CN104558348A - Terpolymer of ethylene/1-butylene/1-hexylene and preparation method thereof as well as composite material prepared therefrom - Google Patents
Terpolymer of ethylene/1-butylene/1-hexylene and preparation method thereof as well as composite material prepared therefrom Download PDFInfo
- Publication number
- CN104558348A CN104558348A CN201310481441.3A CN201310481441A CN104558348A CN 104558348 A CN104558348 A CN 104558348A CN 201310481441 A CN201310481441 A CN 201310481441A CN 104558348 A CN104558348 A CN 104558348A
- Authority
- CN
- China
- Prior art keywords
- terpolymer
- hexene
- gas
- ethylene
- butene
- 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
Abstract
The invention discloses a terpolymer of ethylene/1-butylene/1-hexylene and a preparation method thereof and a composite material prepared by using the terpolymer as an elastomer as well as use of the composite material. According to the terpolymer of ethylene/1-butylene/1-hexylene disclosed by the invention, the weight-average molecular weight Mw s 50000-200000 and the molecular weight distribution index is 2-15, measured by gel permeation chromatography. The preparation method of the terpolymer is mainly a multi-temperature zone vapor phase method. The composite material prepared by the terpolymer disclosed by the invention has a good toughening effect and can be widely applied to tubular products, panels, thin films, fibers and the like. The terpolymer disclosed by the invention has the following repeated unit: formula shown in the description (n is greater than or equal to 3). The molar content of the repeated unit in the terpolymer is 0.1-20%.
Description
Technical field
The present invention relates to a kind of multipolymer and preparation method thereof, the matrix material also relating to and prepared by this multipolymer, specifically, the present invention relates to a kind of Ethylene/1-butene/1-hexene terpolymer and preparation method thereof, and relate to the matrix material of described terpolymer as elastomers.
Background technology
As everyone knows, olefin polymer is one of material of widespread use in every field, the rigidity that it has, toughness, Lightness be that many materials are not replaceable, improving its physicals and processing characteristics is the target constantly pursued.
Polyethylene is a kind of most widely used olefin polymer.At present, producing poly technique has a lot, comprises LDPE, LLDPE and HDPE etc.From technical development situation, it is the most ripe method of technology during polyvinyl resin is produced that high-pressure process produces LDPE, and autoclave method and tubular process technology are all ripe, at present this two kinds of production technology depositing.Developed country generally adopts tubular process production technique.In addition, external each company generally adopts low temperature high activity catalyst initiated polymerization system, can reduce temperature of reaction and pressure.High-pressure process produces LDPE will to maximization, tubular type future development.Low-pressure process produces HDPE and LLDPE, main employing titanium system and chromium-based catalysts, and Europe and Japan adopt Ziegler-Natta catalyst more, and the U.S.'s many employings chromium-based catalysts.Polyethylene production technology kind more than ten of main application in the world, comprises company of Basel vapor phase process Spherilene technique, BP company vapor phase process Innovene technique, Exxon Mobil Corporation's tubular type and still reaction technique, Mitsui Chemicals, Inc. low pressure slurry method CX technique, Basel polyolefins company Hostalen technique etc. at present.
Due to the development of technique, expedite the emergence of out colourful polyethylene product.Mainly comprise Low Density Polyethylene, linear low density of polyethylene, medium-density polyethylene, bimodal resin, high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE), modified poly ethylene (CPE, crosslinked polyethylene), ethylene copolymer (multipolymer of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, ethene-other alkene, ethene-unsaturated ester multipolymer).At present, ethylene copolymer is the series products that in many polyethylene products, application prospect is very wide.
Ethylene copolymer refer to produce high density polyethylene(HDPE) (HDPE) or LLDPE (LLDPE) process in, by add carbonatoms be greater than 3 unsaturated olefin comonomer and ethylene copolymer to obtain the product of excellent properties.Current comonomer type mainly contains 3 kinds: C
4(1-butylene), C
6(1-is alkene) and C
8(1-octene).The polyethylene product innovation about 94.0% employing 1-hexene of offshore company's production development is as comonomer, and butene product only accounts for about 4.0%.With LLDPE and the HDPE resin that 1-hexene is produced for comonomer, compared with 1-butylene copolymer resins, there is better tensile strength, rheological, fast resistance to and cracking behavior, shock resistance, environmental stress cracking resistance reach more than 5000 hours at a slow speed.This polyethylene product innovation is particularly suitable for Production and Packaging film and agricultural mulch films.1-hexene constantly increases as the demand of comonomer, and its exploitation prospect is very wide.
