WO2014063425A1 - 一种超高分子量聚乙烯树脂及其应用 - Google Patents

一种超高分子量聚乙烯树脂及其应用 Download PDF

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WO2014063425A1
WO2014063425A1 PCT/CN2012/087685 CN2012087685W WO2014063425A1 WO 2014063425 A1 WO2014063425 A1 WO 2014063425A1 CN 2012087685 W CN2012087685 W CN 2012087685W WO 2014063425 A1 WO2014063425 A1 WO 2014063425A1
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molecular weight
weight polyethylene
ultrahigh molecular
polyethylene resin
resin
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PCT/CN2012/087685
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English (en)
French (fr)
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周建勇
李晓庆
李留忠
毕晓龙
李文义
于永玲
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中国石油化工股份有限公司
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Priority to BR112015009074-5A priority Critical patent/BR112015009074B1/pt
Priority to EP12887048.2A priority patent/EP2910603B1/en
Priority to US14/437,211 priority patent/US9598512B2/en
Publication of WO2014063425A1 publication Critical patent/WO2014063425A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins

Definitions

  • the present invention relates to the field of polymer resins, and in particular to an ultrahigh molecular weight polyethylene resin and its use in the fiber spinning industry. Background technique
  • Ultra high molecular weight polyethylene fibers are the third generation of high performance fibers that appeared in the early 1990s. Its relative molecular mass is more than 1 million, its molecular shape is linear linear chain structure, its orientation is close to 100%, it has good mechanical properties and excellent comprehensive performance, and its application potential is huge. Ultra-high molecular weight polyethylene fiber has the characteristics of military and civilian use, and is widely used in bulletproof products. Explosion-proof devices, high-strength cables and sports equipment.
  • Ultra high molecular weight polyethylene fibers are processed by ultra high molecular weight polyethylene resins.
  • the preparation method of the ultrahigh molecular weight polyethylene resin mainly adopts the Ziegler low pressure slurry method, that is, ⁇ -TiCl 3 /'Al (C 2 3 ⁇ 4 ) 2 C1 or TiCVAl (C 2 H 5 ) 2 C1 as the main catalyst, Ethyl aluminum is used as a cocatalyst, 60-]20 ⁇ saturated hydrocarbon is a dispersing medium shield, and ethylene is polymerized under certain temperature and pressure conditions to obtain products with different molecular weights.
  • C 1033703 provides a process for the preparation of an ultrahigh molecular weight polyethylene of adjustable molecular weight.
  • the patent uses a MgCi 2 and ZnCb composite carrier-loaded titanium 'Huaihua agent, and an ultra-high molecular weight polyethylene resin with a molecular weight of 60-6.1 million and a good particle size distribution is prepared at 65-85 TTF.
  • the Zn/Ti molar ratio is adjusted to regulate the molecular weight of the product.
  • the catalyst used in the technique is a composite supported catalyst, and the obtained resin is not used for the purpose of the ruthenium.
  • the surface of the resin particles is smooth and does not have a porous and "ditch back" structure.
  • the method can efficiently produce a fiber having a viscosity characteristic [ ⁇ ] of 5 dl/g or more, a strength of 20 g/d or more, and an elastic modulus of 500 g/d or more.
  • the patent uses two ethylene polymers with different intrinsic properties. It is difficult to obtain uniform and stable fibers in the process of preparing fibers from the blends, and the mechanical properties are lower than those of ultrahigh molecular weight polyethylene fibers.
  • the ultrahigh molecular weight polyethylene resin used in the preparation of ultrahigh fibers provided by EP277750 has an intrinsic viscosity [ ⁇ ] of 5 30 dl/g and a particle size of 1-300 ⁇ m.
  • JP2007297763 proposes a high-strength polyethylene fiber production method using a high molecular weight polyethylene resin having an intrinsic viscosity of more than 8 dl/g.
  • CN 101421444 provides a spinning method of high-strength polyethylene fiber which is difficult to obtain by a conventional gel spinning method, and the high molecular weight polyethylene resin used in the invention has an intrinsic viscosity of more than 8 dl/g, in a spinning polymer stock solution
  • a hexanol compound in which a resin is not dissolved is added during the configuration, and a mixture of decahydronaphthalene and a poor solvent and a hexanol compound is used as a solvent to swell and dissolve the polymer, and is spun.
  • High-strength fibers have been obtained.
  • ultra-high molecular weight polyethylene resins with lower intrinsic viscosity than those with lower molecular weight are used in fiber spinning production, which will significantly reduce the mechanical properties of the final products.
  • the production of ultrahigh molecular weight polyethylene fibers mainly adopts a gel spinning process, which requires dissolution of a specific solution before melt spinning and stretching to completely or partially disentangle the ultrahigh molecular weight polyethylene molecular chain. Form a homogeneous solution. Therefore, the solubility of ultrahigh molecular weight polyethylene particles in a solvent is critical, which greatly determines the production efficiency and product properties of the fiber.
  • the ultra-high molecular weight polyethylene has a poor solubility as the molecular weight increases, thereby lowering the production efficiency and product properties in the spinning process.
  • the molecular weight of the ultrahigh molecular weight polyethylene is too low, although It will increase the solubility, but the tensile strength of the fibers spun by it will not achieve the desired effect.
  • the object of the present invention is to provide an ultrahigh molecular weight polyethylene resin and its application in fiber spinning, and solve the defects that the ultrahigh molecular weight polyethylene glycol resin is difficult to dissolve in fiber spinning and has low strength. Problems such as unstable fiber properties.
  • the ultrahigh molecular weight polyethylene resin according to the present invention has a viscosity average molecular weight of 200 to 7 million, a volume average particle diameter of 100 to 350 ⁇ m, a particle size distribution of 1.0 to 2.1, and a tensile fracture stress of 30 to 60 MPa.
  • the resin has a bulk density of 0.10 - 0.50 g/cni 3 and an initial crystallinity of 60.5 ⁇ 90%.
  • the ultra-high molecular weight polyethylene resin of the present invention has a decalin absorption amount of 2 to 50 g of decalin per 100 g of the ultrahigh molecular weight polyethylene resin, and the white oil absorption amount is 100 g of the ultrahigh molecular weight polyethylene per 100 g.
  • the resin absorbs 5 to .60 g of white oil.
  • the ultrahigh molecular weight polyethylene resin preferably has an initial crystallinity of 63 to 85%.
  • the infiltration time of the resin particles in the solvent decalin is 0.5 ⁇ I I rain, preferably 1 ⁇ 8 mm,
  • the ultrahigh molecular weight polyethylene resin preferably has a viscosity average molecular weight of from 250,000 to 6,000,000, more preferably from 350 to 5.5 million.
  • the ultrahigh molecular weight polyacetal resin has an average particle size range of 150 250 ⁇ m.
  • the ultrahigh molecular weight polyethylene resin preferably has a particle size distribution of 1, 2 to 2, 0, more preferably: .4 to: .9, and the ultrahigh molecular weight polyethylene glycol resin has a bulk density of a bulk density. 0.20 ⁇ 0.45 g / cm 3 , more; ⁇ is the bulk density of 0.20 -' 0.35 g / cm 3 .
  • the tensile fracture stress of the ultrahigh molecular weight polyethylene resin is 32 to 60 MPa, preferably 35 to 60 MPa. Good tensile stress is very beneficial to the thermal stretching process of the fiber.
  • the initial crystallinity according to the present invention means that the nascent polymer particles generated from the reactor have not undergone any thermal process, and the crystallinity determination process does not eliminate the crystallinity directly determined by the thermal history, and it is characterized by the initial ecological ultrahigh molecular weight.
  • the solubility of the ultrahigh molecular weight polyethylene in the solvent is related to the degree of entanglement of the macromolecule, and the higher the degree of entanglement of the ultrahigh molecular weight polybenzazole macromolecule, the lower the initial crystallinity of the resin particle.
  • the ultrahigh molecular weight polyethylene resin having a high initial crystallinity has a good solubility.
  • the ultrahigh molecular weight polyethylene resin of the present invention has an initial crystallinity of 60.5 to 90%, and can effectively shorten the dissolution time when the solvent is dissolved. If the initial crystallinity is less than 60,5%, the degree of entanglement is high, the solubility in the solution is poor, and it is not suitable for processing into fibers, and the initial crystallinity is higher than 90%, the production cost is high, the process is complicated, and hard to accomplish.
