CN107987348A - A kind of damage resistant composite polyolefine material - Google Patents
A kind of damage resistant composite polyolefine material Download PDFInfo
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- CN107987348A CN107987348A CN201711213452.8A CN201711213452A CN107987348A CN 107987348 A CN107987348 A CN 107987348A CN 201711213452 A CN201711213452 A CN 201711213452A CN 107987348 A CN107987348 A CN 107987348A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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 relates to a kind of damage resistant composite polyolefine material, belong to technical field of polymer materials.It is existing easy to crack in order to solve the problems, such as, there is provided a kind of damage resistant composite polyolefine material, the composite material include the parts by weight of following component：Vistanex：80~90；Damage resistant agent：1.5~3.0；Toughener：3.0~5.0；Carbon nano-particle：8.0~10；The vistanex has bimodal molecular weight distribution.The present invention can make material realization have preferable rigidity and resistance to rapid crack propagation performance (RCP) and resistance to cracking performance at a slow speed (SCG) performance concurrently.
Description
Technical field
The present invention relates to a kind of damage resistant composite polyolefine material, belong to technical field of polymer materials.
Background technology
Polyolefin is that production scale is maximum in existing synthetic material, yield highest, the most wide a kind of interchangeable heat of application range
Thermoplastic plastic, such as polyethylene or polypropylene.Specifically, polypropylene has heat resisting temperature height, and anti-fatigue performance is excellent, electric exhausted
The advantages that edge performance is good, chemical resistance, processing forming are good.The advantages of these are protruded causes the polyolefin such as polypropylene almost
It can be applied to the every field of national economy.Such as plastic products pipeline material.
With processing of high molecular material, the development and the improvement of people's living standards of modification technology, people are being concerned about polyene
While the intensity of hydrocarbon product, quality and service life, also begin to be concerned about the competition of the appearance of product, production cost and product
Power.
But since the polyolefine material case hardness such as polypropylene or polyethylene is low, it is easy to scratched by hard object,
Scratching the cut produced seriously reduces the performance of product, such as causes pipeline to crack or the defects of crackle increases.Therefore, at present,
The development and exploitation for researching and developing damage resistant polyolefine material have become a new research direction.
For the damage resistant polyolefine material that production performance is excellent, the existing exploitation to polypropylene damage resistant master batch also into
For a research hotspot, but product and few, and all there are it is certain the defects of, it is easy to crack during such as machine-shaping to ask
Topic.
The content of the invention
Present invention defect existing in the prior art for more than, there is provided a kind of damage resistant composite polyolefine material, solves
The problem of be how effectively to realize the performance of crack resistence and scratch.
The purpose of the present invention is what is be achieved by the following technical programs, a kind of damage resistant composite polyolefine material, its
It is characterized in that, which includes the parts by weight of following component：
Vistanex：80~90；Damage resistant agent：1.5~3.0；Toughener：3.0~5.0；Carbon nano-particle：8.0~
10；The vistanex has bimodal molecular weight distribution.
The present invention, as main body base material, makes have height in molecular structure by using the polyolefin of bimodal molecular weight distribution
The high polymer of the molecular weight of distribution, so that both the high polymer with low molecular weight can have material in molecular polyolefin structure
There are high-crystallinity and lubricating action, assign its good rigidity and resistance to rapid crack propagation performance (RCP), meanwhile, make to have compared with high score
The high polymer of son amount distribution ensure that the resistance to cracking performance at a slow speed (SCG) of material, still, due to the hardness of polyolefin in itself compared with
It is low, easily occur phenomena such as scratch in use, and the problem of crushing cracking is easily led to, therefore, the present invention passes through addition
Damage resistant agent improves the integral hardness of material, makes have preferable scratch resistant performance, and the purpose by adding toughener is
In order to improve compatibility, make material that there is preferable toughness, ensure the strength character of material.
In above-mentioned damage resistant composite polyolefine material, preferably, the vistanex for bimodal polyethylene or/and
Bimodal volcanic rocks., can be by using DSC, MFR etc. since polyethylene and polypropylene material are typical non-Newtonian fluid materials
Method test obtains the behavioral data of its isothermal crystal and nonisothermal crystallization, and can be effectively obtained polyene according to these data
The temperature field of hydrocarbon melt and pressure field parameter request.Therefore, using both materials can be conducive in process tubing into
The elimination of type process in which materials internal stress, improves the physical and mechanical property of tubing.
In above-mentioned damage resistant composite polyolefine material, preferably, the bimodal molecular weight distribution, which has, is less than 60kDa
First monomodal molecular weight distribution of weight average molecular weight, and the bimodal molecular weight distribution also has at least 60kDa weight average molecular weight
The second monomodal molecular weight distribution.Equivalent to the high polymer and low for making in molecular polyolefin structure while having high molecular weight to be distributed
The high polymer of molecular weight distribution, and by the way that material with 60kDa weight average molecular weight, can be made to have preferable rigidity concurrently and resistance to quickly open
Fragility energy (RCP) and resistance to cracking performance at a slow speed (SCG) performance, especially makes its resistance to rapid crack propagation performance pC, FS>=1.5 × MOP,
pC, S4≥MOP/2.4-0.072.As further preferably, the bimodal molecular weight distribution includes the height of 20wt%~30wt%
The low molecular weight fraction of molecular weight fraction and 70wt%~80wt%, and by high molecular weight block and the summation of low molecular weight fraction
For 100% meter.Here be the equal of the proportion requirement calculated on the basis of the overall weight of vistanex, make guarantee height
The sum of percentage composition of molecular weight fraction and low molecule reason fraction is just 100%.It is further preferred, it can make wherein double
First monomodal molecular weight distribution of the peak molecular weight distribution with 30kDa~50kDa weight average molecular weight, and the wide/bimodal molecular weight point
Cloth also has the second monomodal molecular weight distribution of 70kDa~120kDa weight average molecular weight.
In above-mentioned damage resistant composite polyolefine material, preferably, the melt index MI of the polyolefin is 2.0g/
Min~10g/min.Can make composite material that there is preferable mobility, beneficial to the machine-shaping of material, and due to mobility compared with
It is good, enable the distribution of each component evenly in composite material, ensure the performance of material.
In above-mentioned damage resistant composite polyolefine material, preferably, the damage resistant agent is dimethyl silicone rubber.Have
Preferable compatibility, makes to play more preferable scratch resistant performance, ensures that material has preferable resistance to cracking energy and strength character.
In above-mentioned damage resistant composite polyolefine material, preferably, the carbon nano-particle is selected from carbon nanotubes, nanometer
One or more in graphene and nano-graphite.The strength character of material can be improved, makes that there is preferable tensile strength
Effect.As further preferably, the average grain diameter of the carbon nano-particle is 50nm~100nm.Can be evenly it is scattered
Into composite material, make to be more evenly distributed, and use nano level material, certain modified function can be played, improve compatible
Property.
In above-mentioned damage resistant composite polyolefine material, preferably, the reinforcing agent is selected from nano silicon dioxide, talcum
It is one or more of in powder and titanium dioxide.Improve the strength character of material.
In conclusion compared with prior art, the present invention has the following advantages：
The present invention can realize material by using the vistanex with bimodal molecular weight distribution and damage resistant agent
Have preferable rigidity and resistance to rapid crack propagation performance (RCP) and resistance to cracking performance at a slow speed (SCG) performance concurrently, and be beneficial to processing and forming
Processing, eliminates the effect of the internal stress of material.
Embodiment
Below by specific embodiment, the technical solutions of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Polyvinyl resin：80；Damage resistant agent dimethyl silicone rubber：1.5；Toughener：3.0；Reinforcing agent titanium dioxide：1.0；
Carbon nano-particle：8.0, the particle diameter of carbon nano-particle is 50nm；Wherein, polyvinyl resin has bimodal molecular weight distribution, and should
Bimodal molecular weight distribution includes the high molecular weight block of 20wt% and the low molecular weight fraction of 80wt%, bimodal molecular weight distribution tool
There is the first monomodal molecular weight distribution (equivalent to low molecular weight fraction) of 60kDa weight average molecular weight and there is 100kDa Weight-average moleculars
The second monomodal molecular weight distribution (equivalent to high molecular weight block) of amount, toughener here can use polyvinyl alcohol or poly-vinegar
Sour ethene.The pigment that 1.0~2.0 parts by weight can also be added according to being actually needed.Certainly, pigment is not neccessary composition, can
Selection adds or is not added with as needed.
Embodiment 2
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Polyvinyl resin：90；Damage resistant agent dimethyl silicone rubber：3.0；Toughener：5.0；Reinforcing agent titanium dioxide：2.0；
Carbon nano-particle：10, the particle diameter of carbon nano-particle is 80nm, and carbon nano-particle is nano-graphene；Wherein, polyvinyl resin
With bimodal molecular weight distribution, and the bimodal molecular weight distribution includes the high molecular weight block of 30wt% and the low molecule of 70wt%
Magnitude point, bimodal molecular weight distribution have the first monomodal molecular weight distribution of 50kDa weight average molecular weight (equivalent to low molecular weight fraction
Point) and with 120kDa weight average molecular weight the second monomodal molecular weight distribution (equivalent to high molecular weight block), toughness reinforcing here
Agent can use polyvinyl alcohol or polyvinyl acetate.The pigment that 1.5 parts by weight can also be added according to being actually needed.
Embodiment 3
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Polyvinyl resin：85；Damage resistant agent dimethyl silicone rubber：2.0；Toughener：4.0；Reinforcing agent talcum powder：1.8；Carbon
Nano particle：9.0, the particle diameter of carbon nano-particle is 90nm, and carbon nano-particle is nano-graphite；Wherein, polyvinyl resin
Melt index MI is 2.0g/min, and polyvinyl resin has bimodal molecular weight distribution, and the bimodal molecular weight distribution includes
The high molecular weight block of 25wt% and the low molecular weight fraction of 75wt%, bimodal molecular weight distribution have 40kDa weight average molecular weight
The first monomodal molecular weight distribution (equivalent to low molecular weight fraction) and with 100kDa weight average molecular weight the second monomodal molecular
(equivalent to high molecular weight block), toughener here can use polyvinyl alcohol or polyvinyl acetate for amount distribution.Can be with root
The pigment for adding 1.5 parts by weight according to being actually needed.
Embodiment 4
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Acrylic resin：82；Damage resistant agent dimethyl silicone rubber：2.5；Toughener：4.5；Reinforcing agent：1.5, wherein strengthening
Agent is the mixture of talcum powder and titanium dioxide and both mass ratioes are 1：0.5；Carbon nano-particle：8.5, carbon nano-particle
Particle diameter is 70nm, and the mixture that carbon nano-particle is carbon nanotubes and nano-graphene and both mass ratio are 0.5：1.0；
Wherein, the melt index MI of acrylic resin is 10g/min, and acrylic resin has bimodal molecular weight distribution, and this is bimodal
Molecular weight distribution includes the high molecular weight block of 30wt% and the low molecular weight fraction of 70wt%, and bimodal molecular weight distribution has
The first monomodal molecular weight distribution (equivalent to low molecular weight fraction) of 30kDa weight average molecular weight and there is 110kDa weight average molecular weight
The second monomodal molecular weight distribution (equivalent to high molecular weight block), toughener here uses polyvinyl acetate.Can be with root
The pigment for adding 2.0 parts by weight according to being actually needed.
Embodiment 5
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Acrylic resin：88；Damage resistant agent dimethyl silicone rubber：2.0；Toughener：3.5；Reinforcing agent：1.8, wherein strengthening
Agent is the mixture of silica and talcum powder and both mass ratioes are 1：0.5, wherein, the particle of silica and talcum powder
Particle diameter is 80nm；Carbon nano-particle：8.8, the particle diameter of carbon nano-particle is 60nm, and carbon nano-particle is nano-graphene；
Wherein, the melt index MI of acrylic resin is 5.0g/min, and acrylic resin has bimodal molecular weight distribution, and this is bimodal
Molecular weight distribution includes the high molecular weight block of 20wt% and the low molecular weight fraction of 80wt%, and bimodal molecular weight distribution has
The first monomodal molecular weight distribution (equivalent to low molecular weight fraction) of 50kDa weight average molecular weight and there is 80kDa weight average molecular weight
The second monomodal molecular weight distribution (equivalent to high molecular weight block), toughener here uses polyvinyl acetate.
Embodiment 6
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Polyvinyl resin：60；Acrylic resin：30；Damage resistant agent dimethyl silicone rubber：2.0；Toughener：3.0；Enhancing
Agent：2.0, wherein reinforcing agent is silica, and silica dioxide granule particle diameter is 90nm；Carbon nano-particle：9.0, carbon nanometer
The particle diameter of grain is 70nm, and carbon nano-particle is nano-graphite；Wherein, the melt index MI of acrylic resin is 6.0g/min,
And acrylic resin has a bimodal molecular weight distribution, the bimodal molecular weight distribution include 25wt% high molecular weight block and
The low molecular weight fraction of 75wt%, bimodal molecular weight distribution have the first monomodal molecular weight distribution (phase of 60kDa weight average molecular weight
When in low molecular weight fraction) and there is the second monomodal molecular weight distribution of 90kDa weight average molecular weight (equivalent to high molecular weight fraction
Point)；Meanwhile the melt index IM that polyethylene tree refers to is 5.0g/min, and polyvinyl resin has bimodal molecular weight distribution, this pair
Peak molecular weight distribution includes the high molecular weight block of 28wt% and the low molecular weight fraction of 72wt%, and bimodal molecular weight distribution has
The first monomodal molecular weight distribution (equivalent to low molecular weight fraction) of 50kDa weight average molecular weight and there is 100kDa weight average molecular weight
The second monomodal molecular weight distribution (equivalent to high molecular weight block), and toughener here uses polyvinyl acetate.
Embodiment 7
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Polyvinyl resin：20；Acrylic resin：60；Damage resistant agent dimethyl silicone rubber：3.0；Toughener：4.0；Enhancing
Agent：1.0, wherein reinforcing agent is titanium dioxide, and titanium dioxide granule particle diameter is 100nm；Carbon nano-particle：10, carbon nanometer
The particle diameter of grain is 80nm, and carbon nano-particle is carbon nanotubes；Wherein, the melt index MI of acrylic resin is 8.0g/min,
And acrylic resin has a bimodal molecular weight distribution, the bimodal molecular weight distribution include 20wt% high molecular weight block and
The low molecular weight fraction of 80wt%, bimodal molecular weight distribution have the first monomodal molecular weight distribution (phase of 30kDa weight average molecular weight
When in low molecular weight fraction) and there is the second monomodal molecular weight distribution of 110kDa weight average molecular weight (equivalent to high molecular weight fraction
Point)；Meanwhile the melt index IM that polyethylene tree refers to is 3.0g/min, and polyvinyl resin has bimodal molecular weight distribution, this pair
Peak molecular weight distribution includes the high molecular weight block of 30wt% and the low molecular weight fraction of 70wt%, and bimodal molecular weight distribution has
The first monomodal molecular weight distribution (equivalent to low molecular weight fraction) of 40kDa weight average molecular weight and there is 120kDa weight average molecular weight
The second monomodal molecular weight distribution (equivalent to high molecular weight block), and toughener here uses polyvinyl acetate.
Embodiment 8
Damage resistant composite polyolefine material in the present embodiment includes the parts by weight of following component：
Polyvinyl resin：40；Acrylic resin：40；Damage resistant agent dimethyl silicone rubber：1.5；Toughener：3.0；Enhancing
Agent：2.0, wherein reinforcing agent is talcum powder, and talcum particles particle diameter is 90nm；Carbon nano-particle：8.0, carbon nano-particle
Particle diameter is 70nm, and carbon nano-particle is nano-graphite；Wherein, the melt index MI of acrylic resin is 3.0g/min, and poly-
Allyl resin has bimodal molecular weight distribution, high molecular weight block and 77wt% of the bimodal molecular weight distribution including 23wt%
Low molecular weight fraction, bimodal molecular weight distribution have the first monomodal molecular weight distribution of 40kDa weight average molecular weight (equivalent to low point
Sub- magnitude point) and the second monomodal molecular weight distribution with 80kDa weight average molecular weight (equivalent to high molecular weight block)；Meanwhile
The melt index IM that polyethylene tree refers to is 8.0g/min, and polyvinyl resin has bimodal molecular weight distribution, the wide/bimodal molecular weight
Distribution includes the high molecular weight block of 20wt% and the low molecular weight fraction of 80wt%, and bimodal molecular weight distribution is with 60kDa weights
The first monomodal molecular weight distribution (equivalent to low molecular weight fraction) of average molecular weight and the second list with 80kDa weight average molecular weight
Peak molecular weight is distributed (equivalent to high molecular weight block), and toughener here uses polyvinyl acetate.
Corresponding composite processing that above-described embodiment obtains is randomly selected into tubing, and makes the caliber of tubing be 1m, into
The relevant performance test of row, wherein, resistance to slow crack growth performance is tested under 80 DEG C, 165h hydraulics.It is specific to survey
Test result is as shown in table 1 below：
Table 1：
It can be seen that the pipe fitting that the composite processing of the present invention is formed has preferably from the test result in above-mentioned table 1
Resistance to rapid crack propagation can and resistance to slow crack growth performance, and longitudinal welds and notch impact strength be respectively provided with it is higher
Strength character.
Specific embodiment described in the present invention is only to spirit institute of the invention explanation for example.Technology belonging to the present invention
The technical staff in field can do described specific embodiment various modifications or additions or in a similar way
Substitute, but without departing from spirit of the invention or beyond the scope of the appended claims.
It is skilled to this area although having been made a detailed description to the present invention and being cited some specific embodiments
For technical staff, as long as it is obvious that can make various changes or correct without departing from the spirit and scope of the present invention.
Claims (9)
1. a kind of damage resistant composite polyolefine material, it is characterised in that the composite material includes the parts by weight of following component：
Vistanex：80~90；Damage resistant agent：1.5~3.0；Toughener：3.0~5.0；Reinforcing agent：1.0~2.0；Carbon is received
Rice grain：8.0~10；The vistanex has bimodal molecular weight distribution.
2. damage resistant composite polyolefine material according to claim 1, it is characterised in that the vistanex is bimodal poly-
Ethene or/and bimodal volcanic rocks.
3. damage resistant composite polyolefine material according to claim 2, it is characterised in that the bimodal molecular weight distribution has
Less than the first monomodal molecular weight distribution of 60kDa weight average molecular weight, and the bimodal molecular weight distribution is also with least 60kDa weights
Second monomodal molecular weight distribution of average molecular weight.
4. according to the 1 or 2 or 3 damage resistant composite polyolefine material of claim, it is characterised in that the wide/bimodal molecular weight point
Cloth includes the high molecular weight block of 20wt%~30wt% and the low molecular weight fraction of 70wt%~80wt%, and presses high molecular weight
The summation of fraction and low molecular weight fraction is 100% meter.
5. according to the 1 or 2 or 3 damage resistant composite polyolefine material of claim, it is characterised in that the melting of the polyolefin
Index M I is 2.0g/min~10g/min.
6. according to the 1 or 2 or 3 damage resistant composite polyolefine material of claim, it is characterised in that the damage resistant agent is two
Methyl silicone rubber.
7. according to the 1 or 2 or 3 damage resistant composite polyolefine material of claim, it is characterised in that the carbon nano-particle choosing
One or more from carbon nanotubes, nano-graphene and nano-graphite.
8. damage resistant composite polyolefine material according to claim 7, it is characterised in that the average grain of the carbon nano-particle
Footpath is 50nm~100nm.
9. according to the 1 or 2 or 3 damage resistant composite polyolefine material of claim, it is characterised in that the toughener is selected from and receives
It is one or more of in rice silica, talcum powder and titanium dioxide.
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| CN201711213452.8A CN107987348A (en) | 2017-11-28 | 2017-11-28 | A kind of damage resistant composite polyolefine material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109749198A (en) * | 2018-12-26 | 2019-05-14 | 浙江瑞堂塑料科技股份有限公司 | A kind of high tenacity rotational moulding flowerpot material and preparation method thereof |
-
2017
- 2017-11-28 CN CN201711213452.8A patent/CN107987348A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109749198A (en) * | 2018-12-26 | 2019-05-14 | 浙江瑞堂塑料科技股份有限公司 | A kind of high tenacity rotational moulding flowerpot material and preparation method thereof |
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Application publication date: 20180504 |