CN108467544A - A kind of high-strength, high rigid and transparent modified polypropylene composite material and preparation method - Google Patents
A kind of high-strength, high rigid and transparent modified polypropylene composite material and preparation method Download PDFInfo
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- CN108467544A CN108467544A CN201810304995.9A CN201810304995A CN108467544A CN 108467544 A CN108467544 A CN 108467544A CN 201810304995 A CN201810304995 A CN 201810304995A CN 108467544 A CN108467544 A CN 108467544A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The present invention discloses a kind of high-strength, high rigid and transparent modified polypropylene composite material and preparation method.The composite material includes polypropylene, fluorophologopite, compatilizer, antioxidant, nucleating agent, lubricant, optional ZnOw and optional nano zine oxide.Fluorophologopite is added by side feeding, gained composite material has high mechanical performance, it can be achieved that the low filling of composite material, high-performance.While PP composite material enhances, transparent feature is shown.Further compounded by ZnOw and fluorophologopite, realize the matrix white space reinforcement and filler that small size ZnOw bridges between sheet mica and generates, and combine nano zine oxide in the nanometer advantage of enhancing by polymer, the collaboration enhancing for taking full advantage of the micro- of different scale, Nano filling the different scale space in basis material, effectively realizes low filling, the high performance of polypropylene material.
Description
Technical field
The invention belongs to PP composite material technical fields, and in particular to a kind of high intensity, high rigidity and transparent modified
PP composite material and preparation method thereof.
Background technology
A kind of thermoplastic resin of prepared by polypropylene plastics is by propylene polymerization, usually semi-transparent clear, odorless nothing
Poison can use moise-heat sterilization, corrosion-resistant, and mechanical performance and the transparency are all better than polyethylene, be a kind of the general of excellent combination property
Plastics.It can be most importantly modified by modes such as blending, enhancing, fillings, to realize that polypropylene material is logical
With plastic engineering, high performance, meet it in household electrical appliance, inner and outer decorative parts of automobile, body-building, office appliance and sanitary ware etc.
The demand of application field.
Fiber glass reinforced polypropylene material has many advantages, such as that mechanical properties strength is high, heat-resist, dimensionally stable, glass fibre
The intensity and modulus of reinforced polypropylene can match in excellence or beauty engineering plastics, can be realized in practical applications to mould Dai Gang and substitution engineering
Plastics meet the requirement of the fields such as automobile, household electrical appliances high strength structure product.But since glass has compared with high length-diameter ratio, in mould
Glass fibre, which is easy to be orientated, during modeling causes the strength of materials and shrinks to generate anisotropy, therefore in relatively thin product product
In, glass fibre orientation easily causes product that warpage occurs, and fiber glass reinforced polypropylene is made to be wanted to precision size type and flatness
Application is restricted in terms of seeking higher machine components.And the floating fibre in glass fibre reinforced composite material can also seriously affect material
Appearance characteristics.And the filled modified polypropylenes composite material such as current other inorganic material such as calcium carbonate, talcum powder, generally there are
Following disadvantage：Mechanical strength, inflexible target are insufficient, and modified composite material is usually opaque milky, sacrifice matrix
The original transparent nature of material, influences material appearance performance etc., this largely limits polyacrylic application range.Cause
This, the exploitation of high intensity, excellent appearance, isotropic high-performance modified polypropylene composite material has become competing with market
Strive the product of power.
Mica is laminated structure, has larger radius-thickness ratio, is typically two-dimentional reinforcing material, therefore mica filled polyene
Hydrocarbon has the characteristics that higher-strength, rigid and good dimensional stability, insulating properties.
Chinese patent CN102093636A discloses a kind of mica modified polypropylene composite material, as a result shows mica more
Effectively improve the polyacrylic mechanical property of materials.It is disadvantageous in that：The additive amount of mica is very high in its composite material (reaches
56wt%), it is far above the content (30%) of resin matrix, causes mica to be reunited serious, does not give full play to two-dimentional mica enhancing
Material property is also unsatisfactory for the light-weighted development trend of current composite material.Moreover, when loading is larger, material is also improved
Expect difficulty of processing.In addition, compatilizer (maleic anhydride inoculated polypropylene) ratio being added in composite material is higher, on the one hand increase
The input of material cost, is on the other hand unfavorable for the TVOC of material and ageing-resistant property.
