CN109503939A - Nano modification coloured polypropylene composite material - Google Patents
Nano modification coloured polypropylene composite material Download PDFInfo
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- CN109503939A CN109503939A CN201811248116.1A CN201811248116A CN109503939A CN 109503939 A CN109503939 A CN 109503939A CN 201811248116 A CN201811248116 A CN 201811248116A CN 109503939 A CN109503939 A CN 109503939A
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
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Abstract
The present invention relates to a kind of nano modification coloured polypropylene composite materials, each component including following weight ratio: attapulgite 1-18%, nylon particles 10-30%, nano silica complex microsphere 3-15%, polypropylene 50-60%, the attapulgite periphery is coated with nano-oxide or nanometer sulfide, wherein the mass ratio of the nano-oxide or nanometer sulfide and the attapulgite is (3-5): (10-20)；The nano silica complex microsphere is that the metal of 50nm partial size or the nano particle of metal oxide are dispersed in the composition formed in 100-500nm silicon dioxide microsphere.The nano modification coloured polypropylene composite material has the characteristics that anti-aging property is strong, mechanical property is good, Steel Properties are high.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of nano modification coloured polypropylene composite material, by bumps
Stick soil nanoparticle is prepared with polypropylene composite materials, which has the spies such as the strong, excellent in mechanical performance of anti-aging property
Point.
Background technique
There are many method of modifying plastics, mainly there is copolymerization, blending, filling, enhancing, plating, fire-retardant and addition nucleating agent etc.
Method.Polypropylene is (abbreviation PP), refers to the high-molecular compound containing propylene group on strand.Polypropylene oil resistant, it is acidproof,
It is corrosion-resistant, there is excellent mechanical property, good processing performance, be using wider one of plastics.Although polyacrylic comprehensive
Conjunction is had excellent performance, but due to this body structure of high molecular material, and polyacrylic rigidity intensity and the performances such as anti-aging are also
Have it is to be strengthened, therefore, to the research of polyacrylic modification, blending and alloy at hot spot concerned by people.Such as: multiple in polypropylene
In the research of condensation material, important achievement is had been achieved for carbon fiber and glass fiber reinforced polypropylene；Meanwhile with montmorillonite, carbon
The nano-material modified polyacrylic research such as sour calcium, talcum powder, nanometer SO2, carbon nanotube, attapulgite is more.
Attapulgite (abbreviation AT) is a kind of crystalloid hydration alumina magnesia silicate with distinct layer chain structure, is mainly contained
Have an elements such as Ag, Al, Si, O, H, crystal be in more it is rodlike or fibrous, the diameter of single stick is in 100nm hereinafter, length about exists
1um, the nanoscale duct and tiny crystalline size that attapulgite has assign its very high interior external surface area, inner surface
Product is about 600m2/g, and external surface area is about 300 m2/g, and therefore, attapulgite had both had the characteristic of nano material, but also with short
The rigidity of fibre reinforced materials, attapulgite/nylon composite materials research have broad application prospects.Such as: Beijing chemical industry is big
Wang Yizhong et al. is learned after being activated to attapulgite, attapulgite/polypropylene composite materials have been synthesized by in-situ polymerization
Material, material mechanical performance have a distinct increment；Though gathering although the domestic and international production method of modified nylon and technique have large development
Propylene is modified, and there are still very big development spaces.Polypropylene under the influence of the factors such as light, heat, oxygen, strand be easy to happen embrittlement,
Xanthochromia, degradation aging is natural quality, not can avoid, main performance characteristic are as follows: first is that product appearance gloss weakens, color is light
Change, yellow colour index increases；Second is that elasticity modulus and shock resistance decline.Polypropylene art standard is coloration changing value and resistance to punching
Retention is hit as the foundation for measuring polypropylene material degree of aging, therefore, polypropylene modification research is especially anti-aging research
Still shoulder heavy responsibilities.
Summary of the invention
The present invention carries out modification to attapulgite using oxide/sulfide nano-material, by attapulgite
It is activated, nanometer coating modification mode on attapulgite duct and surface, forms nano-oxide or sulfur compounds adsorption multiple
Structure nano material is closed, and various color grains are made with polypropylene in the attapulgite nanometer material after modification, and will be different
Color master batch is blended with polypropylene fusion, and colors attapulgite/PP composite material, the nano complex heterophasic polypropylene is made
Material has the characteristics that anti-aging property is strong, mechanical property is good, rigidity is high.
To achieve the above object, the present invention provides a kind of nano modification coloured polypropylene composite material, including it is following heavy
The each component of amount ratio: attapulgite 1-18%, nylon particles 10-30%, nano silica complex microsphere 3-15%, poly- third
Alkene 50-60%.
