CN108219275A - A kind of ultra-toughness polypropylene and preparation method thereof - Google Patents
A kind of ultra-toughness polypropylene and preparation method thereof Download PDFInfo
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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Abstract
The present invention discloses a kind of ultra-toughness polypropylene, and meter includes following component in parts by weight：100 parts of polypropylene；10 ~ 30 parts of ethylene-propylene copolymer；5 ~ 20 parts of ethylene octene copolymer；0.1 ~ 5 part of polyester elastomer；1 ~ 15 part of nano-aluminum hydroxide；1 ~ 15 part of nano-calcium carbonate；0.1 ~ 5 part of anti-aging agent；0.5 ~ 3 part of coupling agent；0.5 ~ 3 part of diluent；5 ~ 10 parts of filler.Polypropylene provided by the invention has high impact strength and ageing-resistant high elongation at tear.
Description
Technical field
The present invention relates to field of high polymer material processing, and in particular to a kind of ultra-toughness polypropylene and preparation method thereof.
Background technology
For polypropylene plastics since synthesis technology is simple, comprehensive performance is good, cheap, the factors such as hygienic environment-protecting, already
It is most short as history in general-purpose thermoplastic plastic material, but develop and increase most fast plastics variety.With this several years people
Improvement of living standard, people it is increasing to the demand of plastics.
According to information, in an automobile in the U.S., the weight using plastics is 150-200kg, is made in European car
The use of the weight of plastics is 130-180kg in Japanese car with the weight of plastics with the very nearly the same of the U.S., and the car of China
The middle weight using plastics is only 80-120kg, and with European and American developed countries and between the Japan in Asia, there is very big differences
Away from.The defects of the main reason is that weatherability is poor, low temperature impact strength is low, and poor toughness is yielding, and inprocess shrinkage is big, significantly
Limit the application of polypropylene material.
Currently for there are many kinds of polyacrylic modification technologies, but two major class physical blendings and chemical modification are broadly divided into,
Chemical modification has certain limitation in itself, and industrialized production is more difficult, and most enterprise is still using physical blending
Mode carries out, but polypropylene, since synthetic method belongs to coordination synthesis mostly, the materials such as itself and polyethylene will in synthesis
It is difficult, and with not UV resistant, it is not low temperature resistant the features such as, black brittleness and resistance to ag(e)ing are all very poor, in physical blending
Middle addition auxiliary agent can improve its effect, although being only that the simple auxiliary agent that increases can improve the above-mentioned of material
Performance, but the compatibility and the influence human health in air that whether can volatilize in use between auxiliary agent and base material are
The greatest problem faced now.
Invention content
In view of this, the present invention provides a kind of ultra-toughness poly- third with high impact strength and ageing-resistant high elongation at tear
Alkene.
For solution more than technical problem, the technical scheme is that using a kind of ultra-toughness polypropylene, count in parts by weight
Including following component：
100 parts of polypropylene
10~30 parts of ethylene-propylene copolymer
5~20 parts of ethylene-octene copolymer
1~5 part of polyester elastomer
1~15 part of nano-aluminum hydroxide
1~15 part of nano-calcium carbonate
0.1~5 part of anti-aging agent
0.5~3 part of coupling agent
0.5~3 part of diluent
5~10 parts of filler.
Preferably, the coupling agent is selected from silane coupling agent, titante coupling agent or zirconium class coupling agent.
Preferably, the anti-aging agent be antioxidant A, antioxidant 264, antioxidant D or antioxidant 4010.
Preferably, the filler in glass fibre, boron fibre, nylon fiber the first or it is a variety of.
Preferably, it further includes：
1~5 part of lubricant；
Preferably, the lubricant is selected from calcium stearate, and stearic acid is one or more in paraffin.
Preferably, the diluent is selected from petroleum ether, acetone or stupid methanol.
The present invention also provides a kind of polyacrylic preparation method of the ultra-toughness, including：
All raw materials described in claim 1 are mixed, and are squeezed out by extruder；
It is squeezed out by different die orifices, and carries out wire drawing or granulation.
