by non-gelatin and strain hardening. The product shows great advantages over a plurality of aspects like color, mechanical property and workability, therefore, the product is suitable for application areas of blowing, thermo-forming, blown film, extrusion and coating, etc.
Description
Technical field
The present invention relates to a kind of high melt strength, propylene that contains long branched chain structure and preparation method thereof.
Background technology
Polypropylene (PP) industrial development is rapid, but the main at present high degree of isotacticity PP (iPP) that adopts Ziegler-Natta and metallocene catalyst catalytic production, generally can not produce the secondary activity center, have only the linear chain structure, cause its narrow molecular weight distribution, shortcoming such as melt strength is low and refractory hangs down poor performance.And PP does not have strain hardening effect under molten state, has therefore limited the range of application of PP greatly.In addition, PP still is a kind of partially crystalline polymer, and softening temperature and fusing point are very approaching, melt strength descends rapidly after surpassing fusing point, cause when adopting thermoforming container wall thickness inhomogeneous, edge curl, contraction occur during extrusion coated calendering, abscess problem such as subside during extrusion foaming.Generally believe that the melt strength that increases PP is its important factor in the quicker growth in plastics market, acquisition broader applications.
The preparation high melt strength, propylene, can be by improving polyacrylic relative molecular mass, increasing methods such as relative molecular weight distribution, long-chain branchization, concrete implementation method has 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 makes foam material.U.S. Pat 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 blend and has extruded the preparation high melt strength, propylene.But owing to only adopt the extremely difficult homodisperse 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 a 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 a large amount of inhomogeneous gels easily, therefore exist the problem of product performance stability.Chinese patent CN1986589A and CN1432596A disclose and have adopted the method for esters of acrylic acid fusion-grafting polypropylene with the raising melt strength, but traditional frit reaction is extruded owing to high temperature causes the serious product over-all properties that influences 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 problems such as the easy oxidative degradation of polypropylene in operation at high temperature.
Summary of the invention
The purpose of this invention is to provide a kind of melt flow rate (MFR) wide ranges, gel-free, preparation technology simply contains high melt strength, propylene of long branched chain structure and preparation method thereof.
The high melt strength, propylene that contains long branched chain structure of the present invention is characterized in that the melt flow rate (MFR) scope is 2-25g/10min, and is composed of the following components:
100 parts of A components
1～10 part of B component
0～0.5 part of antioxidant
0～0.5 part of light and thermally stable agent
Above-mentioned A component is the polar monomer fusion-grafting polyacrylic polymer of percentage of grafting 〉=0.3%, and the B component is amine or alcohol compound.
Among the present invention, the polar monomer fusion-grafting polyacrylic polymer of said percentage of grafting 〉=0.3% be in maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene and the glycidyl methacrylate graft polypropylene any or appoint several compounds or compound grafts.The too low meeting of the percentage of grafting of polypropylene grafted thing causes reactive behavior low, and the product degree of branching is little, does not reach the requirement of melt strength.Percentage of grafting is too high, is easy to generate a large amount of crosslinkedly, and screw torque is big, easily twists off, and percentage of grafting is preferably 0.5%～5%.
Among the present invention, said aminated compounds is thanomin, triethyl diamines, quadrol, the Ursol D, 1 of molecular weight in 50～10000 scopes, 4 butanediamine, 1, one or more compounds in the diamine of 6-hexanediamine, Amino Terminated polyether(ATPE) and the Amino Terminated polyether(ATPE) tertiary amine compound; Alcohol compound is that molecular weight is one or more compounds of polyoxyethylene glycol of 100～20000.
In the present invention, mainly utilize amino in amine, the alcohol compound or the specific functional groups on hydroxyl and the polypropylene grafted thing to react, thereby produce long branched chain structure, reach the final purpose that improves melt strength.The aminated compounds molecular weight is in 50～10000 scopes, the molecular weight of alcohol compound is in 100～20000 scopes, amine or alcohol compound molecular weight are too big, can cause amino or oh group proportion few, low with the reactive behavior of specific functional groups, long-chain branch is difficult to form, and the degree of branching does not reach requirement, and amine or alcohol compound molecular weight are preferably 100～10000.
Among the present invention, said antioxidant 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, the 6-tertiary butyl-4-methylphenol, 2, one or more compounds 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; The light and thermally stable agent can be adopted one or more compounds in two (2,2,6, the 6-tetramethyl-piperidyl) certain herbaceous plants with big flowers two acid esters, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole and the calcium stearate.