In any of the above-described scheme preferably, the partial size of the attapulgite is less than or equal to 100nm, and draw ratio is greater than etc.
In 10, the attapulgite periphery is coated with nano-oxide or nanometer sulfide, wherein the nano-oxide or nano-sulfur
The mass ratio of compound and the attapulgite is (3-5): (10-20)；The nano silica complex microsphere is 50nm partial size
Metal or the nano particle of metal oxide be dispersed in the composition formed in 100-500nm silicon dioxide microsphere.
In any of the above-described scheme preferably, the nano-oxide includes: zinc oxide, titanium oxide, cobalt oxide, oxygen
Change iron, copper oxide, selenium oxide, magnesia, manganese oxide, sodium oxide molybdena, silica, zirconium oxide, calcium oxide, potassium oxide, barium monoxide, oxygen
Change one of tin, strontium oxide strontia, antimony oxide, tungsten oxide, chromium oxide or a variety of, the partial size of the nano-oxide is less than 50nm；
For the partial size of the nanometer sulfide between 3-100nm, the nanometer sulfide includes zinc sulphide, artificial gold, sulphur
Change iron, magnesium sulfide, copper sulfide, cadmium sulfide it is one or more；
The metal is one of zinc, iron, tin, lead, silver, copper, platinum or a variety of, and the metal oxide includes oxidation
Sodium, potassium oxide, calcium oxide, zinc oxide, iron oxide, tin oxide, lead oxide, copper oxide, magnesia, barium monoxide, strontium oxide strontia, oxidation
One of aluminium, gallium oxide, indium oxide, thallium oxide, germanium oxide, tin oxide, lead oxide, antimony oxide, bismuth oxide oxidation polonium are more
Kind；The mass ratio of the nano particle and silica of the metal or metal oxide is (0.1~0.4): 1.
In any of the above-described scheme preferably, the nylon particles be single poly- PP GRANULES, copolymer polypropylene particle,
Single poly- PP GRANULES retrogradation material or copolymer polypropylene particle retrogradation material.
The present invention also provides a kind of preparation methods of nano modification coloured polypropylene composite material, according to sequencing packet
Include following steps:
Step (1): the activation processing of attapulgite: in 70-100 DEG C of sodium salt saturated aqueous solution, while stirring slowly
Nano-attapulgite is added, wherein the mass ratio of sodium salt saturated solution and attapulgite is (1-3): 1；After being warming up to boiling point,
Room temperature is cooled to, solid crystal is precipitated；Deionized water is added, is warmed to 50-100 DEG C and is all dissolved to crystals of sodium salt, filtered off
Except sodium-salt aqueous solution；Attapulgite is obtained, then the attapulgite of acquisition is added in the sodium hydroxide solution of 10-25wt%,
It insulated and stirred 9-12 hours after being heated to 30-50 DEG C, is cooled to room temperature and attapulgite is obtained by filtration, by attapulgite pH >=5
Weak acid neutralization washed once, then be washed with deionized 2-3 times, drying and grinding crushes the attapulgite after being activated
Nano material；
Step (2): the nanometer coating modification of attapulgite: the attapulgite nanometer material difference that step (1) is activated
It is added in the alcohols solvent of the nano-oxide containing different colours or nanometer sulfide, wherein alcohols solvent and concave convex rod
Native nano material, oxide-based nanomaterial/sulfide nano-material three's mass ratio are 100:(10-20): (3-5), under room temperature
Stirring 1-3 hours；Stratification, lower sediment thing are that the attapulgite of oxide coated on surface or sulfide nano-particle is received
Rice material；
Step (3): PP GRANULES is added in the attapulgite modified nano material of step (2) acquisition, wherein change
Property attapulgite nanometer material and nylon particles mass ratio be 1:(3-10), be stirred by ultrasonic 20-45 minutes, obtain mixture；
Under the protection of nitrogen, the mixture of acquisition is heated to 185-200 DEG C, keeps the flow of nitrogen in 40-60mL/min, passes through
After high speed mixing smelting machine is kneaded, pressurization squeezes out granulating, and injection pressure is controlled in 65~85MPa, obtains the color of polypropylene containing attapulgite
Master batch；
Step (4): the polypropylene color masterbatch of step (3) preparation and PP GRANULES or regenerating polypropylene sheet stock are melted altogether
It mixes, addition nano silica complex microsphere and auxiliary agent, the mass ratio of polypropylene color masterbatch and polypropylene material is 100:(100-
700)；The mass ratio of nano silica complex microsphere and polypropylene material is (3-15): 100, after dispersion mixing, using double
Screw extruder carries out extrusion molding to it, obtains attapulgite/PP composite material.
Preferably, the sodium salt is sodium sulphate, sodium acetate trihydrate, anhydrous sodium acetate, sodium formate or sodium propionate；It is described
Alcohols solvent is one of methanol, ethyl alcohol, benzyl alcohol, ethylene glycol, isopropanol or a variety of mixing.
