CN105623080B - Nucleating agent compositions and polypropylene material - Google Patents
Nucleating agent compositions and polypropylene material Download PDFInfo
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Abstract
A kind of polypropylene material the present invention relates to nucleating agent compositions and containing the nucleating agent compositions, the composition contains substituted diaryl organic phosphate, aliphatic monocarboxylic acid metal salt and the magnesium hydroxide shown in following chemical formula (I), in formula (I), R1、R2、R3And R4It is identical or differ, it is each independently hydrogen atom or C1‑C6Substituted or unsubstituted linear chain or branch chain alkyl；M is metal cation, valence mumber=m+n of M；Ligancies of the m for organophosphorous groups, m >=1；N be hydroxyl number, n≤3.The nucleating agent compositions synthesis of the present invention improves the transparency, rigidity, heat resistance and the impact resistance of polypropylene articles.
Description
Technical field
A kind of polypropylene material the present invention relates to nucleating agent compositions and containing the nucleating agent compositions.
Background technology
Polypropylene as in current five big general synthetic resins the most fast kind of concerned growth rate, not only price is low
It is honest and clean and with many good characteristics, but there are the shortcomings such as poor rigidity, poor toughness, transparency be low for polypropylene.Nucleating agent can promote
Non-crystalline type or imperfect crystal type polymer crystallization simultaneously make grain structure miniaturization, so as to improve the crystallinity of polymer.It is logical
The method for crossing addition nucleating agent is greatly improved the stretching, bending and shock resistance of polypropylene articles.In addition, nucleating agent can also
Polypropylene crystals size is made to become smaller, so as to reduce the scattering on the crystalline portion of crystal and amorphous fraction interface, thus makes to gather
The transparency of propylene significantly improves.
Polypropylene nucleater, which chemically forms, can be divided into inorganic, organic two class.
Mainly substituted aryl organic phosphate, glucitol derivative, metal salt of organic carboxylic acid, the dehydrogenation of organic nucleating agent
Abietic acid metal salt and high score subclass etc..Organic nucleating agent has good compatibility with fluoropolymer resin, can significantly improve product
The transparency and lustrous surface.Wherein, 2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) aluminum phosphate is third generation aryl
Phosphoric acid ester nucleating agent plays the role of extremely protruding, but can make the shock resistance of product for the transparency for improving product
It significantly reduces.
Inorganic nucleating agent mainly has talcum powder, silicate, titanium dioxide, aluminium oxide, nano silicon dioxide etc..Often at present
Although titanium dioxide abundance, cheap and easy to get, have a certain impact, use to the transparency and lustrous surface of product
Effect is poor, and application range is limited to.
CN 102850595A disclose a kind of nucleating agent compositions, and the composition contains substituted diaryl organophosphor simultaneously
Hydrochlorate and rutile type nano titanic oxide can improve polyacrylic rigidity, the transparency and heat resistance simultaneously.But the combination
Object is relatively limited to the raising of polypropylene transparent, and can reduce polyacrylic shock resistance.
Invention content
It is an object of the invention to solve the disadvantages mentioned above of the prior art, provide a kind of can improve the transparent of resin simultaneously
Organic phosphate nucleating agent composition of property, rigidity, impact resistance and heat resistance and preparation method thereof and contain the composition
Acrylic resin.
To achieve these goals, the present inventor has done numerous studies and has had been surprisingly found that, will specifically replace two
Aryl organic phosphate, aliphatic monocarboxylic acid metal salt and magnesium hydroxide cooperation are used as nucleating agent, can not only significantly improve poly-
Rigid, the transparent and heat resistance of propylene, and polyacrylic impact resistance can be significantly improved.
The present invention provides a kind of nucleating agent compositions, the composition contains two virtue of substitution shown in following chemical formula (I)
Base organic phosphate, aliphatic monocarboxylic acid metal salt and magnesium hydroxide,
In formula (I), R1、R2、R3And R4It is identical or differ；R1、R2、R3And R4Respectively hydrogen atom or C1-C6Substitution or
The alkyl of unsubstituted linear chain or branch chain；M is metal cation, valence mumber=m+n of M；M is organophosphorous groups (i.e. in bracket
Part) ligancy, m >=1；N be hydroxyl number, n≤3.
