CN101077918A - Polypropylene alloy and preparation method thereof - Google Patents
Polypropylene alloy and preparation method thereof Download PDFInfo
- Publication number
- CN101077918A CN101077918A CN 200610081158 CN200610081158A CN101077918A CN 101077918 A CN101077918 A CN 101077918A CN 200610081158 CN200610081158 CN 200610081158 CN 200610081158 A CN200610081158 A CN 200610081158A CN 101077918 A CN101077918 A CN 101077918A
- Authority
- CN
- China
- Prior art keywords
- titanium
- butyl
- cyclopentadienyl
- zirconium
- phenyl
- 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.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to one kind of polypropylene alloy and its preparation process. The polypropylene alloy is prepared with propylene monomer, Ti, Cl, Mg, diester or diether in certain weight proportion, and through bulk polymerization after adding supported spherical catalyst and composite co-catalyst at 40-80 deg.c and 1.0-4.0 MPa for 1-2hr; and further polymerization after adding monocyclopentadiene Ti or Zr homogeneous catalyst and composite co-catalyst for other 1-3 hr to obtain spherical granular product. The polypropylene alloy has high bending modulus and high impact strength.
Description
Technical field
This invention relates to a kind of polypropylene alloy and preparation method thereof.
Background technology
Polypropylene (PP) alloy technology is the new technology that development in recent years is got up, and the PP alloy product has the advantages that rigidity and toughness are complementary, and can realize by blending and modifying and catalyzed polymerization.The PP alloy of blending and modifying, as systems such as PP/PE, PP/EPR, PP/PA, must be through complicated blending technology, owing to be subjected to the restriction of system degree of scatter, its over-all properties (Blom H.P. that is affected, Teh J.W., Rudin A., J.Appl.Polym.Sci., 1995,58 (8): 995), and cost is higher.The alloy catalytic technology is directly synthesized the PP alloy along with the development of catalyst technology is born in reactor, performance is largely increased, and production cost is far below blending technology, and the alloy catalytic technology has become the main flow of PP alloying process development.
At present, the alloy catalytic technology is the most representative is Catalloy technology (USP4,521,566 of Basell company; DE 43 0429), this technology is to adopt the stage feeding polymerization technology of two or more reactors in series, first section propylene homopolymerization (mass polymerization or vapour phase polymerization, generate porous spherical i-PP particle), second section or the 3rd section copolymerization (vapour phase polymerization, mixture with ethene or ethene and propylene, in the PP particle, proceed homopolymerization or copolyreaction), the characteristics of this technology are embodied in following two aspects: (1) can prevent problems such as coalescent, the sticking still, blocking pipe of copolymerization stage particle effectively, and the introducing of multipolymer phase can be up to 70%; (2) because first section homopolymerization gained i-PP particle inside is uniform-distribution with a large amount of spaces, has the spongy structure of class, thereby other polyene hydrocarbon phase that second, third section polymerization is introduced will increase in these spaces and it be filled up, make the PP particle form the structure (PP/EPR) of " macroscopical interpenetrating(polymer)networks ", physics, the mechanical property of product reach optimum state.Hivalloy technology is on the basis of Catalloy technology, in second section reaction functional monomer is incorporated in the PP particle, directly forms PP/ non-olefinic polymer alloy, and target replaces engineering plastics such as nylon, polycarbonate Alloys and ABS.
In addition, Zhejiang University also discloses a kind of preparation method (CN 1381505A) of polyolefin alloy, and the technology of employing is the double-reactor multi-stage polymeric, introduces ethylene copolymer, and the content of multipolymer phase reaches 30～40%, reaches polypropylene rigidity and flexible balance.According to the introduction of data, preparation is that the key issue of the polyolefin alloy of main raw material is that the rigidity of alloy and toughness are difficult to take into account simultaneously with ethene, propylene.During with the EPR tenacity-increased profax, improve toughness and always cause rigidity to descend.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with the propylene in single reactor, with two kinds of catalyst systems (Ziegler-Natta catalyst system and single-site catalyzed system), in single reactor, implement two-stage polymerization, preparation has higher modulus in flexure and very high resistance to impact shock, polymer beads particle form spherical in shape be the polypropylene alloy of main component with isotatic polypropylene and high-molecular weight atactic polypropylene, can not occur product conglomeration, sticking wall etc. in the polyreaction influences polypropylene alloy of operational stability problem and preparation method thereof.