The preparation method who contains the high melt strength, propylene of long branched chain structure, its step is as follows:
1) take by weighing each component in proportion, it is 20%～80% dilute solution that the B component is diluted to mass concentration with ethanol, acetone or their mixed solution;
2) with A component and antioxidant and thermo-stabilizer in mixing kettle behind the thorough mixing, adding L/D with the speed of 60～200g/min from spout is 24: 1～48: 1 response type twin screw extruder, and the dilute solution that step 1) is made joins the forcing machine supercritical CO from a side line of twin screw extruder with the speed of 1～50g/min
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder with the speed of 0～40g/min
2The fluidic quality is 0～20% of an A constituent mass, and the control screw speed is: 100～300 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180～220 ℃, and other heating zone are 140～200 ℃; Extruding pelletization obtains high bath strength acrylic resin.
In the preparation process of the present invention, preferred supercritical CO
2The fluidic quality be the A constituent mass be 0.2～5%.
Supercritical CO
250 ℃～200 ℃ temperature, 8Mpa～30Mpa pressure prepares by overcritical device, and preferred temperature 80-180 ℃, pressure 8-10Mpa.
In the preparation process of the present invention, amine or alcohol compound are diluted with ethanol, acetone or their mixed solution, make part solid amine, the aspect operation of alcohol compound dissolving back on the one hand, be convenient to control the add-on tolerance range on the other hand.
Beneficial effect of the present invention is:
The present invention prepares high bath strength acrylic resin by the continuous extrusion molding of response type twin screw extruder fusion, uses supercritical CO
2Auxiliary extruding strengthened the diffusion of molecule greatly when having suppressed degradation of polypropylene effectively, further promote the generation of reaction.In the reaction process, amine, alcohol compound react as specific function group in chainextender and the polypropylene grafted thing, the linear polypropylene molecular chain is coupled together, thereby can generate the adjustable novel polypropylene of melt flow rate (MFR) that each grafting site contains two long branched chain structures, have gel-free and 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 foaming, thermoforming, film blowing and extrudes Application Areass such as 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.
Embodiment 1:
Taking by weighing 100 parts of percentage of grafting is 5% maleic anhydride inoculated polypropylene, 0.3 part of oxidation inhibitor four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 0.2 part three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.5 part of stablizer calcium stearate, after stirring thorough mixing, adding length-to-diameter ratio L/D is 48: 1 a twin screw extruder, and rate of feeding is 200g/min; Other takes by weighing 5 parts of quadrols, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of the 20g/min side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 20% of a maleic anhydride inoculated polypropylene quality, and adding speed is: 40g/min, and the control screw speed is: 100 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180 ℃, and other heating zone are 140 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Comparative Examples 1:
Taking by weighing 100 parts of percentage of grafting is 5% maleic anhydride inoculated polypropylene, 0.3 part of oxidation inhibitor four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 0.2 part three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.5 part of stablizer calcium stearate, after stirring thorough mixing, adding length-to-diameter ratio L/D is 48: 1 a twin screw extruder, and rate of feeding is 200g/min; Other takes by weighing 5 parts of quadrols, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of the 20g/min side line from forcing machine behind 50% the solution; Do not add supercritical CO
2Fluid, the control screw speed is: 300 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 220 ℃, and other heating zone are 200 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1
Table 1
| Sequence number | Tensile modulus (MPa) | Tensile strength (MPa) | Elongation at break (%) | Shock strength (kJ/m 2) | Tc (℃) | Melting index (g/10min) |
| Comparative Examples 1 | 1180 | 28.5 | 150 | 3.8 | 158 | 20 |
| Embodiment 1 | 1320 | 31.3 | 720 | 6.1 | 160 | 4 |
By table 1 as seen, in extrusion, add supercritical CO
2After, extrusion temperature descends significantly, and the product mechanical property all improves a lot, and melting index descends.Proved supercritical CO
2Suppress the generation of degraded effectively, and helped the diffusion of molecule, promoted the carrying out of graft reaction.
