CN107200919A - A kind of injection grade micro-foaming polypropylene composite material and preparation method thereof - Google Patents
A kind of injection grade micro-foaming polypropylene composite material and preparation method thereof Download PDFInfo
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- CN107200919A CN107200919A CN201710487379.7A CN201710487379A CN107200919A CN 107200919 A CN107200919 A CN 107200919A CN 201710487379 A CN201710487379 A CN 201710487379A CN 107200919 A CN107200919 A CN 107200919A
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- C—CHEMISTRY; METALLURGY
- 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
- C08L23/10—Homopolymers or copolymers of propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of injection grade micro-foaming polypropylene composite material and preparation method thereof.A kind of injection grade micro-foaming polypropylene composite material, is configured to by following raw material：Polypropylene, toughener, inorganic mineral powder master batch, foaming master batch, nucleator, smell remover, damage resistant auxiliary agent and aging auxiliary agent.The present invention can realize good injection foaming effect on existing commercially available conventional polypropylene base resin by adding inorganic mineral powder master batch, nucleator and foaming master batch.And, the rigid-tough balance of material is realized by adding the various additives such as toughener, scratch resistance auxiliary agent, smell removal auxiliary agent, surface scratch resistance, the various characteristic requirements such as low smell, low VOC environmental protection characteristics, so as to meet the application demand of various automobile injection-moulded plastic parts.
Description
Technical field
The present invention relates to a kind of injection grade micro-foaming polypropylene composite material and preparation method thereof, belong to high polymer material skill
Art field.
Background technology
Lightweight, energy-conserving and environment-protective and efficiently at low cost production be always the target persistently pursued of auto industry.Polypropylene
Material is due to being that one kind has very high cost performance（Relatively low proportion, good mechanical property and recuperability, excellent shaping are special
Property and cheap price）Material, therefore, the application on automobile plastic parts all the time is constantly expanded, when
It is preceding to be widely used in each main automobiles such as bumper, fascia, door-plate, centre gangway, decorations post, luggage case
On plastic items.
However, replace since the polypropylene material the work of expensive engineering plastics or bulky metal material with
Come, develop by the technology of decades, this alternative work for a certain degree it may be said that progressively close to ultimate attainment,
In a short time for the angle of material substitution, it is difficult to have larger progress.Therefore, under existing material system, how to enter
The weight of one step reduction part, the production efficiency of raising product, automobile lightweight, the higher target of energy-saving and emission-reduction, simultaneously
More preferable economic benefit is brought for main engine plants, the focus paid close attention to jointly as domestic and international industry.
Based on automobile industry development such a lasting demand and state of development, it can be applied to if one kind can be developed
The polypropylene micro-foaming material of injection molding, this material can be using polypropylene material as matrix, by Shooting Technique, in gas
In the presence of pressure, product intermediate layer size of gathering is set to have the epidermis knot of densification from ten to tens microns of closed porosity and both sides
Structure, then, this material technology undoubtedly can cause automobile plastic parts to realize the purpose of further material-saving and loss of weight.
It is however known that polypropylene is a kind of Crystalline plastics, its foaming can only enter near crystalline melt point
OK, more than fusing point, melt viscosity declines rapidly.This polyacrylic characteristic make it that its foaming is extremely difficult.Conventional is poly-
The phenomenons such as substantial amounts of and hole, depression generally occur in foaming for propylene material, are not suitable for very much foaming.For
This, people have done substantial amounts of work, it would be desirable to find a kind of modified polypropylene material suitable for foaming.These current works
It is concentrated mainly on following several respects：1. in terms of melt strength：Patent CN201310727868.7 is reported by polypropylene
Metallocene polypropylene elastomer is introduced in basic components, PP and POE compatibility is improved, improves the melt strength of material,
By common injection molding, though optimized in mechanical property, density reduction it is unobvious, only 14%, in addition he used hair
Infusion ADC, it, which foams, decomposes the NH3 of generation environment pollution, is not suitable for popularization and application；Patent CN201511019983.4 is reported
The polyethylene of C60 modifications is introduced in polypropylene basic components to improve the melt strength of material, then adds NaHCO3It is micro-
Capsule foaming agent, obtained expanded material, though abscess is tiny, density reduction, impact property is undesirable, and cost of manufacture is also held high
It is expensive, therefore it is also not suitable for popularization and application；In addition, patent JP 2001-226510 A reports in polypropylene basic components by introducing
Crosslinking agent or Silane Grafted thermoplastic resin improve the melt strength of material, and non-cross-linking PP introduces long-chain branch by radiating
To provide melt strength；Patent JP H09-188774 A report the introducing polyisoprene monomer in polypropylene basic components
And initiator, patent US 8552116 is also similarly reported introduces linear polypropylene, conjugate diene monomer in basic components
And initiator, melt strength is improved by radical polymerization, the foamed plastics of highly expanded rate can be obtained, still, in melting
During resin viscosity increase it is excessive, cause injection molding difficult.In addition, current mark, the apparent mass such as molding defect can not yet
It is good.2. in terms of powder cladding：Patent CN201410357528.4 is reported, by being added in high filled polypropylene basic material
The foaming master batch of cladding, though reducing density after fretting map, reduces material cost, its notched impact properties and melt index
It is smaller, suitable for application in larger plastic items shaping；Patent CN201410112802.1 is reported by polypropylene
Cladded type foaming powder is added in basic components, though obtaining the tiny micro-foaming material of abscess, foam powder body manufacturing process is numerous
It is trivial, using a large amount of solvents, be not suitable for large-scale production.3. in terms of shaping：Patent WO 2009/060792 and WO 2005/
026255, which reports a kind of linear polypropylene, is introduced in melt index≤30g/10 min, melt tension >=5cN polypropylene
In, the mobility of material is improved, the mouldability of material is optimized, but it is when running into area and being more than 0.2m2 large mold, stream
Dynamic property is still inadequate；Introduce polyolefin-wax to improve the mobility of material in patent JP 2008-101060 A report materials, optimize
The mouldability of material, still, being excessively used for wax can reduce the overall physical properties of expanded material.
