CN110938299A - TPU composite material for chemical protective clothing and preparation method thereof - Google Patents
TPU composite material for chemical protective clothing and preparation method thereof Download PDFInfo
- Publication number
- CN110938299A CN110938299A CN201911140379.5A CN201911140379A CN110938299A CN 110938299 A CN110938299 A CN 110938299A CN 201911140379 A CN201911140379 A CN 201911140379A CN 110938299 A CN110938299 A CN 110938299A
- Authority
- CN
- China
- Prior art keywords
- tpu
- protective clothing
- nano
- chemical protective
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a TPU composite material for chemical protective clothing and a preparation method thereof, wherein the TPU composite material for chemical protective clothing comprises the following components in parts by weight: 60-80 parts of TPU particles, 20-40 parts of nano silicon dioxide, 10-20 parts of nano modified montmorillonite, 1-8 parts of triazine flame retardant and 5-10 parts of sodium alginate-calcium sulfate whisker hybrid ions; the TPU material for chemical protective clothing has better flame retardant property, tearing resistance and barrier property; the preparation method of the TPU composite material for chemical protective clothing is simple, the raw materials are easy to obtain, the price is low, the realization is easy, and the industrial large-scale production and application are facilitated.
Description
Technical Field
The invention belongs to the field of high molecular compounds, and relates to a TPU composite material for chemical protective clothing and a preparation method thereof.
Background
Chemical protective clothing is one of the protective clothing of firemen and is divided into fire fighting clothing, fire fighting and fire preventing clothing, fire insulating clothing and heavy protective clothing of firemen. The protective clothing is worn by firefighters in fire fighting and emergency rescue in fire scenes and accident sites with dangerous chemical substances and corrosive substances to protect the firefighters from being damaged by the chemical dangerous substances or the corrosive substances. With the development of science and technology and the development of society, the requirements on chemical protective clothing are gradually improved, and the requirements on chemical protective clothing materials are also gradually improved.
CN103509483A discloses a heat-sealing adhesive tape for chemical protective clothing, which comprises a substrate and a coating, wherein the coating comprises PU40-60 parts, PA (polyamide) 30-40 parts and LLDPE40-60 parts. The invention also provides a method for producing the heat-sealing adhesive tape for chemical protective clothing. The heat-sealing adhesive tape for chemical protective clothing has high bonding strength, excellent acid and alkali resistance and corrosion resistance, and excellent gas, water, oil and peculiar smell resistance; the production method of the heat-sealing adhesive tape for protection is simple, and the processing difficulty of a finished product is low; but the tear strength and the flame retardant property of the flame retardant polyester resin are improved.
CN104032573A discloses a coating waterproof cloth composition, which comprises, by weight, 20-30 parts of linear polyethylene, 2-4 parts of an anti-ultraviolet agent, 90-110 parts of PVC paste resin, 2-10 parts of a stabilizer, 30-40 parts of a plasticizer, 4-6 parts of a flame retardant, 1-5 parts of an antioxidant, 2-6 parts of polyurethane, 1-3 parts of a water repellent and 4-8 parts of bamboo fibers. The flame-retardant anti-ultraviolet flame-retardant coating has simple components and low cost, can be used in an environment with the temperature of-30-70 ℃, has excellent performances of water resistance, flame retardance, enzyme resistance, ultraviolet resistance, high-strength tensile tearing, wear resistance and the like, is widely applied to air films, inflatable materials, automobiles, quick flexible doors, tents, oil barriers, chemical protective clothing, film structures, covering cloth and the like, and has improved flame retardance, tearing resistance and barrier property.
Therefore, it is necessary to provide a chemical protective clothing material with good flame retardant property, good tear resistance and excellent barrier property.