Publication number is that the European patent of EP38119 relates to a kind of terpolymer, comprises ethene and alpha-olefin, and this terpolymer is conducive to manufacturing film.Publication number is that the world patent of WO2006/002778 relates to a kind of tubing system comprising the terpolymer of propylene/ethylene and alpha-olefin, obtains the polymkeric substance with improved properties that can be used for film.Publication number is that the Chinese patent of CN1384844 relates to a kind of ethene and C
3~ C
12the multipolymer of alpha-olefin.Its molar mass distribution M
w/ M
n<10, its density is 0.85g/cm
3to 0.95g/cm
3, co-monomer content 1 to 40wt% comonomer and molar mass M
nbe greater than 150000g/mol and the composition of comonomer distribution breadth index be greater than 70%.This polymkeric substance may be used for fiber, moulded product, paper tinsel or polymeric blends.Publication number is the multipolymer that the Chinese patent of CN101903424A relates to a kind of propylene and 1-hexene, wherein said multipolymer 5 ~ 9wt% is derived from the repeating unit of 1-hexene, melt temperature is 125 DEG C ~ 140 DEG C, melt flow rate (MFR) (ASTMD1238,230 DEG C/2.16kg) is 0.1g/10min ~ 3g/10min.Multipolymer within the scope of this can be used to produce has good mechanics and the blown film of optical property.
For the ethylene copolymer of 1-hexene as comonomer, abroad produce in a large number and obtained a wide range of applications, will further have been developed from now on.But the development degree of China in this direction is but far away from abroad.China HDPE and LLDPE production equipment great majority are the technology of 70 ~ eighties of 20th century of Introduced From Abroad, product grade is less, although there is the 1-hervene copolymer trade mark in the device introduced afterwards, but domestic shortage 1-hexene resource, great majority only driving initial stage examination during produced the 1-hervene copolymer trade mark as a trial, and actual production mostly be l-butylene copolymer.
In sum, accelerate the research, development and production of hervene copolymer polyethylene product, the polymeric articles especially developing the such as 1-hervene copolymer trade mark is very important.
Summary of the invention
For the problems referred to above of the prior art, the invention provides a kind of Ethylene/1-butene/1-hexene terpolymer and preparation method thereof, and provide the matrix material of described terpolymer as elastomers, described terpolymer adds in polymeric matrix as favorable elasticity body and is used for improving matrix material use properties, and prepared matrix material is suitable as tubing, sheet material, film and fiber etc.
A terpolymer for Ethylene/1-butene/1-hexene, is characterized in that containing following repeating unit:
Wherein n >=3, this repeating unit molar content in described terpolymer is 0.1% ~ 20%.
The weight-average molecular weight M of described terpolymer
wbe 50000 ~ 200000, molecular weight distributing index is 2 ~ 15, by gel permeation chromatography.
Described repeating unit molar content in described terpolymer is preferably 0.5% ~ 15%, the weight-average molecular weight M of described terpolymer
wbe preferably 80000 ~ 180000, molecular weight distributing index is preferably 2.5 ~ 12.
In the terpolymer of described Ethylene/1-butene/1-hexene, ethene, 1-butylene and 1-hexene monomers unit mol ratio are (50 ~ 98): (1 ~ 25): (1 ~ 25), preferably (60 ~ 96): (2 ~ 20): (2 ~ 20).
The melt temperature scope of described terpolymer is 100 DEG C to 140 DEG C, preferably 110 DEG C to 130 DEG C.
The crystallization range of described terpolymer is 90 DEG C to 140 DEG C, preferably 100 DEG C to 120 DEG C.
The melt flow index of described terpolymer, namely MFR scope is 0.5g/10min to 5g/10min, and it measures according to ISO method 1133.
The polyreaction preparing the terpolymer of described Ethylene/1-butene/1-hexene is generally carried out at 40 DEG C ~ 120 DEG C temperature.In general vapor phase process polyolefine fluidized-bed reactor, even under condensation mode condition, bed temperature of reaction is also homogeneous, substantially there is not thermograde along height of bed direction.The stuctures and properties of the product obtained like this is comparatively common.
And product of the present invention is on such reactor basis, by increasing the butylene, hexene co-monomer content and the high boiling unreactive hydrocarbons content (cooling medium) that contain in circulation gas or the temperature (lower than 60 DEG C) reducing circulation gas, increase the condensed fluid content (being at least greater than 10wt%) in circulation gas, time like this by reactor bottom, bottom can be maintained be in lesser temps and contain more condensed fluid, for polyreaction manufactures the reaction conditions of a low temperature (50 DEG C ~ 75 DEG C), gas-liquid-solid three-phase simultaneously.In this region, the proportioning of comonomer/ethylene can change in 0.01:1 to 0.8:1 scope.
And bed top remains traditional conversion zone of a high temperature (75 DEG C ~ 110 DEG C), gas-particle two-phase.The reactant gases proportioning of high comonomer/ethene, the existence of the reaction environment of low temperature, gas-liquid-solid three-phase, is extremely conducive to the formation of 1-hexene Multiphase sequences fragment, thus realizes the production of the terpolymer of this patent Ethylene/1-butene/1-hexene.
Specifically, the preparation method of the terpolymer of described Ethylene/1-butene/1-hexene is many humidity provinces vapor phase process, described preparation method is many humidity provinces vapor phase process, the method adopts gas-phase fluidized-bed reactor, in described gas-phase fluidized-bed reactor entrance gas-liquid mixture, liquid mass fraction is greater than 10%, in fluidized-bed, liquid mass fraction is 20% ~ 70%, preferred 25wt% ~ 60wt%;
Two reaction zones territory is there is in described gas-phase fluidized-bed reactor, the gas-liquid-solid three-phase region of bottom and the gas-particle two-phase region on top, the temperature in described gas-liquid-solid three-phase region is 50 ~ 75 DEG C, the temperature in described gas-particle two-phase region is 75 ~ 110 DEG C, and the temperature head in described gas-liquid-solid three-phase region and described gas-particle two-phase region is at least more than 10 DEG C, in described gas-phase fluidized-bed reactor, apparent fluidizing gas velocity is 0.5 ~ 0.8m/s.