Described on end, the report in terms of fretting map is more scattered single at present, otherwise only consider the factor of melt strength,
Only consider the cladding or surface treatment factor of foaming powder, or considering the shaping flowing sexual factor of material, they are all only
The subproblem of micro-foaming material making is solved, generally solving the technology that runs into of fretting map injection polypropylene without system asks
Topic.However, for automobile injection-moulded plastic parts, the polypropylene material that can be applied to micro foaming injection moulding must be same
When meet expandable, material shaping mobility, part outward appearance, the mechanical property of material, the feature of environmental protection and cost of material etc.
The factor that system is integrated.If therefore, wanting the good popularization and application of injection grade micro-foaming polypropylene, it is necessary to which system is synthetically solved
Technical problem between the inherent attribute of material and the use requirement of material.
The content of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of injection grade micro-foaming polypropylene composite material and its
Preparation method.
The present invention is achieved through the following technical solutions：
A kind of fretting map grade polypropylene composite material, is configured to by the raw material of following weight proportion：（%）
Polypropylene 50-85；
Toughener 5-25；
Inorganic mineral powder master batch 5-30；
Foaming master batch 0.5-5；
Nucleator 0.1-0.5；
Smell remover 1-3；
Damage resistant auxiliary agent 1-3；
Aging auxiliary agent 0.3-1.0.
A kind of described fretting map grade polypropylene composite material, polyacrylic type can be copolymerized type propene polymer, also may be used
To be homopolymerization type polypropylene；Polyacrylic melt flow rate (MFR)（230℃×2.16kg）For 30-150g/10min.
A kind of described fretting map grade polypropylene composite material, the foaming master batch through the following steps that obtain：First
By NaHCO3Blowing agent system is mixed with blowing promotor, and then this mixture is coated by organic polymer, is then mixed
Close EVA and master batch is made up of twin-screw extrusion.
A kind of described fretting map grade polypropylene composite material, the NaHCO3Blowing agent system is NaHCO3With citric acid
Sodium equivalent mixture；The blowing promotor is the mixture of zinc oxide and zinc stearate, wherein zinc oxide and zinc stearate
Mass ratio is 3:2.
Further, described organic polymer is organosilicon or polyacrylic acid.The molecule of organosilicon or polyacrylic acid
Measure as 8000-10000.
Further, the NaHCO3, sodium citrate, zinc oxide, zinc stearate, organosilicon and EVA mass ratio be
40:40: 3:2:2:18.Vinyl acetate content is 30% ~ 45% in the EVA.
Further, NaHCO3Size is 3000-5000.
A kind of described fretting map grade polypropylene composite material, inorganic mineral powder master batch is the nothing treated by silane coupler
The blend of machine miberal powder and polyethylene；The mass ratio of the inorganic mineral powder and polyethylene is 80:20.
Hydrolyzable group is methoxy in a kind of described fretting map grade polypropylene composite material, the silane coupler
Base, ethyoxyl or methoxy ethoxy, organo-functional group are vinyl, amino, epoxy radicals or methacryloxy；The nothing
Machine miberal powder is talcum powder, calcium carbonate, magnesium sulfate crystal whisker or wollastonite, and their particle size range is<It is 10 microns, more commonly used to be<2
Micron；The melt flow rate (MFR) of the polyethylene（190℃×2.16kg）For 3-8g/10min.
The nucleator is rare earth beta nucleater, specific for stearic acid and the compound of Lanthanum Stearate, wherein stearic acid：
The mass ratio of Lanthanum Stearate is 3:4.
A kind of described fretting map grade polypropylene composite material, the smell remover is water-absorbing resin, water and reactivity
Castor oil is using mass ratio as 4:2:1 mixture.
A kind of described fretting map grade polypropylene composite material, the water-absorbing resin is carboxymethylated cellulosic, hydroxypropyl
One or more in cellulose, chitosan, methylolation starch.
A kind of described fretting map grade polypropylene composite material, the aging auxiliary agent is by antioxidant 1010, thermal oxidation stabilizer
168 and thermal oxidation stabilizer DSTP with etc. weight mix.
