CN103788472B - A kind of binary composite polypropylene nucleator, preparation method and application - Google Patents
A kind of binary composite polypropylene nucleator, preparation method and application Download PDFInfo
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- CN103788472B CN103788472B CN201210425128.3A CN201210425128A CN103788472B CN 103788472 B CN103788472 B CN 103788472B CN 201210425128 A CN201210425128 A CN 201210425128A CN 103788472 B CN103788472 B CN 103788472B
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/527—Cyclic esters
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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
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses a kind of binary composite polypropylene nucleator, preparation method and application.Described nucleator is made up of benzoic acids nucleator and organic nucleating agent, and benzoic acids nucleator is sodium benzoate or aluminum benzoate；Described organic nucleating agent is 2,2 ' ylidene methyl two (4,6 di-n-butyl phenol) sodium phosphates；Benzoic acids nucleator is 95:5～5:95 with the weight ratio of organic nucleating agent；Nucleator is microemulsion state.Method includes: benzoic acids nucleator is dissolved in water；Organic nucleating agent is dissolved in cosurfactant；The two and surfactant, oil phase are mixed to form microemulsion.The composite nucleating agent of the present invention, adds in polypropylene material, and the crystal property of material and mechanical property can be made to improve, cost declines to a great extent simultaneously, has consumption few, effective, and processing cost is low, the advantages such as preparation technology is simple, are the mechanics modifying agent of a kind of preferable acrylic resin.
Description
Technical field
The present invention relates to polypropylene field, furtherly, relate to a kind of binary composite polypropylene nucleator,
Preparation method and application.
Background technology
Polypropylene is a kind of thermoplastic being widely used, and cheap and combination property is preferable, passes through
Add nucleator and can improve mechanical property and the optical property of polypropylene articles further, it is achieved polypropylene height
Energyization.Polyacrylic nucleator be a class for improving crystalling propylene behavior, thus improve its physical mechanical
Performance and the auxiliary agent of thermodynamic property.Nucleator is divided into mineral-type, glucitols, phosphoric acid salt, rosin
With high score subclass nucleator.
At present, on market, widely used polypropylene nucleater is organic nucleating agent, as NA11 [2,2 '-methylene
-two (4,6-di-tert-butyl-phenyl) sodium phosphate], NA-2l [di-2-ethylhexylphosphine oxide (2,4-di-tert-butyl-phenyl) aluminum phosphate] etc..
Organic nucleating agent consumption is few, and nucleating effect is obvious, can improve polyacrylic crystallization temperature, good stability,
Increase the most effective, can significantly improve polyacrylic heat distortion temperature and mechanical property, but this type of nucleator valency
Lattice are higher.
Sodium benzoate, molecular formula is C6H5CO2Na, is benzoic sodium salt.Sodium benzoate becomes as decentralized
Core agent, can improve polyacrylic crystallization temperature, shortens crystallization time；Under high pressure molding, it is also possible to change
Becoming polyacrylic crystal formation. sodium benzoate nucleator, compared with other nucleators, has that synthesis technique is simple, cost
The advantages such as low, nontoxic, easy storage.
In recent years, for giving full play to the advantage of all kinds of nucleator, research is had to start to focus on the different nucleator of research
Or the cooperative effect between nucleator and other auxiliary agents.Chinese patent CN101845171A discloses a kind of poly-
Propylene increases firm compositions, is by sodium benzoate and double [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl)] sodium phosphates
Improve the bending property of PP goods, impact strength and heat distortion temperature etc. etc. compositions, single group than adding
Divide nucleator modified effect good, there is certain cooperative effect, but required nucleator content is higher.China
Patent 200780012801.8 uses water miscible nucleator HPN-68 to be dissolved in the water as aqueous phase, with it
He forms microemulsion at component such as oil phase, surfactant, cosurfactant etc., after adding polypropylene, becomes
Core agent can be better dispersed in polymer, improves its crystalline rate, but relates only to water miscible nucleation
Agent, and a lot of nucleator is not water miscible.
The polypropylene nucleater how processability is excellent on the basis of consumption is few is a direction of research.
This patent needs the problem overcoming the difficulty of nucleator own to be dissolved in water, obtains a kind of applicable nucleator scattered micro-
Emulsion, promotes its dispersion and synergy further.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of binary composite polypropylene nucleator,
Preparation method and application.Use the preparation side of benzoate nucleator and the microemulsion dissolving of organic nucleating agent
Method prepares polypropylene nucleater, is the nucleator of a kind of acrylic resin preferably with cooperative effect.
The present invention has that addition is few, effect is obvious, scattered, preparation technology simple, it is excellent to improve mechanical property etc.
Point.
An object of the present invention is to provide a kind of binary composite polypropylene nucleator.
Described nucleator is made up of benzoic acids nucleator and organic nucleating agent,
Described benzoic acids nucleator is sodium benzoate or aluminum benzoate；Described organic nucleating agent is 2,2 '-methylene
Base-two (4,6-di-tert-butyl-phenyl) sodium phosphate；Benzoic acids nucleator with the weight ratio of organic nucleating agent is
95:5～5:95；It is preferably 75:25～25:75；
Described nucleator is microemulsion state.
The two of the purpose of the present invention are to provide the preparation method of a kind of binary composite polypropylene nucleator.
Including:
Benzoic acids nucleator is dissolved in water；Organic nucleating agent is dissolved in cosurfactant；
The two and surfactant, oil phase are mixed to form microemulsion；
Wherein,
The consumption of the water dissolving benzoic acids nucleator is 20～80wt%；
The consumption of the cosurfactant dissolving organic nucleating agent is 5～20wt%；
Dosage of surfactant is 10～40wt%；
Oil phase consumption is 5～20wt%；
Described benzoic acids nucleator is sodium benzoate or aluminum benzoate；
Described organic nucleating agent is 2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate；
Benzoic acids nucleator is 95:5～5:95 with the weight ratio of organic nucleating agent；It is preferably 75:25～25:75；
Described cosurfactant is alcohols, includes but not limited to ethanol, propanol, isopropanol, propylene glycol, penta
Alcohol, butanol, capryl alcohol, decanol, Hexalin, preferably ethanol；
Described surfactant is polyoxyethylene-20-sorbitan monooleate, polyoxyethylene-20-dehydration mountain
Pears alcohol monostearate, polyoxyethylene-20-anhydrous sorbitol list myristinate, polyoxyethylene-20-dehydration mountain
One in pears alcohol monolaurate or combination；
Described oil phase is ethyl n-butyrate., white oil, mineral oil, petroleum ether, the one in decahydronaphthalenes or combination,
It is preferably ethyl n-butyrate..
Specifically can be by the following technical solutions:
(1) benzoate nucleator is dissolved in deionized water；
(2) by NA11 by being dissolved in ethanol；
(3) above-mentioned will be dissolved with the aqueous phase of benzoate, be dissolved with the ethanol of NA11 as helping surface activity
Agent (is told with oil phase ethyl n-butyrate., surfactant polyoxyethylene-20-sorbitan monooleate
Temperature 80) mix homogeneously, form microemulsion；
(4) microemulsion containing nucleator and antioxidant are added in polypropylene powder, use twin-screw extrusion
Machine extrusion obtains nucleator composite polypropylene.
Mix and blend equipment in preparation method is the usual mixing apparatus used in manufacture field, such as: magnetic force stirs
Mix device, high shear dispersion machine, homogenizer etc..
Nucleator is dissolved in microemulsion by the present invention, and water miscible nucleator is soluble in aqueous phase, and
NA11 dissolves in ethanol as cosurfactant, adds oil phase, surfactant, obtains microemulsion.
Microemulsion is thermodynamically stable, isotropic, the appearance transparent or semi-transparent that two kinds of immiscible liquids are formed
Bright dispersion, by the microdroplet institute of stable one or both liquid of surfactant interface film on microcosmic
Constitute.(" microemulsion technology and application " China Light Industry Press, Cui Zhenggang, Yin Fushan volume, page 75).
The three of the purpose of the present invention are to provide a kind of binary composite polypropylene nucleator prepared by described method and exist
Prepare the application in RPP.Described binary composite polypropylene nucleator consumption in polypropylene is preferred
It it is 0.025～0.1 weight portion.
The method that the present invention uses benzoate nucleator compounding with organic nucleating agent is prepared a kind of compound poly-
Propylene nucleator.Select the microemulsion system that oil phase, aqueous phase, surfactant, cosurfactant are formed.
Innovatively adding nucleant agent N A11 in cosurfactant, and be dissolved in aqueous phase by benzoate, these are two years old
Plant nucleator and use the system dispersion of microemulsion, mixing, owing to the dispersion phase in microemulsion is nanoscale, institute
Also can reach nanoscale dispersion with nucleator, use micro-emulsion process by while two kinds of nucleator mix homogeneously,
Its super-refinement can also be disperseed, thus effectively expand the contact area of nucleator and polypropylene matrix.From
And be conducive to the dispersion in acrylic resin and nucleating effect.In the case of organic nucleating agent content is identical,
Composite nucleating agent has identical or more preferable nucleating effect, and along with the raising mechanical property of addition can also
Enough raisings further.Therefore, the organic phosphate nucleating agent that prepared by micro-emulsion process and benzoate nucleation
Agent is applied in polypropylene as composite nucleating agent, has consumption few, effective, and processing cost is low, preparation
The advantages such as technique is simple, are the mechanics modifying agent of a kind of preferable acrylic resin.
The present invention has obtained the composite nucleating agent with synergy, and crystal property and the mechanical property of material carry
Height, cost declines to a great extent simultaneously.
Accompanying drawing explanation
Fig. 1 is the polarizing microscope photo of PP pure sample
Fig. 2 is the polarizing microscope photo of comparative example 8 sample
Fig. 3 is the polarizing microscope photo of embodiment 9
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；Sodium benzoate (Tianjin light
Multiple fine chemistry industry institute) dissolve in deionized water with the concentration of 10wt%；Use magnetic stirrer,
It is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, dissolved going of sodium benzoate
Ionized water, said components quality proportioning is 20/20/40/20, uses magnetic stirrer, magnetic stirring apparatus
Rotating speed be 200rpm (rpm), mixing time 5 minutes.The microemulsion mixed obtains 1# binary
Composite nucleating agent.
Embodiment 2
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt% (mass percent)；Sodium benzoate
(Tianjin recovery fine chemistry industry institute) dissolves in deionized water with the concentration of 0.625wt%；Use magnetic
Power agitator stirs, and is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, dissolving
The deionized water of sodium benzoate, said components quality proportioning is 5/5/10/80, uses magnetic stirrer,
The rotating speed of magnetic stirring apparatus is 200rpm (rpm), mixing time 5 minutes.The microemulsion mixed obtains
To 2# binary composite nucleating agent.
Embodiment 3
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 5wt%；Sodium benzoate (recover by Tianjin
Fine chemistry industry institute) dissolve in deionized water with the concentration of 15wt%；Use magnetic stirrer,
It is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, dissolved going of sodium benzoate
Ionized water, said components quality proportioning is 20/20/40/20, uses magnetic stirrer, magnetic stirring apparatus
Rotating speed be 200rpm (rpm), mixing time 5 minutes.The microemulsion mixed obtains 3# binary
Composite nucleating agent.
Embodiment 4
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 5wt% (mass percent)；Sodium benzoate
(Tianjin recovery fine chemistry industry institute) dissolves in deionized water with the concentration of 0.9375wt%；Use magnetic
Power agitator stirs, and is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, dissolving
The deionized water of sodium benzoate, said components quality proportioning is 5/5/10/80, uses magnetic stirrer,
The rotating speed of magnetic stirring apparatus is 200rpm (rpm), mixing time 5 minutes.The microemulsion mixed obtains
To 4# binary composite nucleating agent.
Embodiment 5
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；Sodium benzoate (Tianjin light
Multiple fine chemistry industry institute) dissolve in deionized water with the concentration of 3.33wt%；Use magnetic stirrer,
It is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, dissolved going of sodium benzoate
Ionized water, said components quality proportioning is 20/20/40/20, uses magnetic stirrer, magnetic stirring apparatus
Rotating speed be 200rpm (rpm), mixing time 5 minutes.The microemulsion mixed obtains 5# binary
Composite nucleating agent.
Embodiment 6
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt% (mass percent)；Sodium benzoate
(Tianjin recovery fine chemistry industry institute) dissolves in deionized water with the concentration of 0.205wt%；Use magnetic
Power agitator stirs, and is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, dissolving
The deionized water of sodium benzoate, said components quality proportioning is 5/5/10/80, uses magnetic stirrer,
The rotating speed of magnetic stirring apparatus is 200rpm (rpm), mixing time 5 minutes.The microemulsion mixed obtains
To 6# binary composite nucleating agent.
Comparative example 1
Use magnetic stirring apparatus (model) stirring, be sequentially added into dehydrated alcohol, ethyl n-butyrate., Tween 80,
Deionized water, said components quality proportioning is 20/20/40/20, uses magnetic stirrer, magnetic agitation
The rotating speed of device is 200rpm (rpm), mixing time 5 minutes.The microemulsion mixed is blank microemulsion
Liquid 0#.
Comparative example 2
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；Use magnetic stirrer,
It is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, deionized water, said components
Quality proportioning is 20/20/40/20, uses magnetic stirrer, and the rotating speed of magnetic stirring apparatus is that 200rpm (turns
Per minute), mixing time 5 minutes.The microemulsion mixed obtains 7# binary composite nucleating agent.
Comparative example 3
NA11 [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl) sodium phosphate] (Zhong Da Chemical Co., Ltd., the trade mark
NP-508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；Use magnetic stirrer,
It is sequentially added into and has dissolved the dehydrated alcohol of NA11, ethyl n-butyrate., Tween 80, deionized water, said components
Quality proportioning is 5/5/10/80, uses magnetic stirrer, and the rotating speed of magnetic stirring apparatus is that 200rpm (turns
Per minute), mixing time 5 minutes.The microemulsion mixed obtains 8# binary composite nucleating agent.
Comparative example 4
Sodium benzoate (Tianjin recovery fine chemistry industry institute) is dissolved in deionized water with the concentration of 20wt%
In；Use magnetic stirring apparatus (model) stirring, be sequentially added into dehydrated alcohol, ethyl n-butyrate., Tween 80,
Having dissolved the deionized water of sodium benzoate, said components quality proportioning is 20/20/40/20, uses magnetic agitation
Device stirs, and the rotating speed of magnetic stirring apparatus is 200rpm (rpm), mixing time 5 minutes.Mix
Microemulsion obtains 9# binary composite nucleating agent.
Comparative example 5
Sodium benzoate (Tianjin recovery fine chemistry industry institute) is dissolved in deionized water with the concentration of 10wt%
In；Use magnetic stirring apparatus (model) stirring, be sequentially added into dehydrated alcohol, ethyl n-butyrate., Tween 80,
Having dissolved the deionized water of sodium benzoate, said components quality proportioning is 5/5/10/80, uses magnetic stirring apparatus
Stirring, the rotating speed of magnetic stirring apparatus is 200rpm (rpm), mixing time 5 minutes.Mix is micro-
Emulsion obtains 10# binary composite nucleating agent.
Table 1. microemulsion formula table
Embodiment 7
By the 1# composite nucleating agent of preparation in embodiment 1, (Beijing Chemical Research Institute is raw with copolymerization polypropylene powder
Produce, melt flow rate (MFR) 5.5g/10min), antioxidant 1010 and 168 (Switzerland vapour Ba Jiaji produce, the two with
1/1 ratio is used in mixed way) mix, its particular make-up: polypropylene 100 parts, 1# composite nucleating agent microemulsion
0.625 part, 0.4 part of antioxidant 1010/168 mixture (the most each constituent content is all in terms of parts by weight),
In high speed agitator (Beijing's English spy's plastics machinery head factory, model GH-10DY), mixing one minute, adopts
By convection oven (temperature is set to 60 DEG C) by after moisture drying in microemulsion, with Germany Werner and
The ZSK-25 twin-screw extrusion system (draw ratio 30:1, diameter 25mm) of Pleiderer company is blended and makes
Grain, each section of temperature of extruder is respectively 180 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C of (heads
Temperature), gained pellet is through injector (ningbo of china Hai Tian company produces, model HTF110X/1J) injection, note
Moulding temperature is 220 DEG C, makes sample standard batten.
Embodiment 8
Change 1# composite nucleating agent microemulsion content 0.625 part in embodiment 7 into 1.25 parts, remaining each component
Ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 7.
Embodiment 9
1# composite nucleating agent microemulsion 0.625 part in embodiment 7 is changed to 2# composite nucleating agent microemulsion
2.5 parts, remaining each component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with real
Execute example 7.
Embodiment 10
2# composite nucleating agent in embodiment 9 2.5 parts is changed to 5 parts, and remaining each component ratio is the most constant, altogether
Being mixed even, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 6
By COPP powder 100 parts and 0.4 part of direct mix of antioxidant, remaining operation and extrusion,
Injecting condition is all with embodiment 7.
Comparative example 7
By COPP powder 100 parts, blank microemulsion 0#1.25 part, 0.4 part of mix of antioxidant,
Remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 8
By COPP powder 100 parts, NA11 nucleator 125ppm (parts per million), SB nucleation
Agent 125ppm (1/1000000th), 0.4 part of mix of antioxidant, remaining operation and extrusion, injecting condition
All with embodiment 7.
Comparative example 9
By COPP powder 100 parts, NA11 nucleator 250ppm (parts per million), SB nucleation
Agent 250ppm (1/1000000th), 0.4 part of mix of antioxidant, remaining operation and extrusion, injecting condition
All with embodiment 7.
Comparative example 10
By COPP powder 100 parts, NA11 nucleator 250ppm (parts per million), antioxidant
0.4 part of mix, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 11
By COPP powder 100 parts, NA11 nucleator 500ppm (parts per million), antioxidant
0.4 part of mix, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 12
By COPP powder 100 parts, SB nucleator 250ppm (parts per million), antioxidant 0.4
Part mix, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 13
By COPP powder 100 parts, SB nucleator 500ppm (parts per million), antioxidant 0.4
Part mix, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 14
1# composite nucleating agent microemulsion 0.625 part in embodiment 7 is changed to 7# composite nucleating agent microemulsion
1.25 parts, remaining each component ratio is the most constant, is blended uniformly, remaining operation and extrusion, injecting condition all with
Embodiment 7.
Comparative example 15
7# composite nucleating agent in comparative example 14 1.25 parts is changed to 2.5 parts, and remaining each component ratio is the most constant,
Being blended uniformly, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 16
1# composite nucleating agent microemulsion 0.625 part in embodiment 7 is changed to 8# composite nucleating agent microemulsion 5
Part, remaining each component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with implementing
Example 7.
Comparative example 17
8# composite nucleating agent in comparative example 16 5 parts is changed to 10 parts, and remaining each component ratio is the most constant,
Being blended uniformly, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 18
1# composite nucleating agent microemulsion in embodiment 7 is changed to 9# composite nucleating agent microemulsion, and remaining is each
Component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 19
9# composite nucleating agent in comparative example 18 0.625 part is changed to 1.25 parts, and remaining each component ratio is the most not
Becoming, be blended uniformly, remaining operation and extrusion, injecting condition are all with embodiment 7.
Comparative example 20
1# composite nucleating agent microemulsion in embodiment 7 is changed to 10# composite nucleating agent microemulsion 0.3125
Part, remaining each component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with implementing
Example 7.
Comparative example 21
10# composite nucleating agent in comparative example 20 0.3125 part is changed to 0.625 part, remaining each component ratio
The most constant, it is blended uniformly, remaining operation and extrusion, injecting condition are all with embodiment 7.
Test:
Respectively by embodiment 7～10 and the standard batten that obtains of comparative example 6～21 injection by ISO178 test mark
Standard is curved performance test, carries out tensile property test by ISO527 testing standard, by ISO75-2:2004
Testing standard carries out heat distortion temperature test, and the result obtained is listed in table 2.
Table 2 test recipe and performance table
As shown in table 2, using and nucleator is dissolved in microemulsion the method being redispersed in polypropylene, ratio is directly
Connecing the crystalling propylene performance after adding organic nucleating agent and have more obviously raising, mechanical property is also improved more,
In the case of low content nucleator, advantage becomes apparent from.Such as add and use microemulsion method to add 250ppm's
The embodiment 9 of NA11/SB=50/50 composite nucleating agent, crystallization temperature ratio is directly added into 250ppm NA11/SB
The comparative example 8 of=50/50 is high 2.2 DEG C, and bending stress and bending modulus all improve.NA11/SB is compounding can
To obtain the composite nucleating agent with cooperative effect, and use the method for microemulsion to add and more can improve nucleator
Nucleation efficiencies, crystallization temperature improve.The crystallization temperature of such as embodiment 7 and embodiment 9, relatively example 8
Degree improves more than 2 DEG C.Illustrate that, in the case of nucleator content is relatively low, prepared by microemulsion method is combined into
Core agent is more preferable than the composite nucleating agent effect of same amount.
Meanwhile, the NA11 nucleator composite polypropylene ratio that the data explanation of table 2 uses micro-emulsion process to prepare is straight
The crystallization temperature raising connecing addition NA11 Nucleating Agent on Pp becomes apparent from.Such as comparative example 16 and comparative example
10 compare, and the crystallization temperature of material improves.Comparative example 15, compared with comparative example 11, also can find to use
Composite nucleating agent prepared by microemulsion method can preferably improve the crystallization temperature of material.Illustrate that micro-emulsion process is true
Nucleator nucleating effect is made to improve in fact.
Fig. 1 is the polarizing microscope photo of PP pure sample；Fig. 2 is the polarizing microscope photo of comparative example 8 sample,
The method that comparative example 8 uses Solid nucleating agents powder compound adds 250ppm (NA11/SB=50/50)；Fig. 3
Being the polarizing microscope photo of embodiment 9, embodiment 9 is that the method using microemulsion is by nucleator
250ppm (NA11/SB=50/50) adds in polypropylene.From polarizing microscope photo it can be seen that on Cai Yonging
State two kinds of methods and add nucleator, acrylic sphere Jingjing cuclear density can be made to improve, and use micro-emulsion process
The composite polypropylene prepared, the grain density in visual field is higher, and can reach uniformly dividing of nucleator
Dissipate.
Therefore, composite nucleating agent NA11 Yu SB adds polypropylene by the method for microemulsion, it is possible to produce association
Same effect, makes originally to be difficult to homodisperse inorganic powder the most dispersed, thus reaches more preferable
Nucleating effect.Composite nucleating agent prepared by this microemulsion method can produce cooperative effect, in the feelings that content is low
Under condition, just play good nucleation thus improve material property, and use inorganic nucleator to save
Cost.Therefore, microemulsion method of the present invention prepares the method for composite nucleating agent is a kind of preferably nucleation
Agent preparation method.
Claims (6)
1. a binary composite polypropylene nucleator, it is characterised in that:
Described nucleator is made up of benzoic acids nucleator and organic nucleating agent,
Described benzoic acids nucleator is sodium benzoate or aluminum benzoate；Described organic nucleating agent is 2,2 '-methylene
Base-two (4,6-di-tert-butyl-phenyl) sodium phosphate；Benzoic acids nucleator with the weight ratio of organic nucleating agent is
95:5～5:95；
Described nucleator is microemulsion state；Described nucleator is prepared as follows:
Benzoic acids nucleator is dissolved in water；Organic nucleating agent is dissolved in cosurfactant；
The two and surfactant, oil phase are mixed to form microemulsion；
Wherein,
The consumption of the water dissolving benzoic acids nucleator is 20～80wt%；
The consumption of the cosurfactant dissolving organic nucleating agent is 5～20wt%；
Dosage of surfactant is 10～40wt%；
Oil phase consumption is 5～20wt%；
Described cosurfactant is alcohols；
Described surfactant is polyoxyethylene-20-sorbitan monooleate, polyoxyethylene-20-dehydration mountain
Pears alcohol monostearate, polyoxyethylene-20-anhydrous sorbitol list myristinate, polyoxyethylene-20-dehydration mountain
One in pears alcohol monolaurate or combination；
Described oil phase is ethyl n-butyrate., white oil, mineral oil, petroleum ether, the one in decahydronaphthalenes or combination.
2. binary composite polypropylene nucleator as claimed in claim 1, it is characterised in that:
Described benzoic acids nucleator is 75:25～25:75 with the weight ratio of organic nucleating agent.
3. binary composite polypropylene nucleator as claimed in claim 1, it is characterised in that:
Described cosurfactant is ethanol；
Described oil phase is ethyl n-butyrate..
4. a preparation method for the binary composite polypropylene nucleator as described in one of claims 1 to 3, it is special
Levy and be that described method includes:
Benzoic acids nucleator is dissolved in water；Organic nucleating agent is dissolved in cosurfactant；
The two and surfactant, oil phase are mixed to form microemulsion；
Wherein,
The consumption of the water dissolving benzoic acids nucleator is 20～80wt%；
The consumption of the cosurfactant dissolving organic nucleating agent is 5～20wt%；
Dosage of surfactant is 10～40wt%；
Oil phase consumption is 5～20wt%；
Described cosurfactant is alcohols；
Described surfactant is polyoxyethylene-20-sorbitan monooleate, polyoxyethylene-20-dehydration mountain
Pears alcohol monostearate, polyoxyethylene-20-anhydrous sorbitol list myristinate, polyoxyethylene-20-dehydration mountain
One in pears alcohol monolaurate or combination；
Described oil phase is ethyl n-butyrate., white oil, mineral oil, petroleum ether, the one in decahydronaphthalenes or combination.
5. the binary composite polypropylene nucleator as described in one of claims 1 to 3 strengthens poly-third in preparation
Application in alkene.
6. binary composite polypropylene nucleator application in preparing RPP as claimed in claim 5,
It is characterized in that:
Described binary composite polypropylene nucleator consumption in polypropylene is 0.025～0.1 weight portion.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030682A (en) * | 1987-02-07 | 1991-07-09 | Idemitsu Petrochemical Company Limited | Glass fiber reinforced polyolefin resin composition |
| CN1687201A (en) * | 2005-04-08 | 2005-10-26 | 华东理工大学 | Method for preparing superfine nucleator in organic phosphate class |
| CN101421341A (en) * | 2006-02-27 | 2009-04-29 | 耶路撒冷希伯来大学伊森姆研究发展公司 | Method for nucleating polymers |
| CN101845171A (en) * | 2010-04-20 | 2010-09-29 | 广州呈和科技有限公司 | Polypropylene reinforcement nucleating agent composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030682A (en) * | 1987-02-07 | 1991-07-09 | Idemitsu Petrochemical Company Limited | Glass fiber reinforced polyolefin resin composition |
| CN1687201A (en) * | 2005-04-08 | 2005-10-26 | 华东理工大学 | Method for preparing superfine nucleator in organic phosphate class |
| CN101421341A (en) * | 2006-02-27 | 2009-04-29 | 耶路撒冷希伯来大学伊森姆研究发展公司 | Method for nucleating polymers |
| CN101845171A (en) * | 2010-04-20 | 2010-09-29 | 广州呈和科技有限公司 | Polypropylene reinforcement nucleating agent composition |
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