Described many humidity provinces vapor phase process comprises the following steps:
1) gas-phase fluidized-bed reactor temperature in is set
The fluidized-bed temperature in of gas-phase fluidized-bed reactor is arranged on less than 60 DEG C and lower than the dew-point temperature of entrance gas-liquid mixture at least 10 DEG C;
2) in gas-phase fluidized-bed reactor, cooling medium raw material reaction is passed into
Under the condition of continuity that catalyzer exists, add the gas and vapor permeation raw material of 1-butylene, 1-hexene, ethene, hydrogen, nitrogen and iso-pentane composition, the terpolymer of Ethylene/1-butene/1-hexene is prepared in reaction; The 1-butylene added and the molar ratio range of ethene are 0.01:1 to 0.8:1, preferred 0.05:1 to 0.5:1, and the 1-hexene added and the molar ratio range of ethene are 0.01:1 to 0.8:1, preferred 0.05:1 to 0.5:1;
The method of the application, when content liquid is many, can add liquid refrigerant iso-pentane, in advance in order to avoid cause hydrops; When content liquid is few, also first can not add liquid refrigerant, pass into gas iso-pentane, utilize condensation to form liquid.So, described step 2) in, under the condition of continuity that catalyzer exists, after first can adding liquid iso-pentane in described gas-phase fluidized-bed reactor, then add the gas and vapor permeation raw material of 1-butylene, 1-hexene, ethene, hydrogen, nitrogen and iso-pentane composition.
When gaseous mixture passes into bottom bed, due to liquefaction of gases such as temperature in are low, iso-pentane.Gaseous mixture becomes gas-liquid mixture.
Described iso-pentane, 1-butylene, 1-hexene, ethene, hydrogen, nitrogen composition circulation gas, wherein hydrogen and ethylene molar ratio scope are 1:15 to 1:3, iso-pentane accounts for the 5wt% ~ 40wt% of circulation gas total mass, and 1-butylene and the total molar content of 1-hexene account for the 8mol% ~ 50mol% of circulation gas total mole number.
The preparation method of the terpolymer of Ethylene/1-butene of the present invention/1-hexene; be not limited only to above-described many humidity provinces vapor phase process; for butylene, hexene as reaction medium solution polymerization method or slurry polymerization method can obtain product of the present invention, also belong to the protection domain of this patent.
In preparation method of the present invention, polyreaction can complete under multiple catalysts condition, and described preparation method adopts following at least one catalyzer: Ziegler-Natta catalyst, metallocene catalyst, transition-metal catalyst, inorganic chromium catalyzer, organic chromium catalyzer.
Preferably, described catalyzer is Ziegler-Natta catalyst, its by having the titanium compound of at least one titanium-halogen key, Internal electron donors compound, external electron-donor compound, promotor form;
The described titanium compound with at least one titanium-halogen key is selected from least one in following component: the halogenide of titanium or halogenated alcoholate;
Described Internal electron donors compound is selected from least one in following component: ether, ketone, lactone, the compound containing N, P or S atom, mono carboxylic acid esters and dicarboxyl acid esters;
Described external electron-donor compound is the ester of aromatic acid;
Described promotor is selected from organo-aluminium compound, preferred alkyl aluminum compound, more preferably triethyl aluminum.
Particularly, other combination of many Above-mentioned catalytic agent components also can be used for preparing ethylene copolymer of the present invention.And as previously described, the catalyzer of this polyreaction is also not limited to Ziegler-Natta catalyst.
Terpolymer of the present invention has special 1-hexene Multiphase sequences structure, and the steric hindrance that in this block structure, the existence of butyl side chain makes strand rotate increases, and therefore the kindliness of polymer molecular chain reduces, and molecular chain is rigidity more, and crystallizing power is deteriorated.Meanwhile, the butyl side chain due to 1-hervene copolymer conjunction formation cannot enter lattice and must foreclose, thus the generation of restriction large size platelet.The butyl side-chain structure of 1-hexene Multiphase sequences obviously destroys the regularity and crystallizing power that arrange polyethylene crystal closely, and the fusing point of multipolymer and density are all reduced.The multipolymer of this low-crystalline has good folding and bends and tear strength, and toughness is greatly improved.
Therefore, matrix material prepared by the terpolymer that present invention also offers a kind of described Ethylene/1-butene/1-hexene.
Described matrix material is prepared from by following component:
The terpolymer of described Ethylene/1-butene/1-hexene, PP resin, talcum powder, auxiliary agent, the mol ratio of the terpolymer of wherein said Ethylene/1-butene/1-hexene, PP resin, talcum powder, auxiliary agent is (0.01 ~ 0.5): 1:(0.01 ~ 0.5): (0.001 ~ 0.05).