In addition, the present invention also provides a kind of polypropylene material, the polypropylene material contain acrylic resin and it is above-mentioned into
Core agent composition.
The present invention makes full use of nucleating agent in the different guiding function of polyolefin crystallization process, the nucleating agent combination prepared
Object integrates the transparency, rigidity, heat resistance and the impact resistance for improving polypropylene articles.
Specific embodiment
The present invention provides a kind of nucleating agent compositions, the composition contains two virtue of substitution shown in following chemical formula (I)
Base organic phosphate, aliphatic monocarboxylic acid metal salt and magnesium hydroxide,
In formula (I), R1、R2、R3And R4It is identical or differ；R1、R2、R3And R4Respectively hydrogen atom or C1-C6Substitution or
The alkyl of unsubstituted linear chain or branch chain；M is metal cation, valence mumber=m+n of M；M is organophosphorous groups (i.e. in bracket
Part) ligancy, m >=1；N be hydroxyl number, n≤3.
Nucleating agent compositions according to the present invention, wherein, the content of each component can change in the larger context, preferably
Ground, on the basis of the gross weight of nucleating agent compositions, the substituted diaryl organic phosphate accounts for 10-70 weight %, the fat
Race's monocarboxylic acid metal salt accounts for 10-70 weight %, and the magnesium hydroxide accounts for 5-80 weight %；It is highly preferred that with nucleating agent compositions
Gross weight on the basis of, the substituted diaryl organic phosphate accounts for 30-70 weight %, and the aliphatic monocarboxylic acid metal salt accounts for
15-50 weight %, the magnesium hydroxide account for 5-50 weight %.
Nucleating agent compositions according to the present invention, it is preferable that 10 microns of the average grain diameter of the nucleating agent compositions hereinafter,
It is highly preferred that less than 5 microns.In the present invention, the meaning of the average grain diameter of the nucleating agent compositions is when certain for being tested particle
When kind physical characteristic or physical behavio(u)r most close with the homogenous spheres (or combination) of a certain diameter, just the sphere (or combination)
Equivalent grain size of the diameter as tested particle.
Nucleating agent compositions according to the present invention, in formula (I), R1、R2、R3And R4It can be respectively methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, 2- first
One kind in base amyl, 3- methyl amyls, 2,3- dimethylbutyls and 2,2 '-dimethylbutyl.
Nucleating agent compositions according to the present invention, in formula (I), the metal cation representated by M can be Na (sodium), Li
A kind of metal cation in (lithium), Mg (magnesium), Ca (calcium), Zn (zinc) and Al (aluminium)；Preferably, the metal sun representated by M
Ion is a kind of metal cation in Mg (magnesium), Ca (calcium), Zn (zinc) and Al (aluminium)；It is highly preferred that the metal sun representated by M
Ion is Mg (magnesium) or Al (aluminium).
Nucleating agent compositions according to the present invention, in formula (I), m is preferably 2 or 3.
