CN106930107B - UHMWPE composite material coated with inorganic titanium layer and preparation method thereof - Google Patents

UHMWPE composite material coated with inorganic titanium layer and preparation method thereof Download PDF

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CN106930107B
CN106930107B CN201511028885.7A CN201511028885A CN106930107B CN 106930107 B CN106930107 B CN 106930107B CN 201511028885 A CN201511028885 A CN 201511028885A CN 106930107 B CN106930107 B CN 106930107B
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uhmwpe
ethanol
mode
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product
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CN106930107A (en
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胡江涛
吴国忠
王谋华
高乾宏
邢哲
许璐
李�荣
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Shanghai Institute of Applied Physics of CAS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
    • D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments

Abstract

The invention discloses an inorganic titanium layer coated UHMWPE composite material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing UHMWPE, an alcohol solvent and gamma-methacryloxypropyltrimethoxysilane, carrying out irradiation grafting on the materials at room temperature under an anaerobic condition, and then washing and drying to obtain a grafted product; (2) and coating the surface inorganic titanium layer of the grafted product, washing after reaction, and drying to obtain the grafted product. The UHMWPE composite material coated with the inorganic titanium layer has strong binding force between the inorganic titanium layer on the surface and UHMWPE, the coating layer is uniform, the mechanical property of the composite fiber material is good, the inorganic titanium layer can not produce photodegradation effect on the UHMWPE base material, and the composite fiber material can be further compounded with high-temperature-resistant thermosetting resin and used for preparing advanced composite materials suitable for the fields of aerospace, transportation and the like. The preparation method has the advantages of simple and feasible process and wide applicability.

Description

UHMWPE composite material coated with inorganic titanium layer and preparation method thereof
Technical Field
The invention relates to an inorganic titanium layer coated UHMWPE composite material and a preparation method thereof.
Background
In recent years, the Chinese character 'Yuan' hasTextiles with cleaning, hydrophobic, antistatic, photocatalytic and ultraviolet shielding functions have attracted great attention due to their excellent functionality. The nanometer titanium dioxide is a functional fine inorganic material with high added value and is nontoxic and tasteless powder. Due to its outstanding performance, nano titanium dioxide is widely used in the fields of polymer material industries such as paint, rubber, plastics and the like and polymer-based composite materials. Currently, the research focus on titanium dioxide in functional textile applications is mainly focused on the aspects of photocatalysis and ultraviolet absorption functions. However, titanium dioxide can degrade organic carriers of titanium dioxide nanoparticles, such as fabrics, plastics, resins, and the like, while imparting excellent photocatalytic performance to new materials, and this drawback greatly limits the use of titanium dioxide nanoparticles as photocatalysts and ultraviolet absorbers. In order to retain the excellent photocatalytic and ultraviolet absorption properties of titanium dioxide nanoparticles while avoiding or reducing photodegradation damage to organic carriers, SiO2、Al2O3、CeO2、MgO、ZrO2And the inert inorganic layer coats the surface of the titanium dioxide nano particles. However, the core-shell particles prepared by coating the inorganic particles on the surfaces of the titanium dioxide nanoparticles still have great disadvantages in application. Firstly, the binding force between the prepared core-shell particles and the fabric is weak, so that the durability of the inorganic particles on the surface of the fabric is poor, and the core-shell particles are easy to fall off from the surface of the fabric in the service process of the material, so that the material loses the functionality. Secondly, in the synthesis process of the core-shell particles, titanium dioxide nano particles are easy to agglomerate, so that the synthesized core-shell particles are large in size and poor in uniformity. In addition, because the titanium dioxide nano particles are partially or completely coated by the inorganic particles, the prepared core-shell particles have poor photocatalytic activity and ultraviolet absorption capacity, thereby affecting the performance of the functional material.