It is multiple that Chinese patent CN103554666A, CN106009285A and CN103772816A disclose Mica Reinforced Polypropylene
Condensation material and preparation method thereof, the method are to mix mica, polypropylene, auxiliary agent in plastic barrel or high speed mixer to stir
It mixes uniformly, carries out squeezing out blending molding by main spout, be cut in the blending process by the high intensity of melt zone due to material
It cuts, the big laminated structure of mica is caused to be destroyed, radius-thickness ratio is greatly lowered, mica obtained by the method/PP composite material machinery
Performance boost amplitude is smaller, and modified polypropylene composite material is caused to differ greatly with engineering plastics performance indicator.
In addition, most of patents for preparing mica modified polypropylene composite material all use sericite (CN101580613B
And CN102532691B) or the natural micas powder such as wet method white mica powder (CN104419059A), one side physical grinding mica
The radius-thickness ratio and lamellar spacing of powder are uneven, on the other hand contain more Fe in natural mineral resources2O3(3.0%-6.0%) and
TiO2Metal impurities such as (0.6-0.9%) not only influence mica powder whiteness, but also polymer material can be caused to degrade and influence it
The properties such as anti-aging, transparent.
There are no a kind of while having the polypropylene composite materials material of high intensity, high rigidity and transparent nature in currently available technology
Material.
Invention content
The technical problem of being solved of the invention is exactly that mica in mica/PP composite material in the prior art is overcome to add
Amount is high, composite material machinery performance not prominent and bad material appearance defect, provides a kind of high intensity, high rigidity and transparent
Modified polypropylene composite material and preparation method thereof.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of PP composite material, calculates by weight, including following components：60-90 parts of polypropylene, fluorophologopite
10-40 parts, 1-5 parts of compatilizer, 0.4-0.7 parts of antioxidant, 0.2-0.5 parts of nucleating agent, 0.2-0.5 parts of lubricant.Preferably, gather
70-80 parts of propylene, 20-30 parts of fluorophologopite, 3-5 parts of compatilizer, 0.4-0.6 parts of antioxidant, 0.3-0.4 parts of nucleating agent, lubrication
0.3-0.4 parts of agent.
Preferably, PP composite material of the present invention, calculates by weight, including following components：Polypropylene 60-
90 parts, 10-40 parts of fluorophologopite, 3-8 parts of ZnOw, 1-5 parts of compatilizer, 0.4-0.7 parts of antioxidant, nucleating agent 0.2-
0.5 part, 0.2-0.5 parts of lubricant.Preferably, polypropylene 70-80 parts, 20-25 parts of fluorophologopite, 3-5 parts of ZnOw, phase
Hold 3-5 parts of agent, 0.4-0.6 parts of antioxidant, 0.3-0.4 parts of nucleating agent, 0.3-0.4 parts of lubricant.
It is furthermore preferred that PP composite material of the present invention, calculates by weight, including following components：Polypropylene
60-90 parts, 10-40 parts of fluorophologopite, 3-8 parts of ZnOw, 0.5-1.0 parts of nano zine oxide, 1-5 parts of compatilizer, antioxygen
0.4-0.7 parts of agent, 0.2-0.5 parts of nucleating agent, 0.2-0.5 parts of lubricant.It is preferred that 70-80 parts of polypropylene, fluorophologopite 20-25
Part, 3-5 parts of ZnOw, 0.8-1.0 parts of nano zine oxide, 3-5 parts of compatilizer, 0.4-0.6 parts of antioxidant, nucleating agent 0.3-
0.4 part, 0.3-0.4 parts of lubricant.
Polypropylene of the present invention is one kind in homopolypropylene and/or atactic copolymerized polypropene, melt flows speed
Rate is at 10-60g/10min (230 DEG C, 2.16kg).
The chemical structural formula of fluorophologopite of the present invention is KMg3(AlSi3O10)F2, mica average grain diameter is 20-80 μ
M, draw ratio >=60, whiteness 94-96.
Fe in fluorophologopite of the present invention2O3Content≤0.25wt%, and TiO2≤ 0.1wt%.
