CN106221007B - A kind of improved high-intensitive scraping-resistant polypropylene material - Google Patents
A kind of improved high-intensitive scraping-resistant polypropylene material Download PDFInfo
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- CN106221007B CN106221007B CN201610658580.2A CN201610658580A CN106221007B CN 106221007 B CN106221007 B CN 106221007B CN 201610658580 A CN201610658580 A CN 201610658580A CN 106221007 B CN106221007 B CN 106221007B
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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
- C08L23/12—Polypropene
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- 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
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- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention provides a kind of improved high-intensitive scraping-resistant polypropylene material comprising following parts by weight material: 55~65 parts of polypropylene；5~15 parts of polyethylene terephthalate；5~10 parts of POE-g-MAH；5~10 parts of metallocene PE；10~15 parts of calcium carbonate；1~2 part of aluminate coupling agent；1~1.5 part of dioctyl phthalate；0.2~0.5 part of antioxidant；Wherein, calcium carbonate include the partial size of 15~25wt% be 20nm calcium carbonate, 30~40wt% partial size be 55nm calcium carbonate and 40~50wt% partial size be 120nm calcium carbonate.The present invention can also improve the processing performance of blend while significantly improving polypropylene toughness, rigidity, modulus and dimensioned stability.
Description
Technical field
The present invention relates to a kind of polypropylene materials.It is more particularly related to a kind of improved high-intensitive scratch-resistant
Polypropylene material.
Background technique
Polypropylene (PP) raw material sources are abundant, and cheap, relative density is small, and processing performance is excellent, yield strength, stretching
Intensity and elasticity modulus are higher, and electrical insulating property is good, and proof stress cracking and chemical resistance are preferable, the nontoxic nothing of product
Taste, glossiness are good, therefore are widely used in the fields such as automobile, machinery, household electrical appliances, packaging.But polypropylene shrinking percentage is big,
Matter is crisp, and notch impact strength is low, especially low temperature when be particularly acute, as polypropylene is in the gradually growth of every profession and trade demand and section
The development of technology, people are higher and higher to the comprehensive performance requirement of polypropylene material, its many performance is caused to need to improve.
High molecular be blended can change the physical mechanical property of polymer, improve processing performance, reduce cost and expansion
The big scope of application.It is blended using polyethylene terephthalate (PET) with PP, while filling inorganic rigid particle and being changed
Property, shock resistance, toughness, dimensional stability of PP matrix etc. can be improved, but due to PET and PP two kinds of polymer molecular structure
On difference, poor compatibility is blended that effect is undesirable, and the elastomers that are added in the blend most at present carry out mechanical blendings, though
The so inflexible targets such as tensile modulus of elasticity for effectively increasing the compatibility of PP and PET, but also resulting in blend and intensity
Decline, in addition, the filling of inorganic rigid particle also will affect the mobility of high molecular material to a certain extent, to influence it
Processing performance.
Summary of the invention
As various extensive and careful research and experiment as a result, it has been found by the inventor that using PET
During carrying out blending and modifying to PP, by the addition of POE-g-MAH and the filling of different-grain diameter composite calcium carbonate, improving
While intermingling material compatibility, the mechanical property of polypropylene material can be effectively improved.Based on this discovery, this hair is completed
It is bright.
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
It is a still further object of the present invention to provide a kind of improved high-intensitive scraping-resistant polypropylene materials, are significantly improving
While polypropylene toughness, rigidity, modulus and dimensioned stability, the processing performance of blend can also be improved.
In order to realize these purposes and other advantages according to the present invention, it is poly- to provide a kind of improved high-intensitive scratch-resistant
Propylene material comprising following parts by weight material:
Wherein, calcium carbonate include the partial size of 15~25wt% be 20nm calcium carbonate, 30~40wt% partial size be 55nm
Calcium carbonate and 40~50wt% partial size be 120nm calcium carbonate.