In any of the above-described scheme preferably, the auxiliary agent includes lubricant, toughener, ultraviolet absorber and/or resists
Oxidant；
The lubricant is one of EBS, EB-FFF magnesium stearate, zinc stearate；
The toughener is one of ethylene propylene diene rubber, ethylene octene copolymer, toughener ZR-04 or a variety of mixed
It closes；
The UV absorbers be UV-770, UV-326, UV-327, UV-328, UV-329, UV-360, UV-531 and
One of UV-928 or a variety of mixing；
The antioxidant is antioxidant 1010, antioxidant 1070, antioxidant 168, antioxidant B215, resists
One of oxidant S-9228 or a variety of mixing.
In any of the above-described scheme preferably, the PP GRANULES is copolymer polypropylene particle, single poly- polypropylene
One of grain or two kinds, the PP GRANULES can also be copolymer polypropylene particle, the retrogradation material of single poly- PP GRANULES.
In any of the above-described scheme preferably, user can choose the oxide or sulfide of different colours according to demand
And it is coloured according to required color, or the polypropylene color masterbatch of different colours as desired colours color.
In any of the above-described scheme preferably, this law is suitable for preparing the described in any item nanometers of claim 1-4 and changes
Property coloured polypropylene composite material.
The beneficial effects of the present invention are: the present invention changes attapulgite using oxide/sulfide nano-material
Property, composite construction nano material is formed, it is multiple that assorted attapulgite/polypropylene is made using the color of oxide, sulfide itself
These color tablets are finally blended with polypropylene material and prepare nano complex phase coloured polypropylene material by condensation material color tablets.
During the preparation process, attapulgite is activated first, i.e. sodium salt processing and alkali process.Sodium salt is crystallizing
In the process since volume expansion can expand attapulgite pore size, concave convex rod can be removed by the crystallization of sodium salt and course of dissolution
Impurity in native surface and duct increases attapulgite specific surface area, duct dredging, increased activity；At sodium salt activation
The attapulgite managed is in alcohols solvent to the adsorbance of nano-oxide or nanometer sulfide compared at without sodium salt activation
The attapulgite of reason dramatically increases.Sodium salt processing and alkali process, make attapulgite octahedral cations Mg2+、Al3+、Fe3+By
The successively metathesis at edge to center, chemical key state changes so that its specific surface area increases, meanwhile, in alcohols solvent
Adsorption capacity enhancing.The attapulgite of activated processing is more conducive to absorption, in conjunction with oxide/sulfide nano-particle.
Surface coats the attapulgite of one layer of nano-oxide or nanometer sulfide, forms compound core-shell structure, increases first
The strong rigidity of attapulgite short fiber material, improves conjugation and dispersibility of the attapulgite in polypropylene matrix；Its
It is secondary to enhance the uv absorption property of attapulgite clay nano composite material, improve nylon composite materials anti-aging property；Simultaneously
Make attapulgite nanometer material that there is gay colours, to polypropylene color, is enhanced poly- by nano material self color
The color fastness of propylene.
Nano-oxide or the attapulgite modified step of nanometer sulfide use alcohols solvent, and the boiling point of alcohols solvent compares water
Low, due to the low boiling point of suspension, required temperature is low when dry, meanwhile, the attapulgite's surface after drying adsorbs alcohol molecule,
Due to the presence of alkanol molecule, making to produce repulsive force between attapulgite clay nano composite material particle, material surface stress reduces,
It prevents from reuniting, while being also convenient for being distributed in polypropylene material.
A certain amount of dispersed metal is mixed simultaneously in polypropylene material or the nano silica of metal oxide is compound micro-
Ball can generate synergistic effect with attapulgite modified nano material, improve polypropylene material anti-aging property and mechanical property.
The experimental results showed that nano modification coloured polypropylene composite material of the invention has, anti-aging property is strong, mechanics
The features such as performance is good, color fastness is high, rigidity is high.
Specific embodiment
In order to be further understood that summary of the invention of the invention, the present invention is elaborated below in conjunction with specific embodiment.
The part material source that following embodiment uses is as follows:
Attapulgite: Oubaite Clay Material Co., Ltd., Xuyi's product.
Nano silica microsphere: Jiangsu Shi Ke new material limited liability company product.Product type: SK-100.
The metal or metal oxide being scattered in silicon oxide microsphere are zinc, iron, tin, lead, silver, copper, platinum or sodium oxide molybdena, oxygen
Change potassium, calcium oxide, zinc oxide, iron oxide, tin oxide, lead oxide, copper oxide, magnesia, barium monoxide, strontium oxide strontia, aluminium oxide, oxygen
Change gallium, indium oxide, thallium oxide, germanium oxide, tin oxide, lead oxide, antimony oxide, bismuth oxide and/or oxidation polonium.