A kind of preparation method of described fretting map grade polypropylene composite material, including following steps：
（1）Raw material is weighed by weight ratio；
（2）By polypropylene, toughener, inorganic mineral powder master batch, nucleator, scratch resistant auxiliary agent, smell remover and aging auxiliary agent
It is dry-mixed 3-5 minutes in super mixer；
（3）The raw material of mixing is placed in dual-screw-stem machine through melting extrusion, granulation, its technique is：One 180~190 DEG C of area, 2nd area
200~210 DEG C, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five areas 210~215, six areas 210~215, seven areas 215~
225, eight areas 215~225, nine areas 215~225, ten areas 215~225；Residence time is 1-2 minutes, and pressure is 12-18MPa；
（4）By step（3）The compound of middle extrusion and foaming master batch by weight ratio 50:1 mechanical mixture, is then opened by secondary
Mould injection molding, produces fretting map grade polypropylene composite material.
The beneficial effect that the present invention is reached：
1st, present invention uses a kind of economic and environment-friendly foaming system, gained expanded material is injection grade expanded material, breaks through hair
The limitation of foam material sheet material or tubing.
2nd, the microporous foam PP composite material obtained by the present invention is ensureing that the every physical and mechanical property of material is excellent,
Processability is good, can fully meet the indices requirement of automobile plastic parts.
3rd, the present invention uses thinner cladded type foaming agent, solves blowing-agent particle and is asked because carefully small and scattered uneven
Topic, obtained micro-foaming polypropylene not only closed pore, and the uniform microporous foam PP composite material of distribution of cells.
4th, the present invention can substantially mitigate part weight and shaping week on the basis of basic guarantee product properties is not reduced
Phase, and it is small with internal stress and warpage, and glacing flatness is high, does not shrink, dimensionally stable etc..
5th, microporous foam PP composite material proposed by the present invention is using commercially available conventional raw materials and conventional blending extrusion
Production technology, preparation technology is simple, cost is low.
6th, the microporous foam polypropylene obtained by the present invention is non-crosslinking structure, can be reclaimed modified polypropylene material by
Utilize, do not cause secondary pollution.
The present invention on existing commercially available conventional polypropylene base resin, by add inorganic mineral powder master batch, nucleator and
Foaming master batch can realize good injection foaming effect.Also, by add toughener, scratch resistance auxiliary agent, smell remove help
The various additives such as agent realize the rigid-tough balance of material, surface scratch resistance, and low smell, low VOC environmental protection characteristics etc. are various
Characteristic requirements, so as to meet the application demand of various automobile injection-moulded plastic parts.Further, since in the present invention selected by each component
Raw material are material modified essentially identical with conventional polypropylene, therefore, prepared lower cost for material, are especially suitable for industry
The large-scale promotion application of change.
Brief description of the drawings
Fig. 1 is the electron microscope of material of the present invention.
Fig. 2 is Fig. 1 enlarged drawing.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings.Following examples are only used for clearly illustrating the present invention
Technical scheme, and can not be limited the scope of the invention with this.
Embodiment 1
The material used：
Homopolymerization or co-polypropylene of the polypropylene for different mobility, polyacrylic melt flow rate (MFR)（230℃×2.16kg）For
30-150g/10min；
NaHCO3Size is 3000-5000；
Inorganic mineral powder is talcum powder, and particle size range is 1-2 microns；Inorganic mineral powder master batch be by silane coupler treat it is inorganic
The blend of miberal powder and polyethylene；The mass ratio of the inorganic mineral powder and polyethylene is 80:20.
Nucleator is rare earth beta nucleater, specific for stearic acid and the compound of Lanthanum Stearate, wherein stearic acid：It is stearic
Sour lanthanum=3:4；
Antioxidant 1010 be Ciba companies production, product designation Irganox 1010, chemical name be four (β-（3,5- bis- tertiary fourths
Base -4- hydroxy phenyls）Propionic acid) pentaerythritol ester；Thermal oxidation stabilizer 168 produces for Ciba companies, product designation Irgafos
168, chemical name is three（2,4- di-tert-butyl-phenyls）Phosphite ester；Thermal oxidation stabilizer DSTP produces for ICE companies of Britain, business
Brand number is Negonox DSTP, and chemical name is thio-2 acid octadecyl ester.
This experiment is divided into three groups, is below the specific formula and process of first group of experiment：
Sample 1
By polypropylene 66%, toughener 5%, nucleator 0.2%, talcum powder master batch 25%, smell remover 1.5%, scratch resistant auxiliary agent
1.5%th, aging auxiliary agent 0.8% is dry-mixed 3-5 minutes in super mixer, afterwards, then through melting extrusion in double screw extruder,
Granulate, its technique is：One 180~190 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five
Area 210~215, six areas 210~215, seven areas 215~225, eight areas 215~225, nine areas 215~225, ten areas 215~225；
Residence time is 1-2 minutes, and pressure is 12-18MPa.