Polypropylene (PP) and polyethylene terephthalate (PET) belong to thermodynamically incompatible system, if the two is simple
Single is directly blended, and two-phase interface is clear, and interface is loose.The addition of compatilizer POE-g-MAH can significantly improve PP and PET
Compatibility, and can obviously reduce the partial size of dispersed phase, improve the toughening effect of blending, but also bring blend strength reduction
Apparent counter productive；
Metallocene PE (mPE) intermolecular interaction force is big, and tangling, point is more, and mPE cooperates with use with POE-g-MAH
It can achieve the effect that toughening with lesser additive amount, to negative effect caused by intermingling material while reducing toughening；
The calcium carbonate added in the present invention carries out mixing filling using the calcium carbonate of different-grain diameter, is guaranteeing calcium carbonate dispersion
While property, the packed density of inorganic filler is effectively increased, the collision between calcium carbonate particle in shear flow is reduced, from
And the reduction of blend processing fluidity can be effectively prevent.
Preferably, wherein first at a temperature of 90~100 DEG C, the aluminate coupling agent is mixed with calcium carbonate
5~10min of stirring is closed, the dioctyl phthalate is added and stirs after 7~10min pre-processes calcium carbonate, then
Other components are added to carry out preparing PP composite material.But since calcium carbonate is inorganic filler, and organic matter poor compatibility, and
Easily assemble agglomerating, thus calcium carbonate is pre-processed using aluminate coupling agent first, can be increased and remaining organic copolymer
Compatibility, adding dioctyl phthalate and being modified can be improved its dispersibility in organic molecule chain, to fill
Dividing ensure that reinforcing effect of the inorganic filler calcium carbonate to composite material.
Preferably, wherein the polyacrylic melt index is 2.5~4g/10min, and high melt index, viscosity is low,
Conducive to the dispersibility and mobility of intermingling material, but the impact strength of obtained blend is also lower, and thus appropriate melting refers to
The polyacrylic selection of base material, it is ensured that the balance between intermingling material dispersibility and blend shock resistance mechanical property.
Preferably, wherein the grafting rate of the POE-g-MAH is 1.3~1.5%, and in a certain range, POE's connects
Branch rate is higher, is more obvious to PP and PET compatibility raising, and be remarkably improved the mechanical property of copolymer, but as POE is grafted
The raising of rate, cost is also higher, and the grafting rate of POE-g-MAH is proper in 1.3~1.5% ranges.
Preferably, wherein the POE in the POE-g-MAH is ethylene-l-octane copolymer, octene in the POE
Content is 26~28wt%, and the connection buffering effect of each component, but octene can be improved in the presence of soft octene coiled structure in POE
Content can not be excessively high, otherwise will affect the hardness of copolymeric material instead.
Preferably, wherein the mPE is metallocene linear-low density polyethylene, and melt index is 1.3~1.8g/
10min, the flexible metallocene linear-low density polyethylene being evenly distributed on main chain can significantly modify the morphosis of PP, flexible
Material is interspersed in the rigid framework of PP crystal, is born transmitting and has been dispersed part impact energy, improves the toughening modifying of PP,
The metallocene linear-low density polyethylene of appropriate melt index can guarantee the stability of production.
Preferably, wherein the antioxidant is selected from 2,2- di-2-ethylhexylphosphine oxide (4- methyl -6- butylphenol), 2,6- bis-
One or more of Butylated Hydroxytoluene, 2,6- di-tert-butyl hydroxy toluene, butylated hydroxy anisole.
The present invention is include at least the following beneficial effects:
(1) present invention is modified PP using PET, significantly improves toughness, the impact resistance, environmental stress resistance of PP
Cracking etc., effectively increases the application field and range of PP；
(2) mPE and compatilizer POE-g-MAH cooperate with the use to reach the effect of toughening with lesser additive amount in the present invention
Fruit, to negative effect brought by intermingling material while reducing toughening；
(3) by the present invention in that carrying out cooperation filled high polymer material with different-grain diameter calcium carbonate, poly- third is being significantly improved
While alkene rigidity, modulus and dimensional stability, and improve the processing performance of high molecular material.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, to enable those skilled in the art's reference say
Bright book text can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
<example 1>
A kind of improved high-intensitive scraping-resistant polypropylene material comprising following parts by weight material: 55 parts of polypropylene；Poly- pair
6 parts of ethylene terephthalate；10 parts of POE-g-MAH；10 parts of metallocene PE；15 parts of calcium carbonate；Aluminate coupling agent 2
Part；1.5 parts of dioctyl phthalate；0.5 part of 2,2- di-2-ethylhexylphosphine oxide (4- methyl -6- butylphenol).
Wherein, calcium carbonate include the partial size of 15wt% be 20nm calcium carbonate, 40wt% partial size be the calcium carbonate of 55nm
The calcium carbonate that partial size with 45wt% is 120nm.
Wherein, first at a temperature of 90 DEG C, the aluminate coupling agent and calcium carbonate are subjected to mixing 5min, then plus
Enter after dioctyl phthalate stirring 7min pre-processes calcium carbonate, adds other components and carry out preparing poly- third
Alkene composite material.
Wherein, the polyacrylic melt index is 2.5g/10min；The grafting rate of the POE-g-MAH is 1.3%；Institute
Stating the POE in POE-g-MAH is ethylene-l-octane copolymer, and the content of octene is 26wt% in the POE；The mPE is cyclopentadienyl
Metal linear low density polyethylene (LDPE), melt index 1.3g/10min.The items for the polypropylene material that this example is prepared
Performance is as shown in table 1.
<example 2>
A kind of improved high-intensitive scraping-resistant polypropylene material comprising following parts by weight material: 65 parts of polypropylene；Poly- pair
12.8 parts of ethylene terephthalate；5 parts of POE-g-MAH；5 parts of metallocene PE；10 parts of calcium carbonate；Aluminate coupling agent 1
Part；1 part of dioctyl phthalate；0.2 part of DBPC 2,6 ditertiary butyl p cresol.
Wherein, calcium carbonate include the partial size of 20wt% be 20nm calcium carbonate, 30wt% partial size be the calcium carbonate of 55nm
The calcium carbonate that partial size with 50wt% is 120nm.
Wherein, first at a temperature of 100 DEG C, the aluminate coupling agent and calcium carbonate are subjected to mixing 10min, then
It is added after dioctyl phthalate stirring 10min pre-processes calcium carbonate, adds other components and prepared
PP composite material.
Wherein, the polyacrylic melt index is 4g/10min；The grafting rate of the POE-g-MAH is 1.5%；It is described
POE in POE-g-MAH is ethylene-l-octane copolymer, and the content of octene is 28wt% in the POE；The mPE is cyclopentadienyl gold
Belong to linear low density polyethylene, melt index 1.8g/10min.The items for the polypropylene material that this example is prepared
It can be as shown in table 1.
<example 3>
A kind of improved high-intensitive scraping-resistant polypropylene material comprising following parts by weight material: 60 parts of polypropylene；Poly- pair
10 parts of ethylene terephthalate；7 parts of POE-g-MAH；7 parts of metallocene PE；13 parts of calcium carbonate；Aluminate coupling agent 1.5
Part；1.2 parts of dioctyl phthalate；0.3 part of 2,6- di-tert-butyl hydroxy toluene.
Wherein, calcium carbonate include the partial size of 17wt% be 20nm calcium carbonate, 38wt% partial size be the calcium carbonate of 55nm
The calcium carbonate that partial size with 45wt% is 120nm.
Wherein, the polyacrylic melt index is 3g/10min；The grafting rate of the POE-g-MAH is 1.4%；It is described
POE in POE-g-MAH is ethylene-l-octane copolymer, and the content of octene is 27wt% in the POE；The mPE is cyclopentadienyl gold
Belong to linear low density polyethylene, melt index 1.5g/10min.The items for the polypropylene material that this example is prepared
It can be as shown in table 1.
<example 4>
A kind of improved high-intensitive scraping-resistant polypropylene material comprising following parts by weight material: 56.3 parts of polypropylene；It is poly-
14 parts of ethylene glycol terephthalate；8 parts of POE-g-MAH；8 parts of metallocene PE；11 parts of calcium carbonate；Aluminate coupling agent
1.2 part；1.1 parts of dioctyl phthalate；0.4 part of 2,6- di-tert-butyl hydroxy toluene.
Wherein, calcium carbonate include the partial size of 22wt% be 20nm calcium carbonate, 31wt% partial size be the calcium carbonate of 55nm
The calcium carbonate that partial size with 47wt% is 120nm.
Wherein, first at a temperature of 93 DEG C, the aluminate coupling agent and calcium carbonate are subjected to mixing 6min, then plus
Enter after dioctyl phthalate stirring 9min pre-processes calcium carbonate, adds other components and carry out preparing poly- third
Alkene composite material.
Wherein, the polyacrylic melt index is 2.7g/10min；The grafting rate of the POE-g-MAH is 1.4%；Institute
Stating the POE in POE-g-MAH is ethylene-l-octane copolymer, and the content of octene is 27wt% in the POE；The mPE is cyclopentadienyl
Metal linear low density polyethylene (LDPE), melt index 1.5g/10min.The items for the polypropylene material that this example is prepared
Performance is as shown in table 1.
<example 5>
A kind of improved high-intensitive scraping-resistant polypropylene material comprising following parts by weight material: 62 parts of polypropylene；Poly- pair
7.5 parts of ethylene terephthalate；6 parts of POE-g-MAH；7 parts of metallocene PE；14 parts of calcium carbonate；Aluminate coupling agent
1.8 part；1.3 parts of dioctyl phthalate；0.4 part of butylated hydroxy anisole.
Wherein, calcium carbonate include the partial size of 21wt% be 20nm calcium carbonate, 37wt% partial size be the calcium carbonate of 55nm
The calcium carbonate that partial size with 42wt% is 120nm.
Wherein, first at a temperature of 98 DEG C, the aluminate coupling agent and calcium carbonate are subjected to mixing 8min, then plus
Enter after dioctyl phthalate stirring 8min pre-processes calcium carbonate, adds other components and carry out preparing poly- third
Alkene composite material.
Wherein, the polyacrylic melt index is 3.5g/10min；The grafting rate of the POE-g-MAH is 1.4%；Institute
Stating the POE in POE-g-MAH is ethylene-l-octane copolymer, and the content of octene is 27wt% in the POE；The mPE is cyclopentadienyl
Metal linear low density polyethylene (LDPE), melt index 1.7g/10min.The items for the polypropylene material that this example is prepared
Performance is as shown in table 1.
In order to illustrate effect of the invention, it is as follows that inventor provides comparative experiments:
<comparative example 1>
When preparing the improved high-intensitive scraping-resistant polypropylene material, single POE-g-MAH is only added, is mismatched
Use metallocene PE and POE-g-MAH comprising following parts by weight material: 70 parts of polypropylene；Poly terephthalic acid second two
12.8 parts of alcohol ester；5 parts of POE-g-MAH；10 parts of calcium carbonate；1 part of aluminate coupling agent；1 part of dioctyl phthalate；2,6-
0.2 part of di-tert-butyl p-cresol.Remaining parameter with it is identical in example 2, technical process is also identical.This comparative example system
The properties of standby obtained polypropylene material are as shown in table 1.
<comparative example 2>
When preparing the improved high-intensitive scraping-resistant polypropylene material, aluminate coupling agent and O-phthalic are not used
Dioctyl phthalate pre-processes calcium carbonate comprising following parts by weight material: 62.7 parts of polypropylene；Poly terephthalic acid second two
10 parts of alcohol ester；7 parts of POE-g-MAH；7 parts of metallocene PE；13 parts of calcium carbonate；0.3 part of 2,6- di-tert-butyl hydroxy toluene.
Remaining parameter with it is identical in example 3, technical process is also identical.The polypropylene material that this comparative example is prepared
Properties are as shown in table 1.
<comparative example 3>
When preparing the improved high-intensitive scraping-resistant polypropylene material, it is only filled with the carbonic acid that average grain diameter is 120nm
Calcium.Remaining parameter with it is identical in example 4, technical process is also identical.The polypropylene material that this comparative example is prepared
The properties of material are as shown in table 1.
Product obtained in above-mentioned each example and comparative example is verified, respectively by being surveyed according to ASTM D256 standard
The notch impact strength for determining material, according to ASTM D638 standard universal test aircraft measurements material tensile strength and fracture
Elongation, according to ASTM D790 standard universal test aircraft measurements material bending strength and bending modulus.
The various performance parameters of 1 polypropylene material of table
From upper table 1, it can be seen that comparative example 1 is compared with example, when preparing polypropylene, without addition cyclopentadienyl in material component
Metal polyethylene, the polyacrylic toughening effect being prepared are poor.
For comparative example 2 compared with example, the not preprocessed direct and other components of calcium carbonate carry out modification by copolymerization, have with other
The poor compatibility of machine copolymer can influence the polyacrylic mechanical property being prepared due to causing the defect of material interface instead
Can, polyacrylic impact strength is decreased obviously；
Comparative example 3 is filled modification, the packed density of filler compared with example, using only the calcium carbonate of single particle size
Relatively low, the polypropylene items mechanical property being prepared is relatively low.
As it can be seen that the present invention is modified PP using PET, significantly improves the toughness of PP, impact resistance, resistance to environment and answer
Power cracking etc., effectively increases the application field and range of PP；
In addition, mPE and compatilizer POE-g-MAH cooperate with the use to reach toughening with lesser additive amount in the present invention
Effect, to negative effect caused by intermingling material while reducing toughening；
In addition, by the present invention in that with different-grain diameter calcium carbonate carry out cooperation filled high polymer material, it is poly- significantly improving
While propylene rigidity, modulus and dimensional stability, and improve the processing performance of high molecular material.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With.It can be applied to various suitable the field of the invention completely.It for those skilled in the art, can be easily
Realize other modification.Therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown and described herein.
Claims (3)
1. a kind of improved high-strength polypropylene material, which is characterized in that including following parts by weight material:
Wherein, calcium carbonate include the partial size of 15~25wt% be 20nm calcium carbonate, 30~40wt% partial size be the carbon of 55nm
The partial size of sour calcium and 40~50wt% are the calcium carbonate of 120nm；
Wherein, the grafting rate of the POE-g-MAH is 1.3~1.5%, and the POE in the POE-g-MAH is ethylene -1- octene
Copolymer, the content of octene is 26~28wt% in the POE；
Wherein, the polyacrylic melt index is 2.5~4g/10min, and the mPE is metallocene linear-low density polyethylene,
Its melt index is 1.3~1.8g/10min.
2. improved high-strength polypropylene material as described in claim 1, which is characterized in that first in 90~100 DEG C of temperature
Under, the aluminate coupling agent and calcium carbonate are subjected to 5~10min of mixing, add the dioctyl phthalate
After 7~10min of stirring pre-processes calcium carbonate, adds other components and carry out preparing PP composite material.
3. improved high-strength polypropylene material as described in claim 1, which is characterized in that the antioxidant is selected from 2,2-
One or more of di-2-ethylhexylphosphine oxide (4- methyl -6- butylphenol), DBPC 2,6 ditertiary butyl p cresol, butylated hydroxy anisole.
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| WO2019104570A1 (en) * | 2017-11-30 | 2019-06-06 | 世界家庭用具制品厂有限公司 | Scented, mold-resistant thin film and preparation method therefor |
| CN108570247B (en) * | 2018-04-11 | 2019-11-19 | 湖南师范大学 | A kind of Aluminate modified heavy calcium carbonate and preparation method thereof and a kind of poly styrene composite material |
| CN110804250A (en) * | 2019-12-04 | 2020-02-18 | 苏州炜隆灿防静电包装有限公司 | Improved high-strength scratch-resistant polypropylene material and preparation method thereof |
| CN112592539B (en) * | 2020-11-20 | 2023-03-10 | 金旸（厦门）新材料科技有限公司 | PP/PBT alloy material and preparation method thereof |
| WO2023050259A1 (en) * | 2021-09-30 | 2023-04-06 | 世界家庭用具制品厂有限公司 | Thin film and preparation method therefor |
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| CN101486817A (en) * | 2009-02-20 | 2009-07-22 | 华南理工大学 | High melt strength polypropylene material and preparation |
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| 纳米CaCO3/PET短纤维/聚丙烯复合材料的制备及性能;江兴文等;《高分子材料科学与工程》;20000229;第26卷(第2期);121-124 |
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