CN102040696A - Method for producing high-performance polypropylene pipe material - Google Patents
Method for producing high-performance polypropylene pipe material Download PDFInfo
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- CN102040696A CN102040696A CN2009102361060A CN200910236106A CN102040696A CN 102040696 A CN102040696 A CN 102040696A CN 2009102361060 A CN2009102361060 A CN 2009102361060A CN 200910236106 A CN200910236106 A CN 200910236106A CN 102040696 A CN102040696 A CN 102040696A
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 19
- -1 polypropylene Polymers 0.000 title claims abstract description 19
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 230000000536 complexating effect Effects 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000003384 small molecules Chemical group 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002899 organoaluminium compounds Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 1
- NTHKCSDJQGWPJY-UHFFFAOYSA-N CCCC[SiH](OC)OC Chemical group CCCC[SiH](OC)OC NTHKCSDJQGWPJY-UHFFFAOYSA-N 0.000 description 1
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 description 1
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- ZJJUBGNGLAAGQS-UHFFFAOYSA-N cyclopentyl(dimethoxy)silane Chemical class CO[SiH](OC)C1CCCC1 ZJJUBGNGLAAGQS-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- XZFXULUXIPPWEW-UHFFFAOYSA-N dimethoxy-methyl-propan-2-ylsilane Chemical compound CO[Si](C)(OC)C(C)C XZFXULUXIPPWEW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a method for producing a high-performance polypropylene pipe material. In the method, an ordinary commercial Z-N polymerization catalyst and direct polymerization are adopted, and a wide molecular weight distribution polypropylene composition characterized in that the isotacticity degree of a macromolecule part of the polypropylene is lower and the isotacticity degree of a micromolecule part of the polypropylene is extremely high is obtained through regulating the polymerization steric regularity and the hydrogen regulation sensibility of the catalyst in different reactors so as to realize the comprehensive improvement of the rigidity and the toughness of the material. The material does not need post processing modification, and any copolymerization monomer is not needed in a copolymerization process.
Description
Technical field
The present invention relates to a kind of preparation method of high-performance polypropylene tube material, belong to field of olefin polymerisation.
Technical background
The polypropylene tube material mainly is divided into homo-polypropylene (PP-H), block copolymerization polypropylene (PP-B) and atactic copolymerized polypropene (PP-R).The difference of these three kinds of material structures makes them have different application characteristics, therefore also has different purposes.Wherein PPH is mainly used in the hot industry blow-off pipe because of having chemical resistance and higher heat-drawn wire preferably.Generally speaking, PPH pipe rigidity is better, but impact property is relatively poor.Further improving its impact resistance is the highest priority of technical research.
When prior art is produced the PPH tube material, only by widening molecular weight distribution, suitably reduce the polymkeric substance degree of isotacticity and produce, to satisfy the requirement of machine-shaping.Also have by the post-treatment modification and improve the homo-polypropylene performance,, improve PPH tube material resistance to impact shock such as by adding the brilliant nucleator of β; Mention among the patent CN101168609A with beta nucleater modified Atactic Polypropelene tube material, improve the rigidity and the toughness of Atactic Polypropelene tube material synchronously.But the brilliant nucleator cost of β is higher, and β is brilliant unstable, easily is transformed into the α crystalline substance in life cycle, and then causes the decline of material property.Proposed to prepare the method for high-performance polypropylene tube material among patent US6433087, JP2002295741 and the KR20040048053, but the method for using second third Co-polypropylene, polystyrene elastomerics or ethylene/propene/butene terpolymers and homo-polypropylene blending prepares the high-performance tube material, has also caused the increase of production cost and the instability that material property brings because of raw materials quality and modification operation etc. undoubtedly.
The present invention intends the method by direct polymerization, by adjusting the molecular structure of polypropene composition, realizes the raising of its performance.More particularly, by adjusting polymerization tacticity and the hydrogen response of catalyzer between different reactor, obtaining, rigidity of material can be reached and flexible comprehensively improves than the macromole part of low grade and the small molecules part of higher degree of isotacticity.