Nucleating agent compositions according to the present invention, it is preferable that the substituted diaryl organic phosphate is following compounds
In it is one or more：Two [2,2 '-methylene-bis- (4,6- di-t-butyls phenoxy group) phosphoric acid] magnesium, two [2,2 '-methylene-bis-
(4- methyl-6-terts butyl phenoxy) phosphoric acid] magnesium, two [2,2 '-methylene-bis- (6- methyl -4- tert-butyl benzenes oxygroup) phosphoric acid]
Magnesium, two [2,2 '-methylene-bis- (4- ethyl -6- tert-butyl benzenes oxygroup) phosphoric acid] magnesium, two [2,2 '-methylene-bis- (4- propyl -
6- tert-butyl benzenes oxygroup) phosphoric acid] magnesium, two [2,2 '-methylene-bis- (4- butyl -6- tert-butyl benzenes oxygroup) phosphoric acid] magnesium, two [2,
2 '-methylene-bis- (4,6- di-t-butyls phenoxy group) phosphoric acid] hydroxy Al, two [2,2 '-methylene-bis- (4- methyl-6-tert butyl
Phenoxy group) phosphoric acid] hydroxy Al, two [2,2 '-methylene-bis- (6- methyl -4- tert-butyl benzenes oxygroup) phosphoric acid] hydroxy Als, two [2,
2 '-methylene-bis- (4- ethyl -6- tert-butyl benzenes oxygroup) phosphoric acid] hydroxy Al, two [2,2 '-methylene-bis- (4- propyl -6- uncles
Butyl phenoxy) phosphoric acid] hydroxy Al, two [2,2 '-methylene-bis- (4- butyl -6- tert-butyl benzenes oxygroup) phosphoric acid] hydroxy Als, three
[2,2 '-methylene-bis- (4,6- di-t-butyls phenoxy group) phosphoric acid] aluminium and three [2,2 '-methylene-bis- (4- methyl-6-tert butyl
Phenoxy group) phosphoric acid] aluminium.
Nucleating agent compositions according to the present invention, most preferably, the substituted diaryl organic phosphate are following chemical combination
It is one or more in object：Two [2,2 '-methylene-bis- (4,6- di-t-butyls phenoxy group) phosphoric acid] hydroxy Als, two [2,2 '-Asias
Methyl-bis- (4- methyl-6-terts butyl phenoxy) phosphoric acid] hydroxy Al, three [2,2 '-methylene-bis- (4,6- di-tert-butyl oxygen
Base) phosphoric acid] aluminium, three [2,2 '-methylene-bis- (4- methyl-6-terts butyl phenoxy) phosphoric acid] aluminium, two [2,2 '-methylene-bis-
(4,6- di-t-butyls phenoxy group) phosphoric acid] magnesium and two [2,2 '-methylene-bis- (4- methyl-6-terts butyl phenoxy) phosphoric acid] magnesium.
Nucleating agent compositions according to the present invention, the substituted diaryl organic phosphate representated by formula (I) can be by various
Method obtains, such as is commercially available, and can also be prepared according to existing preparation method, such as may be used including such as
The method of lower step is prepared：By substituted diaryl phenol raw material in the presence of toluene and triethylamine, carried out with phosphorus oxychloride
Phosphorus acylation reaction, it is water-soluble with salt forming agent such as magnesium chloride and/or aluminium chloride then by product in the mixed solution of acetone and water
Liquid carries out salt-forming reaction, according to the molar ratio, substituted diaryl organophosphorus ester：Salt forming agent=1.8-2.2：1, and with such as concentration
Sodium hydroxide solution for 10-30 weight % adjusts pH to neutrality, after steaming solvent, drying, obtains substituted diaryl organophosphor
Hydrochlorate, and, used substituted diaryl phenol raw material is the compound representated by following chemical formula (II),
Wherein, the R in formula (II)1、R2、R3And R4It is identical or differ；R1、R2、R3And R4Respectively hydrogen atom or C1-C6
Substituted or unsubstituted linear or branched alkyl group.The substituted or unsubstituted linear or branched alkyl group of C1-C6 can be methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, just
One kind in hexyl, 2- methyl amyls, 3- methyl amyls, 2,3- dimethylbutyls and 2,2 '-dimethylbutyl.
Nucleating agent compositions according to the present invention, the aliphatic monocarboxylic acid metal salt are by alkali metal, alkaline-earth metal, mistake
Cross the one or more and C in metal6-C29Aliphatic monocarboxylic acid formed salt, it is preferable that the aliphatic monocarboxylic acid metal
Salt is one or more in following compounds：By alkali metal and lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, 17
Alkanoic acid, stearic acid, cis- -4- nonendioic acids, dodecanoic acid, palmitoleic acid, petroselic acid, oleic acid, elaidic acid, vaccenic acid, sub- oil
The salt that acid, linolelaidic acid, gamma-Linolenic acid, leukotrienes, ricinoleic acid, 12- hydroxy stearic acids or aphthenic acids are formed.