As mentioned above, terpolymer of the present invention is owing to having special 1-hexene Multiphase sequences structure, it is made to have excellent physicals, can be used as elastomerics adds in polymeric matrix, obtain good toughening effect, while improving materials'use performance, take into account Drawing abillity simultaneously.The matrix material prepared by the terpolymer of Ethylene/1-butene of the present invention/1-hexene, because it has good toughening effect, described matrix material of the present invention may be used in tubing, sheet material, film, fiber.
Accompanying drawing explanation
Fig. 1 is terpolymer prepared by embodiment 1, i.e. the GPC figure of elastomerics A.
Fig. 2 is terpolymer prepared by embodiment 1, i.e. the DSC figure of elastomerics A.
Fig. 3 is terpolymer prepared by embodiment 1, i.e. elastomerics A
13c nucleus magnetic resonance figure.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited thereto, for the processing parameter do not indicated especially, can refer to routine techniques and carry out.
Characterization method:
Ethene, 1-butylene, 1-hexene and derivative content thereof: by carrying out terpolymer
13c nuclear magnetic resonance spectroscopy measures, and described monomer content refers to the content accounting for the whole ter-polymers of monomeric unit herein.
Melt temperature and Tc is measured according to differential scanning calorimetry (DSC).Concrete grammar is: weigh sample about 6mg, be heated to about 220 DEG C, and keep 2min in nitrogen gas stream, then it is cooled to about 40 DEG C with the speed of 20 DEG C/min with the speed of 20 DEG C/min, keeps 2min with crystallized sample at this temperature.Then this sample is warming up to 220 DEG C with the temperature rise rate of 20 DEG C/min again to melt.Record melting scanning, obtains thermogram, and reads melt temperature and Tc thus.
Weight-average molecular weight (M
w): measured by gpc analysis.
Molecular weight distributing index (polydispersity index PI): being measured by the plate rheometer of the RMS-800 model of Rheometrics company by using, operating from 0.1rad/s is increased to 100rad/s in vibrational frequency.By intersection modulus (crossover modulus), go out PI by following equation inference:
PI=10
5/Gc
Wherein, Gc is for intersecting modulus, and it is the value (representing with Pa) determined as G '=G ' ', and wherein G ' is storage modulus, and G ' ' is out-of-phase modulus.
Melt flow index is measured according to ISO method 1133.
The preparation of embodiment 1 ~ 3 terpolymer
Embodiment 1
Under the condition of continuity that catalyzer exists, in the equipment comprising poly-unit, prepare multipolymer by ethene, 1-butylene, 1-hexene.Polyreaction is carried out in gas-phase fluidized-bed reactor, and ethene, 1-butylene, 1-hexene, as monomer component, in addition with gas composition circulation gas such as nitrogen, iso-pentane, hydrogen, enter bed and react.The temperature of reactor inlet is 58 DEG C, is gas-liquid mixture when circulation gas passes into bottom bed, and bottom bed, polymerization temperature is 75 DEG C, and bed top polymerization temperature is 90 DEG C.In circulation gas, the dew-point temperature of liquid iso-pentane (as condensing agent) is between bed bottom temp and upper temp.Liquid mass fraction 25wt% in fluidized-bed.Apparent fluidizing gas velocity is 0.65m/s.Catalyzer is Ziegler-Natta catalyst.Prepare the terpolymer of Ethylene/1-butene/1-hexene under this condition, be elastomerics A.Each concentration of component of concrete circulation gas is in table 1.
Each concentration of component in table 1 circulation gas
| Circulation gas component | Component concentration/mol% |
| 1-hexene | 5.4% |
| 1-butylene | 4.2% |
| Ethene | 26.0% |
| Hydrogen | 3.6% |
| Nitrogen | 55.6% |
| Iso-pentane | 5.2% |
Embodiment 2
Under the condition of continuity that catalyzer exists, in the equipment comprising poly-unit, prepare multipolymer by ethene, 1-butylene, 1-hexene.Polyreaction is carried out in gas-phase fluidized-bed reactor, and ethene, 1-butylene, 1-hexene, as monomer component, in addition with gas composition circulation gas such as nitrogen, iso-pentane, hydrogen, enter bed and react.The temperature of reactor inlet is 55 DEG C, is gas-liquid mixture when circulation gas passes into bottom bed, and bottom bed, polymerization temperature is 66 DEG C, and bed top polymerization temperature is 86 DEG C.In circulation gas, the dew-point temperature of liquid iso-pentane is between bed bottom temp and upper temp.Liquid mass fraction 35wt% in fluidized-bed.Apparent fluidizing gas velocity is 0.65m/s.Catalyzer is Ziegler-Natta catalyst.Prepare the terpolymer of Ethylene/1-butene/1-hexene under this condition, be elastomerics B.Each concentration of component of concrete circulation gas is in table 2.
Each concentration of component in table 2 circulation gas
| Circulation gas component | Component concentration/mol% |
| 1-hexene | 7.8% |
| 1-butylene | 4.4% |
| Ethene | 24.1% |
| Hydrogen | 3.1% |
| Nitrogen | 53.0% |
| Iso-pentane | 7.6% |
Embodiment 3
Under the condition of continuity that catalyzer exists, in the equipment comprising poly-unit, prepare multipolymer by ethene, 1-butylene, 1-hexene.Polyreaction is carried out in gas-phase fluidized-bed reactor, and ethene, 1-butylene, 1-hexene, as monomer component, in addition with gas composition circulation gas such as nitrogen, iso-pentane, hydrogen, enter bed and react.The temperature of reactor inlet is 45 DEG C, is gas-liquid mixture when circulation gas passes into bottom bed, and bottom bed, polymerization temperature is 58 DEG C, and bed top polymerization temperature is 88 DEG C.In circulation gas, the dew-point temperature of liquid iso-pentane is between bed bottom temp and upper temp.Liquid mass fraction 50wt% in fluidized-bed.Apparent fluidizing gas velocity is 0.66m/s.Catalyzer is Ziegler-Natta catalyst.Prepare the terpolymer of Ethylene/1-butene/1-hexene under this condition, be elastomerics C.Each concentration of component of concrete circulation gas is in table 3.
Each concentration of component in table 3 circulation gas
| Circulation gas component | Component concentration/mol% |
| 1-hexene | 9.7% |
| 1-butylene | 4.5% |
| Ethene | 21.5% |
| Hydrogen | 2.3% |
| Nitrogen | 52.7% |
| Iso-pentane | 9.3% |
Comparative example 1
Under the condition of continuity that catalyzer exists, in the equipment comprising poly-unit, prepare multipolymer by ethene and 1-butylene copolymerization.Polyreaction is carried out in gas-phase fluidized-bed reactor, and ethene, 1-butylene, as monomer component, in addition with gas composition circulation gas such as nitrogen, iso-pentane, hydrogen, enter bed and react.The temperature of reactor inlet is 60 DEG C, is gas-liquid mixture when circulation gas passes into bottom bed, and bottom bed, polymerization temperature is 70 DEG C, and bed upper temp is 80 DEG C.In circulation gas, the dew-point temperature of liquid iso-pentane is between bed bottom temp and upper temp.Liquid mass fraction 40wt% in fluidized-bed.Apparent fluidizing gas velocity is 0.63m/s.Catalyzer is Ziegler-Natta catalyst.Prepare the copolymer of Ethylene/1-butene under this condition, be elastomerics D.Each concentration of component of concrete circulation gas is in table 4.
Each concentration of component in table 4 circulation gas
| Circulation gas component | Component concentration/mol% |
| 1-butylene | 9.0% |
| Ethene | 25.5% |
| Hydrogen | 2.9% |
| Nitrogen | 52.9% |
| Iso-pentane | 9.7% |
Polymer particle in embodiment 1 ~ 3 and comparative example 1 reactor is by steam treatment removing reaction monomers and volatizable material, then dried.The characteristic of the polymkeric substance that embodiment 1 ~ 3 and comparative example 1 are produced is in table 5.Ethene, 1-butylene, 1-hexene monomers unit and hexene ternary sequence unit content (mol%) in table 5, by carrying out terpolymer
13c nuclear magnetic resonance spectroscopy measures.Wherein hexene ternary sequence unit is
(n=3).
Table 5 rubber elastomer characteristics parameter
As can be seen from Table 5, along with the content of high boiling comonomer 1-hexene rises, in fluidized-bed, the temperature of liquid phase region declines, and causes the temperature difference of liquid phase region and gas phase zone to increase.In liquid phase region, comonomer 1-hexene concentration is high, easily generates 1-hexene Multiphase sequences fragment, obtains the polymkeric substance of high molecular; And in gas phase zone, comonomer 1-hexene concentration is low, 1-hexene not easily insertion polymerization is the polymerization of ethene mostly, obtains low-molecular-weight polymkeric substance.
The special 1-hexene Multiphase sequences fragment structure that described polymerization obtains, the steric hindrance that in this block structure, the existence of butyl side chain makes strand rotate increases, and therefore the kindliness of polymer molecular chain reduces, and molecular chain is rigidity more, and crystallizing power is deteriorated.Meanwhile, the butyl side chain due to 1-hervene copolymer conjunction formation cannot enter lattice and must foreclose, thus the generation of restriction large size platelet.The butyl side-chain structure of 1-hexene Multiphase sequences obviously destroys the regularity and crystallizing power that arrange polyethylene crystal closely, and the fusing point of multipolymer and density are all reduced.The multipolymer of this low-crystalline has good folding and bends and tear strength, and toughness is greatly improved.
Embodiment 4 ~ 6 using the terpolymer of prepared Ethylene/1-butene/1-hexene as elastomers matrix material
Embodiment 4
Using polymkeric substance obtained for embodiment 1 as elastomerics A, add in PP resin, filling a prescription is: PP resin+10% elastomerics A+20% talcum powder+1% auxiliary agent, obtained composite A, wherein in PP resin for 100mol% ratio, the per-cent of each component is molar percentage mol%.
Embodiment 5
Using polymkeric substance obtained for embodiment 2 as elastomerics B, add in PP resin, filling a prescription is: PP resin+10% elastomerics B+20% talcum powder+1% auxiliary agent, obtained matrix material B, wherein in PP resin for 100mol% ratio, the per-cent of each component is molar percentage mol%.
Embodiment 6
Using polymkeric substance obtained for embodiment 3 as elastomerics C, add in PP resin, filling a prescription is: PP resin+10% elastomerics C+20% talcum powder+1% auxiliary agent, obtained matrix material C, wherein in PP resin for 100mol% ratio, the per-cent of each component is molar percentage mol%.
Embodiment 7 using the terpolymer of prepared Ethylene/1-butene/1-hexene and POE jointly as elastomers matrix material
The mixed elastomer that POE and elastomerics B forms is added in PP resin, formula is: PP resin+10% elastomerics (it comprises 6%POE, 4% elastomerics B)+20% talcum powder+1% auxiliary agent, obtained matrix material D, wherein in PP resin for 100mol% ratio, the per-cent of each component is molar percentage mol%.
Comparative example 2 using POE as elastomers matrix material
Added in PP resin by POE elastomerics, filling a prescription is: PP resin+10%POE+20% talcum powder+1% auxiliary agent, obtained composite wood E, wherein in PP resin for 100mol% ratio, the per-cent of each component is molar percentage mol%.
Comparative example 3
Using polymkeric substance obtained for comparative example 1 as elastomerics D, add in PP resin, filling a prescription is: PP resin+10% elastomerics D+20% talcum powder+1% auxiliary agent, obtained matrix material F, wherein in PP resin for 100mol% ratio, the per-cent of each component is molar percentage mol%.
Then above-mentioned matrix material be placed in respectively Bitruder and extrude under the following conditions:
Feeding temperature 100 DEG C;
Melt temperature 130 DEG C;
Press mold temperature 120 DEG C;
Flow rate 12.6kg/h;
Screw speed 250rpm.
Analyze above obtained matrix material, characteristic material data is in table 6.
Table 6 composite characteristics data
Associative list 5 and table 6, can find out the existence due to 1-hexene Multiphase sequences fragment, and cause the toughness of elastomerics A, B, C to improve, be packed in PP resin matrix, the property indices of material all exceedes comparative example.And the elastomerics of this invention is not weaker than the elastomerics POE of existing market use, and POE complex process, cost is high, therefore the present invention effectively can substitute POE, thus increases economic efficiency.
Although with reference to preferred embodiment, invention has been described, without departing from the scope of the invention, various process modification can be carried out to it and equivalent process condition replacement condition wherein can be used.Especially, only otherwise there is actually operating infeasibility, the every technology characteristics mentioned in each embodiment all can combine in any way.The present invention is not limited to specific embodiment disclosed in literary composition, but comprises all technical schemes fallen in the scope of claim.
Claims (12)
1. a terpolymer for Ethylene/1-butene/1-hexene, is characterized in that containing following repeating unit:
Wherein n>=3, this repeating unit molar content in described terpolymer is 0.1% ~ 20%; The weight-average molecular weight M of described terpolymer
wbe 50000 ~ 200000, molecular weight distributing index is 2 ~ 15, by gel permeation chromatography.
2. the terpolymer of Ethylene/1-butene according to claim 1/1-hexene, is characterized in that:
Described repeating unit molar content in described terpolymer is 0.5% ~ 15%, the weight-average molecular weight M of described terpolymer
wbe 80000 ~ 180000, molecular weight distributing index is 2.5 ~ 12.
3. the terpolymer of Ethylene/1-butene according to claim 1/1-hexene, is characterized in that:
In described terpolymer, ethene, 1-butylene and 1-hexene monomers unit mol ratio are (50 ~ 98): (1 ~ 25): (1 ~ 25), preferably (60 ~ 96): (2 ~ 20): (2 ~ 20).
4. the terpolymer of the Ethylene/1-butene according to claim 1 or 3/1-hexene, is characterized in that:
The melt temperature scope of described terpolymer is 100 DEG C ~ 140 DEG C, preferably 110 DEG C ~ 130 DEG C.
5. the terpolymer of the Ethylene/1-butene according to claim 1 or 3/1-hexene, is characterized in that:
The crystallization range of described terpolymer is 90 DEG C ~ 140 DEG C, preferably 100 DEG C ~ 120 DEG C.
6. the terpolymer of the Ethylene/1-butene according to claim 1 or 3/1-hexene, is characterized in that:
The melt flow index of described terpolymer, namely MFR scope is 0.5g/10min ~ 5g/10min, is measured by ISO method 1133.
7. a preparation method for the terpolymer of a kind of Ethylene/1-butene/1-hexene as described in one of claim 1 ~ 6, is characterized in that:
Described preparation method adopts following at least one catalyzer: Ziegler-Natta catalyst, metallocene catalyst, transition-metal catalyst, inorganic chromium catalyzer, organic chromium catalyzer.