Sample 2
By polypropylene 61%, toughener 10%, nucleator 0.2%, talcum powder master batch 25%, smell remover 1.5%, scratch resistant auxiliary agent
1.5%th, aging auxiliary agent 0.8% is dry-mixed 3-5 minutes in super mixer, afterwards, then through melting extrusion in double screw extruder,
Granulate, its technique is：One 180~190 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five
Area 210~215, six areas 210~215, seven areas 215~225, eight areas 215~225, nine areas 215~225, ten areas 215~225；
Residence time is 1-2 minutes, and pressure is 12-18MPa.
Sample 3
By polypropylene 51%, toughener 20%, nucleator 0.2%, talcum powder master batch 25%, smell remover 1.5%, scratch resistant auxiliary agent
1.5%th, aging auxiliary agent 0.8% is dry-mixed 3-5 minutes in super mixer, afterwards, then through melting extrusion in double screw extruder,
Granulate, its technique is：One 180~190 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five
Area 210~215, six areas 210~215, seven areas 215~225, eight areas 215~225, nine areas 215~225, ten areas 215~225；
Residence time is 1-2 minutes, and pressure is 12-18MPa.
Sample 4
By polypropylene 66%, toughener 10%, nucleator 0.2%, talcum powder 20%, smell remover 1.5%, scratch resistant auxiliary agent 1.5%,
It is dry-mixed 3-5 minutes in the super mixer of aging auxiliary agent 0.8%, afterwards, then through melting extrusion in double screw extruder, granulate, its
Technique is：One 180~190 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five areas 210~
215, six areas 210~215, seven areas 215~225, eight areas 215~225, nine areas 215~225, ten areas 215~225；Residence time
For 1-2 minutes, pressure was 12-18MPa
Sample 5
Polypropylene 61%, toughener 10%, talcum powder master batch 25%, smell remover 1.5%, scratch resistant auxiliary agent 1.5%, aging are helped
Agent 0.8% is dry-mixed 3-5 minutes in super mixer, afterwards, then through melting extrusion, granulation, its technique in double screw extruder
For：One 180~190 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five areas 210~215,
Six areas 210~215, seven areas 215~225, eight areas 215~225, nine areas 215~225, ten areas 215~225；Residence time is 1-
2 minutes, pressure was 12-18MPa.
The preparation of foaming master batch：By NaHCO3First it is well mixed, is then helped with appropriate foaming with equivalent sodium citrate
Agent（ZnO and Zn (st)2Mixture）Mixing, is then coated with organic polymer, is finally mixed coating with EVA
It is even that master batch is made up of twin-screw extrusion,
Wherein, organic polymer is organosilicon or polyacrylic acid；NaHCO3With sodium citrate, ZnO, Zn (st)2, organic high score
Son, EVA mass ratio are 40:40: 3:2:2:18.
The polypropylene that above-mentioned style 1- styles 5 are extruded and foaming master batch by weight ratio 50:1 mechanical mixture is uniform.
Second group of experiment is the particle difference by weight ratio 50 for extruding first group of experimental sample 1- sample 5:1 with wrapping
The NaHCO covered3It is well mixed；
3rd group of experiment is the particle difference by weight ratio 50 for extruding first group of reality experimental sample 1- sample 5:1 with it is uncoated
NaHCO3It is well mixed.
Performance evaluation mode and implementation standard：
The particulate material for completing granulation as stated above is dried 2~3 hours in 100 DEG C of convection oven in advance, Ran Houzai
Dried particulate material is subjected to injection moulding sample preparation on injection (mo(u)lding) machine（First group of experiment uses common injection molding,
Second and third group uses twice-die-opening injection molding）.
Tensile property test is carried out by ISO 527-1/2, and specimen size is 170*10*4mm, and draw speed is 50mm/
min；Bending property test is carried out by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is
64mm；Impact property is carried out by ISO 179-1eA, and specimen size is 80*10*4mm, notch depth for sample thickness five/
One；Density is carried out by ISO 1183, and specimen size is 10*10*4mm；Melt index is carried out by ISO 1133；Scoring resistance can be pressed
GMW14688-A-10N is carried out；Odor properties are carried out by GMW3205；Thermal-oxidative aging property is carried out by ASTM D3012；Light aging
Performance is carried out by the cycle D of GMW 14162.
