CN103965545B - A kind of polypropylene beta crystal form nucleating agent composition and preparation method thereof and a kind of beta-crystal polypropylene composition and preparation method thereof - Google Patents
A kind of polypropylene beta crystal form nucleating agent composition and preparation method thereof and a kind of beta-crystal polypropylene composition and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The present invention provides a kind of polypropylene beta crystal form nucleating agent composition and preparation method thereof and a kind of beta-crystal polypropylene composition and preparation method thereof.Including A nucleator and B nucleator in polypropylene beta crystal form nucleating agent composition, A is metal carboxylate nucleator, and B is aryl amide beta nucleater, A and B weight ratio is 15:1～1:15.A and B is dissolved in N, N dimethylformamide to saturated, separates out material after natural cooling cooling and be dried, or by the component comprising described A and B is i.e. obtained described nucleating agent compositions by described amount with 500～5000 revs/min of high-speed stirred 0.5～2 minutes.Beta-crystal polypropylene composition, includes blended 100 part weight polyacrylamide resin, 0.3～5 part of compatilizer, 0.1～1 part of auxiliary agent bag, 0.05～1 part of above-mentioned polypropylene beta crystal form nucleating agent composition.Nucleator of the present invention can improve product material Thermal Synthetic and mechanical property, and preparation technology is simple.
Description
Technical field
The present invention relates to polypropylene nucleater field, say further, relate to a kind of polypropylene beta crystal and become
Core agent compositions and preparation method thereof and a kind of beta-crystal polypropylene composition prepared therefrom and preparation method.
Background technology
Acrylic resin is because of abundant raw material source, and synthesis technique is simple, cheap, and combination property is good
Plurality of advantages and become one of most widely used general-purpose plastics.But it is low that acrylic resin exists toughness, anti-
The critical defect of punching performance difference.
In prior art, use introduces beta crystal-type nucleater in acrylic resin more, so that induction during its crystallization
Form beta crystal, with the problem improving polypropylene impact difference.The most ripe beta crystal-type nucleater used is also
Seldom, mainly have 2,6-cyclohexanedimethanol amide (new physics and chemistry company of Japan, patent No. EP 0557721A2),
N, N '-dicyclohexyl-2,6-naphthalene diamides (new physics and chemistry company of Japan, patent No. EP 0865909A1),
N, N, N ', the amides compound such as N '-tetraalkyl terephthalamide.These existing beta crystal-type nucleaters exist
Common defect, when its one pack system uses, β nucleation efficiencies is fluctuated, and impact property is improved inconspicuous, and
And bring the decline of hot strength and modulus simultaneously.These beta nucleaters are on the high side, also limit it in work
Application in industry.
In crystalling propylene nucleation modification, also there are addition sodium benzoate nucleator or addition maleic anhydride grafting poly-
Propylene improves the report of nucleating effect.A small amount of beta crystal can be produced when the two is used alone in polypropylene
Polypropylene, but beta crystal relative amount is the highest, and the improvement to acrylic resin mechanical property is the most inconspicuous.
Patent CN 101993565A reports a kind of high tenacity high impact resistance polypropylene resin combination, main pin
To Propylene-ethylene random copolymer, nucleator is aryl amide compound and the combination of ortho position dicarboxylate,
Different from present composition composition, the part by weight of two kinds of nucleators is the most different.
Patent CN1944515A reports a kind of beta-crystal polypropylene composition and preparation method thereof, wherein nucleation
Agent be the organic dibasic acid of separate constituent or the calcium salt of decanedioic acid, benzoate, substituted aromatic amide compound or
The complex of any one in above-mentioned organic diacid salt and calcium stearate, to the benzoate being used alone with take
Arylimidoyl amines, does not the most provide specific embodiment.
Patent CN102219927A polypropylene increases firm toughness reinforcing nucleating agent compositions, is improving polypropylene toughness
Polyacrylic rigidity can be improved simultaneously, but different with the composition components of the present invention.The present invention combines
Thing composition is simpler, performance increase rate is bigger, price is cheaper.
Summary of the invention
For problem of the prior art, the invention provides a kind of polypropylene beta crystal form nucleating agent composition and
Preparation method, and a kind of beta-crystal polypropylene composition prepared therefrom and preparation method.
An object of the present invention is to provide a kind of polypropylene beta crystal form nucleating agent composition.
A kind of polypropylene beta crystal form nucleating agent composition of the present invention, includes A nucleator and B nucleator；Its
In, the weight ratio of described A nucleator and B nucleator is 15:1～1:15, preferably 10:1～1:10.
The above A nucleator is metal carboxylate nucleator, selected from alkali metal salt or the fragrance of unary fatty acid
At least one in race's carboxylate.Wherein optimization aromatic carboxylate, more preferably benzoate, such as benzene first
Acid sodium, Potassium Benzoate, aluminum benzoate, the most most preferably sodium benzoate.
Described B nucleator is at least one in aryl amide beta nucleater, preferably virtue amide compound, more
Preferably N, N '-dicyclohexyl-2,6-aphthalimide, N, N, N ' N '-tetraalkyl terephthalamide or N, N '-two
At least one in cyclohexyl terephthalamide.
The two of the purpose of the present invention are to provide the preparation method of described polypropylene beta crystal form nucleating agent composition, bag
Include one of the following two kinds method:
Method 1), the component comprising described A nucleator and B nucleator is dissolved in by described weight ratio
To saturated in the DMF of 50～80 DEG C or dimethyl sulfoxide, sonic oscillation, obtain saturated solution,
Natural cooling separates out material after being cooled to 20～50 DEG C, is dried by described precipitation material, obtains described polypropylene beta
Crystal-type nucleater compositions；
Wherein, the power of sonic oscillation can be 50～500W, and each duration of oscillation is 1～5 second/time, is spaced apart
1～2s, total time is 10～30 minutes.Described being dried can be with natural air drying, it is possible to be placed in by precipitate logical
In wind cupboard, after solvent volatilizees, become drying sample.
Owing to A Yu B nucleator is powder nucleator, exist and the shortcomings such as matrix bad dispersibility, and
B nucleator body is strip, and length, several microns to tens micron wider distribution, is passed through in the course of processing
Shearing and present formalness not of uniform size, the uneven of B nucleator surface texture causes it to induce β nucleation
Ability have very big difference, show final products unstable properties.By the method for ultrasonic disperse, make two
Kind of nucleator mix homogeneously, and during cooling separates out, makes the B nucleator can be with less, more homogeneous
Out, nucleator own dimensions is the least for size crystal, and surface can be the biggest, and unit are can induce nucleation
Active site is the most, and nucleation efficiencies is the highest.
Method 2), by comprise the component of described A nucleator and B nucleator by described weight ratio with
The speed high-speed stirred of 500～5000 revs/min is to mix homogeneously, and stand for standby use, to reach two kinds of nucleator mixing
The purpose that uniform and B nucleator size uniform refines.The temperature of high-speed stirred does not has particular requirement, not higher than
The decomposition temperature of nucleator, it is generally preferable to stir under room temperature.The time of high-speed stirred is preferably 0.5～2 point
Clock.
Wherein, the high-speed stirring apparatus of the prior art such as miniature high-speed agitator such as can be used to carry out component
High speed rotating.
The three of the purpose of the present invention are to provide a kind of beta-crystal polypropylene composition.
A kind of beta-crystal polypropylene composition of the present invention includes blended following components: acrylic resin,
Compatilizer, auxiliary agent bag, polypropylene beta crystal form nucleating agent composition of the present invention；
The addition of above-mentioned each component is in terms of 100 parts of weight by acrylic resin, the most described compatilizer be 0.3～
5 weight portions, preferably 0.3～2 weight portions；Described auxiliary agent bag is 0.1～1 weight portion, and described polypropylene beta is brilliant
Type nucleating agent compositions is 0.05～1 weight portion, preferably 0.05～0.5 weight portion；
Wherein said acrylic resin is existing various acrylic resins in prior art, such as HOPP
Or COPP, preferably HOPP.
Described compatilizer is maleic anhydride inoculated polypropylene, and relative molecular weight is 2000～15000, and percent grafting is
0.3～5%；
Described auxiliary agent includes antioxidant and lubricant；The weight ratio of described antioxidant and lubricant be 17:1～
1:15, preferably 5:1～1:1, more preferably 5:1.During wherein antioxidant can be selected for prior art, acrylic resin is commonly used
Various antioxidant.In being embodied as, described antioxidant is [β-(3,5-di-tert-butyl-hydroxy phenyl) selected from four
Propylene] tetramethylolmethane, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 2,2 '-methylene
Double-(4-methyl-6-tert-butylphenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-2-methyl-2-phenylpropane base) butane, tricresyl phosphite
(2,4--di-tert-butyl-phenyl) ester, double (2,4-DTBP) pentaerythritol diphosphites, double (2.6-
Di-t-butyl-4-tolyl) at least one in pentaerythritol diphosphites；Preferably antioxidant is antioxidant
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane and tricresyl phosphites (2,4--di-tert-butyl-phenyl)
The mixture of ester, weight ratio between the two is 10:1～1:10, preferably 5:1～1:5, more preferably 1:1.Xiang Ju
Propylene compositions adds a certain amount of lubricant, the processing characteristics of acrylic resin can be obviously improved.On
State lubricant and can select the various lubricants that in prior art, polypropylene processing is conventional；Wherein, preferably stearic
At least one in acid, calcium stearate, zinc stearate.The addition of lubricant, can improve the poly-of the present invention
The mechanical property of propylene compositions, its processing characteristics is the most excellent.
The four of the purpose of the present invention are to provide the preparation method of described beta-crystal polypropylene composition.
The preparation method of beta-crystal polypropylene composition of the present invention, including by include described acrylic resin,
The polypropylene beta crystal form nucleating agent composition of compatilizer, auxiliary agent bag and the present invention is mixed by described amount in interior component
Close uniformly, and prepare described beta-crystal polypropylene composition through melt blending.
Specifically, the preparation method of beta-crystal polypropylene composition of the present invention can comprise the following steps that
(1) by the polypropylene beta crystal nucleating agent group of described acrylic resin, compatilizer, antioxidant and the present invention
Compound presses described amount mix homogeneously, obtains premix material；
(2) by the premix material that obtains in step (1) through melt blending, extruding pelletization prepares β of the present invention
Crystal form polypropylene composite.
The process of the described each component mix homogeneously in the above step (1), can use institute in prior art
Various mixing equipments, such as blender, kneading machine etc..Can be to carry out in high speed agitator under room temperature
High-speed stirred realizes, and the time of high-speed stirred is 0.5～5 minute, and motor speed may be set to 500～3000
Rev/min.
The melt blending of above method step (2) uses the common melt blending equipment in rubber and plastic processing industry, can
To be double screw extruder, single screw extrusion machine, mill, banbury, the mixing unit of BUSS etc..
As the melt blending in described step (2) is preferably carried out in double screw extruder.The most various parameters
For the parameter that polypropylene in prior art is conventional when double screw extruder is extruded.Such as, double screw extruder
From the temperature of first paragraph to the 5th section control respectively 170～180 DEG C, 180～200 DEG C, 195～230 DEG C,
200～230 DEG C, head temperature is at 200～230 DEG C, and screw speed is at 200～400 revs/min.
Additionally, according to processing needs, acrylic resin processing can be added in described polypropene composition in right amount
During conventional some auxiliary agents, such as: dispersant, surface conditioning agent etc., its consumption is conventional amount used,
Or be adjusted according to the requirement of practical situation.
The polypropylene beta crystal form nucleating agent composition that the present invention provides uses metal carboxylate nucleator and aryl amide
Nucleator compounds according to certain weight ratio, by the acrylic resin of its modification than using one pack system β nucleation
The acrylic resin of agent has more preferable comprehensive mechanical property.The beta-crystal polypropylene composition of gained of the present invention
The impact strength polypropylene more beta nucleater modified than being used alone improves about more than 50%, simultaneously bending modulus,
Bending strength, the heat distortion temperature aspect polypropylene more nucleater modified than one-component has better performance.Carboxylic
Barbiturates nucleator is cheap, reaches good by compounding with expensive aryl amide beta crystal-type nucleater
Good synergism, reduces production cost, improves product material comprehensive mechanical property and hot property.Remove
Outside this, nucleating agent compositions of the present invention and polypropene composition prepared therefrom also have preparation technology simple,
Easily operated, be suitable to the significant advantages such as industrial applications.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.The scope of the present invention is not implemented by these
The restriction of example, the scope of the present invention proposes in detail in the claims.
Raw material:
Metal carboxylate nucleator: sodium benzoate, commercially available prod.
Aryl amide nucleator: N, N '-dicyclohexyl-2,6-aphthalimide, N, N, N ', N '-tetraalkyl is to benzene two
Methanamide, commercially available prod.
N,N-dimethylformamide: commercially available prod.
Compatilizer: maleic anhydride inoculated polypropylene: relative molecular mass is 5000, percent grafting is 0.5%, city
Sell product.
Antioxidant: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane, tricresyl phosphite (2,4--
Di-tert-butyl-phenyl) ester, commercially available prod.
Lubricant: calcium stearate, commercially available prod.
Acrylic resin: HOPP, trade mark PP 2401, melt flow rate (MFR) 2.5g/10min, China
Petrochemical industry Yanshan Mountain branch company product.
Mechanical property and thermal performance analysis test:
Bending modulus is tested by GB/T9341-2000；Izod notched impact strength is pressed
GB/T1843-1996 tests；Heat distortion temperature is tested by GB/T1634-2004, and load is
0.46MPa。
One, prepared by polypropylene beta crystal form nucleating agent composition:
Embodiment 1
Precise sodium benzoate 10g, N, N '-dicyclohexyl-2,6-aphthalimide 1g, it is dissolved in 70 DEG C
To saturated in DMF, sonic oscillation 10 minutes, power 300W, 2s/ time, it is spaced apart 1
Second, obtaining the saturated solution of mix homogeneously, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried
Obtain polypropylene beta crystal form nucleating agent composition 1.
Embodiment 2
Precise sodium benzoate 1g, N, N '-dicyclohexyl-2,6-aphthalimide 10g, it is dissolved in 70 DEG C
To saturated in DMF, sonic oscillation 15 minutes, power 300W, 2s/ time, it is spaced apart 1
Second, obtaining the saturated solution of mix homogeneously, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried
Obtain polypropylene beta crystal form nucleating agent composition 2.
Embodiment 3
Precise sodium benzoate 5g, N, N '-dicyclohexyl-2,6-aphthalimide 1g, it is dissolved in 75 DEG C
To saturated in DMF, sonic oscillation 10 minutes, power 300W, 2s/ time, it is spaced apart 1
Second, obtaining the saturated solution of mix homogeneously, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried
Obtain polypropylene beta crystal form nucleating agent composition 3.
Embodiment 4
Precise sodium benzoate 14g, N, N '-dicyclohexyl-2,6-aphthalimide 1g, is put by described weight
In miniature high-speed agitator, at room temperature with the speed high-speed stirred 1 minute of 500 revs/min, quiet after taking-up
Put, obtain polypropylene beta crystal form nucleating agent composition 4.
Embodiment 5
Precise sodium benzoate 1g, N, N '-dicyclohexyl-2,6-aphthalimide 14g, is put by described weight
In miniature high-speed agitator, at room temperature with the speed high-speed stirred 1 minute of 4500 revs/min, quiet after taking-up
Put, obtain polypropylene beta crystal form nucleating agent composition 5.
Embodiment 6
Precise sodium benzoate 14g, N, N, N ', N '-tetraalkyl terephthalamide 1g, it is dissolved in 75 DEG C
To saturated in DMF, sonic oscillation 10 minutes, power 500W, 2s/ time, it is spaced apart 1
Second, obtaining the saturated solution of mix homogeneously, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried
Obtain polypropylene beta crystal form nucleating agent composition 6.
Embodiment 7
Precise sodium benzoate 1g, N, N, N ', N '-tetraalkyl terephthalamide 14g, it is dissolved in 75 DEG C
To saturated in DMF, sonic oscillation 10 minutes, power 500W, 2s/ time, it is spaced apart 1
Second, obtaining the saturated solution of mix homogeneously, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried
Obtain polypropylene beta crystal form nucleating agent composition 7.
Embodiment 8
Precise sodium benzoate 2g, N, N, N ', N '-tetraalkyl terephthalamide 1g, it is dissolved in 75 DEG C
To saturated in DMF, sonic oscillation 10 minutes, power 500W, 2s/ time, it is spaced apart 1
Second, obtaining the saturated solution of mix homogeneously, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried
Obtain polypropylene beta crystal form nucleating agent composition 8.
Embodiment 9
Precise sodium benzoate 1g, N, N, N ', N '-tetraalkyl terephthalamide 2g, it is dissolved in 75 DEG C
To saturated in DMF, sonic oscillation 10 minutes, power 500W, 2s/ time, it is spaced apart 1
Second, obtaining the saturated solution of mix homogeneously, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried
Obtain polypropylene beta crystal form nucleating agent composition 9.
Embodiment 10
Precise sodium benzoate 14g, N, N, N ', N '-tetraalkyl terephthalamide 1g, it is dissolved in 75 DEG C
To saturated in dimethyl sulfoxide, sonic oscillation 10 minutes, power 50W, 2s/ time, it is spaced apart 1 second, obtains mixed
Closing uniform saturated solution, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried to obtain poly-third
Alkene beta crystal-type nucleater compositions 10.
Embodiment 11
Precise sodium benzoate 1g, N, N, N ', N '-tetraalkyl terephthalamide 14g, it is dissolved in 75 DEG C
To saturated in dimethyl sulfoxide, sonic oscillation 10 minutes, power 50W, 2s/ time, it is spaced apart 1 second, obtains mixed
Closing uniform saturated solution, natural cooling separates out nucleating agent compositions after being cooled to 25 DEG C, is dried to obtain poly-third
Alkene beta crystal-type nucleater compositions 11.
Two, prepared by beta-crystal polypropylene composition:
Embodiment 12～50
By acrylic resin, compatilizer maleic anhydride inoculated polypropylene, auxiliary agent bag and polypropylene beta obtained as above
Crystal-type nucleater compositions is together added in high speed agitator, motor speed 1300 revs/min, at room temperature mixes
Take out after 2 minutes, the premix material mixed is added in the hopper of Ф 25 double screw extruder, be total to through melted
Mixed, extrusion, tank cool down, traction pelletize prepares beta-crystal polypropylene composition.Wherein double screw extruder
From the temperature of first paragraph to the 5th section control respectively 170～180 DEG C, 180～200 DEG C, 195～230 DEG C,
200～230 DEG C, head temperature is at 200～230 DEG C, and screw speed is at 200～400 revs/min；Tank cools down
In the cooling water temperature of use be 20～40 DEG C.Concrete constituent content formula is shown in Table 1, all with parts by weight
Meter.
In embodiment 12～20, [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane in antioxidant four
It is 5:1 with the weight ratio of tricresyl phosphite (2,4--di-tert-butyl-phenyl) ester；In embodiment 21～26, in antioxidant
Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane and tricresyl phosphites (2,4--di-tert-butyl-phenyl)
The weight ratio of ester is 1:5；In embodiment 27～38, [β-(3,5-di-tert-butyl-hydroxy phenyl) in antioxidant four
Propylene] weight ratio of tetramethylolmethane and tricresyl phosphite (2,4--di-tert-butyl-phenyl) ester is 10:1；Embodiment 39～50
In, [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane and tricresyl phosphite (2,4--in antioxidant four
Di-tert-butyl-phenyl) weight ratio of ester is 1:10.
In embodiment 12～44, it it is with lubricator calcium stearate；In embodiment 45～47, institute is with lubricator
For stearic acid；In embodiment 48～50, it it is with lubricator zinc stearate.
It is molded test bars by injection moulding machine after being dried by gained beta-crystal polypropylene composition pellet.Note
Each section of temperature of molding machine is at 190～240 DEG C.Test bars carries out various performance test, and specific performance is tied
Fruit is shown in Table 2.
Comparative example 1～5
In addition to the component formula of polypropene composition is different from embodiment 12～50, other preparation conditions are all with real
Execute example 12～50.Concrete constituent content formula is shown in Table 1, all in terms of parts by weight.Gained test bars is carried out
Various performance tests, specific performance the results are shown in Table 2.
In comparative example 1 and comparative example 2, in antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene]
Tetramethylolmethane is 5:1 with the weight ratio of tricresyl phosphite (2,4--di-tert-butyl-phenyl) ester；Comparative example 3 and comparative example
In 4, [β-(3,5-di-tert-butyl-hydroxy phenyl) propylene] tetramethylolmethane and tricresyl phosphite in antioxidant four (2,
4--di-tert-butyl-phenyl) weight ratio of ester is 1:5；In comparative example 5 and comparative example 6, in antioxidant four [β-(3,
5-di-tert-butyl-hydroxy phenyl) propylene] weight of tetramethylolmethane and tricresyl phosphite (2,4--di-tert-butyl-phenyl) ester
Amount ratio is 10:1；In comparative example 7 and comparative example 8, in antioxidant four [β-(3,5-di-t-butyl-4-hydroxy benzenes
Base) propylene] weight ratio of tetramethylolmethane and tricresyl phosphite (2,4--di-tert-butyl-phenyl) ester is 1:10.
The concrete constituent content formula of table 1
The product of table 2-1 nucleating agent compositions 1～3(embodiment 1～3) heat of modified polypropene, mechanical performance data
When nucleating agent compositions 1～3 is 0.5 part, it is 0.5 part equally that polypropylene impact strength is higher than
N, N '-dicyclohexyl-2,6-aphthalimide individually modifying function played in polypropylene.Thermal deformation simultaneously
Temperature too higher than the N, N '-dicyclohexyl-2,6-aphthalimide of 0.5 number individually played in polypropylene
The modifying function arrived.
The product of table 2-2 nucleating agent compositions 21～26(embodiment 4,5) heat of modified polypropene, mechanical performance data
When nucleating agent compositions 4,5 is 0.5 part, it is 0.5 part equally that polypropylene impact strength is higher than
N, N '-dicyclohexyl-2,6-aphthalimide individually modifying function played in polypropylene.Thermal deformation simultaneously
Temperature too higher than the N, N '-dicyclohexyl-2,6-aphthalimide of 0.5 number individually played in polypropylene
The modifying function arrived.
The product of table 2-3 nucleating agent compositions 27～38(embodiment 6～9) heat of modified polypropene, mechanical performance data
When the number of nucleating agent compositions 6～9 is 0.5 part, polypropylene impact strength ratio is used alone 0.5 part
Number N, N, N ', N '-tetraalkyl terephthalamide improves about 40～93%.Bending modulus and thermal deformation temperature simultaneously
Degree is too higher than 0.5 part of N, N, N ', N '-tetraalkyl terephthalamide individually changing played in polypropylene
Property effect.
The product of table 2-4 nucleating agent compositions 39～44(embodiment 10,11) heat of modified polypropene, mechanical performance data
When nucleator combination 10,11 is 0.5 part, polypropylene impact strength ratio is used alone 0.5 part
N, N, N ', N '-tetraalkyl terephthalamide improves about 50～81%.Heat distortion temperature and bending modulus simultaneously
Too higher than 0.5 part of N, N, N ', the individually modification played in polypropylene of N '-tetraalkyl terephthalamide
Effect.
Nucleating agent compositions is worked as the display of above-mentioned nucleating agent compositions 1～11 and is in same with one pack system nucleator
During sample concentration, nucleating agent compositions has higher impact strength than one pack system nucleator, preferred for some
Compositions, not only polypropylene impact strength is improved largely, under same addition, bending modulus and
The mechanical properties such as heat distortion temperature are also above the effect of one-component nucleator.
Claims (13)
1. a polypropylene beta crystal form nucleating agent composition, includes A nucleator and B nucleator；Wherein said A
The weight ratio of nucleator and B nucleator is 15:1～1:15；
Described A nucleator is metal carboxylate nucleator, selected from alkali metal salt or the aromatic series carboxylic of unary fatty acid
At least one in hydrochlorate；
Described B nucleator is at least one in aryl amide beta nucleater；
Described polypropylene beta crystal form nucleating agent composition is prepared by following methods: will comprise described A nucleator and
B nucleator is dissolved in N,N-dimethylformamide or the diformazan of 50～80 DEG C in interior component by described weight ratio
To saturated in base sulfoxide, sonic oscillation, obtain the saturated solution of mix homogeneously, natural cooling is cooled to 20～50 DEG C
Rear precipitation material, the most i.e. obtains described polypropylene beta crystal form nucleating agent composition by described precipitation material.
2. a kind of polypropylene beta crystal form nucleating agent composition as claimed in claim 1, it is characterised in that:
The weight ratio of described A nucleator and B nucleator is 10:1～1:10.
3. a kind of polypropylene beta crystal form nucleating agent composition as claimed in claim 1, it is characterised in that:
At least one in benzoate of described A nucleator.
4. a kind of polypropylene beta crystal form nucleating agent composition as claimed in claim 3, it is characterised in that:
Described A nucleator is selected from sodium benzoate, Potassium Benzoate, at least one in aluminum benzoate.
5. a kind of polypropylene beta crystal form nucleating agent composition as claimed in claim 1, it is characterised in that:
Described B nucleator is selected from N, N '-dicyclohexyl-2,6-aphthalimide, N, N, N ', N '-tetraalkyl is to benzene
Diformamide, N, N ' at least one in-dicyclohexyl terephthalamide.
6. the preparation method of a kind of polypropylene beta crystal form nucleating agent composition as described in one of Claims 1 to 5, it is special
Levy and be, this preparation method include: by the component that comprises including described A nucleator and B nucleator by described weight
Than being dissolved in the most saturated in the DMF of 50～80 DEG C or dimethyl sulfoxide, sonic oscillation；Merit
Rate is 50～500W, and each duration of oscillation is 1～5 second/time, is spaced apart 1～2s, and total time is 10～30 minutes,
Obtaining the saturated solution of mix homogeneously, natural cooling separates out material, by described precipitation material after being cooled to 20～50 DEG C
It is placed in fume hood, after solvent volatilizees, becomes drying sample, obtain described polypropylene beta crystal nucleating agent group
Compound.
7. a kind of β containing the polypropylene beta crystal form nucleating agent composition described in one of Claims 1 to 5 is brilliant
Type polypropene composition, it is characterised in that:
Include blended following component: acrylic resin, compatilizer, auxiliary agent, described polypropylene beta crystal
Nucleating agent compositions；
Above-mentioned each component is in terms of 100 weight portions by acrylic resin, and described compatilizer is 0.3～5 weight portions,
Described auxiliary agent is 0.1～1 weight portion, and described polypropylene beta crystal form nucleating agent composition is 0.05～1 weight portion；
Described compatilizer is maleic anhydride inoculated polypropylene, relative molecular mass 2000～15000, percent grafting
It is 0.3～5%；
Described auxiliary agent includes antioxidant and lubricant；Wherein the weight ratio of antioxidant and lubricant be 17:1～
1:15。
8. a kind of beta-crystal polypropylene composition as claimed in claim 7, it is characterised in that:
Being in terms of 100 weight portions by acrylic resin, described compatilizer is 0.3～2 weight portions.
9. a kind of beta-crystal polypropylene composition as claimed in claim 7, it is characterised in that:
Being in terms of 100 weight portions by acrylic resin, described polypropylene beta crystal form nucleating agent composition is 0.05～0.5
Weight portion.
10. a kind of beta-crystal polypropylene composition as claimed in claim 7, it is characterised in that:
Antioxidant is 5:1～1:1 with the weight ratio of lubricant.
The 11. a kind of beta-crystal polypropylene compositions as described in any one in claim 7～10, it is characterised in that:
Described antioxidant is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3,5-
Di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 2,2' methylene bis-(4-methyl-6-tert butyl benzene
Phenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-2-methyl-2-phenylpropane base) butane, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester,
Double (2,4-DI-tert-butylphenol compounds) pentaerythritol diphosphites, double (2,6-di-t-butyl-4-tolyl) season
At least one in penta tetrol diphosphites；
At least one in stearic acid, calcium stearate, zinc stearate of described lubricant.
12. a kind of beta-crystal polypropylene compositions as claimed in claim 11, it is characterised in that:
Described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and tricresyl phosphites
The mixture of (2,4-di-tert-butyl-phenyl) ester, its weight ratio is 10:1～1:10.
The preparation method of the 13. a kind of beta-crystal polypropylene compositions as described in any one of claim 7～12:
Including including described acrylic resin, compatilizer, auxiliary agent and polypropylene beta crystal nucleating agent combination
Thing is mixed by described amount in interior component, and prepares described beta-crystal polypropylene composition through melt blending.
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| CN109320765A (en) * | 2018-09-29 | 2019-02-12 | 山西科灜科技有限公司 | A kind of solvay-type beta nucleater and the preparation method and application thereof |
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| CN105633328B (en) * | 2016-01-06 | 2018-12-28 | 河南师范大学 | Lithium ion battery polypropylene porous septum and preparation method thereof |
| CN107674308A (en) * | 2017-10-31 | 2018-02-09 | 山西省化工研究所（有限公司） | A kind of preparation method and application of composite polyolefine nucleator |
| CN107674309A (en) * | 2017-10-31 | 2018-02-09 | 山西省化工研究所（有限公司） | A kind of composite polyolefine nucleator and its preparation method and application |
| CN109369954B (en) * | 2018-09-29 | 2020-10-27 | 山西科灜科技有限公司 | Complex beta nucleating agent and preparation and application thereof |
| WO2022265042A1 (en) * | 2021-06-16 | 2022-12-22 | 株式会社Adeka | Nucleating agent composition, resin composition, molded article thereof, and method for manufacturing resin composition |
| CN114539569B (en) * | 2022-03-29 | 2023-08-11 | 涿州市隽诚化工有限公司 | Polypropylene beta crystal form compound nucleating agent and preparation method thereof |
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