  • the ultra-high molecular weight polyacetal resin of the present invention has a decahydronaphthalene absorption amount of 2 to 50 g of decalin per 100 g of the ultrahigh molecular weight polyethylene resin, and the white oil absorption amount is 5 to 60 g per 100 g of the ultrahigh molecular weight polyethylene resin. .
  • the ultrahigh molecular weight polyethylene resin is first wetted by decalin, and if the ultrahigh molecular weight polyethylene resin can absorb the decahydronaphthalene sufficiently, it has better solubility in the spinning process. More conducive to spinning, the strength and uniformity of the resulting fiber will also increase. If less than 2 g of decahydronaphthalene is absorbed per 100 g of the ultrahigh molecular weight polyethylene resin, it is not sufficiently dissolved, and a good spinning effect cannot be obtained. If it is absorbed by more than 50 g of decalin, it is difficult to achieve, and it is industrially uneconomical. In the wet spinning process, the solvent used is mineral oil.
  • ultra-high molecular weight polyethylene resin absorbs less than 5g of white oil, it will not be fully dissolved, and a good spinning effect cannot be obtained. If it absorbs more than 60g of white oil. , it is difficult to achieve, and industrial is not economic.
  • the ultrahigh molecular weight polyacetal resin particles of the present invention have a porous and "ditch back" structure, the surface cracks are more, wider and deeper, and the solvent is rapidly penetrated into the particles to dissolve the particles, thereby promoting particle dissolution.
  • the infiltration time of the resin particles of the present invention in the solvent decalin has a shorter infiltration time relative to the resin particles of the prior art, and the infiltration time is 0.5 to i lmui, preferably 1 to 8 min. The infiltration time is also evaluated.
  • the index of solubility of the ultrahigh molecular weight polyacetonitrile resin is also evaluated.
  • the infiltration time is less than 0, 5 min, indicating that the resin is easily dissolved in the solution, generally the molecular weight of the resin is lower, the prepared fiber strength is lower, and the infiltration time is greater than] lmi It indicates that the resin is hardly soluble in the solution, and it is easy to form defects, which is easy to cause breakage during fiber preparation.
  • the ultrahigh molecular weight polyethylene resin has a molecular weight of from 2 to 7 million, preferably from 2 to 6 million, more preferably from 350 to 5.5 million, and the molecular weight is too high. For example, if the molecular weight is too high, the process is difficult. The polymer is also difficult to dissolve in the solvent, and the dissolution time is too long; if the molecular weight is too low, for example, less than 2 million, the fiber is prone to breakage during the processing of the fiber, and the fiber strength is lowered, which is difficult to meet the requirements.
  • the fiber preparation process is complicated, and the particle morphology of the ultrahigh molecular weight polyethylene resin is very high.
  • the particle shape, size and particle size distribution of the ultrahigh molecular weight polyethylene resin will affect the dissolution rate of the resin particles in the solvent, thereby affecting Productivity can even ultimately affect product performance.
  • the particles may only swell non-dissolving after most of the particles are sufficiently dissolved, and large particles will form a defect point during spinning.
  • the particle morphology of the resulting sample can be analyzed by photomicrography (see Figures 1-4).
  • the resin particles are uniform, and the average diameter ranges from 10 ⁇ ) to 350 ⁇ , preferably 15 ⁇ ) to 250 ⁇ .
  • the particle size is moderate, and the distribution is narrow, and the particle size distribution is 1.0 to 2.1, preferably 1.2 to 2.0, more. It is preferably 1.4 - 1.9, which is advantageous for the resin to be uniformly dissolved in the spinning solvent.
  • the average particle diameter of the particles exceeds 350 ⁇ m, the dissolution time of the resin is greatly increased, the average particle diameter of the particles is lower than ⁇ , and the fine particles are more in the resin, which greatly increases the difficulty in resin production operation.
  • the particle size distribution is less than 1.0, the process conditions are demanding in the production of the resin, and the production difficulty is increased. If the particle size distribution is larger than 2 ⁇ , the dissolution time of the resin in the solvent will be inconsistent, affecting the uniformity of the spinning solution, the spinning process is unstable and easy to appear. Broken head.
  • the tensile stress of the ultrahigh molecular weight polyethylene resin of the present invention is 32 to 60 MPa, and the tensile stress at break is less than 32 MPa, which lowers the strength of the fiber. Fracture. Stress above 60 MPa will result in difficulty in yarn formation during the multi-stage drawing stage of spinning.
  • the ultrahigh molecular weight polyethylene resin of the invention has a very wide control range of bulk density, the bulk density is (). 0.50 g/cm 3 , and the bulk density is less than 0.10 g/cm 3 , the resin is too loose and is not conducive to packaging and production. When the bulk density is higher than 0.50 g/cm 3 , the resin is too dense and affects the immersion of the solvent.
  • the invention also provides a preparation method of the ultrahigh molecular weight polyethylene resin, wherein the ethylene homopolymerization is carried out by a slurry polymerization process under the conditions of a main catalyst and a cocatalyst to obtain an ultrahigh molecular weight polyethylene resin.
  • the specific preparation method of the ultrahigh molecular weight polyacetal resin is:
  • the solvent is added to start the stirring; then the cocatalyst and the main catalyst are sequentially added to raise the temperature to a certain polymerization temperature; the ethylene monomer is introduced, the pressure is raised to a certain polymerization pressure, and the pressure in the polymerization reactor is maintained. And the temperature is constant.
  • the resulting resin particles are suspended in a solvent to form a polymer slurry; after the polymer slurry is removed and dissolved, the desired ultrahigh molecular weight polyethylene resin is obtained.
  • the cocatalyst is one or more kinds of alkyl aluminum
  • the ratio of the main catalyst to the cocatalyst is Al/Ti molar ratio of 30 ⁇ Step (1)
  • the titanium compound has the general formula Ti (OR 3 ) A-. n , wherein R 3 is an alkyl group having 1 to 6 carbon atoms, X is a halogen, preferably chlorine or bromine, and more preferably chlorine, and Ti is an integer of 0 to 4.
  • Step (1) The titanium-supporting reaction is controlled at a temperature of 0 to 130 Torr for 10 minutes to 5 hours.
  • the solvent used in the polymerization in the step (2) is selected from a C 5 - C ] 5 fatty macro compound or an aromatic bright compound such as pentane, hexane, heptane, octane > decane, decane, 6# solvent oil.
  • the cocatalyst used in the step (2) is one or more aluminum alkyls such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, diethyl Aluminum fluoride, dibutyl aluminum oxide, dibutyl aluminum bromide and similar compounds. Triethylaluminum is preferred.
  • the aluminum alkyls may be used singly or in combination of plural kinds.
  • the invention also provides an application for treating the ultrahigh molecular weight polyacetal resin as a raw material in the processing of polystyrene.
  • the fiber obtained by spinning the ultrahigh molecular weight polyacetal resin of the present invention as a raw material has high tensile strength. Tensile strength can reach above 800 cN/dtex.
  • the main catalyst needs to be used in combination with the cocatalyst aluminum alkyl, and the ratio of use to the cocatalyst can be controlled in the Al/Ti molar ratio of 30 to 1000:1, preferably 50 '400:1.
  • the polymerization temperature in the step (2) is 30 - '100 ⁇ , preferably 50 to 85. C.
  • the polymerization pressure in the step (2) is 0.1 to 1.6 MPa, preferably 0.4 to 0.8 MPa.
  • the polymerization time in the step (2) is 0.5 to 10 hours, preferably 8 hours.
  • step (2) the polymerization stirring speed is 60 to 500 rpm.
  • the smaller reactor can use a faster rotation speed, and the reactor larger than lm 3 uses a lower rotation speed.
  • the stirring paddle of the present invention In the form of the stirring paddle of the present invention, a frame type or anchor type stirring can be used. To enhance the heat removal effect of the reaction kettle, the stirring paddle can also be formed into a form that can be circulated into the circulating water.
  • the addition form of the main catalyst in the present invention may be added by using a thousand powder, or may be premixed with a polymerization solvent and then added to the kettle.
  • the present invention has the following advantages:
  • the ultrahigh molecular weight polyethylene glycol resin has a high initial crystallinity, initial crystal 60, 5 90%, volume average particle diameter between 100 ⁇ 350 ⁇ , molecular weight of 200 - 7 million, tensile fracture stress 30 ⁇ 60MPa, and the resin bulk density is 0.10 0.50 g / cm 3 , the resin particles have a porous and "ditch back" structure, the absorption of decalin is 2 ⁇ 50g, the absorption of white oil is 5 ⁇ 60g, the resin particles are Solvent infiltration time 0,5 ⁇ l lmiru
  • the ultrahigh molecular weight polyethylene resin has excellent spinning properties, fast swelling and dissolution process, stable spinning and hot drawing process, and high fiber modulus and high strength. Modulus ⁇ 25 cN/dtex, strength 800 cN/dtex.
