CN1301273C - Super high molecular weight polyethylene preparation method and its post-treatment process - Google Patents
Super high molecular weight polyethylene preparation method and its post-treatment process Download PDFInfo
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Abstract
The present invention relates to a preparation method of ultrahigh molecular weight polyethylene and a post-treatment process thereof. Under the conditions of alkane solvent as dispersion media, titanium compounds as catalysts, organic aluminum compounds as cocatalysts, polymerization temperature of 40 DEG C to 120 DEG C and polymerization pressure of 0.1 to 3.0MPa, ultrahigh molecular weight polyethylene is prepared from ethene monomers by polymerization reaction. The dispersion media, namely the alkane solvent, is one of hexane, or isohexane, or hexane oil or solvent oil, or the mixture of more than one of hexane, or isohexane, or hexane oil or solvent oil; in the catalysts, the titanium compounds are one of TiCl4, TiBr4, Ti(OCH3)Cl3, Ti(OCH3)Cl2 and Ti(OCH3)4, or the mixture of more than one of TiCl4, TiBr4, Ti(OCH3)Cl3, Ti(OCH3)Cl2 and Ti(OCH3)4; the organic aluminum compounds as are one of triethylaluminum, or diethyl aluminium chloride, or triisobutyl aluminum, or aluminum ethylate or diethoxy aluminium chloride, or the mixture of more than one of triethylaluminum, or diethyl aluminium chloride, or triisobutyl aluminum, or aluminum ethylate or diethoxy aluminium chloride; the weight proportion of the catalysts and the cocatalysts is 1:2 to 15.
Description
Technical field
The present invention relates to the macromolecular compound technical field, be specifically related to have the preparation method and the aftertreatment technology thereof of a kind of ultrahigh molecular weight polyethylene(UHMWPE) of good flow speed and processing characteristics.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (Ultra-high molecular weight polyethylene is called for short UHMWPE) is the thermoplastic engineering plastic of relative molecular mass more than 1,500,000.This material over-all properties is superior, wear-resistant, low temperature resistant, corrosion-resistant, self-lubrication, shock resistance are maximum in all plastics, wear resisting property is better than materials such as tetrafluoroethylene, nylon, carbon steel, can under-169～+ 80 ℃ of conditions, work for a long time, the engineering plastics that are called as " making us surprised " can be widely used in metallurgy, electric power, oil, weaving, papermaking, food, chemical industry, machinery, industry such as electric.Superhigh molecular weight polyethylene material is compared with other plastic materials with metallic substance, has the following advantages:
1. wear resistance and resistance to impact shock excellence; Its wear resisting property is 8 times of iron and steel, 4 times of nylon, and shock resistance is 2 times of polycarbonate, 5 times of acrylonitrile-butadiene-styrene copolymer (Acrylonitrile butadiene-styreneresin is called for short ABS resin).
2. good chemical resistance; Can compare favourably with tetrafluoroethylene, in certain temperature and concentration range, can anti-various corrosive liquid and various organic solvent.
3. self lubricity is good; Frictional coefficient is minimum in plastics, is 0.07～0.11 only, is the ideal self-lubricating material.
4. health is nontoxic fully, does not go mouldy, not breed bacteria; Antiscale is strong, and anti-adhesive and teflon (Teflon, skin friction coefficient are 0.05～0.1) are suitable.
5. good hydrophobic nature; Water-intake rate only is 1% of a nylon less than 0.01%.
6. density is minimum in the engineering plastics, and minor caliber pipe can be crooked arbitrarily, can embrittlement.
7. the striking energy absorptivity is a maximum, and noise reduction is good.