Summary of the invention
The production method of a kind of high-performance homo-polypropylene of the present invention tube material, this method adopts the method for general commercial Z-N polymerizing catalyst and direct polymerization, by adjusting polymerization tacticity and the hydrogen response of catalyzer between different reactor, obtain the broad molecular weight distribution polypropylene composition that macromole part degree of isotacticity is lower, small molecules part degree of isotacticity is high, realize that rigidity of material and flexible comprehensively improve, material need not the post-treatment modification, and polymerization process also need not to add any comonomer.
More particularly, the present invention adjusts hydrogen response and the polymerization tacticity of catalyzer in different reactor, realizes by the method that changes external electron donor kind in the catalyst system.Promptly in different reactor, add external electron donor, reduce macromolecular degree of isotacticity, improve micromolecular degree of isotacticity, realize improving simultaneously the rigidity and the toughness of homo-polypropylene tube material with different hydrogen regulation performances and polymerization tacticity.
In the technology of the present invention, the catalyzer of propylene polymerization comprises but is not limited only to Ziegler-Natta catalyst.The Ziegler-Natta catalyst that uses is by open in a large number, the catalyzer that preferably has high stereoselective, " Ziegler-Natta catalyst of high stereoselective " described herein are meant and can prepare isotactic index greater than 95% alfon.This type of catalyzer contains (1) ingredient of solid catalyst usually, is preferably titaniferous solid catalyst active ingredient; (2) organo-aluminium compound cocatalyst component; (3) and randomly add the external electron donor component.
The specific examples of operational this class ingredient of solid catalyst is disclosed among CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4 and the CN02100900.7.Described catalyzer can directly use, also can be through adding after pre-complexing and/or the prepolymerization.Catalyzer described in CN85100997, CN93102795.0, CN98111780.5 and the CN02100900.7 is used for the present invention and has advantage especially.
Cocatalyst component is an organo-aluminium compound, the preferred alkyl aluminum compound, more preferably trialkylaluminium, for example: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc., wherein ingredient of solid catalyst is 1: 25～1: 100 with the ratio of organo-aluminium compound with the Ti/Al molar ratio computing.
The external electron donor component is silicoorganic compound.Its general formula is R
nSi (OR ')
4-n, 0＜n in the formula≤3, R and R ' they are identical or different alkyl, cycloalkyl, aryl, haloalkyl etc. in the general formula, R also can be halogen or hydrogen atom.Concrete as tetramethoxy-silicane, tetraethoxysilane, the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, isopropyl methyl dimethoxy silane, two phenoxy group dimethoxy silane, the phenylbenzene diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-three fluoro-2-propyl group)-methyl dimethoxysilane etc.Silicoorganic compound can add in the lump in two above serial operation reactors and also can add respectively, can directly join in the reactor, also can be added on the reactor feed relevant equipment or pipeline.
Catalyzer of the present invention can directly join in first reactor, also after the pre-complexing and/or prepolymerization that can know altogether through industry, joins in first reactor again.
Pre-complexing process can have or not have that (in pre-complexing still or polymerization reactor) carries out under the environment of polymerization single polymerization monomer.When carrying out pre-complex reaction separately, the form of reactor can be a continuous stirred tank reactor, also can be other means that can obtain the thorough mixing effect, as annular-pipe reactor, contain one section pipeline of static mixer, even also can be the pipeline that one section material is in turbulence state.The Controllable Temperature of pre-complexing is between-10～60 ℃, and preferred temperature is 0～30 ℃.The time of pre-complexing is controlled at 0.1～180min, and the preferred time is 5～30min.
Through or can also carry out randomly prepolymerization without the catalyzer of pre-complexing and handle.Prepolymerization can be carried out under the liquid phase bulk conditions continuously, also can carry out on inert solvent discontinuous ground.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized Controllable Temperature is between-10～60 ℃, and preferred temperature is 0～40 ℃.Prepolymerized multiple is controlled at 0.5～1000 times, and preferred multiple is 1.0～500 times.
