CN108752691A - A kind of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy and preparation method thereof - Google Patents
A kind of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
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Abstract
The present invention relates to polyethylene high-performance improvement areas, a kind of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy and preparation method thereof is particularly disclosed.The high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy, it is characterised in that：It is made of high density polyethylene (HDPE) matrix, ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer, wherein, the mass percentage of high density polyethylene (HDPE) matrix is 35-80%, the mass percentage of ethylene-propylene random copolymer is 17-50%, and the mass percentage of Ethylene-Propylene Block Copolymer is 3-15%.Present invention process is simple, reasonable design, can significantly improve the shock resistance of high density polyethylene (HDPE), especially low-temperature impact performance；By adjusting technological parameter, the mechanical property of alloy can be fully adjusted, effectively overcomes the drawbacks of HDPE is with toughener poor compatibility in mechanical blending method, while significantly improving the toughening effect of Rigid Particles Toughened method.
Description
（One）Technical field
The present invention relates to polyethylene high-performance improvement areas, more particularly to a kind of high density polyethylene (HDPE)/ethylene-propylene copolymer is in situ
Alloy and preparation method thereof.
（Two）Background technology
High density polyethylene (HDPE) (HDPE) belongs to general-purpose plastics, with nontoxic, light, inexpensive, appropriate rigidity and hardness, it is excellent plus
The advantages that work and chemical stability.However, HDPE generally existing bad mechanical properties, the shortcomings of easy embrittlement, easy stress cracking.Closely
Nian Lai, the increasingly increase with every profession and trade to toughness high molecular material demand, the toughening modifying of HDPE is also increasingly by science
The concern on boundary and enterprise.Currently, to the toughening modifying of HDPE mainly by by elastomer (or resin of low modulus good toughness)
Or/and rigid particles are added method through mechanical blending in HDPE and realize.Fu etc. uses CaCO3 and phosphate modified mistake respectively
CaCO3 toughened HDPEs, it is found that transform AKD can significantly improve the impact strength of HDPE, when the content of transform AKD increases
Impact strength to 50wt%, HDPE can be increased to 580J/m by 230J/m.Bartczak etc. has studied HDPE/ ternary second respectively
Third rubber (EPDM), HDPE/ ethylene-octenes copolymer elastomer (EOR) system, find these rubber in the form of Spherical Inhomogeneity body
It is evenly dispersed in the base, so that the notch impact toughness of HDPE is improved 16 times or more, but stretching yield stress and Young's modulus
But it is greatly reduced.For rubber toughened HDPE material, author thinks the thickness only when base layer between adjacent rubber particles
When less than a certain critical value, brittle-ductile transition could occur for material.And this critical thickness and rubber type or their content,
Size etc. is unrelated, is only determined by matrix nature.Li Aiying etc. is with HDPE grafted maleics anhydride copolymer (HDPE-g-MA)
Bulking agent significantly reduces the interfacial tension between HDPE/NBR system components, reduces the size of dispersed phase, substantially increases two
Adhesive strength between phase.Liao etc. is prepared for HDPE/ aluminium oxide and silane coupler modified using double screw extruder respectively
Aluminium oxide nano composite material.Author has found that the addition of alumina nanoparticles keeps the dimensional stability of HDPE and thermal stability equal
It is significantly improved；Meanwhile alumina nanoparticles also advantageously improve the Young's modulus and yield strength of HDPE, and it is silane-modified
Aluminium oxide has more significant enhancing effect.Although the effect of rubber toughened HDPE is best, HDPE is greatly improved in toughness
Meanwhile rigidity is but significantly reduced.Tracing it to its cause mainly has：HDPE is a kind of non-polar crystalline polymer, with elastomer
Poor compatibility, phase interface bonding strength is small, and interfacial detachment easily occurs；Elastomer is as dispersed phase, such as without appropriately crosslinked, in external force
Intermolecular slippage easily occurs under effect and generates " cavitation ".And use Rigid Particles Toughened or elastomer with rigid particles and with increasing
Tough mode, although the amplitude rigidly declined is little, or even can increase, the effect unobvious of toughening, what toughness improved
Amplitude is smaller, and the density of HDPE can be made to increase.