Disclosure of Invention
The invention aims to provide a TPU composite material for chemical protective clothing and a preparation method thereof, wherein the TPU composite material for chemical protective clothing has better flame retardant property, tearing resistance and barrier property; the preparation method of the TPU composite material for chemical protective clothing is simple, the raw materials are easy to obtain, the price is low, the realization is easy, and the industrial large-scale production and application are facilitated.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a TPU composite material for chemical protective clothing, which comprises the following components in parts by weight:
in the invention, the TPU composite material for chemical protective clothing comprises TPU particles, nano silicon dioxide, nano modified montmorillonite, triazine flame retardant and sodium alginate-calcium sulfate whisker hybrid ions, so that the TPU composite material has better flame retardant property, tear resistance and barrier property; the nanometer silicon dioxide and the nanometer modified montmorillonite are matched for use, so that the barrier property of the TPU material can be improved; the triazine flame retardant can improve the flame retardant property of the TPU composite material; the nano silicon dioxide and the sodium alginate-calcium sulfate whisker hybrid ions can both improve the tear resistance of the TPU composite material.
In the present invention, the addition amount of the TPU particles may be 60 parts by weight, 62 parts by weight, 65 parts by weight, 67 parts by weight, 70 parts by weight, 72 parts by weight, 75 parts by weight, 77 parts by weight, 80 parts by weight, or the like.
In the present invention, the amount of the nano silica added may be 20 parts by weight, 22 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 37 parts by weight, 40 parts by weight, etc.
In the present invention, the nano modified montmorillonite may be added in an amount of 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, etc.
In the present invention, the triazine-based flame retardant may be added in an amount of 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or the like.
In the invention, the addition amount of the sodium alginate-calcium sulfate whisker hybrid ion can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight and the like.
In the present invention, the TPU particles are polyester TPU particles and/or polyether TPU particles.
In the present invention, the TPU particles are a combination of polyester TPU particles and polyether TPU particles.
In the present invention, the mass ratio of the polyester TPU particles to the polyether TPU particles is (1-5: 1), for example, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, etc.
According to the invention, the polyester TPU particles and the polyether TPU particles are selected to act together, and the mass ratio of the polyester TPU particles to the polyether TPU particles is in the range limited by the invention, so that the tear resistance and the elasticity of the TPU composite material can be improved; if the mass ratio of the two is not within the range defined in the present invention, or if either one of the two is absent, the properties of the TPU composite may be degraded.
In the present invention, the particle size of the nano-silica is 10 to 100nm, for example, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc.
In the present invention, the nano silica includes any one of SP15, SP30, SP30S or SP50 or a combination of at least two thereof.
In the invention, the preparation method of the nano modified montmorillonite comprises the following steps: adding nano montmorillonite into deionized water, mixing to obtain a suspension, adding vinyl acetate-acrylic emulsion, reacting, and performing ultrasonic treatment to obtain the nano modified montmorillonite.
In the present invention, the mixing includes first stirring and mixing, and then ultrasonic mixing.
In the present invention, the stirring and mixing time is 30-40min, such as 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, 40min, etc.
In the present invention, the temperature of the ultrasonic mixing is 40-60 ℃, such as 40 ℃, 42 ℃, 45 ℃, 47 ℃, 50 ℃, 52 ℃, 55 ℃, 57 ℃, 60 ℃ and the like.
In the present invention, the time of the ultrasonic mixing is 10-15min, such as 10min, 11min, 12min, 13min, 14min, 15min, etc.
In the present invention, the reaction temperature is 30-40 ℃, such as 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃ and so on.
In the present invention, the reaction time is 1.5 to 2 hours, such as 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, etc.
In the invention, the preparation method of the nano montmorillonite also comprises the steps of carrying out solid-liquid separation and drying on reactants obtained by reaction.
In the invention, the solid-liquid separation mode is suction filtration.
In the invention, the preparation method of the nano montmorillonite comprises the following steps: dispersing the nano-montmorillonite suspension to swell the nano-montmorillonite, adding p-aminobenzoate, and reacting to obtain the nano-montmorillonite.
In the present invention, the dispersion includes first dispersing for 30-40min (e.g., 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, 40min, etc.) at 20-30 ℃ (e.g., 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, etc.), and then dispersing for 10-20min (e.g., 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min, etc.) at 50-70 ℃ (e.g., 50 ℃, 52 ℃, 55 ℃, 57 ℃, 60 ℃, 62 ℃, 65 ℃, 67 ℃, 70 ℃, etc.).
In the present invention, the reaction temperature is 90-95 ℃, such as 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ and the like.