Described polyreaction can be carried out in the propylene liquid phase or in gas phase, or adopts liquid-gas combination technique to carry out.When liquid polymerization, polymerization temperature is 0～150 ℃, with 40～100 ℃ for well; Polymerization pressure should be higher than the saturated vapour pressure of propylene under corresponding polymerization temperature.Polymerization temperature is 0～150 ℃ when vapour phase polymerization, with 40～100 ℃ for well; Polymerization pressure can be a normal pressure or higher, and preferred pressure is 1.0～3.0MPa (gauge pressure, down together).
Polymerization can be to carry out continuously, also may be carried out batchwise.Successive polymerization can be two or more placed in-line Liquid-phase reactor or Gas-phase reactor, Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor or vertical agitated bed reactor or fluidized-bed reactor etc., and above Liquid-phase reactor and Gas-phase reactor be matched combined at random also.
The polymkeric substance of gained can carry out extruding pelletization by use equipment among the present invention, adds the additive that this technical field is used during granulation usually, as oxidation inhibitor, photostabilizer, thermo-stabilizer, tinting material and filler etc.
The present invention need not use special catalyst, also need not add any multi-functional comonomer in addition, adopt the method for direct polymerization, by adjust catalyzer two of serial operation with the hydrogen response in the reactor can and the polymerization tacticity, can realize that polypropylene tube material rigidity, flexible comprehensively improve.
Embodiment
To describe the present invention by specific embodiment below, but it only is to explain rather than limit the present invention.
The polymkeric substance relevant data obtains by following testing method among the embodiment:
1. polymer tacticity index.Measure by the method that GB GB 2412 describes.
2. melt flow rate (MFR) (MFR) is pressed ISO1133,230 ℃, measures under the 2.16kg load.
3. molecular weight distribution: the model of selling with U.S. Rheometric Scientific Inc be the rheometer of ARES (senior rheometer expanding system) at 190 ℃, the viscosity and the modulus value of certain frequency scope working sample, the pattern of sample clamp is flat.Polydispersity index PI=10
5/ G, G are the modulus value at storage modulus (G ')-frequency curve and out-of-phase modulus (G ")-frequency curve intersection point place.The test before with resin sample at 200 ℃ of thin slices that are molded into 2mm.
5. resin stretched intensity is pressed ASTM D638-00 and is measured.
6. the resin modulus in flexure is pressed ASTM D790-97 measurement.
7. the Izod shock strength is pressed ASTM D256-00 measurement.
4. heat-drawn wire (HDT) is pressed ASTM D648-06 measurement
Embodiment 1
Primary Catalysts: titaniferous solid catalyst active ingredient adopts the method that embodiment 1 describes among the CN93102795 to obtain its Ti content: 2.4wt%, Mg content 18.0wt%, n-butyl phthalate content: 13wt%.
Polyreaction is carried out on a collar plumber plants the polypropylene pilot plant.Reactor is two placed in-line annular-pipe reactors.Primary Catalysts, promotor (triethyl aluminum), part external electron donor (cyclohexyl methyl dimethoxy silane) are behind 10 ℃, the pre-contact of 20min, add prepolymerization reactor continuously and carry out pre-polymerization reactor, prepolymerization is carried out under propylene liquid phase bulk environment, temperature is 15 ℃, the residence time is about 4min, and the pre-polymerization multiple of catalyzer is about 120-150 doubly under this condition.The pre-polymerization rear catalyst enters in two placed in-line annular-pipe reactors, finishes the equal polymerization reaction of propylene in annular-pipe reactor.70 ℃ of two endless tube polymeric reaction temperatures, reaction pressure 4.0MPa.The processing condition of gate ring pipe reactor, the productivity ratio that makes first, second endless tube is about 45: 55.