In order to overcome the problems, researchers develop a series of new methods, ① directly generate titanium dioxide nanoparticles on the surface of the fabric through a sol-gel method, ② uses a resin adhesive, ③ improves the polarity of the surface of the fabric through plasma and the like so as to improve the bonding force between the fabric and the nanoparticles, ④ improves the bonding force between the fabric and the nanoparticles through a cross-linking agent.
The ultra-high molecular weight polyethylene (UHMWPE) has excellent mechanical property, the impact resistance of the UHMWPE is also the highest in the current engineering plastics, and is 3-5 times higher than polycarbonate which is known by the impact resistance; the tensile strength is as high as 3-3.5 GPa, and the tensile elastic modulus is as high as 100-125 GPa. In addition, the ultra-high molecular weight polyethylene also has good non-adhesiveness, no toxicity, excellent electrical insulation performance, fatigue resistance, gamma-ray resistance and the like. The unique physical and chemical properties lead the UHMWPE to show attractive application prospects in the aspects of stab-resistant and bulletproof materials, space parachutes, medical sutures, artificial organs and the like. However, these characteristics make the adhesion between UHMWPE and many materials poor, since UHMWPE consists of methylene groups, is highly oriented axially, has a high degree of crystallinity, has a smooth surface (its surface lubricity is second only to that of polytetrafluoroethylene in plastics), and lacks reactive groups. There is no report of the deposition of titanium dioxide nanoparticles on the surface of UHMWPE materials by covalent bonds.
Disclosure of Invention
The invention aims to overcome the defects that the UHMWPE material has a smooth surface and is difficult to modify the surface or form a composite with other materials, and provides an inorganic titanium layer coated UHMWPE composite material and a preparation method thereof. The UHMWPE composite material coated with the inorganic titanium layer has strong binding force between the inorganic titanium layer on the surface and UHMWPE, the coating layer is uniform, the mechanical property of the composite fiber material is good, the inorganic titanium layer can not produce photodegradation effect on the UHMWPE base material, and the composite fiber material can be further compounded with high-temperature-resistant thermosetting resin and used for preparing advanced composite materials suitable for the fields of aerospace, transportation and the like. The preparation method has the advantages of simple and easy process and wide applicability, the preparation method has high controllability, the thickness of the titanium coating layer can be regulated and controlled, the control on the performance of the composite material is realized, the coating layer and the UHMWPE can be uniformly and firmly combined by the preparation method, and the prepared material has good performance.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of an inorganic titanium layer coated UHMWPE composite material, which comprises the following steps:
(1) mixing UHMWPE, an alcohol solvent and gamma-Methacryloxypropyltrimethoxysilane (MAPS), carrying out irradiation grafting on the material at room temperature under an anaerobic condition, and then washing and drying to obtain a grafted product; wherein the weight ratio of the UHMWPE to the gamma-methacryloxypropyltrimethoxysilane is 100: (380-1600); the absorption dose of the irradiation grafting is 5-50 kGy;
(2) coating an inorganic titanium layer on the surface of the grafted product by adopting a one or two-pair mode, washing after reaction, and drying to obtain the grafted product;
the first method is as follows: uniformly mixing the grafted product and a hydrochloric acid aqueous solution of titanium tetrachloride, dropwise adding an ammonia aqueous solution at 40-50 ℃, adjusting the pH value to 2-5, reacting for 3-4 h, heating to 60-80 ℃, and continuing to react for 4-6 h; wherein, the weight ratio of the titanium tetrachloride to the hydrochloric acid is (87.6-131.4): (88-100); the concentration of the hydrochloric acid in the hydrochloric acid aqueous solution is 3.9-5.5 wt%; the weight ratio of titanium tetrachloride to the graft product is (88-100): (25-50);
the second method comprises the following steps: mixing the grafting product with the solution A, reacting at 50-60 ℃ for 10-18 h, adding an ethanol aqueous solution, and continuing to react for 4-6 h; wherein the solution A is prepared by the following method: uniformly mixing ethanol, organic acid and water, then dropwise adding the mixture into an ethanol solution of tetrabutyl titanate, and uniformly mixing to obtain the product; wherein in the operation of uniformly mixing ethanol, organic acid and water, the weight ratio of the organic acid to the water is (30-55): (30-50); the weight ratio of the tetrabutyl titanate to the grafting product is (966-1200): (25-50).