The polypropylene alloy that the present invention proposes is a main component with isotatic polypropylene and high-molecular weight atactic polypropylene, and high-molecular weight atactic polypropylene accounts for the 1-40% of weight alloy; The weight-average molecular weight of high-molecular weight atactic polypropylene is 5～400,000; Resulting polymerisate is a spherical morphology.
The preparation method of polypropylene alloy comprises prepolymerization and alloying polymerization process, and preparation method's step is as follows:
(1) with the propylene is monomer, the fine particle solid of the regular spheroid form of apparatus, the particulate median size is 30～150 μ m, weight percentage is a titanium 1.5～3.0%, chlorine 52～60%, magnesium 10～20%, diester or diether 6.0～20.0%, hexane or heptane 1～6%, specific surface area is greater than 250m
2The loading type spherical catalyst of/g (Ziegler-Natta catalyst system) carries out the body prepolymerization, and promotor is that triethyl aluminum, triisobutyl aluminium or the mixture of the two and molecular formula are R
2Si (OCH
3)
2The dimethoxy silane compound, wherein R can be phenyl, cyclohexyl, isobutyl-, tertiary butyl or isopentyl; Be reflected in the intermittent bulk poly-unit and carry out, 10～80 ℃ of polymerization temperatures, polymerization pressure 1.0～4.0MPa, the prepolymerization time is 1～2h, the mol ratio of titanium is 10～10000: 1 in aluminium in the promotor and the catalyzer, R
2Si (OCH
3)
2The mol ratio of titanium is 5～100: 1 in middle silicon and the catalyzer; Propylene is 15mg catalyzer/1000g propylene with the catalyst consumption ratio.
(2) then with list luxuriant titanium or the zirconium homogeneous catalyst adding reaction system of activatory structure for restriction geometrical configuration and unrestricted geometrical configuration, further bulk propylene polymerization, generating main component is the polypropylene alloy of isotatic polypropylene and high-molecular weight atactic polypropylene, the alloying polymerization process is controlled at 1～3h, promotor is the mixture of triethyl aluminum or triisobutyl aluminium and trityl phenyl-pentafluoride boron, the titanium in the promotor in aluminium and the homogeneous catalyst or the mol ratio of zirconium are 10～10000: 1, in the trityl phenyl-pentafluoride boron in boron and the homogeneous catalyst mol ratio of titanium or zirconium be 1～1000: 1, single luxuriant titanium or zirconium homogeneous catalyst add-on are the single luxuriant titanium of 1.5～15mg or zirconium homogeneous catalyst/1000g propylene.