The formula and properties test result of three groups of samples see below each table：
Table 1：First group of sample 1-5 formula and material property table
| Composite title | Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 |
| Polypropylene（%） | 66 | 61 | 51 | 66 | 61.2 |
| Toughener（%） | 5 | 10 | 20 | 10 | 10 |
| Nucleator（%） | 0.2 | 0.2 | 0.2 | 0.2 | 0 |
| Inorganic mineral powder master batch（%） | 25 | 25 | 25 | 20 (pure powders) | 25 |
| Scratch resistant auxiliary agent（%） | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Smell remover（%） | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Aging auxiliary agent（%） | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Unnotched impact strength (kJ/m2) | Constantly | Constantly | Constantly | Constantly | Constantly |
| Notch impact strength (kJ/m2) | 6.5 | 30 | 45 | 26 | 28 |
| Yield strength（MPa） | 22 | 19.5 | 18.3 | 20 | 19.7 |
| Elongation at break（%） | 65 | 156 | 305 | 132 | 141 |
| Bending modulus（MPa） | 2220 | 1930 | 1820 | 2065 | 1975 |
| Melt flow rate (MFR)（g/10min） | 60 | 52 | 43 | 48 | 53 |
| Density（g/cm3） | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 |
| It is odor profiles（Level） | 6 | 6 | 6 | 6 | 6 |
| Scratch resistant performance | 0. 8 | 0.65 | 0.47 | 0.72 | 0.53 |
| Illumination ageing | 4 | 4 | 4 | 4 | 4 |
| Thermo-oxidative ageing | Not efflorescence | Not efflorescence | Not efflorescence | Not efflorescence | Not efflorescence |
Table 2：Second group of formula of sample 1 ' -5 ' and material property table
Table 3：' -5 ' of sample 1 ' ' it is formulated and material property table
| Composite title | Sample 1 ' ' | Sample 2 ' ' | Sample 3 ' ' | Sample 4 ' ' | Sample 5 ' ' |
| Polypropylene（%） | 66 | 61 | 51 | 66 | 61.2 |
| Toughener（%） | 5 | 10 | 20 | 10 | 10 |
| Nucleator（%） | 0.2 | 0.2 | 0.2 | 0.2 | 0 |
| Inorganic mineral powder master batch（%） | 25 | 25 | 25 | 20 (pure powders) | 25 |
| Scratch resistant auxiliary agent（%） | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Smell remover（%） | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Aging auxiliary agent（%） | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Foaming master batch（%） | 2 | 2 | 2 | 2 | 2 |
| Unnotched impact strength (kJ/m2) | Constantly | Constantly | Constantly | Constantly | Constantly |
| Notch impact strength (kJ/m2) | - | - | - | - | - |
| Yield strength（MPa） | - | - | - | - | - |
| Elongation at break（%） | - | - | - | - | - |
| Bending modulus（MPa） | - | - | - | - | - |
| Melt flow rate (MFR)（g/10min） | - | - | - | - | - |
| Density（g/cm3） | - | - | - | - | - |
| It is odor profiles（Level） | 6 | 6 | 6 | 6 | 6 |
| Scratch resistant performance | 0. 95 | 0.88 | 0.74 | 0.82 | 0.79 |
| Illumination ageing | 4 | 4 | 4 | 4 | 4 |
| Thermo-oxidative ageing | Not efflorescence | Not efflorescence | Not efflorescence | Not efflorescence | Not efflorescence |
| Section foaming effect | Macropore, and hole is serious | Macropore, and hole is serious | Macropore, and hole is serious | Macropore, and hole is serious | Macropore, and hole is serious |
| Apparent mass | Gas trace is serious, without concave point | Gas trace is serious, without concave point | Gas trace is serious, without concave point | Apparent without gas trace but have concave point | Gas trace is serious, but without concave point |
By table 1（Sample 2 and sample 4）As can be seen that in polypropylene basic components, common talcum powder inorganic mineral powder is modified to
Talcum powder master batch, the notch shock of material is by 26 kJ/m2Become 30 kJ/m2, bending modulus becomes 2065 by 1930MPa
MPa, i.e. material impact have certain amplitude lifting, and modulus has certain amplitude reduction, but overall amplitude is little, can accord with completely
Close automobile-used material modified standard requirement；Equally, by table 1（Sample 2 and sample 5）As can be seen that the addition of beta nucleater whether,
Effect on Mechanical Properties amplitude to material is also little, and automobile-used material modified standard requirement equally can be also met completely；Meanwhile,
Both auxiliary agents can be with without big influence, completely to the adhesion strength, odor profiles and heat oxygen aging resistance, weatherability of material
Meet automobile-used material modified standard requirement.Nucleator is added it can be seen from table 2 and filler is handled by powder surface
System, the foaming effect of material is good, and the reservation degree of material mechanical performance is high, and the good appearance of obtained injected sample.It is logical
The contrast of sample 2 ' and sample 4 ' is crossed as can be seen that the Surface coating of filling powder has considerable influence, powder table to foaming effect
The untreated sample surfaces in face have pit and stomata is thicker, this be due to melt strength difference between material melt substantially, simultaneously
Getting angry excessively acutely causes.Can be seen that nucleator by the contrast of sample 2 ' and sample 5 ' also has larger shadow to foaming effect
Ring, although the sample uniform in foaming of non-Added Nucleating Agents is fine and close, substantially, the cooldown rate of this explanation material is relatively low for surface gas trace,
The compacted zone contacted with mold cavity surface, which fails rapid cooling, causes fatal layer a certain degree of foaming also occur.Pass through sample
The contrast of 1 '-sample 3 ' is as can be seen that material system carries out toughness reinforcing according to conventional material modified scheme and addition is other often
Rule functional aid does not have any influence to the foaming effect of material.From table 2,3, foaming agent whether by coating modification into
Foaming master batch is very big to Effect of Materials, without modified foaming agent because prepared material abscess and hole are serious and apparent mass
Severe exacerbation, does not possess practical value.This is due to non-modified NaHCO3Scattered inequality, blowing temperature is low, foaming
It is uncontrollable, cause that abscess is uneven, percent opening is high, therefore be difficult the apparent and mechanical property having had.
In summary, in the material modified basic components of polypropylene tradition by introduce nucleator, modification NaHCO3
Foaming master batch and special inorganic mineral powder master batch, substantially increase material it is expandable, in addition, material system considers
The system factor such as product outward appearance, the mechanical property of material and feature of environmental protection after the shaping mobility of material, injection, so as to prepare
A kind of micro-foaming material for going for current various automobile plastic parts completely.This material have intermediate layer be from
Ten to tens microns not wait closed porosity, superficial layer be compacted zone skin-core structure（See Fig. 1）.This micro foaming injection moulding
Material breaches many limitations of traditional injection moulding, on the basis of which kind of current automobile decoration piece standard requirement is fully met, can be with
Substantially mitigate part weight and molding cycle, and it is small with internal stress and warpage, and glacing flatness is high, does not shrink, dimensionally stable etc.
Feature.
Embodiment 2
The material used：
Homopolymerization or co-polypropylene of the polypropylene for different mobility, polyacrylic melt flow rate (MFR)（230℃×2.16kg）For
30-100g/10min；
NaHCO3Size is 3000-5000；
Inorganic mineral powder is calcium carbonate, and particle size range is 1-2 microns；Inorganic mineral powder master batch be by silane coupler treat it is inorganic
The blend of miberal powder and polyethylene；The mass ratio of the inorganic mineral powder and polyethylene is 80:20.
Nucleator is rare earth beta nucleater, specific for stearic acid and the compound of Lanthanum Stearate, wherein stearic acid：It is stearic
Sour lanthanum=3:4；
Antioxidant 1010 be Ciba companies production, product designation Irganox 1010, chemical name be four (β-（3,5- bis- tertiary fourths
Base -4- hydroxy phenyls）Propionic acid) pentaerythritol ester；Thermal oxidation stabilizer 168 produces for Ciba companies, product designation Irgafos
168, chemical name is three（2,4- di-tert-butyl-phenyls）Phosphite ester；Thermal oxidation stabilizer DSTP produces for ICE companies of Britain, business
Brand number is Negonox DSTP, and chemical name is thio-2 acid octadecyl ester.
By polypropylene 50%, toughener 5%, nucleator 0.1%, calcium carbonate master batch 5%, smell remover 1%, scratch resistant auxiliary agent
3%th, aging auxiliary agent 1% is dry-mixed 3-5 minutes in super mixer, afterwards, then through melting extrusion in double screw extruder, makes
, its technique is：One 180~190 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 210~215 DEG C of areas, 5th area
210~215, six areas 210~215, seven areas 215~225, eight areas 215~225, nine areas 215~225, ten areas 215~225；Stop
It is 1-2 minutes to stay the time, and pressure is 12-18MPa.
The NaHCO of cladding3It is prepared by foaming master batch：By NaHCO3First be well mixed with equivalent sodium citrate, then with right amount
Blowing promotor（ZnO and Zn (st)2Mixture）Mixing, is then coated with organosilicon macromolecule, finally by coating
It is well mixed with EVA and master batch is made up of twin-screw extrusion, wherein NaHCO3With sodium citrate, ZnO, Zn (st)2, organosilicon,
EVA mass ratio is 40:40: 3:2:2:18.
By the polypropylene of above-mentioned extrusion and the NaHCO of cladding3Foaming master batch by weight ratio 50:1 mechanical mixture, Ran Houtong
Twice-die-opening injection molding is crossed, automobile microporous foam PP composite material is produced.
Embodiment 3
The material used：
Homopolymerization or co-polypropylene of the polypropylene for different mobility, polyacrylic melt flow rate (MFR)（230℃×2.16kg）For
30-100g/10min；
NaHCO3Size is 3000-5000；
Inorganic mineral powder is wollastonite, and particle size range is 1-2 microns；Inorganic mineral powder master batch be by silane coupler treat it is inorganic
The blend of miberal powder and polyethylene；The mass ratio of the inorganic mineral powder and polyethylene is 80:20.
Nucleator is rare earth beta nucleater, specific for stearic acid and the compound of Lanthanum Stearate, wherein stearic acid：It is stearic
Sour lanthanum=3:4；
Antioxidant 1010 be Ciba companies production, product designation Irganox 1010, chemical name be four (β-（3,5- bis- tertiary fourths
Base -4- hydroxy phenyls）Propionic acid) pentaerythritol ester；Thermal oxidation stabilizer 168 produces for Ciba companies, product designation Irgafos
168, chemical name is three（2,4- di-tert-butyl-phenyls）Phosphite ester；Thermal oxidation stabilizer DSTP produces for ICE companies of Britain, business
Brand number is Negonox DSTP, and chemical name is thio-2 acid octadecyl ester.