In step (1), the UHMWPE may be UHMWPE conventionally used in the art, and the number average molecular weight thereof is generally 150 to 600 ten thousand.
In the present invention, the form and specification of the UHMWPE are not limited, and may be in the form of fiber, sheet, plate, or any other form. In a preferred embodiment of the invention, the UHMWPE is in the form of UHMWPE fibers.
In step (1), the alcohol solvent may be an alcohol solvent conventionally used in the art, preferably methanol and/or ethanol.
In the step (1), the dosage of the UHMWPE and the gamma-methacryloxypropyltrimethoxysilane needs to be controlled within the range. If the dosage of MAPS is too high, the polymerization speed of free radicals in the irradiation process is too high, so that implosion and a large amount of gel are generated, and the grafting rate of MAPS monomers on the fiber surface is influenced.
In step (1), the weight ratio of the UHMWPE to the alcohol solvent is preferably 1: (32-56).
In step (1), the oxygen-free condition can be achieved by means conventional in the art, for example, an inert gas can be introduced into the material to remove oxygen from the material. The inert gas is a gas which does not react with the material, is not limited to a rare gas which is conventionally referred to, and may be, for example, nitrogen. In a preferred embodiment of the present invention, the anaerobic condition is achieved by introducing nitrogen for 20-40 min. Following the removal of oxygen to create oxygen-free conditions, the reaction vessel of the materials, which is typically an irradiation tube, may be sealed to allow subsequent irradiation grafting to be carried out in oxygen-free conditions (preferably a nitrogen atmosphere), as is common in the art.
In step (1), the method and conditions for the radiation grafting may be those conventional in the art. The radiation source for the radiation grafting is preferably a cobalt source. The irradiation time of the irradiation grafting is preferably 5-17 h. The absorption dose of the irradiation grafting needs to be controlled within the previously defined range, and the absorption dose is too low to reach the grafting degree required by the subsequent titanium coating layer; too high a level easily causes the decrease of the mechanical properties of the polymer material and the self-polymerization of MAPS graft monomers.
In step (1), the washing method and conditions may be those conventional in the art. The washing is preferably ultrasonic washing. The washing time is preferably 1 to 1.5 hours. The solvent for washing can be selected according to the common knowledge in the field, does not react with the product after reaction, and can remove the ungrafted material. The washing solvent is preferably an alcohol solvent, more preferably methanol and/or ethanol.
In step (1), the drying method and conditions may be those conventional in the art. The drying temperature is preferably 50 to 70 ℃. The drying time is preferably 1 to 3 hours.
In the step (2), the first mode: uniformly mixing the grafted product and a hydrochloric acid aqueous solution of titanium tetrachloride, dropwise adding an ammonia aqueous solution at 40-50 ℃, adjusting the pH value to 2-5, reacting for 3-4 h, heating to 60-80 ℃, and continuing to react for 4-6 h; wherein, the weight ratio of the titanium tetrachloride to the hydrochloric acid is (87.6-131.4): (88-100); the concentration of the hydrochloric acid in the hydrochloric acid aqueous solution is 3.9-5.5 wt%; the weight ratio of titanium tetrachloride to the graft product is (88-100): (25-50).
In the first embodiment, the hydrochloric acid aqueous solution of titanium tetrachloride is preferably prepared in the following manner: dropwise adding the titanium tetrachloride into the hydrochloric acid aqueous solution according to the proportion, and stirring for 10-15 min after dropwise adding; the dripping time is controlled to be 20-30 min.
In the first mode: the concentration of the ammonia water is preferably 5 to 8 wt%.