Preferably, the extruder selects double screw extruder, and screw speed is 150~200rad/min,
Extruder is divided into three sections, and first segment heating temperature is 180 DEG C~200 DEG C, second segment heating temperature for 200 DEG C~
210 DEG C, third section heating temperature is 210 DEG C~225 DEG C,
Preferably, described mix raw material all in claim 1 is specially：
Coupling agent is dispersed in diluent, obtains mixture；
The mixture with nano-calcium carbonate and nano-aluminum hydroxide is mixed, obtains slurry；
The slurry and other raw materials are mixed, form mixture.
The primary improvements of the present invention to provide a kind of ultra-toughness polypropylene and preparation method thereof, using ethylene-propylene copolymer,
The plasticized modifier of ethylene octene copolymer and polyester elastomer as polypropylene base, and ethylene-propylene copolymer is as polypropylene
The form of " crosslinking agent " similar with ethylene octene copolymer exists, and the compatibility that can allow three kinds of materials is more preferable, and binding force is more
By force, toughness can be improved again while promoting intensity.Polyester elastomer preferred thermoplastic polyesters elastomer, a small amount of thermoplastic elastic
Body can provide stronger toughness for polypropylene, since thermoplastic polyester elastomer has soft segment and hard section, and contain in hard section
Phenyl ring can be good at filling the position that other linear components leave, make strength of PP more preferable.In addition, the present invention also provides
Diluent carries out coupling processing to material using dilution technology, increases the contact area of coupling agent and material, improve place
The effect of reason, and diluent is volatile matter, just volatilizees, material will not be caused any completely before material is extruded
It influences.The present invention makes material have high impact-resistant and height also using novel nano-calcium carbonate, and carried out surface activation process
During the performance of elongation, the bending modulus of material is also improved, the physical property of material is made to basically reach a dynamic equilibrium.After improvement
Material system compatibility it is very good so that impact strength and elongation have no small raising, while the rigidity of material
Be not in decline.To sum up, the ultra-toughness polypropylene obtained by the formula and technique of the present invention is as follows by detection performance：
Elongation at break >=350%
IZOD notch impact strengths >=45KJ/m2
Bending modulus >=1700Mpa
Heat distortion temperature >=100 DEG C (0.45Mpa, 120 DEG C/h)
Vicat softening point >=150 DEG C (10N, 120 DEG C/h)
Specific embodiment
In order to which those skilled in the art is made to more fully understand technical scheme of the present invention, With reference to embodiment
The present invention is described in further detail.
A kind of ultra-toughness polypropylene, in parts by weight meter include following component：
100 parts of polypropylene
10~30 parts of ethylene-propylene copolymer
5~20 parts of ethylene-octene copolymer
1~5 part of polyester elastomer
1~15 part of nano-aluminum hydroxide
1~15 part of nano-calcium carbonate
0.1~5 part of anti-aging agent
0.5~3 part of coupling agent
0.5~3 part of diluent
5~10 parts of filler.
According to the present invention, the parts by weight are the weight that a weight has equivalent grams, for example a is 1000g
Or 1 part is 1g, specific weight is arranged according to the content that actual production occurs, but as long as just at this in the content ratio
In the protection domain of invention.
According to the present invention, polypropylene is divided into random polypropylene according to the difference of synthesis technology and molecular weight distribution and isotactic gathers
Propylene, present invention preferably uses be to use weight average molecular weight as more than 10w, molecular weight distribution is selected between 5~7
Polypropylene, the hardness and toughness of material meet the requirement of the technology of the present invention.
In order to enable polypropylene in raw material and ethylene propylene polymerization and ethylene-octene copolymer have it is good common
Mixed to combine, coupling agent of the present invention is selected from silane coupling agent, titante coupling agent or zirconium class coupling agent, is more selected as silane coupled
Agent or titante coupling agent, most preferably monoalkoxytitanates.
For the weatherability of reinforced polypropylene, it is necessary to which selection has the anti-old of good associativity with other raw materials of the invention
Agent, it is preferred that anti-aging agent of the present invention is preferably antioxidant A, and antioxidant 264, antioxidant D or antioxidant 4010 are more excellent
Choosing is selected from antioxidant D or antioxidant 4010.