In the present invention, the reaction time is 1 to 1.5h, such as 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, etc.
In the invention, the preparation method of the nano montmorillonite also comprises the steps of carrying out solid-liquid separation, drying and grinding on reactants obtained after reaction.
In the invention, the solid-liquid drying mode is suction filtration.
In the present invention, the triazine-based flame retardant has the following structure:
in the invention, the preparation method of the sodium alginate-calcium sulfate whisker hybrid ion comprises the following steps: mixing a sodium alginate solution and a nitrate solution, adjusting the pH value to 10-11 (such as 10, 10.5, 11 and the like), then adding calcium sulfate whiskers, and reacting to obtain the sodium alginate-calcium sulfate whisker hybrid ions.
In the present invention, the concentration of the sodium alginate solution is 3-4%, such as 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, etc.
In the present invention, the solute of the nitrate solution is sodium nitrate and/or potassium nitrate.
In the present invention, the nitrate solution has a concentration of 1 to 1.5mol/L, for example, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, etc.
In the present invention, the mass ratio of the alginic acid solution to the nitrate solution is (6-8):1, for example, 6:1, 6.2:1, 6.5:1, 6.7:1, 7:1, 7.2:1, 7.5:1, 7.7:1, 8:1, etc.
In the present invention, the mixing temperature is 70-90 ℃, such as 70 ℃, 72 ℃, 75 ℃, 77 ℃, 80 ℃, 82 ℃, 85 ℃, 87 ℃, 90 ℃ and the like.
In the present invention, the mixing time is 30-60min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc.
In the present invention, the amount of the barium sulfate whiskers is 10 to 20% of the amount of the alginic acid solution, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, and the like.
In the present invention, the reaction comprises first stirring and then ultrasonic treatment.
In the present invention, the stirring rate is 2000-3000r/min, such as 2000r/min, 2100r/min, 2200r/min, 2300r/min, 2400r/min, 2500r/min, 2600r/min, 2700r/min, 2800r/min, 2900r/min, 3000r/min, etc.
In the present invention, the stirring time is 2 to 3 hours, such as 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3 hours and the like.
In the present invention, the time of the ultrasonic treatment is 10-30min, such as 10min, 12min, 15min, 17min, 20min, 22min, 25min, 27min, 30min, etc.
In the invention, the preparation method of the sodium alginate-calcium sulfate whisker hybrid ion further comprises the steps of carrying out solid-liquid separation and drying on a reactant obtained after the reaction.
In the present invention, the solid-liquid separation method is centrifugation.
In the present invention, the TPU composite for chemical protective clothing further comprises 1 to 5 parts by weight (e.g., 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, etc.) of a processing aid.
In the present invention, the processing aid includes any one of a defoaming agent, a light stabilizer or an adhesive, or a combination of at least two thereof.
The invention also aims to provide a preparation method of the TPU composite material for chemical protective clothing, which comprises the following steps: and mixing TPU particles, nano silicon dioxide, nano modified montmorillonite, triazine flame retardant, sodium alginate-calcium sulfate whisker hybrid ions and optional processing aids to obtain the TPU composite material for chemical defense clothing.
The TPU composite material disclosed by the invention is simple in preparation method, easy in obtaining of raw materials, low in price, easy to realize and convenient for industrial large-scale production and application.
In the present invention, the temperature for the kneading is 100-120 ℃, for example, 100 ℃, 102 ℃, 105 ℃, 107 ℃, 110 ℃, 112 ℃, 115 ℃, 117 ℃, 120 ℃ and the like.
In the present invention, the mixing time is 1 to 5 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, etc.
Compared with the prior art, the invention has the following beneficial effects:
the TPU composite material prepared by the invention has better flame retardant property, tearing resistance and barrier property; wherein the oxygen transmission coefficient is as low as 16.2cm3·mm/m2d.Pa, water vapor transmission coefficient as low as 17.0 g.mm/m2d.Pa, the tearing strength is up to 179kg/cm, the vertical burning grade is V-0 grade, and the oxygen index is up to 31 percent; the preparation method of the TPU composite material is simple, the raw materials are easy to obtain, the price is low, the realization is easy, and the industrial large-scale production and application are facilitated.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In this embodiment, the preparation method of the nano modified montmorillonite comprises the following steps:
(1) preparing 0.5g of sodium-based montmorillonite and 10mL of deionized water into a suspension, firstly stirring at a high speed for 35min at 25 ℃, then heating to 60 ℃, stirring at a high speed for dispersing for 20min until the sodium-based montmorillonite is completely swelled;
(2) adding p-aminobenzoate, heating to 95 ℃, stirring at constant temperature for 1h, cooling, filtering, vacuum drying and grinding to obtain nano-montmorillonite;
(3) preparing nano montmorillonite and a proper amount of deionized water into a suspension, specifically, firstly stirring at high speed for 35min at room temperature, then heating to 50 ℃, carrying out primary ultrasonic treatment for 10min, then dropwise adding vinyl acetate-acrylic emulsion, regulating the temperature to 35 ℃, stirring and dispersing for 2h, carrying out secondary ultrasonic treatment for 12min, then cooling, carrying out suction filtration, vacuum drying and grinding to obtain the nano modified montmorillonite.
The preparation method of the sodium alginate-calcium sulfate whisker hybrid ion in the embodiment comprises the following steps: adding sodium alginate into deionized water, stirring uniformly to obtain a sodium alginate solution with the mass concentration of 3.55%, then adding a sodium nitrate aqueous solution into the obtained sodium alginate solution under stirring to form a reaction system, wherein the addition amount of the nitrate aqueous solution is 15% of the mass of the sodium alginate solution, heating to 80 ℃, keeping the temperature for 45min, then adjusting the pH value of the reaction system to 10.5, adding calcium sulfate whiskers with the mass of 25% of the sodium alginate solution into the reaction system, stirring at the rotating speed of 2500r/min for 2.5 hours, then carrying out ultrasonic treatment for 20min, standing for 2 hours, then carrying out suction filtration, cleaning a suction filtration product to be neutral by using deionized water, and carrying out vacuum drying to constant weight to obtain the sodium alginate-calcium sulfate whisker hybrid particles.
Example 1
The embodiment provides a TPU composite material for chemical protective clothing, which comprises the following components in parts by weight:
wherein the TPU particles are a combination of polyester TPU particles (German Bayer 5377) and polyether TPU particles (basf 1185A), and the mass ratio of the polyester TPU particles to the polyether TPU particles is 3: 1; the nano silicon dioxide is SP 30S; the nano modified montmorillonite and sodium alginate-calcium sulfate whisker hybrid ion is prepared by the preparation method; the triazine flame retardant has the following structure:
the embodiment provides a preparation method of a TPU composite material for chemical protective clothing, which comprises the following steps: and (2) mixing TPU particles, nano silicon dioxide, nano modified montmorillonite, triazine flame retardant, sodium alginate-calcium sulfate whisker hybrid ions and optional processing aid at 110 ℃ for 3h to obtain the TPU composite material for chemical defense clothing.
Example 2
The embodiment provides a TPU composite material for chemical protective clothing, which comprises the following components in parts by weight:
wherein the TPU particles are a combination of polyester TPU particles (German Bayer 5377) and polyether TPU particles (basf 1185A), and the mass ratio of the polyester TPU particles to the polyether TPU particles is 1: 1; the nano silicon dioxide is SP 30; the nano modified montmorillonite and sodium alginate-calcium sulfate whisker hybrid ion is prepared by the preparation method; the triazine flame retardant has the following structure:
the embodiment provides a preparation method of a TPU composite material for chemical protective clothing, which comprises the following steps: and (2) mixing TPU particles, nano silicon dioxide, nano modified montmorillonite, triazine flame retardant, sodium alginate-calcium sulfate whisker hybrid ions and optional processing aid at 120 ℃ for 1h to obtain the TPU composite material for chemical defense clothing.