In the first mode: the mixing is preferably carried out by means of stirring. The mixing time is preferably 1 to 1.5 hours.
In the step (2), the second mode: mixing the grafting product with the solution A, reacting at 50-60 ℃ for 10-18 h, adding an ethanol aqueous solution, and continuing to react for 4-6 h; wherein the solution A is prepared by the following method: uniformly mixing ethanol, organic acid and water, then dropwise adding the mixture into an ethanol solution of tetrabutyl titanate, and uniformly mixing to obtain the product; wherein in the operation of uniformly mixing ethanol, organic acid and water, the weight ratio of the organic acid to the water is (30-55): (30-50); the weight ratio of the tetrabutyl titanate to the grafting product is (966-1200): (25-50).
In the second mode: the organic acid may be an organic acid conventionally used in the art, and preferably one or more of formic acid, acetic acid and oxalic acid.
In the second mode: in the operation of uniformly mixing ethanol, organic acid and water, the weight ratio of ethanol, organic acid and water is preferably 790: (30-55): (30-50).
In the second mode: the dropwise addition can be carried out according to a conventional mode in the field, and the dropwise addition time is preferably 30-45 min.
In the second mode: in the operation of adding the ethanol aqueous solution, the ethanol concentration of the ethanol aqueous solution is preferably 86 wt% to 90 wt%. The weight ratio of the ethanol aqueous solution to the grafting product is preferably (440-455): (25-50). The adding mode is preferably dropwise adding, and the adding time is preferably 10-15 min.
In step (2), the washing method and conditions may be those conventional in the art. The washing is preferably carried out as follows: and (3) treating the reaction product in boiling water for 1-3 h, and then carrying out ultrasonic cleaning. The boiling water treatment is to immerse the product after the reaction into boiling water for boiling, so that titanium dioxide mainly comprising anatase can be formed in the inorganic titanium layer, and better ultraviolet absorption performance and photocatalysis performance are achieved. The ultrasonic cleaning is performed at room temperature, water is generally used as a solvent for the ultrasonic cleaning, and the time for the ultrasonic cleaning is preferably 2-3 hours.
In step (2), the drying method and conditions may be those conventional in the art. The drying temperature is preferably 50 to 70 ℃. The drying time is preferably 1-2 h.
The invention also provides the UHMWPE composite material coated with the inorganic titanium layer, which is prepared by the preparation method.
In the invention, the room temperature is the normal room temperature in the field, and is generally 10-25 ℃.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
In the invention, the methanol is anhydrous methanol; the ethanol is absolute ethanol.
The positive progress effects of the invention are as follows:
1) MAPS is grafted at a lower dose by adopting a co-irradiation grafting means, so that the influence on the mechanical property of the UHMWPE is reduced to the greatest extent;
2) the control of the grafting degree of the surface of the UHMWPE material is realized by adopting a mode of controlling the concentration and the absorption measurement of MAPS, and the thickness of the inorganic titanium layer can be regulated and controlled by controlling the sol-gel reaction condition, so that the control of the performance of the composite material is realized;
3) in the invention, after MAPS is grafted by radiation, the inorganic titanium layer is coated on the surface of the fiber by a covalent bond by adopting a sol-gel method. The binding force between the inorganic particles and the fiber surface is stronger, and the coating layer is more uniform.
4) The composite material prepared by the preparation method of the invention separates an organic-inorganic hybrid layer between the UHMWPE base material and the titanium dioxide nano particles, and forms an isolation layer formed by Si-O-Si and Si-O-Ti between the hybrid layer and the titanium layer nano particles, thereby avoiding the photodegradation effect of the titanium dioxide nano particles on the organic base material.
5) The UHMWPE composite material coated with the inorganic titanium layer has the advantages of simple and easy preparation process and wide applicability. The composite material prepared by the invention can be compounded with high-temperature-resistant thermosetting resin, so that the advanced composite material suitable for the fields of aerospace, transportation and the like can be prepared.