For the intensity of reinforced polypropylene, the filler in glass fibre, boron fibre, nylon fiber the first or it is more
Kind.The millimetre-sized superfine fibre of the fiber.It can be specifically adjusted according to raw material.
In order to make preferably compatible material can be made to be molded rear surface quality higher between raw material, the present invention preferably further includes
1~5 part of lubricant；Preferably, the lubricant is selected from calcium stearate, and stearic acid is one or more in paraffin.
Another key point of the invention is first to disperse coupling agent etc. using diluent, forms uniform system, then
Diluent selection must can work in-process volatilize system, that is, the diluent that boiling point is relatively low, diluent
Effect be that can allow the surface for being dispersed in other materials that coupling agent can be evenly, reduce the viscous of coupling agent and other materials
Degree, makes material more uniform, it is proposed, according to the invention, the diluent is selected from petroleum ether, acetone or stupid methanol.
The present invention is also using novel nano-calcium carbonate, and carried out surface activation process, and it is preferable to use this for activation process
Method known to field technology personnel, such as calcium carbonate surface is carried out at activation using activators such as stearic acid or stearate
Reason.When calcium carbonate after activation can make the material have the performance of high impact-resistant and high elongation rate, the bending of material is also improved
Modulus makes the physical property of material basically reach a dynamic equilibrium.The compatibility of improved material system is very good so that impact
Intensity and elongation have no small raising, while the rigidity of material will not decline.It is of the invention more preferably to use nanometer
Calcium carbonate, have better surface property can organic matter it is preferably compatible.
The present invention also provides nano-aluminum hydroxides so that polypropylene has better toughness and flame retardant property.
The present invention also provides a kind of polyacrylic preparation method of the ultra-toughness, including：
All raw materials for weighing described are mixed, and are squeezed out by extruder；
It is squeezed out by different die orifices, and carries out wire drawing or granulation.
Preferably, the extruder selects double screw extruder, and screw speed is 150~200rad/min,
Extruder is divided into three sections, and first segment heating temperature is 180 DEG C~200 DEG C, second segment heating temperature for 200 DEG C~
210 DEG C, third section heating temperature is 210 DEG C~225 DEG C,
Specifically, coupling agent is dispersed in diluent by the mixing first, mixture is obtained；By the mixture with receiving
Rice calcium carbonate and nano-aluminum hydroxide mixing, obtain slurry；The slurry and other raw materials are mixed, form mixture.
It is the specific embodiment of the invention below, it should be noted that all raw materials that the present invention uses can select
It is commercially available.
Embodiment 1
Select the following raw material
100 parts of polypropylene
10 parts of ethylene-propylene copolymer
5 parts of ethylene-octene copolymer
1 part of thermoplastic polyester elastomer
1 part of nano-aluminum hydroxide
1 part of nano-calcium carbonate
0.1 part of antioxidant 4010
0.5 part of monoalkoxytitanates
0.5 part of petroleum ether
5 parts of Fypro.
Monoalkoxytitanates are dispersed in diluent, obtain mixture；By the mixture and nano-calcium carbonate and
Nano-aluminum hydroxide mixes, and obtains slurry；The slurry and other raw materials are mixed, form mixture.And pass through extruder and squeeze
Go out the extruder and select double screw extruder, screw speed 150rad/min,
Extruder is divided into three sections, and first segment heating temperature is 180 DEG C, and second segment heating temperature is 200 DEG C, the heating of third section
Temperature is 210 DEG C, is granulated after extrusion.Obtain ultra-toughness polypropylene.
Embodiment 2
Select the following raw material
100 parts of polypropylene
30 parts of ethylene-propylene copolymer
20 parts of ethylene-octene copolymer
5 parts of thermoplastic polyester elastomer
15 parts of nano-aluminum hydroxide
15 parts of nano-calcium carbonate
5 parts of antioxidant 4010
3 parts of monoalkoxytitanates
3 parts of petroleum ether
10 parts of glass fibre.