The used catalyzer of alloying process is a kind of single metallocene catalyst, its structure is the luxuriant titanium of list or the zirconium homogeneous catalyst of restriction geometrical configuration and unrestricted geometrical configuration, it is a 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-titanium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group titanium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group) titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy zirconium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group zirconium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4-di-t-butyl phenoxy group zirconium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group)-titanium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,6-di-t-butyl phenoxy group)-titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl titanous chloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl tri-chlorination zirconium, 1,2,3,4,5-pentamethyl-cyclopentadienyl titanous chloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl tri-chlorination zirconium, 1,2-phenylbenzene-3-methyl tri-chlorination zirconium or 1,2-phenylbenzene-3-methyl titanous chloride.The metal of single active center is titanium or zirconium; The used promotor of this homogeneous catalyst is the mixture of triethyl aluminum, triisobutyl aluminium and trityl phenyl-pentafluoride boron; In the promotor in aluminium and the homogeneous catalyst mol ratio of titanium be 10～10000: 1, in the trityl phenyl-pentafluoride boron in boron and the homogeneous catalyst mol ratio of titanium be 1～1000: 1;
Step 1: need conscientiously select the alr mode and the stirring velocity of prepolymerization reaction, not destroy the ball-type structure of polymkeric substance and catalyst particle.Prepolymerized degree is advisable to form stable polypropylene ball-type particle.The prepolymerization time is too short, does not form firm spheroidal particle, causes the active decline of W-response, and particle form is undesirable; The pre-polymerization overlong time, the porosity of isotatic polypropylene spheroid is low, is unfavorable for the uniform distribution of high-molecular weight atactic polypropylene elasticity phase, makes to produce between particle to stick phenomenon.In prepolymerized process, the pre-complexing time of Primary Catalysts is very crucial, Primary Catalysts, promotor and external electron donor mix in hexane or heptane solvent in given ratio, shaking mixer, the isotactic active centre is fully activated, poison or shift non-isotactic active centre, improve the catalytic activity of catalyzer and the taxis of polymkeric substance.Under cold condition the activatory catalyst system is entered reactive system, with propylene reaction 10～20min, Reinforced Polypropylene particulate intensity is avoided increasing of alloy polymers fine powder.If there is not this low-temp reaction process, then the polypropylene particles of gained is broken irregular particle or serious rimose spheroid form substantially, easily cause problems such as particle unity, sticking wall in the second step reaction process, and cause bonding force variation between different polymer phases, product property descends.Cause the reason of this phenomenon to be, the polypropylene particles interior porosity is lower, and the rate of polymerization of Atactic Polypropelene is apparently higher than the rate of polymerization of isotatic polypropylene, and the high-molecular weight atactic polypropylene that generates fast in the polypropylene hole is very easily burst particle, destroys original spherical morphology.Thereby prepolymerized effect is the pattern that guarantees polymer particle, can reappear the spherical morphology of catalyst particle, and significantly improve polymerization activity, makes alloy polymers that the ideal outward appearance be arranged.
Step 2: alloying polymerization process subsequent steps one bulk technique.The monomer of alloying polymerization process still is a propylene, after carrying out step 1, with high-pressure inert gas activatory homogeneous phase metallocene catalyst is pressed into reaction system, for guaranteeing the high reactivity of catalyzer, used rare gas element must be a polymerization-grade, just foreign matter content lacking very, purity reaches 99.99%.In the alloying polymerization process, the activation method of homogeneous phase metallocene catalyst is very crucial.At first the homogeneous phase metallocene catalyst is mixed with the organoaluminum promotor and carry out alkylated reaction, the effect part of organoaluminum promotor participates in reaction, detrimental impurity in another part removing system, as water, alcohol etc., with trityl phenyl-pentafluoride boron complex reaction taking place further, forms random active centre then.Process in alkylation homogeneous phase metallocene catalyst and the further complexing of trityl phenyl-pentafluoride boron must be fast, make catalyst system enter reactive system with the fastest speed, otherwise alkylation homogeneous catalyst and trityl phenyl-pentafluoride boron deep reaction, cause the generation of side reaction, reduce activity of such catalysts, reduce the molecular weight of Atactic Polypropelene.The alloying polymerization process is controlled at 1～3h, when the isotatic polypropylene spheroid is grown up, the high-molecular weight atactic polypropylene elastomerics progressively enters in the hole of polypropylene spheroid, the outside in polymer spheres coats one deck isotatic polypropylene and high-molecular weight atactic polypropylene, thereby make high-molecular weight atactic polypropylene elasticity phase region be dispersed in isotatic polypropylene alternate of high-crystallinity, give full play to the effect that elasticity improves resistance to impact shock mutually.Therefore, compare with existing alloy catalytic patented technology, other wards off a new road of improving the polypropylene over-all properties, simplifying technology, reduce production costs and enlarge aspect such as alloy property regulation range, more superiority is arranged.