Example 3
The embodiment provides a TPU composite material for chemical protective clothing, which comprises the following components in parts by weight:
wherein the TPU particles are a combination of polyester TPU particles (German Bayer 5377) and polyether TPU particles (basf 1185A), and the mass ratio of the polyester TPU particles to the polyether TPU particles is 5: 1; the nano silicon dioxide is SP 50; the nano modified montmorillonite and sodium alginate-calcium sulfate whisker hybrid ion is prepared by the preparation method; the triazine flame retardant has the following structure:
the embodiment provides a preparation method of a TPU composite material for chemical protective clothing, which comprises the following steps: and (3) mixing TPU particles, nano silicon dioxide, nano modified montmorillonite, triazine flame retardant, sodium alginate-calcium sulfate whisker hybrid ions and optional processing aid at 100 ℃ for 5 hours to obtain the TPU composite material for chemical defense clothing.
Example 4
The difference from example 1 is only that the mass ratio of the polyester type TPU particles to the polyether type TPU particles is 0.5:1, and the rest of the composition and the preparation method are the same as those of example 1.
Example 5
The difference from example 1 is only that the mass ratio of the polyester TPU particles to the polyether TPU particles is 8:1, and the rest of the composition and the preparation method are the same as those of example 1.
Comparative example 1
The only difference from example 1 is that the TPU particles are only polyester TPU particles, no polyether TPU particles are included, and the rest of the composition and the preparation method are the same as those of example 1.
Comparative example 2
The only difference from example 1 is that the TPU particles are only polyether TPU particles, polyester TPU particles are not included, and the rest of the composition and the preparation method are the same as those of example 1.
Comparative example 3
The difference from the example 1 is that the TPU composite material for chemical protective clothing does not comprise nano silicon dioxide, the addition amount of the nano modified montmorillonite is the sum of the addition amounts of the nano silicon dioxide and the nano modified montmorillonite in the example 1, and the rest components and the preparation method are the same as those in the example 1.
Comparative example 4
The difference from the example 1 is that the TPU composite material for chemical defense clothing does not comprise the nano modified montmorillonite, the addition amount of the nano silicon dioxide is the sum of the addition amounts of the nano silicon dioxide and the nano modified montmorillonite in the example 1, and the rest components and the preparation method are the same as those in the example 1.
Comparative example 5
The method is different from the example 1 only in that the sodium alginate-calcium sulfate whisker hybrid ions are replaced by the same mass of sodium alginate, and the rest components and the preparation method are the same as the example 1.
Comparative example 6
The difference from the example 1 is only that calcium sulfate whiskers with the same mass are used for replacing sodium alginate-calcium sulfate whisker hybrid ions, and the rest of the composition and the preparation method are the same as the example 1.
Comparative example 7
The difference from the example 1 is only that the sodium alginate-calcium sulfate whisker hybrid ions are replaced by a mixture of sodium alginate and calcium sulfate whiskers, and the rest of the composition and the preparation method are the same as the example 1.
Comparative example 8
The only difference from example 1 is that the TPU composite material does not comprise triazine flame retardant, and the rest of the composition and the preparation method are the same as those of example 1.
The TPU composite materials for chemical protective clothing obtained in examples 1 to 5 and comparative examples 1 to 8 are subjected to flame retardant performance, tear resistance and barrier performance tests, wherein the vertical burning is in accordance with UL-94 vertical burning test standard, the oxygen index is in accordance with GB/T2406, the tear strength is in accordance with GB/T528-1998(ISO37:2005), the oxygen transmission rate is in accordance with GB/T1038-2000, the water vapor transmission rate is in accordance with GB/T1037-2000, and the test results are shown in Table 1:
TABLE 1
As shown in Table 1, the TPU composite material for chemical protective clothing has good flame retardant property,Tear strength and barrier properties; wherein the oxygen transmission coefficient is as low as 16.2cm3·mm/m2d.Pa, water vapor transmission coefficient as low as 17.0 g.mm/m2d.Pa, tear strength up to 179kg/cm, vertical burn rating V-0, and oxygen index up to 31%. As can be seen from the comparison between example 1 and examples 4 to 5, when the mass ratio of the polyester TPU particles to the polyether TPU particles is not within the range defined by the present invention, the tear strength of the TPU composite material for chemical protective clothing is reduced; as can be seen from the comparison between example 1 and comparative examples 1 to 2, when the TPU particle is selected from either a polyether TPU particle or a polyester TPU particle, the tear strength of the TPU composite material for chemical protective clothing is greatly reduced; as can be seen from the comparison between the example 1 and the comparative examples 3 to 4, when any one of the nano silicon dioxide or the nano modified montmorillonite is lacked in the TPU composite material for chemical protective clothing, the water and oxygen resisting performance of the TPU composite material for chemical protective clothing is greatly reduced; as can be seen from the comparison between example 1 and comparative examples 5 to 7, when sodium alginate and/or calcium sulfate whisker are used for replacing sodium alginate-calcium sulfate whisker hybrid ions, the tearing performance of the TPU composite material for chemical protective clothing is greatly reduced; as can be seen from the comparison of example 1 and comparative example 8, when triazine flame retardants are not included, the flame retardant property of the TPU composite material for chemical protective clothing is greatly reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The TPU composite material for the chemical protective clothing is characterized by comprising the following components in parts by weight:
2. the TPU composite for chemical protective clothing according to claim 1, wherein the TPU particles are polyester TPU particles and/or polyether TPU particles;
preferably, the TPU particles are a combination of polyester TPU particles and polyether TPU particles;
preferably, the mass ratio of the polyester TPU particles to the polyether TPU particles is (1-5): 1.