ZnOw of the present invention is three-dimensional four acicular textures, and needle-shaped body length is 1-10 μm.
Nano zine oxide of the present invention is fibrous whisker, and grain size is about 20-100nm.
It is sweet that compatilizer of the present invention is maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, acrylic acid shrink
It is one or more in grease graft polypropylene and butyl methacrylate graft polypropylene.
Antioxidant of the present invention includes primary antioxidant and auxiliary anti-oxidant, and the primary antioxidant includes hindered phenol and hindered amine
It is one or more in kind antioxidant；The auxiliary anti-oxidant includes one kind or more in thioesters class and phosphite ester kind antioxidant
Kind.
Preferably, the mass ratio of primary antioxidant and auxiliary anti-oxidant of the present invention is 0.5-1：1.
Primary antioxidant of the present invention is preferably N, and N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono)
Hexamethylene diamine (antioxidant 1098), β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol ester (antioxidant 1076),
N, N '-bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazines (antioxidant 1024) and four (β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid) it is one or more in pentaerythrite (antioxidant 1010).
Auxiliary anti-oxidant of the present invention is preferably three (2,4- di-tert-butyl-phenyls) phosphite esters (irgasfos 168), double
One kind in (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites (antioxidant 626) and the double octadecyls of thio-2 acid
Or it is a variety of.
Nucleating agent of the present invention is the organic transparent nucleater of polypropylene, preferably aromatic acid metal soap, two
It is one or more in benzylidene sorbitol alcohols and organic phosphate.
Lubricant of the present invention includes in the double hard amides of atoleine, stearate, butyl stearate and ethylene
It is one or more.
Prepare PP composite material of the present invention can be to carry out in equipment known in the art, preferred twin-screw
Extruder.
The present invention also provides a kind of methods preparing PP composite material, include the following steps：Proportionally, by poly- third
Alkene, compatilizer, antioxidant, nucleating agent, lubricant are uniformly mixed in high mixer, are then added to twin-screw by main spout
Extruder, while fluorophologopite is added by the lateral spout of double screw extruder, melting extrusion is granulated, by water cooling, cuts
Grain obtains sheet mica modified polypropylene composite material；To reduce the failure by shear of fluorophologopite, it is fed in the side of postposition
Material mouth is added.
When containing ZnOw in the composition of PP composite material of the present invention, the polypropylene for preparing is answered
The method of condensation material, includes the following steps：Proportionally, polypropylene, compatilizer, antioxidant, nucleating agent and lubricant are existed
High mixer is uniformly mixed, and is then added to double screw extruder by main spout, while fluorophologopite passes through twin-screw extrusion
The lateral spout of postposition of machine is added, and ZnOw is added by main spout and/or side spout, melting extrusion is made
Grain obtains sheet mica modified polypropylene composite material by water cooling, pelletizing；Preferably, by ZnOw and fluorine gold cloud
Mother stock is not added by the preposition of extruder, the lateral spout of postposition.
When containing ZnOw and nano zine oxide in the composition of PP composite material of the present invention, in order to
So that nano zine oxide obtains more preferable dispersion, the present invention uses nano zine oxide master batch (nano zine oxide and polyacrylic mixing
Object) form.The method for preparing PP composite material, includes the following steps：Proportionally, by polypropylene, nano oxygen
Change zinc master batch, compatilizer, antioxidant, nucleating agent and lubricant, is uniformly mixed in high mixer, is then added by main spout
Pass through the preposition of extruder, the lateral spout of postposition respectively to double screw extruder, while by ZnOw and fluorophologopite
It is added, melting extrusion is granulated, and by water cooling, pelletizing, that is, obtains sheet mica modified polypropylene composite material.
The temperature of double screw extruder of the present invention is 170-230 DEG C, and rotating speed is 150-300 revs/min, and twin-screw squeezes
Go out machine draw ratio (L/D) be 35-50, be respectively equipped with after the main spout of double screw extruder preposition lateral spout and
The lateral spout of postposition；Preferably, the preposition lateral spout is located at 1/3 of spiro rod length after main spout, described
The lateral spout of postposition is located at 2/3 of spiro rod length after main spout.
