CN113527814A - Special polypropylene composite material added with non-woven fabric reclaimed material for automobile - Google Patents
Special polypropylene composite material added with non-woven fabric reclaimed material for automobile Download PDFInfo
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention relates to a polypropylene composite material added with non-woven fabric reclaimed materials and specially used for automobiles, which comprises the following raw materials in parts by weight: 30-40 parts of polypropylene resin, 20-30 parts of high impact polypropylene, 10-15 parts of non-woven regenerated fiber, 5-8 parts of modified silicon dioxide, 3-5 parts of toughening agent and 1-3 parts of antioxidant; the non-woven regenerated fiber is obtained by taking waste non-woven fabrics as raw materials through cleaning, alkaline leaching and grafting modification, the waste non-woven fabrics are taken as the raw materials, the secondary utilization of resources is realized, the pollution of waste materials is reduced, the modified silicon dioxide combines the high heat conduction and ultraviolet resistance of silicon dioxide, and the dispersibility of the modified silicon dioxide in a polymer is improved through the treatment of a coupling agent KH-550.
Description
Technical Field
The invention belongs to the technical field of preparation of polypropylene composite materials, and particularly relates to a special polypropylene composite material added with a non-woven fabric reclaimed material for an automobile.
Background
The non-woven fabric is also called as non-woven fabric, is composed of directional or random fibers, is called as fabric because of having the appearance and certain properties of the fabric, has the characteristics of moisture resistance, ventilation, flexibility, light weight, no combustion supporting, easy decomposition, no toxicity or irritation, rich color, low price, recycling and the like, is widely used in disposable clothes at present, and can be divided into polypropylene fibers, terylene, chinlon, spandex, acrylic fibers and the like according to the components; the different components will have distinct nonwoven styles.
The polypropylene non-woven fabric is one of non-woven fabrics, is formed by high-temperature wire drawing and polymerization of polypropylene into a net and then bonding the net into cloth by a hot pressing method, has simple process flow and no harm to human bodies, and is widely applied to the fields of sanitary materials, clothing, glove lining cloth and the like.
Disclosure of Invention
The invention aims to provide a polypropylene composite material added with non-woven fabric reclaimed materials and specially used for automobiles.
The technical problems to be solved by the invention are as follows:
in the prior art, the waste of disposable polypropylene non-woven fabrics is increased, which causes a great waste of resources, and the polypropylene composite material for the automobile at present has low toughness and poor flame retardance, and is easy to age and become brittle after being used for a long time.
The purpose of the invention can be realized by the following technical scheme:
the polypropylene composite material added with the non-woven fabric reclaimed material for the automobile comprises the following raw materials in parts by weight: 30-40 parts of polypropylene resin, 20-30 parts of high impact polypropylene, 10-15 parts of non-woven regenerated fiber, 5-8 parts of modified silicon dioxide, 3-5 parts of toughening agent and 1-3 parts of antioxidant;
the polypropylene composite material added with the non-woven fabric reclaimed material special for the automobile is prepared by the following steps:
firstly, adding polypropylene resin and high impact polypropylene into a reaction kettle, heating to 180-class temperature of 200 ℃ at a heating rate of 3 ℃/min, stirring for 30min at a rotating speed of 200-class temperature of 300r/min, adding non-woven regenerated fiber, modified silicon dioxide, a toughening agent and an antioxidant into the reaction kettle, heating to 400-class temperature of 600r/min, and stirring for 30-60min to obtain a mixture;
and secondly, adding the mixture obtained in the first step into a double-screw extruder, extruding, drawing and granulating at the temperature of 200-230 ℃ to obtain the special polypropylene composite material added with the non-woven fabric reclaimed material for the automobile.
Further, the non-woven regenerated fiber is prepared by the following steps:
s11, collecting waste polyester non-woven fabrics, cutting the waste polyester non-woven fabrics into fragments, soaking the fragments in acetone at 55 ℃ and absolute ethyl alcohol at 70 ℃ for 1 hour respectively to obtain impurity-removed polyester non-woven fabrics, placing the impurity-removed polyester non-woven fabrics in sodium hydroxide solution with the mass fraction of 5%, carrying out alkali etching at the temperature of 80 ℃ for 30 minutes, filtering, washing with deionized water for 3-5 times, and finally drying in an oven at 50 ℃ for 3-5 hours to obtain alkali-treated non-woven fabrics;
step S12, mixing tetrabutyl titanate and absolute ethyl alcohol according to the mass ratio of 8: 100, adding the mixture into a reaction kettle, stirring the mixture for 20min at the rotating speed of 80r/min, adding the alkali-treated non-woven fabric obtained in the step S11 into the reaction kettle, reacting the mixture for 5h under the water bath heating condition at the temperature of 90 ℃ and the rotating speed of 100-plus-150 r/min, filtering the mixture, and drying a filter cake in an oven at the temperature of 100-plus-110 ℃ to constant weight to obtain a modified non-woven fabric;
s13, crushing and grinding brucite, sieving with a 400-mesh sieve, adding the brucite into a three-neck flask, adding a titanate coupling agent and toluene into the flask, uniformly mixing to obtain a titanate coupling agent dispersion liquid, dropwise adding the titanate coupling agent dispersion liquid into the three-neck flask, controlling the dropwise adding speed to be 1-3 drops/second, stirring for 1-3 hours at 70 ℃ and 300r/min at the rotation speed of 200-;
and S14, adding the modified non-woven fabric obtained in the step S12, the modified brucite obtained in the step S13, sodium stearate and acetyl tributyl citrate into an internal mixer, mixing for 2-4h under the conditions of controlling the temperature at 120 ℃ and 140 ℃ and the rotating speed at 80-100r/min, and then carrying out electrostatic spinning to obtain the non-woven fabric regenerated fiber.
Further, in step S12, the mass ratio of tetrabutyl titanate to the alkali-treated nonwoven fabric is 1: 30, in the step S13, the dosage ratio of the brucite to the titanate coupling agent to the toluene is 20 g: 3-5 g: 60-80mL, and the titanate coupling agent is one or more of TMC-201, JTW-311 and NDZ-201 which are mixed according to any proportion; in the step S14, the mass ratio of the modified non-woven fabric to the modified brucite to the sodium stearate to the acetyl tributyl citrate is 10: 2: 1-3: 1.
further, the modified silica is prepared by the following steps:
mixing a silane coupling agent KH-550, deionized water and absolute ethyl alcohol according to a volume ratio of 1: 3: 1, adding the mixture into a three-neck flask, hydrolyzing for 30min at the rotating speed of 60r/min under the condition of oil bath at the temperature of 30 ℃ to obtain silane hydrolysate, then adding the silane hydrolysate into a mixer filled with silicon dioxide in an equivalent manner for three times, controlling the reaction temperature to be 110 ℃, reacting for 1-3h at the rotating speed of 200-300r/min, then carrying out vacuum filtration, washing a filter cake for 3-5 times by using an ethanol solution with the mass fraction of 25%, and finally drying in an oven at the temperature of 110-120 ℃ to constant weight to obtain the modified silicon dioxide.
Further, the dosage ratio of the silane hydrolysate to the silicon dioxide is 10 mL: 1-3g of high impact polypropylene K8303, antioxidant 1010 and antioxidant 168 according to the mass ratio of 1: 1 are mixed.
Further, the toughening agent is prepared by the following steps:
step A1: adding mixed acid into a reaction kettle, dropwise adding o-nitrotoluene at the rotation speed of 150-plus-200 r/min and the temperature of 60-70 ℃, the dropwise adding time is 30-40min, heating to the temperature of 85-90 ℃ after the dropwise adding is finished, reacting for 1-1.5h to obtain an intermediate 1, adding the intermediate 1 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 100-plus-110 ℃, reacting for 5-6h to obtain an intermediate 2, adding the intermediates 2, 1,2,2,6, 6-pentamethylpiperidinol and concentrated sulfuric acid into the reaction kettle, and reacting for 3-5h at the temperature of 110-plus-120 ℃ to obtain an intermediate 3;
the reaction process is as follows:
step A2: adding the intermediate 3, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 1-1.5h under the condition of boiling water bath, adjusting the pH value of a reaction solution to 10-11 to obtain an intermediate 4, dissolving the intermediate 4 in chlorobenzene, introducing phosgene, refluxing for 2-4h under the condition of temperature of 130-140 ℃ to obtain an intermediate 5, uniformly mixing polycaprolactone polyol and polytetrahydrofuran ether glycol, dehydrating for 1-2h under the condition of temperature of 110-115 ℃, adding the intermediate 5, and reacting for 3-5h under the condition of temperature of 85-90 ℃ to obtain the toughening agent.
The reaction process is as follows:
further, the mixed acid in the step a1 is nitric acid with a mass fraction of 68% and sulfuric acid with a mass fraction of 95% in a volume ratio of 1: 3, mixing, wherein the dosage ratio of the o-nitrotoluene to the mixed acid is 1 g: 10mL, wherein the dosage ratio of the intermediate 1, the deionized water and the potassium permanganate is 5 g: 100mL of: 8.6g, the dosage ratio of the intermediate 2, the 1,2,2,6, 6-pentamethylpiperidinol and concentrated sulfuric acid is 0.01 mol: 0.01 mol: 10 mL.
Further, the dosage ratio of the intermediate 3, the tin powder and the concentrated hydrochloric acid in the step A2 is 3 g: 4.2 g: 20mL, the mass fraction of concentrated hydrochloric acid is 38%, and the molar ratio of the intermediate 4 to phosgene usage is 1: 2.1, the using amount mass ratio of polycaprolactone polyol to polytetrahydrofuran ether glycol to the intermediate 5 is 3: 5: 1.6, the molecular weight of the polycaprolactone polyol is 1000, the hydroxyl value is 112mgKOH/g, the molecular weight of the polytetrahydrofuran ether glycol is 1000, and the hydroxyl value is 112 mgKOH/g.
The invention has the beneficial effects that: the invention takes polypropylene resin and high-impact polypropylene as main materials, and adds non-woven fabric regenerated fiber, modified silicon dioxide, toughening agent and antioxidant to prepare the polypropylene composite material special for automobiles, wherein the non-woven fabric regenerated fiber takes waste non-woven fabrics as raw materials, impurities carried on the surfaces and gaps of the waste non-woven fabrics are removed by cleaning, hydrolysis of polypropylene is promoted by alkaline immersion, the surfaces of the waste non-woven fabrics are in a rugged structure by alkaline etching, meanwhile, hydroxyl is formed on the degradation surface of the polypropylene, which is beneficial to increasing the specific surface area of grafted titanium dioxide at the later stage, so that the grafting rate is improved, nano titanium dioxide is grafted on the non-woven fabrics by a hydrothermal method, brucite is modified by a titanate coupling agent, the dispersibility of the brucite in polymers is improved, and the nano titanium dioxide is combined with excellent ultraviolet absorption performance, The self-cleaning performance and the brucite green environment-friendly flame retardant performance are combined, the non-woven regenerated fiber with the flame retardant, ageing resistance and self-cleaning performance is prepared, the non-woven regenerated fiber is added into the composite material, the toughness, the flame retardant performance and the ageing resistance of the composite material are improved, in addition, the nano titanium dioxide has super-hydrophilicity and super-permanence under illumination, water drops are not easily formed on the surface, the non-woven regenerated fiber has the antifouling characteristic, the nano titanium dioxide can act on hydrocarbon under the illumination of visible light, the organic pollutants adsorbed on the surface of the titanium dioxide can be decomposed into carbon dioxide and oxygen by utilizing the characteristic, the carbon dioxide and the residual inorganic matters are flushed by water, the self-cleaning function is realized, the waste non-woven fabric is taken as the raw material, the secondary utilization of resources is realized, the pollution of waste matters is reduced, and the modified silicon dioxide combines the high heat conduction property, the environment-resistance and the self-cleaning property of the silicon dioxide, The ultraviolet resistance is improved by treating with a coupling agent KH-550, the dispersibility of the epoxy resin in a polymer is improved, a toughening agent is prepared, the toughening agent takes o-nitrotoluene as a raw material to react to prepare an intermediate 1, the intermediate 1 is oxidized to prepare an intermediate 2, the intermediate 2 is esterified with 1,2,2,6, 6-pentamethylpiperidinol to prepare an intermediate 3, the intermediate 3 is reduced to prepare an intermediate 4, the intermediate 4 is reacted with phosgene to prepare an intermediate 5, the molecular structure of the intermediate 5 contains 2 isocyanate groups, the epoxy resin can be used as a chain extender to be polymerized with polycaprolactone polyol and polytetrahydrofuran ether glycol to prepare the toughening agent, the toughening agent belongs to elastic polyurethane, the toughness of the polypropylene composite material can be enhanced, meanwhile, the side chain contains a hindered amine structure, the aging resistance of the polypropylene composite material can be enhanced, therefore, the special polypropylene composite material for the automobile, prepared by the invention, has the characteristics of low cost, environmental protection, high efficiency, impact resistance, high flame retardance, high heat dissipation and the like, and has great application value in automobile windshields, automobile lamps and automobile body shell plastics thereof.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The polypropylene composite material added with the non-woven fabric reclaimed material for the automobile comprises the following raw materials in parts by weight: 30 parts of polypropylene resin, 20 parts of high impact polypropylene, 10 parts of non-woven regenerated fiber, 5 parts of modified silicon dioxide, 3 parts of toughening agent and 1 part of antioxidant;
the polypropylene composite material added with the non-woven fabric reclaimed material special for the automobile is prepared by the following steps:
adding polypropylene resin and high impact polypropylene into a reaction kettle, heating to 180 ℃ at a heating rate of 3 ℃/min, stirring at a rotating speed of 200r/min for 30min, adding non-woven regenerated fiber, modified silicon dioxide, a toughening agent and an antioxidant into the reaction kettle, increasing the rotating speed to 400r/min, and stirring for 30min to obtain a mixture;
and secondly, adding the mixture obtained in the first step into a double-screw extruder, extruding, drawing and granulating at the temperature of 200 ℃ to obtain the special polypropylene composite material added with the non-woven fabric reclaimed material for the automobile.
The non-woven regenerated fiber is prepared by the following steps:
s11, collecting waste polyester non-woven fabrics, cutting the waste polyester non-woven fabrics into fragments, soaking the fragments in acetone at 55 ℃ and absolute ethyl alcohol at 70 ℃ for 1 hour respectively to obtain impurity-removed polyester non-woven fabrics, placing the impurity-removed polyester non-woven fabrics in sodium hydroxide solution with the mass fraction of 5%, carrying out alkali etching at the temperature of 80 ℃ for 30 minutes, filtering, washing with deionized water for 3 times, and finally drying in an oven at 50 ℃ for 3 hours to obtain alkali-treated non-woven fabrics;
step S12, mixing tetrabutyl titanate and absolute ethyl alcohol according to the mass ratio of 8: 100, adding the mixture into a reaction kettle, stirring at the rotating speed of 80r/min for 20min, adding the alkali-treated non-woven fabric obtained in the step S11 into the reaction kettle, reacting for 5h under the water bath heating condition of 90 ℃ and the rotating speed of 100r/min, filtering, and drying a filter cake in a 100 ℃ oven to constant weight to obtain a modified non-woven fabric;
step S13, crushing and grinding brucite, sieving with a 400-mesh sieve, adding the brucite into a three-neck flask, adding a titanate coupling agent and toluene into the flask, uniformly mixing to obtain a titanate coupling agent dispersion liquid, dropwise adding the titanate coupling agent dispersion liquid into the three-neck flask, controlling the dropwise adding speed to be 1 drop/second, stirring for 1 hour at 70 ℃ and 200r/min, filtering, washing a filter cake with deionized water for 3 times, and finally drying in an oven at 100 ℃ for 5 hours to obtain modified brucite;
and S14, adding the modified non-woven fabric obtained in the step S12, the modified brucite obtained in the step S13, sodium stearate and acetyl tributyl citrate into an internal mixer, mixing for 2 hours at the temperature of 120 ℃ and the rotating speed of 80r/min, and then performing electrostatic spinning to obtain the non-woven fabric regenerated fiber.
In the step S12, the mass ratio of tetrabutyl titanate to the alkali-treated nonwoven fabric is 1: 30, in the step S13, the dosage ratio of the brucite to the titanate coupling agent to the toluene is 20 g: 3 g: 60mL, and the titanate coupling agent is TMC-201; in the step S14, the mass ratio of the modified non-woven fabric to the modified brucite to the sodium stearate to the acetyl tributyl citrate is 10: 2: 1: 1.
the modified silica is prepared by the following steps:
mixing a silane coupling agent KH-550, deionized water and absolute ethyl alcohol according to a volume ratio of 1: 3: 1, adding the mixture into a three-neck flask, hydrolyzing for 30min at the rotating speed of 60r/min under the condition of an oil bath at the temperature of 30 ℃ to obtain silane hydrolysate, then adding the silane hydrolysate into a mixer filled with silicon dioxide in an equivalent manner for three times, controlling the reaction temperature to be 110 ℃, reacting for 1h at the rotating speed of 200r/min, then carrying out vacuum filtration, washing a filter cake for 3 times by using an ethanol solution with the mass fraction of 25%, and finally drying in an oven at the temperature of 110 ℃ to constant weight to obtain the modified silicon dioxide.
The toughening agent is prepared by the following steps:
step A1: adding mixed acid into a reaction kettle, dropwise adding o-nitrotoluene at the rotation speed of 150r/min and the temperature of 60 ℃, dropwise adding for 30min, heating to 85 ℃ after dropwise adding, reacting for 1h to obtain an intermediate 1, adding the intermediate 1 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 100 ℃, reacting for 5h to obtain an intermediate 2, adding the intermediates 2, 1,2,2,6, 6-pentamethylpiperidinol and concentrated sulfuric acid into the reaction kettle, and reacting for 3h at the temperature of 110 ℃ to obtain an intermediate 3;
step A2: adding the intermediate 3, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 1h under the condition of boiling water bath, adjusting the pH value of a reaction solution to 10 to prepare an intermediate 4, dissolving the intermediate 4 in chlorobenzene, introducing phosgene, refluxing for 2h under the condition of the temperature of 130 ℃ to prepare an intermediate 5, uniformly mixing polycaprolactone polyol and polytetrahydrofuran ether glycol, dehydrating for 1h under the condition of the temperature of 110 ℃, adding the intermediate 5, and reacting for 3h under the condition of the temperature of 85 ℃ to prepare the toughening agent.
Example 2
The polypropylene composite material added with the non-woven fabric reclaimed material for the automobile comprises the following raw materials in parts by weight: 30 parts of polypropylene resin, 20 parts of high impact polypropylene, 10 parts of non-woven regenerated fiber, 5 parts of modified silicon dioxide, 3 parts of toughening agent and 1 part of antioxidant;
the polypropylene composite material added with the non-woven fabric reclaimed material special for the automobile is prepared by the following steps:
adding polypropylene resin and high impact polypropylene into a reaction kettle, heating to 180 ℃ at a heating rate of 3 ℃/min, stirring at a rotating speed of 200r/min for 30min, adding non-woven regenerated fiber, modified silicon dioxide, a toughening agent and an antioxidant into the reaction kettle, increasing the rotating speed to 400r/min, and stirring for 30min to obtain a mixture;
and secondly, adding the mixture obtained in the first step into a double-screw extruder, extruding, drawing and granulating at the temperature of 200 ℃ to obtain the special polypropylene composite material added with the non-woven fabric reclaimed material for the automobile.
The non-woven regenerated fiber is prepared by the following steps:
s11, collecting waste polyester non-woven fabrics, cutting the waste polyester non-woven fabrics into fragments, soaking the fragments in acetone at 55 ℃ and absolute ethyl alcohol at 70 ℃ for 1 hour respectively to obtain impurity-removed polyester non-woven fabrics, placing the impurity-removed polyester non-woven fabrics in sodium hydroxide solution with the mass fraction of 5%, carrying out alkali etching at the temperature of 80 ℃ for 30 minutes, filtering, washing with deionized water for 3 times, and finally drying in an oven at 50 ℃ for 3 hours to obtain alkali-treated non-woven fabrics;
step S12, mixing tetrabutyl titanate and absolute ethyl alcohol according to the mass ratio of 8: 100, adding the mixture into a reaction kettle, stirring at the rotating speed of 80r/min for 20min, adding the alkali-treated non-woven fabric obtained in the step S11 into the reaction kettle, reacting for 5h under the water bath heating condition of 90 ℃ and the rotating speed of 100r/min, filtering, and drying a filter cake in a 100 ℃ oven to constant weight to obtain a modified non-woven fabric;
step S13, crushing and grinding brucite, sieving with a 400-mesh sieve, adding the brucite into a three-neck flask, adding a titanate coupling agent and toluene into the flask, uniformly mixing to obtain a titanate coupling agent dispersion liquid, dropwise adding the titanate coupling agent dispersion liquid into the three-neck flask, controlling the dropwise adding speed to be 1 drop/second, stirring for 1 hour at 70 ℃ and 200r/min, filtering, washing a filter cake with deionized water for 3 times, and finally drying in an oven at 100 ℃ for 5 hours to obtain modified brucite;
and S14, adding the modified non-woven fabric obtained in the step S12, the modified brucite obtained in the step S13, sodium stearate and acetyl tributyl citrate into an internal mixer, mixing for 2 hours at the temperature of 120 ℃ and the rotating speed of 80r/min, and then performing electrostatic spinning to obtain the non-woven fabric regenerated fiber.
In the step S12, the mass ratio of tetrabutyl titanate to the alkali-treated nonwoven fabric is 1: 30, in the step S13, the dosage ratio of the brucite to the titanate coupling agent to the toluene is 20 g: 3 g: 60mL, and the titanate coupling agent is TMC-201; in the step S14, the mass ratio of the modified non-woven fabric to the modified brucite to the sodium stearate to the acetyl tributyl citrate is 10: 2: 1: 1.
the modified silica is prepared by the following steps:
mixing a silane coupling agent KH-550, deionized water and absolute ethyl alcohol according to a volume ratio of 1: 3: 1, adding the mixture into a three-neck flask, hydrolyzing for 30min at the rotating speed of 60r/min under the condition of an oil bath at the temperature of 30 ℃ to obtain silane hydrolysate, then adding the silane hydrolysate into a mixer filled with silicon dioxide in an equivalent manner for three times, controlling the reaction temperature to be 110 ℃, reacting for 1h at the rotating speed of 200r/min, then carrying out vacuum filtration, washing a filter cake for 3 times by using an ethanol solution with the mass fraction of 25%, and finally drying in an oven at the temperature of 110 ℃ to constant weight to obtain the modified silicon dioxide.
The toughening agent is prepared by the following steps:
step A1: adding mixed acid into a reaction kettle, dropwise adding o-nitrotoluene at the rotation speed of 150r/min and the temperature of 70 ℃, wherein the dropwise adding time is 30min, heating to the temperature of 90 ℃ after the dropwise adding is finished, reacting for 1h to obtain an intermediate 1, adding the intermediate 1 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 110 ℃, reacting for 5h to obtain an intermediate 2, adding the intermediates 2, 1,2,2,6, 6-pentamethylpiperidinol and concentrated sulfuric acid into the reaction kettle, and reacting for 3h at the temperature of 120 ℃ to obtain an intermediate 3;
step A2: adding the intermediate 3, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 1.5h under the condition of boiling water bath, adjusting the pH value of a reaction solution to 10 to prepare an intermediate 4, dissolving the intermediate 4 in chlorobenzene, introducing phosgene, refluxing for 2h at the temperature of 140 ℃ to prepare an intermediate 5, uniformly mixing polycaprolactone polyol and polytetrahydrofuran ether glycol, dehydrating for 1h under the temperature of 115 ℃, adding the intermediate 5, and reacting for 3h at the temperature of 90 ℃ to prepare the toughening agent.
Example 3
The polypropylene composite material added with the non-woven fabric reclaimed material for the automobile comprises the following raw materials in parts by weight: 30 parts of polypropylene resin, 20 parts of high impact polypropylene, 10 parts of non-woven regenerated fiber, 5 parts of modified silicon dioxide, 3 parts of toughening agent and 1 part of antioxidant;
the polypropylene composite material added with the non-woven fabric reclaimed material special for the automobile is prepared by the following steps:
adding polypropylene resin and high impact polypropylene into a reaction kettle, heating to 180 ℃ at a heating rate of 3 ℃/min, stirring at a rotating speed of 200r/min for 30min, adding non-woven regenerated fiber, modified silicon dioxide, a toughening agent and an antioxidant into the reaction kettle, increasing the rotating speed to 400r/min, and stirring for 30min to obtain a mixture;
and secondly, adding the mixture obtained in the first step into a double-screw extruder, extruding, drawing and granulating at the temperature of 200 ℃ to obtain the special polypropylene composite material added with the non-woven fabric reclaimed material for the automobile.
The non-woven regenerated fiber is prepared by the following steps:
s11, collecting waste polyester non-woven fabrics, cutting the waste polyester non-woven fabrics into fragments, soaking the fragments in acetone at 55 ℃ and absolute ethyl alcohol at 70 ℃ for 1 hour respectively to obtain impurity-removed polyester non-woven fabrics, placing the impurity-removed polyester non-woven fabrics in sodium hydroxide solution with the mass fraction of 5%, carrying out alkali etching at the temperature of 80 ℃ for 30 minutes, filtering, washing with deionized water for 3 times, and finally drying in an oven at 50 ℃ for 3 hours to obtain alkali-treated non-woven fabrics;
step S12, mixing tetrabutyl titanate and absolute ethyl alcohol according to the mass ratio of 8: 100, adding the mixture into a reaction kettle, stirring at the rotating speed of 80r/min for 20min, adding the alkali-treated non-woven fabric obtained in the step S11 into the reaction kettle, reacting for 5h under the water bath heating condition of 90 ℃ and the rotating speed of 100r/min, filtering, and drying a filter cake in a 100 ℃ oven to constant weight to obtain a modified non-woven fabric;
step S13, crushing and grinding brucite, sieving with a 400-mesh sieve, adding the brucite into a three-neck flask, adding a titanate coupling agent and toluene into the flask, uniformly mixing to obtain a titanate coupling agent dispersion liquid, dropwise adding the titanate coupling agent dispersion liquid into the three-neck flask, controlling the dropwise adding speed to be 1 drop/second, stirring for 1 hour at 70 ℃ and 200r/min, filtering, washing a filter cake with deionized water for 3 times, and finally drying in an oven at 100 ℃ for 5 hours to obtain modified brucite;
and S14, adding the modified non-woven fabric obtained in the step S12, the modified brucite obtained in the step S13, sodium stearate and acetyl tributyl citrate into an internal mixer, mixing for 2 hours at the temperature of 120 ℃ and the rotating speed of 80r/min, and then performing electrostatic spinning to obtain the non-woven fabric regenerated fiber.
In the step S12, the mass ratio of tetrabutyl titanate to the alkali-treated nonwoven fabric is 1: 30, in the step S13, the dosage ratio of the brucite to the titanate coupling agent to the toluene is 20 g: 3 g: 60mL, and the titanate coupling agent is TMC-201; in the step S14, the mass ratio of the modified non-woven fabric to the modified brucite to the sodium stearate to the acetyl tributyl citrate is 10: 2: 1: 1.
the modified silica is prepared by the following steps:
mixing a silane coupling agent KH-550, deionized water and absolute ethyl alcohol according to a volume ratio of 1: 3: 1, adding the mixture into a three-neck flask, hydrolyzing for 30min at the rotating speed of 60r/min under the condition of an oil bath at the temperature of 30 ℃ to obtain silane hydrolysate, then adding the silane hydrolysate into a mixer filled with silicon dioxide in an equivalent manner for three times, controlling the reaction temperature to be 110 ℃, reacting for 1h at the rotating speed of 200r/min, then carrying out vacuum filtration, washing a filter cake for 3 times by using an ethanol solution with the mass fraction of 25%, and finally drying in an oven at the temperature of 110 ℃ to constant weight to obtain the modified silicon dioxide.
The toughening agent is prepared by the following steps:
step A1: adding mixed acid into a reaction kettle, dropwise adding o-nitrotoluene at the rotation speed of 200r/min and the temperature of 70 ℃, wherein the dropwise adding time is 40min, heating to the temperature of 90 ℃ after the dropwise adding is finished, reacting for 1.5h to obtain an intermediate 1, adding the intermediate 1 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 110 ℃, reacting for 6h to obtain an intermediate 2, adding the intermediates 2, 1,2,2,6, 6-pentamethylpiperidinol and concentrated sulfuric acid into the reaction kettle, and reacting for 5h at the temperature of 120 ℃ to obtain an intermediate 3;
step A2: adding the intermediate 3, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 1.5h under the condition of boiling water bath, adjusting the pH value of a reaction solution to 11 to prepare an intermediate 4, dissolving the intermediate 4 in chlorobenzene, introducing phosgene, refluxing for 4h at the temperature of 140 ℃ to prepare an intermediate 5, uniformly mixing polycaprolactone polyol and polytetrahydrofuran ether glycol, dehydrating for 2h under the temperature of 115 ℃, adding the intermediate 5, and reacting for 5h at the temperature of 90 ℃ to prepare the toughening agent.
Comparative example 1
Compared with the example 1, the comparative example does not add the non-woven regenerated fiber, and the rest steps are the same.
Comparative example 2
Compared with the example 1, the comparative example does not add the toughening agent, and the rest steps are the same.
Comparative example 3
The comparative example is a polypropylene composite material disclosed in Chinese patent CN 107434885A.
The composites of examples 1 to 3 and comparative examples 1 to 3 were dried in a 105 ℃ forced air drying cabinet for 2h, freed of water, prepared by means of an injection machine at a temperature of 190 ℃ and 205 ℃ and a pressure of 60 to 75MPa, and then subjected to a performance test, tensile strength at 50mm/min according to standard ISO527/2 to 93, flexural modulus at 2mm/min according to ISO178-93, flexural modulus at ISO 180: 2000, notched impact strength at 230 ℃ and 2.75J, vertical burning according to UL94, delta-3.2 mm, light resistance according to the color difference variation of SAEJ2527-2004, and melt flow rate at 230 ℃ and 2.16Kg according to ISO 1133. The test results are shown in the following table:
as can be seen from the above table, the test results of examples 1-3 are superior to the comparative examples in the test processes of tensile strength, flexural modulus, notched impact strength, vertical burning, light resistance and melt flow rate, which shows that the composite material for automobiles prepared by the invention has the characteristics of high strength, impact resistance, flame retardance and aging resistance, and has great application value in the field of automobile manufacturing.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The special polypropylene composite material added with the non-woven fabric reclaimed material for the automobile is characterized in that: the feed comprises the following raw materials in parts by weight: 30-40 parts of polypropylene resin, 20-30 parts of high impact polypropylene, 10-15 parts of non-woven regenerated fiber, 5-8 parts of modified silicon dioxide, 3-5 parts of toughening agent and 1-3 parts of antioxidant;
the non-woven regenerated fiber is prepared by the following steps:
s11, collecting waste polyester non-woven fabrics, cutting the waste polyester non-woven fabrics into fragments, soaking the fragments in acetone and ethanol to obtain impurity-removed polyester non-woven fabrics, placing the impurity-removed polyester non-woven fabrics in a sodium hydroxide solution, carrying out alkali etching, filtering, washing with deionized water, and drying to obtain alkali-treated non-woven fabrics;
step S12, uniformly mixing tetrabutyl titanate and absolute ethyl alcohol, adding alkali to treat the non-woven fabric, heating in a water bath for reaction, filtering, and drying a filter cake to obtain a modified non-woven fabric;
step S13, crushing and grinding brucite, sieving with a 400-mesh sieve, adding the brucite into a three-neck flask, adding a titanate coupling agent and toluene into the flask, uniformly mixing to obtain a titanate coupling agent dispersion liquid, dropwise adding the titanate coupling agent dispersion liquid into the three-neck flask, uniformly stirring, filtering, washing a filter cake with deionized water, and drying to obtain modified brucite;
and step S14, adding the modified non-woven fabric, the modified brucite, the sodium stearate and the acetyl tributyl citrate into an internal mixer, mixing and carrying out electrostatic spinning to obtain the non-woven fabric regenerated fiber.
2. The polypropylene composite material added with non-woven fabric reclaimed materials special for automobiles as claimed in claim 1, wherein: in the step S12, the mass ratio of tetrabutyl titanate to the alkali-treated nonwoven fabric is 1: 30.
3. the polypropylene composite material added with non-woven fabric reclaimed materials special for automobiles as claimed in claim 1, wherein: in the step S13, the dosage ratio of brucite, titanate coupling agent and toluene is 20 g: 3-5 g: 60-80mL, and the titanate coupling agent is one or more of TMC-201, JTW-311 and NDZ-201 which are mixed according to any proportion.
4. The polypropylene composite material added with non-woven fabric reclaimed materials special for automobiles as claimed in claim 1, wherein: in the step S14, the mass ratio of the modified non-woven fabric to the modified brucite to the sodium stearate to the acetyl tributyl citrate is 10: 2: 1-3: 1.
5. the polypropylene composite material added with non-woven fabric reclaimed materials special for automobiles as claimed in claim 1, wherein: the toughening agent is prepared by the following steps:
step A1: stirring the mixed acid, dropwise adding o-nitrotoluene, heating for reaction after dropwise adding to obtain an intermediate 1, adding the intermediate 1 and deionized water into a reaction kettle, refluxing, adding potassium permanganate, reacting to obtain an intermediate 2, adding the intermediate 2, 1,2,2,6, 6-pentamethylpiperidinol and concentrated sulfuric acid into the reaction kettle, and reacting for 3-5 hours to obtain an intermediate 3;
step A2: adding the intermediate 3, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting under the condition of boiling water bath, adjusting the pH value of reaction liquid to prepare an intermediate 4, dissolving the intermediate 4 in chlorobenzene, introducing phosgene, refluxing to prepare an intermediate 5, uniformly mixing polycaprolactone polyol and polytetrahydrofuran ether glycol, performing vacuum dehydration, adding the intermediate 5, and reacting to prepare the toughening agent.
6. The polypropylene composite material added with non-woven fabric reclaimed materials specially used for the automobile according to claim 5, is characterized in that: the mixed acid in the step A1 is prepared by mixing nitric acid with a mass fraction of 68% and sulfuric acid with a mass fraction of 95% in a volume ratio of 1: 3, mixing.
7. The polypropylene composite material added with non-woven fabric reclaimed materials specially used for the automobile according to claim 5, is characterized in that: the mass fraction of the concentrated hydrochloric acid in the step A2 is 38%, the molecular weight of the polycaprolactone polyol is 1000, the hydroxyl value is 112mgKOH/g, the molecular weight of the polytetrahydrofuran ether glycol is 1000, and the hydroxyl value is 112 mgKOH/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115748009A (en) * | 2022-11-15 | 2023-03-07 | 安徽南澳地毯有限公司 | Preparation method of water-repellent carpet non-woven fabric |
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| CN112341710A (en) * | 2020-11-25 | 2021-02-09 | 安徽冠泓塑业有限公司 | Special polypropylene composite material added with non-woven fabric reclaimed material for automobile |
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| CN103396527A (en) * | 2013-07-29 | 2013-11-20 | 湖北诚宇信诺科技有限公司 | Thermal aging-resistant polyurethane elastomer and preparation method thereof |
| CN112341710A (en) * | 2020-11-25 | 2021-02-09 | 安徽冠泓塑业有限公司 | Special polypropylene composite material added with non-woven fabric reclaimed material for automobile |
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| CN115748009A (en) * | 2022-11-15 | 2023-03-07 | 安徽南澳地毯有限公司 | Preparation method of water-repellent carpet non-woven fabric |
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Application publication date: 20211022 |