Nucleating agent compositions according to the present invention, it is preferable that the aliphatic monocarboxylic acid metal salt is lauric acid, tridecane
Acid, tetradecanoic acid, pentadecanoic acid, Heptadecanoic acide, stearic acid and 12- hydroxy stearic acids lithium salts in it is one or more.
Nucleating agent compositions according to the present invention, it is preferable that the average grain diameter of the magnesium hydroxide is 10nm-10 μm；More
Preferably, the average grain diameter of the magnesium hydroxide is 50-500nm.
Nucleating agent compositions according to the present invention, the magnesium hydroxide are commercially available or by known method systems
It is standby, but the present invention is preferably prepared by method comprising the following steps：
1) under conditions of stirring, magnesium chloride brine is mixed with magnesium oxide powder, until magnesium oxide powder is completely molten
Solution；
2) the magnesium oxide powder dissolved solution obtained in step 1) is stood, is filtered successively after solid precipitation
And washing, obtain solid intermediate product；
3) in the presence of deionized water, the solid intermediate product that step 2) is obtained reacts in a kettle, Ran Houyi
It is secondary to be cooled down, be filtered, washed and dried, obtain magnesium hydroxide product；
Wherein, in step 1), in molar ratio, magnesium chloride：Magnesia=5-15：1；Preferably, in molar ratio, chlorination
Magnesium：Magnesia=10-12：1；
Wherein, in step 2), the time of the standing can be 10-50 hours, preferably 20-30 hours；
Wherein, in step 3), the temperature reacted in a kettle can be 100-200 DEG C, and the time can be 1-
10 hours；Preferably, the temperature reacted in a kettle is 120-180 DEG C, and the time is 5-8 hours.
Using magnesium hydroxide of the magnesium hydroxide made from the above method compared with the prior art or commercially available magnesium hydroxide, to improving
The performance of polypropylene material is more advantageous.
Nucleating agent compositions according to the present invention can also further contain other nucleating agents and additive as needed.
As the nucleating agent other than the nucleating agent of the present invention, can enumerate：Lithium benzoate, sodium benzoate, aluminum benzoate, 4- tertiary butyls peace
Carboxylate metals' salt such as the fragrant sour aluminium salt of breath, adipic acid sodium；Two (4- tert-butyl-phenyls) sodium phosphates, dibenzyl sorbitol, two (first
Base benzal) polyol derivatives such as sorbierite and two (dimethyl benzylidene) sorbierites etc..In addition, as using as needed
Additive, can enumerate：Steric hindrance amine light stabilizer, ultra-violet absorber, phosphorus antioxidants, phenol antioxidant and sulphur
The additive generally used known in class antioxidant etc..
The preparation method of above-mentioned nucleating agent compositions provided by the invention is fairly simple, such as can be by by above-mentioned formula
(I) the substituted diaryl organic phosphate shown in is mixed to get with aliphatic monocarboxylic acid metal salt and magnesium hydroxide.
According to the present invention, on the basis of the gross weight of nucleating agent compositions, the dosage of the substituted diaryl organic phosphate
Can be 10-70 weight %, the dosage of the aliphatic monocarboxylic acid metal salt can be 10-70 weight %, the magnesium hydroxide
Dosage can be 5-80 weight %；Preferably, on the basis of the gross weight of nucleating agent compositions, the substituted diaryl organophosphor
Hydrochlorate accounts for 30-70 weight %, and the aliphatic monocarboxylic acid metal salt accounts for 15-50 weight %, and the magnesium hydroxide accounts for 5-50 weights
Measure %.
According to the present invention, there are many kinds of the mixed methods, as long as mixed method commonly used in the art is all unrestricted,
It is preferred that mixed grinding in the ball mill.Grinder used in mixed grinding can be mortar, ball mill, rod mill, tube mill
Machine, taper grinding machine, vibrator, Hai Siwen ball mills, roller mill, vial-type grinding machine, hammer-mill, grinding mill, injector-type mill,
Jet-O-Mizer, ultra tiny metal grinding machine, nanometer miser, fine grinding machine, colloidal mill, general class mayer colloidal mill,
Micron grinding machine, charlotte colloid mill machine and rotation stage property etc., preferably ball mill.The mixed grinding time is according to the grinder used
Type, model, severity of grind, the type of raw material powder etc. selected, usually -10 hours 5 minutes, preferably 0.5-4 was small
When, most preferably 1 hour.