Do not add hydrogen in the charging of first annular-pipe reactor, density of hydrogen＜10ppmV that on-line chromatograph detects adds a certain amount of hydrogen in the second annular-pipe reactor charging, and the density of hydrogen that on-line chromatograph detects is 300ppmV.The triethyl aluminum flow that advances prepolymerization reactor is 5.5g/hr, and cyclohexyl methyl dimethoxy silane flow rate is for being 0.12g/hr, and the Primary Catalysts flow is 0.01g/hr.Because these catalyst components directly enter first annular-pipe reactor after prepolymerization, first annular-pipe reactor no longer includes any other charging except that propylene, and therefore, the Al/Si ratio is 45.8 (weight ratios) in first annular-pipe reactor.Add the into two cyclopentyl dimethoxy silanes of 0.68g/hr in second annular-pipe reactor, concrete processing condition see Table 1.
After the polymkeric substance that comes out from second endless tube goes out propylene through flash separation, remove the activity of such catalysts and the heat drying of unreacted device again through wet nitrogen, obtain polymer powders.
Add the IRGAFOS 168 of 0.1wt% in the powder that polymerization is obtained, the IRGANOX1010 of 0.2wt% and the calcium stearate of 0.05wt% are used the twin screw extruder granulation.The gained pellet is carried out performance test by existing relevant ASTM standard.
Comparative example 1
With embodiment 1, but second reactor does not add external electron donor.Processing condition see Table 2 more specifically.
The analytical test of sample sees Table 3 in embodiment and the comparative example.
With the Tc of two samples of DSC method test, embodiment 1 resulting polymers Tc is 115 ℃, 110 ℃ of Comparative Examples 1 resulting polymers Tcs.Known from institute, the raising of Tc is for shortening the machine-shaping cycle, raising the efficiency very key.
Table 1. embodiment 1 polymerization process condition
Table 2. comparative example 1 polymerization process condition
Table 3. embodiment/comparative example polymkeric substance test data
Claims (6)
1. the production method of a high-performance homo-polypropylene tube material, it is characterized in that, this method adopts the method for general commercial Z-N polymerizing catalyst and direct polymerization, by adjusting polymerization tacticity and the hydrogen response of catalyzer between different reactor, obtain the broad molecular weight distribution polypropylene composition that polypropylene macromole part degree of isotacticity is lower, small molecules part degree of isotacticity is high, realize that rigidity of material and flexible comprehensively improve, material need not the post-treatment modification, and polymerization process also need not to add any comonomer.
2. the production method of high-performance homo-polypropylene tube material according to claim 1, it is characterized in that described general commercial Z-N polymerizing catalyst is the catalyzer described in Chinese patent CN85100997, CN93102795.0, CN98111780.5 or the CN02100900.7.
3. the production method of high-performance homo-polypropylene tube material according to claim 1, it is characterized in that adjusting polymerization tacticity and the hydrogen response of catalyzer between different reactor is to realize by the method that changes external electron donor kind in the catalyst system.
4. the production method of high-performance homo-polypropylene tube material according to claim 1 is characterized in that, its several components of described catalyzer were carried out pre-complexing and/or prepolymerization earlier before entering reactor.
5. the production method of high-performance homo-polypropylene tube material according to claim 1 is characterized in that, described high melt strength, propylene preparation method is a continuous polymerization method.
6. the production method of high-performance homo-polypropylene tube material according to claim 4 is characterized in that, the reactor that described high melt strength, propylene preparation method uses is a placed in-line annular-pipe reactor more than two.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102361060A CN102040696A (en) | 2009-10-20 | 2009-10-20 | Method for producing high-performance polypropylene pipe material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102361060A CN102040696A (en) | 2009-10-20 | 2009-10-20 | Method for producing high-performance polypropylene pipe material |
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| CN102040696A true CN102040696A (en) | 2011-05-04 |
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| CN105440181A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Propylene polymer and preparation method thereof |
| CN105440181B (en) * | 2014-08-15 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of acrylic polymers and preparation method thereof |
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