Embodiment 2:
Taking by weighing 100 parts of percentage of grafting is 0.5% methacrylic acid graft polypropylene, 0.5 part of oxidation inhibitor 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester and 0.5 part of stablizer calcium stearate, after stirring thorough mixing, adding length-to-diameter ratio L/D is 36: 1 a twin screw extruder, and rate of feeding is 200g/min; Other takes by weighing 1 part of thanomin, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of the 50g/min side line from forcing machine behind 20% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 0.2% of a methacrylic acid graft polypropylene quality, adding speed is: 0.2g/min, and the control screw speed is: 100 rev/mins, it is 8 heating zone that twin screw extruder is divided into, wherein: first heating zone is 200 ℃, and other heating zone are 180 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 2
Embodiment 3:
Taking by weighing 100 parts of percentage of grafting is 2% glycidyl methacrylate graft polypropylene, 0.3 part of four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester and 0.3 part of stablizer calcium stearate, after stirring thorough mixing, adding length-to-diameter ratio L/D is 24: 1 a twin screw extruder, and rate of feeding is 60g/min; Other takes by weighing 10 part of 1,4 butanediamine, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of the 1g/min side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 0.5% of a glycidyl methacrylate graft polypropylene quality, adding speed is: 0.5g/min, and the control screw speed is: 100 rev/mins, it is 8 heating zone that twin screw extruder is divided into, wherein: first heating zone is 180 ℃, and other heating zone are 160 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 2
Embodiment 4:
Take by weighing 100 parts of percentage of grafting and be 0.5% acrylic acid-grafted polypropylene, do not add oxidation inhibitor and stablizer, add length-to-diameter ratio L/D and be 36: 1 twin screw extruder, rate of feeding is 100g/min; Other takes by weighing 8 parts of Ursol D, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of the 10g/min side line from forcing machine behind 80% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 5% of an acrylic acid-grafted polypropylene quality, and adding speed is: 5g/min, and the control screw speed is: 200 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180 ℃, and other heating zone are 150 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 2
Embodiment 5:
Take by weighing 100 parts of percentage of grafting and be 2% maleic anhydride inoculated polypropylene, do not add oxidation inhibitor and stablizer, add length-to-diameter ratio L/D and be 48: 1 twin screw extruder, rate of feeding is 100g/min; Other takes by weighing 10 parts of Amino Terminated polyether(ATPE)s, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of the 20g/min side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 1% of a maleic anhydride inoculated polypropylene quality, and adding speed is: 1g/min, and the control screw speed is: 100 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180 ℃, and other heating zone are 150 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 6:
Take by weighing 100 parts of percentage of grafting and be 2% maleic anhydride inoculated polypropylene, do not add oxidation inhibitor and stablizer, add length-to-diameter ratio L/D and be 48: 1 twin screw extruder, 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 the 20g/min side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 1% of a polypropylene grafted amount, and adding speed is: 1g/min, and the control screw speed is: 100 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180 ℃, and other heating zone are 150 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 7:
Take by weighing 50 parts of percentage of grafting and be 5% maleic anhydride inoculated polypropylene, 50 parts of percentage of grafting and be 3% acrylic acid-grafted polypropylene, do not add oxidation inhibitor and stablizer, after stirring thorough mixing, adding length-to-diameter ratio L/D is 36: 1 a twin screw extruder, 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 the 20g/min side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 20% of a polypropylene grafted amount, and adding speed is: 20g/min, and the control screw speed is: 300 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180 ℃, and other heating zone are 140 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 8:
Take by weighing 50 parts of percentage of grafting and be 2% maleic anhydride inoculated polypropylene, 50 parts of percentage of grafting and be 2% methacrylic acid graft polypropylene, do not add oxidation inhibitor and stablizer, after stirring thorough mixing, adding length-to-diameter ratio L/D is 36: 1 a twin screw extruder, 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 the 20g/min side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder
2The fluidic quality is 10% of a polypropylene grafted amount, and adding speed is: 10g/min, and the control screw speed is: 300 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180 ℃, and other heating zone are 150 ℃; Extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
The testing tool that the performance test of above embodiment is adopted is as follows:
(1) tensile property: measure on the Zwick Z020 universal testing machine.Tensile strength is according to the GB1040-92 standard test, and rate of extension is 50mm/min;
(2) shock strength: measure on the CEAST impact tester, shock strength is according to the GB-1843 standard test;
(3) Tc: adopt Perkin Elmer DSC7 type differential scanning calorimeter to analyze;
(4) melting index: adopt CEAST to measure, measuring condition is 230 ℃, 2.16kg.