Drawings
FIG. 1 is a reaction scheme of examples 1 to 6.
FIG. 2 is an infrared spectrum of the samples of examples 1 to 6.
FIG. 3 is a scanning electron micrograph of the samples of examples 1 to 6.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, the parts used are parts by weight.
FIG. 1 is a reaction scheme in the production processes in examples 1 to 6.
In the following examples, the number average molecular weight of UHMWPE is not strictly limited, and usually 150 to 600 tens of thousands can be carried out.
Example 1
(1) 100 parts of UHMWPE were added to a mixed solution consisting of 3200 parts of methanol and 380 parts of gamma-Methacryloxypropyltrimethoxysilane (MAPS) at room temperature. The system is placed in a cobalt source for irradiation after nitrogen is introduced for 20min at room temperature, the absorbed dose is 5kGy, and the irradiation time is 17 h. And ultrasonically cleaning the grafted product by using methanol for 1h, then placing the product in an oven, and drying the product at 60 ℃ for 3h to obtain the grafted product.
(2) At room temperature, 240 parts (36.5 wt%) of hydrochloric acid were added to 2000 parts of deionized water to prepare an aqueous solution of hydrochloric acid. 88 parts of titanium tetrachloride was added dropwise to the above aqueous hydrochloric acid solution over a period of 20 minutes, and the mixture was stirred for 10 minutes after completion of the addition. 25 parts of the graft product was added to an aqueous solution containing titanium tetrachloride and stirred for 1 hour. At 40 ℃, 5% ammonia solution was added dropwise, pH was adjusted to 2, temperature was raised to 60 ℃ after 3h reaction and stirring was continued for 4 h. And treating the obtained sample in boiling water for 1h, ultrasonically cleaning the sample for 2h by using water, and then drying the sample for 1h at the temperature of 60 ℃ to obtain the UHMWPE composite fiber material coated with the inorganic titanium layer.
Example 2
(1) 100 parts of UHMWPE were added to a mixed solution consisting of 5600 parts of ethanol and 1600 parts of gamma-Methacryloxypropyltrimethoxysilane (MAPS) at room temperature. The system is placed in a cobalt source for irradiation after nitrogen is introduced for 40min at room temperature, the absorbed dose is 50kGy, and the irradiation time is 5 h. And ultrasonically cleaning the grafted product by using ethanol for 1.5h, then placing the product in an oven, and drying the product at 50 ℃ for 1h to obtain the grafted product.
(2) Solution 1, solution 2 and solution 3 were prepared. Solution 1: 966 parts of tetrabutyl titanate are dissolved in 790 parts of ethanol. Solution 2: uniformly mixing 790 parts of ethanol, 30 parts of formic acid and 30 parts of deionized water. Solution 3: 45 parts of deionized water are dissolved in 395 parts of ethanol.
And slowly dripping the solution 2 into the solution 1 within 30min, and adding 25 parts of the grafting product after uniformly stirring. After stirring at 50 ℃ for 10h, solution 3 was added dropwise to the above mixture over 10 minutes. And (3) continuing stirring for 4h, stopping the reaction, treating the obtained sample in boiling water for 3h, ultrasonically cleaning the sample for 2h by using water, and drying the sample at 50 ℃ for 2h to obtain the UHMWPE composite material coated with the inorganic titanium layer.
Example 3
(1) 100 parts of UHMWPE were added to a mixed solution consisting of 2200 parts methanol, 2800 parts ethanol and 1200 parts gamma-Methacryloxypropyltrimethoxysilane (MAPS) at room temperature. The system is placed in a cobalt source for irradiation after nitrogen is introduced for 30min at room temperature, the absorbed dose is 30kGy, and the irradiation time is 17 h. And ultrasonically cleaning the grafted product by using ethanol for 1.5h, then placing the product in an oven, and drying the product at the temperature of 60 ℃ for 1h to obtain the grafted product.