But ultrahigh molecular weight polyethylene(UHMWPE) has special unworkability, and its molecular weight is huge, molecular arrangement is regular, and its melt viscosity is high, reaches 10
9PaS, the flowing property extreme difference, the melting index of melt is almost nil.Add man-hour on conventional screw forcing machine and injector, material is difficult to before screw rod and then forms " material plug ".In addition, powder very easily skids in fill process, and the critical shear rate of ultra-high molecular weight is very low, is 10
-2/ S can cause when extruding and melt breaking of body, pore and delamination can occur during injection.Above-mentioned drawbacks limit its Application and Development.Just begin to realize industrialization up to late nineteen seventies, thereby opened the prelude of ultrahigh molecular weight polyethylene(UHMWPE) large-scale application by the research institution and the major company of states such as Germany, the U.S., Japan.Along with various countries
Continue to increase the research dynamics, develop gradually and that sintering, plunger are extruded, screw rod is extruded and forming method such as injection moulding, for the large-scale application ultrahigh molecular weight polyethylene(UHMWPE) is laid a good foundation.Ultrahigh molecular weight polyethylene(UHMWPE) is mainly used to make sheet material, bar, tubing, and the ultrahigh molecular weight polyethylene(UHMWPE) that has good flow speed in addition can also be used to being processed as film, is applied in the high-tech products such as lithium ion battery.
At present, the working method of ultrahigh molecular weight polyethylene(UHMWPE) is mainly to suppress a sintering process and plunger expressing technique.These method explained hereafter cycles are long, efficient is lower, and use range is limited, and this also is the basic reason that becomes present restriction ultrahigh molecular weight polyethylene(UHMWPE) development.Realize processing continuously in order to enhance productivity, in recent years, except taking equipment transformed, main research object concentrates on carries out the technical of modification to ultrahigh molecular weight polyethylene(UHMWPE), and known method of modifying is mechanical-physical blending and modifying and modification by copolymerization.
Usually blending and modifying is meant that adding one or more can make the unfolded material of the intermeshing molecule long-chain of ultrahigh molecular weight polyethylene(UHMWPE) part, thereby reduces its melt viscosity, improves processing characteristics.The blending and modifying product is layering easily in the course of processing, adopting the flow ability modifying agent blending and modifying is with flow ability modifying agent and super-high molecular weight polythene blending, though this method is the processing fluidity that has improved ultrahigh molecular weight polyethylene(UHMWPE), it is extruded be processed into possibility, but many performances of its goods have very big-difference than pure ultra-high molecular mass polyethylene, and its stability is also bad.
United States Patent (USP) 4281070, Japanese Patent 6024748A, 57177037 have reported the method with ultrahigh molecular weight polyethylene(UHMWPE) and low molecular weight polyethylene blend; United States Patent (USP) 4853427,4487857 discloses the method with compound lubricant blending and modifying;
The Chinese patent application 01100016.3 of publication number 1306034 also provides a kind of ultrahigh molecular weight polyethylene(UHMWPE) and clay nano to carry out the compound technology through situ-formed graft intercalation process.Above-mentioned remodeling technology is to be cost with the premium properties of sacrificing ultrahigh molecular weight polyethylene(UHMWPE), and the large usage quantity of properties-correcting agent, has influenced the application performance of ultrahigh molecular weight polyethylene(UHMWPE) excellence.
Someone continues again to improve, and adopts transition metal part halides and forms catalyst system with aluminum alkyls, makes the alhpa olefin copolymerization of vinyl monomer and 3～12 carbon atoms, produces ultrahigh molecular weight polyethylene(UHMWPE), and this method still need adopt " copolymerization ".
Summary of the invention
Purpose of the present invention provides a kind of preparation method that the alhpa olefin copolymerization can make vinyl monomer generation polymeric ultrahigh molecular weight polyethylene(UHMWPE) that need not.
The technical solution used in the present invention is as follows:
Develop a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE), it is characterized in that:
With the alkane solvents is dispersion medium, is catalyzer with the titanium compound, is promotor with the organo-aluminium compound; At polymerization temperature is 40～120 ℃, and polymerization pressure is under 0.1～3.0Mpa condition; Make the vinyl monomer polymerization reaction take place obtain the polymerisate ultrahigh molecular weight polyethylene(UHMWPE); Wherein:
Described dispersion medium alkane solvents is meant one or more the mixture in normal hexane, isohexane, hexane oil or the solvent oil;
Titanium compound is TiCl in the described catalyzer
4, TiBr
4, Ti (OCH
3) Cl
3, Ti (OCH
3) Cl
2, Ti (OCH
3)
4In one or more mixture;
Described organo-aluminium compound is meant one or more the mixture in triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, aluminum ethylate or the diethoxy aluminum chloride.
Above-mentioned polymerization temperature the best is 70～95 ℃.
Above-mentioned catalyzer and promotor weight proportion are 1: 2～15; Or catalyzer and promotor weight proportion are 1: 6～10.