In the alloying polymerization process, adjust the melt flow index of polymkeric substance by the add-on of adjusting molecular weight regulator, by adjusting the proportioning of Ziegler-Natta catalyst and homogeneous phase metallocene catalyst, adjust the content of high-molecular weight atactic polypropylene in the alloy polymers, obtain the alloy polymers of different performance and purposes.
Advantage of the present invention is: prepared alloy has higher modulus in flexure and very high resistance to impact shock simultaneously, prepared polymer beads has the spherical morphology of rule, has guaranteed can not occur in the polyreaction problem that product conglomeration, sticking wall etc. influence operational stability.Only be raw material with the propylene in single reactor, simplifying technical process, reducing the product cost aspect has remarkable advantages.
Embodiment
Embodiment 1
(1) pre-polymerization process
On 5L mass polymerization evaluating apparatus, carry out the prepolymerization reaction.At first vacuumize the replacement(metathesis)reaction system 5 times, use the propylene exchange system again 3 times with high pure nitrogen.In system, add molecular weight regulator 100mmol, (main component has: titanium content is 2.5%, chlorine 58% with activatory Ziegler-Natta spherical catalyst 20mg, magnesium 15%, the spherical particle of diester or diether 14.0%, particle diameter 20～150 μ), promotor Al (C
2H
5)
3(mol ratio of titanium is 1000 in aluminium in the promotor and the Zeigler-Natta catalyst), the external electron donor dimethoxydiphenylsilane, (in the dimethoxydiphenylsilane in silicon and the Zeigler-Natta catalyst mol ratio of titanium be 100) adds in the catalyzer feed pot.With liquid propene catalyzer is poured reactive system, the propylene add-on is 1300g.Under 20 ℃ of conditions, react 10min, back elevated temperature to 70 ℃, stirring velocity is 200 commentaries on classics/min, total prepolymerization reaction times changes next step operation over to after being 1h.
(2) alloying polymerization process
The prepolymerization that continues in 5L mass polymerization evaluation system reaction, with activatory 1-phenyl one 2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride catalyzer is pressed into reaction system rapidly.The monomer of alloying polymerization process still is a propylene, the alloying polymerizing condition is: 70 ℃ of polymerization temperatures, the alloying reaction time is 2h, promotor is the mixture of triisobutyl aluminium and boron additive, the mol ratio of the titanium in the promotor in aluminium and the homogeneous catalyst is 1000, the mol ratio of the titanium in the trityl phenyl-pentafluoride boron in boron and the homogeneous catalyst is 200, the add-on of homogeneous phase single metallocene-titanium catalyst is 4mg, with high-pressure inert gas the activatory homogeneous catalyst is pressed into reaction system, the soak time of homogeneous catalyst is 60sec.Be to guarantee the high reactivity of catalyzer, used rare gas element must be a polymerization-grade, and just foreign matter content lacking very, purity reaches 99.99%.After total reaction time reaches 3h, obtain polymerisate 945g, the spheroidal particle of rule, median size is 2.1mm, tap density is 0.45gcm
-3, degree of isotacticity is 90.5%, shock strength 13.5KJm
-2, modulus in flexure 1100MPa.
Comparative examples 2
Compare with embodiment 1, except that not carrying out reacting 10min one step under 20 ℃ of conditions in the pre-polymerization process, all the other operations are all identical.Get polymerisate 420g, product is the irregular fine powder material of particle shape, and average particulate size is less than 1mm, and fine powder is many.
Embodiment 3,4,5,6,7,8
Among the embodiment 3,4,5,6,7,8, catalyst proportion is a homogeneous phase single metallocene-titanium catalyst 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride and Ziegler-Natta catalyst (industrial DQ-2) weight ratio were respectively 1: 1.5; 1: 4; 1: 6; 1: 8; 1: 10; 0: 1, molecular weight regulator hydrogen was fixed as 100mmol, and other operational condition and embodiment 1 are identical, the results are shown in table 1.