Compared with prior art, the present invention having the advantages that：By adjusting each group distribution ratio and processing technology, system
The composite material for obtaining Mica Reinforced Polypropylene has the following advantages：
(1) present invention by side feeding manner be added low impurity, high-purity fluorophologopite, and carry based on formula is preferred
Compatibility between high polypropylene and mica, the invention, which prepares composite material, has high mechanical performance, with existing similar formula
For example natural sericite of material etc. is compared, it can be achieved that the low filling of composite material, high-performance, the composite material of gained have high intensity,
The characteristics of high rigidity.
(2) modified composite material that obtains of the present invention has both high-strength, high rigidity matter simultaneously, more standby transparent feature,
For composite material light transmittance between 44%-52%, it is visual to meet material for presentation and transparent feature similar in resin matrix
It is required that.Mica by the way that specific structure is added improves the transparency of product, at present in polypropylene modification application not yet
It is related to.This point, which is largely different from the fillings such as other inorganic material such as calcium carbonate, talcum powder, can all sacrifice modified material
Transparent nature, and opaque milky appearance is presented.
(3) present invention is further in such a way that ZnOw and mica compound according to a certain percentage, and based on processing
The regulation and control of technique enable to the ZnOw of reduced size during being coated to mica with polypropylene matrix, very
The matrix white space for bridging well and generating between sheet mica carries out reinforcement and filler, has given full play to two kinds of filler complementations
Enhancing effect is cooperateed with, the tensile strength of composite material, bending strength and bending modulus are enhanced.
(4) the present invention is based on zinc oxide cooperateed with mica enhancing while, filled out than conventional micron grade in conjunction with nano zine oxide
Material size advantage in terms of enhancing by polymer so that fluorophologopite, ZnOw and nano zine oxide can make full use of not
Same scale, the micron of shape, Nano filling the different scale spatial cooperation enhancing effect in basis material, it is mica filled reducing
While amount, composite material still has excellent mechanical performance (tensile strength, bending strength, bending modulus), effectively realizes
The low filling of polypropylene material, high performance.
(5) mechanical property and appearance characteristics of present invention gained modified polypropylene composite material have excellent effect, can expire
The field manufacture of sufficient high rigidity, high rigidity needs, especially in auto industry, aerospace industry.
Specific implementation mode
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited solely to implement
Example should also include other any well known changes in scope of the presently claimed invention.
Double screw extruder：(Nanjing) Machinery Co., Ltd. grand again of section, model C TE35PLUS.
Polypropylene：Homopolypropylene, sandstoneization 6012 in Tianjin；
Mica, Hua Jing micas Co., Ltd, model synthetic mica fluorophologopite HC800 and wet method muscovite W800；
Antioxidant：Ciba fine chemicals, model 1010 and 168,626；
Compatilizer：Maleic anhydride inoculated polypropylene, Jiangsu Jia Yirong compatilizers Co., Ltd, model 9801；
Nucleating agent：Glucitol derivative Millad3988, Milliken companies of the U.S.；
Lubricant：Calcium stearate；
ZnOw:Hao Xi nanosecond science and technology (Shanghai) Co., Ltd., three-dimensional four acicular textures, needle-shaped body length are
3.0μm；
Nano zine oxide is fibrous whisker, and grain size is about 40nm.
Embodiment 1
1), weigh by weight 90 parts of polypropylene, 1 part, 0.3 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.4 part
Irgasfos 168,0.5 portion of nucleating agent, 0.3 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and with postposition
Lateral feeding 10 parts of micas (HC800) of (Section eight) addition, melt under conditions of 180 DEG C of temperature and rotating speed are 150 revs/min
It squeezes out, is extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son carries out injection molding and breaks into batten, carries out Mechanics Performance Testing respectively, the results are shown in Table 1.
Embodiment 2
1), take 80 parts of polypropylene, 3 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.4 part of irgasfos 168,
0.4 portion of nucleating agent, 0.4 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and postposition side
To feeding 20 parts of micas (HC800) of (Section eight) addition, melting is crowded under conditions of 200 DEG C of temperature and rotating speed are 180 revs/min
Go out, is extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son, then plastic pellet is cut by pelleter, it carries out injection molding and breaks into batten, carry out Mechanics Performance Testing respectively, the results are shown in Table 1.
Embodiment 3
1), take 70 parts of polypropylene, 5 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.3 part of irgasfos 168,
0.3 portion of nucleating agent, 0.5 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and postposition side
To feeding 30 parts of micas (HC800) of (Section eight) addition, melting is crowded under conditions of 210 DEG C of temperature and rotating speed are 200 revs/min
Go out, is extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son, then plastic pellet is cut by pelleter, it carries out injection molding and breaks into batten, carry out Mechanics Performance Testing respectively, the results are shown in Table 1.
Embodiment 4
1), take 60 parts of polypropylene, 7 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.2 part of irgasfos 168,
0.2 portion of nucleating agent, 0.3 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and postposition side
To feeding 40 parts of micas (HC800) of (Section eight) addition, melting is crowded under conditions of 220 DEG C of temperature and rotating speed are 300 revs/min
Go out, is extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son, then plastic pellet is cut by pelleter, it carries out injection molding and breaks into batten, carry out Mechanics Performance Testing respectively, the results are shown in Table 1.
Comparative example 1
1), take 70 parts of polypropylene, 5 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.2 part of irgasfos 168,
0.3 portion of nucleating agent and 0.4 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and postposition side
30 parts of another wet method mica W800, the condition for being 180 revs/min in 210 DEG C of temperature and rotating speed is added for (Section eight) to feeding
Lower melting extrusion, is extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son, then plastic pellet is cut by pelleter, it carries out injection molding and breaks into batten, carry out Mechanics Performance Testing respectively, the results are shown in Table 1.
1 properties of sample test result of table
| Performance | PP resins | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Density (g/cm3, ISO 1183) | 0.86 | 0.95 | 1.03 | 1.13 | 1.21 | 1.12 |
| MFI (g/10min, 230 DEG C, 2.16kg) | 11.3 | 9.6 | 7.8 | 6.1 | 5.3 | 7.4 |
| Tensile strength (MPa, ISO 527-2) | 38 | 43.4 | 46.5 | 56.8 | 45.7 | 44.2 |
| Elasticity modulus (MPa, ISO 527-2) | 2358 | 3897 | 5045 | 6226 | 7058 | 4240 |
| Elongation at break (%, ISO 527-2) | 40 | 16 | 10 | 3.2 | 3.8 | 12 |
| Bending strength (MPa, ISO 178) | 60.4 | 64.5 | 68.3 | 73.8 | 74.7 | 62.6 |
| Bending modulus (MPa, ISO 178) | 2032 | 3696 | 4705 | 5815 | 6230 | 3791 |
| Light transmittance (%, 1mm) | 56% | 52% | 48% | 48% | 36% | 12% |
As can be seen from Table 1：Compared to polypropylene pure resin, sheet fluorophologopite is added in polypropylene and obtains being modified poly- third
Alkene composite material, the tensile strength of material, elasticity modulus, bending strength, bending modulus are obtained with mica content increase
It is significantly promoted, especially elasticity modulus and bending modulus, the rigidity and intensity of modified material is greatly improved.Prepared
There are modified material very good mechanical properties, batten tensile strength to be up to 56.8MPa, and increasing degree is about 49% compared with PP；
For bending strength up to 73.8MPa, increasing degree is about 22%；Bending modulus reaches 5815MPa, and increasing degree is about 186%.System
Standby material has high intensity and rigidity, can substitute the engineering plastics of higher costs, cost purpose is reduced to reach.System
Standby composite material have high mechanical performance, compared with such as natural wet method mica of existing similar formula materials, it can be achieved that
The low filling of composite material, high-performance.
In comparative example 1, opaque Dark grey is presented in wet method mica (W800) modified polypropylene composite material, is modified
Tensile strength and bending strength, the bending modulus promotion amplitude of composite material are only (real with 10 parts of fluorophologopite modified composite materials
Apply example 1) performance it is suitable.