Table 2
| Sequence number | Tensile modulus (MPa) | Tensile strength (MPa) | Elongation at break (%) | Shock strength (kJ/m 2) | Tc (℃) | Melting index (g/10min) |
| Example 2 | 1230 | 31.0 | 730 | 6.5 | 161 | 2 |
| Example 3 | 1300 | 31.3 | 680 | 6.2 | 162 | 3 |
| Example 4 | 1330 | 31.9 | 320 | 6.2 | 161 | 2 |
| Example 5 | 1240 | 31.3 | 850 | 7.5 | 159 | 20 |
| Example 6 | 1330 | 35.6 | 900 | 7.6 | 158 | 25 |
| Example 7 | 1280 | 38.4 | 673 | 7.2 | 160 | 5 |
| Example 8 | 1320 | 34.1 | 688 | 7.4 | 161 | 4 |
Claims (7)
1. the high melt strength, propylene that contains long branched chain structure is characterized in that the melt flow rate (MFR) scope is 2-25g/10min, and is composed of the following components:
100 parts of A components
1～10 part of B component
0～0.5 part of antioxidant
0～0.5 part of light and thermally stable agent
Above-mentioned A component is the polar monomer fusion-grafting polyacrylic polymer of percentage of grafting 〉=0.3%, and the B component is amine or alcohol compound.
2. the high melt strength, propylene that contains long branched chain structure according to claim 1, the percentage of grafting that it is characterized in that said polar monomer fusion-grafting polyacrylic polymer is 0.5%～5%.
3. the high melt strength, propylene that contains long branched chain structure according to claim 1 and 2, it is characterized in that said polar monomer fusion-grafting polyacrylic polymer be in maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene and the glycidyl methacrylate graft polypropylene any or appoint several compounds or compound grafts.
4. the high melt strength, propylene that contains long branched chain structure according to claim 1, it is characterized in that said aminated compounds is thanomin, triethyl diamines, quadrol, the Ursol D, 1 of molecular weight in 50～10000 scopes, 4 butanediamine, 1, one or more compounds in the diamine of 6-hexanediamine, Amino Terminated polyether(ATPE) and the Amino Terminated polyether(ATPE) tertiary amine compound; Alcohol compound is that molecular weight is one or more compounds of polyoxyethylene glycol of 100～20000.
5. the high melt strength, propylene that contains long branched chain structure according to claim 1, it is characterized in that said 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, the 6-tertiary butyl-4-methylphenol, 2, one or more compounds 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.
6. the high melt strength, propylene that contains long branched chain structure according to claim 1, it is characterized in that said light and thermally stable agent is two (2,2,6,6-tetramethyl-piperidyl) one or more compounds in certain herbaceous plants with big flowers two acid esters, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole and the calcium stearate.
7. the preparation method who contains the high melt strength, propylene of long branched chain structure according to claim 1, its step is as follows:
1) take by weighing each component in proportion, it is 20%～80% dilute solution that the B component is diluted to mass concentration with ethanol, acetone or their mixed solution;
2) with A component and antioxidant and thermo-stabilizer in mixing kettle behind the thorough mixing, adding L/D with the speed of 60～200g/min from spout is 24: 1～48: 1 response type twin screw extruder, and the dilute solution that step 1) is made joins the forcing machine supercritical CO from a side line of twin screw extruder with the speed of 1～50g/min
2Fluid joins forcing machine, supercritical CO from another side line of twin screw extruder with the speed of 0～40g/min
2The fluidic quality is 0～20% of an A constituent mass, and the control screw speed is: 100～300 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180～220 ℃, and other heating zone are 140～200 ℃; Extruding pelletization obtains high bath strength acrylic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100703702A CN101125947A (en) | 2007-08-01 | 2007-08-01 | High fused mass strength polypropylene containing long branched chain structure and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100703702A CN101125947A (en) | 2007-08-01 | 2007-08-01 | High fused mass strength polypropylene containing long branched chain structure and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101125947A true CN101125947A (en) | 2008-02-20 |