POE: Tao Shi Chemical Co., Ltd.'s product of toughener.
EB-FF lubricant: Malaysian KAO. Corp. SA's product.
Antioxidant 1010, antioxidant 168: Shandong Yantai City rising star chemical article Co., Ltd product.
A kind of nano modification coloured polypropylene composite material provided by the invention, each component including following weight ratio:
Attapulgite 1-18%, nylon particles 10-30%, nano silica complex microsphere 3-15%, polypropylene 50-60%.
Embodiment 1: black attapulgite soil/PP composite material is prepared
(1) sodium acetate trihydrate and pure water 100:13 in mass ratio are configured into sodium acetate aqueous solution 500g, are warmed to 90
DEG C, after crystal all dissolution, it is slowly stirred and 250g nano-attapulgite is added, after being warming up to boiling point, cool to room temperature to vinegar
After sour sodium crystallization is precipitated, continue to be warmed to 80 DEG C to crystals of sodium salt all dissolutions, filtering removal natrium brine after deionized water is added
250g sodium hydroxide (15%) solution is added in solution, insulated and stirred 10 hours, mixing speed 120r/min after 40 DEG C of heating, drop
It to room temperature solid-liquor separation, is washed with pH=5 aqueous hydrochloric acid solution, then with ion water washing 2 times, drying and grinding crushes to obtain bumps
Stick soil nano material.By attapulgite nanometer material and 45g nano manganese oxide, that 20g nano-titanium oxide is added to 1650g methanol is molten
In agent, after stirring 2 hours, 60 minutes are stood, system solution layering obtains attapulgite modified nanometer after removing upper layer solvent
Material.
(2) 1400g PP GRANULES is added in attapulgite modified nano material container, is stirred by ultrasonic 30 minutes
Afterwards, it keeps the flow of nitrogen in 45mL/min, attapulgite modified and polyacrylic mixture is heated to 195 DEG C, passes through height
After fast kneading machine is kneaded, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the master batch of black polypropylene containing attapulgite.
(3) take above-mentioned black polypropylene master batch 1000g and 3200g PP GRANULES, 350g SiO 2 composite microsphere,
105gEB-FF lubricant, 205g toughener POE, 30g antioxidant 1010,20g antioxidant 168,25g ultraviolet absorber UV-
770,25g ultraviolet absorber UV-531 is stirred evenly and melt blending, temperature are controlled at 195 DEG C, and double screw extruder is granulated into
Type obtains black attapulgite soil/PP composite material.
Embodiment 2: green attapulgite/PP composite material is prepared
(1) sodium acetate trihydrate and pure water 100:14 in mass ratio are configured into sodium acetate aqueous solution 550g, are warmed to 90
DEG C, after crystal all dissolution, it is slowly stirred and 250g nano-attapulgite is added, after being warming up to boiling point, cool to room temperature to vinegar
After sour sodium crystallization is precipitated, continue to be warmed to 80 DEG C to crystals of sodium salt all dissolutions, filtering removal natrium brine after deionized water is added
250g sodium hydroxide (11%) solution is added in solution, insulated and stirred 12 hours, mixing speed 150r/min after 40 DEG C of heating, drop
It is washed after to room temperature solid-liquor separation with pH=5 aqueous hydrochloric acid solution, then with ion water washing 2 times, drying and grinding crushes to obtain bumps
Stick soil nano material.By attapulgite nanometer material and 12g nano chromium oxide, that 6g nano zine oxide is added to 1650g ethyl alcohol is molten
In agent, after stirring 2 hours, 50 minutes are stood, system solution layering obtains attapulgite modified nanometer after removing upper layer solvent
Material.
(2) 950g PP GRANULES is added in attapulgite modified nano material container, after being stirred by ultrasonic 35 minutes,
It keeps the flow of nitrogen in 45mL/min, attapulgite modified and polyacrylic mixture is heated to 290 DEG C, it is mixed by high speed
After mill is kneaded, injection pressure control is pressurizeed in 85MPa squeezes out granulating, obtains the polypropylene agglomerate of green containing attapulgite.
(3) take above-mentioned green polypropylene agglomerate 900g and 6000g PP GRANULES, 220g SiO 2 composite microsphere,
145gEB-FF lubricant, 350gPOE, 30g antioxidant 1010,20g antioxidant 168,30g ultraviolet absorber UV-770,
25g ultraviolet absorber UV-531 is stirred evenly and melt blending, and temperature is controlled at 195 DEG C, and double screw extruder granulating and forming obtains
To green attapulgite/PP composite material.
