CN106279482A - A kind of preparation method of ultra-high molecular weight polyethylene - Google Patents
A kind of preparation method of ultra-high molecular weight polyethylene Download PDFInfo
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- CN106279482A CN106279482A CN201510241610.5A CN201510241610A CN106279482A CN 106279482 A CN106279482 A CN 106279482A CN 201510241610 A CN201510241610 A CN 201510241610A CN 106279482 A CN106279482 A CN 106279482A
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Abstract
The present invention provides the preparation method of a kind of ultra-high molecular weight polyethylene, including: under conditions of catalyst, promoter exist, add external electron donor and carry out ethylene and alhpa olefin copolymerization, prepare super
Description
Technical field
The present invention relates to chemical field, especially relate to the preparation method of a kind of ultra-high molecular weight polyethylene.
Background technology
According to the regulation of ASTM D4020-81, ultra-high molecular weight polyethylene refers to
: 135 DEG C, 100ml 0.05% decahydronaphthalene solution in measure relative viscosity be 2.30 or higher branched polyethylenes, viscosity-average molecular weight polyethylene more than 1,500,000.Ultra-high molecular weight polyethylene chain length is 10 to 20 times of general HDPE.Ultra-high molecular weight polyethylene has wearability, impact resistance and absorption impact energy, self-lubricating property, chemical resistance, resistance to low temperature, the insulating properties etc. of excellence,
It is the engineering plastics prepared by common raw material.
The catalyst of industrial production polyethylene is the most all not applied for producing ultra-high molecular weight polyethylene, and the prior art therefore producing ultra-high molecular weight polyethylene is all to use special catalyst system.In prior art,
Use composite titanium series catalysts, by changing the Zn/Ti in catalytic component,
Molecular regulator amount, prepares the molecular weight ultra-high molecular weight polyethylene at 80～8,000,000 all sizes.But the molecular weight of technology regulation polyethylene needs to change catalytic component, i.e. needing to prepare different catalyst, therefore the molecular weight operation easier for regulation ultra-high molecular weight polyethylene is bigger.
Summary of the invention
In order to solve the drawbacks described above that prior art exists,
The present invention provides the preparation method of a kind of ultra-high molecular weight polyethylene.
For reaching above-mentioned purpose,
The present invention provides the preparation method of a kind of ultra-high molecular weight polyethylene, said method comprising the steps of:
Catalyst,
Under conditions of promoter exists, add external electron donor and carry out ethylene and alhpa olefin copolymerization, prepare ultra-high molecular weight polyethylene；
Wherein,
Described catalyst is included on a kind of solids containing magnesium and titanium, at least one titanium compound and at least one electron donor in load: described magnesium and the solids of titanium are to be dissolved in dicyandiamide solution by magnesium compound, form uniform solution, then in the presence of the halogenide of titanium, it is optionally added into precipitation additive, again separating out containing magnesium and the precipitation of solid material of titanium, wherein magnesium compound is the halogenide of magnesium, the alcoholates of magnesium or the halogenated alcoholate of magnesium；Described electron donor is selected from aliphatic ether, cyclic aliphatic ether and aliphatic ketone；The formula of described titanium compound is Ti (OR) a X b, in formula
R is aliphatic hydrocarbyl or the aromatic hydrocarbyl of C 1～C 14, and X is halogen, a
Being 0,1 or 2, b is the integer of 1 to 4, a+b=3 or 4, and described precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone.
Wherein,
Under conditions of catalyst, promoter exist, add external electron donor and carry out ethylene and alhpa olefin copolymerization, prepare ultra-high molecular weight polyethylene, specifically include following steps:
In reactor add promoter,
Catalyst and hexene and external electron donor, carry out reactor intensification, when temperature rises to polymerization temperature, disposable adds enough chain-transferring agent H2, then is continuously added to ethylene,
After polymerization terminates, obtain ultra-high molecular weight polyethylene.
Wherein,
Polymerization temperature is 50～130 DEG C.
Wherein,
Polymerization pressure is 0.5～5.0MPa.Wherein, described alhpa olefin is selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl isophthalic acid-amylene
Or their mixture.
Wherein,
Described external electron donor is following at least one or multiple: oxolane, diethyl ether, dipropyl ether, methyl-propyl ether, butyl oxide, dioctyl ether, oxetanes and tetrahydrochysene pyrrole furan.
Wherein,
Described promoter is organo-aluminum compound.
Wherein,
Described organo-aluminum compound is alkyl aluminum compound.
Wherein,
Described alkyl aluminum compound is trialkylaluminium.
Wherein,
Described external electron donor addition is: external electron donor is 0.01～50 with the mol ratio ratio of Ti.
The present invention has the beneficial effect that
:
The present invention can significantly improve the molecular weight of polyethylene,
Obtain ultra-high molecular weight polyethylene, and the method experiment condition is gentle, simple to operate, possess the strongest industrial application value.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that concrete reality described herein
Execute example only in order to explain the present invention, do not limit the present invention.
It is an object of the invention to produce the ultra-high molecular weight polyethylene that MW is 80～10,000,000, under conditions of catalyst, promoter exist, add external electron donor and carry out ethylene and alhpa olefin copolymerization.Because the present invention is on the premise of catalyst composition is constant,
Ultra-high molecular weight polyethylene is prepared by adjusting comonomer and external electron donor consumption, simple to operate, possess significant industrial value.
Polymerization process: the reactor of polymerization is autoclave or annular-pipe reactor, uses 5L tank reactor,
By after purging at least 3 times except the polymeric kettle N 2 of water, deoxygenation before charging, inject 1.5L through molecular sieve drying, the hexane of drum nitrogen, be sequentially added into promoter, catalyst and deoxidation, be dehydrated, purify after hexene and external electron donor.Wherein, external electron donor addition is: external electron donor and Ti
Mol ratio ratio be 0.01～50, preferably 0.03～5.Then, add
1.0L's is own
Alkane rinses catalyst line, carries out reactor intensification,
Polymerization temperature is 50～130 DEG C, preferably 60～95 DEG C；Polymerization pressure is 0.5
～5.0MPa, preferably 0.5～2.0MPa.When temperature rises to polymerization temperature, the chain-transferring agent H2 that disposable addition is enough, then it is continuously added to ethylene,
Carry out constant voltage Clocked operation, after polymerization terminates, reactor cooling aerofluxus, reclaim polymer slurries, from hexane, isolate polymer powders.
The present invention can be with ethylene and alhpa olefin copolymerization, and wherein alhpa olefin is selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl isophthalic acid-amylene, or their mixture.
Wherein, external electron donor is following at least one or multiple: oxolane, diethyl ether, dipropyl ether, methyl-propyl ether, butyl oxide, dioctyl ether, oxetanes and tetrahydrochysene pyrrole furan.
The present invention use organo-aluminum compound as promoter, preferably alkyl aluminum compound, more preferably include trialkylaluminium, as: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc., wherein, the ratio of active solid catalyst component and organo-aluminum compound cocatalyst component is 1: 25～1: 500 with Ti/Al molar ratio computing.
In the present invention, the catalyst of vinyl polymerization uses BCS01 catalyst series, and it is included on a kind of solids containing magnesium and titanium, at least one titanium compound and at least one electron donor in load
: described magnesium and the solids of titanium are to be dissolved in dicyandiamide solution by magnesium compound, form uniform solution, then in the presence of the halogenide of titanium, are optionally added into precipitation additive,
Again separating out containing magnesium and the precipitation of solid material of titanium, wherein magnesium compound is the halogenide of magnesium, the alcoholates of magnesium or the halogenated alcoholate of magnesium；Described electron donor is selected from aliphatic ether, cyclic aliphatic ether and aliphatic ketone；The formula of described titanium compound is Ti (OR) a X b,
In formula, R is C 1～C
The aliphatic hydrocarbyl of 14 or aromatic hydrocarbyl, X is halogen, and a is 0,1 or 2, and b is the integer of 1 to 4, a+b=3 or 4, and described precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone.
Wherein, solids containing magnesium and titanium is to be prepared by following method: be dissolved in by magnesium compound in the dicyandiamide solution containing organic epoxy compound thing and organic phosphorus compound, mix with the halogenide of titanium after forming homogeneous solution, in the presence of precipitation additive, separate out containing magnesium and the solids of titanium.Magnesium compound one of them halogen atom in magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula is replaced the one in the magnesium compound obtained, or their mixture by oxyl or halogenated hydrocarbons epoxide.Organic epoxy compound thing include carbon number 2～8 aliphatic alkene, alkadienes or halogenated aliphatic alkene or the oxide of alkadienes, glycidyl ether and inner ether at least one.Organic phosphorus compound is orthophosphoric acid or the hydrocarbyl carbonate of phosphorous acid or halohydrocarbyl ester.
Polymeric articles test uses following methods to carry out: viscosity-average molecular weight
Assay method use Chinese national standard GB1841-1980 measure polymer intrinsic viscosity, then according toK and
α is constant, thus calculates viscosity-average molecular weight。
It is described in detail with specific embodiment below: [0030]
Embodiment 1
Use 5L tank reactor, by after purging at least 3 times except the polymeric kettle N 2 of water, deoxygenation before charging, inject
1.5L is through molecular sieve drying, the hexane of drum nitrogen, be sequentially added into a certain amount of triethyl aluminum and BCS01 catalyst 20mg and deoxidation, be dehydrated, purify after hexene 600ml and oxolane (THF), control THF/Ti=0.3 (mol ratio), the hexane finally adding 1.0L rinses catalyst line, then reactor intensification is carried out
Enough chain-transferring agent H 2 are disposably added when temperature rises to 58 DEG C, controlling H 2/C 2 H 4=0.05 (mol ratio), then be continuously added to ethylene, ethylene partial pressure is 1.0MPa, carrying out constant voltage 1 hour, the experimental result obtained is shown in Table 1.
Embodiment 2
Controlling hexene addition is 100ml, and THF/Ti=1.8 (mol ratio), other experimental procedures are shown in Table 1 with embodiment 1, the experimental result obtained.
Embodiment 3
Controlling hexene addition is 100ml, THF/Ti=1 (mol ratio
), other experimental procedures are shown in Table 1 with embodiment 1, the experimental result obtained.
Table 1
Above-described embodiment result of the test shows, uses BCS01 catalyst, after carrying out ethylene and hervene copolymer and a certain amount of external electron donor of addition,
The molecular weight of polymer is significantly improved, and obtains ultra-high molecular weight polyethylene, simultaneously by adjusting hexene addition and the addition of external electron donor, in that context it may be convenient to the molecular weight of regulation ultra-high molecular weight polyethylene, under controlling added hydrogen,
The molecular weight ultra-high molecular weight polyethylene more than 8,000,000 can be obtained.The method experiment condition is gentle, simple to operate, possesses the strongest industrial application value.
Obviously, those skilled in the art can carry out various change and modification without departing from the spirit and scope of the present invention to the present invention.So, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof,
Then the present invention is also intended to comprise these change and modification.
Claims (10)
1. the preparation method of a ultra-high molecular weight polyethylene, it is characterised in that said method comprising the steps of:
Catalyst,
Under conditions of promoter exists, add external electron donor and carry out ethylene and alhpa olefin copolymerization,
Prepare ultra-high molecular weight polyethylene；Wherein, described catalyst is included on a kind of solids containing magnesium and titanium, at least one titanium compound and at least one electron donor in load: described magnesium and the solids of titanium are to be dissolved in dicyandiamide solution by magnesium compound, form uniform solution, then in the presence of the halogenide of titanium, being optionally added into precipitation additive, again separate out containing magnesium and the precipitation of solid material of titanium, wherein magnesium compound is the halogenide of magnesium, the alcoholates of magnesium or the halogenated alcoholate of magnesium；Described electron donor is selected from aliphatic ether, cyclic aliphatic ether and aliphatic ketone；The formula of described titanium compound is Ti (OR) a X b, and in formula, R is aliphatic hydrocarbyl or the aromatic hydrocarbyl of C 1～C 14, and X is halogen, and a is 0,1 or 2, and b is the integer of 1 to 4, a+b
=3 or 4, described precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone.
2. the preparation method of the ultra-high molecular weight polyethylene as described in claim 1, it is characterised in that catalyst,
Under conditions of promoter exists, add external electron donor and carry out ethylene and alhpa olefin copolymerization,
Prepare ultra-high molecular weight polyethylene, specifically include following steps: reactor adds promoter, catalyst and hexene and external electron donor, carry out reactor intensification, when temperature rises to polymerization temperature, the chain-transferring agent H 2 that disposable addition is enough, it is continuously added to ethylene again, after polymerization terminates
Obtain ultra-high molecular weight polyethylene.
3. the preparation method of the ultra-high molecular weight polyethylene as described in claim 2, it is characterised in that
Polymerization temperature is 50～130 DEG C.
4. the preparation method of ultra-high molecular weight polyethylene as claimed in claim 2, it is characterised in that polymerization pressure is 0.5～5.0MPa.
5. the preparation method of the ultra-high molecular weight polyethylene as described in any one of claim 1～4, it is characterized in that, described alhpa olefin is selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl isophthalic acid-amylene or their mixture.
6. the preparation method of the ultra-high molecular weight polyethylene as described in any one of Claims 1 to 4, it is characterized in that, described external electron donor is following at least one or multiple: oxolane, diethyl ether, dipropyl ether, methyl-propyl ether, butyl oxide, dioctyl ether, oxetanes and tetrahydrochysene pyrrole furan.
7. the preparation method of the ultra-high molecular weight polyethylene as described in any one of Claims 1 to 4, it is characterised in that described promoter is organo-aluminum compound.
8. the preparation method of the ultra-high molecular weight polyethylene as described in claim 7, it is characterised in that described organo-aluminum compound is alkyl aluminum compound.
9. the preparation method of the ultra-high molecular weight polyethylene as described in claim 8, it is characterised in that described alkyl aluminum compound is trialkylaluminium.
10. the preparation method of the ultra-high molecular weight polyethylene as described in any one of claim 1～4, it is characterised in that described external electron donor addition is: external electron donor is 0.01～50 with the mol ratio ratio of Ti.
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| CN108034124A (en) * | 2017-12-28 | 2018-05-15 | 宁波俐辰新能源有限公司 | A kind of super high molecular weight porous polyethylene foamed plastics and its manufacture method |
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Cited By (1)
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| CN108034124A (en) * | 2017-12-28 | 2018-05-15 | 宁波俐辰新能源有限公司 | A kind of super high molecular weight porous polyethylene foamed plastics and its manufacture method |
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