Family
ID=39094092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100703702A Pending CN101125947A (en) | 2007-08-01 | 2007-08-01 | High fused mass strength polypropylene containing long branched chain structure and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101125947A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011005856A1 (en) * | 2009-07-08 | 2011-01-13 | Dow Global Technologies Inc. | Imide-coupled propylene-based polymer and process |
| CN102127281A (en) * | 2010-12-31 | 2011-07-20 | 浙江大学 | Method for extruding and preparing high melt strength polypropylene with long branched chain structure through supercritical reaction |
| CN101376683B (en) * | 2008-10-07 | 2011-09-21 | 中国科学院长春应用化学研究所 | Preparation of high melt strength polypropylene |
| CN104788932A (en) * | 2015-04-28 | 2015-07-22 | 上海锦湖日丽塑料有限公司 | Antistatic PC/ASA alloy material with excellent thermal stability and preparation method thereof |
| CN108285511A (en) * | 2017-01-10 | 2018-07-17 | 神华集团有限责任公司 | Melt strength modifying agent and its preparation method and application and polypropene composition and polypropylene material and preparation method thereof |
| CN110483829A (en) * | 2019-08-22 | 2019-11-22 | 中国科学院青岛生物能源与过程研究所 | A kind of low irradiation intensity prepares the preparation method of high-strength polypropylene expanded bead (EPP) |
| CN110791024A (en) * | 2019-12-05 | 2020-02-14 | 万华化学（宁波）有限公司 | Modified polypropylene reinforced material for foaming and preparation method and application thereof |
| CN112080100A (en) * | 2019-06-12 | 2020-12-15 | 中国科学院化学研究所 | High melt strength polypropylene and preparation method and application thereof |
| CN112759768A (en) * | 2019-10-21 | 2021-05-07 | 国家能源投资集团有限责任公司 | Polypropylene modifier and preparation method thereof, polypropylene composition, polypropylene material and preparation method thereof |
| CN113429521A (en) * | 2021-07-20 | 2021-09-24 | 汕头市三马塑胶制品有限公司 | High-melt-strength polypropylene and preparation method thereof |
| CN113956600A (en) * | 2021-11-17 | 2022-01-21 | 中核同辐（长春）辐射技术有限公司 | Pre-irradiation graft modified PP melt-blown material and preparation process thereof |
| CN114456509A (en) * | 2021-11-15 | 2022-05-10 | 廊坊北化高分子材料有限公司 | Modified polyolefin for low-melting-point carbon black master batch and preparation method thereof |
| CN115651204A (en) * | 2022-12-27 | 2023-01-31 | 广州鹿山新材料股份有限公司 | N-carbonyl-bisamide-polyolefin compound, and preparation method and application thereof |
-
2007
- 2007-08-01 CN CNA2007100703702A patent/CN101125947A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376683B (en) * | 2008-10-07 | 2011-09-21 | 中国科学院长春应用化学研究所 | Preparation of high melt strength polypropylene |
| WO2011005856A1 (en) * | 2009-07-08 | 2011-01-13 | Dow Global Technologies Inc. | Imide-coupled propylene-based polymer and process |
| CN102127281A (en) * | 2010-12-31 | 2011-07-20 | 浙江大学 | Method for extruding and preparing high melt strength polypropylene with long branched chain structure through supercritical reaction |
| CN104788932A (en) * | 2015-04-28 | 2015-07-22 | 上海锦湖日丽塑料有限公司 | Antistatic PC/ASA alloy material with excellent thermal stability and preparation method thereof |
| CN108285511B (en) * | 2017-01-10 | 2020-07-28 | 神华集团有限责任公司 | Polymer melt strength modifier, preparation method and application thereof, polypropylene composition, polypropylene material and preparation method thereof |
| CN108285511A (en) * | 2017-01-10 | 2018-07-17 | 神华集团有限责任公司 | Melt strength modifying agent and its preparation method and application and polypropene composition and polypropylene material and preparation method thereof |
| CN112080100A (en) * | 2019-06-12 | 2020-12-15 | 中国科学院化学研究所 | High melt strength polypropylene and preparation method and application thereof |
| CN112080100B (en) * | 2019-06-12 | 2022-03-29 | 中国科学院化学研究所 | High melt strength polypropylene and preparation method and application thereof |
| CN110483829A (en) * | 2019-08-22 | 2019-11-22 | 中国科学院青岛生物能源与过程研究所 | A kind of low irradiation intensity prepares the preparation method of high-strength polypropylene expanded bead (EPP) |