Embodiment 3: red attapulgite soil/nylon composite materials are prepared
(1) sodium acetate trihydrate and pure water 100:18 in mass ratio are configured into sodium acetate aqueous solution 400g, are warmed to 90
DEG C, after crystal all dissolution, it is slowly stirred and 250g nano-attapulgite is added, after being warming up to boiling point, cool to room temperature to vinegar
After sour sodium crystallization is precipitated, continue to be warmed to 80 DEG C to crystals of sodium salt all dissolutions, filtering removal natrium brine after deionized water is added
270g sodium hydroxide (25%) solution is added in solution, insulated and stirred 10 hours, mixing speed 120r/min after 45 DEG C of heating, drop
It is washed after to room temperature solid-liquor separation with pH=5 aqueous hydrochloric acid solution, then with ion water washing 2 times, drying and grinding crushes to obtain bumps
Stick soil nano material.By attapulgite nanometer material and 50g nano iron oxide, that 25 nanometers of g cadmium sulfides are added to 1650g ethyl alcohol is molten
In agent, after stirring 2.5 hours, 50 minutes are stood, system solution layering obtains attapulgite modified receive after removing upper layer solvent
Rice material.
(2) 2400g PP GRANULES is added in attapulgite modified nano material container, is stirred by ultrasonic 40 minutes
Afterwards, it keeps the flow of nitrogen in 45mL/min, attapulgite modified and nylon mixture is heated to 1950 DEG C, passes through high speed
After kneading machine is kneaded, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the master batch of red polypropylene containing attapulgite.
(3) take above-mentioned red polypropylene master batch 1500g and 1600g PP GRANULES, 230g SiO 2 composite microsphere,
65gEB-FF lubricant, 80gPOE, 22g antioxidant 1010,25g ultraviolet absorber UV-770 are stirred evenly and melt blending,
Temperature is controlled at 195 DEG C, and double screw extruder granulating and forming obtains red attapulgite soil/PP composite material.
Embodiment 4: white attapulgite/PP composite material is prepared
(1) sodium acetate trihydrate and pure water 100:15 in mass ratio are configured into sodium acetate aqueous solution 400g, are warmed to 90
DEG C, after crystal all dissolution, it is slowly stirred and 250g nano-attapulgite is added, after being warming up to boiling point, cool to room temperature to vinegar
After sour sodium crystallization is precipitated, continue to be warmed to 80 DEG C to crystals of sodium salt all dissolutions, filtering removal natrium brine after deionized water is added
270g sodium hydroxide (13%) solution is added in solution, insulated and stirred 11 hours, mixing speed 130r/min after 45 DEG C of heating, drop
It is washed after to room temperature solid-liquor separation with pH=5 aqueous hydrochloric acid solution, then with ion water washing 2 times, drying and grinding crushes to obtain bumps
Stick soil nano material.By attapulgite nanometer material and 16g nano aluminium oxide, that 10g nano calcium oxide is added to 1650g ethyl alcohol is molten
In agent, after stirring 2 hours, 60 minutes are stood, system solution layering obtains attapulgite modified nanometer after removing upper layer solvent
Material.
(2) 1000g PP GRANULES is added in attapulgite modified nano material container, is stirred by ultrasonic 30 minutes
Afterwards, it keeps the flow of nitrogen in 45mL/min, attapulgite modified and nylon mixture is heated to 195 DEG C, passes through high speed
After kneading machine is kneaded, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the master batch of white polypropylene containing attapulgite.
(3) take above-mentioned white polypropylene master batch 1000g and 6000g PP GRANULES, 320g SiO 2 composite microsphere,
170gEB-FF lubricant, 280gPOE, 45g antioxidant 1010,50g ultraviolet absorber UV-770 are stirred evenly and are melted altogether
Mixed, temperature is controlled at 200 DEG C, and double screw extruder granulating and forming obtains white attapulgite/PP composite material.
Embodiment 5: Yellow attapulgite soil/PP composite material is prepared
(1) anhydrous sodium acetate and pure water 100:30 in mass ratio are configured into sodium acetate aqueous solution 550g, are warmed to 100 DEG C,
After crystal all dissolution, it is slowly stirred and 250g nano-attapulgite is added, after being warming up to boiling point, cool to room temperature to sodium acetate
After crystallization precipitation, continuing to be warmed to 85 DEG C to crystals of sodium salt all dissolutions after deionized water is added, filtering removes sodium-salt aqueous solution,
260g sodium hydroxide (21%) solution is added, insulated and stirred 10 hours after 42 DEG C of heating, mixing speed 120r/min is down to room temperature
It is washed after solid-liquor separation with pH=5 aqueous hydrochloric acid solution, then with ion water washing 2 times, drying and grinding, which crushes to obtain attapulgite, to be received
Rice material.Attapulgite nanometer material and 15g nanometer tungsten oxide, 55g nanometer tin sulfide are added in 1650g alcohol solvent,
After stirring 2.5 hours, 50 minutes are stood, system solution layering obtains attapulgite modified nanometer material after removing upper layer solvent
Material.