Since the Himont companies eighties in last century (existing Ba Saier companies) propose the concept of " reactor granules ", poly- third
Alloy is just rapidly developed in alkene/ethylene-propylene copolymer (PP/EPR) kettle.Alloy usually utilizes spherical supported in PP/EPR kettles
Type Ziegler-Natta catalyst generates polypropylene homopolymer in the first stage reactor, is then set in the second stage reactor
Family planning is dispersed at ethylene-propylene copolymer elastomer, in the course of the polymerization process elastomer in the hole of polypropylene matrix.Due to PP/
There are stronger interactions between composition of alloy diversity and each component in EPR kettles, thus show compared with PP homopolymers compared with
Good rigidity-toughness balanced.However, nonetheless, for the application in terms of some high performance structures materials, alloy in PP/EPR kettles
Rigid-tough balance still need to further increase.
The beginning of this century, Ba Saier companies (BASELL) are successfully developed based on multizone circulating reactor (MZCR) technology
Spherizone techniques are current PP Production Technologies state-of-the-art in the world.The principle of MZCR is the shape in 1 reactor
At the different reaction environment of 2 monomer compositions, polymer beads Rapid Circulation in the two reaction zones of intercommunication generates not respectively
With the polymer of composition and performance, and it can be uniformly dispersed.In single reaction kettle, if gaseous environment can be made to change in kettle periodically
Become, then equally achievable switching of the polymer beads under gas with various environment.Based on this, by gas handover control system,
Realize the simulation to MZCR technologies in laboratory.It is applied to and prepares high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy, energy
Ethylene-propylene copolymer content is improved, to improve the toughening effect to base polyethylene.At the same time, it can be achieved that ethylene-propylene copolymer exists
It is evenly dispersed in base polyethylene, to improve the rigid-tough balance of alloy.
（Three）Invention content
In order to compensate for the shortcomings of the prior art, the present invention provides it is a kind of it is simple for process, shock resistance is high, toughening effect is good
High density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy and preparation method thereof.
The present invention is achieved through the following technical solutions：
A kind of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy, it is characterised in that：By high density polyethylene (HDPE) matrix, ethylene-the third
Olefinic random copolymer and Ethylene-Propylene Block Copolymer composition, wherein the mass percentage of high density polyethylene (HDPE) matrix is
The mass percentage of 35-80%, ethylene-propylene random copolymer are 17-50%, the quality hundred of Ethylene-Propylene Block Copolymer
It is 3-15% to divide content.
High density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy of the present invention can significantly improve the toughness of polyethylene, according to GB/
T 528-2009 are measured, and elongation at break is at least 1000%-1500%.The alloy has excellent low-temperature flexibility simultaneously,
In subzero 50 DEG C of environment, the impact strength of base polyethylene is 39.45KJ/m2, and the test bars of alloy sample can not
It thrusts.
The present invention more excellent technical solution be：
The high density polyethylene (HDPE) matrix is the second that weight average molecular weight is 150-800kg/mol, molecular weight distributing index is 5-15
The copolymer of polyamino alkenyl object or ethylene and comonomer production, wherein the molar content of ethylene unit monomer is 97-
99.9%, comonomer is propylene, 1- butylene, 1- hexenes or 1- octenes；Preferably, consider the rigid of Alathon
And processing performance, the weight average molecular weight of Alathon is 250-500kg/mol, molecular weight distributing index 5-10, ethylene with
In the copolymer of comonomer production, it is contemplated that matrix should have certain toughness, and matrix particle should have good particle
The molar content of pattern, ethylene unit monomer is 98.5-99.5%.
In the ethylene-propylene random copolymer, the molar content of ethylene monomer unit is 20-80%；Ethylene-propylene is embedding
In section copolymer, the molar content of ethylene monomer unit is 60-95%, average sequence length 5-15；Preferably, according to GPC
Measurement result, the weight average molecular weight of the ethylene-propylene random copolymer is 50-150kg/mol, and molecular weight distributing index is
5-10, wherein in view of random copolymer has good toughening effect, the molar content of ethylene monomer unit is 40-65%；
The melting temperature of Ethylene-Propylene Block Copolymer is 117-120 DEG C, wherein the molar content of ethylene monomer unit is 80-90%,
Average sequence length is 9-13.
The content of Ethylene-Propylene Block Copolymer and the sequence distribution of ethylene propylene monomer unit are random to ethylene-propylene
Dispersing uniformity of the copolymer in ethene polymers matrix has great influence.The matter of the Ethylene-Propylene Block Copolymer
Amount percentage composition is 5-10%.
The preparation method of high density polyethylene (HDPE) of the present invention/ethylene-propylene copolymer in-situ alloy, includes the following steps：
（1）Slurry prepolymerization：Using MgCl2/ID/TiCl4 Ziegler-Natta Catalysts as major catalyst, alkyl aluminum
For co-catalyst, alkane is solvent, and comonomer is passed through in reactor and carries out slurry prepolymerization；
（2）The homopolymerization of ethylene slurry or copolymerization：Pre-polymerization terminates heel row sky olefinic monomer, vinyl monomer is passed through in reaction kettle, with hydrogen
For molecular weight regulator, carries out ethylene homo reaction or comonomer is added to carry out copolyreaction, obtain high-density polyethylene alkenyl
Body；
（3）Gas-phase polymerization：Gas-phase polymerization is broadly divided into following two step sequentially in time：A) ethylene propylene of 30 min is first carried out
Alkene gas phase copolymerization；B) according to preset switching frequency and time, it is reacted in ethylene propylene copolymer reaction and ethylene homo
Between carry out periodical atmosphere switching.
It is preferably：
Step（1）In, alkyl aluminum is one or both of triethyl aluminum and triisobutyl aluminium；Prepolymerization conditions are pressure
0.1MPa, 15-50 DEG C of temperature, sustained response 5-30min.
Step（2）In, homopolymerization gas is the ethylene containing hydrogen, wherein the molar content of hydrogen is 1-10%,
Poly- reaction condition is the sustained response 15-30min under 60 DEG C, 0.4-0.7MPa.
Step（3）In, the copolymerization gas in ethylene, propylene gas phase copolymerization is ethylene, propylene mixed gas, wherein second
The molar ratio of alkene and propylene is 1：1-1.2.
High density polyethylene (HDPE) prepared by the present invention/ethylene-propylene copolymer in-situ alloy has higher ethylene-propylene rubber content, energy
The toughness for significantly improving polyethylene, measures according to GB/T 528-2009, and elongation at break is at least 1000%-1500%.Simultaneously
The preparation process being combined with atmosphere switching polymerization using slurry polymerization, is not susceptible to particle bonding and viscous kettle phenomenon, chemical group
At adjustable in wider range.Compared with traditional slurry-gas phase polymerization two-step process, alloy can get higher EP rubbers
Content simultaneously keeps good granule-morphology, and has better rigid-tough balance.
In addition, in subzero 50 DEG C of test environment, the survey of the high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy sample
Testing bar can not be thrust in Chalpy impact test, had excellent low-temperature flexibility, be can be applied to the life of low temperature resistant product
Production, can also be used as the modifying agent of toughened polyethylene.
Present invention process is simple, reasonable design, can significantly improve the shock resistance of high density polyethylene (HDPE), especially low
Warm erosion-resisting characteristics；By adjusting technological parameter, the mechanical property of alloy can be fully adjusted, HDPE in mechanical blending method is effectively overcome
The drawbacks of with toughener poor compatibility, while significantly improving the toughening effect of Rigid Particles Toughened method.
（Four）Specific implementation mode
With reference to embodiment, the present invention will be further described.
The preparation of high density polyethylene (HDPE) matrix：
（1）Propylene normal pressure slurry prepolymerization
Before polymerization, reaction kettle vacuumizes roasting kettle (>=2h) under 95 DEG C of circulator bath, to remove residual solvents in kettle, moisture etc.
Impurity.Bath temperature is stablized to 30 DEG C afterwards, connects pipeline under n 2 atmosphere.System is replaced with propylene 3 times, and is filled with propylene
To 0.1MPa.Start stirring to 300r/min, then sequentially adds 50mL normal heptane solvents, alkyl aluminum (Al/Ti=100), outer
Electron donor (Si/Ti=5) is used in combination 50mL normal heptanes to pour major catalyst (~50mg) in reaction kettle.Pre-polymerization in 30 DEG C,
Continue 15min under 0.1MPa；
（2）Propylene normal pressure slurry prepolymerization
Prepolymerization terminates, and the hydrogen of set amount is added, is filled with ethylene, and the rapid ethylene pressure that improves switches water-bath to 0.6MPa
Temperature is to 60 DEG C.After 10min, adjustment stir speed (S.S.) to 100r/min.Ethylene slurry polymerization continues in 60 DEG C under 0.6MPa
30min obtains the spherical high density polyethylene (HDPE) particle of grain size about 0.5mm.
The preparation of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy：
Embodiment 1：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.2, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 30min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 30min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.Whole cycle atmosphere is cut
It changes polymerization stage and amounts to 60min, carried out 1 cycle period altogether, note switching frequency is 1.
Embodiment 2：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.2, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 15min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 15min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 2 circulating cycles altogether
Phase, note switching frequency are 2.
Embodiment 3：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.2, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 7.5min.After, control system closes copolymerization gas by pipeline electromagnetic valve,
The solenoid valve for opening simultaneously another pipeline, into ethene gas-phase homopolymerization process, (gas is formed by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 7.5min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 4 circulating cycles altogether
Phase, note switching frequency are 4.
Embodiment 4：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.2, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 5min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 5min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 6 circulating cycles altogether
Phase, note switching frequency are 6.
Embodiment 5：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.2, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 3min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 3min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 10 cycles altogether
Period, note switching frequency are 10.
Embodiment 6：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.2, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 2min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 2min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 15 cycles altogether
Period, note switching frequency are 15.
Embodiment 7：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.2, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 1min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 1min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 30 cycles altogether
Period, note switching frequency are 30.
Embodiment 8：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of the third gaseous mixture of second becomes ethylene/propene=1/1.5 by intrinsic standoff ratio,
Hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), pressure in kettle
For 0.3MPa, jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 5min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 5min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 6 circulating cycles altogether
Phase, note switching frequency are 6.
Embodiment 9：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.5 hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with the third gas-phase copolymerization of second, carries out 10min.After, control system closes copolymerization gas by pipeline electromagnetic valve, together
When open the solenoid valve of another pipeline, into ethene gas-phase homopolymerization process, (gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=
95/5) 5min, is carried out.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to ethylene homo, this is a complete cycle period.It then again switches to altogether
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 90min, has carried out 6 circulating cycles altogether
Phase, note switching frequency are 6.
Embodiment 10：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.5, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with ethene gas-phase homopolymerization, carries out 5min, and gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=95/5.After, control
System closes homopolymerization gas by pipeline electromagnetic valve, the solenoid valve of another pipeline is opened simultaneously, into second the third gas-phase copolymerization mistake
Journey carries out 5min.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is 0.3MPa in kettle,
Jacket temperature is 60 DEG C.Terminate to Propylene polymerization, this is a complete cycle period.Homopolymerization is then again switched to, is entered
Next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 60min, has carried out 6 cycle periods altogether, note is cut
It is 6 to change frequency.
Embodiment 11：
High density polyethylene (HDPE) matrix is prepared by identical method.
Vinyl polymerization terminates, and stops leading to ethylene gas, and system pressure is emitted into normal pressure state, vacuum pump takes out solvent
Go out, then enters gas phase polymerization stage.Gas-phase polymerization is broadly divided into following two step sequentially in time：
（1）Carry out 30min ethylene, propylene gas-phase copolymerizations.The composition of wherein the third gaseous mixture of second is by intrinsic standoff ratio：Ethylene/propene=1/
1.5, hydrogen containing 1mol%.The stage control feed rate is 5.0L/min (under standard state N2 demarcate gas flow), in kettle
Pressure is 0.3MPa, and jacket temperature is 60 DEG C；
（2）According to preset switching frequency and time, carries out periodical atmosphere and switch polymerization process.Concrete operations：Switching polymerization
Stage is started with ethene gas-phase homopolymerization, carries out 5min, and gas composition is by intrinsic standoff ratio：Ethylene/hydrogen=95/5.After, control
System closes homopolymerization gas by pipeline electromagnetic valve, the solenoid valve of another pipeline is opened simultaneously, into second the third gas-phase copolymerization mistake
Journey carries out 10min.Entirely the polymerizing condition of switch step is：Control feed rate is 5.0L/min, and pressure is in kettle
0.3MPa, jacket temperature are 60 DEG C.Terminate to Propylene polymerization, this is a complete cycle period.It then again switches to
It is poly-, into next cycle period.Whole cycle atmosphere switches polymerization stage and amounts to 90min, has carried out 6 circulating cycles altogether
Phase, note switching frequency are 6.
Embodiment detects：
（1）The composition of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy
Classification step：About 2g polymer is weighed in 500mL eggplant-shape bottles, the antioxidant of about 250mL normal octanes and 0.1wt% is added
BHT is heated to boiling and flowing back 1 hour, and polymer normal octane solution is transferred quickly in Centrifuge Cup after stopping heating.Again
250mL normal octanes are added to repeat the above process.It is isolated through multiple centrifugation after polymer solution cools down 8-12 hours
The solvable fraction of room temperature normal octane (C8-sol) and insoluble fraction.After the insoluble fraction vacuum drying of room temperature normal octane, with 250mL positive heptan
Alkane extracts 12h.Respectively obtain the solvable fraction of boiling n-heptane (C7-sol) and the insoluble fraction of boiling n-heptane (C7-insol).It will
3 fractions are weighed after being dried in vacuo 6h at 50 DEG C.Here C8-sol fractions can represent ethylene-propylene random copolymer, C7-sol substantially
Fraction can represent ethylene-propylene block copolymer substantially, and C7-insol fractions can represent high density polyethylene (HDPE) substantially.
Following table is the basic composition of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy obtained by embodiment 1-11.
（2）Weight average molecular weight and molecular weight distribution
The molecular chain conformation of polymer uses PL-GPC220 type high-temperature gel permeation chromatography instrument (Polymer
Laboratories companies) it measures.5-15mg samples are weighed, is that solvent fully dissolves at 160 DEG C with 1,2,4- trichloro-benzenes, matches
It is about the polymer solution of 3 ‰ g/ml at concentration.Afterwards with filter rifle filtering, it is stored in be measured in special test bottle.Use three PLgel
10 μm of MIXED-B, 300 × 7.5mm pillars, chromatographic column efficiently separate ranging from 500-1 × 107, and 1,2,4- trichloro-benzenes is flowing
Phase, flow rate 1.0mL/min elute 150 DEG C of temperature.The calculating of molecular weight is based on the pervasive school of Narrow distribution polystyrene standard specimen
It executes.
Following table is the molecular weight and molecular weight distribution of the polymers obtained each components of embodiment 1-11：
（3）The sequence of ethylene-propylene random copolymer and ethylene-propylene block copolymer is distributed
The sequence distribution of polymer each component is composed with 13C-NMR to be measured, and instrument is Varian mercury plus 300MHz cores
Magnetic resonance device.30-50mg polymer is weighed in 5mm nuclear magnetic tubes, 3-5mg praseodyniums chromium (Cr (acac) 3) conduct is added
Relaxation reagents, using deuterated o-dichlorohenzene as solvent, configuration concentration is the sample of 10W/V%.Test condition：Test temperature is 120
DEG C, sampling time 0.8s, pulse delay time 3s, 90 ° of pulse angle are scanned 5000 times using gated decoupling without NOE.
Following table is that the sequence of ethylene-propylene random copolymer is distributed.In three embodiments, the molar content of ethylene unit is 55%
Left and right, and [EP] two tuple proportion is about 45%, shows stronger copolymerization trend.The average sequence of ethylene and propylene units
Row length is about 2, the two ratio (nE:NP) close to 1:1, and the reactivity ratio product of ethylene and propylene is about 1.4, shows strand
Structure is intended to ideal random distribution state.The typical sequence characteristic distributions of random copolymer are shown above.
Following table is that the sequence of ethylene-propylene block copolymer is distributed.The molar content of ethylene unit is far above propylene list in block copolymer
Member, and stepped up with the increase of switching frequency.Improve switching frequency, the average sequence length ratio of ethylene and propylene units
(nE/nP) it is also continuously improved, shows that the block copolymer for being more advantageous to long ethylene sequence under high switching frequency generates.
（4）The hot property of block copolymer
The heat analysis test of polymer carries out on U.S. TA Q200 types differential scanning calorimeters (DSC).Weigh about 5mg polymerizations
Object sample, which is placed in aluminum cup, to be sealed, and sample cell is put into, and is run according to the test program set.Record crystallization and secondary liter
The fusing point (Tm) and melting enthalpy (△ Hm) of polymer is calculated in warm curve.Whole process carries out under N2 protections.Test program
For：160 DEG C are warming up to from 40 DEG C with the heating rate of 10 DEG C/min first, constant temperature 5min；Then with the cooling of 10 DEG C/min speed
Rate is down to 40 DEG C, constant temperature 1min；Finally 160 DEG C are warming up to from 40 DEG C with the heating rate of 10 DEG C/min again.
Following table is the fusing point and melting enthalpy of two kinds of components of ethylene-propylene block copolymer and high density polyethylene (HDPE).With switching frequency
Raising, the melting enthalpy and fusing point of high density polyethylene (HDPE) are substantially unchanged, and the melting enthalpy of ethylene-propylene block copolymer gradually carries
Height, this is mainly due to the raising of crystallizable constituent content.The ratio of high ethylene contents block copolymer is continuous with switching frequency
It improves, the increase of ethylene contents and sequence length makes the crystallinity of block copolymer improve.For the molten of ethylene-propylene block copolymer
Point, in addition to the fusing point of embodiment 7 is relatively low, the fusing point of remaining sample is with switching frequency without significant change.
（5）The mechanical property of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy
Crooked test is according to GB/T 9341-2008, and in microcomputer controlled electronic universal tester, (CMT4104, Shenzhen newly think carefully
Material tests Co., Ltd) on carry out.Using 20kN wedge shapes stretching clamp (XSA204B), 10kN three point bending test devices
(WA104A).Izodtest press GB/T 1843-2008 test methods, using balance weight impact testing machine (ZBC1251-2,
Shenzhen Sans Material Detection Co., Ltd) test, pendulum maximum impact energy is 5.5J.The equal parallel testing of all battens 5
More than secondary, it is averaged.
Low temperature izodtest is carried out by GB/T 1843-2008 test methods, uses Italian Xi Site (CE Λ
ST) the pendulum percussion instrument of Scientific Instruments Corporation, pendulum maximum impact energy are 4J, and test temperature is -50 DEG C.
Tensile property test is carried out by GB/T 528-2009 test methods, newly thinks carefully Materials Co., Ltd using Shenzhen
Electronic universal tester, rate of extension 50mm/min.All samples parallel testing 5 times or more, is averaged.
Following table is the mechanical property of embodiment 1-7 resulting polymers, and wherein NB represents test bars and can not be thrust.This hair
The high density polyethylene (HDPE) of bright preparation/ethylene-propylene copolymer in-situ alloy matter is soft, has higher ethylene-propylene rubber content, can significantly improve
The toughness of polyethylene.It is measured according to GB/T 528-2009, elongation at break is more than 1000%.In addition, in subzero 50 DEG C of survey
In test ring border, the cantilever beam impact strength of high density polyethylene (HDPE) is 39.45KJ/m2, and the present invention prepares high density polyethylene (HDPE)/second third
The test bars of copolymer in-situ alloy sample can not be thrust in Chalpy impact test, have excellent low-temperature flexibility,
The production that can be applied to low temperature resistant product can also be used as the modifying agent of toughened polyethylene.
Claims (10)
1. a kind of high density polyethylene (HDPE)/ethylene-propylene copolymer in-situ alloy, it is characterised in that：By high density polyethylene (HDPE) matrix, ethylene-
Random copolymer of propylene and Ethylene-Propylene Block Copolymer composition, wherein the mass percentage of high density polyethylene (HDPE) matrix is
The mass percentage of 35-80%, ethylene-propylene random copolymer are 17-50%, the quality hundred of Ethylene-Propylene Block Copolymer
It is 3-15% to divide content.
2. high density polyethylene (HDPE) according to claim 1/ethylene-propylene copolymer in-situ alloy, it is characterised in that：It is described highly dense
Degree base polyethylene is the Alathon or second that weight average molecular weight is 150-800kg/mol, molecular weight distributing index is 5-15
The copolymer of alkene and comonomer production, wherein the molar content of ethylene unit monomer is 97-99.9%, and comonomer is
Propylene, 1- butylene, 1- hexenes or 1- octenes.
3. high density polyethylene (HDPE) according to claim 1/ethylene-propylene copolymer in-situ alloy, it is characterised in that：The ethylene-
In random copolymer of propylene, the molar content of ethylene monomer unit is 20-80%；In Ethylene-Propylene Block Copolymer, ethylene list
The molar content of body unit is 60-95%, average sequence length 5-15.
4. high density polyethylene (HDPE) according to claim 1/ethylene-propylene copolymer in-situ alloy, it is characterised in that：The ethylene-
The mass percentage of propylene-based block copolymer is 5-10%.
5. high density polyethylene (HDPE) according to claim 2/ethylene-propylene copolymer in-situ alloy, it is characterised in that：The ethylene
The weight average molecular weight of homopolymer is 250-500kg/mol, molecular weight distributing index 5-10, and ethylene is total to what comonomer produced
In polymers, the molar content of ethylene unit monomer is 98.5-99.5%.
6. high density polyethylene (HDPE) according to claim 3/ethylene-propylene copolymer in-situ alloy, it is characterised in that：The ethylene-
The weight average molecular weight of random copolymer of propylene is 50-150kg/mol, molecular weight distributing index 5-10, wherein vinyl monomer list
The molar content of member is 40-65%；The melting temperature of Ethylene-Propylene Block Copolymer is 117-120 DEG C, wherein vinyl monomer list
The molar content of member is 80-90%, average sequence length 9-13.
7. the preparation method of high density polyethylene (HDPE) according to claim 1/ethylene-propylene copolymer in-situ alloy, it is characterized in that,
Include the following steps：（1）With MgCl2/ID/TiCl4Ziegler-Natta Catalyst is major catalyst, and alkyl aluminum is to help
Catalyst, alkane are solvent, and comonomer is passed through in reactor and carries out slurry prepolymerization；（2）Pre-polymerization terminates heel row sky alkene
Monomer is passed through vinyl monomer in reaction kettle, using hydrogen as molecular weight regulator, carries out ethylene homo reaction or comonomer is added
Copolyreaction is carried out, high density polyethylene (HDPE) matrix is obtained；（3）The ethylene, propylene gas phase copolymerization for first carrying out 30min, then exists
Ethylene propylene copolymer is reacted carries out periodical atmosphere switching between ethylene homo reaction.
8. the preparation method of high density polyethylene (HDPE) according to claim 7/ethylene-propylene copolymer in-situ alloy, feature exist
In：Step（1）In, alkyl aluminum is one or both of triethyl aluminum and triisobutyl aluminium；Prepolymerization conditions are pressure
0.1MPa, 15-50 DEG C of temperature, sustained response 5-30min.
9. the preparation method of high density polyethylene (HDPE) according to claim 7/ethylene-propylene copolymer in-situ alloy, feature exist
In：Step（2）In, homopolymerization gas is the ethylene containing hydrogen, wherein the molar content of hydrogen is 1-10%, homopolymerization
Condition is the sustained response 15-30min under 60 DEG C, 0.4-0.7MPa.
10. the preparation method of high density polyethylene (HDPE) according to claim 7/ethylene-propylene copolymer in-situ alloy, feature exist
In：Step（3）In, the copolymerization gas in ethylene, propylene gas phase copolymerization is ethylene, propylene mixed gas, wherein ethylene and third
The molar ratio of alkene is 1：1-1.2.
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