CN103788473B - A kind of modified polypropylene resin and preparation method - Google Patents
A kind of modified polypropylene resin and preparation method Download PDFInfo
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- CN103788473B CN103788473B CN201210425129.8A CN201210425129A CN103788473B CN 103788473 B CN103788473 B CN 103788473B CN 201210425129 A CN201210425129 A CN 201210425129A CN 103788473 B CN103788473 B CN 103788473B
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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
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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 modified polypropylene resin and preparation method.Described acrylic resin includes: the following components being blended: acrylic resin and modified additive, described modified additive is liquid antioxidant and the microemulsion of organic composite nucleator；Described organic composite nucleator is sodium benzoate and 2, and 2 ' ylidene methyl two (4,6 di-n-butyl phenol) sodium phosphates, the weight ratio of the two is 95:5～5:95.The modified polypropylene resin crystal property of the present invention and mechanical property improve, and cost declines to a great extent simultaneously.
Description
Technical field
The present invention relates to field of plastics processing, say further, relate to a kind of modified polypropylene resin and preparation method.
Background technology
Polypropylene is a kind of thermoplastic being widely used, and cheap and combination property is preferable, is become by interpolation
Core agent can improve mechanical property and the optical property of polypropylene articles further, it is achieved polypropylene high performance.Polyacrylic one-tenth
Core agent be a class for improving crystalling propylene behavior, thus improve the auxiliary agent of its physical and mechanical properties and thermodynamic property.Become
Core agent is divided into mineral-type, glucitols, phosphoric acid salt, rosin and high score subclass nucleator.
At present, on market, widely used polypropylene nucleater is organic nucleating agent, as NA11 [2,2 '-ylidene methyl-two
(4,6-di-n-butyl phenol) sodium phosphate], NA-2l [di-2-ethylhexylphosphine oxide (2,4-di-tert-butyl-phenyl) aluminum phosphate] etc..Organic nucleation
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 price is higher.The price of sodium benzoate is slightly lower, but becomes
Core effect is general.
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 nucleation
Cooperative effect between agent and other auxiliary agents.Chinese patent CN101845171A discloses a kind of polypropylene and increases firm compositions, is
Improve PP goods by compositionss such as sodium benzoate and double [2,2 '-methylene-two (4,6-di-tert-butyl-phenyl)] sodium phosphates
Bending property, impact strength and heat distortion temperature etc., nucleater modified more effective than adding one-component, there is certain working in coordination with
Effect, but required nucleator content is higher.Chinese patent 200780012801.8 uses water miscible nucleator HPN-68 molten
As aqueous phase in Xie Yushui, form microemulsion with other components such as oil phase, surfactant, cosurfactant etc., add poly-
After propylene, nucleator 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.
Antioxidant is the processing aid that the widely used class of processing polypropylene improves resin non-oxidizability.Liquid antioxidant
Generally use in rubber, but less in polypropylene.Liquid antioxidant in modified powdered rubber of the present invention be
All kinds of compounds with antioxidant function and auxiliary antioxidant function in liquid condition nd various combinations thereof under room temperature.Specifically
Can be selected for (1) Hinered phenols antioxidant: such as Irganox 1520(4,6-dioctyl thiomethyl orthoresol), Irganox 1141
(by 2,4-dimethyl-6-(1-methyl-pentadecyl) phenol of 80% weight)) and the Irganox 1076(β-(3,5-of 20% weight
Di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester) composition), Irganox 1135(3,5-di-t-butyl-4-hydroxy benzenes
The different monooctyl ester of propanoic acid), Ansox132(2,6-di-t-butyl-4-sec-butyl phenol) etc.；(2) phosphite antioxidant: such as Irganox
1178(tri-nonylated phenyl phosphite ester) etc.；(3) monothioester kind antioxidant: such as the DLTP(thio-2 acid two ester 8th lunar month)；(4)
One or more in amine antioxidants etc..Wherein preferably Hinered phenols antioxidant or its combination with other antioxidant, more excellent
Select 4,6-dioctyl thiomethyl orthoresol and/or three nonylated phenyl phosphite esters.
How to obtain the nucleator that nucleating effect is excellent, the polypropylene how processability is excellent on the basis of consumption is few
Nucleator is a direction of research.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of modified polypropylene resin and preparation method.
Nucleator is dispersed in containing liquid antioxidant as in the microemulsion of oil phase, by Tong Bu with antioxidant for nucleator addition resin base
In body.On the one hand, this patent overcomes the difficulty of nucleator own and is dissolved in the problem of water, obtains a kind of applicable nucleator scattered micro-
Emulsion, promotes its dispersion and synergy further.On the other hand, liquid antioxidant can be by the method and poly-third of microemulsion
Alkene nucleator is blended, it is possible to spread out in microemulsion, and is more easy to diffusion in polypropylene, so that acrylic resin has
Better performance.
An object of the present invention is to provide a kind of modified polypropylene resin.
Following components including being blended:
Acrylic resin and modified additive,
Described modified additive is liquid antioxidant and the microemulsion of organic composite nucleator；
Described organic composite nucleator is sodium benzoate and 2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate,
The weight ratio of the two is 95:5～5:95, preferably 75:25～25:75.
Described liquid antioxidant is preferably Hinered phenols antioxidant, phosphite antioxidant or monothioester kind antioxidant.More
Be preferably liquid antioxidant Irganox 1520(4,6-dioctyl thiomethyl orthoresol), Irganox 1141(is by 80% weight
2,4-dimethyl-6-(1-methyl-pentadecyl) phenol)) and the Irganox1076(β-(3,5-di-t-butyl-4-of 20% weight
Hydroxy phenyl) propanoic acid positive octadecanol ester) composition), Irganox 1135(3,5-di-t-butyl-4-hydroxy phenylpropionic acid different pungent
Ester), Ansox 132(2,6-di-t-butyl-4-sec-butyl phenol), Irganox 1178(tri-nonylated phenyl phosphite ester),
The DLTP(thio-2 acid two ester 8th lunar month) in one or combination；
In microemulsion, the content of liquid antioxidant is 10～20wt%；
Being in terms of 100 weight portions by acrylic resin, the content of binary composite nucleating agent is 0.025～0.05 weight portion.
Described modified additive is to be prepared by the method comprised the following steps:
(1) sodium benzoate is dissolved in deionized water；By 2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) phosphoric acid
Sodium is dissolved in cosurfactant；
(2) above-mentioned will dissolve the aqueous phase of sodium benzoate, be dissolved with 2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol)
The cosurfactant of sodium phosphate, liquid antioxidant, surfactant mix homogeneously, form microemulsion；
Described cosurfactant is alcohols；
Described surfactant is polyoxyethylene-20-sorbitan monooleate, polyoxyethylene-20-anhydrous sorbitol
Monostearate, polyoxyethylene-20-anhydrous sorbitol list myristinate, polyoxyethylene-20-anhydrous sorbitol mono laurate
One in ester or combination；
Wherein, in microemulsion,
The content of aqueous phase is 10～20wt%；
The content of liquid antioxidant is 10～20wt%；
The content of surfactant is 10～20wt%；
The content of cosurfactant is 40～60wt%
Mix and blend equipment in preparation method is the usual mixing apparatus used in manufacture field, such as: magnetic stirring apparatus,
High shear dispersion machine etc..
Nucleator is dissolved in microemulsion by the present invention, and NA11 dissolves in ethanol as cosurfactant, adds
Liquid antioxidant, aqueous phase, surfactant, obtain microemulsion.Microemulsion is the Thermodynamically stable that two kinds of immiscible liquids are formed
, isotropic, appearance transparent or translucent dispersion, by the one that surfactant interface film is stable on microcosmic
Or the microdroplet of two kinds of liquid is constituted.(" microemulsion technology and application " China Light Industry Press, Cui Zhenggang, Yin Fushan volume, 75
Page).
The present invention innovatively adds nucleant agent N A11 in cosurfactant, and is dissolved in aqueous phase by sodium benzoate,
Both nucleators use the system dispersion of microemulsion, mixing, owing to the dispersion phase in microemulsion is nanoscale, so nucleator
Also can reach nanoscale dispersion, use micro-emulsion process by while two kinds of nucleator mix homogeneously, moreover it is possible to be divided by its super-refinement
Dissipate, thus effectively expand the contact area of nucleator and polypropylene matrix.Thus be conducive to dividing in acrylic resin
Dissipate and nucleating effect.
The two of the purpose of the present invention are to provide the preparation method of a kind of modified polypropylene resin.
Including:
By described component by preparing described modified polypropylene resin after described consumption melt blending.
The present invention uses liquid antioxidant can help nucleation as the oil phase of microemulsion, the ingredient as microemulsion
The dispersion of agent.And due to the antioxidant effect of liquid antioxidant itself, forming microemulsion and help nucleator scattered while,
Self also can fine dispersion in polypropylene matrix, thus reach the effect of antioxygen.
The method that the present invention uses two kinds of nucleators compounding prepares a kind of composite polypropylene nucleator.Use microemulsion side
Method is by while two kinds of nucleator mix homogeneously, moreover it is possible to is disperseed by its super-refinement, thus effectively expands nucleator and poly-third
The contact area of thiazolinyl body.In the case of nucleator content is identical, composite nucleating agent has identical or more preferable nucleating effect,
And along with the raising mechanical property of addition can also improve further.Therefore, the organic phosphate that prepared by micro-emulsion process
Nucleator and sodium benzoate nucleator are applied in polypropylene as composite nucleating agent, have consumption few, effective, processing cost
Low, the advantages such as preparation technology is simple, are the mechanics modifying agent of a kind of preferable acrylic resin.
The crystal property of the acrylic resin of the present invention and mechanical property improve, and cost declines to a great extent simultaneously.
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
NA11 [2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 3.33wt%；Sodium benzoate (Tianjin recovery fine chemistry industry research
Institute) dissolve in deionized water with the concentration of 18wt%；Use magnetic stirrer, be sequentially added into and dissolved the anhydrous of NA11
[β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid isooctanol ester, Guangzhou will one trade is limited for ethanol, 1135 liquid antioxidants
Company], Tween 80 (commercially available), deionized water, the weight/mass percentage composition of said components be respectively 54wt%, 18wt%, 18wt%,
10wt%, uses magnetic stirrer, and the rotating speed of magnetic stirring apparatus is 200rpm(rpm), mixing time 5 minutes.Mixed
The microemulsion got togather obtains 1# binary composite nucleating agent.
Embodiment 2
NA11 [2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 3.33wt%；Sodium benzoate (Tianjin recovery fine chemistry industry research
Institute) dissolve in deionized water with the concentration of 18wt%；Use magnetic stirrer, be sequentially added into and dissolved the anhydrous of NA11
Ethanol, 1520 liquid antioxidants [2,4-bis-(n-octylthiomethylene) orthoresol, Guangzhou will one trade Co., Ltd], Tween 80
(commercially available), deionized water, the weight/mass percentage composition of said components is respectively 54wt%, 18wt%, 18wt%, 10wt%, uses magnetic force
Agitator stirs, and 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 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；Sodium benzoate (Tianjin recovery fine chemistry industry institute)
Dissolve in deionized water with the concentration of 10wt%；Use magnetic stirrer, be sequentially added into the anhydrous second having dissolved NA11
Alcohol, 1135 liquid antioxidants [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid isooctanol ester, the limited public affairs of Guangzhou will one trade
Department], Tween 80 (commercially available), dissolved the deionized water of sodium benzoate, said components weight/mass percentage composition be respectively 40wt%,
20wt%, 20wt%, 20wt%, use magnetic stirrer, and the rotating speed of magnetic stirring apparatus is 200rpm(rpm), stirring
5 minutes time.The microemulsion mixed obtains 3# binary composite nucleating agent.
Embodiment 4
NA11 [2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 3.33wt%；Sodium benzoate (Tianjin recovery fine chemistry industry research
Institute) dissolve in deionized water with the concentration of 20wt%；Use magnetic stirring apparatus (model) stirring, be sequentially added into and dissolved NA11
Dehydrated alcohol, 1520 liquid antioxidants [2,4-bis-(n-octylthiomethylene) orthoresol, Guangzhou will one trade Co., Ltd],
Tween 80 (commercially available), dissolved the deionized water of sodium benzoate, said components weight/mass percentage composition be respectively 60wt%, 10wt%,
10wt%, 20wt%, use magnetic stirrer, and the rotating speed of magnetic stirring apparatus is 200rpm(rpm), mixing time 5 points
Clock.The microemulsion mixed obtains 4# binary composite nucleating agent.
Comparative example 1
NA11 [2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；Use magnetic stirrer, be sequentially added into dissolving
The dehydrated alcohol of NA11,1135 liquid antioxidants [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid isooctanol ester, Guangzhou will
One trade Co., Ltd], Tween 80 (commercially available), deionized water, said components weight/mass percentage composition be respectively 54wt%, 18wt%,
18wt%, 10wt%, use magnetic stirrer, and the rotating speed of magnetic stirring apparatus is 200rpm(rpm), mixing time 5 points
Clock.The microemulsion mixed obtains 5# composite nucleating agent.
Comparative example 2
Sodium benzoate (Tianjin recovery fine chemistry industry institute) dissolves in deionized water with the concentration of 20wt%；Use
Magnetic stirring apparatus (model) stirs, and is sequentially added into dehydrated alcohol (commercially available), 1135 liquid antioxidants [β-(3,5-di-t-butyl-4-
Hydroxy phenyl) propanoic acid isooctanol ester, Guangzhou will one trade Co., Ltd], Tween 80 (commercially available), dissolved sodium benzoate go from
Sub-water, said components weight/mass percentage composition is respectively 54wt%, 18wt%, 18wt%, 10wt%, uses magnetic stirrer, magnetic
The rotating speed of power agitator is 200rpm(rpm), mixing time 5 minutes.The microemulsion mixed obtains 6# and is combined nucleation
Agent.
Comparative example 3
NA11 [2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；；Use magnetic stirrer, be sequentially added into dissolving
The dehydrated alcohol of NA11,1520 liquid antioxidants [2,4-bis-(n-octylthiomethylene) orthoresol, the limited public affairs of Guangzhou will one trade
Department], Tween 80 (commercially available), deionized water, said components weight/mass percentage composition is respectively 54wt%, 18wt%, 18wt%, 10wt%,
Using magnetic stirrer, the rotating speed of magnetic stirring apparatus is 200rpm(rpm), mixing time 5 minutes.Mix
Microemulsion obtains 7# composite nucleating agent.
Comparative example 4
Sodium benzoate (Tianjin recovery fine chemistry industry institute) dissolves in deionized water with the concentration of 20wt%；Use
Magnetic stirring apparatus (model) stirs, and is sequentially added into dehydrated alcohol (commercially available), 1520 liquid antioxidants [2,4-bis-(n-octyl sulfur Asias
Methyl) orthoresol, Guangzhou will one trade Co., Ltd], Tween 80 (commercially available), dissolved the deionized water of sodium benzoate, above-mentioned
Constituent mass percentage composition is respectively 54wt%, 18wt%, 18wt%, 10wt%, uses magnetic stirrer, magnetic stirring apparatus
Rotating speed is 200rpm(rpm), mixing time 5 minutes.The microemulsion mixed obtains 8# composite nucleating agent.
Comparative example 5
NA11 [2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 10wt%；Use magnetic stirrer, be sequentially added into dissolving
The dehydrated alcohol of NA11, ethyl n-butyrate. (commercially available), Tween 80, (commercially available) deionized water, said components weight/mass percentage composition is respectively
For 54wt%, 18wt%, 18wt%, 10wt%, using magnetic stirrer, the rotating speed of magnetic stirring apparatus is that 200rpm(turns every point
Clock), mixing time 5 minutes.The microemulsion mixed obtains 9# composite nucleating agent.
Comparative example 6
Sodium benzoate (Tianjin recovery fine chemistry industry institute) dissolves in deionized water with the concentration of 20wt%；Use
Magnetic stirring apparatus (model) stirs, and is sequentially added into dehydrated alcohol, ethyl n-butyrate. (commercially available), Tween 80 (commercially available), has dissolved benzene first
The deionized water of acid sodium, said components weight/mass percentage composition is respectively 54wt%, 18wt%, 18wt%, 10wt%, uses magnetic agitation
Device stirs, and the rotating speed of magnetic stirring apparatus is 200rpm(rpm), mixing time 5 minutes.The microemulsion mixed obtains 10#
Composite nucleating agent.
Comparative example 7
NA11 [2,2 '-ylidene methyl-two (4,6-di-n-butyl phenol) sodium phosphate] (Zhong Da Chemical Co., Ltd., trade mark NP-
508) it is dissolved in dehydrated alcohol (analytical pure) with the concentration of 3.33wt%；Sodium benzoate (Tianjin recovery fine chemistry industry research
Institute) dissolve in deionized water with the concentration of 18wt%；Use magnetic stirrer, be sequentially added into and dissolved the anhydrous of NA11
Ethanol, ethyl n-butyrate. (commercially available), Tween 80 (commercially available), deionized water, the weight/mass percentage composition of said components be respectively 54wt%,
18wt%, 18wt%, 10wt%, use magnetic stirrer, and the rotating speed of magnetic stirring apparatus is 200rpm(rpm), stirring
5 minutes time.The microemulsion mixed obtains 11# composite nucleating agent.
Table 1 microemulsion formula
Embodiment 5
By the 1# composite nucleating agent of preparation in embodiment 1 and copolymerization polypropylene powder (Beijing Chemical Research Institute's production, melt
Flow rate 5.5g/10min) mix, its particular make-up: polypropylene 100 parts, 1# composite nucleating agent microemulsion 0.694 part,
Mixing one minute in high speed agitator (Beijing's English spy's plastics machinery head factory, model GH-10DY), with Germany Werner and
The ZSK-25 twin-screw extrusion system (draw ratio 30:1, diameter 25mm) of Pleiderer company is blended pelletize, each section of temperature of extruder
Degree is respectively 180 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C (head temperature), and (China is peaceful through injector for gained pellet
Bo Haitian company produces, model HTF110X/1J) injection, injection temperature is 220 DEG C, makes sample standard batten.
Embodiment 6
1# composite nucleating agent in embodiment 5 0.694 part is changed to 1.39 parts, and remaining each component ratio is the most constant, is blended
Uniformly, remaining operation and extrusion, injecting condition are all with embodiment 5.
Embodiment 7
1# composite nucleating agent microemulsion in embodiment 5 is changed to 2# composite nucleating agent microemulsion, remaining each component ratio
Example is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 5.
Embodiment 8
2# composite nucleating agent in embodiment 7 0.694 part is changed to 1.39 parts, and remaining each component ratio is the most constant, is blended
Uniformly, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 8
1# composite nucleating agent microemulsion 0.694 part in embodiment 5 is changed to 5# composite nucleating agent microemulsion 0.463
Part, remaining each component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 9
Changing 5# composite nucleating agent microemulsion content 0.463 part in comparative example 8 into 0.927 part, remaining each component ratio is equal
Constant, it is blended uniformly, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 10
1# composite nucleating agent microemulsion 0.694 part in embodiment 5 is changed to 6# composite nucleating agent microemulsion 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 5.
Comparative example 11
6# composite nucleating agent in comparative example 10 1.25 parts is changed to 2.5 parts, and remaining each component ratio is the most constant, is blended all
Even, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 12
1# composite nucleating agent microemulsion 0.694 part in embodiment 5 is changed to 7# composite nucleating agent microemulsion 0.463
Part, remaining each component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 13
7# composite nucleating agent in comparative example 12 0.463 part is changed to 0.927 part, and remaining each component ratio is the most constant, altogether
Being mixed even, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 14
1# composite nucleating agent microemulsion 0.694 part in embodiment 5 is changed to 8# composite nucleating agent microemulsion 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 5.
Comparative example 15
8# 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, is blended all
Even, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 16
By COPP powder 100 parts and 0.083 part of direct mix of antioxidant, remaining operation and extrusion, injection
Condition is all with embodiment 5.
Comparative example 17
By COPP powder 100 parts and 0.167 part of direct mix of antioxidant, remaining operation and extrusion, injection
Condition is all with embodiment 5.
Comparative example 18
COPP powder 100 parts, NA11 nucleator 250ppm (parts per million), 0.083 part of antioxidant are mixed
Closing dispensing, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 19
COPP powder 100 parts, NA11 nucleator 500ppm (parts per million), 0.167 part of antioxidant are mixed
Closing dispensing, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 20
By COPP powder 100 parts, SB nucleator 250ppm (parts per million), the mixing of 0.083 part of antioxidant
Dispensing, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 21
By COPP powder 100 parts, SB nucleator 500ppm (parts per million), the mixing of 0.167 part of antioxidant
Dispensing, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 22
By COPP powder 100 parts, NA11 nucleator 125ppm (parts per million), SB nucleator 125ppm
0.083 part of mix of (parts per million), antioxidant, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 23
By COPP powder 100 parts, NA11 nucleator 250ppm (parts per million), SB nucleator 250ppm
0.167 part of mix of (parts per million), antioxidant, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 24
1# composite nucleating agent microemulsion 0.694 part in embodiment 5 is changed to 9# composite nucleating agent microemulsion 0.463
Part, remaining each component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 25
9# composite nucleating agent in comparative example 24 0.463 part is changed to 0.927 part, and remaining each component ratio is the most constant, altogether
Being mixed even, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 26
5# composite nucleating agent microemulsion 0.694 part in embodiment 5 is changed to 10# composite nucleating agent microemulsion 1.25
Part, remaining each component ratio is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 27
10# composite nucleating agent in comparative example 26 1.25 parts is changed to 2.5 parts, and remaining each component ratio is the most constant, is blended
Uniformly, remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 28
1# composite nucleating agent microemulsion in embodiment 5 is changed to 11# composite nucleating agent microemulsion, remaining each component ratio
Example is the most constant, is blended uniformly, and remaining operation and extrusion, injecting condition are all with embodiment 5.
Comparative example 29
11# composite nucleating agent in comparative example 28 0.694 part is changed to 1.39 parts, and remaining each component ratio is the most constant, altogether
Being mixed even, remaining operation and extrusion, injecting condition are all with embodiment 5.
Test:
Respectively by embodiment 5～8 and the standard batten that obtains of comparative example 8～29 injection carry out curved by ISO178 testing standard
Bent performance test, carries out tensile property test by ISO527 testing standard, carries out thermal deformation by ISO75-2:2004 testing standard
Temperature test, the result obtained is listed in table 3.
Table 2 test recipe table
Table 3
As shown in table 3, using and nucleator is dissolved in microemulsion the method being redispersed in polypropylene, ratio is directly added into
Crystalling propylene temperature after powder organic nucleating agent is higher, and mechanical property is also improved.Such as, NA11/SB=50/50
When addition is 250ppm, be respectively adopted 1135,1520 or ethyl n-butyrate. as oil phase microemulsion add polyacrylic enforcement
Example 5, embodiment 7 and comparative example 28, crystallization temperature is all high than the comparative example 10 being directly added into powder nucleants, and microemulsion method is described
Nucleator can be helped to disperse in polypropylene.
Ethyl n-butyrate., as oil phase, does not adds the comparative example 24～29 of antioxidant, and the oxidation induction time of material is 0 point
Clock.And liquid antioxidant 1135 or 1520 as microemulsion oil phase add polyacrylic after, the oxidation induction time of material with add
Enter 1010/168 identical the most longer, and mechanical property is also obviously improved.Such as, the modulus of elasticity in static bending of comparative example 22 is
1.21GPa, and the modulus of elasticity in static bending of embodiment 5 and embodiment 7 is respectively increased to 1.30GPa and 1.29GPa, stretches, impact
Performance is also improved.And comparative example 24～29 uses ethyl n-butyrate. to add nucleator as the microemulsion of oil phase, although material
Crystallization temperature also improves, but because not adding antioxidant in system, work in-process has degraded, and therefore mechanical property is not dominant
Gesture.So using liquid antioxidant 1135,1520 nucleator can be made to be uniformly dispersed in the base, again as the microemulsion of oil phase
The effect of antioxygen can be played.
Therefore, composite nucleating agent NA11 Yu SB adds polypropylene by the method for microemulsion, it is possible to produces cooperative effect, makes
Originally it is difficult to homodisperse inorganic powder the most dispersed, thus reaches more preferable nucleating effect.This microemulsion
Composite nucleating agent prepared by method can produce cooperative effect, in the case of content is low, just play good nucleation thus
Improve material property, and use inorganic nucleator energy cost-effective.Therefore, microemulsion method of the present invention preparation is combined into
The method of core agent is a kind of preferably nucleator preparation method.
Claims (6)
1. a modified polypropylene resin, it is characterised in that include the following components being blended:
Acrylic resin and modified additive,
Described modified additive is liquid antioxidant and the microemulsion of organic composite nucleator；
Described organic composite nucleator is sodium benzoate and 2,2 '-methylene-two (4,6-di-n-butyl phenol) sodium phosphate, the two
Weight ratio be 95:5～5:95；
In microemulsion, the content of liquid antioxidant is 10～20wt%；
Being in terms of 100 weight portions by acrylic resin, the content of organic composite nucleator is 0.025～0.05 weight portion；
Described liquid antioxidant is Hinered phenols antioxidant, phosphite antioxidant, monothioester kind antioxidant or amine antioxidants；
Described liquid antioxidant is as the oil phase of microemulsion.
2. modified polypropylene resin as claimed in claim 1, it is characterised in that:
Described sodium benzoate and 2, the weight ratio of 2 '-methylene-two (4,6-di-n-butyl phenol) sodium phosphate is 75:25～25:
75。
3. modified polypropylene resin as claimed in claim 1, it is characterised in that:
Described liquid antioxidant is 4,6-dioctyl thiomethyl orthoresol, Irganox 1141,3,5-di-t-butyl-4-hydroxyl
The different monooctyl ester of benzenpropanoic acid, 2,6-di-t-butyl-4-sec-butyl phenol, three nonylated phenyl phosphite esters, thiodipropionic acid dilauryl osmanthus
One in ester or combination.
4. the modified polypropylene resin as described in one of claims 1 to 3, it is characterised in that:
Described modified additive is to be prepared by the method comprised the following steps:
(1) sodium benzoate is dissolved in deionized water；By molten for 2,2 '-methylene-two (4,6-di-n-butyl phenol) sodium phosphate
Solution is in cosurfactant；
(2) above-mentioned will dissolve the aqueous phase of sodium benzoate, be dissolved with 2,2 '-methylene-two (4,6-di-n-butyl phenol) phosphoric acid
The cosurfactant of sodium, liquid antioxidant, surfactant mix homogeneously, form microemulsion；
Described cosurfactant is alcohols；
Described surfactant is polyoxyethylene-20-sorbitan monooleate, and polyoxyethylene-20-anhydrous sorbitol list is hard
Fat acid ester, polyoxyethylene-20-anhydrous sorbitol list myristinate, in polyoxyethylene-20-sorbitan mono-laurate
One or combination；
Wherein, in microemulsion,
The content of aqueous phase is 10～20wt%；
The content of liquid antioxidant is 10～20wt%；
The content of surfactant is 10～20wt%；
The content of cosurfactant is 40～60wt%.
5. modified polypropylene resin as claimed in claim 4, it is characterised in that:
Described cosurfactant is ethanol；
Described surfactant is polyoxyethylene-20-sorbitan monooleate.
6. the method for the modified polypropylene resin prepared as described in one of Claims 1 to 5, it is characterised in that described method
Including:
By described component by preparing described modified polypropylene resin after described consumption melt blending.
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| 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 |
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| 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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