| CN112759768A (en) * | 2019-10-21 | 2021-05-07 | 国家能源投资集团有限责任公司 | Polypropylene modifier and preparation method thereof, polypropylene composition, polypropylene material and preparation method thereof |
| CN112759768B (en) * | 2019-10-21 | 2022-01-28 | 国家能源投资集团有限责任公司 | Polypropylene modifier and preparation method thereof, polypropylene composition, polypropylene material and preparation method thereof |
| DE112020005088T5 (en) | 2019-10-21 | 2022-07-28 | China Energy Investment Corporation Limited | POLYPROPYLENE MODIFIER AND ITS PREPARATION METHOD, POLYPROPYLENE COMPOSITION AND POLYPROPYLENE MATERIAL PREPARATION METHOD |
| CN110791024A (en) * | 2019-12-05 | 2020-02-14 | 万华化学（宁波）有限公司 | Modified polypropylene reinforced material for foaming and preparation method and application thereof |
| CN113429521A (en) * | 2021-07-20 | 2021-09-24 | 汕头市三马塑胶制品有限公司 | High-melt-strength polypropylene and preparation method thereof |
| CN114456509A (en) * | 2021-11-15 | 2022-05-10 | 廊坊北化高分子材料有限公司 | Modified polyolefin for low-melting-point carbon black master batch and preparation method thereof |
| CN114456509B (en) * | 2021-11-15 | 2023-12-05 | 廊坊北化高分子材料有限公司 | Modified polyolefin for low-melting-point carbon black master batch and preparation method thereof |
| CN113956600A (en) * | 2021-11-17 | 2022-01-21 | 中核同辐（长春）辐射技术有限公司 | Pre-irradiation graft modified PP melt-blown material and preparation process thereof |
| CN115651204A (en) * | 2022-12-27 | 2023-01-31 | 广州鹿山新材料股份有限公司 | N-carbonyl-bisamide-polyolefin compound, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101125947A (en) | High fused mass strength polypropylene containing long branched chain structure and preparing method thereof | |
| CN102030960B (en) | Preparation method of high-melt-strength polyolefine comprising hybrid long branch-chain structure | |
| CN102417561B (en) | Ultrahigh-mobility propenyl elastomer grafting copolymer and preparation method thereof | |
| CN109306109A (en) | A kind of thermoplasticity cross-linking polyethylene materials, preparation method and applications | |
| CN102391432B (en) | High-fluidity ethylene-alpha-octene graft copolymer and preparation method thereof | |
| CN101747600A (en) | Method for preparing polyethylene terephthalate (PET) blend | |
| CN112708207B (en) | Polypropylene composite material without tiger stripes and preparation method thereof | |
| CN108440716A (en) | Preparation method based on draft flowing deformation technology maleic anhydride stem grafting polyolefin compatilizer | |
| CN102079841A (en) | High-flowability impact-resistant polypropylene composite and preparation method thereof | |
| CN111423689B (en) | Modified polypropylene material and preparation method and application thereof | |
| CN102127281A (en) | Method for extruding and preparing high melt strength polypropylene with long branched chain structure through supercritical reaction | |
| CN100497454C (en) | High Melt strength polypropylene resin and its preparing method | |
| CN111154237A (en) | Polyethylene terephthalate/high-density polyethylene blend and preparation method thereof | |
| CN110724332B (en) | Polyethylene composition with excellent comprehensive performance for double-wall corrugated pipe and preparation method thereof | |
| CN103374171A (en) | metallocene polyethylene resin composition with high melt strength and preparation method thereof | |
| JPS63182349A (en) | Production of ultrahigh molecular weight polyolefin composition | |
| CN109627539B (en) | Polyethylene composition having excellent crack resistance and method for preparing the same | |
| WO2024037000A1 (en) | Styrene-polyolefin functional polymer and preparation method therefor | |
| CN108503934A (en) | A kind of drip irrigation pipe/belt polyethylene composition | |
| CN100448902C (en) | Acrylic resin with high bath strength, and preparation method | |
| CN107365405A (en) | A kind of preparation method of the compound graft products of PP/EVA | |
| CN101117372A (en) | High fondant-strength profax and preparation method thereof | |
| CN112063031A (en) | HDPE steel strip spiral pipe and preparation method thereof | |
| CN103788447B (en) | A kind of preparation method of long-branched high density polyethylene (HDPE) | |
| CN1986589B (en) | Polypropylene resin with high melt strength and its preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080220 |