Table 1
| Embodiment | 3 | 4 | 5 | 6 | 7 | 8 |
| Polymer morphology tap density/gcm -3 MI/g·(10min) -1Degree of isotacticity/% shock strength/KJm -2Modulus in flexure/MPa | Spherical 0.45 1.390 86.11 17.5 1245 | Spherical 0.45 1.463 90.52 13.5 1348 | Spherical 0.45 1.757 93.28 14.7 1225 | Spherical 0.45 2.012 94.63 9.8 1180 | Spherical 0.45 2.684 95.37 8.2 1230 | Spherical 0.45 3.300 98.1 4.7 1410 |
Catalyst propylene polymerization result from different proportionings, minimizing along with the metallocene catalyst add-on, the impact property of polymkeric substance reduces, and this is owing to the minimizing along with the metallocene catalyst add-on, and the content of high-molecular weight atactic polypropylene reduces in the polymkeric substance; Compare with pure isotatic polypropylene, shock strength improves 2-4 doubly.
Embodiment 9,10,11,12,13,14,15
Among the embodiment 9,10,11,12,13,14,15, the stagnant catalyst proportioning is a 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride catalyzer and Ziegler-Natta catalyst weight ratio are 1: 4, the add-on of molecular weight regulator hydrogen is respectively 0,60,100,130,160,200,260mmol, and other operational conditions and embodiment 1 are identical, the results are shown in table 2.
Table 2
| Embodiment | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| Polymer morphology tap density/gcm -3 MI/g(10min) -1Degree of isotacticity/% shock strength/KJm -2Modulus in flexure/MPa | Spherical 0.45 0.052 95.64 37.2 1580 | Spherical 0.45 1.463 93.52 18.5 1348 | Spherical 0.45 1.982 93.28 17.7 1234 | Spherical 0.45 3.691 94.63 12.2 1080 | Spherical 0.45 9.748 92.37 7.3 910 | Spherical 0.45 9.812 94.32 7.1 924 | Spherical 0.45 12.60 84.2 7.9 870 |
Result from embodiment, increase along with the hydrogen add-on, the melt flow index of polymkeric substance increases, molecular-weight average reduces, improvement to the shock resistance of polymkeric substance reduces gradually, impact property increase rate to low index product is very big, and the hydrogen response of alloy catalyst system is fine.
Embodiment 16
The mol ratio of titanium is 100 in aluminium in the change promotor and the Zeigler-Natta catalyst, in the external electron donor dimethoxydiphenylsilane in silicon and the Zeigler-Natta catalyst mol ratio of titanium be 10, other operational conditions and embodiment 1 are identical, obtain polymerisate 875g, product is the spheroidal particle of rule, median size is 2.1mm, and tap density is 0.45gcm
-3, degree of isotacticity is 89.8%, shock strength 14.1KJm
-2, modulus in flexure 1050MPa.
Embodiment 17
The mol ratio of titanium is 2000 in aluminium in the change promotor and the Zeigler-Natta catalyst, in the external electron donor dimethoxydiphenylsilane in silicon and the Zeigler-Natta catalyst mol ratio of titanium be 50, other operational conditions and embodiment 1 are identical, obtain polymerisate 960g, product is the spheroidal particle of rule, median size is 2.1mm, and tap density is 0.45gcm
-3, degree of isotacticity is 87.8%, shock strength 14.8KJm
-2, modulus in flexure 1040MPa.
Embodiment 18
The mol ratio of titanium is 10000 in aluminium in the change promotor and the Zeigler-Natta catalyst, in the external electron donor dimethoxydiphenylsilane in silicon and the Zeigler-Natta catalyst mol ratio of titanium be 100, other operational conditions and embodiment 1 are identical, obtain polymerisate 1050g, product is the spheroidal particle of rule, median size is 2.1mm, and tap density is 0.45gcm
-3, degree of isotacticity is 83.5%, shock strength 15.9KJm
-2, modulus in flexure 940MPa.
Embodiment 19
The titanium in the change promotor in aluminium and the homogeneous catalyst or the mol ratio of zirconium are 100, in the trityl phenyl-pentafluoride boron in boron and the homogeneous catalyst mol ratio of titanium or zirconium be 10, other operational conditions and embodiment 1 are identical, obtain polymerisate 1060g, product is the spheroidal particle of rule, median size is 2.1mm, and tap density is 0.44gcm
-3, degree of isotacticity is 90.8%, shock strength 14.1KJm
-2, modulus in flexure 1140MPa.
Embodiment 20
The titanium in the change promotor in aluminium and the homogeneous catalyst or the mol ratio of zirconium are 10000, in the trityl phenyl-pentafluoride boron in boron and the homogeneous catalyst mol ratio of titanium or zirconium be 1000, other operational conditions and embodiment 1 are identical, obtain polymerisate 860g, product is the spheroidal particle of rule, median size is 2.1mm, and tap density is 0.44gcm
-3, degree of isotacticity is 92.5%, shock strength 12.6KJm
-2, modulus in flexure 1240MPa.
Embodiment 21
Homogeneous catalyst 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-the zirconium dichloride compound, other operational conditions and embodiment 1 are identical, obtain polymerisate 1150g, and product is the spheroidal particle of rule, median size is 2.1mm, and tap density is 0.45gcm
-3, degree of isotacticity is 82.5%, shock strength 15.1KJm
-2, modulus in flexure 1105MPa.
Embodiment 22
Homogeneous catalyst is with 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy titanium dichloride compound, other operational conditions and embodiment 1 are identical, obtain polymerisate 1020g, product is the spheroidal particle of rule, and median size is 2.0mm, and tap density is 0.43gcm
-3, degree of isotacticity is 92.5%, shock strength 13.1KJm
-2, modulus in flexure 1305MPa.
Embodiment 23
Homogeneous catalyst is with 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy zirconium dichloride compound, other operational conditions and embodiment 1 are identical, obtain polymerisate 1220g, product is the spheroidal particle of rule, and median size is 2.1mm, and tap density is 0.41gcm
-3, degree of isotacticity is 81.5%, shock strength 14.9KJm
-2, modulus in flexure 1105MPa.
Embodiment 24
Homogeneous catalyst is with 1,2, and 3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride compound, other operational conditions and embodiment 1 are identical, obtain polymerisate 980g, product is the spheroidal particle of rule, and median size is 2.1mm, and tap density is 0.42gcm
-3, degree of isotacticity is 91.5%, shock strength 12.9KJm
-2, modulus in flexure 1305MPa.
Embodiment 25
Homogeneous catalyst is with 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-the zirconium dichloride compound, other operational conditions and embodiment 1 are identical, obtain polymerisate 1260g, product is the spheroidal particle of rule, and median size is 2.1mm, and tap density is 0.43gcm
-3, degree of isotacticity is 81.5%, shock strength 15.9KJm
-2, modulus in flexure 985MPa.
Embodiment 25
Homogeneous catalyst 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl titanium trichloride compound, other operational conditions and embodiment 1 are identical, obtain polymerisate 850g, and product is the spheroidal particle of rule, and median size is 2.1mm, and tap density is 0.43gcm
-3, degree of isotacticity is 94.5%, shock strength 11.9KJm
-2, modulus in flexure 1385MPa.
Embodiment 26
Homogeneous catalyst 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl tri-chlorination zirconium compounds, other operational conditions and embodiment 1 are identical, obtain polymerisate 1150g, product is the spheroidal particle of rule, and median size is 2.1mm, and tap density is 0.43gcm
-3, degree of isotacticity is 84.5%, shock strength 13.9KJm
-2, modulus in flexure 1265MPa.
Claims (3)
1. the preparation method of a polypropylene alloy, it is characterized in that: the preparation method of polypropylene alloy comprises prepolymerization and alloying polymerization process, and preparation method's step is as follows:
(1) with the propylene is monomer, the fine particle solid of the regular spheroid form of apparatus, the particulate median size is 30～150 μ m, weight percentage is a titanium 1.5～3.0%, chlorine 52～60%, magnesium 10～20%, diester or diether 6.0～20.0%, hexane or heptane 1～6%, specific surface area is greater than 250m
2The loading type spherical catalyst of/g carries out the body prepolymerization, and promotor is that triethyl aluminum, triisobutyl aluminium or the mixture of the two and molecular formula are R
2Si (OCH
3)
2The dimethoxy silane compound, wherein R is phenyl, cyclohexyl, isobutyl-, tertiary butyl or isopentyl; Be reflected in the intermittent bulk poly-unit and carry out, 10～80 ℃ of polymerization temperatures, polymerization pressure 1.0～4.0MPa, the prepolymerization time is 1～2h, the mol ratio of titanium is 10～10000: 1 in aluminium in the promotor and the catalyzer, R
2Si (OCH
3)
2The mol ratio of titanium is 5～100: 1 in middle silicon and the catalyzer; Propylene is 15mg catalyzer/1000g propylene with the catalyst consumption ratio,
(2) then with list luxuriant titanium or the zirconium homogeneous catalyst adding reaction system of activatory structure for restriction geometrical configuration and unrestricted geometrical configuration, further bulk propylene polymerization, generating main component is the polypropylene alloy of isotatic polypropylene and high-molecular weight atactic polypropylene, the alloying polymerization process is controlled at 1～3h, promotor is the mixture of triethyl aluminum or triisobutyl aluminium and trityl phenyl-pentafluoride boron, the titanium in the promotor in aluminium and the homogeneous catalyst or the mol ratio of zirconium are 10～10000: 1, the mol ratio of titanium or zirconium is 1～1000: 1 in boron and the homogeneous catalyst, and single luxuriant titanium or zirconium homogeneous catalyst add-on are than the single luxuriant titanium of 1.5～15mg or zirconium homogeneous catalyst/1000g propylene.
2. the preparation method of a kind of polypropylene alloy according to claim 1, it is characterized in that: single luxuriant titanium or zirconium homogeneous catalyst are 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-titanium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group titanium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group) titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy zirconium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group zirconium dichloride, 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4-di-t-butyl phenoxy group zirconium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride; 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group)-and titanium dichloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride; 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,6-di-t-butyl phenoxy group)-titanium dichloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl titanous chloride, 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl tri-chlorination zirconium, 1,2,3,4,5-pentamethyl-cyclopentadienyl titanous chloride, 1,2,3,4,5-pentamethyl-cyclopentadienyl tri-chlorination zirconium, 1,2-phenylbenzene-3-methyl tri-chlorination zirconium or 1,2-phenylbenzene-3-methyl titanous chloride.
3. the polypropylene alloy of the preparation method of a kind of polypropylene alloy according to claim 1 preparation, it is characterized in that: resulting polypropylene alloy is a spherical morphology; High-molecular weight atactic polypropylene accounts for 1%～40% of weight alloy; The weight-average molecular weight of high-molecular weight atactic polypropylene is 1～400,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100811581A CN100537651C (en) | 2006-05-23 | 2006-05-23 | Polypropylene alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100811581A CN100537651C (en) | 2006-05-23 | 2006-05-23 | Polypropylene alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101077918A true CN101077918A (en) | 2007-11-28 |
| CN100537651C CN100537651C (en) | 2009-09-09 |
Family
ID=38905598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100811581A Active CN100537651C (en) | 2006-05-23 | 2006-05-23 | Polypropylene alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100537651C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2225251A1 (en) * | 2007-12-31 | 2010-09-08 | SK Energy Co., Ltd. | Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same |
| CN102127263A (en) * | 2011-01-27 | 2011-07-20 | 中国汽车工程研究院股份有限公司 | Method for modifying in-reactor alloy polypropylene material for automobile |
| CN101747458B (en) * | 2008-12-11 | 2011-12-07 | 中国石油天然气股份有限公司 | Preparation method of polypropylene for preparation of chlorinated polypropylene with high chlorination rate |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
| CN112457441A (en) * | 2020-11-30 | 2021-03-09 | 刘城 | Random copolymerization polypropylene, preparation method thereof, polypropylene cast film containing random copolymerization polypropylene and application of polypropylene cast film |
-
2006
- 2006-05-23 CN CNB2006100811581A patent/CN100537651C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2225251A1 (en) * | 2007-12-31 | 2010-09-08 | SK Energy Co., Ltd. | Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same |
| EP2225251A4 (en) * | 2007-12-31 | 2012-03-21 | Sk Innovation Co Ltd | Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same |
| CN101747458B (en) * | 2008-12-11 | 2011-12-07 | 中国石油天然气股份有限公司 | Preparation method of polypropylene for preparation of chlorinated polypropylene with high chlorination rate |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
| CN102464733B (en) * | 2010-11-18 | 2013-09-25 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
| CN102127263A (en) * | 2011-01-27 | 2011-07-20 | 中国汽车工程研究院股份有限公司 | Method for modifying in-reactor alloy polypropylene material for automobile |
| CN102127263B (en) * | 2011-01-27 | 2013-01-23 | 中国汽车工程研究院股份有限公司 | Method for modifying in-reactor alloy polypropylene material for automobile |
| CN112457441A (en) * | 2020-11-30 | 2021-03-09 | 刘城 | Random copolymerization polypropylene, preparation method thereof, polypropylene cast film containing random copolymerization polypropylene and application of polypropylene cast film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100537651C (en) | 2009-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102268160B (en) | Polybutene alloy material and preparation method thereof | |
| US4354009A (en) | Catalyst composition for copolymerizing ethylene | |
| US4379758A (en) | Catalyst composition for polymerizing ethylene | |
| CN1249101C (en) | Method for prodn. of olefin polymers and selected catalysts | |
| FI105820B (en) | Process for the preparation of homopolymers or copolymers of propylene | |
| AU2005245592C1 (en) | Process for producing heterophasic alpha-olefin polymers | |
| US8916649B2 (en) | Multistage process for producing ethylene polymer compositions | |
| JP5837424B2 (en) | Multi-stage process for polymerizing ethylene | |
| CN100537651C (en) | Polypropylene alloy and preparation method thereof | |
| CN1882616A (en) | Spray-dried, mixed metal ziegler catalyst compositions | |
| CN103360522A (en) | Preparation method for multiphase polyolefin | |
| US5019633A (en) | Catalyst composition for polymerizing ethylene | |
| CN100427509C (en) | Method of preparing polyolefin alloy | |
| US7867939B2 (en) | Catalyst for ethylene polymerization, preparation thereof, and method for controlling the polymerization kinetic behavior of said catalyst | |
| CN109929185B (en) | Method for producing polypropylene composition | |
| CN103571045B (en) | The preparation method of anti-impact polypropylene in-reactor alloy | |
| CN104774394B (en) | A kind of preparation method of polyolefin alloy | |
| JP2002212219A (en) | METHOD FOR HOMOPOLYMERIZATION OR COPOLYMERIZATION OF alpha-OLEFIN | |
| JP2019518858A (en) | Solid catalysts for the preparation of nucleation polyolefins | |
| CN1202144C (en) | Process for preparing polyolefin alloy | |
| US6630544B1 (en) | Propylene polymerization process with enhanced catalyst activity | |
| CN1405191A (en) | Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof | |
| JP5577219B2 (en) | Propylene polymerization reactor and method for producing propylene polymer | |
| TW494111B (en) | High activity catalysts for the preparation of polyethylene with an intermediate molecular weight distribution | |
| EP0083456B1 (en) | Improved process for copolymerizing ethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |