CN110483902A - A kind of high rigidity high-toughness glass fibre enhancing PP material and preparation method thereof - Google Patents
A kind of high rigidity high-toughness glass fibre enhancing PP material and preparation method thereof Download PDFInfo
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- CN110483902A CN110483902A CN201910803195.6A CN201910803195A CN110483902A CN 110483902 A CN110483902 A CN 110483902A CN 201910803195 A CN201910803195 A CN 201910803195A CN 110483902 A CN110483902 A CN 110483902A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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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
- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a kind of high rigidity high-toughness glass fibre enhancing PP materials and preparation method thereof.High rigidity high-toughness glass fibre of the invention enhances PP material, by weight percentage, the raw material of the high rigidity high-toughness glass fibre enhancing PP material includes following component: copolymerization PP55~59%, glass fibre 40%, nucleating agent 0.05~0.15%, coupling agent 0.5~2.5%, dispersing agent 0.2%, light stabilizer 0.2~0.4%.Preparation method of the invention is simple, and glass fiber reinforcement PP material obtained has high rigidity and high toughness simultaneously, realizes the balance of rigidity and toughness, can be widely applied to automotive field.
Description
Technical field
The present invention relates to polypropylene technology field, it is related to a kind of glass fiber reinforcement PP material and preparation method thereof, especially
It is related to a kind of high rigidity high-toughness glass fibre enhancing PP material and preparation method thereof.
Background technique
PA material has many advantages, such as excellent mechanical property, and corrosion-resistant, oil resistivity outstanding, heat resistance, high-modulus pass through
After long glass fiber reinforced, intensity, anti-collision performance, absorptivity of energy etc. have all obtained large increase, therefore, long glass
Fibre enhancing PA material can be applied to automotive field.But since PA material feedstock price is higher, density is bigger, so market
There is the trend of PP glass fiber reinforced materials substitution long glass fiber reinforced PA material.
Polypropylene (PP) is a kind of thermoplastic resin as prepared by propylene polymerization.It is divided into isotactic by methyl arrangement position
Polypropylene (isotactic polypropylene), random polypropylene (atactic polypropylene) and syndiotactic polypropylene
Three kinds of (syndiotactic polypropylene).Polypropylene material has nontoxic, tasteless, small specific of density, intensity,
Rigidity, hardness heat resistance are superior to low pressure polyethylene, can use at 100 DEG C or so, have good dielectric properties and high frequency exhausted
Edge, and do not influenced by humidity, but become fragile when low temperature, it is not wear-resisting, easy to aging, it is suitable for production common mechanical part, corrosion-resistant zero
Part and insulating part.
But polypropylene material is there are brittleness, impact resistant strength are low, poor rigidity, molding shrinkage be big, easy to aging etc. lacks
Point using glass fibre (abbreviation glass) modified heat distortion temperature that PP can be improved, the stability for increasing product size, reduces
Molding shrinkage, raising rigidity etc..The addition of glass is also used as the reinforcing filler of PP, can not only significantly improve PP's
Rigidity, surface hardness, creep resistant, electrical insulating property can also improve the impact strength of PP, improve PP impact resistance.However,
Glass fiber reinforcement PP material is all made of homopolymerization PP as enhancing object at present.
Currently, glass fiber reinforcement PP material existed general problem is to be difficult to control rigidity and impact property to put down on the market
Weighing apparatus.Such as 40 parts of glass fiber reinforcement PP materials, some material bending modulus can accomplish 10500MPa, but notch impact strength
Only 10KJ/m2；Some material impact intensities can accomplish 25KJ/m2, but bending modulus only has 5600MPa.
CN108148286A discloses a kind of low after-contraction PP composite material and preparation method thereof, by following weight
The component of part is made: polypropylene, high density polyethylene (HDPE), glass fiber powder, high mesh number glass fiber powder, toughener, nucleating agent, profit
Lubrication prescription, coupling agent, antioxidant.The invention is fed simultaneously by the way that glass fiber powder is added, and by main, side spout, Yi Jiyu
High mesh number glass fiber powder, high density polyethylene (HDPE) are used in compounding, and obtain the PP composite material of excellent combination property, while substantially dropping
The shrinking percentage of low PP composite material can be used in high-end automobile using as bumper.The PP composite material of the invention
With preferable impact strength, but bending modulus and tensile strength be not high, needs to be further increased, therefore the invention is poly-
Acrylic composite cannot have preferable rigidity and toughness simultaneously.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of high rigidity high-toughness glass fibres to enhance PP
Material and preparation method thereof, glass fiber reinforcement PP material obtained have high rigidity and high toughness simultaneously, realize just
The balance of property and toughness, can be widely applied to automotive field.
