CN104558348B - Terpolymer of the hexene of the butylene of a kind of ethene/1/1 and preparation method thereof and composite prepared therefrom - Google Patents
Terpolymer of the hexene of the butylene of a kind of ethene/1/1 and preparation method thereof and composite prepared therefrom Download PDFInfo
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Abstract
The invention discloses hexene terpolymer of the butylene of a kind of ethene/1/1 and preparation method thereof, and disclose the composite that the terpolymer is prepared as elastomer, and the composite purposes.A kind of terpolymer of the hexene of the butylene of ethene/1 of the present invention/1, its weight average molecular weight MwFor 50000~200000, molecular weight distributing index is 2~15, is determined by gel permeation chromatography.The preparation method of the terpolymer is mainly multi-temperature area vapor phase method.Composite prepared by the terpolymer of the present invention, with good toughening effect, can be widely used in terms of tubing, sheet material, film, fiber.The terpolymer of the present invention contains following repeat unit：（n≥3）, repeat unit molar content in the terpolymer is 0.1%~20%.
Description
Technical field
The present invention relates to a kind of copolymer and preparation method thereof, the composite for further relating to and being prepared by the copolymer, tool
For body, the present invention relates to a kind of Ethylene/1-butene/1- hexene terpolymers and preparation method thereof, and it is related to the ternary
The composite that copolymer is prepared as elastomer.
Background technology
It is well known that olefin polymer is one of wide variety of material in every field, it is rigid, tough that it has
Property, it is Lightness be that many materials are not replaceable, it is the target constantly pursued to improve its physical property and processing characteristics.
Polyethylene is a kind of most widely used olefin polymer.At present, the technique of production polyethylene has a lot, including
LDPE, LLDPE and HDPE etc..In terms of technology development, high-pressure process production LDPE be polyvinyl resin production in technology most into
Ripe method, autoclave method and tubular process technology are ripe, and both current production Technologies are simultaneously deposited.Developed country is general
All over using tubular process production technology.In addition, polymerization system generally triggers using low temperature high activity catalyst in external each company, it can drop
Low reaction temperatures and pressure.High-pressure process production LDPE will develop to maximization, tubular type direction.Low-pressure process produce HDPE and
LLDPE, main to use titanium system and chromium-based catalysts, Europe and Japan uses Ziegler-Natta catalyst, and adopts more in the U.S.
Use chromium-based catalysts.The polyethylene production technology kind more than ten mainly applied in the world at present, including company of Basel vapor phase method
Spherilene techniques, BP companies vapor phase method Innovene techniques, Exxon Mobil Corporation's tubular type and still reaction technique, three wells
Chemical company's low pressure slurry method CX techniques, Basel's polyolefins company Hostalen techniques etc..
Due to the development of technique, colourful polyethylene product is expedited the emergence of out.Mainly include low density polyethylene (LDPE), linear low
Density polyethylene, medium density polyethylene, bimodal resin, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, modified poly ethylene
（CPE, crosslinked polyethylene）, ethylene copolymer（Ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene co-polymers,
Copolymer, the ethene-beta-unsaturated esters copolymer of ethene-other alkene）.At present, during ethylene copolymer is many polyethylene products
An application prospect very wide class product.
Ethylene copolymer refers in production high density polyethylene (HDPE)（HDPE）Or linear low density polyethylene (LLDPE)（LLDPE）Process
In, the product of excellent properties can be obtained by adding unsaturated olefin comonomer of the carbon number more than 3 and ethylene copolymer.
Current comonomer type mainly has 3 kinds：C4（1- butylene）、C6（1- alkene）And C8（1- octenes）.Offshore company's production development
Polyethylene new product about 94.0% is using 1- hexenes as comonomer, and butene product only accounts for 4.0% or so.With 1- hexenes
The LLDPE and HDPE resin produced for comonomer, has more preferable tensile strength, rheological characteristic, resistance to compared with 1- butene resins
It is quick and cracking behavior, impact resistance, environmental stress cracking resistance reach more than 5000 hours at a slow speed.The polyethylene new product is special
It is not suitable for production packaging film and agricultural mulch films.1- hexenes are being continuously increased as the demand of comonomer, and it is developed
Utilization prospects are very wide.
Publication No. EP38119 European patent is related to a kind of terpolymer, including ethene and alpha-olefin, and the ternary is total to
Polymers is conducive to manufacturing film.Publication No. WO2006/002778 world patent is related to a kind of including propylene/ethylene and α-alkene
The pipe-line system of the terpolymer of hydrocarbon, obtains the polymer with improved properties available for film.Publication No.
CN1384844 Chinese patent is related to a kind of ethene and C3~C12The copolymer of alpha-olefin.Its molar mass distribution Mw/Mn<10,
Its density is 0.85g/cm3To 0.95g/cm3, co-monomer content 1 to 40wt% comonomers and molal weight MnIt is more than
The breadth index of the composition distribution of 150000g/mol and comonomer is more than 70%.The polymer can be used for fiber, molding
Product, paper tinsel or polymeric blends.Publication No. CN101903424A Chinese patent is related to the copolymerization of a kind of propylene and 1- hexenes
Thing, wherein the 5~9wt% of copolymer be derived from 1- hexenes repeat unit, melting temperature be 125 DEG C~140 DEG C, melt flow
Dynamic speed（ASTMD1238,230 DEG C/2.16kg）For 0.1g/10min~3g/10min.Copolymer within this range can be by
For producing the blown film with good mechanics and optical property.
For ethylene copolymer of the 1- hexenes as comonomer, foreign countries, which largely produce and obtained, widely should
With will further be developed from now on.However, China this direction development degree but far away from foreign countries.China
Most of HDPE and LLDPE process units is the technology of 70~eighties of 20th century of Introduced From Abroad, and product grade is less, draws later
Although there is the 1- hervene copolymer trades mark in the device entered, the country lacks 1- hexene resources, most of only to be tested in driving examination at initial stage
Produced the 1- hervene copolymer trades mark during receipts as a trial, and actual production is generally l- butylene copolymers.
In summary, accelerate the research, development and production of hervene copolymer polyethylene product, especially develop such as 1- hexenes
The polymeric articles of the copolymerization trade mark are particularly significant.
The content of the invention
For above mentioned problem of the prior art, the invention provides a kind of Ethylene/1-butene/1- hexene terpolymers
And preparation method thereof, and there is provided the composite that the terpolymer is prepared as elastomer, the terpolymer is made
It is added to for favorable elasticity body in polymeric matrix and is used for improving composite performance, prepared composite is adapted to use
Make tubing, sheet material, film and fiber etc..
The terpolymer of a kind of Ethylene/1-butene/1- hexenes, it is characterised in that contain following repeat unit：
Wherein n >=3, repeat unit molar content in the terpolymer is 0.1%~20%.
The weight average molecular weight M of the terpolymerwFor 50000~200000, molecular weight distributing index is 2~15, by
Gel permeation chromatography is determined.
Repeat unit molar content in the terpolymer is preferably 0.5%~15%, the terpolymer
Weight average molecular weight MwPreferably 80000~180000, molecular weight distributing index is preferably 2.5~12.
In the terpolymer of the Ethylene/1-butene/1- hexenes, ethene, 1- butylene and 1- hexene monomers units mole
Than for (50~98):(1~25):(1~25), preferably (60~96):(2~20):(2~20).
The melt temperature scope of the terpolymer is 100 DEG C to 140 DEG C, preferably 110 DEG C to 130 DEG C.
The crystallization range of the terpolymer is 90 DEG C to 140 DEG C, preferably 100 DEG C to 120 DEG C.
The melt flow index of the terpolymer, i.e. MFR scopes are 0.5g/10min to 5g/10min, its basis
ISO method 1133 is determined.
The polymerisation for preparing the terpolymer of the Ethylene/1-butene/1- hexenes is general in 40 DEG C~120 DEG C temperature
It is lower to carry out.In general vapor phase method polyolefin fluidized-bed reactor, even under the conditions of condensation mode, bed reaction temperature is also
Homogeneous, it is substantially not present thermograde along height of bed direction.The structure and performance of the product so obtained are relatively common.
And the product of the present invention is butylene, the hexene contained by increasing in circulating air on the basis of such reactor
Co-monomer content and high boiling inertia hydrocarbon content（Cooling medium）Or the temperature of reduction circulating air（Less than 60 DEG C）, to increase
Condensed fluid content in circulating air（At least above 10wt%）, when so by reactor bottom, be able to maintain that bottom be in compared with
Low temperature simultaneously contains more condensed fluid simultaneously, is that polymerisation manufactures a low temperature（50 DEG C~75 DEG C）, gas-liquid-solid three-phase
Reaction condition.The proportioning of comonomer/ethylene can be 0.01 in this region:1 to 0.8:Change in the range of 1.
And bed top is still a high temperature（75 DEG C~110 DEG C）, gas-particle two-phase traditional conversion zone.High copolymerization
The reacting gas proportioning of monomer/ethene, low temperature, the presence of the reaction environment of gas-liquid-solid three-phase are advantageous to 1- hexenes polynary
The formation of sequence fragment, so as to realize the production of the terpolymer of this patent Ethylene/1-butene/1- hexenes.
Specifically, the preparation method of the terpolymer of the Ethylene/1-butene/1- hexenes is multi-temperature area gas phase
Method, the preparation method is multi-temperature area vapor phase method, and this method uses gas-phase fluidized-bed reactor, the gas-phase fluidized-bed reaction
Liquid mass fraction is more than 10% in device entrance gas-liquid mixture, and liquid mass fraction is 20%~70% in fluid bed, preferably
25wt%~60wt%；
There is two reaction zones domain in the gas-phase fluidized-bed reactor, the gas-liquid-solid three-phase region of bottom and top
Gas-particle two-phase region, the temperature in the gas-liquid-solid three-phase region is 50~75 DEG C, the temperature in the gas-particle two-phase region for 75~
110 DEG C, and the gas-liquid-solid three-phase region and the gas-particle two-phase region temperature difference at least more than 10 DEG C, the gas phase
Apparent fluidizing gas velocity is 0.5~0.8m/s in fluidized-bed reactor.
Multi-temperature area vapor phase method comprises the following steps：
1）Gas-phase fluidized-bed reactor inlet temperature is set
The fluid bed inlet temperature of gas-phase fluidized-bed reactor is arranged on less than 60 DEG C and than entrance gas-liquid mixture
Dew-point temperature is low at least 10 DEG C；
2）The reaction of cooling medium raw material is passed through into gas-phase fluidized-bed reactor
Under the condition of continuity that catalyst is present, 1- butylene, 1- hexenes, ethene, hydrogen, nitrogen and isopentane composition are added
Gas mixing raw material, reaction prepares the terpolymers of Ethylene/1-butene/1- hexenes；The 1- butylene and second added
The molar ratio range of alkene is 0.01:1 to 0.8:1, preferably 0.05:1 to 0.5:1, the 1- hexenes and the mol ratio of ethene added
Scope is 0.01:1 to 0.8:1, preferably 0.05:1 to 0.5:1；
The present processes can add liquid refrigerant isopentane, Yi Mianzao in advance in the case of more than content liquid
Into hydrops；In the case where content liquid is few, liquid refrigerant can not also be first added, gas isopentane is passed through, utilizes condensation
Form liquid.So, the step 2）In, can be first to described gas-phase fluidized-bed anti-under the condition of continuity that catalyst is present
Answer in device and add after liquid isopentane, add the gas of 1- butylene, 1- hexenes, ethene, hydrogen, nitrogen and isopentane composition
Mixture material.
When admixture of gas is passed through bed bottom, because inlet temperature is low, the gas liquefaction such as isopentane.Admixture of gas becomes
For gas-liquid mixture.
The isopentane, 1- butylene, 1- hexenes, ethene, hydrogen, wherein nitrogen composition circulating air, hydrogen and ethylene molar
It is 1 than scope:15 to 1:3, isopentane accounts for 5wt%~40wt% of circulating air gross mass, 1- butylene and 1- hexene total moles contents
Account for 8mol%~50mol% of circulating air total mole number.
The preparation method of the terpolymer of Ethylene/1-butene of the present invention/1- hexenes, is not limited only to above-described
Multi-temperature area vapor phase method, for butylene, hexene as reaction medium solution polymerization method or slurry polymerization method energy
Product of the present invention is obtained, the protection domain of this patent is fallen within.
In preparation method of the present invention, polymerisation can be completed under the conditions of multiple catalysts, the preparation method use with
Lower at least one catalyst：Ziegler-Natta catalyst, metallocene catalyst, transition-metal catalyst, inorganic chromium catalysis
Agent, organic chrome catalysts.
It is preferred that, the catalyst is Ziegler-Natta catalyst, and it is closed by the titanizing with least one titanium-halogen key
Thing, Internal electron donors compound, external electron-donor compound, co-catalyst composition；
The titanium compound with least one titanium-halogen key is selected from least one of following components：The halide of titanium or
Halogenated alcoholate；
The Internal electron donors compound is selected from least one of following components：Ether, ketone, lactone is former containing N, P or S
The compound of son, mono carboxylic acid esters and dicarboxyl acid esters；
The external electron-donor compound is the ester of aromatic acid；
The co-catalyst is selected from organo-aluminum compound, preferably alkyl aluminum compound, more preferably triethyl aluminum.
Particularly, other combinations of many Above-mentioned catalytic agent components can also be used for preparing the ethylene copolymer of the present invention.And
And, as previously described, the catalyst of this polymerisation is also not limited to Ziegler-Natta catalyst.
Terpolymer of the present invention has butyl side in special 1- hexene Multiphase sequences structures, this block structure
The presence of chain causes the steric hindrance of single-stranded rotation to increase, therefore the compliance reduction of polymer molecular chain, and strand is more rigid, knot
It is brilliant less able.It cannot be introduced into lattice simultaneously as 1- hervene copolymers close the butyl side chain to be formed and must foreclose, so that
Limit the generation of large scale platelet.It is brilliant that the butyl side-chain structure of 1- hexene Multiphase sequences substantially destroys the close polyethylene of arrangement
The regularity and crystallizing power of body so that the fusing point and density of copolymer are all reduced.The copolymer of this low-crystalline has good
Good folding is bent and tear resistance, and toughness is greatly improved.
Therefore, present invention also offers prepared by a kind of terpolymer of described Ethylene/1-butene/1- hexenes being combined
Material.
The composite is prepared from the following components：
Terpolymer, PP resins, talcum powder, the auxiliary agent of the Ethylene/1-butene/1- hexenes, wherein the ethene/1-
The terpolymer of butylene/1- hexenes, PP resins, talcum powder, the mol ratio of auxiliary agent are (0.01~0.5):1:(0.01~
0.5):(0.001~0.05).
As described above, the terpolymer of the present invention is due to special 1- hexene Multiphase sequences structures so that it has
There is excellent physical property, can be added to as elastomer in polymeric matrix, obtain good toughening effect, while improving
The processing characteristics of material is taken into account while materials'use performance.By the terpolymer of Ethylene/1-butene/1- hexenes of the present invention
The composite of preparation, because it has good toughening effect, the composite of the invention can be used for tubing, plate
In material, film, fiber.
Brief description of the drawings
Fig. 1 is terpolymer prepared by embodiment 1, i.e. the GPC figures of elastomer A.
Fig. 2 is terpolymer prepared by embodiment 1, i.e. the DSC figures of elastomer A.
Fig. 3 is terpolymer prepared by embodiment 1, i.e. elastomer A's13C nuclear magnetic resonance figuress.
Embodiment
The present invention is more specifically described in detail with reference to specific embodiment, but embodiments of the present invention are not limited
In this, for the technological parameter not indicated especially, routine techniques progress can refer to.
Characterization method：
Ethene, 1- butylene, 1- hexenes and its derivative content：By being carried out to terpolymer13C nuclear magnetic resonance spectroscopies are surveyed
Fixed, content of monomer specifically described herein refers to the content for accounting for the whole ter-polymers of monomeric unit.
According to differential scanning calorimetry（DSC）Determine melting temperature and crystallization temperature.Specific method is：Weigh sample 6mg
Left and right, 220 DEG C or so are heated to 20 DEG C/min speed, and keep 2min in nitrogen stream, then by it with 20 DEG C/min
Speed be cooled to 40 DEG C or so, at this temperature keep 2min with crystallized sample.Then by the sample with 20 DEG C/min liter
Warm speed is warming up to 220 DEG C and melted again.Record melting scanning, obtains thermal analysis curue, and thus reads melting temperature and crystallization
Temperature.
Weight average molecular weight（Mw）：Determined by gpc analysis.
Molecular weight distributing index（Polydispersity index PI）：By using the RMS-800 models by Rheometrics companies
Plate rheometer is determined, and is operated in the case where vibration frequency increases to 100rad/s from 0.1rad/s.By intersection modulus（crossover
modulus）, PI can be derived by below equation：
PI=105/Gc
Wherein, Gc is intersects modulus, and it is the value determined as G '=G ' '（Represented with Pa）, wherein G ' is storage modulus,
G ' ' is loss modulus.
Melt flow index is determined according to ISO method 1133.
The preparation of the terpolymer of embodiment 1~3
Embodiment 1
Catalyst exist the condition of continuity under, in the equipment including polyplant, by ethene, 1- butylene, 1- oneself
Alkene prepares copolymer.Polymerisation is carried out in gas-phase fluidized-bed reactor, ethene, 1- butylene, 1- hexenes as monomer component,
In addition with the gas such as nitrogen, isopentane, hydrogen composition circulating air, reacted into bed.The temperature of reactor inlet is 58
DEG C, circulating air is gas-liquid mixture when being passed through bed bottom, and bed bottom polymerization temperature is 75 DEG C, and bed top polymerization temperature
For 90 DEG C.Liquid isopentane in circulating air（It is used as condensing agent）Dew-point temperature between bed bottom temp and upper temp it
Between.Liquid mass fraction 25wt% in fluid bed.Apparent fluidizing gas velocity is 0.65m/s.Catalyst is that Ziegler-Natta is urged
Agent.The terpolymer of Ethylene/1-butene/1- hexenes, as elastomer A are prepared under the conditions of this.Specific circulating air
Each component concentration be shown in Table 1.
Each component concentration in the circulating air of table 1
| Circulating air component | Constituent content/mol% |
| 1- hexenes | 5.4% |
| 1- butylene | 4.2% |
| Ethene | 26.0% |
| Hydrogen | 3.6% |
| Nitrogen | 55.6% |
| Isopentane | 5.2% |
Embodiment 2
Catalyst exist the condition of continuity under, in the equipment including polyplant, by ethene, 1- butylene, 1- oneself
Alkene prepares copolymer.Polymerisation is carried out in gas-phase fluidized-bed reactor, ethene, 1- butylene, 1- hexenes as monomer component,
In addition with the gas such as nitrogen, isopentane, hydrogen composition circulating air, reacted into bed.The temperature of reactor inlet is 55
DEG C, circulating air is gas-liquid mixture when being passed through bed bottom, and bed bottom polymerization temperature is 66 DEG C, and bed top polymerization temperature
For 86 DEG C.The dew-point temperature of liquid isopentane is between bed bottom temp and upper temp in circulating air.In fluid bed
Liquid mass fraction 35wt%.Apparent fluidizing gas velocity is 0.65m/s.Catalyst is Ziegler-Natta catalyst.Under the conditions of being somebody's turn to do
Prepare the terpolymer of Ethylene/1-butene/1- hexenes, as elastomer B.The each component concentration of specific circulating air is shown in
Table 2.
Each component concentration in the circulating air of table 2
| Circulating air component | Constituent content/mol% |
| 1- hexenes | 7.8% |
| 1- butylene | 4.4% |
| Ethene | 24.1% |
| Hydrogen | 3.1% |
| Nitrogen | 53.0% |
| Isopentane | 7.6% |
Embodiment 3
Catalyst exist the condition of continuity under, in the equipment including polyplant, by ethene, 1- butylene, 1- oneself
Alkene prepares copolymer.Polymerisation is carried out in gas-phase fluidized-bed reactor, ethene, 1- butylene, 1- hexenes as monomer component,
In addition with the gas such as nitrogen, isopentane, hydrogen composition circulating air, reacted into bed.The temperature of reactor inlet is 45
DEG C, circulating air is gas-liquid mixture when being passed through bed bottom, and bed bottom polymerization temperature is 58 DEG C, and bed top polymerization temperature
For 88 DEG C.The dew-point temperature of liquid isopentane is between bed bottom temp and upper temp in circulating air.In fluid bed
Liquid mass fraction 50wt%.Apparent fluidizing gas velocity is 0.66m/s.Catalyst is Ziegler-Natta catalyst.Under the conditions of being somebody's turn to do
Prepare the terpolymer of Ethylene/1-butene/1- hexenes, as elastomer C.The each component concentration of specific circulating air is shown in
Table 3.
Each component concentration in the circulating air of table 3
| Circulating air component | Constituent content/mol% |
| 1- hexenes | 9.7% |
| 1- butylene | 4.5% |
| Ethene | 21.5% |
| Hydrogen | 2.3% |
| Nitrogen | 52.7% |
| Isopentane | 9.3% |
Comparative example 1
Under the condition of continuity that catalyst is present, in the equipment including polyplant, pass through ethene and 1- butenes
Conjunction prepares copolymer.Polymerisation is carried out in gas-phase fluidized-bed reactor, ethene, 1- butylene as monomer component, in addition with
The gases such as nitrogen, isopentane, hydrogen constitute circulating air, are reacted into bed.The temperature of reactor inlet is 60 DEG C, circulation
Gas is gas-liquid mixture when being passed through bed bottom, and bed bottom polymerization temperature is 70 DEG C, and bed upper temp is 80 DEG C.Circulation
The dew-point temperature of liquid isopentane is between bed bottom temp and upper temp in gas.Liquid mass fraction in fluid bed
40wt%.Apparent fluidizing gas velocity is 0.63m/s.Catalyst is Ziegler-Natta catalyst.Should under the conditions of prepare ethene/
The bipolymer of 1- butylene, as elastomer D.The each component concentration of specific circulating air is shown in Table 4.
Each component concentration in the circulating air of table 4
| Circulating air component | Constituent content/mol% |
| 1- butylene | 9.0% |
| Ethene | 25.5% |
| Hydrogen | 2.9% |
| Nitrogen | 52.9% |
| Isopentane | 9.7% |
Polymer particle in embodiment 1~3 and the reactor of comparative example 1 removes reaction monomers by steam treatment and can
Volatile substance, is then dried.The characteristic for the polymer that embodiment 1~3 and comparative example 1 are produced is shown in Table 5.Ethene in table 5,
1- butylene, 1- hexene monomers unit and hexene ternary sequence unit content（mol%）, by being carried out to terpolymer13C nuclear-magnetisms
Resonance analyzing is determined.Wherein hexene ternary sequence unit is（n=3）.
The rubber elastomer characteristics parameter of table 5
As can be seen from Table 5, rise with the content of high boiling comonomer 1- hexenes, the temperature of liquid phase region in fluid bed
Degree declines, and causes the temperature difference of liquid phase region and gas phase zone to increase.In liquid phase region, comonomer 1- hexene concentrations are high, easily generate 1-
Hexene Multiphase sequences fragment, obtains the polymer of HMW；And in gas phase zone, comonomer 1- hexene concentrations are low, 1- hexenes
Insertion polymerization is difficult, is the polymerization of ethene mostly, obtains the polymer of low molecule amount.
Butyl side chain deposits in the special 1- hexene Multiphase sequences fragment structures that the polymerization is obtained, this block structure
The steric hindrance of single-stranded rotation is increased, therefore the compliance of polymer molecular chain is reduced, strand is more rigid, crystallizing power
It is deteriorated.It cannot be introduced into lattice simultaneously as 1- hervene copolymers close the butyl side chain to be formed and must foreclose, so as to limit big
The generation of size platelet.The butyl side-chain structure of 1- hexene Multiphase sequences substantially destroys the rule for arranging close polyethylene crystal
Whole property and crystallizing power so that the fusing point and density of copolymer are all reduced.The copolymer of this low-crystalline has well resistance to
Folding is bent and tear resistance, and toughness is greatly improved.
Embodiment 4~6 prepares the terpolymer of prepared Ethylene/1-butene/1- hexenes as elastomer compound
Material
Embodiment 4
Using polymer made from embodiment 1 as elastomer A, it is added in PP resins, is formulated and is：The elasticity of PP resins+10%
The auxiliary agent of body A+20% talcum powder+1%, is made composite A, wherein ratio is counted by 100mol% of PP resins, the percentage of each component is
Molar percentage mol%.
Embodiment 5
Using polymer made from embodiment 2 as elastomer B, it is added in PP resins, is formulated and is：The elasticity of PP resins+10%
The auxiliary agent of body B+20% talcum powder+1%, is made composite B, wherein ratio is counted by 100mol% of PP resins, the percentage of each component is
Molar percentage mol%.
Embodiment 6
Using polymer made from embodiment 3 as elastomer C, it is added in PP resins, is formulated and is：The elasticity of PP resins+10%
The auxiliary agent of body C+20% talcum powder+1%, is made composite C, wherein ratio is counted by 100mol% of PP resins, the percentage of each component is
Molar percentage mol%.
Embodiment 7 is by the terpolymer of prepared Ethylene/1-butene/1- hexenes and POE collectively as elastic system
Standby composite
POE and elastomer the B mixed elastomer constituted are added in PP resins, is formulated and is：The elastomer of PP resins+10%
（It includes 6%POE, 4% elastomer B）The auxiliary agent of+20% talcum powder+1%, is made composite D, wherein using PP resins as 100mol%
Than meter, the percentage of each component is molar percentage mol%.
POE is prepared composite by comparative example 2
POE elastomers are added in PP resins, is formulated and is：The auxiliary agent of PP resin+10%POE+20% talcum powder+1%, is made
Composite wood E, wherein ratio is counted by 100mol% of PP resins, the percentage of each component is molar percentage mol%.
Comparative example 3
Using polymer made from comparative example 1 as elastomer D, it is added in PP resins, is formulated and is：The elasticity of PP resins+10%
The auxiliary agent of body D+20% talcum powder+1%, is made composite F, wherein ratio is counted by 100mol% of PP resins, the percentage of each component is
Molar percentage mol%.
Then above-mentioned composite is respectively placed in Bitruder and extruded under the following conditions：
100 DEG C of feeding temperature；
130 DEG C of melting temperature；
120 DEG C of press mold temperature；
Flow rate 12.6kg/h；
Screw speed 250rpm.
Composite produced above is analyzed, characteristic material data is shown in Table 6.
The composite characteristics data of table 6
With reference to table 5 and table 6, it can be seen that due to the presence of 1- hexene Multiphase sequences fragments, cause elastomer A, B, C's tough
Property improve, be filled with PP resin matrixes, the property indices of material are above comparative example.Moreover, the bullet of the invention
Property body be not weaker than the elastomer POE that existing market is used, and POE complex process, cost is high, therefore can effectively replace of the present invention
POE, so as to increase economic efficiency.
Although by reference to preferred embodiment, invention has been described, is not departing from the situation of the scope of the present invention
Under, various process modifications can be carried out to it and condition therein can be replaced with equivalent process condition.Especially, as long as not
There is practical operation infeasibility, the every technology characteristics being previously mentioned in each embodiment can combine in any way.
The invention is not limited in specific embodiment disclosed herein, but all technical sides including falling within the scope of the appended claims
Case.
Claims (16)
1. the terpolymer of a kind of Ethylene/1-butene/1- hexenes, it is characterised in that contain following repeat unit：
Wherein n >=3, repeat unit molar content in the terpolymer is 0.1%~20%；The terpolymer
Weight average molecular weight MwFor 50000~200000, molecular weight distributing index is 2~15, is determined by gel permeation chromatography；It is described
The scope of the melt flow index of terpolymer, i.e. MFR is 0.941g/10min~5g/10min, is surveyed by ISO method 1133
It is fixed；
The preparation method of the terpolymer is multi-temperature area vapor phase method, and this method uses gas-phase fluidized-bed reactor, and it is wrapped
Include following steps：
1) gas-phase fluidized-bed reactor inlet temperature is set
The fluid bed inlet temperature of gas-phase fluidized-bed reactor is arranged on less than 60 DEG C and than the dew point of entrance gas-liquid mixture
Temperature is low at least 10 DEG C；
2) reaction of cooling medium raw material is passed through into gas-phase fluidized-bed reactor
Under the condition of continuity that catalyst is present, the gas of 1- butylene, 1- hexenes, ethene, hydrogen, nitrogen and isopentane composition is added
The terpolymer of Ethylene/1-butene/1- hexenes is prepared in body mixture material, reaction；The 1- butylene that is added and ethene
Molar ratio range is (4.2/26):1 to 0.8:1, the 1- hexenes and the molar ratio range of ethene added is (5.4/26):1 to
0.8:1；
The isopentane, 1- butylene, 1- hexenes, ethene, hydrogen, wherein nitrogen composition circulating air, hydrogen and ethylene molar ratio model
Enclose for 1:15 to 1:3, isopentane accounts for 5wt%~40wt% of circulating air gross mass, and 1- butylene is accounted for 1- hexene total moles contents
8mol%~50mol% of circulating air total mole number.
2. the terpolymer of Ethylene/1-butene according to claim 1/1- hexenes, it is characterised in that：
Repeat unit molar content in the terpolymer is 0.5%~15%, and the weight of the terpolymer is equal
Molecular weight MwFor 80000~180000, molecular weight distributing index is 2.5~12.
3. the terpolymer of Ethylene/1-butene according to claim 1/1- hexenes, it is characterised in that：
In described terpolymer, ethene, 1- butylene and 1- hexene monomers units mol ratio are (50~98):(1~25):
(1~25).
4. the terpolymer of Ethylene/1-butene according to claim 3/1- hexenes, it is characterised in that：
In described terpolymer, ethene, 1- butylene and 1- hexene monomers units mol ratio are (60~96):(2~20):
(2~20).
5. the terpolymer of Ethylene/1-butene/1- hexenes according to claim 1 or 3, it is characterised in that：
The melt temperature scope of the terpolymer is 100 DEG C~140 DEG C.
6. the terpolymer of Ethylene/1-butene according to claim 5/1- hexenes, it is characterised in that：
The melt temperature scope of the terpolymer is 110 DEG C~130 DEG C.
7. the terpolymer of Ethylene/1-butene/1- hexenes according to claim 1 or 3, it is characterised in that：
The crystallization range of the terpolymer is 90 DEG C~140 DEG C.
8. the terpolymer of Ethylene/1-butene according to claim 7/1- hexenes, it is characterised in that：
The crystallization range of the terpolymer is 100 DEG C~120 DEG C.
9. a kind of a kind of preparation side of the terpolymer of Ethylene/1-butene/1- hexenes as described in one of claim 1~8
Method, it is characterised in that：
The preparation method uses following at least one catalyst：It is Ziegler-Natta catalyst, metallocene catalyst, inorganic
Chrome catalysts, organic chrome catalysts.
10. the preparation method of the terpolymer of Ethylene/1-butene according to claim 9/1- hexenes, its feature exists
In：
The catalyst is Ziegler-Natta catalyst, and it is by the titanium compound with least one titanium-halogen key, internal electricity
Sub- compound donator, external electron-donor compound, co-catalyst composition；
The titanium compound with least one titanium-halogen key is selected from least one of following components：The halide or halo of titanium
Alcoholates；
The Internal electron donors compound is selected from least one of following components：Ether, ketone, lactone, containing N, P or S atom
Compound, mono carboxylic acid esters and dicarboxyl acid esters；
The external electron-donor compound is the ester of aromatic acid；
The co-catalyst is selected from organo-aluminum compound.
11. the preparation method of the terpolymer of Ethylene/1-butene according to claim 10/1- hexenes, its feature exists
In：
The co-catalyst is selected from alkyl aluminum compound.
12. the preparation method of the terpolymer of Ethylene/1-butene according to claim 11/1- hexenes, its feature exists
In：
The co-catalyst is triethyl aluminum.
13. the preparation method of the terpolymer of Ethylene/1-butene according to claim 9/1- hexenes, its feature exists
In：
The preparation method is multi-temperature area vapor phase method, and this method uses gas-phase fluidized-bed reactor, described gas-phase fluidized-bed anti-
Liquid mass fraction is answered in device entrance gas-liquid mixture to be more than in 10%, fluid bed liquid mass fraction 20%~70%；
There is two reaction zones domain, the gas-liquid-solid three-phase region of bottom and the gas-solid on top in the gas-phase fluidized-bed reactor
Two phase region, the temperature in the gas-liquid-solid three-phase region is 50~75 DEG C, and the temperature in the gas-particle two-phase region is 75~110
DEG C, and the gas-liquid-solid three-phase region and the gas-particle two-phase region temperature difference at least more than 10 DEG C, the gas phase stream
Apparent fluidizing gas velocity is 0.5~0.8m/s in fluidized bed reactor.
14. the preparation method of the terpolymer of Ethylene/1-butene according to claim 13/1- hexenes, its feature exists
In：
Liquid mass fraction is in 25wt%~60wt% in the fluid bed.
15. the preparation method of the terpolymer of Ethylene/1-butene according to claim 13/1- hexenes, its feature exists
In：
Multi-temperature area vapor phase method comprises the following steps：
1) gas-phase fluidized-bed reactor inlet temperature is set
The fluid bed inlet temperature of gas-phase fluidized-bed reactor is arranged on less than 60 DEG C and than the dew point of entrance gas-liquid mixture
Temperature is low at least 10 DEG C；
2) reaction of cooling medium raw material is passed through into gas-phase fluidized-bed reactor；
Under the condition of continuity that catalyst is present, the gas of 1- butylene, 1- hexenes, ethene, hydrogen, nitrogen and isopentane composition is added
The terpolymer of Ethylene/1-butene/1- hexenes is prepared in body mixture material, reaction；The 1- butylene that is added and ethene
Molar ratio range is (4.2/26):1 to 0.8:1, the 1- hexenes and the molar ratio range of ethene added is (5.4/26):1 to
0.8:1；
The isopentane, 1- butylene, 1- hexenes, ethene, hydrogen, wherein nitrogen composition circulating air, hydrogen and ethylene molar ratio model
Enclose for 1:15 to 1:3, isopentane accounts for 5wt%~40wt% of circulating air gross mass, and 1- butylene is accounted for 1- hexene total moles contents
8mol%~50mol% of circulating air total mole number.
16. the preparation method of the terpolymer of Ethylene/1-butene according to claim 15/1- hexenes, its feature exists
In：
The step 2) in, under the condition of continuity that catalyst is present, liquid is added into the gas-phase fluidized-bed reactor different
After pentane, the gas mixing raw material of 1- butylene, 1- hexenes, ethene, hydrogen, nitrogen and isopentane composition is added.
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| 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 |
| CN111363102B (en) * | 2020-03-18 | 2021-06-01 | 浙江大学 | Ethylene-alpha olefin-polyfluorosiloxane ternary graft copolymer and preparation method 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 |
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