CN108192262A - A kind of high tenacity, high convergency, high-flowability polypropylene composite material and preparation method thereof - Google Patents
A kind of high tenacity, high convergency, high-flowability polypropylene composite material and preparation method thereof Download PDFInfo
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- CN108192262A CN108192262A CN201711432562.3A CN201711432562A CN108192262A CN 108192262 A CN108192262 A CN 108192262A CN 201711432562 A CN201711432562 A CN 201711432562A CN 108192262 A CN108192262 A CN 108192262A
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- composite material
- convergency
- polypropylene composite
- polypropylene
- antioxidant
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses one kind to have high tenacity, high convergency, high-flowability polypropylene composite material and preparation method thereof, and the raw material of following weight percent is formulated：Polypropylene 48~90%, superfine function calcium carbonate 5~35%, toughener POE1~15%, coupling agent 0.1~2%, antioxidant 0.1~1%, other auxiliary agents 0~2%.It is an advantage of the invention that：1st, the present invention adds in superfine function calcium carbonate by way of the feeding of side, solves the problems, such as that the dispersion that directly mixing addition is brought is uneven.2nd, compared with tradition is calcium carbonate-filled, the PP composite material obtained by the present invention has excellent toughness and higher material shrinkage, while have higher mobility.3rd, preparation process of the invention is simple, at low cost, can be widely applied to the fields such as automobile, household electrical appliances.
Description
Technical field
The present invention relates to a kind of PP composite materials, and in particular to a kind of high tenacity, high convergency, high-flowability polypropylene
Composite material and preparation method thereof is a kind of PP composite material simple for process, at low cost, has higher toughness, height
The advantages that shrinking percentage and high fluidity, is mainly used in the fields such as household electrical appliance, automobile interior exterior decorations, belongs to polymer modification and add
Work technical field.
Background technology
Polypropylene is while light inexpensive because having many advantages, such as preferable processing performance and excellent oil resistant, chemical species,
It is widely used in the industries such as inner and outer decorative parts of automobile, household electrical appliance and electronic component, is most fast universal of current growth rate
Thermoplastic.But since polypropylene glass transition temperature is higher, material thermal resistance is poor, and toughness is low, and especially low temperature is tough
The shortcomings of property is poor, limits its application in many fields.
In current Filling and modifying of polypropylene field, it is inorganic with high length-diameter ratio to be usually added into glass fibre, talcum powder etc.
Filler improves polyacrylic intensity and heat resistance, while reduce material cost.In most cases, the addition meeting of these fillers
The shrinking percentage of polypropylene material is substantially reduced, improves the dimensional stability of product.But for needing to improve PP composite material
The situation of shrinking percentage, opens such as mold shrinkage and cannot get position, causes product size bigger than normal, if the content of excessive reduction filler
The performance of material will certainly be influenced, while will also result in the increase of material cost.
Calcium carbonate is a kind of inorganic particle in nature ore, is divided into precipitated calcium carbonate and heavy according to density
Calcium carbonate；Ordinary calcium carbonate and function calcium carbonate can be divided into according to surface-active again.It is cheap since it is derived from a wealth of sources, nothing
Toxicity can not only reduce the cost of plastics, moreover it is possible to improve the physical properties such as the rigidity, hardness, dimensional stability of material, extensively
Applied to fields such as plastics, coating, rubber.But since also there is energy high, easy agglomerating, surface in surface to be not easy in highly polar for it
So research at present is concentrated mainly on surface and is modified, such as increase wettability, reduce polarity, promote the shortcomings of disperseing in the plastic
Into its dispersion etc..
Invention content
The object of the present invention is to provide a kind of high tenacity, high convergency, high-flowability polypropylene composite materials, have solved existing
The above problem of technology.This composite material has excellent toughness and relatively high material shrinkage and higher flowing
Property.
Modified polypropylene composite material of the present invention is achieved through the following technical solutions its purpose：
One kind has high tenacity, high convergency, high-flowability polypropylene composite material, matches by the raw material of following weight percent
It makes：
In the PP composite material system that the present invention is applicable in,
For the polypropylene under 230 DEG C, 2.16kg loading condictions, melt flow rate (MFR) is 5~60g/10min.
The polypropylene is homo-polypropylene or block copolymerization propylene；The crystallinity of the homo-polypropylene more than 70%, etc.
Normality is more than 99%；The comonomer of the block copolymerization polypropylene is ethylene, and vinyl monomer repetitive unit molar content is 4
~10%.
The superfine function calcium carbonate is fine white powder, and relative density is 2.5~2.6g/cm3, average grain diameter
D50 is 1 μm, and 2 μm of contents are about 85%.
The toughener POE is the group of ethylene-octene linear copolymer or Ethylene/Butylene linear copolymer or both
It closes, density is 0.88~0.90g/cm3, melt flow rate (MFR) is 0.5~10g/10min.
The coupling agent is any one in silane coupling agent, titanate coupling agent and aluminate coupling agent.
The antioxidant includes primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is hindered phenol or sulphur ester antioxidant；It is auxiliary
Antioxidant is phosphorite kind antioxidant.
The primary antioxidant is one or more of 3114,1010 and DSTP mixing；Auxiliary anti-oxidant is 618 and 168
One or both of.
Other described additives are a variety of colors additive, light stabilizer, various esters or fatty acid lubricant etc..
It is above-mentioned with high tenacity, high convergency, high-flowability polypropylene composite material preparation method, specific steps are such as
Under：
(1) each component is weighed by above-mentioned weight proportion；
(2) by each component in step (1) in addition to superfine function calcium carbonate dry-mixed 3~5 minutes in super mixer；
(3) raw material that step (2) is uniformly mixed is added in into double screw extruder, superfine function from the main spout of screw rod tail
Calcium carbonate lateral spout in the middle part of screw rod adds in double screw extruder, is granulated by melting extrusion postcooling, technique is：One
190~200 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is 100-
1000r/min；The residence time of entire extrusion is 1~2 minute, and pressure is 12~18MPa, purging vacuum degree reaches 5~
20kPa。
It is an advantage of the invention that：
1st, the present invention adds in superfine function calcium carbonate by way of the feeding of side, solves point that directly mixing addition is brought
Dissipate the problem of uneven.
2nd, compared with tradition is calcium carbonate-filled, the PP composite material obtained by the present invention have excellent toughness and compared with
High material shrinkage, while there is higher mobility.
3rd, preparation process of the invention is simple, at low cost, can be widely applied to the fields such as automobile, household electrical appliances.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.The scope of the present invention is not by these embodiments
Limitation, the scope of the present invention propose in detail in the claims.
In the composite-material formula of embodiment and comparative example, polypropylene used is the copolymerization poly- third of oil of SPC production
Alkene, melt flow rate (MFR) 15g/10min.The superfine function calcium carbonate is fine white powder, relative density for 2.5~
2.6g/cm3, average grain diameter D50 is 1 μm, and 2 μm of contents are about 85%.The talcum powder is 1250 mesh, and average grain diameter is
10μm.Toughener POE used is ethylene-octene copolymer Engage8150, the density 0.868g/cm3 of DOW companies,
Melt index is 0.5g/10min (test conditions：190℃×2.16kg).Coupling agent used is Silane coupling agent KH550.Institute
Primary antioxidant be BASF AG production 3114, product designation Irganox 3114, chemical name 3,5- di-t-butyls-
4- hydroxybenzyl phosphates diethylester and the DSTP of ICE companies of Britain production, product designation Negonox DSTP, chemical name
For thio-2 acid octadecyl ester.Auxiliary anti-oxidant is 168, product designation Irgafos 168 of BASF AG's production, and chemical name is
Three (2,4- di-tert-butyl-phenyls) phosphite esters.Other auxiliary agents used include a variety of colors additive, light stabilizer, various esters
Class or fatty acid lubricant etc..
Before use, weigh raw material according to said components and weight proportion, will remove superfine function calcium carbonate (or talcum powder) it
Outer each component is dry-mixed 3~5 minutes in super mixer；Then uniformly mixed raw material is added from the main spout of screw rod tail
Entering double screw extruder, superfine function calcium carbonate (or talcum powder) lateral spout in the middle part of screw rod adds in double screw extruder,
It is granulated by melting extrusion postcooling, technique is：One 190~200 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas,
Four 205~215 DEG C of areas；Screw speed is 100-1000r/min；The residence time of entire extrusion is 1~2 minute, pressure
For 12~18MPa, purging vacuum degree reaches 5~20kPa.
Embodiment 1
PP composite material key component of the present invention includes 86.6% polypropylene, 5% superfine function calcium carbonate, 5% increasing
Tough dose of POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2% its
Its auxiliary agent.
Embodiment 2
PP composite material key component of the present invention includes 81.6% polypropylene, 10% superfine function calcium carbonate, 5% increasing
Tough dose of POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2% its
Its auxiliary agent.
Embodiment 3
PP composite material key component of the present invention includes 71.6% polypropylene, 15% superfine function calcium carbonate, 10%
Toughener POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2%
Other auxiliary agents.
Embodiment 4
PP composite material key component of the present invention includes 66.6% polypropylene, 20% superfine function calcium carbonate, 10%
Toughener POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2%
Other auxiliary agents.
Embodiment 5
PP composite material key component of the present invention includes 51.6% polypropylene, 30% superfine function calcium carbonate, 15%
Toughener POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2%
Other auxiliary agents.
Talcum powder is selected to substitute superfine function calcium carbonate in comparative example, other components are consistent with embodiment, specific to compare
Under such as.
Comparative example 1
PP composite material key component of the present invention include 86.6% polypropylene, 5% talcum powder, 5% toughener POE,
1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2% other auxiliary agents.
Comparative example 2
PP composite material key component of the present invention include 81.6% polypropylene, 10% talcum powder, 5% toughener POE,
1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2% other auxiliary agents.
Comparative example 3
PP composite material key component of the present invention includes 71.6% polypropylene, 15% talcum powder, 10% toughener
It POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2% other helps
Agent.
Comparative example 4
PP composite material key component of the present invention includes 66.6% polypropylene, 20% talcum powder, 10% toughener
It POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2% other helps
Agent.
Comparative example 5
PP composite material key component of the present invention includes 51.6% polypropylene, 30% talcum powder, 15% toughener
It POE, 1% coupling agent, 0.1% antioxidant 3314,0.1% antioxidant DSTP and 0.2% auxiliary anti-oxidant 168 and 2% other helps
Agent.
Embodiment and comparative example main component mass percentage are shown in Table 1.
1~5 material prescription table (weight %) of 1 Examples 1 to 5 of table and comparative example
Performance evaluation mode and implementation standard：
The particulate material that will be prepared as stated above, it is 2~3 hours dry in 90~100 DEG C of air dry oven, then
Again by dried particle on injection molding machine injection molding sample.
Density measurement：It is carried out by ISO 1183-1 standards, specimen size is 10 × 10 × 4mm；
Tensile property is tested：It is carried out by ISO 527-2 standards, specimen size is 170 × 10 × 4mm, and tensile speed is
50mm/min；
Bending property is tested：It is carried out by 178 standards of ISO, specimen size is 80 × 10 × 4mm, rate of bending 2mm/
Min, span 64mm；
Notch impact strength is tested：It is carried out by ISO 179-1 standards, specimen size is 80 × 10 × 4mm, and notch depth is
/ 3rd of sample thickness, test temperature are 23 DEG C；
Material shrinkage is tested：Shrinking percentage is carried out by 2577 standards of ISO, and specimen size is 150 × 100 × 3.2mm；
Melt flow rate (MFR) is tested：It is carried out by ISO 1133-1 standards, test condition is 230 DEG C, 2.16kg.
Density, tensile strength, bending modulus, notch impact strength and melt of the comprehensive performance of material as obtained by test
Flow rate is judged.The performance test results difference of 1~5 PP composite material of the embodiment of the present invention 1~5 and comparative example
It is shown in Table 2.
1~5 material property table of 2 Examples 1 to 5 of table and comparative example
It can be seen that from the performance test results of Examples 1 to 5 and comparative example 1~5 compound with talc powder filled polypropylene
Material is compared, and the notch shock that the calcium carbonate-filled reinforced polypropylene compound material of superfine function can increase substantially material is strong
Degree improves the toughness of material, while tensile strength and bending modulus fall are smaller.When superfine function calcium carbonate is 15%
When, notch impact strength improves the toughness of material, while tensile strength and bending modulus rebound extremely；The contraction of material simultaneously
Rate and the flow rate of melt increase.
In addition, substituting composite talcum powder filled material of polypropylene with superfine function calcium carbonate, material can be increased substantially
Shrinking percentage promotes the melt flow rate (MFR) of material, while the reduction of density of material can also mitigate the weight of product, to product light weight
Changing has positive effect.
Claims (10)
1. one kind has high tenacity, high convergency, high-flowability polypropylene composite material, it is characterised in that：By following weight percent
The raw material of ratio is formulated：
It is 2. according to claim 1 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：For the polypropylene under 230 DEG C, 2.16kg loading condictions, melt flow rate (MFR) is 5~60g/10min.
It is 3. according to claim 1 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：The polypropylene is homo-polypropylene or block copolymerization propylene.
It is 4. according to claim 3 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：For the crystallinity of the homo-polypropylene more than 70%, isotacticity is more than 99%；The copolymerization of the block copolymerization polypropylene
Monomer is ethylene, and vinyl monomer repetitive unit molar content is 4~10%.
It is 5. according to claim 1 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：The superfine function calcium carbonate is fine white powder, and relative density is 2.5~2.6g/cm3, average grain diameter D50 is
1 μm, and 2 μm of contents are about 85%.
It is 6. according to claim 1 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：The toughener POE is the combination of ethylene-octene linear copolymer or Ethylene/Butylene linear copolymer or both,
Density is 0.88~0.90g/cm3, melt flow rate (MFR) is 0.5~10g/10min.
It is 7. according to claim 1 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：The coupling agent is any one in silane coupling agent, titanate coupling agent and aluminate coupling agent.
It is 8. according to claim 1 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：The antioxidant includes primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is hindered phenol or sulphur ester antioxidant；Auxiliary antioxygen
Agent is phosphorite kind antioxidant.
It is 9. according to claim 1 a kind of with high tenacity, high convergency, high-flowability polypropylene composite material, feature
It is：The primary antioxidant is one or more of 3114,1010 and DSTP mixing；During auxiliary anti-oxidant is 618 and 168
It is one or two kinds of.
There is the preparation of high tenacity, high convergency, high-flowability polypropylene composite material described in 10. claim 1-9 is one of arbitrary
Method, it is characterised in that：Its step are as follows：
(1) each component is weighed by weight ratio；
(2) by each component in step (1) in addition to superfine function calcium carbonate dry-mixed 3~5 minutes in super mixer；
(3) raw material that step (2) is uniformly mixed is added in into double screw extruder, superfine function carbonic acid from the main spout of screw rod tail
Calcium lateral spout in the middle part of screw rod adds in double screw extruder, is granulated by melting extrusion postcooling, technique is：One area
190~200 DEG C, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is 100-1000r/
min；The residence time of entire extrusion is 1~2 minute, and pressure is 12~18MPa, and purging vacuum degree reaches 5~20kPa.
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Cited By (2)
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