To achieve this purpose, the present invention adopts the following technical scheme:
A kind of high rigidity high-toughness glass fibre enhancing PP material, by weight percentage, the high rigidity high tenacity glass
The raw material of glass fiber reinforcement PP material includes following component:
It should be noted that high rigidity of the present invention refer to the bending modulus of PP material in 5000MPa or more, especially
Refer to the bending modulus of PP material in 5000~8200MPa；High tenacity of the present invention refers to the notch impact strength of PP material
10KJ/m2More than, the impact strength of PP material is referred in particular in 11~22KJ/m2。
It in the present invention, uses copolymerization PP for major ingredient, adds glass fibre as reinforcing material, and nucleating agent, coupling is added
Agent, dispersing agent and light stabilizer and consumption proportion by adjusting each component make glass fiber reinforcement PP material obtained simultaneously
With high rigidity and high toughness.
Specifically, a kind of high rigidity high-toughness glass fibre of the invention enhances PP material, by weight percentage, described
The raw material that high rigidity high-toughness glass fibre enhances PP material includes following component:
It is copolymerized PP55~59%, such as the weight percent of copolymerization PP is 55%, 56%, 57%, 58%, 59%；
Glass fibre 40%；
Nucleating agent 0.05~0.15%, for example, nucleating agent weight percent be 0.05%, 0.06%, 0.07%,
0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, preferably 0.1%；
Coupling agent 0.5~2.5%, for example, coupling agent weight percent be 0.5%, 0.6%, 0.7%, 0.8%,
0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%,
2.2%, 2.3%, 2.4%, 2.5%；
Dispersing agent 0.2%；
Light stabilizer 0.2~0.4%, for example, light stabilizer weight percent be 0.2%, 0.25%, 0.3%,
0.35%, 0.4%.
In the present invention, the melt index of the copolymerization PP is 10~20g/10min, such as the melt index of copolymerization PP is
10g/10min、11g/10min、12g/10min、13g/10min、14g/10min、15g/10min、16g/10min、17g/
10min,18g/10min,19g/10min,20g/10min；Simple beam impact strength is 15~25KJ/m2, such as simply supported beam punching
Hit intensity is 15KJ/m2、16KJ/m2、17KJ/m2、18KJ/m2、19KJ/m2、20KJ/m2、21KJ/m2、22KJ/m2、23KJ/m2、
24KJ/m2、25KJ/m2；Bending modulus be 1300~1500MPa, such as bending modulus be 1300MPa, 1350MPa, 1400MPa,
1450MPa,1500MPa.Select the copolymerization PP of this type as basis material, it is ensured that the high rigidity and toughness of PP material.
In the present invention, the diameter of the glass fibre is 10~13 μm, for example, the diameter of glass fibre is 10 μm, 11 μm,
12 μm, 13 μm, preferably 10 μm.The diameter of glass fibre is smaller, and the rigidity of material and toughness can be made better, but if glass
The diameter of fiber is too small, and less than 10 μm, the rigidity of material increases preferably but toughness improvement is bad；If glass fibre
Diameter is too big, is greater than 13 μm, the dispersibility of material is deteriorated, and the improvement of rigidity and toughness is unobvious.
Preferably, the length of the glass fibre be 3~4.5mm, such as glass fibre length be 3mm, 3.1mm,
3.2mm、3.3mm、3.4mm、3.5mm、3.6mm、3.7mm、3.8mm、3.9mm、4mm、4.1mm、4.2mm、4.3mm、4.4mm、
4.5mm, preferably 4.5mm.
The nucleating agent is the compound of alpha-crystal form nucleating agent and beta crystal-type nucleater；It is brilliant by adjusting alpha-crystal form nucleating agent and β
The consumption proportion of type nucleating agent, while the rigidity and toughness of PP material are improved, and the dosage of glass fibre can be effectively reduced.
Preferably, the mass ratio of the alpha-crystal form nucleating agent and the beta crystal-type nucleater is (1~3): 2；Such as the α is brilliant
The mass ratio of type nucleating agent and the beta crystal-type nucleater is 1:1,1:2,3:2 etc..
Preferably, the alpha-crystal form nucleating agent is nucleator in organic phosphate class；Preferably, the organic phosphate at
Core agent is bis- (the 4,6- di-t-butyl phenoxy group) phosphalugels (NA-21) of 2,2 '-methylene-；Select organic nucleation of this type
Agent can more efficiently improve the rigidity of PP material.
Preferably, the beta crystal-type nucleater is aromatic amine nucleating agent, selects the nucleating agent of this type can be more efficiently
Improve the toughness of PP material, hence it is evident that improve the impact property of material.
The coupling agent is maleic anhydride.
The dispersing agent is sodium tripolyphosphate, calgon, triethyl group hexyl phosphoric acid, appointing in lauryl sodium sulfate
It anticipates a kind of or at least two mixtures.The mixture is typical but unrestricted group is combined into sodium tripolyphosphate, calgon
Mixture, the mixture of calgon, triethyl group hexyl phosphoric acid, triethyl group hexyl phosphoric acid, lauryl sodium sulfate it is mixed
Close object, the mixture of calgon, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, sodium tripolyphosphate, calgon,
The mixture of triethyl group hexyl phosphoric acid, sodium tripolyphosphate, calgon, lauryl sodium sulfate mixture, tripolyphosphate
Sodium, calgon, triethyl group hexyl phosphoric acid, lauryl sodium sulfate mixture, said mixture is only list one
Point, it can also be other combinations of above-mentioned dispersing agent, not list one by one herein.
The light stabilizer is hindered amine light stabilizer, salicylate light stabilizer and benzophenones light stabilizer
In any one or at least two mixture.The mixture can be hindered amine light stabilizer, salicylic acid esters light
The mixture of stabilizer, the mixture of hindered amine light stabilizer, benzophenones light stabilizer, salicylate light stabilizer
With the mixture of benzophenones light stabilizer, hindered amine light stabilizer, salicylate light stabilizer and benzophenones
The mixture of light stabilizer.
The second object of the present invention is to provide high rigidity high-toughness glass fibre enhancing PP described in a kind of first purpose
The preparation method of material, the preparation method comprises the following steps:
1) according to the ratio, copolymerization PP, nucleating agent, coupling agent, dispersing agent, light stabilizer are mixed evenly；
2) the mixed material of step 1) is added in extruder, by glass fibre side feed material, through pelletizing, mistake after extruding pelletization
After sieve, drying, the high rigidity high-toughness glass fibre enhancing PP material is prepared.
In step 1), the speed of the stirring is 100~300r/min, such as the speed of stirring is 100r/min, 150r/
min,200r/min,250r/min,300r/min；The time of the stirring be 10~20min, such as mixing time be 10min,
11min、12min、13min、14min、15min、16min、17min、18min、19min、20min。
Preferably, in step 2), the screw speed of the extruder is 300~500rpm, such as the screw rod of extruder turns
Speed is 300rpm, 350rpm, 400rpm, 450rpm, 500rpm；The temperature of the extrusion is 180~240 DEG C, such as extrusion
Temperature is 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C；The pressure of the extrusion be 0.75~
0.95MPa, such as the pressure of extrusion is 0.75MPa, 0.8MPa, 0.85MPa, 0.9MPa, 0.95MPa.
As a preferred solution of the present invention, the preparation method comprises the following steps:
1) according to the ratio, copolymerization PP, nucleating agent, coupling agent, dispersing agent, light stabilizer are sequentially added in high-speed mixer,
It is uniform to material that 10~20min is mixed in the speed of 100~300r/min；
2) the mixed material of step 1) is added twin-screw extrude, by glass fibre side feed material, screw speed 300
~500rpm, the temperature of extrusion are 180~240 DEG C, and the pressure of extrusion is 0.75~0.95MPa, through pelletizing, mistake after extruding pelletization
After sieve, drying, the high rigidity high-toughness glass fibre enhancing PP material is prepared.
Compared with prior art, the invention has the benefit that
(1) glass fibre is added as strengthening material to be copolymerized PP as base-material in glass fiber reinforcement PP material of the invention
Material, and nucleating agent, coupling agent, dispersing agent and light stabilizer and the consumption proportion by adjusting each component is added, make glass obtained
Glass fiber reinforcement PP material has high rigidity and high toughness simultaneously, and tensile strength is 55~80MPa, bending strength 104
~130MPa, bending modulus are 5080~8200MPa, and notch impact strength is 11~22KJ/m2。
(2) preparation method of the invention is simple, and PP material obtained realizes the balance of rigidity and toughness well, can be wide
It is general to be applied in automotive field.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field
It obtains.
Embodiment 1
The high rigidity high-toughness glass fibre of the present embodiment enhances PP material, by weight percentage, by following components group
At:
Wherein, nucleating agent 2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphalugel (NA-21) and fragrance
The compound of amine nucleating agent, mass ratio 1:2, coupling agent are maleic anhydride, and dispersing agent is lauryl sodium sulfate, and light is stablized
Agent is salicylate light stabilizer；The melt index for being copolymerized PP is 15g/10min, simple beam impact strength 25KJ/m2, curved
Bent modulus is 1500MPa, and the diameter of glass fibre is 10 μm, and the length of glass fibre is 3mm.
The present embodiment high rigidity high-toughness glass fibre enhancing PP material the preparation method is as follows: according to the ratio, will be copolymerized
PP, nucleating agent, coupling agent, dispersing agent, light stabilizer sequentially add in high-speed mixer, are mixed with the speed of 200r/min
15min adds twin-screw extrude the material mixed, then 10 μm of diameter of glass fibre is added in No. three side spouts
Enter, control screw speed is 350r/min, controls extrusion temperature are as follows: the 1st 180 DEG C of region, the 2nd~9 240 DEG C of region, the 10th~
11 regional temperatures are 230 DEG C, vacuum pump pressure 0.8MPa, and Gao Gang is prepared after pelletizing, sieving, drying in the material of extrusion
Property high-toughness glass fibre enhance PP material.
Embodiment 2
The high rigidity high-toughness glass fibre of the present embodiment enhances PP material, by weight percentage, by following components group
At:
Wherein, nucleating agent 2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphalugel (NA-21) and fragrance
The compound of amine nucleating agent, mass ratio 3:2, coupling agent are maleic anhydride, and dispersing agent is sodium tripolyphosphate, and light stabilizer is
Hindered amine light stabilizer；The melt index for being copolymerized PP is 15g/10min, simple beam impact strength 25KJ/m2, bending modulus
For 1500MPa, the diameter of glass fibre is 13 μm, and the length of glass fibre is 4mm.
The present embodiment high rigidity high-toughness glass fibre enhancing PP material the preparation method is as follows: according to the ratio, will be copolymerized
PP, nucleating agent, coupling agent, dispersing agent, light stabilizer sequentially add in high-speed mixer, are mixed with the speed of 300r/min
10min adds twin-screw extrude the material mixed, then 12 μm of diameter of glass fibre is added in No. three side spouts
Enter, control screw speed is 450r/min, controls extrusion temperature are as follows: the 1st 180 DEG C of region, the 2nd~9 240 DEG C of region, the 10th~
11 regional temperatures are 230 DEG C, vacuum pump pressure 0.85MPa, and height is prepared after pelletizing, sieving, drying in the material of extrusion
Rigid high-toughness glass fibre enhances PP material.
Embodiment 3
The high rigidity high-toughness glass fibre of the present embodiment enhances PP material, by weight percentage, by following components group
At:
Wherein, nucleating agent 2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphalugel (NA-21) and fragrance
The compound of amine nucleating agent, mass ratio 3:2, coupling agent are maleic anhydride, and dispersing agent is sodium tripolyphosphate, and light stabilizer is
Hindered amine light stabilizer；The melt index for being copolymerized PP is 20g/10min, simple beam impact strength 25KJ/m2, bending modulus
For 1400MPa, the diameter of glass fibre is 12 μm, and the length of glass fibre is 4.5mm.
The present embodiment high rigidity high-toughness glass fibre enhancing PP material the preparation method is as follows: according to the ratio, will be copolymerized
PP, nucleating agent, coupling agent, dispersing agent, light stabilizer sequentially add in high-speed mixer, are mixed with the speed of 200r/min
15min adds twin-screw extrude the material mixed, then 13 μm of diameter of glass fibre is added in No. three side spouts
Enter, control screw speed is 350r/min, controls extrusion temperature are as follows: the 1st 180 DEG C of region, the 2nd~9 240 DEG C of region, the 10th~
11 regional temperatures are 230 DEG C, vacuum pump pressure 0.85MPa, and height is prepared after pelletizing, sieving, drying in the material of extrusion
Rigid high-toughness glass fibre enhances PP material.
Embodiment 4
The high rigidity high-toughness glass fibre of the present embodiment enhances PP material, by weight percentage, by following components group
At:
Wherein, nucleating agent 2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphalugel (NA-21) and fragrance
The compound of amine nucleating agent, mass ratio 1:2, coupling agent are maleic anhydride, and dispersing agent is lauryl sodium sulfate, and light is stablized
Agent is salicylate light stabilizer；The melt index for being copolymerized PP is 15g/10min, simple beam impact strength 25KJ/m2, curved
Bent modulus is 1500MPa, and the diameter of glass fibre is 13 μm, and the length of glass fibre is 4mm.
The present embodiment high rigidity high-toughness glass fibre enhancing PP material the preparation method is as follows: according to the ratio, will be copolymerized
PP, nucleating agent, coupling agent, dispersing agent, light stabilizer sequentially add in high-speed mixer, are mixed with the speed of 200r/min
15min adds twin-screw extrude the material mixed, then 13 μm of diameter of glass fibre is added in No. three side spouts
Enter, control screw speed is 350r/min, controls extrusion temperature are as follows: the 1st 180 DEG C of region, the 2nd~9 240 DEG C of region, the 10th~
11 regional temperatures are 230 DEG C, vacuum pump pressure 0.85MPa, and height is prepared after pelletizing, sieving, drying in the material of extrusion
Rigid high-toughness glass fibre enhances PP material.
Embodiment 5
The high rigidity high-toughness glass fibre of the present embodiment enhances PP material, by weight percentage, by following components group
At:
Wherein, nucleating agent 2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphalugel (NA-21) and fragrance
The compound of amine nucleating agent, mass ratio 1:1, coupling agent are maleic anhydride, and dispersing agent is 0.1% sodium tripolyphosphate, 0.1%
The mixture of lauryl sodium sulfate, light stabilizer are that 0.1% salicylate light stabilizer and 0.1% benzophenones light are steady
Determine the mixture of agent；The melt index for being copolymerized PP is 15g/10min, simple beam impact strength 15KJ/m2, bending modulus is
1300MPa, the diameter of glass fibre are 13 μm, and the length of glass fibre is 4.5mm.
The present embodiment high rigidity high-toughness glass fibre enhancing PP material the preparation method is as follows: according to the ratio, will be copolymerized
PP, nucleating agent, coupling agent, dispersing agent, light stabilizer sequentially add in high-speed mixer, are mixed with the speed of 200r/min
15min adds twin-screw extrude the material mixed, then 13 μm of diameter of glass fibre is added in No. three side spouts
Enter, control screw speed is 350r/min, controls extrusion temperature are as follows: the 1st 180 DEG C of region, the 2nd~9 240 DEG C of region, the 10th~
11 regional temperatures are 230 DEG C, vacuum pump pressure 0.85MPa, and height is prepared after pelletizing, sieving, drying in the material of extrusion
Rigid high-toughness glass fibre enhances PP material.
Embodiment 6
It is in place of the difference of the present embodiment and embodiment 1, nucleating agent replaces with talcum powder, others and 1 phase of embodiment
Together.
Embodiment 7
It is in place of the present embodiment and the difference of embodiment 1, nucleating agent replaces with bis- (4, the 6- bis- tertiary fourths of 2,2 '-methylene-
Phenoxyl) phosphalugel (NA-21), it is other same as Example 1.
Embodiment 8
It is in place of the difference of the present embodiment and embodiment 1, nucleating agent replaces with aromatic amine nucleating agent, other and real
It is identical to apply example 1.
Embodiment 9
It is in place of the difference of the present embodiment and embodiment 1, the bending modulus for being copolymerized PP is 800MPa, other and implementation
Example 1 is identical.
Embodiment 10
It is in place of the difference of the present embodiment and embodiment 1, the bending modulus for being copolymerized PP is 2000MPa, other and real
It is identical to apply example 1.
Embodiment 11
It is in place of the difference of the present embodiment and embodiment 1, the diameter of glass fibre is 5 μm, others and 1 phase of embodiment
Together.
Embodiment 12
It is in place of the difference of the present embodiment and embodiment 1, the diameter of glass fibre is 15 μm, other and embodiment 1
It is identical.
Embodiment 13
It is in place of the difference of the present embodiment and embodiment 1, the length of glass fibre is 1mm, others and 1 phase of embodiment
Together.
Embodiment 14
It is in place of the difference of the present embodiment and embodiment 1, the length of glass fibre is 10mm, other and embodiment 1
It is identical.
Comparative example 1
The glass fiber reinforcement PP material of this comparative example, by weight percentage, composed of the following components:
The preparation method of the glass fiber reinforcement PP material of this comparative example is same as Example 1.
Comparative example 2
It is in place of the difference of this comparative example and embodiment 1, PP material replaces with homopolymerization PP, others and 1 phase of embodiment
Together.
Comparative example 3
It is in place of this comparative example and the difference of embodiment 1, the dosage for being copolymerized PP is 40%, the weight of the copolymerization PP of reduction
It averagely increases in other components, guarantees that total amount is constant.
Comparative example 4
It is in place of this comparative example and the difference of embodiment 1, the dosage for being copolymerized PP is 85%, the weight of increased copolymerization PP
It is deducted from other components, guarantees that total amount is constant.
Comparative example 5
It is in place of this comparative example and the difference of embodiment 1, the dosage of glass fibre is 10%, the glass fibre of reduction
Weight average increases in other components, guarantees that total amount is constant.
Comparative example 6
It is in place of this comparative example and the difference of embodiment 1, the dosage of glass fibre is 50%, increased glass fibre
Weight is deducted from other components, guarantees that total amount is constant.
Comparative example 7
It is in place of this comparative example and the difference of embodiment 1, be not added with nucleating agent, the weight average of the nucleating agent of reduction increases
It adds in other components, guarantees that total amount is constant.
By glass made from the enhancing PP material of high rigidity high-toughness glass fibre made from embodiment 1-14 and comparative example 1-7
Fiber reinforcement PP material is tested for the property, and test result is as shown in table 1.
Tensile strength, bending strength and the bending modulus of material embody the rigidity quality of material, the notch shock of material
Intensity embodies the toughness quality of material.Wherein, the testing standard of tensile strength is carried out referring to the testing standard of ISO527, bending
The testing standard of intensity is carried out referring to the testing standard of ISO178, the test of bending modulus referring to ISO178 testing standard into
The testing standard of row, notch impact strength is carried out referring to the testing standard of ISO179.
Table 1
As can be seen from Table 1, glass fibre is added to be copolymerized PP as base-material in glass fiber reinforcement PP material of the invention
As reinforcing material, and nucleating agent, coupling agent, dispersing agent and stabilizer and the consumption proportion by adjusting each component is added, makes
Glass fiber reinforcement PP material obtained has high rigidity and high toughness simultaneously, and tensile strength is 55~80MPa, and bending is strong
Degree is 104~130MPa, and bending modulus is 5080~8200MPa, and notch impact strength is 11~22KJ/m2。
Nucleating agent is replaced with talcum powder by embodiment 6, and the rigidity and toughness of PP material reduce.
Embodiment 7 individually uses bis- (the 4,6- di-t-butyl phenoxy group) phosphalugel (NA- of nucleating agent 72,2 '-methylene-
21), embodiment 8 individually uses nucleating agent aromatic amine nucleating agent, and without the compound using the two, rigidity and toughness are
It reduces, and to achieve the effect that rigidity and good toughness need to increase the dosage of glass fibre.
The bending modulus that embodiment 9 is copolymerized PP is too low, and the toughness of PP material obtained can be made to increase, but under rigidity
Drop, i.e. tensile strength, bending strength, bending modulus reduce.
The bending modulus that embodiment 10 is copolymerized PP is too high, and the rigidity of PP material obtained can be made to improve, but degraded toughness.
Embodiment 11, the diameter of 12 glass fibres are too big or too small, can make the rigidity and toughness effect of PP material obtained
Optimum efficiency cannot be reached.The length of 13 glass fibre of embodiment is too short, the rigidity of PP material obtained can be made to improve, still
Degraded toughness；The length of 14 glass fibre of embodiment is too long, and the toughness of PP material obtained can be made to improve, but rigidity is deteriorated,
The length of glass fibre is too long or too short rigidity and toughness effect cannot be made to reach best.
Comparative example 1 is not added with nucleating agent and dispersing agent, can make tensile strength, the bending strength, bending of PP material obtained
Modulus and impact strength can all decline, i.e., rigidity and toughness effect cannot reach optimum efficiency.
PP material is replaced with homopolymerization PP by comparative example 2, then can make the tensile strength of PP material obtained, bending strength, curved
Bent modulus decline.
In comparative example 3 and 4, if the dosage of homopolymerization PP not in the amount ranges of the application, PP material obtained it is rigid
Property and toughness can decline.
Comparative example 5, the dosage of 6 glass fibres, also can rigidity and toughness to material not within the scope of the restriction of the application
Generate influences in various degree, and the rigidity and toughness effect of PP material obtained cannot reach optimum efficiency.
Comparative example 7 is not added with nucleating agent, and the rigidity and toughness of PP material obtained can be greatly reduced.
Detailed process equipment and process flow of the invention that the present invention is explained by the above embodiments, but the present invention is not
It is confined to above-mentioned detailed process equipment and process flow, that is, does not mean that the present invention must rely on above-mentioned detailed process equipment and work
Skill process could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to product of the present invention
The equivalence replacement of each raw material and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention and public affairs
Within the scope of opening.
Claims (10)
1. a kind of high rigidity high-toughness glass fibre enhances PP material, which is characterized in that by weight percentage, the high rigidity
The raw material that high-toughness glass fibre enhances PP material includes following component:
2. high rigidity high-toughness glass fibre according to claim 1 enhances PP material, which is characterized in that the copolymerization PP
Melt index be 10~20g/10min, simple beam impact strength be 15~25KJ/m2, bending modulus be 1300~
1500MPa。
3. high rigidity high-toughness glass fibre according to claim 1 or 2 enhances PP material, which is characterized in that the glass
The diameter of glass fiber is 10~13 μm；
Preferably, the length of the glass fibre is 3~4.5mm.
4. high rigidity high-toughness glass fibre described in one of -3 enhances PP material according to claim 1, which is characterized in that described
Nucleating agent is the compound of alpha-crystal form nucleating agent and beta crystal-type nucleater；
Preferably, the mass ratio of the alpha-crystal form nucleating agent and the beta crystal-type nucleater is (1~3): 2；
Preferably, the alpha-crystal form nucleating agent is nucleator in organic phosphate class；
Preferably, the nucleator in organic phosphate class is bis- (4, the 6- di-t-butyl phenoxy group) phosphalugels of 2,2 '-methylene-
(NA-21)；
Preferably, the beta crystal-type nucleater is aromatic amine nucleating agent.
5. high rigidity high-toughness glass fibre described in one of -4 enhances PP material according to claim 1, which is characterized in that described
Coupling agent is maleic anhydride.
6. high rigidity high-toughness glass fibre described in one of -5 enhances PP material according to claim 1, which is characterized in that described
Dispersing agent be sodium tripolyphosphate, calgon, triethyl group hexyl phosphoric acid, in lauryl sodium sulfate any one or at least
Two kinds of mixture.
7. high rigidity high-toughness glass fibre described in one of -6 enhances PP material according to claim 1, which is characterized in that described
Light stabilizer is any one in hindered amine light stabilizer, salicylate light stabilizer and benzophenones light stabilizer
Or at least two mixture.
8. a kind of preparation method for enhancing PP materials such as the described in any item high rigidity high-toughness glass fibres of claim 1-7,
It is characterized in that, the preparation method comprises the following steps:
1) according to the ratio, copolymerization PP, nucleating agent, coupling agent, dispersing agent, light stabilizer are mixed evenly；
2) the mixed material of step 1) is added in extruder, by glass fibre side feed material, after extruding pelletization through pelletizing, sieving,
After drying, the high rigidity high-toughness glass fibre enhancing PP material is prepared.
9. preparation method according to claim 8, which is characterized in that in step 1), the speed of the stirring is 100~
300r/min, the time of the stirring are 10~20min；
Preferably, in step 2), the screw speed of the extruder is 300~500rpm, the temperature of the extrusion is 180~
240 DEG C, the pressure of the extrusion is 0.75~0.95MPa.
10. preparation method according to claim 8 or claim 9, which is characterized in that the preparation method comprises the following steps:
1) according to the ratio, copolymerization PP, nucleating agent, coupling agent, dispersing agent, light stabilizer are sequentially added in high-speed mixer, 100~
It is uniform to material that 10~20min is mixed in the speed of 300r/min；
2) the mixed material of step 1) is added twin-screw extrude, by glass fibre side feed material, screw speed is 300~
500rpm, the temperature of extrusion are 180~240 DEG C, and the pressure of extrusion is 0.75~0.95MPa, through pelletizing, mistake after extruding pelletization
After sieve, drying, the high rigidity high-toughness glass fibre enhancing PP material is prepared.
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