Modified polypropylene composite material still keeps its transparent nature, composite material by different numbers are mica filled modified
With higher light transmittance, the regulation and control to the apparent property of material are more advantageous to, are met under different application field to material appearance
Demand.Wet method mica (W800) modified polypropylene composite material, is presented opaque Dark grey in comparative example 1, and light transmittance is only
12%.
Embodiment 5
1), take 70 parts, 5 parts ZnOws of polypropylene, 5 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene,
0.2 part of antioxidant, 626,0.3 portions of nucleating agents and 0.4 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and postposition side
To spout 25 parts of micas (HC800) of (Section eight) addition, melted under conditions of 210 DEG C of temperature and rotating speed are 180 revs/min
It squeezes out, is extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son carries out injection molding and breaks into batten, carries out Mechanics Performance Testing respectively, the results are shown in Table 2.
Embodiment 6
1), take 70 parts of polypropylene, 5 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.2 part of antioxidant 626,
0.3 portion of nucleating agent and 0.4 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and preposition side
5 parts of ZnOws and the lateral feeding of postposition (Section eight) 25 parts of micas (HC800) of mouth are added for (Section five) to spout, in temperature
210 DEG C of degree and rotating speed are melting extrusion under conditions of 180 revs/min, are extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son carries out injection molding and breaks into batten, carries out Mechanics Performance Testing respectively, the results are shown in Table 2.
Embodiment 7
1), take 70 parts of polypropylene, 5 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.2 part of antioxidant 626,
0.3 portion of nucleating agent and 0.4 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and postposition side
To spout (Section eight) while 25 parts of micas (HC800) and 5 parts of ZnOws are added, are 180 in 210 DEG C of temperature and rotating speed
Melting extrusion under conditions of rev/min is extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son carries out injection molding and breaks into batten, carries out Mechanics Performance Testing respectively, the results are shown in Table 2.
Embodiment 8
1), take 70 parts of polypropylene, 5 parts, 0.2 part antioxidant 1010 of maleic anhydride inoculated polypropylene, 0.2 part of antioxidant 626,
0.3 portion of nucleating agent and 0.4 part of lubricant were uniformly mixed in high-speed mixer and mixing 2-3 minutes；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and preposition side
To (Section five) addition 22 parts of micas (HC800) of 8 parts of ZnOws and the lateral spout of postposition (Section eight) of spout, in temperature
210 DEG C of degree and rotating speed are melting extrusion under conditions of 180 revs/min, are extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son carries out injection molding and breaks into batten, carries out Mechanics Performance Testing respectively, the results are shown in Table 2.
Embodiment 9
1) content that nano zine oxide, first, is prepared into nano zine oxide with polypropylene by screw extruder is
50wt% master batch forms take 5 parts, 1 part 69.5 parts of polypropylene, maleic anhydride inoculated polypropylene nano zine oxide polypropylene female later
Grain, 0.2 part of antioxidant 1010,0.2 part of antioxidant, 626,0.2 portions of nucleating agents and 0.4 part of lubricant are at high-speed mixer and mixing 2-3 points
Clock is uniformly mixed；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and preposition side
To (Section five) addition 24 parts of micas (HC800) of 4 parts of ZnOws and the lateral spout of postposition (Section eight) of spout, in temperature
210 DEG C of degree and rotating speed are melting extrusion under conditions of 180 revs/min, are extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son carries out injection molding and breaks into batten, carries out Mechanics Performance Testing respectively, the results are shown in Table 2.
Embodiment 10
1) content that nano zine oxide, first, is prepared into nano zine oxide with polypropylene by screw extruder is
50wt% master batch forms take 5 parts, 2 parts 69 parts of polypropylene, maleic anhydride inoculated polypropylene nano zine oxide polypropylene female later
Grain, 0.2 part of antioxidant 1010,0.2 part of antioxidant, 626,0.2 portions of nucleating agents and 0.4 part of lubricant are at high-speed mixer and mixing 2-3 points
Clock is uniformly mixed；
2), the raw material in the step 1) after mixing is taken out, pours into twin-screw extrusion machine inlet, and preposition side
To (Section five) addition 23 parts of micas (HC800) of 3 parts of ZnOws and the lateral spout of postposition (Section eight) of spout, in temperature
210 DEG C of degree and rotating speed are melting extrusion under conditions of 180 revs/min, are extruded into the initial material of strip；
3), by the initial material obtained in the step 2) through cooling in water-carrying groove and air, then plastic pellet is cut by pelleter
Son carries out injection molding and breaks into batten, carries out Mechanics Performance Testing respectively, the results are shown in Table 2.
2 properties of sample test result of table
| Performance | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Density (g/cm3, ISO 1183) | 1.13 | 1.13 | 1.13 | 1.14 | 1.11 | 1.10 |
| MFI (g/10min, 230 DEG C, 2.16kg) | 5.9 | 5.6 | 6.4 | 5.4 | 5.5 | 5.2 |
| Tensile strength (MPa, ISO 527-2) | 54.8 | 62.5 | 52.3 | 60.5 | 63.9 | 65.6 |
| Elasticity modulus (MPa, ISO 527-2) | 6254 | 6670 | 6060 | 6430 | 6874 | 7054 |
| Elongation at break (%, ISO 527-2) | 3.0 | 2.8 | 3.4 | 3.2 | 3.0 | 2.6 |
| Bending strength (MPa, ISO 178) | 74.4 | 80.4 | 72.2 | 76.6 | 82.3 | 84.4 |
| Bending modulus (MPa, ISO178) | 5610 | 6260 | 5626 | 6074 | 6521 | 6650 |
| Light transmittance (%, 1mm) | 44% | 49% | 46% | 44% | 47% | 52% |
The present invention is based on material feeding process further in such a way that ZnOw and mica compound according to a certain percentage
Regulation and control such as embodiment 5, embodiment 6 and embodiment 7, optimize composite material preparation process, improve the performance of composite material.
It is found by comparing, ZnOw is first passed through into (embodiment in preposition lateral spout in advance evenly dispersed polypropylene matrix
6) it, on the one hand avoids melt zone high shear when whisker is added in main feeding manner to cause damaged (embodiment 5), on the other hand again not
When being introduced simultaneously as mica in embodiment 7 and whisker, big sheet mica barrier whisker intercalation is evenly dispersed.Added by embodiment 6
Work mode makes the ZnOw of reduced size during being coated to mica with polypropylene matrix, well to sheet
The matrix white space for bridging and generating between mica carries out reinforcement and filler, has given full play to two kinds of filler complementation collaboration enhancing effects
Fruit, tensile strength and bending strength, the bending modulus for further improving composite material are as shown in table 2.
While the present invention is based further on ZnOw and cooperates with enhancing with mica, nano zine oxide is combined than conventional
Micron order material unique quantum size effect, skin effect and synergistic effect etc. in terms of enhancing by polymer is nano combined excellent
Gesture introduces nano zine oxide by main feeding in the form of master batch, takes full advantage of different scale, the micron of shape, Nano filling
The spatial cooperation enhancing effect in basis material further improves the drawing of composite material while reducing mica filled amount
Intensity and rigidity are stretched, low filling, the high performance (embodiment 9, embodiment 10) of polypropylene material are effectively realized.
Above example is only described to the preferred embodiment of the present invention, rather than to the limit of the scope of the present invention
System, although being explained in detail to the present invention with reference to preferred embodiment, it will be understood by those of ordinary skill in the art that, to this hair
Bright technical solution is modified or replaced equivalently all variations and modifications made, and should all fall into the claim of the present invention
In the protection domain that book determines.
Claims (11)
1. a kind of PP composite material, calculates by weight, including following components：60-90 parts of polypropylene, fluorophologopite 10-
40 parts, 1-5 parts of compatilizer, 0.4-0.7 parts of antioxidant, 0.2-0.5 parts of nucleating agent, 0.2-0.5 parts of lubricant；Preferably, including
Following components：70-80 parts of polypropylene, 20-30 parts of fluorophologopite, 3-5 parts of compatilizer, 0.4-0.6 parts of antioxidant, nucleating agent 0.3-
0.4 part, 0.3-0.4 parts of lubricant.
