CN1508302A - Preparation method of nanoparticle reinforced and toughened ultra-high molecular weight polyethylene fiber - Google Patents

Abstract

The invention is a nano particle strengthened-flexibilized superhigh relative polythene polythene fiber preparing method, including the steps: (1) nano particle surface dispersing treatment; (2) preparing nano particle denatured superhigh relative molecular weight polythene spinning mass; (3) preparing nano particle denatured superhigh relative molecular weight polythene fiber by the spinning mass; and the mechanical module can be raised by 20-70%, and the mechanical intensity also raised to a certain degree.

Description

Nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method

Technical field

The present invention relates to nano particle in superelevation average molecular weight northylen (the weight average relative molecular weight is 100～5,000,000) fiber preparation method.

Background technology

Ultra high molecular weight polyethylene (English UHMWPE) fiber is the third generation high-performance fiber that occurs after carbon fiber and aramid fiber, have other high-performance fiber incomparable mechanical property.In addition, the ultra high molecular weight polyethylene fiber also has excellent chemical resistance and weather resisteant, high-energy absorption, low electric conductivity, can see through x-ray and certain characteristics such as water proofing property, thereby in military affairs, space flight navigation engineering and fields such as high-performance, light composite material and sports apparatus wide application prospect is arranged.Particularly militarily, the ultra high molecular weight polyethylene fiber has progressively replaced aramid fiber, is used for the making of bulletproof jacket.But by the bulletproof jacket that the ultra high molecular weight polyethylene fiber is made, can only resist penetrating of pistol and low speed rifle bullet mostly, then not have resistance for the high speed rifle.Improve the impact resistance of bulletproof jacket, except that the preparation method that will improve bulletproof jacket, the mechanical moduli of the most basic mechanical property, particularly fiber that still will improve the ultra high molecular weight polyethylene fiber.

Many bibliographical informations make composite with nano-particles filled in polyethylene, can improve poly performance greatly.

As He Peng etc. at " Wear Resistance of nanometer particle-modified high density polyethylene (HDPE) " (plastics, 2001, the method of disperseing by ultrasonic dispersing or vibromill 1:39) adds nano-silicon dioxide particle in the high density polyethylene (HDPE), can make nano particle in high density polyethylene (HDPE), reach nanoscale and disperse, improve the mechanical property and the ABRASION RESISTANCE of material greatly; Huang Rui etc. disclose the preparation method of nm particles reinforced and toughened polyethylene composition in patent CN1283650A, be characterized in nano particle, solvent and surface dispersant add and have supersonic oscillations generator or vibration agitating device, in the presence of a small amount of solvent, utilize ball mill grinding that dispersant and nano particle are evenly disperseed, then surface treated nano particle is carried out drying back and polyethylene mixing preparation masterbatch on mill or double screw extruder, again masterbatch and polyethylene are strengthened toughened polyethylene composition through the preparation of double screw extruder extruding pelletization.But above-mentioned two methods institute modified polyethylene is relatively low high density polyethylene (HDPE) of molecular weight or low density polyethylene (LDPE), and the ultra high molecular weight polyethylene molecular weight is higher, viscosity is big especially, and the adding method of above-mentioned several nano particles all can not make nano particle reach the nanoscale dispersion in ultra high molecular weight polyethylene.

Wang Haibao etc. " nanometer Al2O3 is to polyethylene engineering material Effect on Performance " (University Of Chongqing's journal, 2002,4:26) in ultra high molecular weight polyethylene powder and nano-aluminium oxide (Al ₂O ₃) particle puts into mould, at high temperature (200 ± 5 ℃) and high pressure (150Mpa) sintering 2 hours down, cooling makes the polyethylene engineering plastics, can significantly improve the hardness and the ABRASION RESISTANCE of ultra high molecular weight polyethylene engineering plastics.But the method can't make nano particle reach nanoscale in ultra high molecular weight polyethylene disperses.

In order effectively to solve the even scattering problem of nano particle in the polymer body, people have proposed the compound new method of in-situ polymerization, promptly on the nano particle of polymolecularity, be written into component, and then on this nanoparticle surface, carry out polymerisation and prepare composite with catalytic activity.As disclosing a kind of preparation method of olefin polymerization nanometer composite material among the USP6465543, this composite is the dispersion thing of nano particle in polyolefin that is made by layered metal oxide or metal oxide salt.At first, remove water then and make the hydrophobicity organic clay that can in non-polar organic solvent, disperse untreated clay swelling in water.This organic clay is formed a kind of complex compound that causes alkene or styrene polymerization with catalyst treatment again with the alkyl aluminum compound processing.Alkene or styrene are directly carried out the nano composite material that in-situ polymerization can make polyolefin or polystyrene in nanoparticle surface under no shearing condition.CN1255510A and USP6444742 disclose the nanocomposite of a kind of polyolefin and clay, this composite is made up of 40～99.9% polyethylene and 0.1～60% fiber rod stone kind clay (weight proportion), transistion metal compound with the nanoscale clay is a catalyst, with the organo-aluminum compound is co-catalyst, carry out the in-situ polymerization of alkene, prepared composite has excellent mechanical property and hot property.This method can make nano particle be evenly dispersed in the ultra high molecular weight polyethylene, but situ aggregation method is comparatively loaded down with trivial details, the cost of gained composite is higher, and can gained ultra high molecular weight polyethylene composite be spun into high-performance fiber and yet there are no research report.

Summary of the invention

The object of the present invention is to provide a kind of nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method, its processing is simple, and production cost is low, and the mechanical property of fiber is good.

Technical scheme of the present invention is: a kind of nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method may further comprise the steps

(1) nanoparticle surface dispersion treatment;

With nano particle, nano particle solvent and surface dispersant, by the weight ratio of nano particle and nano particle solvent be 1: 1～5, the weight ratio of nano particle and surface dispersant is 1: 0.01～0.05, add in the device that has the supersonic oscillations stirring and stir, nano particle and surface dispersant are evenly disperseed;

(2) preparation of nanometer particle-modified ultra high molecular weight polyethylene spinning solution;

Nano particle through surperficial dispersion treatment is carried out drying, be to join the container that have supersonic generator in carry out high-speed stirred at 0.003～0.1: 100 more by weight with dried nano particle and ultra high molecular weight polyethylene solvent, make nano particle in the ultra high molecular weight polyethylene solvent, evenly disperse to form nano-particle solution, weight ratio by nano-particle solution and ultra high molecular weight polyethylene powder is 0.1～1: 100 then, the weight ratio of ultra high molecular weight polyethylene powder and antioxidant is 100: 0.1～1 mixed nano-particle solution, the ultra high molecular weight polyethylene powder, antioxidant, under stirring, heat up, being warming up to the best swelling temperature of ultra high molecular weight polyethylene in this solvent earlier stopped 1 hour, make the abundant swelling of polyethylene powders, and then be warming up to about 185 ℃ and stopped 1 hour, polyethylene is fully dissolved, to prepare the homodisperse ultra high molecular weight polyethylene spinning solution of nano particle;

(3) prepare nanometer particle-modified ultra high molecular weight polyethylene fiber by spinning solution;

By the ultra high molecular weight polyethylene spinning solution of above-mentioned preparation,, make nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber through twin-screw spinning, extraction, stretching.

The present invention compared with prior art has following advantage:

The mechanical moduli of this fiber can improve 20～70% on the original basis, and mechanical strength also improves.

The specific embodiment

Nano particle silica 250 grams, nano particle solvent acetone 150 grams, surface dispersant γ-(methacryloxypropyl) propyl trimethoxy silicane 2 grams are added and have in the reaction vessel of supersonic oscillations, at room temperature handled 20 minutes, the nano silicon after the processing places 50 ℃ baking oven inner drying 2 hours.

With dried nano silicon (SiO ₂) with the ultra high molecular weight polyethylene solvent---mineral oil joins by 0.018: 100 ratio and carries out high-speed stirred formation in 20 minutes nano-particle solution in the container that has supersonic generator, be that 0.18: 60 ratio is that 3,500,000 ultra high molecular weight polyethylene powder (being that the concentration of UHMWPE condensate in mineral oil is 6wt%) mixes mutually with nano-particle solution and weight average relative molecular weight in the nano-particle solution and the weight ratio of ultra high molecular weight polyethylene then, in the ultra high molecular weight polyethylene powder and the ratio of antioxidant is that 60: 0.3 ratio is mixed both, under stirring, be warming up to 130 ℃ of swellings 1 hour, be warming up to 180 ℃ of dissolvings 1 hour again, make nascent gel spun fiber through twin-screw spinning (The hole diameter of spinneret is 0.8mm) then, put into fiber barrel and place a period of time and be separated fully.