Monoalkoxytitanates are dispersed in diluent, obtain mixture；By the mixture and nano-calcium carbonate and
Nano-aluminum hydroxide mixes, and obtains slurry；The slurry and other raw materials are mixed, form mixture.And pass through extruder and squeeze
Go out the extruder and select double screw extruder, screw speed 200rad/min,
Extruder is divided into three sections, and first segment heating temperature is 200 DEG C, and second segment heating temperature is 210 DEG C, the heating of third section
Temperature is 220 DEG C, is granulated after extrusion.Obtain ultra-toughness polypropylene.
Embodiment 3
Select the following raw material
100 parts of polypropylene
20 parts of ethylene-propylene copolymer
15 parts of ethylene-octene copolymer
2 parts of thermoplastic polyester elastomer
10 parts of nano-aluminum hydroxide
10 parts of nano-calcium carbonate
3 parts of anti-aging agent
3 parts of coupling agent
3 parts of diluent
7 parts of filler.
Monoalkoxytitanates are dispersed in diluent, obtain mixture；By the mixture and nano-calcium carbonate and
Nano-aluminum hydroxide mixes, and obtains slurry；The slurry and other raw materials are mixed, form mixture.And pass through extruder and squeeze
Go out the extruder and select double screw extruder, screw speed 150rad/min,
Extruder is divided into three sections, and first segment heating temperature is 190 DEG C, and second segment heating temperature is 205 DEG C, the heating of third section
Temperature is 215 DEG C, is granulated after extrusion.Obtain ultra-toughness polypropylene.
Embodiment 4
Select the following raw material
100 parts of polypropylene
15 parts of ethylene-propylene copolymer
15 parts of ethylene-octene copolymer
2 parts of thermoplastic polyester elastomer
8 parts of nano-aluminum hydroxide
7 parts of nano-calcium carbonate
2 parts of antioxidant A
1 part of vinyltriethoxysilane
1 part of diluent
6 parts of nylon fiber；
10 parts of paraffin.
Monoalkoxytitanates are dispersed in diluent, obtain mixture；By the mixture and nano-calcium carbonate and
Nano-aluminum hydroxide mixes, and obtains slurry；The slurry and other raw materials are mixed, form mixture.And pass through extruder and squeeze
Go out the extruder and select double screw extruder, screw speed 180rad/min,
Extruder is divided into three sections, and first segment heating temperature is 195 DEG C, and second segment heating temperature is 200 DEG C, the heating of third section
Temperature is 220 DEG C, is granulated after extrusion.Obtain ultra-toughness polypropylene.
Embodiment 5
Select the following raw material
100 parts of polypropylene
25 parts of ethylene-propylene copolymer
15 parts of ethylene-octene copolymer
4 parts of polyester elastomer
5 parts of nano-aluminum hydroxide
5 parts of nano-calcium carbonate
0.5 part of antioxidant D
2 parts of chain alkyl trimethoxy silane
2 parts of acetone
5 parts of nylon fiber；
2 parts of stearic acid.
Monoalkoxytitanates are dispersed in diluent, obtain mixture；By the mixture and nano-calcium carbonate and
Nano-aluminum hydroxide mixes, and obtains slurry；The slurry and other raw materials are mixed, form mixture.And pass through extruder and squeeze
Go out the extruder and select double screw extruder, screw speed 160rad/min,
Extruder is divided into three sections, and first segment heating temperature is 180 DEG C, and second segment heating temperature is 200 DEG C, the heating of third section
Temperature is 210 DEG C, is granulated after extrusion.Obtain ultra-toughness polypropylene.
Comparative example 1
100 parts of polypropylene
Nano-aluminum hydroxide 10
5 parts of antioxidant 4010
3 parts of chain alkyl trimethoxy silane
5 parts of nylon fiber；
2 parts of stearic acid.
Above-mentioned raw materials are subjected to melt blending, screw speed 160rad/min in an extruder, extruder is divided into three sections,
First segment heating temperature is 180 DEG C, and second segment heating temperature is 200 DEG C, and third section heating temperature is 210 DEG C, is carried out after extrusion
It is granulated.Obtain ultra-toughness polypropylene.