(2) 360 parts (36.5 wt%) of hydrochloric acid was added to 2000 parts of deionized water at room temperature to prepare an aqueous solution of hydrochloric acid. 100 parts of titanium tetrachloride was added dropwise to the above aqueous hydrochloric acid solution over a period of 30 minutes, and the mixture was stirred for 15 minutes after completion of the addition. 50 parts of the graft product was added to an aqueous solution containing titanium tetrachloride and stirred for 1.5 hours. At 50 ℃, 8% ammonia solution was added dropwise, pH was adjusted to 5, temperature was raised to 80 ℃ after 3h reaction and stirring was continued for 6 h. And treating the obtained sample in boiling water for 2 hours, ultrasonically cleaning the sample for 1 hour by using water, and then drying the sample for 1 hour at 70 ℃ to obtain the UHMWPE composite material coated with the inorganic titanium layer.
Example 4
(1) 100 parts of UHMWPE were added to a mixed solution consisting of 3200 parts of ethanol and 380 parts of gamma-Methacryloxypropyltrimethoxysilane (MAPS) at room temperature. The system is placed in a cobalt source for irradiation after nitrogen is introduced for 30min at room temperature, the absorbed dose is 30kGy, and the irradiation time is 17 h. And ultrasonically cleaning the grafted product by using a methanol/ethanol (volume ratio is 2:1) mixed solvent for 1h, placing the cleaned product in an oven, and drying the cleaned product at 60 ℃ for 1h to obtain the grafted product.
(2) Solution 1, solution 2 and solution 3 were prepared. Solution 1: 1200 parts of tetrabutyltitanate are dissolved in 790 parts of ethanol. Solution 2: uniformly mixing 790 parts of ethanol, 55 parts of oxalic acid and 50 parts of deionized water. Solution 3: 60 parts of deionized water are dissolved in 395 parts of ethanol.
Slowly dripping the solution 2 into the solution 1 within 45min, stirring uniformly, adding 50 parts of grafting product, stirring at 50 ℃ for 18h, and dripping the solution 3 into the mixed solution within 15 min. And (3) continuing stirring for 6h, stopping reaction, treating the obtained sample in boiling water for 1h, ultrasonically cleaning the sample for 1h by using water, and drying the sample at 60 ℃ for 1h to obtain the UHMWPE composite material coated with the inorganic titanium layer.
Example 5
(1) 100 parts of UHMWPE were added to a mixed solution consisting of 2000 parts of ethanol, 2500 parts of methanol and 1200 parts of gamma-Methacryloxypropyltrimethoxysilane (MAPS) at room temperature. The system is placed in a cobalt source for irradiation after nitrogen is introduced for 35min at room temperature, the absorbed dose is 45kGy, and the irradiation time is 17 h. The grafted product is ultrasonically cleaned for 1.5h by using a mixed solvent of methanol/ethanol (volume ratio is 2:1), then placed in an oven, and dried for 1h at 60 ℃ to obtain the grafted product.
(2) Solution 1, solution 2 and solution 3 were prepared. Solution 1: 966 parts of tetrabutyl titanate are dissolved in 790 parts of ethanol. Solution 2: 790 parts of ethanol, 45 parts of acetic acid and 30 parts of deionized water are mixed homogeneously. Solution 3: 45 parts of deionized water are dissolved in 395 parts of ethanol.
Slowly dripping the solution 2 into the solution 1 within 30min, stirring uniformly, adding 25 parts of grafting product, stirring at 60 ℃ for 18h, and dripping the solution 3 into the mixed solution within 10 min. And (3) continuing stirring for 4h, stopping reaction, treating the obtained sample in boiling water for 2h, ultrasonically cleaning the sample for 1h by using water, and drying the sample at 60 ℃ for 1h to obtain the UHMWPE composite material coated with the inorganic titanium layer.
Example 6
(1) 100 parts of UHMWPE were added to a mixed solution consisting of 3200 parts of ethanol and 380 parts of gamma-Methacryloxypropyltrimethoxysilane (MAPS) at room temperature. The system is placed in a cobalt source for irradiation after nitrogen is introduced for 30min at room temperature, the absorbed dose is 30kGy, and the irradiation time is 17 h. And ultrasonically cleaning the grafted product by using a methanol/ethanol (volume ratio is 2:1) mixed solvent for 1h, placing the cleaned product in an oven, and drying the cleaned product at 60 ℃ for 1h to obtain the grafted product.
(2) Solution 1, solution 2 and solution 3 were prepared. Solution 1: 966 parts of tetrabutyl titanate are dissolved in 790 parts of ethanol. Solution 2: 790 parts of ethanol, a mixed acid (25 parts of acetic acid and 20 parts of oxalic acid) and 30 parts of deionized water were mixed uniformly. Solution 3: 45 parts of deionized water are dissolved in 395 parts of ethanol.
Slowly dripping the solution 2 into the solution 1 within 30min, stirring uniformly, adding 50 parts of grafting product, stirring at 60 ℃ for 18h, and dripping the solution 3 into the mixed solution within 10 min. And (3) continuing stirring for 4h, stopping reaction, treating the obtained sample in boiling water for 3h, ultrasonically cleaning the sample for 1h by using water, and drying the sample at 60 ℃ for 1h to obtain the UHMWPE composite material coated with the inorganic titanium layer.
Effect example 1
The UHMWPE composite coated with an inorganic titanium layer prepared in examples 1 to 6 was examined. FIG. 2 is an infrared spectrum of the sample, and FIG. 3c is a scanning electron micrograph of the sample.
As can be seen from FIG. 2, 2919 and 2851cm in the three curves-1is-CH in UHMWPE fiber2Characteristic peaks of (A), 1082 and 820cm in the curve of grafting MAPS to UHMWPE fibres-1Si-O-C and Si-C stretching vibration peaks in MAPS molecular structure respectively show that MAPS molecules are successfully grafted to the surface of UHMWPE fiber. 2500-3700 cm in the curve of the UHMWPE fiber coated titanium layer-1Is the stretching vibration peak of Ti-OH, 630cm-1The above shows that the titanium dioxide nano particles are successfully coated on the surface of the fiber for the stretching vibration of Ti-O-Ti.
In fig. 3, fig. 3a is an electron micrograph of the UHMWPE fiber fabric, fig. 3b is an electron micrograph of the UHMWPE fiber grafted MAPS, and fig. 3c is an electron micrograph of the UHMWPE composite coated with the inorganic titanium layer prepared in examples 1 to 6, wherein each of fig. 3a, b, and c is magnified 5000 times. It can be seen that the surface of the fiber before and after grafting was very smooth, and when the fiber was coated with a titanium layer (fig. 3.c), the surface of the fiber became very rough and a particulate coating appeared, indicating that the titanium dioxide nanoparticles had successfully coated the surface of the fiber.