  • Figure 4 is a scanning electron micrograph of ultrahigh molecular weight polyethylene resin particles prepared in Comparative Example 1.
  • the obtained ⁇ ⁇ is the molecular weight of the polymer.
  • Tensile fracture stress The compression molded specimen is prepared according to GB/T 21461.2 and tested. The tensile speed is 50mm/miiio.
  • ⁇ is the melting enthalpy of the polymer
  • the unit is J.g' 1 , using DSC 2910 produced by American TA Company, according to the method of GB/T 19466.3-2004, the melting heat enthalpy value of the first scan is selected.
  • 293 is the heat of fusion when the crystallinity of polyethylene is 100%, and the unit is Jg- !.
  • m 0 is the mass of the solvent absorbed by the absorbent cotton in the blank test, in g;
  • Mi is the mass of the centrifuge tube plus absorbent cotton, the unit is g;
  • N3 ⁇ 4 is the mass of the centrifuge tube plus the cotton wool and resin sample, the unit is g;
  • m 3 is the shield of the centrifuged tube and the sample and the absorbed solvent after centrifugation, in g .
  • the resin of the present invention can be prepared by using a conventional one-method or wet ultra-high molecular weight polyethylene fiber.
  • a typical process is: dissolving the ultra-high molecular weight polyethylene resin in decalin, using twin-screw extrusion, circular Spinning of single-hole spinneret, the same process conditions are used for each sample, the highest spinning temperature is 260-280 ⁇ , and the jelly fiber of the obtained sample is fully extracted in the extractant, and the tension is dried and dried. Used in the next step test, ie, super-high heat stretching. ⁇ Three-stage drawing process, the third-stage temperature is 80 ⁇ for the first stage and 100 for the second stage. C, the third-stage stretching is 120 °C.
  • the solvent is added to start the stirring; then, 4 ml of the promoter triethylaluminum and 1.5 mg of the main catalyst prepared above are sequentially added, the stirring speed is 210 rpm, and the polymerization temperature is raised to 601; The ethylene monomer was introduced, the polymerization pressure was raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After the reaction for 1 hour, the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • the ultrahigh molecular weight polyethylene resin is dissolved in decalin, and is spun by twin-screw extrusion, circular single-hole spinneret. The same process conditions are used for each sample, and the highest spinning temperature is 260-280.
  • the jelly fiber is sufficiently extracted in the extractant, tensioned and dried, and the obtained dry gel fiber is used in the next step test, that is, ultra-high heat stretching.
  • the three-stage temperature is 80 for the first stage.
  • C the secondary stretch is ⁇
  • the third stretch 120 °C.
  • the spinning properties are shown in Table 2.
  • the solvent is added to start the stirring; then, 4 ml of the promoter triethylaluminum and 1.5 mg of the main catalyst prepared above are sequentially added, the stirring speed is 210 rpm, and the polymerization temperature is raised to 551; The ethylene monomer was introduced, the polymerization pressure was raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After the reaction for 1 hour, the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • Dissolving lg magnesium chloride in n-hexane under an inert atmosphere adding n-butanol to react at 70 Torr to form a solution or dispersion of magnesium chloride-alcohol adduct; adding diethylaluminum chloride and the magnesium chloride-addition Reacting to form an intermediate product; then turning on the ultrasonic device to ultrasonically treat the intermediate product; adding titanium tetrachloride to carry out the titanium-supporting reaction; and then turning on the ultrasonic device to ultrasonically treat the titanium-loaded reaction mixture; Recovering solid particles to obtain an ultrahigh molecular weight polyethylene catalyst;
  • the solvent was added to start the stirring; then, the promoter triethylaluminum 4mi and ⁇ 5 mg of the above-prepared catalyst were sequentially added, and the stirring speed was 2]0 rpm, and the polymerization temperature was raised to 65. °C; ethylene monomer was introduced, the polymerization pressure was raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant.
  • the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • the properties of the obtained ultrahigh molecular weight polyethylene resin are shown in Table 1, and the scanning electron micrograph of the resin particles is shown in the figure.
  • the ultra-high molecular weight polyethylene resin is dissolved in decalin, and extruded by Han screw, and the circular spinneret is spun.
  • Each of the products adopts the same process conditions, and the highest spinning temperature is 260-2801:
  • the obtained jelly fiber of the product is fully extracted in the extractant, tensioned and dried, and the obtained jelly fiber is used in the next step test, that is, ultra-high heat stretching.
  • a three-stage drawing process is employed, and the third-stage temperature is 80 for the first-stage drawing.
  • the secondary stretching is 100 ° C
  • the tertiary stretching is 120 ° C.
  • the spinning properties are shown in Table 2.
  • the polymerization reactor was replaced with nitrogen, and then the solvent was added to start the stirring; then, 4 ml of the promoter triethylaluminum and 1.5 mg of the main catalyst prepared above were sequentially added, and the stirring speed was 210 rpm, and the polymerization temperature was raised to 721; The ethylene monomer was introduced, and the polymerization pressure was raised to 0,6 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After reacting for 1 hour, the resulting resin particles are suspended in a solvent to form a polymer slurry; after the polymer slurry is removed from the solvent, the desired ultra-high molecular weight polyethylene resin is obtained.
  • the ultrahigh molecular weight polyethylene resin is dissolved in decalin, and is spun by twin-screw extrusion, circular single-hole spinneret. The same process conditions are used for each sample, and the highest spinning temperature is 260-280.
  • the jelly fiber is sufficiently extracted in the extractant, tensioned and dried, and the obtained dry gel fiber is used in the next step test, that is, ultra-high heat stretching.
  • the three-stage temperature is 80 for the first stage.
  • C the secondary stretch is ⁇
  • the third stretch 120 °C.
  • the spinning properties are shown in Table 2.
  • the polymerization reactor was purged with nitrogen, and a solvent was added thereto to start the stirring. Then, 4 ml of a promoter of triethylaluminum and 1.5 mg of the above-prepared catalyst were sequentially added thereto at a stirring speed of 210 rpm, and the polymerization temperature was raised to 60. C; The ethylene monomer was introduced, the polymerization pressure was raised to 0.4 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After the reaction for 1 hour, the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • the solvent was added to start the stirring; then, 4 ml of the promoter triethylaluminum and 1.5 mg of the main catalyst prepared above were sequentially added, the stirring speed was 210 rpm, and the polymerization temperature was raised to 60 ° C; The ethylene monomer was introduced, the polymerization pressure was raised to 0.8 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After the reaction for 1 hour, the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • magnesium chloride is divided into n-hexane; adding n-butanol to react at 70 Torr to form a solution or dispersion of magnesium chloride-alcohol adduct; then adding diethylaluminum chloride and the magnesium chloride-alcohol Adduct reaction, forming a An intermediate product; then, an ultrasonic device is turned on to ultrasonically treat the intermediate product; titanium tetrachloride is added to carry out the titanium-supporting reaction; the ultrasonic device is further turned on to ultrasonically treat the titanium-loaded reaction mixture; and finally, the solid particles are recovered to obtain Ultra high molecular weight polyethylene catalyst;
  • the polymerization reactor was purged with nitrogen, and a solvent was added thereto to start the stirring; then, 4 ml of a promoter of triethylaluminum and 0.5 mg of the above-prepared catalyst were sequentially added thereto, the stirring speed was 210 rpm, and the polymerization temperature was raised to 60. C; ethylene monomer was introduced, the polymerization pressure was raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After the reaction for 1 hour, the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • the solvent was added to start the stirring; then, the promoter, triethylaluminum 4mi and 1.0 mg of the main catalyst prepared above were sequentially added, the stirring speed was 210 rpm, and the polymerization temperature was raised to 601; The ethylene monomer was introduced, the polymerization pressure was raised to 0,6 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After the reaction for 1 hour, the resulting resin particles were suspended in a solvent to form a polymer slurry: After the polymer vegetable liquid was removed, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • the solvent is added to start the stirring; then the cocatalyst is added three times in sequence.
  • the resulting resin particles are suspended in a solvent to form a polymer slurry; after the polymer slurry is removed from the solvent, the desired ultrahigh molecular weight polyethylene resin is obtained.
  • magnesium chloride is divided into n-hexane; adding n-butanol to react at 70 Torr to form a solution or dispersion of magnesium chloride-alcohol adduct; then adding diethylaluminum chloride and the magnesium chloride-alcohol
  • the adduct reacts to form an intermediate product; then, an ultrasonic device is turned on to ultrasonically treat the intermediate product; titanium tetrachloride is added to carry out the titanium-supporting reaction; and the ultrasonic device is turned on to ultrasonically treat the titanium-loaded reaction mixture.
  • the solvent was added to start the stirring; then, 4 ml of the promoter triethylaluminum and 2.5 mg of the main catalyst prepared above were sequentially added, the stirring speed was 210 rpm, and the polymerization temperature was raised to 60 Torr.
  • the monomer was introduced into the acetonitrile monomer, and the polymerization pressure was raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant.
  • the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • the solvent is added to start the stirring; then, 3 ml of the catalytically-triethylaluminum and 1.5 mg of the main catalyst prepared above are sequentially added, the stirring speed is 210 rpm, and the polymerization temperature is raised to 60". C; ethylene monomer is introduced, the polymerization pressure is raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel are kept constant. After 1 hour, the resulting resin particles are suspended in a solvent to form a polymer slurry; after the polymer slurry is removed from the solvent That is, the desired ultrahigh molecular weight polyethylene resin is obtained.
  • the solvent was added to start the stirring; then, 5 ml of the promoter triethylaluminum and 1.5 mg of the main catalyst prepared above were sequentially added, the stirring speed was 210 rpm, and the polymerization temperature was raised to 601; The ethylene monomer was introduced, the polymerization pressure was raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After reacting for 1 hour, the resulting resin particles are suspended in a solvent to form a polymer slurry; after the polymer slurry is removed from the solvent, the desired ultra-high molecular weight polyethylene resin is obtained.
  • the solvent was added to start the stirring; then, the promoter, triethylaluminum 4mi and ruthenium, 5 mg of the above-prepared catalyst were sequentially added, and the stirring speed was 2]0 rpm, and the polymerization temperature was raised to 60. . C;
  • the ethylene monomer was fed to a polymerization pressure of 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant.
  • the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, the desired ultrahigh molecular weight polyethylene resin was obtained.
  • magnesium chloride is divided into n-hexane; adding n-butanol to react at 70 Torr to form a solution or dispersion of magnesium chloride-alcohol adduct; then adding diethylaluminum chloride and the magnesium chloride-alcohol The adduct reacts to form an intermediate product; then the ultrasonic device is turned on to ultrasonically treat the intermediate product; titanium tetrachloride is added Carrying a titanium-supporting reaction; further opening an ultrasonic device to ultrasonically treat the titanium-loaded reaction mixture; finally recovering the solid particles to obtain an ultra-high molecular weight polyethylene catalyst;
  • the solvent was added to start the stirring; then, 4 ml of the promoter triethylaluminum and 0.5 mg of the main catalyst prepared above were sequentially added, the stirring speed was 300 rpm, and the polymerization temperature was raised to 60 ° C; The ethylene monomer was introduced, the polymerization pressure was raised to 0.6 MPa, and the pressure and temperature in the polymerization vessel were kept constant. After 1 hour, the resulting resin particles were suspended in a solvent to form a polymer slurry; after the polymer slurry was removed from the solvent, Ultra high molecular weight polyethylene resin required.
  • a spinning test was conducted using a commercially available ultrahigh molecular weight polyethylene resin A having a molecular weight of 1.85 million and a spinning process as in Example 1.
  • the properties obtained by the performance test method according to the present invention are shown in Table 1, and the spinning properties are shown in Table 2.
  • a scanning electron micrograph of the resin particles of this comparative example is shown in Fig. 4.
  • Example 1 the resin particles in Example 1, Example 3, and Example 5 were uniform in shape with respect to Comparative Example 1, and the proportion of larger particles and fine powder particles was small.
  • the surface of the resin has a large number of cracks and a "ditch back" structure, which facilitates the penetration of the solvent into the particles and greatly shortens the swelling and dissolution time of the resin.
  • the spinning test was carried out using a commercially available ultrahigh molecular weight polyethylene resin B having a molecular weight of 2.77 million, and the spinning process was the same as the example: ⁇ .
  • the performance obtained by the performance test method according to the present invention is shown in Table i, and the spinning performance is as shown in Table 2.
  • a commercially available ultrahigh molecular weight polyethylene resin C was used for the spinning test.
  • the molecular weight of the resin was 3.59 million, and the spinning process was the same as in Example 1.
  • the properties obtained by the performance test method according to the present invention are shown in Table 1, and the spinning properties are shown in Table 2.
  • the spinning test was carried out using a commercially available ultrahigh molecular weight polyethylene resin D having a molecular weight of 4.33 million, and the spinning process was the same as in Example 1.
  • the properties obtained by the performance test method according to the present invention are shown in Table 1, and the spinning properties are shown in Table 2.
  • Three-stage puller 15 25,0 870.8 3.25
  • Three-stage pull-up 18 19.5 606,8 3.41 First-stage pull-up 23 13,9 370.3 3.92 Comparative example 3

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Abstract

一种纤维用超高分子量聚乙烯树脂及其制备方法。该树脂初始结晶度60.5~90%，体积平均粒径介于100~350μm之间，粒径分布度1.0-2.1，分子量200-700万，拉伸断裂应力30~60MPa，树脂堆密度0.10~0.50g/cm3，在溶剂十氢萘的浸润时间为0.5~11min，该树脂的十氢萘吸收量为每100g超高分子量聚乙烯树脂吸收2~50g十氢萘，白油吸收量为每100g超高分子量聚乙烯树脂吸收5~60g。该树脂的制备方法为在主催化剂和助催化剂条件下，采用淤浆聚合工艺进行乙烯均聚。该树脂具有优异的纤维纺丝性能，溶胀、溶解过程快，纺丝、热拉伸过程稳定，生产的纤维具有高模量和高强度的特点，其模量≥25cN/dtex，强度≥800cN/dtex。

Description

一种超高分子量聚乙烯树脂及其应用 技术领域
本发明涉及聚合物树脂领域， 具体涉及一种超高分子量聚乙烯树脂及其在纤维紡丝 行业中的应用。 背景技术
超高分子量聚乙烯纤维是 20世纪 90年代初出现的笫三代高性能纤维。 它的相对分 子质量在 100万以上， 分子形状为线性伸直链结构， 取向度接近 100%, 具有良好的机械 性能和优异的综合性能， 应用潜力巨大。 超高分子量聚乙烯纤维具有军、 民两用的特点， 广泛应用于防弹制品.。 防爆装置、 高强度缆绳和体育器材等方面。
超高分子量聚乙烯纤维是通过超高分子量聚乙烯树脂加工而成。 目前 超高分子量 聚乙烯树脂的制备方法主要是采用 Ziegler低压淤浆法， 即以 β- TiCl3/'Al ( C2¾ ) 2C1或 TiCVAl ( C2H5 ) 2C1为主催化剂，三乙基铝为助催化剂， 60-】20Ό饱和烃为分散介盾， 乙 烯于一定温度和压力条件下聚合， 制得不同分子量的产品 .
C 1033703提供了一种可调节分子量的超高分子量聚乙烯的制备方法。 该专利采用 MgCi2和 ZnCb复合载体载钛 '淮化剂 , 在 65- 85 TTF制备得到了分子量在 60-610万之间可 调、粒径分布良好的超高分子量聚乙烯树脂， 该发明通过调节 Zn/Ti摩尔比来调控产物分 子量。 该技术所用催化剂是一种复合载体催化剂， 聚合所得树脂非针对纾维用途， 树脂颗 粒表面平滑， 不具有多孔和 "沟回 "状结构。
CN99809336提.供一种用含有特性粘数 [ η ] 为 5 dl/g以上， 且其重均分子量和数均 分子量的比 ( Mw / Mn )在 4以下的聚乙烯类高分子量聚合物 ( A ) 99 ~ 50重量份、 和特 性粘数至少为 A的 1.2倍的超高分子量聚合物 ( B ) 1 ~ 50重量份的混合物的 5 ~ 80 %溶 剂溶液， 对纤维进行纺丝及拉伸的方法， 可以高效生产具有纤维特性粘数 [ η ] 为 5 dl/g 以上， 强度在 20g/d以上， 弹性模量在 500g/d以上。 该专利采用的是两种不同特性黏数 的乙烯聚合物， 用其共混物制备纤维的过程中难以得到均匀的、性能稳定的纤维， 其力学 性能也低于超高分子量聚乙烯纤维
EP277750提供的超高纤维制备过程中采用的超高分子量聚乙烯树脂特性粘数 [ η ] 为 5 30dl/g, 粒径在 1- 300μηι之间。 JP2007297763提出一种高强度聚乙烯纤维生产方法， 采用的高分子量聚乙烯树脂的特性黏数大于 8dl/g。 CN 101421444提供了一种难以用以往 凝胶纺丝方法得到的高强度聚乙烯纤維的纺丝方法，该发明采用的高分子量聚乙烯树脂的 特性黏数大于 8dl/g, 在紡丝聚合物原液配置时添加了不溶解树脂的己醇类化合物， 采用 十氢萘与不良溶剂以及己醇类化合物的混合物作为溶剂对聚合物进行溶胀溶解，并经纺丝 得到了高强度的纤维 目前纤维纺丝生产多采用特性黏数较诋 即分子量较低的超高分子 量聚乙烯树脂， 这样会明显降低最终纾维制品的力学性能„
目前超高分子量聚乙烯纤维的生产主要采用凝胶纺丝工艺, 该工艺需要在熔体纺丝 和拉伸之前釆用特定溶 溶解，以完全或部分使超高分子量聚乙烯分子链解缠结，形成均 匀溶液。所以超高分子量聚乙烯顆粒在溶劑中的溶解性至关重要，它很大程 决定了纤维 的生产效率和产品性能。
然而， 超高分子量聚乙烯随着分子量的增加， 其溶解性能越差， 从而会降低在纺丝 过程中的生产效率和产品性能， 另一方面， 如果超高分子量聚乙烯的分子量过低， 虽然 会增加溶解性能， 但经其紡丝的纤维的拉伸强度又达不到理想的效果。 目前的现有技术 中无法得到同时具有良好溶解性、 高分子量、 且经其纺丝得到的 If维拉伸强度高的超高 分子量聚乙婦。 发明内容
本发明的目的在于提供一种超高分子量聚乙烯树脂及其在纤维纺丝中的应用 , 解决 了目前超高分子量聚乙浠树脂在纤维紡丝中难溶解、强度低等缺陷、 且得到的纤维性能不 稳定等问题。
本发明涉及的超高分子量聚乙烯树脂 所述聚乙烯树脂粘均分子量为 200 ~ 700万， 体积平均粒径为 100 ~ 350μιη, 粒径分布度为 1.0 ~ 2.1 , 拉伸断裂应力 30 ~ 60MPa, 树脂 堆密度为 0.10 - 0.50 g/cni3 , 初始结晶度为 60.5 ~ 90% ,
本发明的超高分子量聚乙婦树脂的十氢萘吸收量为每 100g 所述超高分子量聚乙婦 树脂吸收 2〜50g十氢萘， 白油吸收量为每 100g所述超高分子量聚乙烯树脂吸收 5〜.60g白 油。
在本.发明的优选实施方式中，
所述超高分子量聚乙烯树脂的初始结晶度较好为 63 ~ 85%。
所述树脂颗粒在溶剂十氢萘的浸润时间 0.5 ~ I I rain, 较好为 1 ~ 8mm,,
所述超高分子量聚乙烯树脂的粘均分子量较好为 250-600万, 更好为 350 ~ 550万。 所迷超高分子量聚乙婦树脂的平均粒径范围较 f为 150 250μηι。
所述超高分子量聚乙烯树脂的粒径分布度较好为 1 ,2 ~ 2,0, 更好为：.4〜 ： .9 所述超高分子量聚乙蟑树脂堆密度较好为堆密度 0.20 ~ 0.45 g/ cm3 , 更;^为堆密度 0.20 -' 0.35 g/ cm3。
所述超高分子量聚乙烯树脂的拉伸断裂应力 32 ~ 60MPa, 较好为 35 ~ 60MPa。 良好 的拉伸断裂应力十分有利于纤维的热拉伸过程。
本发明所述的初始结晶度是指从反应器生成的初生态聚合物颗粒没有经过任何热过 程， 而且结晶度测定过程不消除热历史直接测定的结晶度，它表征的是初生态超高分子量 聚乙浠树脂颗粒的缠结程度。 另外，超高分子量聚乙烯在溶剂中的溶解性能与其大分子的 缠结程度有关， 超高分子量聚乙浠大分子的缠结程度越高， 树脂颗粒的初始结晶度越低， 导致其在溶剂中的溶解性能越差，反之缠结程度越低， 树脂颗粒的初始结晶度越高， 其在 溶剂中的溶解性能越好。因此，初始结晶度高的超高分子量的聚乙烯树脂的溶解性能较好。
本发明的超高分子量聚乙烯树脂的初始结晶度为 60.5 ~ 90%, 在溶剂溶解时可以有 效缩短溶解时间。如果初始结晶度低于 60,5%,则其缠结程度高，在溶 中的溶解性能差， 不利于加工成纤维, 初始结晶度高于 90%, 则其生产成本高， 工艺复杂, 且难以实现。
本发明的超高分子量聚乙炼树脂的十氢萘吸收量每 100g 为超高分子量聚乙烯树脂 吸收 2〜50g十氢萘, 白油吸收量为每 100g超高分子量聚乙烯树脂吸收 5~60g。
在千法纺丝工艺中， 超高分子量聚乙烯树脂首先经十氢萘浸润， 若所述超高分子量 聚乙烯树脂能够吸充分收十氢萘， 则其在纺丝过程中溶解性更好， 更利于紡丝，得到的纤 維的强度和均匀性也会提高。若每 100g超高分子量聚乙烯树脂吸收 2g以下十氢萘,则不 能充分溶解， 不能得到很好的纺丝效果， 若吸收超过 50g十氢萘， 则很难实现， 且工业上 不经济。 在湿法纺丝工艺中， 所用溶剂则是矿物油， 若每 100g超高分子量聚乙烯树脂吸 收 5g以下白油， 则不能充分溶解， 不能得到很好的纺丝效果, 若吸收超过 60g白油， 则 很难实现， 工业上也不经济。
由于本发明的超高分子量聚乙婦树脂颗粒具有多孔和"沟回''状结构，表面裂隙较多、 较宽而且较深， 溶解纺丝时有 于溶劑快速渗透于粒子内部， 促进粒子溶解， 使得本发明 树脂颗粒在溶剂十氢萘的浸润时间相对于现有技术中的树脂颗粒具有较短的浸润时间，其 浸润时间为 0.5〜i lmui, 较好为 l ~ 8min。 浸润时间也是评价所述超高分子量聚乙蟑树脂 溶解性的指标。 浸润时间小于 0,5min则表明该树脂极易溶解于溶 ^中， 一般树脂分子量 较低， 制备的纤维强度较低， 浸润时间大于】lmi 表明树脂难溶于溶 中， 易形成缺陷 点， 在纤維制备过程中容易造成断头。
该超高分子量聚乙烯树脂的分子量介于 200 - 700万之间，较好为 250-600万, 更好 350 ~ 550万， 分子量过高， 例如高于 700万则纾维加工过程难度大， 聚合物也难以溶于 溶剂， 溶解时间过长； 分子量过.低， 例如低于 200万， 则纤维加工过程中容易出现断头， 且纤维强度降低， 难以满足要求。
纤维制备过程工艺复杂， 对超高分子量聚乙烯树脂的颗粒形态有着很高要求， 超高 分子量聚乙烯树脂的颗粒形态和大小、 粒径分布将会影响树脂颗粒在溶剂中的溶解速度， 从而影响生产效率， 甚至会最终影响产品性能。 在纤维生产中， 如果树脂中存在大颗粒， 该颗粒在多数颗粒充分溶解后，仍可能仅仅是溶胀 非溶解，在纺丝时大颗粒就将形成一 个缺陷点。 采用显微照相技术可以对所得样品的颗粒形态进行分析 (见附图 1-4 )。 本发 明中树脂颗粒均匀， 平均 径范围 10ί) ~ 350μηι, 较好为 15ί) ~ 250μ.ηι, 颗粒粒径适中， 且分布窄， 粒径分布度 1.0 ~ 2.1 , 较好为 1.2 - 2.0, 更好为 1.4 - 1.9, 有利于树脂均匀的 溶于纺丝溶剂中。 颗粒平均粒径超过 350μιη, 则会大大增加树脂的溶解时间， 颗粒平均 粒径低于 ΙΟΟμιη, 树脂中则会细颗粒较多， 会大大增加树脂生产操作难度。 粒径分布小 于 1.0, 则会造成树脂生产中对工艺条件要求苛刻， 加大生产难度。 粒径分布大于 2丄 则 会造成树脂在溶剂中溶解的时间不一致， 影响纺丝溶液均匀性,纺丝过程不稳定和易出现 断头。
良好的拉伸断裂应力十分有利于纤维的热拉伸过程„ 本发明的超高分子量聚乙烯树 脂的拉伸断裂应力 32 ~ 60MPa, 拉伸断裂应力低于 32MPa则会降低所得纤维强度。 拉伸 断裂.应力高于 60MPa, 会造成在紡丝多级拉伸阶段不易成丝。
本发明超高分子量聚乙烯树脂堆密度调控范围非常宽泛， 堆密度为 （).】0 0.50 g/ cm3,堆密度低于 0.10 g/ cm3,则树脂过于疏松不利于包装和生产中加料，堆密度高于 0. 50 g/ cm3 , 则树脂过于致密， 影响溶剂的浸入。
本发.明还提供了一种所述超高分子量聚乙烯树脂的制备方法，在主催化剂和助催化剂 条件下， 采用淤浆聚.合工艺进行乙烯均聚，得到超高分子量聚乙烯树脂， 该超高分子量聚 乙婦树脂的具体制备方法为：
( 1 )主催化躬的制备
在惰性气氛下 将卤化镁分散在惰性溶剂中； 加入醇反应， 形成卤化镁 -醇加合物的 溶液或分散体； 再加入 化烷 1·铝与所述 化镁-醇加合物反应， 形成一种中间产物； 然 后开启超声波装置以对所述中间产物进行超声波处理；加入钛化合物以进行载钛反应；再 开启超声波装置以对上述载钛反.应混合物进行超声波处理； 最后回收固体颗粒，得到超高 分子量聚乙烯催化剂；
( 2 )超高分子量聚乙烯的制备
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂和主 催化 ， 升温至一定聚合温度； 通入乙烯单体， 升至一定聚-合压力， 并保持聚合釜内压力 和温度恒定。反应一定时间， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆 液脱除溶躬后， 印得到所需超高分子量聚乙烯树脂。
其中：
助催化剂为一种或多种烷基铝， 主催化剂与助催化剂的比例为 Al/Ti摩尔比为 30 ~ 步骤 ( 1 )中钛化合物通式为 Ti ( OR3 ) A-.n,其中 R3为含有 1 ~ 6个碳原子的烷基， X为卤素， 优选氯或溴， 更铌选氯， Ti是 0 ~ 4的整数。
步骤 ( 1 ) 中载钛反应控制在 0 ~ 130Ό的温度下进行 10分钟 - 5小时。
步骤（2 )中聚合所用溶剂选自 C5 - C] 5的脂肪炫类化合物或芳香炫类化合物, 如戊 烷、 己烷、 庚烷、 辛烷 > 壬烷、 癸烷、 6#溶剂油、 120#溶剂油 > 甲苯、 二甲苯等， 其中优 选己烷、 庚烷 > 6#溶剂油, 更优选 6#溶剂油。
步骤（2 )中所用助催化躬为一种或多种烷基铝， 如三甲基铝、 三乙基铝、 三异丙基 铝、 三异丁基铝、 三正己基铝、 二乙基氟化铝、 二丁基氣化铝、 二丁基溴化铝及相近似化 合物。 优选三乙基铝。 烷基铝可以单独使用， 也可多种组合使用。
本发明还提供了一种将所述超高分子量聚乙蟑树脂诈为原料在聚乙婦纾维加工的应 用。
利用本发明的超高分子量聚乙婦树脂作为原料纺丝得到的纤维具有高的拉伸强度， 拉伸强度可达 800 cN/dtex以上。
主催化剂需与助催化剂烷基铝配合使用，与助催化剂之间的使用比例可控制在 Al/Ti 摩尔比为 30〜· 1000 : 1 , 优选 50 ' 400: 1。
步骤（2 ) 中聚合反应温度为 30 - ' 100Ό , 优选 50 ~ 85。C。
步驟 ( 2 ) 中聚合反应压力为 0.1 ~ 1.6MPa, 优选 0.4 ~ 0.8 MPa。
步骤 ( 2 ) 中聚合反应时间为 0.5-10小时, 优选卜 8小时。
步骤（2 ) 中聚合搅拌转速为 60 ~ 500转 /分†。 体积较小的反应釜可采用较快转速， 大于 lm3的反应釜则采用较低转速。
本发明中搅拌桨形式可以采用框式或锚式搅捽， 为加强反应釜撤热效杲， 也可将搅 拌桨倣成可以通入循环水的形式。
本发明中主催化劑的加入形式可以采用千粉加入， 也可以与聚合溶剂预混后加入釜 内
与现有技术相比， 本发明具有以下优点:
(】）该超高分子量聚乙浠树脂具有较高的初始结晶度， 初始结晶 60,5 90%, 体积 平均粒径介于 100 ~ 350μηι之间 , 分子量为 200 - 700万， 拉伸断裂应力 30 ~ 60MPa, 同 时该树脂堆密度 0.10 0.50 g/ cm3 , 树脂颗粒具有多孔和"沟回"状结构， 十氢萘吸收量为 2〜50g, 白油吸收量为 5〜60g, 树脂颗粒在溶剂的浸润时间 0,5 ~ l lmiru
( 2 ) 该超高分子量聚乙烯树脂具有优异的纾维纺丝性能， 溶胀 溶解过程快， 纺 丝、 热拉伸过程稳定， 生产的纤维具有高模量和高强度的特点。 模量≥ 25 cN/dtex ， 强 度 800 cN/dtex. 附图说明
附图用来提:供对本.发明的进一步理解， 并且构成说明书的一部分， 与本发明的实施 例共同用于解释本发.明， 并不构成对本发.明的限制。
图 i实施例 i制备的超高分子量聚乙烯树脂颗粒扫描电鏡照片
图 2实施例 3制备的超高分子量聚乙浠树脂颗粒扫描电镜照片
图 3实施例 5制备的超高分子量聚乙浠树脂颗粒扫描电镜照片
图 4对比例 1制备的超高分子量聚乙烯树脂颗粒扫描电镜照片 具体实施方式
以下将结合附图及实施例来详细说明本发明的实施方式， 借此对本发明如何应用技 术手段来解决技术问题， 并达成技术效果的实现过程能充分理解并据以实施。 需要说明 的是, 只要不构成冲突, 本发明中的各个实施例以及各实施例中的各个特征可以相互结 合， 所形成的技术方案均在本发明的保护范围之内。 本发明中所述的特征性能的测试方法及条件如下：
1 )堆密度测定： 采用 BMY-1表观密度测定仅， 按照 GB/T 1636-2008进行。
2 ) 分子量测定： 采用粘度法测量， 用十氢萘作溶剂， 温度 采用乌氏粘度计 测量聚乙烯溶液流出的时间， 然后算出聚^ "物的特性粘数1|。 按照公式
Μγ - 5.37 χ 104 X [η]1-37
所得的 Μγ 为聚合物的分子量。
3 )树脂的颗粒粒径及分布采用光学显微镜拍照， 计算机系统处理得到。
4 ) 拉伸断裂应力： 按 GB/T 21461.2 制备压塑试样， 并进行测试， 拉伸速度 50mm/miiio
5 )电镜： 采用英国 ZEISS公司生产的 EV018型扫描电镜观测聚合树脂的微观形貌，
6 )初始结晶度测定方法： 树脂初始结晶度 X,按下式计算：
Δ¾
式中： Δ 为聚合物的熔融热焓, 单位为 J.g'1, 采用美国 TA公司产 DSC 2910, 按照 GB/T 19466.3-2004方法测试， 选取第一次扫描的熔融热焓值。
293为聚乙烯结晶度 100%时的熔融热焓， 单位为 J.g-!。
溶剂吸收量测定方法：
①采用脱脂棉离心管， 其底部为圓锥形带有直径约为 0.8mm孔德玻璃管， 于离心管 中称取脱脂棉 （ 100ί2 ) mg , 并轻轻推入底部， 称取脱脂棉和离心管的质量， 精确至 O.lmg, 而后在管中称取祥品约 lg, 精确至 O.lmg ， 用滴定管加入 2mi溶剂 (白油或十 氢萘） ， 放置 10min。
②将离 管装入管套中， 然后将套管放入离心机转子的定位孔中， 应注意所放位置 要对称， 保持平衡。
③开动离心机， 使其祥品底部位置的离心加速度为 ( 11000-13000 ) m/s2 ， 转动 60min, 待离心机静止后， 取出离心管, 仔细擦去外壁上残留的溶剂并称量 , 精确至 0,img。
④测试前， 需按上述步骤不加树脂祥品进行空白祥测试。
⑤室温下 100g树脂吸收的溶剂的克数 Xs按下式计算：
( mrm0 ) ~m7
Χ, - ~― xlOO
m2-mi 式中: m0由脱脂棉在空白试验中吸收溶剂的质量， 单位为 g; mi为离心管加脱脂棉的质量， 单位为 g;
n¾为离心管加脱脂棉和树脂样品的质量， 单位为 g;
m3为离心后脱脂棉离心管与样品及吸收的溶剂的盾量， 单位为 g。
8 )浸润速度测试方法： 取 lg超高分子量聚乙烯树脂, 放入 50mi容量瓶中， 加入十 氢萘溶 至刻度线， 盖上玻璃塞； 将容量瓶放置入 120Ό油浴中， 同时按下秒表、 记录 肉眼观察各组份在溶剂中消失的时间。
9 )本发明树脂可采用通常千法或湿法超高分子量聚乙烯纤维的制备方法， 典型的工 艺为： 将超高分子量聚乙烯树脂溶于十氢萘中， 采用双螺杆挤出， 圆形单孔喷丝头纺 丝， 各样品采用相同的工艺条件, 最高纺丝温度为 260-280Ό , 将所得样品的冻胶纤维在 萃取剂中充分萃取， 张紧千燥， 所得千冻胶紆维用于下步试验， 即超倍热拉伸。 釆用三 级拉伸工艺， 三级温度分别为一级拉伸为 80Ό , 二级拉伸为 100。C、 三级拉伸为 120°C。 实施例 1
( 1 )超高分子量聚乙炼催化剂的制备：
在惰性气氛下， 将 ig氯化镁分散在正己烷中； 加入正丁醇在 70 反应， 形成氯化镁 -醇加合物的溶液或分散体； 再加入一氯二乙 铝与所述氯化镁―醇加合物反应， 形成一 种中间产物; 然后开启超声波装置以对所述中间产物进行超声波处理; 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 ) 超高分子量聚乙烯树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4ml和 1.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 601; ; 通入乙烯单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 i 所示， 树脂颗粒扫描电镜照片见图
L,
( 3 )所得聚合树脂进行纺丝试验， 工艺为：
将超高分子量聚乙烯树脂溶于十氢萘中， 采用双螺杆挤出， 圓形单孔喷丝头纺丝， 各样品采用相同的工艺条件， 最高纺丝温度为 260-280 , 将所得样品的冻胶纤维在萃取 剂中充分萃取， 张紧干燥， 所得干冻胶纤维用于下步试验， 即超倍热拉伸。 采用三级拉 伸工艺， 三级温度分别为一级拉伸为 80。C , 二级拉伸为 ΙΟΟΌ , 三级拉伸为 120°C。 纺丝 性能如表 2所示。
实施例 2 ( 1 )超高分子量聚乙炼催化剂的制备：
在惰性气氛下， 将 ig氯化镁分散在正己烷中； 加入正丁醇在 70 反应， 形成氯化镁 -醇加合物的溶液或分散体； 再加入一氯二乙 铝与所述氯化镁―醇加合物反应， 形成一 种中间产物; 然后开启超声波装置以对所述中间产物进行超声波处理; 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 ) 超高分子量聚乙烯树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4ml和 1.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 551; ; 通入乙烯单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示„
实施例 3
( 1 )超高分子量聚乙婦催化剂的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中： 加入正丁醇在 70Ό反应， 形成氯化镁 -醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁 - 加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所迷中间产物进行超声波处理; 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理； 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙蟑树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4mi 和 〗,5mg 上述制备的主催化劑， 搅拌转速为 2】0 转 /分钟， 聚合温度升温至 65 °C ; 通入乙烯单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1 所示， 树脂颗粒扫描电鏡照片见图
2,
( 3 )所得聚合树脂进行纺丝试验， 工艺为：
将超高分子量聚乙烯树脂溶于十氢萘中， 采用汉螺杆挤出， 圓形单礼喷丝头纺丝， 各祥品采用相同的工艺条件， 最高纺丝温度为 260-2801：, 将所得祥品的冻胶纤维在萃取 剂中充分萃取， 张紧千燥， 所得千冻胶纤维用于下步试验， 即超倍热拉伸。 采用三级拉 伸工艺， 三级温度分别为一级拉伸为 80。C , 二级拉伸为 100°C , 三级拉伸为 120 °C。 纺丝 性能如表 2所示。 实施例 4
( 1 )超高分子量聚乙炼催化剂的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中； 加入正丁醇在 70Ό反应， 形成氯 .ί匕镁 -醇加合物的溶液或分散体； 再加入一氯二乙 铝与所述氯化镁―醇加合物反应， 形成一 种中间产物; 然后开启超声波装置以对所述中间产物进行超声波处理; 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 ) 超高分子量聚乙烯树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4ml 和 1.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟, 聚合温度升温至 721; ; 通入乙烯单体， 聚合压力升至 0,6MPa， 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超.高分子量聚乙烯树脂
得到的超高分子量聚乙烯树脂的各项性能如表 1所示
( 3 )所得聚合树脂进行纺丝试验， 工艺为：
将超高分子量聚乙烯树脂溶于十氢萘中， 采用双螺杆挤出， 圓形单孔喷丝头纺丝， 各样品采用相同的工艺条件， 最高纺丝温度为 260-280 , 将所得样品的冻胶纤维在萃取 剂中充分萃取， 张紧干燥， 所得干冻胶纤维用于下步试验， 即超倍热拉伸。 采用三级拉 伸工艺， 三级温度分别为一级拉伸为 80。C , 二级拉伸为 ΙΟΟΌ , 三级拉伸为 120°C。 纺丝 性能如表 2所示。
实施例 5
( 1 )超高分子量聚乙烯催化剂的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中； 加入正丁醇在 70°C反应、 形成氯化镁 —醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁—醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙婦树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅捽； 然后依次加入助催化 ^三乙 基铝 4ml 和 1.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 60。C ; 通入乙烯单体， 聚合压力升至 0.4MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙浠树脂的各项性能如表 1 所示。 树脂颗粒扫描电镜照片见图 3.,
实施例 6
( 1 )超高分子量聚乙婦催化剂的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中； 加入正丁醇在 70Ό反应， 形成氯 .ί匕镁 -醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁 - 加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所迷中间产物进行超声波处理; 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理； 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙蟑树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4ml 和 1.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟, 聚合温度升温至 60 °C ; 通入乙烯单体， 聚合压力升至 0.8MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示
实施例 7
( 1 )超高分子量聚乙婦催化^的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中； 加入正丁醇在 70'Ό反应， 形成氯化镁 —醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁-醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理； 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙烯树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4mi 和 L5mg 上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 60。C ; 通入乙烯单体 聚合压力升至 i.OMPa, 并保持聚合釜内压力和温度恒定。 反应 i 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙浠树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示。
实施例 8
( 1 ) 超高分子量聚乙烯催化剂的制备：
在惰性气氛下， 将 lg氯化镁分 t在正己烷中； 加入正丁醇在 70Ό反应， 形成氯化镁 -醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁 -醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应; 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙婦树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅捽； 然后依次加入助催化 ^三乙 基铝 4ml 和 0.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 60。C ; 通入乙烯单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙浠树脂的各项性能如表 1所示。
实施例 9
( 1 )超高分子量聚乙烯催化剂的制备：
在惰性气氛下， 将 ig氯化镁分散在正己烷中； 加入正丁醇在 70 反应， 形成氯化镁 —醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁—醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙婦树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4mi 和 l.Omg 上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 601; ; 通入乙烯单体， 聚合压力升至 0,6MPa， 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液： 将聚合物菜液脱除溶 ^后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示。
实施例 10
( 1 )超高分子量聚乙炼催化剂的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中； 加入正丁醇在 70Ό反应， 形成氯 .ί匕镁 -醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁 - 加合物反应， 形成一 种中间产物; 然后开启超声波装置以对所述中间产物进行超声波处理; 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙蟑树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4ml 和 2.0mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 60。C ; 通入乙烯单体 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 i 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙浠树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示。
实施例 1ί
( 1 ) 超高分子量聚乙烯催化剂的制备：
在惰性气氛下， 将 lg氯化镁分 t在正己烷中； 加入正丁醇在 70Ό反应， 形成氯化镁 -醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁 -醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗 ， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙炼树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4ml和 2.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 60 Ό ; 通入乙浠单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 I 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示。
实施例 12
( 1 )超高分子量聚乙烯催化剂的制备:
在惰性气氛下， 将 lg氯化镁分散在正己烷中； 加入正丁醇在 70°C反应、 形成氯化镁 —醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁—醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应; 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙婦树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅捽； 然后依次加入助催化 ^三乙 基铝 3ml和 1.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟， 聚合温度升温至 60 "C ; 通入乙烯单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示。 ( 1 )超高分子量聚乙炼催化剂的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中； 加入正丁醇在 70Ό反应， 形成氯 .ί匕镁 -醇加合物的溶液或分散体； 再加入一氯二乙 铝与所述氯化镁―醇加合物反应， 形成一 种中间产物; 然后开启超声波装置以对所述中间产物进行超声波处理; 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 ) 超高分子量聚乙烯树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 5ml 和 1.5mg上述制备的主催化剂， 搅拌转速为 210 转 /分钟, 聚合温度升温至 601; ; 通入乙烯单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超.高分子量聚乙烯树脂
得到的超高分子量聚乙烯树脂的各项性能如表 1所示
实施例 14
( 1 )超高分子量聚乙婦催化^的制备：
在惰性气氛下， 将 lg氯化镁分散在正己烷中： 加入正丁醇在 70Ό反应， 形成氯化镁 —醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁-醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应； 再开启超声波装置以对上述载钛反应混合物进行超声波处理； 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙烯树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4mi 和 〗,5mg 上述制备的主催化劑， 搅拌转速为 2】0 转 /分钟， 聚合温度升温至 60。C ; 通入乙烯单体 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 2 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后， 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示。
实施例 15
(】 )超高分子量聚乙婦催化剂的制备：
在惰性气氛下， 将 lg氯化镁分 t在正己烷中； 加入正丁醇在 70Ό反应， 形成氯化镁 —醇加合物的溶液或分散体； 再加入一氯二乙基铝与所述氯化镁 -醇加合物反应， 形成一 种中间产物； 然后开启超声波装置以对所述中间产物进行超声波处理； 加入四氯化钛以 进行载钛反应; 再开启超声波装置以对上述载钛反应混合物进行超声波处理; 最后回收 固体颗粒， 得到超高分子量聚乙烯催化剂；
( 2 )超高分子量聚乙婦树脂的制备：
首先将聚合反应釜氮气置换后， 加入溶剂， 开启搅拌； 然后依次加入助催化剂三乙 基铝 4ml和 0.5mg上述制备的主催化剂， 搅拌转速为 300 转 /分钟， 聚合温度升温至 60 "C ; 通入乙烯单体， 聚合压力升至 0.6MPa, 并保持聚合釜内压力和温度恒定。 反应 1 小时， 生成的树脂颗粒悬浮在溶剂中形成聚合物浆液； 将聚合物浆液脱除溶剂后 即得 到所需超高分子量聚乙烯树脂。
得到的超高分子量聚乙烯树脂的各项性能如表 1所示。
对比例 1
采用一种市售超高分子量聚乙烯树脂 A进行紡丝试验， 该树脂分子量为 185万、 纺 丝工艺同实施例 1。 其根据本发明记载的性能测试方法得到的各项性能如表 1所示， 纺丝 性能如表 2所示。 本对比例的树脂颗粒扫描电镜照片见图 4。
从图 1中可以看出相对于对比例 1 , 实施例 1、 实施例 3、 实施例 5中的树脂颗粒形 态均匀， 较大颗粒和细粉状颗粒比例较少。 树脂表面有大量的裂隙和"沟回"状结构， 这 样有利于溶剂渗入颗粒内， 大大缩短树脂溶胀和溶解时间。
对比例 2
采用一种市售超高分子量聚乙婦树脂 B进行纺丝试验， 该树脂分子量为 277万， 纺 丝工艺同实施例： ί。 其裉据本发明记载的性能测试方法得到的各项性能如表 i所示， 纺丝 性能如表 2所示
对比例 3
采用一种市售超高分子量聚乙烯树脂 C进.行纺丝试验， 该树脂分子量为 359万、 纺 丝工艺同实施例 1。 其根据本发明记载的性能测试方法得到的各项性能如表 1所示， 纺丝 性能如表 2所示。
对比例 4
采用一种市售超高分子量聚乙烯树脂 D进行纺丝试验， 该树脂分子量为 433万， 纺 丝工艺同实施例 1。 其根据本发明记载的性能测试方法得到的各项性能如表 1所示， 纺丝 性能如表 2所示。 表 : 实施例和比较例超高分子量聚乙烯树脂的性能
Figure imgf000016_0001
Figure imgf000016_0002
三级拉件 15 25,0 870.8 3.25
-—级拉升 28 10,8 280.8 3,75 对比例 1 — &.^SL-) 26 15.4 378,5 3.56
三级; j立升 23 18.7 502.4 3.24 一级拉升 25 12,4 331.2 3,84 对比例 2 二级拉升 22 16.7 450.1 3.67
三级拉-升 18 19.5 606,8 3.41 一级拉升 23 13,9 370.3 3.92 对比例 3 二级拉升 20 17,3 580.1 3,78
二 &.^SL-) 16 20.6 795.4 3.56
-一级拉升 19 14.4 399,2 4.01 对比例 4 二级拉升 16 18,6 645.6 3,84
三！? L拉升 14 22.】 858.9 3.66 从表〗和表 2中， 可以看出相对于对比例, 实施例中树脂具有较高的初始结晶度, 平 均粒径适宜 粒径分布较窄， 分子量可控， 而且树脂的拉伸断裂应力大幅提高， 溶剂吸 牧.量也大大增加， 最终表现为在纤维纺丝过程中 , 树脂溶解速度较快， 所得纤维强度和 模量更高。

Claims

权利要求书
1. 一种超高分子量聚乙烯树脂， 所述聚乙烯树脂的粘均分子量为 200 - 700 万, 体 积平均粒径为 100 ~ 350μπι, 粒径分布度为 1.0 ~ 2.1 , 拉伸断裂应力 30 - 60MPa, 树脂堆 密度为 0.10 ~ 0.50 g/cm3, 初始结晶度为 60.5 - 90%。
2. 根据权^要求〗所述的超高分子量聚乙烯树脂， 其特征在于， 所述超高分子量聚 乙烯树脂的十氢萘吸收量为每】00g所述超高分子量聚乙婦树脂吸收 2〜50g十氢萘， 白油 吸收量为每 100g所述超高分子量聚乙烯树脂吸收 5〜60g白油。
3. 根据权利要求 I或 2所述的超高分子量聚乙烯树脂， 其特征在于， 所述超高分子 量聚乙烯树脂的初始结晶度为 63 ~ 85%,
4. 根据权利要求 1-3中任一项所述的超高分子量聚乙婦树脂， 其特征在于， 所述树 脂颗粒在溶剂十氢萘的浸润时间 0.5 -' l lmin, 较好为 1 ~ 8min。
5. 裉据权 要求〗-4中任一项所述的超高分子量聚乙婦树脂， 其特征在于， 所述超 高分子量聚乙烯树脂的粘均分子量为 250-600万, 更好为 350 ~ 550万。
6. 裉据权 要求 : -5 中任一项所述的超高分子量聚乙烯树脂 , 其特征在于， 所述超 高分子量聚乙烯树脂的平均粒径范围为 150〜 250μηι。
7. 裉据杈刮要求 1-6中任一项所述的超高分子量聚乙烯树脂, 其特征在于， 所述超 高分子量聚乙烯树脂的粒径分布度为 1.2 - 2.0, 更好为 1.4 - 1.9.
8. 根据权利要求 1-7中任一项所述的超高分子量聚乙烯树脂， 其特征在于， 所述超 高分子量聚乙烯树脂堆密度为堆密度 0.20 ~ 0.45 g/ cm3 , 更好为堆密度 0,20 ~ 0.35 g/ cmJ.,
9. 根据权利要求 1-8中任一项所述的超高分子量聚乙婦树脂， 其特征在于， 所述超 高分子量聚乙烯树脂的拉伸断裂应力 32 ~ 60MPa, 较好为 35 -' 60MPa。
1 0. 一种根据权利要求 】-9 中任一项所述超高分子量聚乙烯树脂作为原料在聚乙婦 纤维加工的应用。
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