Above-mentioned hexane oil or solvent oil are meant that boiling range is at 55～120 ℃ commercial goods hexane oil or solvent oil.
Because the polymerisate that produces has corrodibility to deep processing Carbon Steel Die, machinery, smell big, mobile bad,
Go out cellular bubble during condition of high temperature press table in the sheet material, be difficult for the performance that demoulding etc. has influenced product during pressing plate, so the present invention has also designed aftertreatment technology.
The aftertreatment technology of above-mentioned ultrahigh molecular weight polyethylene(UHMWPE) comprises filtration, solvent wash, and drying, washing and screening is characterized in that:
During the polymerisate solvent wash, solvent for use is one or more the mixture in normal hexane, the isohexane, and the weight proportion of polymerisate and solvent is 1: 1～2 during washing, washs 1～2 time;
When dry, vacuum tightness is that 53.3～93.3Kpa (is equivalent to 400～700mmHg), 50～120 ℃ of drying temperatures;
During the polymerisate water washing, with 80～90 ℃ of hot water making beating washings, the weight proportion of polymerisate and described hot water is 1: 1～20 during washing, washs 1～2 time; Get product through routine oven dry and screening at last.
Beneficial effect of the present invention is, this method preparation and handle after ultrahigh molecular weight polyethylene(UHMWPE), not only kept all excellent mechanical properties of ultrahigh molecular weight polyethylene(UHMWPE) substantially, have good flow rate and processing characteristics again; Can be directly used in that screw rod is extruded or injection moulding production without mechanical blending and chemical treatment.
The multipolymer that adopts this catalyst system to produce not only has the excellent mechanical properties of ultrahigh molecular weight polyethylene(UHMWPE), has reasonable processing characteristics again, can adopt the mode of extruding to process, avoided the shortcoming of blending method effectively, make working (machining) efficiency significantly improve, end-use further expands.
Embodiment
Embodiment 1
Processing parameter
Reaction: dispersion medium selects for use Qilu Petrochemical company to produce hexane oil (55～80 ℃ of boiling ranges); Catalyzer: promotor=1: 10 (w/w); Catalyzer---TiCl
4Promotor---triethyl aluminum; 90～95 ℃ of polymerization temperatures; Polymerization pressure 2.5～3.0Mpa;
Aftertreatment: reaction is finished, hexane oil wash, polymerisate: hexane oil=1: 1 (w/w); Washing times 1 time; Dry vacuum tightness 53.3～66.6Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 1～5 (w/w); Washing times 1 time; 100～120 ℃ of drying temperatures.
Concrete operations: in the stainless steel cauldron of 1 liter of strap clamp cover, add 600ml hexane oil, stir and be warming up to 70 ℃, add triethyl aluminum 50mg, add TiCl after 5 minutes
45mg, feeding ethene after 5 minutes and keeping its dividing potential drop is 2.5～3.0MPa, and the controlled polymerization temperature of reaction is at 90～95 ℃, and discharging behind the polymerization 5h is with the feed liquid filtering separation solvent after the polymerization; With hexane oil wash 1 time, the weight proportion of polymerisate and solvent is 1: 1 (w/w) during solvent wash; Solvent wash 20min, behind the filtering separation solvent, (be equivalent to 400～500mmHg), 100～120 ℃ of dryings of temperature are dry terminal point no longer to go out solvent in vacuum tightness 53.3～66.6Kpa.
During the polymerisate water washing, with 80～90 ℃ of hot water making beating washings, the weight proportion of polymerisate and described hot water is 1: 1～5 (w/w) during washing, washs 1 time, and churning time is 20min; The filtering separation washing water are dried to moisture content less than 0.15% at 100～120 ℃, and screening gets product.
The test event of ultrahigh molecular weight polyethylene(UHMWPE) of the present invention and use standard:
Test event is used standard and method
Molecular weight ASTM D4020-81
Tensile strength GB/T 1040-92
Elongation at break GB/T 1040-92
Socle girder (breach) shock strength GB/T 1843-96
Abrasion intensity (sand milling consumption) ASTM MPC method
Melt flow rate (MFR) GB 3682-83
(standard mouth mould internal diameter 2.095mm, 190 ℃ of temperature, mouthful mode coefficient 4635g.mm
2, meet 21kg)
Test result is as follows:
Quality, 190g; Molecular weight, 2,300,000; Tensile strength, 27Mpa; Elongation at break, 475%; Socle girder (breach)
Shock strength, 150kJ/m
2Abrasion intensity (sand milling consumption), 30mg; Melt flow rate (MFR) 8mg/10min.
Embodiment 2 reactions: dispersion medium is selected normal hexane for use; Catalyzer: promotor=1: 10 (w/w); Catalyzer---TiBr
4Promotor---triisobutyl aluminium; 40～50 ℃ of polymerization temperatures; Polymerization pressure 2.5～3.0Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 1 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 194g; Molecular weight, 2,500,000; Tensile strength, 31Mpa; Elongation at break, 475%; Socle girder (breach) shock strength, 140kJ/m
2Abrasion intensity (sand milling consumption), 31mg; Melt flow rate (MFR) 10mg/10min.
All the other are with embodiment 1.
Embodiment 3 reactions: dispersion medium is selected isohexane for use; Catalyzer: promotor=1: 2 (w/w); Catalyzer---Ti (OCH
3) Cl
3Promotor---diethyl aluminum chloride; 70～75 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa;
Aftertreatment: reaction is finished, isohexane washing, polymerisate: isohexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 170g; Molecular weight, 2,600,000; Tensile strength, 29Mpa; Elongation at break, 575%; Socle girder (breach) shock strength, 155kJ/m
2Abrasion intensity (sand milling consumption), 40mg; Melt flow rate (MFR) 25mg/10min.
All the other are with embodiment 1.
Embodiment 4 reactions: dispersion medium is selected No. 6 solvent oils (60～90 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 12 (w/w); Catalyzer---Ti (OCH
3) Cl
3Promotor---diethyl aluminum chloride; 80～85 ℃ of polymerization temperatures; Polymerization pressure 0.1～0.5Mpa;
Aftertreatment: reaction is finished, No. 6 solvent oil washings, polymerisate: No. 6 solvent oil=1: 1 (w/w); Inferior 12 times of washing; Dry vacuum tightness 66.6～79.9Kpa, 50～60 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 190g; Molecular weight, 2,650,000; Tensile strength, 30Mpa; Elongation at break, 675%; Socle girder (breach) shock strength, 175kJ/m
2Abrasion intensity (sand milling consumption), 32mg; Melt flow rate (MFR) 20mg/10min.
All the other are with embodiment 1.
Embodiment 5 reactions: dispersion medium is selected special No. 1 solvent oil (80～120 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 15 (w/w); Catalyzer---TiCl
4Promotor---triisobutyl aluminium; 110～120 ℃ of polymerization temperature; Polymerization pressure 1.0～1.5Mpa; Aftertreatment: reaction is finished, special No. 1 solvent oil washing, polymerisate: special No. 1 solvent oil=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 15～20 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 182g; Molecular weight, 1,520,000; Tensile strength, 15Mpa; Elongation at break, 700%; Socle girder (breach) shock strength, 145kJ/m
2Abrasion intensity (sand milling consumption), 40mg; Melt flow rate (MFR) 30mg/10min.
All the other are with embodiment 1.
Embodiment 6 reactions: dispersion medium is selected special No. 2 solvent oils (60～90 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 6 (w/w); Catalyzer---Ti (OCH
3) Cl
3Promotor---diethyl aluminum chloride; 100～110 ℃ of polymerization temperature; Polymerization pressure 2.0～2.5Mpa; Aftertreatment: reaction is finished, special No. 2 solvent oils washing, polymerisate: special No. 2 solvent oil=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 79.9～93.3Kpa, 90～100 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 195g; Molecular weight, 2,800,000; Tensile strength, 31Mpa; Elongation at break, 475%; Socle girder (breach) shock strength, 145kJ/m
2Abrasion intensity (sand milling consumption), 26mg; Melt flow rate (MFR) 10mg/10min.
All the other are with embodiment 1.
Embodiment 7 reactions: dispersion medium is selected No. 90 solvent oils (60～90 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 7.5 (w/w); Catalyzer---Ti (OCH
3) Cl
2Promotor---aluminum ethylate; 90～100 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Aftertreatment: reaction is finished, No. 90 solvent oil washings, polymerisate: No. 90 solvent oil=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 190g; Molecular weight, 2,300,000; Tensile strength, 27Mpa; Elongation at break, 485%; Socle girder (breach) shock strength, 145kJ/m
2Abrasion intensity (sand milling consumption), 20mg; Melt flow rate (MFR) 5mg/10min.
All the other are with embodiment 1.
Embodiment 8 reactions: dispersion medium is selected hexane oil or solvent oil (55～80 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 8.5 (w/w); Catalyzer---Ti (OCH
3)
4Promotor---diethyl aluminum chloride; 80～90 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Washing times 2 times; Dry vacuum tightness 79.9～93.3; 100～120 ℃ of drying temperatures.
Product detected result: quality, 195g; Molecular weight, 2,450,000; Tensile strength, 29Mpa; Elongation at break, 695%; Socle girder (breach) shock strength, 158kJ/m
2Abrasion intensity (sand milling consumption), 30mg; Melt flow rate (MFR) 15mg/10min.
All the other are with embodiment 1.
Embodiment 9 reactions: dispersion medium is selected isohexane for use; Catalyzer: promotor=1: 13 (w/w); Catalyzer---TiBr
4Promotor---triethyl aluminum; 70～80 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 1 (w/w); Washing times 1 time; Dry vacuum tightness 66.6～79.9Kpa, 110～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 185g; Molecular weight, 2,190,000; Tensile strength, 24Mpa; Elongation at break, 685%; Socle girder (breach) shock strength, 160kJ/m
2Abrasion intensity (sand milling consumption), 35mg; Melt flow rate (MFR) 25mg/10min.
All the other are with embodiment 1.
Embodiment 10 reactions: dispersion medium is selected normal hexane or isohexane for use; Catalyzer: promotor=1: 4 (w/w); Catalyzer---TiCl
4Promotor---the basic aluminum chloride of two skills; 50～60 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Product: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 190g; Molecular weight, 2,300,000; Tensile strength, 27Mpa; Elongation at break, 485%; Socle girder (breach) shock strength, 145kJ/m
2Abrasion intensity (sand milling consumption), 20mg; Melt flow rate (MFR) 5mg/10min.
All the other are with embodiment 1.
Embodiment 11 reactions: dispersion medium is selected No. 6 solvent oils (60～90 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 7 (w/w); Catalyzer---Ti (OCH
3) Cl
3+ TiBr
4Promotor---triisobutyl aluminium+diethyl aluminum chloride; 60～70 ℃ of polymerization temperatures; Polymerization pressure 0.1～0.5Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 53.3～66.6Kpa, 90～100 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 194g; Molecular weight, 2,500,000; Tensile strength, 31Mpa; Elongation at break, 475%; Socle girder (breach) shock strength, 140kJ/m
2Abrasion intensity (sand milling consumption), 31mg; Melt flow rate (MFR) 10mg/10min.
All the other are with embodiment 1.
Embodiment 12 reactions: dispersion medium is selected special No. 1 solvent oil (80～120 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 3 (w/w); Catalyzer---TiBr
4Promotor---diethyl aluminum chloride; 70～75 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 90～100 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 190g; Molecular weight, 2,650,000; Tensile strength, 30Mpa; Elongation at break, 675%; Socle girder (breach) shock strength, 175kJ/m
2Abrasion intensity (sand milling consumption), 32mg; Melt flow rate (MFR) 20mg/10min.
All the other are with embodiment 1.
Embodiment 13 reactions: dispersion medium is selected No. 90 solvent oils (60～90 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 10 (w/w); Catalyzer---Ti (OCH
3) Cl
3+ TiBr
4Promotor---aluminum ethylate+diethoxy aluminum chloride; 80～85 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 53.3～66.6Kpa, 100～120 ℃ of temperature;
Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 195g; Molecular weight, 2,560,000; Tensile strength, 35Mpa; Elongation at break, 575%; Socle girder (breach) shock strength, 135kJ/m
2Abrasion intensity (sand milling consumption), 31mg; Melt flow rate (MFR) 10mg/10min.
All the other are with embodiment 1.
Embodiment 14 reactions: dispersion medium is selected isohexane for use; Catalyzer: promotor=1: 6 (w/w); Catalyzer---TiBr
4Promotor---diethoxy aluminum chloride; 90～95 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 185g; Molecular weight, 2,190,000; Tensile strength, 24Mpa; Elongation at break, 685%; Socle girder (breach) shock strength, 160kJ/m
2Abrasion intensity (sand milling consumption), 35mg; Melt flow rate (MFR) 25mg/10min.
All the other are with embodiment 1.
Embodiment 15 reactions: dispersion medium is selected hexane oil (55～80 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 10 (w/w); Catalyzer---TiCl
4Promotor---diethyl aluminum chloride; 40～50 ℃ of polymerization temperatures; Polymerization pressure 1.0～1.5Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 50～6120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 175g; Molecular weight, 2,390,000; Tensile strength, 28Mpa; Elongation at break, 475%; Socle girder (breach) shock strength, 155kJ/m
2Abrasion intensity (sand milling consumption), 25mg; Melt flow rate (MFR) 20mg/10min.
All the other are with embodiment 1.
Embodiment 16 reactions: dispersion medium is selected normal hexane for use; Catalyzer: promotor=1: 6 (w/w); Catalyzer---Ti (OCH
3) Cl
2Promotor---triethyl aluminum; 60～70 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 79.9～93.3Kpa, 70～80 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 235g; Molecular weight, 2,480,000; Tensile strength, 28Mpa; Elongation at break, 385%; Socle girder (breach) shock strength, 167kJ/m
2Abrasion intensity (sand milling consumption), 32mg; Melt flow rate (MFR) 15mg/10min.
All the other are with embodiment 1.
Embodiment 17
Reaction: dispersion medium is selected hexane oil for use; Catalyzer: promotor=1: 15 (w/w); Catalyzer---Ti (OCH
3) Cl
3Promotor---triethyl aluminum+triisobutyl aluminium; 80～90 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～110 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w) washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 315g; Molecular weight, 2,590,000; Tensile strength, 34Mpa; Elongation at break, 450%; Socle girder (breach) shock strength, 155kJ/m
2Abrasion intensity (sand milling consumption), 18mg; Melt flow rate (MFR) 22mg/10min.
All the other are with embodiment 1.
Embodiment 18 reactions: dispersion medium is selected normal hexane for use; Catalyzer: promotor=1: 2 (w/w); Catalyzer---TiBr
4+ Ti (OCH
3) Cl
3Promotor---diethyl aluminum chloride; 50～60 ℃ of polymerization temperatures; Polymerization pressure 2.5～3.0Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w);
Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 185g; Molecular weight, 2,190,000; Tensile strength, 24Mpa; Elongation at break, 685%; Socle girder (breach) shock strength, 160kJ/m
2Abrasion intensity (sand milling consumption), 35mg; Melt flow rate (MFR) 25mg/10min.
All the other are with embodiment 1.
Embodiment 19 reactions: dispersion medium is selected isohexane for use; Catalyzer: promotor=1: 8 (w/w); Catalyzer---Ti (OCH
3) Cl
3Promotor---aluminum ethylate+triethyl aluminum; 70～75 ℃ of polymerization temperatures; Polymerization pressure 0.10～0.5Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 12 (w/w); Inferior 12 times of washing; Dry vacuum tightness 66.6～79.9Kpa, 80～90 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 182g; Molecular weight, 1,520,000; Tensile strength, 15Mpa; Elongation at break, 700%; Socle girder (breach) shock strength, 145kJ/m
2Abrasion intensity (sand milling consumption), 40mg; Melt flow rate (MFR) 30mg/10min.
All the other are with embodiment 1.
Embodiment 20 reactions: dispersion medium is selected No. 90 solvent oils (60～90 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 9 (w/w); Catalyzer---Ti (OCH
3) Cl
3+ TiBr
4Promotor---triethyl aluminum+aluminum ethylate; 90～95 ℃ of polymerization temperatures; Polymerization pressure 0.5～1.5Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 182g; Molecular weight, 1,520,000; Tensile strength, 15Mpa; Elongation at break, 700%; Socle girder (breach) shock strength, 145kJ/m
2Abrasion intensity (sand milling consumption), 40mg; Melt flow rate (MFR) 30mg/10min.
All the other are with embodiment 1.
Embodiment 21 reactions: dispersion medium is selected special No. 1 solvent oil (80～120 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 8 (w/w); Catalyzer---TiBr
4Promotor---diethoxy aluminum chloride; 70～75 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 1.5 (w/w); Washing times 2 times; 100～120 ℃ of dry vacuum tightness 79.9～93.3 dry temperature.
Product detected result: quality, 232g; Molecular weight, 1,920,000; Tensile strength, 35Mpa; Elongation at break, 550%; Socle girder (breach) shock strength, 180kJ/m
2Abrasion intensity (sand milling consumption), 20mg; Melt flow rate (MFR) 20mg/10min.
All the other are with embodiment 1.
Embodiment 22 reactions: dispersion medium is selected No. 6 solvent oils (60～90 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 2 (w/w); Catalyzer---TiCl
4Promotor---diethoxy aluminum chloride; 80～85 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 60～70 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 252g; Molecular weight, 2,320,000; Tensile strength, 18Mpa; Elongation at break, 590%; Socle girder (breach) shock strength, 185kJ/m
2Abrasion intensity (sand milling consumption), 38mg; Melt flow rate (MFR) 26mg/10min.
All the other are with embodiment 1.
Embodiment 23 reactions: dispersion medium is selected isohexane for use; Catalyzer: promotor=1: 10 (w/w); Catalyzer---Ti (OCH
3)
4Promotor---triethyl aluminum; 110～120 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 1 (w/w); Washing times 1 time; Dry
Vacuum tightness 66.6～79.9Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 222g; Molecular weight, 1,590,000; Tensile strength, 35Mpa; Elongation at break, 555%; Socle girder (breach) shock strength, 195kJ/m
2Abrasion intensity (sand milling consumption), 30mg; Melt flow rate (MFR) 15mg/10min.
All the other are with embodiment 1.
Embodiment 24 reactions: dispersion medium is selected normal hexane for use; Catalyzer: promotor=1: 10 (w/w); Catalyzer---Ti (OCH
3) Cl
3Promotor---aluminum ethylate; 70～75 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa;
Aftertreatment: reaction is finished, normal hexane washing, polymerisate: normal hexane=1: 1.5 (w/w); Washing times 2 times; Dry vacuum tightness 66.6～79.9Kpa, 50～60 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 232g; Molecular weight, 2,520,000; Tensile strength, 45Mpa; Elongation at break, 650%; Socle girder (breach) shock strength, 195kJ/m
2Abrasion intensity (sand milling consumption), 40mg; Melt flow rate (MFR) 20mg/10min.
All the other are with embodiment 1.
Embodiment 25 reactions: dispersion medium is selected hexane oil (55～80 ℃ of boiling ranges) for use; Catalyzer: promotor=1: 10 (w/w); Catalyzer---Ti (OCH
3) Cl
2Promotor---triisobutyl aluminium; 90～100 ℃ of polymerization temperatures; Polymerization pressure 2.0～2.5Mpa; Aftertreatment: reaction is finished, hexane oil wash, polymerisate: hexane oil=1: 2 (w/w); Washing times 2 times; Dry vacuum tightness 79.9～93.3Kpa, 100～120 ℃ of temperature; Water washing, polymerisate: washing water=1: 10～15 (w/w); Washing times 2 times; 100～120 ℃ of drying temperatures.
Product detected result: quality, 182g; Molecular weight, 1,520,000; Tensile strength, 15Mpa; Elongation at break, 700%; Socle girder (breach) shock strength, 145kJ/m
2Abrasion intensity (sand milling consumption), 40mg; Melt flow rate (MFR) 30mg/10min.
All the other are with embodiment 1.
Claims (5)
1, a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE) is characterized in that: with the alkane solvents is dispersion medium, is catalyzer with the titanium compound, is promotor with the organo-aluminium compound; At polymerization temperature is 40～120 ℃, and polymerization pressure is under 0.1～3.0Mpa condition; Make the vinyl monomer polymerization reaction take place obtain the polymerisate ultrahigh molecular weight polyethylene(UHMWPE); Wherein:
Described dispersion medium alkane solvents is meant one or more the mixture in normal hexane, isohexane, hexane oil or the solvent oil;
Titanium compound is TiCl in the described catalyzer
4, TiBr
4, Ti (OCH
3) Cl
3, Ti (OCH
3) Cl
2, Ti (OCH
3)
4In one or more mixture;
Described organo-aluminium compound is meant one or more the mixture in triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, aluminum ethylate or the diethoxy aluminum chloride;
Described catalyzer and promotor weight proportion are 1: 2～15.
2, the preparation method of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1 is characterized in that described polymerization temperature is 70～95 ℃.
3, the preparation method of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1 is characterized in that described catalyzer and promotor weight proportion are 1: 6～10.
4, the preparation method of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1 is characterized in that described hexane oil or solvent oil are meant that boiling range is at 55～120 ℃ commercial goods hexane oil or solvent oil.
5, the aftertreatment technology of ultrahigh molecular weight polyethylene(UHMWPE) according to claim 1 comprises filtration, solvent wash, and drying, washing and screening is characterized in that:
During the polymerisate solvent wash, solvent for use is one or more the mixture in normal hexane, the isohexane, and the weight proportion of polymerisate and solvent is 1: 1～2 during washing, washs 1～2 time;
When dry, vacuum tightness is 53.3～93.3Kpa, 50～120 ℃ of drying temperatures;
During the polymerisate water washing, with 80～90 ℃ of hot water making beating washings, the weight proportion of polymerisate and described hot water is 1: 1～20 during washing, washs 1～2 time; Get product through routine oven dry and screening at last.
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| CN103102438B (en) * | 2013-01-16 | 2015-02-04 | 河南科技大学 | Ultrahigh molecular weight polyethylene graphene composite material prepared by liquid-phase in situ polymerization method |
| CN107778388B (en) * | 2016-08-29 | 2019-12-27 | 中国石油化工股份有限公司 | Continuous washing device and method for ultrahigh molecular weight polyethylene |
| CN111571923B (en) * | 2020-05-25 | 2022-07-01 | 绍兴市希比斯新材料有限公司 | Preparation process of ultrahigh molecular weight polyethylene for skis |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100569A (en) * | 1987-02-11 | 1988-10-05 | 斯塔米卡本公司 | Be used for ethene high temperature (being total to) polymeric catalyst system |
| CN1080933A (en) * | 1992-06-24 | 1994-01-19 | 赫彻斯特股份公司 | Be suitable for making vinyl polymerization and copolymerization to become the preparation method of the catalyst system of ultra high molecular polyethylene |
| CN1106025A (en) * | 1993-09-27 | 1995-08-02 | 赫彻斯德股份公司 | Process for the preparation of ultrahigh molecular weight polyethylene having a high bulk density |
| EP0909769A2 (en) * | 1997-10-14 | 1999-04-21 | Phillips Petroleum Company | Olefin polymerization processes and products thereof |
| TW446717B (en) * | 1998-05-25 | 2001-07-21 | Usi Corp | Catalyst composition for the production of ultra-high molecular weight polyethylene |
| CN1452637A (en) * | 2000-04-24 | 2003-10-29 | 三星综合化学株式会社 | Catalyst for producing ultra high molecular weight polyethylene and method for producing ultra high molecular weight polyethylene using same |
-
2004
- 2004-05-13 CN CNB2004100241038A patent/CN1301273C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100569A (en) * | 1987-02-11 | 1988-10-05 | 斯塔米卡本公司 | Be used for ethene high temperature (being total to) polymeric catalyst system |
| CN1080933A (en) * | 1992-06-24 | 1994-01-19 | 赫彻斯特股份公司 | Be suitable for making vinyl polymerization and copolymerization to become the preparation method of the catalyst system of ultra high molecular polyethylene |
| CN1106025A (en) * | 1993-09-27 | 1995-08-02 | 赫彻斯德股份公司 | Process for the preparation of ultrahigh molecular weight polyethylene having a high bulk density |
| EP0909769A2 (en) * | 1997-10-14 | 1999-04-21 | Phillips Petroleum Company | Olefin polymerization processes and products thereof |
| TW446717B (en) * | 1998-05-25 | 2001-07-21 | Usi Corp | Catalyst composition for the production of ultra-high molecular weight polyethylene |
| CN1452637A (en) * | 2000-04-24 | 2003-10-29 | 三星综合化学株式会社 | Catalyst for producing ultra high molecular weight polyethylene and method for producing ultra high molecular weight polyethylene using same |
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