2. PP composite material according to claim 1, it is characterised in that：It calculates by weight, including following components：
60-90 parts of polypropylene, 10-40 parts of fluorophologopite, 3-8 parts of ZnOw, 1-5 parts of compatilizer, 0.4-0.7 parts of antioxidant, at
0.2-0.5 parts of core agent, 0.2-0.5 parts of lubricant；Preferably, including following components：70-80 parts of polypropylene, fluorophologopite 20-25
Part, 3-5 parts of ZnOw, 3-5 parts of compatilizer, 0.4-0.6 parts of antioxidant, 0.3-0.4 parts of nucleating agent, lubricant 0.3-0.4
Part.
3. PP composite material according to claim 1 or 2, it is characterised in that：It calculates by weight, including with the following group
Point：60-90 parts of polypropylene, 10-40 parts of fluorophologopite, 3-8 parts of ZnOw, 0.5-1.0 parts of nano zine oxide, compatilizer 1-
5 parts, 0.4-0.7 parts of antioxidant, 0.2-0.5 parts of nucleating agent, 0.2-0.5 parts of lubricant；Preferably, including following components：Poly- third
70-80 parts of alkene, 3-5 parts of ZnOw, 0.8-1.0 parts of nano zine oxide, 3-5 parts of compatilizer, resists 20-25 parts of fluorophologopite
0.4-0.6 parts of oxygen agent, 0.3-0.4 parts of nucleating agent, 0.3-0.4 parts of lubricant.
4. according to claim 1-3 any one of them PP composite materials, it is characterised in that：The polypropylene is selected from homopolymerization
Polypropylene and/or atactic copolymerized polypropene, melt flow rate (MFR) is at 10-60g/10min (230 DEG C, 2.16kg).
5. according to claim 1-4 any one of them PP composite materials, it is characterised in that：The change of the fluorophologopite
Structural formula is KMg3(AlSi3O10)F2, average grain diameter is 20-80 μm, draw ratio >=60, whiteness 94-96.
6. according to claim 1-5 any one of them PP composite materials, it is characterised in that：In the fluorophologopite
Fe2O3Content≤0.25wt%, and TiO2≤ 0.1wt%.
7. according to claim 1-6 any one of them PP composite materials, it is characterised in that：The ZnOw is
Three-dimensional four acicular textures, needle-shaped body length are 1-10 μm.
8. according to claim 1-7 any one of them PP composite materials, it is characterised in that：The nano zine oxide is
Fibrous whisker, grain size 20-100nm.
9. a kind of method preparing PP composite material described in claim 1, includes the following steps：Proportionally, will gather
Propylene, compatilizer, antioxidant, nucleating agent, lubricant are uniformly mixed in high mixer, are then added to double spiral shells by main spout
Bar extruder, while fluorophologopite is added by the lateral spout of extruder, melting extrusion is granulated, and by water cooling, pelletizing, is obtained
To the PP composite material；Preferably, fluorophologopite is added by the postposition side spout of extruder.
10. a kind of method preparing the PP composite material described in claim 2, includes the following steps：Proportionally, will gather
Propylene, compatilizer, antioxidant, nucleating agent and lubricant are uniformly mixed in high mixer, are then added to by main spout double
Screw extruder, while fluorophologopite is added by the lateral spout of postposition of extruder, and ZnOw is passed through main feeding
Mouth and/or lateral spout are added, and melting extrusion is granulated, and by water cooling, pelletizing, obtains the PP composite material；It is preferred that
, ZnOw is added by the preposition lateral spout of extruder.
11. a kind of method preparing the PP composite material described in claim 3, includes the following steps：Proportionally, will gather
Propylene, nano zine oxide master batch, compatilizer, antioxidant, nucleating agent and lubricant are uniformly mixed in high mixer, then pass through
Main spout is added to double screw extruder, while ZnOw being added by the preposition lateral spout of extruder, fluorine
Phlogopite is added by the lateral spout of postposition of extruder, and melting extrusion is granulated, and by water cooling, pelletizing, obtains described poly- third
Alkene composite material.
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| CN111763379A (en) * | 2020-07-16 | 2020-10-13 | 金发科技股份有限公司 | High-light-transmittance and light-weight polypropylene composite material and preparation method thereof |
| CN113372651A (en) * | 2021-07-16 | 2021-09-10 | 北海市传创环保科技有限公司 | High-strength and high-toughness polypropylene injection molding material |
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