By the method for standard GB/T/T 12670-2008 to polypropylene prepared by Examples 1 to 5 and comparative example 1 into
Row sample preparation is simultaneously detected, obtained result such as following table：
The mechanical performance of 1 embodiment 1 of table and comparative example 1 compares
Formula provided by the invention can be seen that by above-mentioned comparison and have according to polypropylene prepared by the method for the present invention
Good toughness and good weather resistance can bear higher impact and be used in various environment, in automobile
Using more preferably in field.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
The limitation of the present invention, protection scope of the present invention should be subject to claim limited range.For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
Protection scope of the present invention is also should be regarded as into retouching.
Claims (10)
1. a kind of ultra-toughness polypropylene, which is characterized in that meter includes following component in parts by weight：
100 parts of polypropylene
10 ~ 30 parts of ethylene-propylene copolymer
5 ~ 20 parts of ethylene-octene copolymer
0.1 ~ 5 part of polyester elastomer
1 ~ 15 part of nano-aluminum hydroxide
1 ~ 15 part of nano-calcium carbonate
0.1 ~ 5 part of anti-aging agent
0.5 ~ 3 part of coupling agent
0.5 ~ 3 part of diluent
5 ~ 10 parts of filler.
2. ultra-toughness polypropylene according to claim 1, which is characterized in that the coupling agent is selected from silane coupling agent, metatitanic acid
Esters coupling agent or zirconium class coupling agent.
3. ultra-toughness polypropylene according to claim 1, which is characterized in that the anti-aging agent be antioxidant A, antioxidant 264,
Antioxidant D or antioxidant 4010.
4. ultra-toughness polypropylene according to claim 1, which is characterized in that the filler is selected from glass fibre, boron fibre, Buddhist nun
The first in imperial fiber is a variety of.
5. ultra-toughness polypropylene according to claim 1, which is characterized in that further include：
1 ~ 5 part of lubricant.
6. ultra-toughness polypropylene according to claim 5, which is characterized in that the lubricant be selected from calcium stearate, stearic acid,
It is one or more in paraffin.
7. ultra-toughness polypropylene according to claim 1, which is characterized in that the diluent is selected from petroleum ether, acetone or stupid
Methanol.
8. a kind of polyacrylic preparation method of ultra-toughness described in claim 1, which is characterized in that including：
All raw materials described in claim 1 are mixed, and are squeezed out by extruder；
It is squeezed out by different die orifices, and carries out wire drawing or granulation.
9. preparation method according to claim 8, which is characterized in that the extruder selects double screw extruder, screw rod
Rotating speed is 150 ~ 200rad/min,
Extruder is divided into three sections, and first segment heating temperature is 180 DEG C ~ 200 DEG C, and second segment heating temperature is 200 DEG C ~ 210 DEG C,
Third section heating temperature is 210 DEG C ~ 225 DEG C.
10. preparation method according to claim 7, which is characterized in that described to mix raw material all in claim 1
Specially：
Coupling agent is dispersed in diluent, obtains mixture；
The mixture with nano-calcium carbonate and nano-aluminum hydroxide is mixed, obtains slurry；
The slurry and other raw materials are mixed, form mixture.
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| CN110396244A (en) * | 2019-07-31 | 2019-11-01 | 黄山华塑新材料科技有限公司 | The PP Wood plastic composite and preparation method fire-retardant, low-temperature impact resistance toughness is excellent |
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| CN110396244A (en) * | 2019-07-31 | 2019-11-01 | 黄山华塑新材料科技有限公司 | The PP Wood plastic composite and preparation method fire-retardant, low-temperature impact resistance toughness is excellent |
| CN113736182A (en) * | 2021-09-26 | 2021-12-03 | 金旸（厦门）新材料科技有限公司 | Polypropylene composite material with low linear expansion coefficient and preparation method thereof |
| CN114456489A (en) * | 2022-01-21 | 2022-05-10 | 台州市盛尔达塑业有限公司 | Gallon basin material and preparation method thereof |
| CN114456489B (en) * | 2022-01-21 | 2024-01-23 | 台州市盛尔达塑业有限公司 | Gallon basin material and preparation method thereof |
| CN115477808A (en) * | 2022-08-15 | 2022-12-16 | 单成敏 | Preparation method of carbon fiber reinforced high-precision template |
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