(2) 2000g PP GRANULES is added in attapulgite modified nano material container, is stirred by ultrasonic 30 minutes
Afterwards, it keeps the flow of nitrogen in 45mL/min, attapulgite modified and polyacrylic mixture is heated to 200 DEG C, passes through height
After fast kneading machine is kneaded, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the polypropylene agglomerate of yellow containing attapulgite.
(3) take above-mentioned yellow polypropylene agglomerate 1200g and 2600g PP GRANULES, 300g SiO 2 composite microsphere,
105g magnesium, 95gPOE, 35g antioxidant 1010,30g ultraviolet absorber UV-770 are stirred evenly and are melted
It is blended, temperature is controlled at 200 DEG C, and double screw extruder granulating and forming obtains Yellow attapulgite soil/PP composite material.
Embodiment 6: blue attapulgite soil/PP composite material is prepared
(1) sodium acetate and pure water 100:16 in mass ratio are configured into sodium acetate aqueous solution 500g, are warmed to 100 DEG C, to
Crystal all after dissolution, is slowly stirred and 250g nano-attapulgite is added, after being warming up to boiling point, cool to room temperature to crystalline solid
After precipitation, continue to be warmed to 85 DEG C to crystals of sodium salt all dissolutions after deionized water is added, filtering removal sodium-salt aqueous solution is added
In 260g sodium hydroxide (18%) solution, insulated and stirred 10 hours after 48 DEG C of heating, mixing speed 140r/min is down to room temperature liquid
Gu being washed after separation with pH=5 aqueous hydrochloric acid solution, then with ion water washing 2 times, drying and grinding crushes to obtain attapulgite clay nano
Material.Attapulgite nanometer material and 55g nano cupric oxide are added in 1650g alcohol solvent, it is quiet after stirring 2.5 hours
It sets 60 minutes, system solution layering obtains attapulgite modified nano material after removing upper layer solvent.
(2) 1700g PP GRANULES is added in attapulgite modified nano material container, is stirred by ultrasonic 30 minutes
Afterwards, it keeps the flow of nitrogen in 45mL/min, attapulgite modified and nylon mixture is heated to 200 DEG C, passes through high speed
After kneading machine is kneaded, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the polypropylene agglomerate of blue containing attapulgite.
(3) take above-mentioned blue polypropylene agglomerate 1200g and 4000g PP GRANULES, 220g SiO 2 composite microsphere,
100g magnesium, 285gPOE, 65g antioxidant 1010,70g ultraviolet absorber UV-770 are stirred evenly and are melted
It is blended, temperature is controlled at 200 DEG C, and double screw extruder granulating and forming obtains blue attapulgite soil/PP composite material.
Comparative example 1: red attapulgite soil/PP composite material is prepared
6000g PP GRANULES is added in 550g attapulgite nanometer material container, and 230g Propylene polymerization is added
Object dispersing agent, 145g magnesium, 245gPOE, 30g antioxidant 1010,20g antioxidant 168, the ultraviolet suction of 25g
Receive agent UV-770,25g ultraviolet absorber UV-531,48g pigment red 149 after mixing evenly, melt blending, temperature is controlled 200
DEG C, double screw extruder granulating and forming obtains red attapulgite soil/PP composite material.
Comparative example 2: Yellow attapulgite soil/PP composite material is prepared
(1) disperse 250g attapulgite in 500mL deionized water, ultrasonic activation stirs 20 minutes, is formed uniform
Clay suspension liquid is placed in 80 DEG C of water-baths by clay suspension liquid, and 14g Silane coupling agent KH550 is added, cold after stirring 4 hours
But, it is washed with distilled water 3 times, filters, is dry, grinding, obtaining attapulgite modified by silane coupling agent nano material.
(2) 1400g PP GRANULES is added in attapulgite modified by silane coupling agent nano material container, ultrasound is stirred
It after mixing 30 minutes, keeps the flow of nitrogen in 45mL/min, attapulgite modified and nylon mixture is heated to 285 DEG C,
After being kneaded by high speed mixing smelting machine, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the mother of polypropylene containing attapulgite
Grain.
(3) above-mentioned polypropylene agglomerate 1000g and 3200g PP GRANULES, 105gEB-FF lubricant, 205gPOE, 30g are taken
Antioxidant 1010,20g antioxidant 168,25g ultraviolet absorber UV-770,25g ultraviolet absorber UV-531,8g pigment titanium
Huang stirs evenly and melt blending, and it is native/poly- to obtain Yellow attapulgite in 200 DEG C, double screw extruder granulating and forming for temperature control
Acrylic composite.
Comparative example 3: black attapulgite soil/PP composite material is prepared
(1) 250g attapulgite nanometer material and 45g nano manganese oxide, 20g nano-titanium oxide are added to 1650g methanol
In solvent, after stirring 2 hours, 60 minutes are stood, system solution layering obtains attapulgite modified receive after removing upper layer solvent
Rice material.
(2) 1400g PP GRANULES is added in attapulgite modified nano material container, is stirred by ultrasonic 30 minutes
Afterwards, it keeps the flow of nitrogen in 45mL/min, attapulgite modified and nylon mixture is heated to 195 DEG C, passes through high speed
After kneading machine is kneaded, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the master batch of black polypropylene containing attapulgite.
(3) take above-mentioned black polypropylene master batch 1000g and 3200g PP GRANULES, 350g SiO 2 composite microsphere,
105gEB-FF lubricant, 205gPOE, 30g antioxidant 1010,20g antioxidant 168,25g ultraviolet absorber UV-326,
25g ultraviolet absorber UV-531 is stirred evenly and melt blending, and temperature is controlled at 200 DEG C, and double screw extruder granulating and forming obtains
To black attapulgite soil/PP composite material.
Comparative example 4: black attapulgite soil/PP composite material is prepared
(1) sodium acetate trihydrate and pure water 100:13 in mass ratio are configured into sodium acetate aqueous solution 500g, are warmed to 90
DEG C, after crystal all dissolution, it is slowly stirred and 250g nano-attapulgite is added, after being warming up to boiling point, cool to room temperature to vinegar
After sour sodium crystallization is precipitated, continue to be warmed to 80 DEG C to crystals of sodium salt all dissolutions, filtering removal natrium brine after deionized water is added
250g sodium hydroxide (15%) solution is added in solution, insulated and stirred 10 hours, mixing speed 120r/min after 40 DEG C of heating, drop
It is washed after to room temperature solid-liquor separation with PH=5.5 aqueous hydrochloric acid solution, then with ion water washing 2 times, drying and grinding crushes to obtain recessed
Convex stick soil nano material.Attapulgite nanometer material and 45g nano manganese oxide, 20g nano-titanium oxide are added to 1650g methanol
In solvent, after stirring 2 hours, 60 minutes are stood, system solution layering obtains attapulgite modified receive after removing upper layer solvent
Rice material.
(2) 1400g PP GRANULES is added in attapulgite modified nano material container, is stirred by ultrasonic 30 minutes
Afterwards, it keeps the flow of nitrogen in 45mL/min, attapulgite modified and nylon mixture is heated to 195 DEG C, passes through high speed
After kneading machine is kneaded, injection pressure control is pressurizeed in 65MPa squeezes out granulating, obtains the master batch of black polypropylene containing attapulgite.
(3) take above-mentioned black polypropylene master batch 1000g and 3200g PP GRANULES, 105gEB-FF lubricant,
205gPOE, 30g antioxidant 1010,20g antioxidant 168,25g ultraviolet absorber UV-770,25g ultraviolet absorber UV-
531 stir evenly and melt blending, and temperature control is at 195 DEG C, double screw extruder granulating and forming, obtain black attapulgite soil/
PP composite material.
Embodiment 7: attapulgite/PP composite material anti-aging property test experience
Attapulgite/the nylon composite materials prepared to embodiment 1-6 and comparative example 1-2 carry out anti-aging property respectively
Experiment, experimental facilities select Wuxi Zhong Tian engineering Technology Co., Ltd. ZN-P type ultraviolet light and aging chamber, detecting step and side
Method: attapulgite/PP composite material (particle) prepared by embodiment 1-6 and comparative example 1-2 is added in injection molding machine and is infused
It is moulded into type, is molded 195 DEG C of area's temperature, obtains experiment tensile bars (length 80mm × width 8mm × thickness 4mm) and impact piece
Laboratory sample is kept sample and is sent into chamber progress ageing management after identifying by material (length 80mm × width 65mm × thickness 4mm),
It is calculated according to radiation amount=radiated time × irradiation intensity formula and determines experimental data, selection limit radiation parameter, with irradiation
Afterwards the distinguishable variation of naked eyes (such as: local dusting, rupture, hair check, deformation or discoloration, colour fading color change, with predose
Object of reference compares) it is used as the most short irradiation time, referring to GB/T16422.3-2014 national standard.Testing result is shown in Table one.
One embodiment sample of table and comparative example ageing properties detection case table
Embodiment 8: attapulgite/PP composite material tensile property test experience
To the tensile bars after 7 ageing properties test experience of embodiment 1-6, comparative example 1-2 tensile bars and embodiment point
Not carry out stretching test, detecting step: the upper and lower side of tensile bars (unaged test) of comparative example 1-2 preparation presss from both sides respectively
In the upper and lower holder of cupping machine, according to data such as the tensile strength (Mpa) set and tensile speeds, it is stretched to
Complete breaking part stops, and records stretching distance, every group sample number 10,20, sample, takes distance at longest tension failure altogether
Degree is used as sample marking distance, carries out tensile strength performance experiment to the tensile bars after 7 ageing properties test experience of embodiment respectively,
And it will test result record (being shown in Table two).
Two embodiment sample of table and comparative example tensile property test case table
Embodiment 9: attapulgite/PP composite material impact property test experience
Impact sheet material point after impacting sheet material and 7 ageing properties test experience of embodiment to embodiment 1-6, comparative example 1-2
Not carry out performance test, detecting step: impact sheet material (unaged test) sample of comparative example 1-2 preparation is fixed on the support,
With the pendulum strike support of known energy at the sample of horizontal beam, truncation Line is located at the center of two supports, by pendulum one-shot
Sample is set to destroy (fragment into two sections) completely, according to data such as the impact energys (J) and impact velocity (m/s) set, respectively
Impact strength (kJ/ ㎡) performance test is carried out to the impact batten after 7 ageing properties test experience of embodiment, and will test result
It records (being shown in Table three).Experiment is referring to rigid plastics charpy impact test method (GB/T 1049-93) national standard.
Three embodiment sample of table and comparative example impact property test case table
It learns from above-mentioned laboratory test results and (is shown in Table one), attapulgite/PP composite material produced by the present invention is anti-
Ageing properties are strong, color fastness is high, mechanical property is good.
It will be apparent to those skilled in the art that nano modification coloured polypropylene composite material of the invention includes above-mentioned hair
The summary of the invention and specific embodiment part of bright specification, as space is limited and to keep specification concise without combining these
Each scheme constituted describes one by one.All within the spirits and principles of the present invention, any modification, equivalent substitution and improvement done
Deng should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of nano modification coloured polypropylene composite material, each component including following weight ratio: attapulgite 1-18%,
Nylon particles 10-30%, nano silica complex microsphere 3-15%, polypropylene 50-60%.
2. nano modification coloured polypropylene composite material according to claim 1, which is characterized in that the attapulgite
Partial size is less than or equal to 100nm, and draw ratio is more than or equal to 10；The attapulgite periphery is coated with nano-oxide or nanometer vulcanization
The mass ratio of object, the nano-oxide or nanometer sulfide and the attapulgite is (3-5): (10-20)；The nanometer two
To be dispersed in 100-500nm silica micro- for the metal or the nano particle of metal oxide that silica complex microsphere is 50nm partial size
The composition formed in ball.
3. nano modification coloured polypropylene composite material according to claim 2, which is characterized in that the nano-oxide
Including zinc oxide, titanium oxide, cobalt oxide, iron oxide, copper oxide, selenium oxide, magnesia, manganese oxide, sodium oxide molybdena, silica, oxygen
Change one or more of zirconium, calcium oxide, potassium oxide, barium monoxide, tin oxide, strontium oxide strontia, antimony oxide, tungsten oxide, chromium oxide；Institute
The partial size for stating nano-oxide is less than 50nm.
4. nano modification coloured polypropylene composite material according to claim 2, which is characterized in that the nanometer sulfide
Including one or more of zinc sulphide, artificial gold, iron sulfide, magnesium sulfide, copper sulfide, cadmium sulfide；The nanometer sulfide
Partial size is 3-100nm.
5. nano modification coloured polypropylene composite material according to claim 2, which is characterized in that the metal be zinc,
One or more of iron, tin, lead, silver, copper, platinum.
6. nano modification coloured polypropylene composite material according to claim 2, which is characterized in that the metal oxygen
Compound be sodium oxide molybdena, potassium oxide, calcium oxide, zinc oxide, iron oxide, tin oxide, lead oxide, copper oxide, magnesia, barium monoxide,
Strontium oxide strontia, aluminium oxide, gallium oxide, indium oxide, thallium oxide, germanium oxide, tin oxide, lead oxide, antimony oxide, bismuth oxide, oxidation polonium
One or more of；The mass ratio of the nano particle and silica of the metal or metal oxide is (0.1-0.4): 1.
7. nano modification coloured polypropylene composite material according to claim 1, which is characterized in that the nylon particles are
The retrogradation of single poly- PP GRANULES, copolymer polypropylene particle, single poly- PP GRANULES is expected, in the retrogradation material of copolymer polypropylene particle
Any one.
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| CN110592766A (en) * | 2019-09-19 | 2019-12-20 | 界首市远航织带有限公司 | Preparation method of nylon woven tape with high dye-uptake |
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