8. the preparation method of the terpolymer of Ethylene/1-butene according to claim 7/1-hexene, is characterized in that:
Described catalyzer is Ziegler-Natta catalyst, its by having the titanium compound of at least one titanium-halogen key, Internal electron donors compound, external electron-donor compound, promotor form;
The described titanium compound with at least one titanium-halogen key is selected from least one in following component: the halogenide of titanium or halogenated alcoholate;
Described Internal electron donors compound is selected from least one in following component: ether, ketone, lactone, the compound containing N, P or S atom, mono carboxylic acid esters and dicarboxyl acid esters;
Described external electron-donor compound is the ester of aromatic acid;
Described promotor is selected from organo-aluminium compound, preferred alkyl aluminum compound, more preferably triethyl aluminum.
9. the preparation method of the terpolymer of Ethylene/1-butene according to claim 7/1-hexene, is characterized in that:
Described preparation method is many humidity provinces vapor phase process, the method adopts gas-phase fluidized-bed reactor, in described gas-phase fluidized-bed reactor entrance gas-liquid mixture, liquid mass fraction is greater than 10%, and in fluidized-bed, liquid mass fraction is 20% ~ 70%, preferred 25wt% ~ 60wt%;
Two reaction zones territory is there is in described gas-phase fluidized-bed reactor, the gas-liquid-solid three-phase region of bottom and the gas-particle two-phase region on top, the temperature in described gas-liquid-solid three-phase region is 50 ~ 75 DEG C, the temperature in described gas-particle two-phase region is 75 ~ 110 DEG C, and the temperature head in described gas-liquid-solid three-phase region and described gas-particle two-phase region is at least more than 10 DEG C, in described gas-phase fluidized-bed reactor, apparent fluidizing gas velocity is 0.5 ~ 0.8m/s.
10. the preparation method of the terpolymer of Ethylene/1-butene according to claim 9/1-hexene, is characterized in that:
Described many humidity provinces vapor phase process comprises the following steps:
1) gas-phase fluidized-bed reactor temperature in is set
The fluidized-bed temperature in of gas-phase fluidized-bed reactor is arranged on less than 60 DEG C and lower than the dew-point temperature of entrance gas-liquid mixture at least 10 DEG C;
2) in gas-phase fluidized-bed reactor, cooling medium raw material reaction is passed into;
Under the condition of continuity that catalyzer exists, add the gas and vapor permeation raw material of 1-butylene, 1-hexene, ethene, hydrogen, nitrogen and iso-pentane composition, the terpolymer of Ethylene/1-butene/1-hexene is prepared in reaction; The 1-butylene added and the molar ratio range of ethene are 0.01:1 to 0.8:1, preferred 0.05:1 to 0.5:1, and the 1-hexene added and the molar ratio range of ethene are 0.01:1 to 0.8:1, preferred 0.05:1 to 0.5:1;
Described iso-pentane, 1-butylene, 1-hexene, ethene, hydrogen, nitrogen composition circulation gas, wherein hydrogen and ethylene molar ratio scope are 1:15 to 1:3, iso-pentane accounts for the 5wt% ~ 40wt% of circulation gas total mass, and 1-butylene and the total molar content of 1-hexene account for the 8mol% ~ 50mol% of circulation gas total mole number.
The preparation method of the terpolymer of 11. Ethylene/1-butene according to claim 10/1-hexenes, is characterized in that:
Described step 2) in, under the condition of continuity that catalyzer exists, add liquid iso-pentane in described gas-phase fluidized-bed reactor after, then add the gas and vapor permeation raw material of 1-butylene, 1-hexene, ethene, hydrogen, nitrogen and iso-pentane composition.
12. 1 kinds of matrix materials prepared according to the terpolymer of the Ethylene/1-butene one of claim 1 ~ 6 Suo Shu/1-hexene, is characterized in that being prepared from by following component:
In the terpolymer of described Ethylene/1-butene/1-hexene, PP resin, talcum powder, auxiliary agent, the mol ratio of the terpolymer of described Ethylene/1-butene/1-hexene, PP resin, talcum powder, auxiliary agent is (0.01 ~ 0.5): 1:(0.01 ~ 0.5): (0.001 ~ 0.05).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310481441.3A CN104558348B (en) | 2013-10-15 | 2013-10-15 | Terpolymer of the hexene of the butylene of a kind of ethene/1/1 and preparation method thereof and composite prepared therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310481441.3A CN104558348B (en) | 2013-10-15 | 2013-10-15 | Terpolymer of the hexene of the butylene of a kind of ethene/1/1 and preparation method thereof and composite prepared therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558348A true CN104558348A (en) | 2015-04-29 |
| CN104558348B CN104558348B (en) | 2017-10-17 |
Family
ID=53075493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310481441.3A Active CN104558348B (en) | 2013-10-15 | 2013-10-15 | Terpolymer of the hexene of the butylene of a kind of ethene/1/1 and preparation method thereof and composite prepared therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558348B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632783A (en) * | 2015-10-30 | 2017-05-10 | 中国石油天然气股份有限公司 | Metallocene transparent film resin and preparation method thereof, and thin film |
| CN111087511A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | 1-butene/ethylene/higher α -olefin terpolymer and preparation method and application thereof |