Claims (10)

1. A preparation method of UHMWPE composite material coated with an inorganic titanium layer is characterized by comprising the following steps:
(1) mixing UHMWPE, an alcohol solvent and gamma-methacryloxypropyltrimethoxysilane, carrying out irradiation grafting on the materials at room temperature under an anaerobic condition, and then washing and drying to obtain a grafted product; wherein the weight ratio of the UHMWPE to the gamma-methacryloxypropyltrimethoxysilane is 100: (380-1600); the absorption dose of the irradiation grafting is 5-50 kGy;
(2) coating an inorganic titanium layer on the surface of the grafted product by adopting a one or two-pair mode, washing after reaction, and drying to obtain the grafted product;
the first method is as follows: uniformly mixing the grafted product and a hydrochloric acid aqueous solution of titanium tetrachloride, dropwise adding an ammonia aqueous solution at 40-50 ℃, adjusting the pH value to 2-5, reacting for 3-4 h, heating to 60-80 ℃, and continuing to react for 4-6 h; wherein, the weight ratio of the titanium tetrachloride to the hydrochloric acid is (87.6-131.4): (88-100); the concentration of the hydrochloric acid in the hydrochloric acid aqueous solution is 3.9-5.5 wt%; the weight ratio of titanium tetrachloride to the graft product is (88-100): (25-50);
the second method comprises the following steps: mixing the grafting product with the solution A, reacting at 50-60 ℃ for 10-18 h, adding an ethanol aqueous solution, and continuing to react for 4-6 h; wherein the solution A is prepared by the following method: uniformly mixing ethanol, organic acid and water, then dropwise adding the mixture into an ethanol solution of tetrabutyl titanate, and uniformly mixing to obtain the product; wherein in the operation of uniformly mixing ethanol, organic acid and water, the weight ratio of the organic acid to the water is (30-55): (30-50); the weight ratio of the tetrabutyl titanate to the grafting product is (966-1200): (25-50).
2. The production method according to claim 1, wherein in step (1), the UHMWPE is in the form of UHMWPE fibers;
and/or, in the step (1), the alcohol solvent is methanol and/or ethanol;
and/or, in the step (1), the weight ratio of the UHMWPE to the alcohol solvent is 1: (32-56).
3. The method according to claim 1, wherein in the step (1), the oxygen-free condition is achieved by introducing an inert gas into the material to expel oxygen from the material;
and/or, in the step (1), the irradiation source of the irradiation grafting is a cobalt source; the irradiation time of the irradiation grafting is 5-17 h;
and/or, in the step (1), the washing is ultrasonic washing;
and/or in the step (1), the washing time is 1-1.5 h;
and/or, in the step (1), the washed solvent is an alcohol solvent;
and/or in the step (1), the drying temperature is 50-70 ℃, and the drying time is 1-3 h.
4. The method according to claim 3, wherein in the step (1), the inert gas is nitrogen;
and/or, in the step (1), the washed solvent is methanol and/or ethanol.
5. The method according to claim 1, wherein in the first mode, the aqueous hydrochloric acid solution of titanium tetrachloride is prepared by: dropwise adding the titanium tetrachloride into the hydrochloric acid aqueous solution according to the proportion, and stirring for 10-15 min after dropwise adding; the dripping time is controlled to be 20-30 min;
and/or, in the first mode: the concentration of the ammonia water is 5-8 wt%;
and/or, in the first mode: the mixing is carried out in a stirring mode;
and/or, in the first mode: the mixing time is 1-1.5 h.
6. The method of claim 1, wherein in mode two: the organic acid is one or more of formic acid, acetic acid and oxalic acid;
and/or, in mode two: in the operation of uniformly mixing ethanol, organic acid and water, the weight ratio of the ethanol to the organic acid to the water is 790: (30-55): (30-50);
and/or, in mode two: the dripping time is 30-45 min.
7. The method of claim 1, wherein in mode two: in the operation of adding the ethanol aqueous solution, the ethanol concentration of the ethanol aqueous solution is 86-90 wt%; the weight ratio of the ethanol aqueous solution to the grafting product is (440-455): (25-50);
and/or, in mode two: in the operation of adding the ethanol water solution, the adding mode is dropwise adding;
and/or, in mode two: and in the operation of adding the ethanol water solution, the adding time is 10-15 min.
8. The method according to claim 1, wherein in the step (2), the washing is carried out by: treating the reaction product in boiling water for 1-3 h, and then ultrasonically cleaning;
and/or in the step (2), the drying temperature is 50-70 ℃, and the drying time is 1-2 h.
9. The preparation method according to claim 8, wherein in the step (2), the ultrasonic cleaning time is 2-3 h.
10. An inorganic titanium layer coated UHMWPE composite material prepared by the preparation method of any one of claims 1 to 9.
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