3. The TPU composite for chemical protective clothing according to claim 1 or 2, wherein the nano silica has a particle size of 10 to 100 nm;
preferably, the nanosilica comprises any one of, or a combination of at least two of, SP15, SP30, SP30S or SP 50.
4. The TPU composite material for chemical protective clothing according to any one of claims 1 to 3, wherein the preparation method of the nano modified montmorillonite comprises the following steps: adding nano montmorillonite into deionized water, mixing to obtain a suspension, adding vinyl acetate-acrylic emulsion, reacting, and performing ultrasonic treatment to obtain nano modified montmorillonite;
preferably, the mixing comprises first mixing with stirring and then ultrasonic mixing;
preferably, the stirring and mixing time is 30-40 min;
preferably, the temperature of the ultrasonic mixing is 40-60 ℃;
preferably, the time of ultrasonic mixing is 10-15 min;
preferably, the temperature of the reaction is 30-40 ℃;
preferably, the reaction time is 1.5-2 h;
preferably, the preparation method of the nano montmorillonite also comprises the steps of carrying out solid-liquid separation and drying on reactants obtained by reaction;
preferably, the solid-liquid separation mode is suction filtration.
5. The TPU composite material for chemical protective clothing according to claim 4, wherein the preparation method of the nano montmorillonite comprises the following steps: dispersing the nano-montmorillonite suspension to swell nano-montmorillonite, adding para aminobenzoate, and reacting to obtain nano-montmorillonite;
preferably, the dispersing comprises dispersing for 30-40min at 20-30 ℃ and then for 10-20min at 50-70 ℃;
preferably, the temperature of the reaction is 90-95 ℃;
preferably, the reaction time is 1-1.5 h;
preferably, the preparation method of the nano montmorillonite also comprises the steps of carrying out solid-liquid separation, drying and grinding on reactants obtained after reaction;
preferably, the solid-liquid drying mode is suction filtration.
6. The TPU composite for chemical protective clothing according to any one of claims 1 to 5, wherein the triazine flame retardant has the following structure:
7. the TPU composite material for chemical defense clothing according to any one of claims 1 to 6, wherein the preparation method of the sodium alginate-calcium sulfate whisker hybrid ion comprises the following steps: mixing a sodium alginate solution and a nitrate solution, adjusting the pH value to 10-11, then adding calcium sulfate whiskers, and reacting to obtain the sodium alginate-calcium sulfate whisker hybrid ions;
preferably, the concentration of the sodium alginate solution is 3-4%;
preferably, the solute of the nitrate solution is sodium nitrate and/or potassium nitrate;
preferably, the concentration of the nitrate solution is 1-1.5 mol/L;
preferably, the mass ratio of the alginic acid solution to the nitrate solution is (6-8): 1;
preferably, the temperature of the mixing is 70-90 ℃;
preferably, the mixing time is 30-60 min;
preferably, the addition amount of the barium sulfate whiskers is 10-20% of the addition amount of the alginic acid solution;
preferably, the reaction comprises first stirring and then ultrasonic treatment;
preferably, the stirring speed is 2000-3000 r/min;
preferably, the stirring time is 2-3 h;
preferably, the time of the ultrasonic treatment is 10-30 min;
preferably, the preparation method of the sodium alginate-calcium sulfate whisker hybrid ion further comprises the steps of carrying out solid-liquid separation and drying on a reactant obtained after the reaction;
preferably, the solid-liquid separation mode is centrifugation.