Through the ultra high molecular weight polyethylene gel spun fiber after being separated, at room temperature carry out 3 times of predrafts, enter then and carry out ultrasonic tensioning extraction in the extraction bath, enter air dry oven and carry out room temperature tensioning drying, the one-level of ultra high molecular weight polyethylene dry freeze glue fiber being carried out 8 times under 100 ℃ stretches, under 110 ℃, carry out 1.4 times of secondary drawing, under 120 ℃, carry out 1.1 times of three grades of stretchings, the intensity of the nanometer particle-modified ultra high molecular weight polyethylene fiber of gained is 31.6cN/dtex, modulus is 1850cN/dtex, and extension at break is 3.61%.

Comparing embodiment:

Do not add nano particle, the additional proportion of ultra high molecular weight polyethylene powder, antioxidant and mineral oil and swelling, dissolving, spinning, extraction and the drawing process of ultra high molecular weight polyethylene are all identical with above-mentioned example, the intensity of prepared ultra high molecular weight polyethylene fiber is 30.2cN/dtex, modulus is 1130cN/dtex, extension at break is 3.97%, and its mechanical property is relatively poor.

Claims (8)

1. A method for preparing nanoparticle-reinforced and toughened ultra-high molecular weight polyethylene fibers, characterized in that: comprising the following steps (1) nanoparticle surface dispersion treatment; Nanoparticles, nanoparticle solvent and surface dispersant, according to the weight ratio of nanoparticles to nanoparticle solvent is 1:1 ~ 5, the weight ratio of nanoparticles to surface dispersant is 1:0.01 ~ 0.05, add the Stir in a stirring device to evenly disperse the nanoparticles and the surface dispersant; (2) Preparation of nanoparticle-modified ultra-high molecular weight polyethylene spinning stock solution; Drying the surface-dispersed nanoparticles, and then adding the dried nanoparticles and ultra-high molecular weight polyethylene solvent in a weight ratio of 0.003 to 0.1:100 into a container with an ultrasonic generator for high-speed stirring, The nanoparticles are uniformly dispersed in the ultra-high molecular weight polyethylene solvent to form a nanoparticle solution, and then the weight ratio of the nanoparticle solution to the ultra-high molecular weight polyethylene powder is 0.1 to 1:100, and the ultra-high molecular weight polyethylene The weight ratio of ethylene powder to antioxidant is 100:0.1~1, mix nano particle solution, ultra-high molecular weight polyethylene powder, and antioxidant, heat up under stirring, firstly heat up to ultra-high molecular weight The optimal swelling temperature of polyethylene in the solvent (different from different solvents) stays for 1 hour to make the polyethylene powder fully swell, and then heats up to about 185°C and stays for 1 hour to fully dissolve the polyethylene to prepare Ultra-high molecular weight polyethylene spinning dope with uniform dispersion of nanoparticles; (3) Prepare ultra-high molecular weight polyethylene fibers modified by nanoparticles by spinning dope; From the ultra-high molecular weight polyethylene spinning dope prepared above, through twin-screw spinning, extraction, and stretching, nano-particle reinforced and toughened ultra-high molecular weight polyethylene fibers are obtained. 2. The method for preparing nanoparticle-reinforced and toughened ultra-high molecular weight polyethylene fibers according to claim 1, wherein the nanoparticle is silicon dioxide, calcium carbonate or aluminum oxide. 3. The method for preparing nanoparticle-reinforced and toughened ultra-high molecular weight polyethylene fibers according to claim 1, characterized in that: the weight-average relative molecular weight of the ultra-high molecular weight polyethylene is 1 million to 5 million. 4. The method for preparing nanoparticle-reinforced and toughened ultra-high molecular weight polyethylene fibers according to claim 1, characterized in that: the nanoparticle solvent is isopropanol, ethanol or acetone. 5. The method for preparing nanoparticle-reinforced and toughened ultra-high molecular weight polyethylene fibers according to claim 1, characterized in that: the surface dispersant is titanate or aluminate or silane coupling agent . 6. The method for preparing nanoparticle-reinforced and toughened UHMWPE fibers according to claim 1, wherein the weight ratio of the nanoparticle solution to UHMWPE powder is 0.1 ~0.7:100. 7. The method for preparing nanoparticle-reinforced and toughened ultra-high molecular weight polyethylene fibers according to claim 1, characterized in that: when the nanoparticle surface is dispersed, it is stirred under ultrasonic conditions for 10-30 minutes. 8. The method for preparing nanoparticle-reinforced and toughened ultra-high molecular weight polyethylene fibers according to claim 1, characterized in that: the drying of the surface-dispersed nanoparticles is at a temperature of 40-80°C Dry under certain conditions for 2 to 5 hours.