Smell remover is water-absorbing resin, water and reactive castor oil using mass ratio as 4:2:1 mixture.
Polypropylene 85%, toughener 25%, nucleator 0.5%, wollastonite master batch 30%, smell remover 3%, scratch resistant are helped
Agent 1%, aging auxiliary agent 0.3% are dry-mixed 3-5 minutes in super mixer, afterwards, then through melting extrusion in double screw extruder,
Granulate, its technique is：One 180~190 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five
Area 210~215, six areas 210~215, seven areas 215~225, eight areas 215~225, nine areas 215~225, ten areas 215~225；
Residence time is 1-2 minutes, and pressure is 12-18MPa.
The NaHCO of cladding3It is prepared by foaming master batch：By NaHCO3First be well mixed with equivalent sodium citrate, then with right amount
Blowing promotor（ZnO and Zn (st)2Mixture）Mixing, is then coated with organosilicon macromolecule, finally by coating
It is well mixed with EVA and master batch is made up of twin-screw extrusion, wherein NaHCO3With sodium citrate, ZnO, Zn (st)2, organosilicon,
EVA mass ratio is 40:40: 3:2:2:18.
By the polypropylene of above-mentioned extrusion and the NaHCO of cladding3Foaming master batch by weight ratio 85:5 mechanical mixtures, Ran Houtong
Twice-die-opening injection molding is crossed, automobile microporous foam PP composite material is produced.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvement and deformation can also be made, these improve and deformed
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of injection grade micro-foaming polypropylene composite material, it is characterized in that, including the raw material of following weight proportion is configured to：
（%）
Polypropylene 50-85；
Toughener 5-25；
Inorganic mineral powder master batch 5-30；
Foaming master batch 0.5-5；
Nucleator 0.1-0.5；
Smell remover 1-3；
Damage resistant auxiliary agent 1-3；
Aging auxiliary agent 0.3-1.0.
2. a kind of injection grade micro-foaming polypropylene composite material according to claim 1, it is characterized in that, polyacrylic melt
Flow rate（230℃×2.16kg）For 30-150g/10min.
3. a kind of injection grade micro-foaming polypropylene composite material according to claim 1, it is characterized in that, the foaming master batch
Through the following steps that obtain：First by NaHCO3Blowing agent system is mixed with blowing promotor, then by this mixture by having
Machine macromolecule is coated, and then mixes EVA and master batch is made up of twin-screw extrusion.
4. a kind of injection grade micro-foaming polypropylene composite material according to claim 3, it is characterized in that, the NaHCO3Hair
Infusion system is NaHCO3With sodium citrate equivalent mixture；The blowing promotor is the mixing of zinc oxide and zinc stearate
Thing.
5. a kind of injection grade micro-foaming polypropylene composite material according to claim 3, it is characterized in that, described is organic high
Molecule is organosilicon or polyacrylic acid.The molecular weight of organosilicon or polyacrylic acid is 8000-10000.
6. a kind of injection grade micro-foaming polypropylene composite material according to claim 1, it is characterized in that, the inorganic mineral powder
Master batch is the blend of the inorganic mineral powder and polyethylene treated by silane coupler；The quality of the inorganic mineral powder and polyethylene
Ratio is 80:20.
7. a kind of injection grade micro-foaming polypropylene composite material according to claim 6, it is characterized in that, it is described silane coupled
Hydrolyzable group is methoxyl group, ethyoxyl or methoxy ethoxy in agent, and organo-functional group is vinyl, amino, epoxy radicals
Or methacryloxy；The inorganic mineral powder is talcum powder, calcium carbonate, magnesium sulfate crystal whisker or wollastonite；The polyethylene
Melt flow rate (MFR)（190℃×2.16kg）For 3-8g/10min.
8. a kind of injection grade micro-foaming polypropylene composite material according to claim 1, it is characterized in that, the nucleator is
The mass ratio of the compound of stearic acid and Lanthanum Stearate, wherein stearic acid and Lanthanum Stearate is 3:4.
9. a kind of injection grade micro-foaming polypropylene composite material according to claim 1, it is characterized in that, the smell is removed
Agent is water-absorbing resin, water and reactive castor oil using mass ratio as 4:2:1 mixture.
10. a kind of preparation method of injection grade micro-foaming polypropylene composite material according to any of the above claim, its
It is characterized in, including following steps：
（1）Raw material is weighed by weight ratio；
（2）By polypropylene, toughener, inorganic mineral powder master batch, nucleator, scratch resistant auxiliary agent, smell remover and aging auxiliary agent
It is dry-mixed 3-5 minutes in super mixer；
（3）The raw material of mixing is placed in dual-screw-stem machine through melting extrusion, granulation, its technique is：One 180~190 DEG C of area, 2nd area
200~210 DEG C, three 200~210 DEG C of areas, four 210~215 DEG C of areas, five areas 210~215, six areas 210~215, seven areas 215~
225, eight areas 215~225, nine areas 215~225, ten areas 215~225；Residence time is 1-2 minutes, and pressure is 12-18MPa；
（4）By step（3）The compound of middle extrusion and foaming master batch by weight ratio 50:1 mechanical mixture, is then opened by secondary
Mould injection molding, produces fretting map grade polypropylene composite material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759903A (en) * | 2017-10-19 | 2018-03-06 | 中广核俊尔（上海）新材料有限公司 | PP composite material and its preparation method and application |
| CN108503954A (en) * | 2018-05-09 | 2018-09-07 | 苏州润佳工程塑料股份有限公司 | A kind of micro-foaming polypropylene and preparation method thereof |
| CN108690267A (en) * | 2018-05-29 | 2018-10-23 | 芜湖创科新材料科技有限公司 | A kind of micro-foaming polypropylene material and preparation method thereof |
| CN109535562A (en) * | 2018-11-28 | 2019-03-29 | 广州仕天材料科技有限公司 | A kind of scratch-resistant high-strength vehicle interior trim PP material and preparation method thereof |
| CN112029190A (en) * | 2020-08-06 | 2020-12-04 | 盘锦海兴科技股份有限公司 | Micro-foaming polypropylene material and preparation method thereof |
| WO2021012558A1 (en) * | 2019-07-22 | 2021-01-28 | 苏州润佳工程塑料股份有限公司 | Chiral silicon dioxide fiber-reinforced foamed polypropylene composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353460A (en) * | 2008-09-11 | 2009-01-28 | 丹阳市华东工程塑料有限公司 | Environment-friendly type micro-foaming polypropylene sheet and preparation thereof |
| CN102977458A (en) * | 2012-12-11 | 2013-03-20 | 苏州工业园区润佳工程塑料有限公司 | Micropore foaming agent for polypropylene, microcellular foamed polypropylene composite material and methods for preparing micropore foaming agent for polypropylene and microcellular foamed polypropylene composite material |
| CN103160020A (en) * | 2011-12-13 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene micro-foam bamboo plastic composite, and preparation method thereof |
| CN104072881A (en) * | 2013-03-28 | 2014-10-01 | 滁州格美特科技有限公司 | Thermoplastic micro-foaming damping material and preparation method thereof |
| CN105885240A (en) * | 2016-04-25 | 2016-08-24 | 中山诗兰姆汽车零部件有限公司 | Microcellular foaming composite material and preparation method thereof |
-
2017
- 2017-06-23 CN CN201710487379.7A patent/CN107200919A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353460A (en) * | 2008-09-11 | 2009-01-28 | 丹阳市华东工程塑料有限公司 | Environment-friendly type micro-foaming polypropylene sheet and preparation thereof |
| CN103160020A (en) * | 2011-12-13 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene micro-foam bamboo plastic composite, and preparation method thereof |
| CN102977458A (en) * | 2012-12-11 | 2013-03-20 | 苏州工业园区润佳工程塑料有限公司 | Micropore foaming agent for polypropylene, microcellular foamed polypropylene composite material and methods for preparing micropore foaming agent for polypropylene and microcellular foamed polypropylene composite material |
| CN104072881A (en) * | 2013-03-28 | 2014-10-01 | 滁州格美特科技有限公司 | Thermoplastic micro-foaming damping material and preparation method thereof |
| CN105885240A (en) * | 2016-04-25 | 2016-08-24 | 中山诗兰姆汽车零部件有限公司 | Microcellular foaming composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 洪定一 主编: "《塑料工业手册 聚烯烃》", 31 March 1999, 化学工业出版社 * |
| 王善勤 主编: "《塑料配方设计问答》", 31 January 2003, 中国轻工业出版社 * |
| 辛忠 著: "《小分子调控大分子结晶——理论与实践》", 31 August 2016, 华东理工大学出版社 * |
Cited By (7)
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| CN107759903A (en) * | 2017-10-19 | 2018-03-06 | 中广核俊尔（上海）新材料有限公司 | PP composite material and its preparation method and application |
| CN108503954A (en) * | 2018-05-09 | 2018-09-07 | 苏州润佳工程塑料股份有限公司 | A kind of micro-foaming polypropylene and preparation method thereof |
| CN108690267A (en) * | 2018-05-29 | 2018-10-23 | 芜湖创科新材料科技有限公司 | A kind of micro-foaming polypropylene material and preparation method thereof |
| CN109535562A (en) * | 2018-11-28 | 2019-03-29 | 广州仕天材料科技有限公司 | A kind of scratch-resistant high-strength vehicle interior trim PP material and preparation method thereof |
| WO2021012558A1 (en) * | 2019-07-22 | 2021-01-28 | 苏州润佳工程塑料股份有限公司 | Chiral silicon dioxide fiber-reinforced foamed polypropylene composite material |
| CN112029190A (en) * | 2020-08-06 | 2020-12-04 | 盘锦海兴科技股份有限公司 | Micro-foaming polypropylene material and preparation method thereof |
| CN112029190B (en) * | 2020-08-06 | 2023-02-21 | 盘锦海兴科技股份有限公司 | Micro-foaming polypropylene material and preparation method thereof |
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