8. The TPU composite for chemical protective clothing according to any one of claims 1 to 7, wherein the TPU composite for chemical protective clothing further comprises 1 to 5 parts by weight of a processing aid;
preferably, the processing aid comprises any one or a combination of at least two of a defoamer, a light stabilizer or an adhesive.
9. The method of making the TPU composite for chemical protective clothing according to any of claims 1-8, comprising: and mixing TPU particles, nano silicon dioxide, nano modified montmorillonite, triazine flame retardant, sodium alginate-calcium sulfate whisker hybrid ions and optional processing aids to obtain the TPU composite material for chemical defense clothing.
10. The preparation method according to claim 9, wherein the mixing temperature is 100-120 ℃;
preferably, the mixing time is 1-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911140379.5A CN110938299A (en) | 2019-11-20 | 2019-11-20 | TPU composite material for chemical protective clothing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911140379.5A CN110938299A (en) | 2019-11-20 | 2019-11-20 | TPU composite material for chemical protective clothing and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110938299A true CN110938299A (en) | 2020-03-31 |
Family
ID=69907160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911140379.5A Pending CN110938299A (en) | 2019-11-20 | 2019-11-20 | TPU composite material for chemical protective clothing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110938299A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592748A (en) * | 2020-05-21 | 2020-08-28 | 莫国军 | Biodegradable material and preparation method thereof |
| CN112094494A (en) * | 2020-08-28 | 2020-12-18 | 东莞市吉鑫高分子科技有限公司 | Super-barrier thermoplastic polyurethane elastomer and preparation method thereof |
| CN113004331A (en) * | 2021-03-08 | 2021-06-22 | 江苏极易新材料有限公司 | Synthetic method of antioxidant |
| CN113072805A (en) * | 2021-03-16 | 2021-07-06 | 浙江洛克新材料股份有限公司 | TPU film for protective clothing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059552A (en) * | 2012-12-11 | 2013-04-24 | 张萍 | Nano-particle modified polyurethane synthetic leather sizing agent |
| CN104231595A (en) * | 2014-09-18 | 2014-12-24 | 东莞市吉鑫高分子科技有限公司 | Transparent blocking thermoplastic polyurethane elastomer and preparation method thereof |
| CN106883565A (en) * | 2017-03-29 | 2017-06-23 | 四会市恒星智能科技有限公司 | A kind of high-barrier composite film |
| CN107880531A (en) * | 2016-09-30 | 2018-04-06 | 万华化学集团股份有限公司 | A kind of thermoplastic polyurethane elastomer composite material, Its Preparation Method And Use |
| CN108948442A (en) * | 2018-06-19 | 2018-12-07 | 界首市诚信玩具有限公司 | A kind of natural rubber that tear-resistant intensity is high |
-
2019
- 2019-11-20 CN CN201911140379.5A patent/CN110938299A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059552A (en) * | 2012-12-11 | 2013-04-24 | 张萍 | Nano-particle modified polyurethane synthetic leather sizing agent |
| CN104231595A (en) * | 2014-09-18 | 2014-12-24 | 东莞市吉鑫高分子科技有限公司 | Transparent blocking thermoplastic polyurethane elastomer and preparation method thereof |
| CN107880531A (en) * | 2016-09-30 | 2018-04-06 | 万华化学集团股份有限公司 | A kind of thermoplastic polyurethane elastomer composite material, Its Preparation Method And Use |
| CN106883565A (en) * | 2017-03-29 | 2017-06-23 | 四会市恒星智能科技有限公司 | A kind of high-barrier composite film |
| CN108948442A (en) * | 2018-06-19 | 2018-12-07 | 界首市诚信玩具有限公司 | A kind of natural rubber that tear-resistant intensity is high |
Non-Patent Citations (5)
| Title |
|---|