| CN111363102A (en) * | 2020-03-18 | 2020-07-03 | 浙江大学 | Ethylene- α olefin-polyfluorosiloxane ternary graft copolymer and preparation method thereof |
| CN115232239A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Ethylene-butene-octene terpolymer and preparation method and system thereof |
| CN116143958A (en) * | 2023-03-07 | 2023-05-23 | 浙江大学 | Preparation method of polypropylene-based composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6147152A (en) * | 1997-05-26 | 2000-11-14 | Toyota Jidosha Kabushiki Kaisha | Polypropylene resin compositions and interior automotive trim parts |
| WO2008116396A1 (en) * | 2007-03-28 | 2008-10-02 | China Petroleum & Chemical Corporation | Composite catalyst for production of polyethylene |
| US20110237762A1 (en) * | 2010-03-29 | 2011-09-29 | Sumitomo Chemical Company, Limited | Reactor, Process for Producing Prepolymerization Catalyst for Olefin Polymerization, and Process for Producing Olefin Polymer |
| CN103183753A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Method for preparing polymer |
-
2013
- 2013-10-15 CN CN201310481441.3A patent/CN104558348B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6147152A (en) * | 1997-05-26 | 2000-11-14 | Toyota Jidosha Kabushiki Kaisha | Polypropylene resin compositions and interior automotive trim parts |
| WO2008116396A1 (en) * | 2007-03-28 | 2008-10-02 | China Petroleum & Chemical Corporation | Composite catalyst for production of polyethylene |
| US20110237762A1 (en) * | 2010-03-29 | 2011-09-29 | Sumitomo Chemical Company, Limited | Reactor, Process for Producing Prepolymerization Catalyst for Olefin Polymerization, and Process for Producing Olefin Polymer |
| CN103183753A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Method for preparing polymer |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632783A (en) * | 2015-10-30 | 2017-05-10 | 中国石油天然气股份有限公司 | Metallocene transparent film resin and preparation method thereof, and thin film |
| CN106632783B (en) * | 2015-10-30 | 2019-02-15 | 中国石油天然气股份有限公司 | Metallocene transparent membrane resin and preparation method thereof and film |
| CN111087511A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | 1-butene/ethylene/higher α -olefin terpolymer and preparation method and application thereof |
| CN111363102A (en) * | 2020-03-18 | 2020-07-03 | 浙江大学 | Ethylene- α olefin-polyfluorosiloxane ternary graft copolymer and preparation method thereof |
| CN111363102B (en) * | 2020-03-18 | 2021-06-01 | 浙江大学 | Ethylene-alpha olefin-polyfluorosiloxane ternary graft copolymer and preparation method thereof |
| CN115232239A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Ethylene-butene-octene terpolymer and preparation method and system thereof |
| CN115232239B (en) * | 2021-04-22 | 2024-01-19 | 中国石油化工股份有限公司 | Ethylene-butene-octene terpolymer and preparation method and system thereof |
| CN116143958A (en) * | 2023-03-07 | 2023-05-23 | 浙江大学 | Preparation method of polypropylene-based composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558348B (en) | 2017-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103890081B (en) | For the method preparing heterophasic propylene copolymer | |
| CN102449056B (en) | Polymer composition for crosslinked articles | |
| KR101667906B1 (en) | Polyethylene composition for blow molding having high stress cracking resistance | |
| CN102816271B (en) | High-melt-strength propylene/ethylene/butene copolymer and preparation method thereof | |
| CN102816269B (en) | High-melt-strength propylene/ethylene copolymer and preparation method thereof | |
| CN104558348B (en) | Terpolymer of the hexene of the butylene of a kind of ethene/1/1 and preparation method thereof and composite prepared therefrom | |
| CN102361927A (en) | Polyolefin masterbatch and composition suitable for injection molding | |
| CA2629576A1 (en) | Closures for bottles | |
| KR102008590B1 (en) | Polyethylene composition having high mechanical properties | |
| CN102884093A (en) | Propylene homopolymer having high melt strength and preparation method thereof | |
| CN103748163A (en) | Unoriented film | |
| BRPI0716062A2 (en) | improved clear polypropylene composition | |
| CA2478513A1 (en) | Polyolefin masterbatch for preparing impact-resistant polyolefin articles | |
| CN105377977B (en) | The polypropene composition with improved impact resistance for tubing purposes | |
| CN102816270B (en) | High-melt-strength propylene/butene copolymer and preparation method thereof | |
| CN105283505A (en) | Propylene random copolymer composition for pipe applications | |
| CN105264007A (en) | Multimodal polypropylene composition for pipe applications | |
| AU2004262683A1 (en) | Polyolefin composition having a high balance of stiffness and impact strength | |
| US7816478B2 (en) | Polyethylene thick film and process for preparing polyethylene | |
| WO2014105292A1 (en) | A composition, articles made therefrom, and method of making the articles | |
| KR20150143523A (en) | Multimodal polypropylene composition for pipe applications | |
| CN104736625B (en) | Blend polymer and by its product obtained | |
| WO2013096308A2 (en) | Methods for improving multimodal polyethylene and films produced therefrom | |
| EP3877464B1 (en) | Polyolefin composition with improved impact and whitening resistance | |
| CN102575074B (en) | Polyolefinic compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |