CN102952222B - Ultra-high molecular weight polyethylene resin and preparation method thereof - Google Patents
Ultra-high molecular weight polyethylene resin and preparation method thereof Download PDFInfo
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- CN102952222B CN102952222B CN201110253287.5A CN201110253287A CN102952222B CN 102952222 B CN102952222 B CN 102952222B CN 201110253287 A CN201110253287 A CN 201110253287A CN 102952222 B CN102952222 B CN 102952222B
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Abstract
The invention discloses an ultra-high molecular weight polyethylene resin and a preparation method thereof, particularly an ultra-high molecular weight polyethylene resin prepared by using an ultrasonic-treated supported titanium catalyst and a preparation method thereof, belonging to the technical field of high polymer materials. The preparation method comprises the following steps: by using an ultra-high molecular weight polyethylene catalyst as a main catalyst and alkyl aluminum as a cocatalyst, adding a polymerization solvent and an outer electron donor to carry out homopolymerization under non-hydrogen conditions by a slurry polymerization technique. The preparation method disclosed by the invention can easily implement industrialization, and has the advantages of favorable adjustability of technological conditions and high reaction kinetic stability of the catalyst. The ultra-high molecular weight polyethylene resin prepared by the method has the advantages of higher viscosity-average molecular weight and adjustable molecular weight, and effectively lowers the content of fine powder in resin granules.
Description
Technical field
The present invention relates to a kind of polyvinyl resin with super-high molecular weight and preparation method thereof, belong to technical field of polymer materials, be specifically related to a kind of polyvinyl resin with super-high molecular weight utilizing the load-type Titanium series catalyst of ultrasonication to manufacture and preparation method thereof.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) refers to the linear structure polyethylene of viscosity-average molecular weight more than 1,500,000.Its molar mass average is tens times of conventional high density polyethylene (HDPE), the molecular weight of superelevation invests its outstanding properties not available for other polymer materialss many, as: both made still to there is high shock resistance, high wear resisting property, high erosion resistance, self lubricity, high comprehensive temperature tolerance, good performance muffler, good anti-stress cracking ability at quite low temperatures, meet the advantages such as hygienic standard.UHMWPE is widely used in the numerous areas such as weaving, papermaking, transport, packaging, machinery, chemical industry, mining, oil, agricultural, building, electrical equipment, medical treatment, physical culture and Refrigeration Technique because of its distinctive performance advantage, and its high-strength modulus and high tensile can be utilized in addition to produce high-performance fiber.
At present, the preparation method of polyvinyl resin with super-high molecular weight mainly adopts Ziegler low pressure slurry process, namely with β-TiCl
3/ Al (C
2h
5)
2cl or TiCl
4/ Al (C
2h
5)
2cl is catalyzer, and 60 ~ 120 DEG C of stable hydrocarbon are dispersion medium, and ethene is polymerized under normal pressure and 75 ~ 85 DEG C of conditions, the product of obtained different molecular weight.
CN1746197A discloses a kind of extra high-molecular polythene catalyst and preparation method thereof and application, this catalyzer forming containing titanium component and silicon containing component by magnesium-containing compound load, under organo-aluminium compound coordinates, during for the preparation of ultrahigh molecular weight polyethylene(UHMWPE), fine powder and coarse particles growing amount can be reduced, improve bulk density.
CN101161690A discloses a kind of Catalysts and its preparation method for the preparation of ultrahigh molecular weight polyethylene(UHMWPE), the Primary Catalysts of this catalyzer by titaniferous and the promotor containing aluminium form, wherein Primary Catalysts is reacted by nascent state magnesium chloride and electron donor and titanium compound and obtains, the ultrahigh molecular weight polyethylene(UHMWPE) that catalyzer is obtained thus, bulk density is at 0.35 ~ 0.40 grams per milliliter, and fine powder content is few.
CN101654492A discloses a kind of ultrahigh molecular weight polyethylene(UHMWPE), its preparation method and application thereof, this invention adopts a kind of specific load type non-metallocene catalyst for the manufacture of ultrahigh molecular weight polyethylene(UHMWPE), during for scale production, effectively can avoid dust from flying and reduce the danger that dust explosion occurs.The bulk density of ultrahigh molecular weight polyethylene(UHMWPE) constructed in accordance is high, good fluidity, narrow diameter distribution, and the mass content of fine powder is low, and has high simple beam impact strength.
CN101831015A discloses a kind of catalyzer preparing ultrahigh molecular weight polyethylene(UHMWPE), this catalyst system comprises the carrier loaded titanium catalyst solid major constituent of magnesium compound and alkylaluminium cpd cocatalyst component, be characterized in adding carbonic acid gas in the preparation process of catalyst solid major constituent, alcohol and silicon compound process magnesium compound carrier, and the content by regulating the add-on of titanic acid ester to regulate titanium and ester in catalyst system in the process of supported titanium, change the energy for growth of polymkeric substance on catalyst activity position, regulate catalyzer initial activity, improve polymer performance.By this catalyst preparing ultrahigh molecular weight polyethylene(UHMWPE) particle diameter within the specific limits, and fine powder and coarse grained growing amount reduce, and tap density is high.
In existing document, also do not find preparation process ultrasonic technology being applied to extra high-molecular polythene catalyst, thus improve the particle form of fluoropolymer resin, reduce the report of fine powder content.
Summary of the invention
The object of the present invention is to provide a kind of polyvinyl resin with super-high molecular weight and preparation method thereof, the method is utilized to carry out the production of ultrahigh molecular weight polyethylene(UHMWPE), simple process, cost are low, easy handling controls, the polyvinyl resin with super-high molecular weight obtained thus has higher viscosity-average molecular weight, and fine powder content is few.
Polyvinyl resin with super-high molecular weight of the present invention, be take extra high-molecular polythene catalyst as Primary Catalysts, aluminum alkyls is promotor, adopts slurry polymerization processes, by adding polymer solvent and external electron donor, under the condition of not facing hydrogen, carrying out ethylene homo obtain;
The amount ratio of promotor and Primary Catalysts is 0.05 ~ 5.0 moles per gram, and promotor is with aluminium element molar basis, and the consumption of external electron donor is 0.2 ~ 6.0 × 10
-6mol/L polymer solvent, the consumption of external electron donor is with the molar basis in polymer solvent unit volume;
The preparation method of described Primary Catalysts is as follows:
(1) magnesium halide and alcohol reaction form magnesium alkoxide compound, and the add-on of alcohol, with the use gauge of magnesium halide, is 2 ~ 10mol alcohol/mol magnesium halide;
(2) magnesium alkoxide compound and SiCl
4reaction formation one intermediate product, SiCl
4add-on, with the use gauge of magnesium halide, is 1.5 ~ 15mol SiCl
4/ mol magnesium halide;
(3) carry out ultrasonication to gained intermediate product, ultrasonic generator power is 15 ~ 400W; Ultrasonic generator frequency is 20 ~ 200KHz; Treatment time is 0.5 ~ 60 minute;
(4) after ultrasonication terminates, then add titanium compound and be obtained by reacting catalyzer, the add-on of titanium compound with magnesium halide with gauge, be 2 ~ 6mol titanium compound/mol magnesium halide.
Described magnesium halide is: one or more in halogenated magnesium compound, alkoxy magnesium compound or alkyl halide magnesium compound;
Described halogenated magnesium compound is: magnesium chloride, magnesium bromide or magnesium fluoride, preferred magnesium chloride;
Described alkyl halide magnesium compound is: methylmagnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, methyl-magnesium-bromide, ethylmagnesium bromide, propyl group magnesium bromide or butyl magnesium bromide, preferable methyl magnesium chloride;
Described alkoxy magnesium compound is: methoxyl group magnesium chloride, oxyethyl group magnesium chloride, propoxy-magnesium chloride, butoxy magnesium chloride, methoxyl group magnesium bromide, oxyethyl group magnesium bromide, propoxy-magnesium bromide or butoxy magnesium bromide, preferred methoxyl group magnesium chloride;
Described magnesium halide most preferably magnesium chloride.
Described hydrocarbon solvent is: C
5~ C
15aliphatic compound or compound fragrant hydrocarbon;
Described C
5~ C
15aliphatic compound be preferably: Skellysolve A, iso-pentane, normal hexane, heptane, octane or decane;
Described compound fragrant hydrocarbon is preferably: benzene or toluene;
Described hydrocarbon solvent is normal hexane and heptane most preferably.
Described alcohol is: C
2~ C
20alcohol; Preferred: C
2~ C
8alcohol, as ethanol, n-propyl alcohol, propyl carbinol, isooctyl alcohol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, preferred alcohol, butanols, 2-ethyl butanol, more preferably ethanol, butanols, the add-on of alcohol uses gauge with magnesium halide.
Described titanium compound is: titanium tetrachloride, butyl (tetra) titanate, methoxytitanium trichloride or three butoxy titanium chlorides, preferred titanium tetrachloride.
Described ultrasonication: ultrasonic generator power preferably 40 ~ 150W, more preferably 50 ~ 100W; Ultrasonic generator frequency preferably 30 ~ 100KHz, more preferably 40 ~ 80KHz; Ultrasonic treatment time preferably 1 ~ 30 minute, more preferably 2 ~ 10 minutes.
Described polymer solvent is C
5~ C
15aliphatic compound or compound fragrant hydrocarbon;
Described C
5~ C
15aliphatic compound be pentane, hexane, heptane, octane, nonane, decane, 6# solvent oil or 120# solvent oil, preferred hexane, heptane, 6# solvent oil, more preferably 6# solvent oil;
Described compound fragrant hydrocarbon is toluene or dimethylbenzene.
Described external electron donor is silane compound, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dipropyl dimethoxysilane or diphenyl diethoxy silane, preferred dimethyldiethoxysilane.The consumption of external electron donor with the molar basis in solvent unit volume, preferably 1.0 ~ 3.0 × 10
-6mol/L polymer solvent.
Described aluminum alkyls is one or more in trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride or dibutyl aluminum bromide.
In the present invention, Primary Catalysts need with promotor aluminum alkyls with the use of, described Primary Catalysts is load-type Titanium series catalyst, and described promotor is aluminum alkyls, amount ratio preferably 0.2 ~ 2.0 moles per gram of promotor and Primary Catalysts, promotor is with aluminium element molar basis.
In described polymerization technique, temperature of reaction is 30 ~ 95 DEG C, and reaction pressure is 0.2 ~ 1.2MPa.
The method of described polyvinyl resin with super-high molecular weight, comprises the following steps:
(1) preparation of Primary Catalysts-extra high-molecular polythene catalyst:
1. under protection of inert gas, magnesium halide is put into the container with whipping appts, add hydrocarbon solvent, heat up and stir;
2. add alcohol by step solution 1., form a kind of magnesium alkoxide compound with magnesium halide, under constant temperature, stir 0.5 ~ 3 hour, the add-on of alcohol with magnesium halide with gauge, be 2 ~ 10mol alcohol/mol magnesium halide;
3. SiCl is added in the magnesium alkoxide compound 2. obtained to step
4, constant temperature stirs 0.5 ~ 1 hour, SiCl
4add-on, with the use gauge of magnesium halide, is 1.5 ~ 15mol SiCl
4/ mol magnesium halide;
4. step solution is 3. carried out ultrasonication, ultrasonic generator frequency is 20 ~ 200KHz, and ultrasonic generator power is 15 ~ 400W, and the treatment time is 0.5 ~ 60 minute; After ultrasonication terminates, continue constant temperature and stir 0.5 ~ 2 hour;
5. in the solution through ultrasonication, add titanium compound, constant temperature stirs 1 ~ 3 hour, and the add-on of titanium compound, with the use gauge of magnesium halide, is 2 ~ 6mol titanium compound/mol magnesium halide;
6. stop stirring, carry out slurries and leave standstill, after slurries layering, by the clear liquid sucking-off not containing granules of catalyst, add hydrocarbon solvent and granules of catalyst is washed, dry obtained extra high-molecular polythene catalyst;
(2) be polymerized: first polymerization reaction kettle to be vacuumized or after nitrogen replacement, add polymer solvent and external electron donor, open and stir, then promotor and Primary Catalysts is added, heat up, pass into vinyl monomer, cause vinyl monomer by catalyzer and carry out polyreaction, temperature of reaction is by chuck refrigeration cycle water management, the resin particle generated is suspended in polymer solvent and forms polymer slurries, by obtained after polymer slurries desolvation, the amount ratio of promotor and Primary Catalysts is 0.05 ~ 5.0 moles per gram, promotor is with aluminium element molar basis, the consumption of external electron donor is 0.2 ~ 6.0 × 10
-6mol/L polymer solvent, the consumption of external electron donor is with the molar basis in polymer solvent unit volume, and temperature of reaction is 30 ~ 95 DEG C, and reaction pressure is 0.2 ~ 1.2MPa.
Specifically, first polymerization reaction kettle vacuumized or after nitrogen replacement, add solvent and external electron donor, opening and stir, then promotor and above-mentioned Primary Catalysts is added, heat up, pass into vinyl monomer, cause vinyl monomer by catalyzer and carry out polyreaction, temperature of reaction is by chuck refrigeration cycle water management, the resin particle generated suspends and forms polymer slurries in a solvent, after polymer slurries desolvation, namely obtains required polyvinyl resin with super-high molecular weight.Wherein, solvent add that volume is generally reactor volume 0.6 ~ 0.8.Temperature of reaction 30 ~ 95 DEG C, preferably 50 ~ 85 DEG C, reaction pressure 0.2 ~ 1.2MPa, preferably 0.4 ~ 0.8MPa.Stirring velocity can be selected according to reactor volume size, and be generally 60 ~ 300 revs/min, the reactor of small volume can adopt very fast rotating speed, is greater than 1m
3reactor then adopt the comparatively slow speed of revolution, stirring rake form can adopt frame or anchor formula to stir, and removing thermal effect, also stirring rake can be made the form that can pass into recirculated water for strengthening reactor.The adding form dry powder can be adopted to add of Primary Catalysts, also can with polymer solvent premix after add in still.
The present invention, by introducing ultrasonication technology, can make catalyst carrier particle obtain rapid homogenization, reduce the agglomeration of carrier granule simultaneously, obtain highly active extra high-molecular polythene catalyst.With above-mentioned gained catalyzer for Primary Catalysts, under the cooperation of promotor, adopt slurry polymerization processes, by adding external electron donor, under the condition of not facing hydrogen, carry out ethylene homo, can fine powder content be obtained low, the polyvinyl resin with super-high molecular weight that molecular weight is higher, and the Primary Catalysts kinetics of polymerization reaction used is steady, is easy to production operation and controls.
Adopt ultrahigh molecular weight polyethylene Preparation Method of the present invention, effectively can reduce dust hazard, improve operating environment.Because the kinetics of polymerization reaction of catalyzer is steady, production operation is very easy to control, and by changing polymeric reaction condition, also can regulate the molecular weight of polyvinyl resin with super-high molecular weight, viscosity-average molecular weight is more than 3,000,000.The particle diameter of polyvinyl resin with super-high molecular weight particle obtained thus mainly concentrates on 20 ~ 140 orders, particle diameter is less than the mass content of the fine powder resin particle of 200 orders (75 microns) lower than 1%, can be applicable to manufacture high molecular weight polyethylene board material, tubing, bar, sheet material, profiled material, film and special fibre.
Compared with prior art, the advantage of the polyvinyl resin with super-high molecular weight adopting the present invention to prepare is as follows:
(1) method for preparing catalyst is simple, is convenient to implement.
(2) catalyst activity is high, and under polymerization temperature 60 DEG C, polymerization pressure 0.6MPa condition, polyreaction 1 hour, the polymerization activity of catalyzer can reach more than 50KgPE/gCat.
(3) fine powder content of polymkeric substance is low, and granularity is more concentrated.
(4) resin preparation process is simple, and be easy to industrial implementation, stable polymerization reaction, production process is easily controlled.
Accompanying drawing explanation
Fig. 1 is kinetics of polymerization reaction graphic representation.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
In this specification sheets embodiment, the salient features testing method of catalyst performance and polymerisate is as follows:
The calculating of polymerization catalyst activity: the polymerization UHMWPE gross weight of gained and the ratio of catalyzer dosage in the unit time, unit is KgPE/gCat.
Molecular weight determination: adopt viscosimetry to measure, make solvent, temperature 135 DEG C with perhydronaphthalene, adopts Ubbelohde viscometer to measure the time of polyethylene solution outflow, then calculates the intrinsic viscosity η of polymkeric substance.According to formula
M
γ＝5.37×10
4×[η]
1·37
The M of gained
γbe the molecular weight of polymkeric substance.
The size distribution of polyvinyl resin with super-high molecular weight adopts method of sieving.
Embodiment 1:
(1) preparation of extra high-molecular polythene catalyst
The glass flask of being furnished with whipping appts and reflux condensation mode system is fully cleaned with nitrogen, under nitrogen protection, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, and add 5ml propyl carbinol, at 70 DEG C, under stirring velocity 250 revs/min of conditions, constant temperature stirs 0.5 hour, obtains magnesium alkoxide compound solution; Be cooled to 20 DEG C, slowly drip 5ml SiCl
4, after carrier magnesium chloride is separated out, stir 0.5 hour at being warming up to 70 DEG C; Open ultrasonic generator, setpoint frequency was 40KHz, and power is 50W, to suspension process 3 minutes; Close ultrasonic generator, continue constant temperature at 70 DEG C and stir 0.5 hour; Be cooled to 20 DEG C, slowly add 4ml titanium tetrachloride, at 70 DEG C, constant temperature stirs 2 hours; With normal hexane cleaning catalyst particle several, drying obtains catalyst fines.
(2) preparation of polyvinyl resin with super-high molecular weight
After carrying out vacuum pump drainage to 2L stainless steel polymeric kettle, adding polymer solvent is the industrial 6# solvent oil and 1.2 × 10 of 1.2L after processed
-6the dimethyldiethoxysilane of mol/L polymer solvent, then Primary Catalysts 1.5mg prepared by promotor triethyl aluminum 5ml and step (1) is added, open and stir, mixing speed is 210 revs/min, and raise temperature in the kettle to 60 DEG C by chuck recirculated water, then passing into ethene to polymeric kettle pressure is 0.6MPa, keep polymeric kettle temperature, constant pressure, polyreaction was lowered the temperature after 1 hour, and discharging is also dry, obtains Powdered polyvinyl resin with super-high molecular weight.Polymerization result is in table 1, and product size data is in table 2, and polymerization kinetics curve is shown in Fig. 1.
Embodiment 2:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, the ultrasonic generator treatment time is 0.5 minute, ultrasonic generator frequency setting is 60KHz, and power setting is 300W.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 3:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, the ultrasonic generator treatment time is 5 minutes, and ultrasonic generator power setting is 80W, and hydrocarbon solvent changes heptane into.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 4:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, the ultrasonic generator treatment time is 10 minutes, ultrasonic generator power setting is 150W.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 5:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, ultrasonic generator frequency setting is 80KHz, power setting is 100W, and the ultrasonic generator treatment time is 20 minutes.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 6:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, ultrasonic generator frequency setting is 120KHz, power setting is 200W, and the ultrasonic generator treatment time is 30 minutes.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 7:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, ultrasonic generator frequency setting is 20KHz, power setting is 400W, and the ultrasonic generator treatment time is 40 minutes.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 8:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, ultrasonic generator frequency setting is 160KHz, power setting is 30W, and the ultrasonic generator treatment time is 50 minutes.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 9:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, ultrasonic generator frequency setting is 200KHz, power setting is 15W, and the ultrasonic generator treatment time is 60 minutes.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 10:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, propyl carbinol dosage is 2ml, SiCl
4dosage is 2ml, and titanium tetrachloride dosage is 2ml.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 11:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, propyl carbinol dosage is 5ml, SiCl
4dosage is 10ml, and titanium tetrachloride dosage is 6ml.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 12:
(1) preparation of extra high-molecular polythene catalyst
Adopt the catalyst component identical with embodiment 1 and preparation process, but in preparation process, propyl carbinol dosage is 8ml, SiCl
4dosage is 15ml, and titanium tetrachloride dosage is 4ml.
(2) preparation of polyvinyl resin with super-high molecular weight
Adopt the polymerizing condition identical with embodiment 1 and polymerization process, polymerization result is in table 1, and product size data is in table 2.
Embodiment 13:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, but polymerization temperature controls at 65 DEG C, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 14:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, but polymerization temperature controls at 72 DEG C, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 15:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is substantially the same manner as Example 1, but polymerization temperature controls at 72 DEG C, and polymerization pressure controls at 0.4MPa, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 16:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, but polymerization temperature controls at 72 DEG C, and polymerization pressure controls at 0.8MPa, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 17:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and polymer solvent changes hexane into, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 18:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and polymer solvent changes 120# solvent oil into, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 19:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and promotor changes triisobutyl aluminium into, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 20:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and external electron donor changes dimethyldimethoxysil,ne into, and polymerization result is in table 1, and product size data is in table 2.
Embodiment 21:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and external electron donor consumption is 2.4 × 10
-6mol/L polymer solvent, polymerization result is in table 1, and product size data is in table 2.
Embodiment 22:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and external electron donor consumption is 3.6 × 10
-6mol/L polymer solvent, polymerization result is in table 1, and product size data is in table 2.
Embodiment 23:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and external electron donor consumption is 0.2 × 10
-6mol/L polymer solvent, polymerization result is in table 1, and product size data is in table 2.
Embodiment 24:
(1) preparation of extra high-molecular polythene catalyst
Adopt catalyst component, preparation process and the supersonic treatment identical with embodiment 1.
(2) preparation of polyvinyl resin with super-high molecular weight
Polymerization process is identical with embodiment 1, and external electron donor consumption is 6.0 × 10
-6mol/L polymer solvent, polymerization result is in table 1, and product size data is in table 2.
Comparative example 1:
Primary Catalysts adopts commercially available extra high-molecular polythene catalyst, this catalyzer take magnesium chloride as carrier, active centre is titanium elements, most domestic UHMWPE manufacturer uses all to some extent, Primary Catalysts dosage is 10mg, process for preparing resins is with embodiment 1, and polymerization result is in table 1, and product size data is in table 2.
Table 1 ultrahigh molecular weight polyethylene(UHMWPE) polymerization result data sheet
The screening result table of table 2 polyvinyl resin with super-high molecular weight
As can be seen from table 1 data, the polymerization activity of catalyzer of the present invention is high, is the several times of catalyst activity in comparative example, and gained UHMWPE molecular resin amount is high, molecular resin amount is comparatively large by the impact of polymerization temperature, can control molecular resin amount by changing polymerization process condition., from the screening result table of table 2 resin, can find out, the UHMWPE resin particle using polymerization process of the present invention to prepare mainly concentrates between 30 ~ 120 orders meanwhile, is less than 200 object granule fines content below 1%, can reduces dust hazard.
Claims (7)
1. a preparation method for polyvinyl resin with super-high molecular weight, is characterized in that comprising the following steps:
(1) preparation of Primary Catalysts-extra high-molecular polythene catalyst:
1. under protection of inert gas, magnesium halide is put into the container with whipping appts, add hydrocarbon solvent, heat up and stir;
2. add alcohol by step solution 1., form a kind of magnesium alkoxide compound with magnesium halide, under constant temperature, stir 0.5 ~ 3 hour, the add-on of alcohol with magnesium halide with gauge, be 2 ~ 10mol alcohol/mol magnesium halide;
3. SiCl is added in the magnesium alkoxide compound 2. obtained to step
4, constant temperature stirs 0.5 ~ 1 hour, SiCl
4add-on, with the use gauge of magnesium halide, is 1.5 ~ 15mol SiCl
4/ mol magnesium halide;
4. step solution is 3. carried out ultrasonication, ultrasonic generator frequency is 20 ~ 200KHz, and ultrasonic generator power is 15 ~ 400W, and the treatment time is 0.5 ~ 60 minute; After ultrasonication terminates, continue constant temperature and stir 0.5 ~ 2 hour;
5. in the solution through ultrasonication, add titanium compound, constant temperature stirs 1 ~ 3 hour, and the add-on of titanium compound, with the use gauge of magnesium halide, is 2 ~ 6mol titanium compound/mol magnesium halide;
6. stop stirring, carry out slurries and leave standstill, after slurries layering, by the clear liquid sucking-off not containing granules of catalyst, add hydrocarbon solvent and granules of catalyst is washed, dry obtained extra high-molecular polythene catalyst;
(2) be polymerized: first polymerization reaction kettle to be vacuumized or after nitrogen replacement, add polymer solvent and external electron donor, open and stir, then promotor aluminum alkyls and Primary Catalysts is added, heat up, pass into vinyl monomer, cause vinyl monomer by catalyzer and carry out polyreaction, temperature of reaction is by chuck refrigeration cycle water management, the resin particle generated is suspended in polymer solvent and forms polymer slurries, by obtained after polymer slurries desolvation, the amount ratio of promotor and Primary Catalysts is 0.05 ~ 5.0 moles per gram, promotor is with aluminium element molar basis, the consumption of external electron donor is 0.2 ~ 6.0 × 10
-6mol/L polymer solvent, the consumption of external electron donor is with the molar basis in polymer solvent unit volume, temperature of reaction is 30 ~ 95 DEG C, and reaction pressure is 0.2 ~ 1.2MPa,
Described polymer solvent is: pentane, hexane, heptane, octane, nonane, decane, 6# solvent oil, 120# solvent oil, toluene or dimethylbenzene.
2. the preparation method of polyvinyl resin with super-high molecular weight according to claim 1, is characterized in that in the preparation method of described Primary Catalysts, magnesium halide is: one or more in halogenated magnesium compound, alkoxy magnesium compound or alkyl halide magnesium compound; Described hydrocarbon solvent is: C
5~ C
15aliphatic compound or compound fragrant hydrocarbon; Described alcohol is: C
2~ C
20alcohol; Described titanium compound is: titanium tetrachloride, butyl (tetra) titanate, methoxytitanium trichloride or three butoxy titanium chlorides.
3. the preparation method of polyvinyl resin with super-high molecular weight according to claim 2, is characterized in that described halogenated magnesium compound is: magnesium chloride, magnesium bromide or magnesium fluoride; Described alkyl halide magnesium compound is: methylmagnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, methyl-magnesium-bromide, ethylmagnesium bromide, propyl group magnesium bromide or butyl magnesium bromide; Described alkoxy magnesium compound is: methoxyl group magnesium chloride, oxyethyl group magnesium chloride, propoxy-magnesium chloride, butoxy magnesium chloride, methoxyl group magnesium bromide, oxyethyl group magnesium bromide, propoxy-magnesium bromide or butoxy magnesium bromide.
4. the preparation method of polyvinyl resin with super-high molecular weight according to claim 2, is characterized in that described C
5~ C
15aliphatic compound be: Skellysolve A, iso-pentane, normal hexane, heptane, octane or decane; Described compound fragrant hydrocarbon is: benzene or toluene.
5. the preparation method of polyvinyl resin with super-high molecular weight according to claim 2, is characterized in that described C
2~ C
20alcohol be: ethanol, n-propyl alcohol, propyl carbinol, isooctyl alcohol, 2-ethyl butanol or 2-Ethylhexyl Alcohol.
6. the preparation method of polyvinyl resin with super-high molecular weight according to claim 1, is characterized in that described external electron donor is: dimethyldimethoxysil,ne, dimethyldiethoxysilane, dipropyl dimethoxysilane or diphenyl diethoxy silane.
7. the preparation method of polyvinyl resin with super-high molecular weight according to claim 1, is characterized in that described aluminum alkyls is: one or more in trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride or dibutyl aluminum bromide.
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| CN103772560B (en) * | 2012-10-22 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of fiber polyvinyl resin with super-high molecular weight and preparation method thereof |
| CN108203481A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | The production method of ultra-high molecular weight polyethylene |
| CN107674134A (en) * | 2017-09-27 | 2018-02-09 | 中玺新材料（安徽）有限公司 | A kind of preparation method of ultra-high molecular weight polyethylene |
| CN108359033A (en) * | 2018-01-31 | 2018-08-03 | 公安县瑞凯高分子材料股份有限公司 | A kind of High molecular weight polyethylene and preparation method thereof and corrosion-resistant sand streak wax |
| CN110498873A (en) * | 2018-05-17 | 2019-11-26 | 中国石油天然气股份有限公司 | The preparation method and olefine polymerizing process of a kind of preprocess method of alkylaluminoxane, metallocene catalyst |
| CN114249851B (en) * | 2020-09-24 | 2023-03-14 | 中国科学院上海有机化学研究所 | Low bulk density ultra-high molecular weight polyethylene micro-powder |
| JP2024504507A (en) * | 2021-02-01 | 2024-01-31 | 中国石油化工股▲ふん▼有限公司 | Ultra-high molecular weight polyethylene and its manufacturing method |
| CN115584003A (en) * | 2021-07-05 | 2023-01-10 | 中国石油天然气股份有限公司 | High-density polyethylene resin for lithium battery diaphragm and preparation method thereof, lithium battery diaphragm and preparation method thereof |
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