| QINGBO ZHANG,等: ""The Mechanical Properties and Thermal Performances of Polypropylene with a Novel Intumescent Flame Retardant"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 化工部合成材料研究院，等编: "《聚合物防老化实用手册》", 30 June 1999, 化学工业出版社 * |
| 张玉龙主编: "《纳米复合材料手册》", 31 July 2005, 中国石化出版社 * |
| 汪胜，等: ""新型无孔透湿TPU薄膜的制备及其服用性能研究"", 《化工新型材料》 * |
| 蔡佑星，等: ""改性蒙脱土提高PET阻隔性的研究"", 《包装工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592748A (en) * | 2020-05-21 | 2020-08-28 | 莫国军 | Biodegradable material and preparation method thereof |
| CN112094494A (en) * | 2020-08-28 | 2020-12-18 | 东莞市吉鑫高分子科技有限公司 | Super-barrier thermoplastic polyurethane elastomer and preparation method thereof |
| CN112094494B (en) * | 2020-08-28 | 2022-07-19 | 东莞市吉鑫高分子科技有限公司 | Super-barrier thermoplastic polyurethane elastomer and preparation method thereof |
| CN113004331A (en) * | 2021-03-08 | 2021-06-22 | 江苏极易新材料有限公司 | Synthetic method of antioxidant |
| CN113072805A (en) * | 2021-03-16 | 2021-07-06 | 浙江洛克新材料股份有限公司 | TPU film for protective clothing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110938299A (en) | TPU composite material for chemical protective clothing and preparation method thereof | |
| EP0927223B1 (en) | Organoclay-polymer composites | |
| CN102040790A (en) | Fireproof polyvinyl acetate emulsion and preparation method thereof | |
| CN101747859A (en) | Silicone fireproof sealant for construction and preparation method thereof | |
| CN105521717A (en) | Method for preparing organic-inorganic hybridized full heat exchange film with coupling agent method | |
| CN113773735A (en) | Flame-retardant waterborne polyurethane material | |
| CN110577708A (en) | Modified floating bead/graphene oxide flame-retardant runway particle material | |
| CN113444374A (en) | Wear-resistant asphalt waterproof coiled material and preparation method thereof | |
| CN112251840A (en) | Electret polymer melt-blown fabric and preparation method thereof | |
| CN110760135A (en) | Gas mask and mask composite material and production process thereof | |
| CN114058084A (en) | Molybdenum substrate layer modified magnesium hydroxide and preparation method and application thereof | |
| CN110845779B (en) | Modified composite flame-retardant TPO resin and preparation method thereof | |
| CN112159585A (en) | High-weather-resistance shading film and preparation method thereof | |
| CN117487422B (en) | Water-based ceramic particle heat reflection coating and preparation method thereof | |
| CN113389059B (en) | High-water-pressure-resistance flame-retardant waterborne polyurethane coating adhesive for outdoor tent cloth and preparation method thereof | |
| EP3708616A1 (en) | Compact graphene comprising silanized hydroxyl graphene with thermosetting polymer | |
| CN112323255A (en) | Oil-smoke-resistant efficient filtering melt-blown fabric and preparation method thereof | |
| CN111704817A (en) | Water-resistant breathable water-based inorganic coating and preparation method thereof | |
| CN109679161B (en) | Carboxyl nitrile rubber/graphene oxide nanocomposite capable of blocking hazardous chemical solvents and preparation method thereof | |
| CN111500129A (en) | Multicolor paint and preparation method thereof | |
| CN108410152A (en) | A kind of fire-retardant fireproof plank and preparation method thereof | |
| CN114015399A (en) | High-strength flame-retardant two-component silane modified polyether adhesive and preparation method thereof | |
| CN109914117B (en) | Flame-retardant leather, preparation method and application | |
| CN108641451A (en) | Coating efficient flame-retarding agent and preparation method thereof, coating | |
| CN114395167A (en) | Carbon microsphere @ hydrotalcite @ polyphosphazene hybrid flame retardant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |