CN107236298B - Modification and coloring method of nylon composite material - Google Patents
Modification and coloring method of nylon composite material Download PDFInfo
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- CN107236298B CN107236298B CN201710455777.0A CN201710455777A CN107236298B CN 107236298 B CN107236298 B CN 107236298B CN 201710455777 A CN201710455777 A CN 201710455777A CN 107236298 B CN107236298 B CN 107236298B
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Abstract
The invention relates to a method for modifying and coloring nylon composite material, which adopts oxide/sulfide nano material to modify attapulgite, sodium salt crystallization and alkali liquor soaking are carried out to activate the attapulgite, then nano oxide or sulfide is absorbed on the pore canal and the surface of the attapulgite by adopting a nano coating modification mode to form a composite structure nano material, the modified attapulgite nano material and nylon are prepared into various colored master batches, and the master batches with different colors and the nylon are melted and blended to prepare the attapulgite/nylon composite material with various colors.
Description
Technical Field
The invention relates to a preparation method of modified plastic, and in particular relates to a preparation method of a composite material which is prepared by compounding attapulgite nanoparticles and nylon and has strong ageing resistance and excellent mechanical property.
Background
The modified plastic is a new industry with high scientific and technological content and wide related range, and is a new material industry developed in the key point of the twelve-five national planning. The plastic modification method is various, and mainly comprises copolymerization, blending, filling, reinforcing, electroplating, flame retarding, nucleating agent adding and the like. Polyamide (abbreviated as PA), which is nylon, is a polymer compound having an amide group in its molecular chain. The polyamide can be prepared by the polycondensation of diamine and diacid or the self polymerization of caprolactam. The nylon is wear-resistant, oil-resistant, acid-resistant and corrosion-resistant, has excellent mechanical properties, better electrical properties and good processability, and is one of plastics with wider application. Although the overall performance of nylon is very excellent, the strength, aging resistance and other properties of nylon are still to be enhanced due to the structure of the polymer material, and therefore, researches on modification, blending and alloy of nylon become a focus of attention. Such as: in the research of nylon composite materials, the carbon fiber, aramid fiber and glass fiber reinforced nylon have achieved important achievements; meanwhile, montmorillonite, calcium carbonate, talcum powder and nano SO2And many researches on modified nylon made of nano materials such as carbon nano tubes and attapulgite.
Attapulgite (AT for short) is a crystalline hydrated magnesium aluminum silicate mineral with a unique layer chain structure, mainly contains Ag, Al, Si, O, H and other elements, the crystal is mostly rod-shaped or fibrous, the diameter of a single rod is below 100nm, the length is about 1um, the attapulgite has a nano-scale pore canal and fine crystal size, so that the attapulgite has a very high internal and external specific surface area, and the internal surface area is about 600m2Per g, external surface area of about 300m2Therefore, the attapulgite not only has the characteristics of the nano material, but also has the rigidity of the short fiber reinforced material, and the research on the attapulgite/nylon composite material has wide application prospect. Such as: beijingAfter the attapulgite is subjected to activation treatment, the attapulgite/nylon composite material is synthesized by in-situ polymerization by Wangyi Zhongren of chemical university, so that the mechanical property of the material is greatly improved; the surface grafting modification of the attapulgite is carried out by using a silane coupling agent by Nanjing university of science history construction and the like, and the attapulgite/nylon composite material is prepared by a melt blending technology, so that the impact resistance of the material is improved by 30 percent, and the thermal stability is improved by 10 percent; in addition, a modified attapulgite coupling agent (patent No. ZL201210248441.4) was invented by Lijinchun et al, university of Changzhou, and the attapulgite modified by the silane coupling agent plays a good coupling role in the preparation process of the attapulgite modified nylon 6 composite material, so as to obtain a high-performance attapulgite modified nylon composite material and the like. Although the nylon modified production method and process at home and abroad are greatly developed, the nylon modification still has a great development space. Under the influence of factors such as light, heat, oxygen, moisture and the like, phthalamine bonds and end groups in molecular chains are easy to embrittle and yellow, degradation and aging are natural attributes and cannot be avoided, and the nylon has the main characteristic that: firstly, the product has reduced appearance gloss, reduced color and increased yellow index; secondly, the elastic modulus and the impact resistance are reduced. The standard of nylon industry takes the chromaticity change value and the impact resistance retention value as the basis for measuring the aging degree of nylon materials, so the research on nylon modification, particularly the research on aging resistance, is still far from the priority.
Disclosure of Invention
The invention adopts an oxide/sulfide nano material to modify attapulgite, adsorbs nano oxide or sulfide on the pore canal and the surface of the attapulgite by activating the attapulgite and modifying the nano coating to form a composite structure nano material, prepares various colored master batches from the modified attapulgite nano material and nylon, and fuses and blends the master batches with different colors and the nylon to prepare various attapulgite/nylon composite materials.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for modifying and coloring a nylon composite, the method comprising the steps of:
A. preparation of modified attapulgite nano material
(1) Activating treatment of attapulgite: preparing a sodium salt saturated aqueous solution at 70-100 ℃, slowly adding nano attapulgite while stirring, cooling to room temperature, and crystallizing and separating out solid; adding deionized water until the sodium salt crystals are completely dissolved, and filtering to remove the sodium salt water solution; adding the obtained attapulgite into 10-25 wt% of sodium hydroxide solution, heating to 30-50 ℃, keeping the temperature and stirring for 9-12 hours, cooling to room temperature, filtering out the solution, washing the attapulgite with weak acid solution to be neutral, washing the attapulgite with deionized water for 2-3 times, drying, grinding and crushing to obtain the activated attapulgite nano material;
(2) nano coating modification of attapulgite: respectively adding the activated nano attapulgite into alcohol solvents containing oxide or sulfide nano materials with different colors, wherein the mass ratio of the attapulgite to the oxide nano materials/the sulfide nano materials is (10-20) to (3-5), and stirring for 1-3 hours at normal temperature; standing, layering and filtering to obtain a precipitate which is a modified attapulgite nano material;
B. preparing a nylon color master batch containing modified attapulgite: adding nylon particles into the modified attapulgite nano material obtained in the step A, wherein the mass ratio of the modified attapulgite nano material to the nylon particles is 1: 3-10, ultrasonically stirring for 20-45 minutes, mixing by a high-speed mixing mill, and then extruding into particles under pressure to obtain nylon color master batch containing attapulgite;
C. b, preparing an attapulgite/nylon composite material, namely melting and blending the nylon color master batch prepared in the step B with nylon particles or slices, and adding nano-silica composite microspheres and an auxiliary agent, wherein the mass ratio of the nylon color master batch to the nylon material is 100: 100 (700-); the mass ratio of the nano silicon dioxide composite microspheres to the nylon material is as follows: (3-15) to 100; dispersing and mixing, and extruding under pressure to obtain the attapulgite/nylon composite material.
In the method for modifying and coloring a nylon composite material, preferably, the specific operation of step a is as follows:
(1) activating treatment of attapulgite: preparing a sodium salt saturated aqueous solution at 70-100 ℃, slowly adding nano attapulgite under stirring, wherein the mass ratio of the sodium salt saturated solution to the attapulgite is (1-3) to 1; after the temperature is increased to the boiling point, the temperature is reduced to the room temperature, and solid crystals are separated out; adding deionized water, heating to 50-100 deg.C until sodium salt crystal is completely dissolved, and filtering to remove sodium salt water solution; adding the obtained attapulgite into 10-25 wt% of sodium hydroxide solution, heating to 30-50 ℃, keeping the temperature, stirring for 9-12 hours, cooling to room temperature, filtering out the solution, neutralizing and washing the attapulgite with weak acid with the pH value of more than or equal to 5 for one time, washing the attapulgite with deionized water for 2-3 times, drying, grinding and crushing to obtain an activated attapulgite nano material;
(2) nano coating modification of attapulgite: respectively adding the activated nano attapulgite into alcohol solvents containing nano oxides or sulfides with different colors, wherein the mass ratio of the alcohol solvents to the attapulgite nano materials to the oxide nano materials to the sulfide nano materials is 100 to (10-20) to (3-5), and stirring for 1-3 hours at normal temperature; standing and layering, wherein the lower precipitate is the attapulgite nano material with the surface coated with the oxide or sulfide nano particles.
In the method for modifying and coloring a nylon composite material, the attapulgite preferably has a particle diameter of 100nm or less and an aspect ratio of 10 or more.
The method for modifying and coloring the nylon composite material as described above, preferably, the sodium salt is sodium sulfate, sodium acetate trihydrate, anhydrous sodium acetate, sodium formate or sodium propionate; the alcohol solvent is one or more of methanol, ethanol, benzyl alcohol, ethylene glycol and isopropanol.
In the method for modifying and coloring a nylon composite material, preferably, the oxide nano material in the step a is zinc oxide, titanium oxide, cobalt oxide, iron oxide, copper oxide, selenium oxide, magnesium oxide, manganese oxide, sodium oxide, silicon oxide, zirconium oxide, calcium oxide, potassium oxide, barium oxide, tin oxide, strontium oxide, antimony oxide, tungsten oxide and/or chromium oxide; the particle size of the oxide nano material is less than 50 nm.
In the method for modifying and coloring a nylon composite material, preferably, the sulfide nano material in the step a is zinc sulfide, tin sulfide, iron sulfide, magnesium sulfide, copper sulfide and/or cadmium sulfide; the grain diameter of the sulfide nano material is 3-100 nm.
In the method for modifying and coloring a nylon composite material, preferably, the specific operation of step B is as follows: adding nylon particles into the modified attapulgite nano material obtained in the step A, wherein the mass ratio of the modified attapulgite nano material to the nylon particles is 1: 3-10, and ultrasonically stirring for 20-45 minutes; under the protection of nitrogen, heating the obtained mixture to 275-300 ℃, keeping the flow of the nitrogen at 40-60mL/min, mixing by a high-speed mixing roll, pressurizing and extruding into granules, and controlling the injection pressure at 80-100 MPa to obtain the attapulgite-containing nylon color master batch.
In the method for modifying and coloring a nylon composite material, preferably, the specific operation of step C is as follows: b, melting and blending the nylon color master batch prepared in the step B with nylon particles or slices, and adding the nano silicon dioxide composite microspheres and the auxiliary agent, wherein the mass ratio of the nylon color master batch to the nylon material is 100: 100-; the mass ratio of the nano silicon dioxide composite microspheres to the nylon material is (3-15) to 100, and after dispersion and mixing, a double-screw extruder is adopted to obtain the attapulgite/nylon composite material.
The method for modifying and coloring the nylon composite material is preferably that the nylon material is one or more than one of polycaprolactam, polyhexamethylene adipamide, polyundecanamide, polydodecanamide, polyhexamethylene sebacamide, polyhexamethylene dodecanamide, poly 9-aminononanoic acid, polytriacontamide and polysebacate decamethylene diamine, and comprises a regrind material of the materials;
the method for modifying and coloring nylon composite as described above, preferably, the nano-silica composite microspheres are metal or metal oxide nanoparticles having a particle size of 50nm dispersed in 100-500nm silica microspheres, the metal or metal oxide being zinc, iron, tin, lead, silver, copper, platinum, sodium oxide, potassium oxide, calcium oxide, zinc oxide, iron oxide, tin oxide, lead oxide, copper oxide, magnesium oxide, barium oxide, strontium oxide, aluminum oxide, gallium oxide, indium oxide, thallium oxide, germanium oxide, antimony oxide, bismuth oxide and/or polonium oxide; the mass ratio of the metal or metal oxide nano particles to the silicon dioxide is (0.1-0.4) to 1.
In the method for modifying and coloring the nylon composite material, the auxiliary agent is preferably a lubricant, a toughening agent, an ultraviolet absorber and/or an antioxidant;
in the method for modifying and coloring the nylon composite material, preferably, the temperatures of the feed inlet and the discharge outlet of the twin-screw extruder are both controlled at 240-; the temperature of the middle section is controlled at 275 ℃ to 300 ℃.
In the method for modifying and coloring the nylon composite material, preferably, the toughening agent is at least one of ethylene propylene diene monomer, ethylene octene copolymer and toughening agent ZR-04;
in the method for modifying and coloring the nylon composite material, preferably, the lubricant is N-octadecyl-13-docosanamide or resin C100;
the method for modifying and coloring the nylon composite material, preferably, the antioxidant is at least one of antioxidant 1098, antioxidant 1076, antioxidant B225, antioxidant B215 and antioxidant S-9228;
in the method for modifying and coloring the nylon composite material, the ultraviolet light absorber is preferably at least one of UV-P, UV-326, UV-327, UV-328, UV-329, UV-360, UV-531 and UV-928.
The method for modifying and coloring a nylon composite material as described above preferably comprises the step of blending different colored oxide or sulfide materials according to the desired color in the step (2) or blending different colored nylon color masterbatches according to the desired color in the step C.
In the method for modifying and coloring a nylon composite material, the nylon material is preferably one or more selected from nylon 6 (polycaprolactam), nylon 66 (polyhexamethylene adipamide), nylon 11 (polyundecanamide), nylon 12 (polydodecanamide), nylon 610 (polyhexamethylene sebacamide), nylon 612 (polyhexamethylene dodecanamide), nylon 9 (poly 9-aminononanoic acid), nylon 13 (polytridecylamide), nylon 1010 (polyhexamethylene sebacamide), and reclaimed materials containing the nylon 6 and nylon 66 are preferred.
The invention has the beneficial effects that: the invention adopts oxide/sulfide nano material to modify attapulgite to form composite structure nano material, prepares attapulgite/nylon composite material color particles with various colors by utilizing the self colors of the oxide and the sulfide, and finally blends the color particles and the nylon material to prepare the nano composite bulk phase coloring nylon material.
First, the attapulgite is subjected to activation treatment, i.e., sodium salt treatment and alkali treatment. The size of the attapulgite pore channel can be enlarged due to volume expansion of the sodium salt in the crystallization process, impurities on the surface of the attapulgite and in the pore channel can be removed in the crystallization and dissolution processes of the sodium salt, so that the specific surface area of the attapulgite is increased, the pore channel is dredged, and the activity is enhanced; the adsorption amount of the attapulgite subjected to sodium salt activation treatment on nano oxides or nano sulfides in an alcohol solvent is obviously increased compared with that of the attapulgite not subjected to sodium salt activation treatment. Sodium salt treatment and alkali treatment to make attapulgite octahedral cation Mg2+、Al3+、Fe3+The sequential displacement from the edge to the center changes the chemical bond state, so that the specific surface area is increased, and meanwhile, the adsorption force in the alcohol solvent is enhanced. The attapulgite subjected to activation treatment is more beneficial to adsorbing and combining oxide/sulfide nano particles.
The attapulgite with the surface coated with a layer of nano oxide or nano sulfide forms a composite core-shell structure, so that the rigidity of the attapulgite short fiber material is enhanced, and the combination degree and the dispersibility of the attapulgite in a nylon matrix are improved; the ultraviolet absorption performance of the attapulgite nano composite material is enhanced, and the ageing resistance of the nylon composite material is improved; meanwhile, the attapulgite nano material has bright color, and nylon is colored by the self color of the nano material, so that the color fastness of the nylon is enhanced.
The step of modifying the attapulgite by the nano oxide or the nano sulfide adopts an alcohol solvent, the boiling point of the alcohol solvent is lower than that of water, the temperature required during drying is low due to the low boiling point of the suspension, meanwhile, alcohol molecules are adsorbed on the surface of the dried attapulgite, and due to the existence of the alcohol molecules, repulsive force is generated among attapulgite nano composite material particles, the surface stress of the material is reduced, the agglomeration is prevented, and the attapulgite is convenient to disperse into a nylon material.
The nano silicon dioxide composite microspheres doped with a certain amount of dispersed metal or metal oxide in the nylon material can generate a synergistic effect with the modified attapulgite nano material, so that the ageing resistance and the mechanical property of the nylon material are improved.
Experimental results show that the nano modified colored nylon composite material has the characteristics of strong ageing resistance, good mechanical property, high color fastness and the like.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Some of the raw material sources used in the following examples are as follows:
attapulgite clay: xuyi Euro herborist clay materials Co.
Nano silicon dioxide composite microspheres: jiangsu Visco New Material Co., Ltd.
Toughening agent ZR-04: zhejiang Yongkang Chifeng plastication Co., Ltd.
Resin C100 lubricant: shanghai Yin environmental protection science and technology Limited company products.
Antioxidant S-9228, antioxidant B225: changzhou city new policy polymers, Inc.
Example 1: preparation of Black Attapulgite/Nylon composite Material
(1) Preparing 500g of sodium acetate aqueous solution from sodium acetate trihydrate and purified water according to the mass ratio of 100: 13, heating to 90 ℃, slowly stirring and adding 250g of nano-attapulgite after crystals are completely dissolved, heating to boiling point, cooling to room temperature until sodium acetate crystals are separated out, adding deionized water, continuously heating to 80 ℃ until sodium salt crystals are completely dissolved, filtering to remove sodium salt aqueous solution, adding 250g of sodium hydroxide (15%) solution, heating to 40 ℃, keeping the temperature and stirring for 10 hours, stirring at the speed of 120r/min, cooling to room temperature, performing liquid-solid separation, washing with hydrochloric acid aqueous solution with the pH value of 5, washing with ionized water for 2 times, drying, grinding and crushing to obtain the attapulgite nano-material. Adding the attapulgite nano material, 45g of nano manganese oxide and 20g of nano titanium oxide into 1650g of methanol solvent, stirring for 2 hours, standing for 60 minutes, layering the system solution, and removing the upper layer solvent to obtain the modified attapulgite nano material.
(2) 1400g of nylon 66 particles are added into a modified attapulgite nano material container, after ultrasonic stirring is carried out for 30 minutes, the flow rate of nitrogen is kept at 45mL/min, the mixture of the modified attapulgite and the nylon is heated to 285 ℃, and after mixing is carried out by a high-speed mixing roll, the mixture is pressurized and extruded into granules under the injection pressure controlled at 85MPa, so as to obtain the black nylon 66 master batch containing the attapulgite.
(3) And uniformly stirring 1000g of the black nylon 66 master batch, 3200g of nylon 66 particles, 350g of nano silicon dioxide composite microspheres (15 wt% of zinc oxide nanoparticles and 15 wt% of aluminum oxide nanoparticles are dispersed in the silicon dioxide microspheres), 105g of resin C100 lubricant, 205g of toughening agent ZR-04, 30g of antioxidant S-9228, 20g of antioxidant B225, 25g of ultraviolet absorbent UV-326 and 25g of ultraviolet absorbent UV-531, melting and blending, controlling the temperature at 290 ℃, and granulating and molding by using a double-screw extruder to obtain the black attapulgite/nylon composite material.
Example 2: preparation of green attapulgite/nylon composite material
(1) Preparing 550g of sodium acetate aqueous solution from sodium acetate trihydrate and purified water according to the mass ratio of 100: 14, heating to 90 ℃, slowly stirring and adding 250g of nano-attapulgite after crystals are completely dissolved, heating to a boiling point, cooling to room temperature until sodium acetate crystals are separated out, adding deionized water, continuously heating to 80 ℃ until sodium salt crystals are completely dissolved, filtering to remove the sodium salt aqueous solution, adding 250g of sodium hydroxide (11%) solution, heating to 40 ℃, keeping the temperature and stirring for 12 hours, stirring at the speed of 150r/min, cooling to room temperature, performing liquid-solid separation, washing with a hydrochloric acid aqueous solution with the pH of 5, washing with ionized water for 2 times, drying, grinding and crushing to obtain the attapulgite nano-material. Adding the attapulgite nano material, 12g of nano chromium oxide and 6g of nano zinc oxide into 1650g of ethanol solvent, stirring for 2 hours, standing for 50 minutes, layering the system solution, and removing the upper layer solvent to obtain the modified attapulgite nano material.
(2) Adding 950g of nylon 66 particles into a modified attapulgite nano material container, ultrasonically stirring for 35 minutes, keeping the flow of nitrogen at 45mL/min, heating the mixture of the modified attapulgite and the nylon to 290 ℃, mixing by a high-speed mixing roll, controlling the injection pressure at 85MPa, pressurizing and extruding to form granules, and obtaining the attapulgite-containing green nylon 66 master batch.
(3) Taking 900g of the green nylon 66 master batch, 6000g of nylon 66 particles, 220g of nano silicon dioxide composite microspheres (30 wt% of zinc oxide nano particles are dispersed in the silicon dioxide microspheres), 145g of resin C100 lubricant, 350g of toughening agent ZR-04, 30g of antioxidant S-9228, 20g of antioxidant B225, 30g of ultraviolet absorbent UV-326 and 25g of ultraviolet absorbent UV-531, uniformly stirring, melting and blending, controlling the temperature at 280 ℃, and granulating and molding by using a double screw extruder to obtain the green attapulgite/nylon composite material.
Example 3: preparation of Red Attapulgite/Nylon composite Material
(1) Preparing 400g of sodium acetate aqueous solution from sodium acetate trihydrate and purified water according to the mass ratio of 100: 18, heating to 90 ℃, slowly stirring and adding 250g of nano-attapulgite after crystals are completely dissolved, heating to a boiling point, cooling to room temperature until sodium acetate crystals are separated out, adding deionized water, continuously heating to 80 ℃ until sodium salt crystals are completely dissolved, filtering to remove the sodium salt aqueous solution, adding 270g of sodium hydroxide (25%) solution, heating to 45 ℃, keeping the temperature and stirring for 10 hours, stirring at the speed of 120r/min, cooling to room temperature, performing liquid-solid separation, washing with a hydrochloric acid aqueous solution with the pH value of 5, washing with ionized water for 2 times, drying, grinding and crushing to obtain the attapulgite nano-material. Adding the attapulgite nano material, 50g of nano iron oxide and 25 nm of cadmium sulfide into 1650g of ethanol solvent, stirring for 2.5 hours, standing for 50 minutes, layering the system solution, and removing the upper-layer solvent to obtain the modified attapulgite nano material.
(2) 2400g of nylon 66 particles are added into a modified attapulgite nano material container, after ultrasonic stirring is carried out for 40 minutes, the flow of nitrogen is kept at 45mL/min, the mixture of the modified attapulgite and the nylon is heated to 290 ℃, and after mixing is carried out by a high-speed mixing roll, the mixture is pressurized and extruded into particles under the injection pressure controlled at 85MPa, so as to obtain the red nylon 66 master batch containing the attapulgite.
(3) And (2) taking 1500g of the red nylon 66 master batch, 1600g of nylon 66 particles, 230g of nano-silica composite microspheres (15 wt% of iron oxide nano-particles and 15 wt% of zinc oxide nano-particles are dispersed in the silica microspheres), 65g of resin C100 lubricant, 80g of flexibilizer POE, 22g of antioxidant S-9228 and 25g of ultraviolet absorbent UV-326, uniformly stirring, melting and blending, controlling the temperature at 290 ℃, and granulating and molding by using a double-screw extruder to obtain the red attapulgite/nylon composite material.
Example 4: preparation of white attapulgite/nylon composite material
(1) Preparing 400g of sodium acetate aqueous solution from sodium acetate trihydrate and purified water according to the mass ratio of 100: 15, heating to 90 ℃, slowly stirring and adding 250g of nano-attapulgite after crystals are completely dissolved, heating to a boiling point, cooling to room temperature until sodium acetate crystals are separated out, adding deionized water, continuously heating to 80 ℃ until sodium salt crystals are completely dissolved, filtering to remove the sodium salt aqueous solution, adding 270g of sodium hydroxide (13%) solution, heating to 45 ℃, keeping the temperature and stirring for 11 hours, stirring at the speed of 130r/min, cooling to room temperature, performing liquid-solid separation, washing with a hydrochloric acid aqueous solution with the pH value of 5, washing with ionized water for 2 times, drying, grinding and crushing to obtain the attapulgite nano-material. Adding the attapulgite nano material, 16g of nano aluminum oxide and 10g of nano calcium oxide into 1650g of ethanol solvent, stirring for 2 hours, standing for 60 minutes, layering the system solution, and removing the upper layer solvent to obtain the modified attapulgite nano material.
(2) Adding 1000g of nylon 66 particles into a modified attapulgite nano material container, ultrasonically stirring for 30 minutes, keeping the flow of nitrogen at 45mL/min, heating the mixture of the modified attapulgite and the nylon to 290 ℃, mixing by a high-speed mixing mill, controlling the injection pressure at 85MPa, pressurizing and extruding to form granules, and thus obtaining white nylon 66 master batches containing attapulgite.
(3) And uniformly stirring 1000g of the white nylon 66 master batch, 6000g of nylon 66 particles, 320g of nano-silica composite microspheres (15 wt% of alumina nano-particles and 15 wt% of calcium oxide nano-particles are dispersed in the silica microspheres), 170g of resin C100 lubricant, 280g of flexibilizer POE, 45g of antioxidant S-9228 and 50g of ultraviolet absorbent UV-326, melting and blending, controlling the temperature at 290 ℃, and granulating and molding by using a double-screw extruder to obtain the white attapulgite/nylon composite material.
Example 5: preparation of yellow Attapulgite/Nylon composite Material
(1) Preparing 550g of sodium acetate aqueous solution from anhydrous sodium acetate and purified water according to the mass ratio of 100: 30, heating to 100 ℃, slowly stirring and adding 250g of nano-attapulgite after crystals are completely dissolved, heating to a boiling point, cooling to room temperature until sodium acetate crystals are separated out, adding deionized water, continuously heating to 85 ℃ until sodium salt crystals are completely dissolved, filtering to remove the sodium salt aqueous solution, adding 260g of sodium hydroxide (21%) solution, heating to 42 ℃, keeping the temperature and stirring for 10 hours, stirring at the speed of 120r/min, cooling to room temperature, performing liquid-solid separation, washing with a hydrochloric acid aqueous solution with the pH of 5, washing with ionized water for 2 times, drying, grinding and crushing to obtain the attapulgite nano-material. Adding the attapulgite nano material, 15g of nano tungsten oxide and 55g of nano tin sulfide into 1650g of ethanol solvent, stirring for 2.5 hours, standing for 50 minutes, layering the system solution, and removing the upper layer solvent to obtain the modified attapulgite nano material.
(2) Adding 2000g of nylon 66 particles into a modified attapulgite nano material container, ultrasonically stirring for 30 minutes, keeping the flow of nitrogen at 45mL/min, heating the mixture of the modified attapulgite and the nylon to 290 ℃, mixing by a high-speed mixing roll, controlling the injection pressure at 85MPa, pressurizing and extruding into granules to obtain the yellow nylon 66 master batch containing the attapulgite.
(3) 1200g of the yellow nylon 66 master batch, 2600g of nylon 66 particles, 300g of nano silicon dioxide composite microspheres (30 wt% of tin oxide is dispersed in the silicon dioxide microspheres), 105g N-octadecyl-13-docosanamide lubricant, 95g of the toughening agent POE, 35g of the antioxidant 1098 and 30g of the ultraviolet absorbent UV-360 are uniformly stirred and melted and blended, the temperature is controlled at 290 ℃, and a double-screw extruder is used for granulation and molding, so that the yellow attapulgite/nylon composite material is obtained.
Example 6: preparation of blue attapulgite/nylon composite material
(1) Preparing 500g of sodium acetate aqueous solution from sodium acetate and purified water according to the mass ratio of 100: 16, heating to 100 ℃, slowly stirring and adding 250g of nano-attapulgite after crystals are completely dissolved, heating to boiling point, cooling to room temperature until crystalline solids are separated out, adding deionized water, continuously heating to 85 ℃ until sodium salt crystals are completely dissolved, filtering to remove the sodium salt aqueous solution, adding 260g of sodium hydroxide (18%) solution, heating to 48 ℃, keeping the temperature and stirring for 10 hours, stirring at the speed of 140r/min, cooling to room temperature, performing liquid-solid separation, washing with a hydrochloric acid aqueous solution with the pH value of 5, washing with ionized water for 2 times, drying, grinding and crushing to obtain the attapulgite nano-material. Adding the attapulgite nano material and 55g of nano copper oxide into 1650g of ethanol solvent, stirring for 2.5 hours, standing for 60 minutes, layering the system solution, and removing the upper layer solvent to obtain the modified attapulgite nano material.
(2) Adding 1700g of nylon 66 particles into a modified attapulgite nano material container, ultrasonically stirring for 30 minutes, keeping the flow of nitrogen at 45mL/min, heating the mixture of the modified attapulgite and the nylon to 290 ℃, mixing by a high-speed mixing mill, controlling the injection pressure at 85MPa, pressurizing and extruding to form granules, and thus obtaining the blue nylon 66 master batch containing attapulgite.
(3) 1200g of the blue nylon 66 master batch, 4000g of nylon 66 particles, 220g of nano silicon dioxide composite microspheres (30 wt% of copper oxide is dispersed in the silicon dioxide microspheres), 100g N-octadecyl-13-docosanamide lubricant, 285g of toughener POE, 65g of antioxidant 1098 and 70g of ultraviolet absorbent UV-360 are uniformly stirred and melted and blended, the temperature is controlled at 290 ℃, and a double screw extruder is used for granulation and molding to obtain the blue attapulgite/nylon composite material.
Comparative example 1: preparation of Red Attapulgite/Nylon composite Material
6000g of nylon 66 particles are added into a 550g of attapulgite nano material container, 230g of ethylene-propylene copolymer dispersant, 145g of resin C100 lubricant, 245g of flexibilizer ZR-04, 30g of antioxidant S-9228, 20g of antioxidant B225, 25g of ultraviolet absorbent UV-326, 25g of ultraviolet absorbent UV-531 and 48g of pigment red 149 are added and stirred uniformly, then the mixture is melted and blended, the temperature is controlled at 290 ℃, and a double screw extruder is used for granulation and molding, so that the red attapulgite/nylon composite material is obtained.
Comparative example 2: preparation of yellow Attapulgite/Nylon composite Material
(1) Dispersing 250g of attapulgite in 500mL of deionized water, performing ultrasonic vibration stirring for 20 minutes to form uniform clay suspension, placing the clay suspension in a water bath at 80 ℃, adding 14g of silane coupling agent KH550, stirring for 4 hours, cooling, washing with distilled water for 3 times, performing suction filtration, drying and grinding to obtain the silane coupling agent modified attapulgite nano material.
(2) 1400g of nylon 66 particles are added into a silane coupling agent modified attapulgite nano material container, after ultrasonic stirring is carried out for 30 minutes, the flow rate of nitrogen is kept at 45mL/min, the mixture of the modified attapulgite and the nylon is heated to 285 ℃, and after the mixture is mixed by a high-speed mixing roll, the injection pressure is controlled at 85MPa, and the mixture is pressurized and extruded into granules, so that the master batch containing the attapulgite nylon 66 is obtained.
(3) And uniformly stirring 1000g of the nylon 66 master batch, 3200g of nylon 66 particles, 105g of resin C100 lubricant, 205g of toughening agent ZR-04, 30g of antioxidant S-9228, 20g of antioxidant B225, 25g of ultraviolet absorbent UV-326, 25g of ultraviolet absorbent UV-531 and 6g of pigment yellow 107, melting and blending, controlling the temperature at 290 ℃, and granulating and molding by using a double-screw extruder to obtain the yellow attapulgite/nylon composite material.
Comparative example 3: preparation of Black Attapulgite/Nylon composite Material
(1) Adding 250g of attapulgite nano material, 45g of nano manganese oxide and 20g of nano titanium oxide into 1650g of methanol solvent, stirring for 2 hours, standing for 60 minutes, layering the system solution, and removing the upper layer solvent to obtain the modified attapulgite nano material.
(2) 1400g of nylon 66 particles are added into a modified attapulgite nano material container, after ultrasonic stirring is carried out for 30 minutes, the flow rate of nitrogen is kept at 45mL/min, the mixture of the modified attapulgite and the nylon is heated to 285 ℃, and after mixing is carried out by a high-speed mixing roll, the mixture is pressurized and extruded into granules under the injection pressure controlled at 85MPa, so as to obtain the black nylon 66 master batch containing the attapulgite.
(3) And uniformly stirring 1000g of the black nylon 66 master batch, 3200g of nylon 66 particles, 350g of nano silicon dioxide composite microspheres (15 wt% of zinc oxide nanoparticles and 15 wt% of aluminum oxide nanoparticles are dispersed in the silicon dioxide microspheres), 105g of resin C100 lubricant, 205g of toughening agent ZR-04, 30g of antioxidant S-9228, 20g of antioxidant B225, 25g of ultraviolet absorbent UV-326 and 25g of ultraviolet absorbent UV-531, melting and blending, controlling the temperature at 290 ℃, and granulating and molding by using a double-screw extruder to obtain the black attapulgite/nylon composite material.
Comparative example 4: preparation of Black Attapulgite/Nylon composite Material
(1) Preparing 500g of sodium acetate aqueous solution from sodium acetate trihydrate and purified water according to the mass ratio of 100: 13, heating to 90 ℃, slowly stirring and adding 250g of nano-attapulgite after crystals are completely dissolved, heating to a boiling point, cooling to room temperature until sodium acetate crystals are separated out, adding deionized water, continuously heating to 80 ℃ until sodium salt crystals are completely dissolved, filtering to remove the sodium salt aqueous solution, adding 250g of sodium hydroxide (15%) solution, heating to 40 ℃, keeping the temperature and stirring for 10 hours, stirring at the speed of 120r/min, cooling to room temperature, performing liquid-solid separation, washing with 5.5 PH hydrochloric acid aqueous solution, washing with ionized water for 2 times, drying, grinding and crushing to obtain the attapulgite nano-material. Adding the attapulgite nano material, 45g of nano manganese oxide and 20g of nano titanium oxide into 1650g of methanol solvent, stirring for 2 hours, standing for 60 minutes, layering the system solution, and removing the upper layer solvent to obtain the modified attapulgite nano material.
(2) 1400g of nylon 66 particles are added into a modified attapulgite nano material container, after ultrasonic stirring is carried out for 30 minutes, the flow rate of nitrogen is kept at 45mL/min, the mixture of the modified attapulgite and the nylon is heated to 285 ℃, and after mixing is carried out by a high-speed mixing roll, the mixture is pressurized and extruded into granules under the injection pressure controlled at 85MPa, so as to obtain the black nylon 66 master batch containing the attapulgite.
(3) And (2) uniformly stirring 1000g of the black nylon 66 master batch, 3200g of nylon 66 particles, 105g of resin C100 lubricant, 205g of toughening agent ZR-04, 30g of antioxidant S-9228, 20g of antioxidant B225, 25g of ultraviolet absorbent UV-326 and 25g of ultraviolet absorbent UV-531, melting and blending, controlling the temperature at 290 ℃, and granulating and molding by using a double-screw extruder to obtain the black attapulgite/nylon composite material.
Example 7: attapulgite/nylon composite material ageing resistance detection experiment
The attapulgite/nylon composite materials prepared in examples 1-6 and comparative examples 1-2 were subjected to aging resistance tests, the test equipment was a tin-free uv light aging test box of the ministry of engineering technologies ltd, and the test procedure and method were as follows: the attapulgite/nylon composite material (particles) prepared in examples 1-6 and comparative examples 1-2 are added into an injection molding machine for injection molding, the temperature of an injection molding area is 230 ℃, tensile sample strips (the length is 80mm multiplied by the width is 8mm multiplied by the thickness is 4mm) and impact sheets (the length is 80mm multiplied by the width is 65mm multiplied by the thickness is 4mm) for experiments are obtained, the samples of the experiments are marked and then are sent into a test box for aging detection, the experimental data are calculated and determined according to the formula of total radiation amount which is radiation time multiplied by radiation intensity, the limit radiation conditions are selected, the changes (such as local pulverization, crack, fine crack, deformation or discoloration, fading and the like) can be distinguished by naked eyes after radiation are used as the shortest radiation time, and the national standard GB/T16422.3-2014 is referred. The detection results are shown in the table I.
Table of the aging Properties of the samples of examples and comparative examples
Example 8: experiment for detecting tensile property of attapulgite/nylon composite material
Tensile property tests were conducted on the tensile specimens of examples 1 to 6, comparative examples 1 to 2, and the tensile specimens after the aging property test of example 7, respectively, and the test procedure was as follows: the upper and lower ends of the tensile sample strips (non-aged test) prepared in comparative examples 1-2 were respectively clamped in upper and lower clamps of a tensile testing machine, and according to the set data such as tensile strength (Mpa) and tensile speed, the tensile test was stopped until the complete fracture was reached, the tensile distance was recorded, 10 samples per group were counted, and 20 samples in total were counted, the longest distance at the tensile fracture was taken as the sample gauge length, the tensile strength performance test was performed on the tensile sample strips after the aging performance test of example 7, and the test results were recorded (see table two).
Table two tensile property test conditions of the samples of examples and the samples of comparative examples
Example 9: impact property detection experiment for attapulgite/nylon composite material
The impact sheets of examples 1-6, comparative examples 1-2 and example 7 after the aging performance test were subjected to performance tests, respectively, the test procedure being: the impact sheet (non-aging test) samples prepared in comparative examples 1 to 2 were fixed on supports, the samples supported on a horizontal beam were hit with a pendulum of known energy, the impact line was located at the center of the supports, the samples were completely destroyed (broken into two pieces) by one impact of the pendulum, and the impact strength (kJ/m) was measured on each of the impact specimens after the aging test of example 7 based on the set impact energy (J) and impact velocity (m/s) and the like2) And (5) performing experiments, and recording detection results (see table three). The test refers to the national standard of the impact test method (GB/T1049-93) of the rigid plastic simple supported beam.
Table showing impact property test conditions of the samples of the three examples and the samples of the comparative example
The experimental detection results show that the attapulgite/nylon composite material prepared by the invention has strong ageing resistance, high color fastness and good mechanical property.
Claims (10)
1. A method for modifying and coloring a nylon composite material, comprising the steps of:
A. preparation of modified attapulgite nano material
(1) Activating treatment of attapulgite: preparing a sodium salt saturated aqueous solution at 70-100 ℃, slowly adding nano attapulgite while stirring, cooling to room temperature, and crystallizing and separating out solid; adding deionized water until the sodium salt crystals are completely dissolved, and filtering to remove the sodium salt water solution; adding the obtained attapulgite into 10-25 wt% of sodium hydroxide solution, heating to 30-50 ℃, keeping the temperature and stirring for 9-12 hours, cooling to room temperature, filtering out the solution, washing the attapulgite with weak acid solution to be neutral, washing the attapulgite with deionized water for 2-3 times, drying, grinding and crushing to obtain the activated attapulgite nano material;
(2) nano coating modification of attapulgite: respectively adding the activated nano attapulgite into alcohol solvents containing oxide or sulfide nano materials with different colors, wherein the mass ratio of the attapulgite to the oxide nano materials/the sulfide nano materials is (10-20) to (3-5), and stirring for 1-3 hours at normal temperature; standing, layering and filtering to obtain a precipitate which is a modified attapulgite nano material;
B. preparing a nylon color master batch containing modified attapulgite: adding nylon particles into the modified attapulgite nano material obtained in the step A, wherein the mass ratio of the modified attapulgite nano material to the nylon particles is 1: 3-10, ultrasonically stirring for 20-45 minutes, mixing by a high-speed mixing mill, and then extruding into particles under pressure to obtain nylon color master batch containing attapulgite;
C. b, preparing an attapulgite/nylon composite material, namely melting and blending the nylon color master batch prepared in the step B with nylon particles or slices, and adding nano-silica composite microspheres and an auxiliary agent, wherein the mass ratio of the nylon color master batch to the nylon material is 100: 100 (700-); the mass ratio of the nano silicon dioxide composite microspheres to the nylon material is as follows: (3-15) to 100; dispersing and mixing, and then extruding under pressure to form particles to obtain the attapulgite/nylon composite material; the nano-silica composite microspheres are prepared by dispersing metal or metal oxide nanoparticles with the particle size of 50nm in 100-500nm silica microspheres, wherein the metal or metal oxide is zinc, iron, tin, lead, silver, copper, platinum, sodium oxide, potassium oxide, calcium oxide, zinc oxide, iron oxide, tin oxide, lead oxide, copper oxide, magnesium oxide, barium oxide, strontium oxide, aluminum oxide, gallium oxide, indium oxide, thallium oxide, germanium oxide, antimony oxide, bismuth oxide and/or polonium oxide; the mass ratio of the metal or metal oxide nano particles to the silicon dioxide is (0.1-0.4) to 1.
2. The method for modifying and coloring a nylon composite material according to claim 1, wherein the specific operation of step a is as follows:
(1) activating treatment of attapulgite: preparing a sodium salt saturated aqueous solution at 70-100 ℃, slowly adding nano attapulgite under stirring, wherein the mass ratio of the sodium salt saturated solution to the attapulgite is (1-3) to 1; after the temperature is increased to the boiling point, the temperature is reduced to the room temperature, and solid crystals are separated out; adding deionized water, heating to 50-100 deg.C until sodium salt crystal is completely dissolved, and filtering to remove sodium salt water solution; adding the obtained attapulgite into 10-25 wt% of sodium hydroxide solution, heating to 30-50 ℃, keeping the temperature, stirring for 9-12 hours, cooling to room temperature, filtering out the solution, neutralizing and washing the attapulgite with weak acid with the pH value of more than or equal to 5 for one time, washing the attapulgite with deionized water for 2-3 times, drying, grinding and crushing to obtain an activated attapulgite nano material;
(2) nano coating modification of attapulgite: respectively adding the activated nano attapulgite into alcohol solvents containing nano oxides or sulfides with different colors, wherein the mass ratio of the alcohol solvents to the attapulgite nano materials to the oxide nano materials to the sulfide nano materials is 100 to (10-20) to (3-5), and stirring for 1-3 hours at normal temperature; standing and layering, wherein the lower precipitate is the attapulgite nano material with the surface coated with the oxide or sulfide nano particles.
3. The method for modifying and coloring a nylon composite of claim 1,
the particle size of the attapulgite is less than 100nm, and the length-diameter ratio is more than 10;
the sodium salt is sodium sulfate, sodium acetate trihydrate, anhydrous sodium acetate, sodium formate or sodium propionate;
the alcohol solvent is one or more of methanol, ethanol, benzyl alcohol, ethylene glycol and isopropanol.
4. The method for modifying and coloring a nylon composite material according to claim 1, wherein the oxide nanomaterial in step a is zinc oxide, titanium oxide, cobalt oxide, iron oxide, copper oxide, selenium oxide, magnesium oxide, manganese oxide, sodium oxide, silicon oxide, zirconium oxide, calcium oxide, potassium oxide, barium oxide, tin oxide, strontium oxide, antimony oxide, tungsten oxide, and/or chromium oxide; the particle size of the oxide nano material is less than 50 nm;
the sulfide nano material in the step A is zinc sulfide, tin sulfide, iron sulfide, magnesium sulfide, copper sulfide and/or cadmium sulfide; the grain diameter of the sulfide nano material is 3-100 nm.
5. The method for modifying and coloring a nylon composite material according to claim 1, wherein the specific operation of step B is as follows: adding nylon particles into the modified attapulgite nano material obtained in the step A, wherein the mass ratio of the modified attapulgite nano material to the nylon particles is 1: 3-10, and ultrasonically stirring for 20-45 minutes; under the protection of nitrogen, heating the obtained mixture to 275-300 ℃, keeping the flow of the nitrogen at 40-60mL/min, mixing by a high-speed mixing roll, pressurizing and extruding into granules, and controlling the injection pressure at 80-100 MPa to obtain the attapulgite-containing nylon color master batch.
6. The method for modifying and coloring a nylon composite material according to claim 1, wherein the specific operation of step C is as follows: b, melting and blending the nylon color master batch prepared in the step B with nylon particles or slices, and adding the nano silicon dioxide composite microspheres and the auxiliary agent, wherein the mass ratio of the nylon color master batch to the nylon material is 100: 100-; the mass ratio of the nano silicon dioxide composite microspheres to the nylon material is (3-15) to 100, and after dispersion and mixing, a double-screw extruder is adopted to obtain the attapulgite/nylon composite material.
7. The method of claim 1, wherein the nylon material is at least one of polycaprolactam, polyhexamethylene adipamide, polyundecanoamide, polydodecanoamide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide, poly-9-aminononanoic acid, polytriacontamide, and decamethylene sebacamide, and comprises a regrind material of the above material.
8. The method for modifying and coloring a nylon composite of claim 1 wherein the auxiliary agent is a lubricant, a toughening agent, an ultraviolet absorber and/or an antioxidant.
9. The method of claim 8, wherein the nylon composite is modified and colored,
the toughening agent is at least one of ethylene propylene diene monomer, ethylene octene copolymer and toughening agent ZR-04;
the lubricant is N-octadecyl-13-docosanamide or resin C100;
the antioxidant is at least one of antioxidant 1098, antioxidant 1076, antioxidant B225, antioxidant B215 and antioxidant S-9228;
the ultraviolet light absorber is at least one of UV-P, UV-326, UV-327, UV-328, UV-329, UV-360, UV-531 and UV-928.
10. The method for modifying and coloring a nylon composite according to any one of claims 1 to 9, wherein the color blending method of the method for modifying and coloring a nylon composite is to blend oxide or sulfide materials of different colors in accordance with a desired color in step (2) or to blend nylon color concentrates of different colors in accordance with a desired color in step C.
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| A study on attapulgite reinforced PA6 composites;Binglin Pan et al;《Polymer Testing》;20061231;第25卷;第384-391页 * |
| 高凹凸棒土含量的尼龙66母粒的制备与表征;姚一一 等;《化工新型材料》;20170331;第45卷(第3期);第228-229、232页 * |
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| CN107236298A (en) | 2017-10-10 |
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