According to the invention, it is further possible to by further disperseing mixed mixture in a solvent, then it is dried,
To obtain grain size and the better nucleating agent compositions of uniformity.The solvent is solvent commonly used in the art, can be water, first
One kind or more in alcohol, ethyl alcohol, propyl alcohol, butanol, acetone, ethyl acetate, benzene, toluene, tetrahydrofuran, hexamethylene and n-hexane
Kind, preferably hexamethylene.What the method for the dispersion was known to the skilled person can disperse solid in a liquid
Even method, details are not described herein.The drying can use the method and apparatus for drying commonly used in the art, preferably make
It is dried with spray dryer.
According to the present invention, the substituted diaryl organic phosphate, aliphatic monocarboxylic acid metal salt and magnesium hydroxide etc. are former
The selection of material can be identical in nucleating agent compositions provided by the invention, and details are not described herein.
The present invention also provides a kind of polypropylene material, which contains acrylic resin and above-mentioned nucleating agent
Composition.
Polypropylene material according to the present invention, relative to the acrylic resin of 100 parts by weight, the content of nucleating agent compositions
Can be 0.1-1 parts by weight, preferably 0.1-0.4 parts by weight.
The present invention is more fully described with preparation example, embodiment and application examples below.But the present invention be not exposed to it is following
Any restrictions of embodiment.
Preparation example 1 prepares substituted diaryl organic phosphate
2,2 '-methylene-bis- (4,6- DI-tert-butylphenol compounds) are added in reaction bulb, and (Shanghai Taurus Chemical Co., Ltd. gives birth to
Production, the trade mark 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid and fully dissolves, nitrogen is passed through solution
In, flow velocity 80ml/min, and under room temperature, phosphorus oxychloride 20ml, drop are added in uniform rate within 0.5 hour time
It is reacted again after adding 12 hours；Into reaction bulb plus water 150ml, under the conditions of 75 DEG C of temperature, stir 0.5 hour, then in 85
Solvent toluene is steamed under the conditions of DEG C, filters remaining solidliquid mixture, after washing solid product, as intermediate product 2,2 '-
Methylene-bis- (4,6- di-t-butyls phenoxy group) phosphate；By 2,2 '-methylene of gained intermediate product-bis- (4,6- di-t-butyls
Phenoxy group) phosphate is dissolved in into the mixed liquor of salt solvent acetone and water, and the mass ratio of acetone and water is 4 into salt solvent：6,
Organophosphorus ester and into salt solvent mass ratio be 1：30, a concentration of 30% weight aluminum chloride aqueous solution is added in the substitution
Diaryl organophosphorus ester is carried out into salt, aluminium chloride and 2, and 2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphate rubs
You are than being 1：2, a concentration of 10 weight % sodium hydrate regulator solutions pH value is added dropwise to neutrality, steams acetone, obtains white solid
Product after filtering, is washed with deionized to pH=7-8, and after heat drying, the fusing point of the product is more than 300 DEG C, through mass spectrum
Product two [2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphoric acid] hydroxy Al No.1 is confirmed as obtaining with infrared analysis, is passed through
High performance liquid chromatography confirms that purity is 99%.
Preparation example 2 prepares substituted diaryl organic phosphate
2,2 '-methylene-bis- (4- methyl-6-tert-butylphenols) (limited public affairs of Shanghai Taurus chemical industry are added in reaction bulb
Department's production, the trade mark 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid and fully dissolves, nitrogen is passed through molten
In liquid, flow velocity 80ml/min, and under room temperature, phosphorus oxychloride 20ml is added in uniform rate within 0.5 hour time,
It is reacted again after being added dropwise 12 hours.Into reaction bulb plus water 150ml, 75 DEG C of temperature stir 0.5 hour, then steam solvent,
Filtering obtains solid product, as intermediate product 2,2 '-methylene-bis- (4- methyl-6-terts butyl phenoxy) phosphoric acid after washing
Ester；2,2 '-methylene of gained intermediate product-bis- (4- methyl-6-terts butyl phenoxies) phosphate is dissolved in into salt solvent acetone
In the mixed liquor of water, the mass ratio of acetone and water is 4 into salt solvent：6, organophosphorus ester and the mass ratio into salt solvent are
1：30, a concentration of 30% weight aluminum chloride aqueous solution is added in into described 2,2 '-methylene-bis- (4- methyl-6-tert butyl benzene oxygen
Base) phosphate carried out into salt, aluminium chloride and 2, the molar ratio of 2 '-methylene-bis- (4- methyl-6-terts butyl phenoxy) phosphate
It is 1：2, a concentration of 10 weight % sodium hydrate regulator solutions pH value of dropwise addition to neutrality steams acetone, obtains white solid product,
It after filtering, is washed with deionized to pH=7-8, heat drying, the fusing point of the product is more than 300 DEG C, through mass spectrum and infrared
It is analyzed to identify as two [2,2 '-methylene-bis- (4- methyl-6-terts butyl phenoxy) phosphoric acid] hydroxy Al No.2, through efficient liquid phase
Chromatography confirms that purity is 99.1%.
Preparation example 3 prepares substituted diaryl organic phosphate
2,2 '-methylene-bis- (4,6- DI-tert-butylphenol compounds) are added in reaction bulb, and (Shanghai Taurus Chemical Co., Ltd. gives birth to
Production, the trade mark 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid and fully dissolves, nitrogen is passed through solution
In, flow velocity 80ml/min, and under room temperature, phosphorus oxychloride 20ml is added in uniform rate in 0.5 hour, is dripped
It is reacted again 12 hours after finishing.Into reaction bulb plus water 150ml, under the conditions of 75 DEG C of temperature, stir 0.5 hour, then in 85 DEG C of items
Solvent toluene is steamed under part, filters remaining solidliquid mixture, solid product, as intermediate product 2,2 '-methylene are obtained after washing
Base-bis- (4,6- di-t-butyls phenoxy group) phosphate.By intermediate product 2,2 '-methylene-bis- (4,6- di-t-butyls phenoxy groups)
Phosphate is dissolved in into the mixed liquor of salt solvent acetone and water, and the mass ratio of acetone and water is 4 into salt solvent：6, organic phosphoric acid
Ester and into salt solvent mass ratio be 1：30, the aluminum chloride aqueous solution of a concentration of 30 weight % is added to 2,2 '-methylene-bis-
It is carried out in (4,6- di-t-butyl phenoxy group) phosphate ester solution into salt, aluminium chloride and 2,2 '-methylene-bis- (4,6- di-t-butyls
Phenoxy group) phosphate molar ratio be 1：3.5, the sodium hydrate regulator solution pH value of a concentration of 10 weight % is added dropwise to neutrality,
Steam acetone, obtain white solid product, after filtering, be washed with deionized to pH=7-8, after heat drying solid production
The solid product is added in solvent methanol, a concentration of 30 weight % of product in acquired solution, then will be equivalent to first by object
The water of 50 volume % of alcohol is added in acquired solution that sedimentation is precipitated, and filters and obtains product No.3, institute after solid is dried
Solid product fusing point is stated more than 300 DEG C, be confirmed as three through mass spectrum and infrared analysis result [2,2 '-methylene-bis- (4,6- bis- uncles
Butyl phenoxy) phosphoric acid] aluminium No.3 is 90% with high effective liquid chromatography for measuring purity.
Preparation example 4 prepares substituted diaryl organic phosphate
2,2 '-methylene-bis- (4,6- DI-tert-butylphenol compounds) are added in reaction bulb, and (Shanghai Taurus Chemical Co., Ltd. gives birth to
Production, the trade mark 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid and fully dissolves, nitrogen is passed through solution
In, flow velocity 80ml/min, and under room temperature, phosphorus oxychloride 20ml is added in uniform rate in 0.5 hour, is dripped
It is reacted again 12 hours after finishing.Into reaction bulb plus water 150ml, 75 DEG C of temperature stir 0.5 hour, then steam solvent, filter,
Solid product, as intermediate product 2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphate are obtained after washing；By gained
Intermediate product 2,2 '-methylene-bis- (4,6- di-t-butyls phenoxy group) phosphate is dissolved in into the mixed liquor of salt solvent acetone and water
In, the mass ratio of acetone and water is 4 into salt solvent：6, organophosphorus ester and the mass ratio into salt solvent are 1：30, by concentration
It is molten that described 2,2 '-methylene-bis- (the 4,6- di-t-butyls phenoxy groups) phosphate is added to for 30% weight magnesium chloride brine
It is carried out in liquid into salt, magnesium chloride and 2, the molar ratio of 2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphate is 1：2, drop
A concentration of 10% weight sodium hydroxide is added to adjust solution ph to neutrality, acetone is steamed, obtains white solid product, after filtering,
Be washed with deionized to pH=7-8, after heat drying solid product No.4, the fusing point of the product is more than 300 DEG C, through matter
Spectrum and infrared analysis are confirmed as [2,2 '-methylene-bis- (4,6- di-t-butyl phenoxy group) phosphoric acid] magnesium No.4, through high-efficient liquid phase color
Spectrum confirms that purity is 99.5%.
Preparation example 5 prepares magnesium hydroxide
500mL 2M magnesium chloride brines are added in reaction bulb, are added with stirring 0.1mol magnesium oxide powders, stirring is extremely
Magnesia is completely dissolved, and stops stirring；Solution is being stored at room temperature 24 hours, there is Precipitation；Precipitation is filtered, is washed with water；
Above-mentioned precipitation is added in reaction kettle, deionized water is added in, is reacted 6 hours at 180 DEG C；After cooling, product filtering is washed with water
It washs, magnesium hydroxide is made after dry.It is determined as magnesium hydroxide No.5 through X-ray diffractometer, laser particle analyzer measures average grain diameter
For 127nm.
Preparation example 6 prepares magnesium hydroxide
500mL 2M magnesium chloride brines are added in reaction bulb, are added with stirring 0.1mol magnesium oxide powders, stirring is extremely
Magnesia is completely dissolved, and stops stirring；Solution is being stored at room temperature 24 hours, there is Precipitation；Precipitation is filtered, is washed with water；
Above-mentioned precipitation is added in reaction kettle, deionized water is added in, is reacted 5 hours at 160 DEG C；After cooling, product filtering is washed with water
It washs, magnesium hydroxide is made after dry.It is determined as magnesium hydroxide No.6 through X-ray diffractometer, laser particle analyzer measures average grain diameter
For 235nm.
Preparation example 7 prepares magnesium hydroxide
500mL 2M magnesium chloride brines are added in reaction bulb, 0.1mol magnesium oxide powders is added with stirring and stirs to oxygen
Change magnesium to be completely dissolved, stop stirring；Solution is being stored at room temperature 24 hours, there is Precipitation；Precipitation is filtered, is washed with water；It will
Above-mentioned precipitation is added in reaction kettle, is added in deionized water, is reacted 8 hours at 120 DEG C；After cooling, product filtering is washed with water
It washs, magnesium hydroxide is made after dry.It is determined as magnesium hydroxide No.7 through X-ray diffractometer, laser particle analyzer measures average grain diameter
For 472nm.
Embodiment 1-8 and comparative example 1-5
Three kinds of substances are mixed in the following proportions, by various component compositions mixed grinding 1 hour in the ball mill, by sample
Product are uniformly dispersed in cyclohexane solution, are then dried using spray dryer, and uniform nucleating agent compositions powder is made, into
The average grain diameter of core agent composition is at 5 μm hereinafter, the magnesium hydroxide of embodiment 8 is purchased from the limited public affairs of the vast and boundless brightness mining development of Shenzhen's brocade
Department, trade mark JLH-QD2, the magnesia of comparative example 5 is purchased from Hangzhou Wanjing New Material Co., Ltd., trade mark VK-Mg50D, tool
The composition and ratio of body are as shown in table 1.
Application examples
100 parts of weight of polypropylene (Yangtze petrochemical iy produced, trade mark F401) are taken, respectively Example 1-8 and comparative example
0.2 part of weight of nucleating agent compositions made from 1-3, mixing is squeezed out after TE-34 types double screw extruder in super mixer,
Then 220 DEG C of extrusion temperature is molded (230 DEG C of injection temperature) into sample standard batten through injector (ST125 types)；It will be added without
The polypropylene of nucleating agent compositions is through similary processing, as blank sample.
Obtained batten is subjected to bending modulus test (by GB/T 9341-2008 testing standards), Izod notched impact
Strength test (pressing GB/T 1843-2008 testing standards), mist degree test (pressing GB/T2410-2008 testing standards) and thermal deformation
The result that temperature test obtains (by GB/T 1634.2-2004 testing standards) is listed in table 2.
Table 1
Application effect of 2 nucleating agent compositions of table in Polymer Processing
From table 2 it can be seen that using nucleating agent compositions in the embodiment of the present invention 1-8, compared to individually using each group
Point (comparative example 3 and comparative example 4) either the composition (comparative example 1 and comparative example 2) of two of which component or uses magnesia
The obtained nucleating agent compositions of comparative example 5 significantly improve the bending modulus, impact strength and thermal deformation of polypropylene articles
Temperature simultaneously reduces mist degree.Wherein, compared with the polypropylene of comparative example 1, the polypropylene of embodiment 1 only more contains hydroxide
Magnesium, but the polyacrylic notch impact strength of embodiment 1 significantly improves, and mist degree, bending modulus and heat distortion temperature are more preferably
It is or similar.Moreover, it is compared in nucleating agent compositions containing magnesium hydroxide prepared by method produced according to the present invention containing commercially available
Magnesium hydroxide can improve bending modulus, impact strength and the heat distortion temperature of polypropylene articles and reduce mist degree.Therefore originally
The nucleating agent compositions of invention can improve the transparency, rigidity, toughness and the heat resistance of acrylic resin, can meet completely poly-
It closes object and proposes high performance requirement in application field.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
Claims (12)
1. a kind of nucleating agent compositions, which is characterized in that the substituted diaryl that the composition contains shown in following chemical formula (I) has
Machine phosphate, aliphatic monocarboxylic acid metal salt and magnesium hydroxide,
In formula (I), R1、R2、R3And R4It is identical or differ, it is each independently hydrogen atom or C1-C6It is substituted or unsubstituted
The alkyl of linear chain or branch chain；M is metal cation, valence mumber=m+n of M；Ligancies of the m for organophosphorous groups, m >=1；N is hydroxyl
Base number, n≤3,
On the basis of the gross weight of nucleating agent compositions, the substituted diaryl organic phosphate accounts for 10-70 weight %, the fat
Race's monocarboxylic acid metal salt accounts for 10-70 weight %, and the magnesium hydroxide accounts for 5-80 weight %.
2. composition according to claim 1, wherein, the average grain diameter of the nucleating agent compositions is less than 10 μm.
3. composition according to claim 2, wherein, the average grain diameter of the nucleating agent compositions is less than 5 μm.
4. according to the composition described in any one in claim 1-3, wherein, the metal cation representated by M is Mg, Ca,
A kind of metal cation in Zn and Al.
5. according to the composition described in any one in claim 1-3, wherein, the substituted diaryl organic phosphate is choosing
From one or more in following compounds：Two [2,2 '-methylene-bis- (4,6- di-t-butyls phenoxy group) phosphoric acid] hydroxy Als,
Two [2,2 '-methylene-bis- (4- methyl-6-terts butyl phenoxy) phosphoric acid] hydroxy Als, three [2,2 '-methylene-bis- (4,6- bis-
Tert-butyl benzene oxygroup) phosphoric acid] aluminium, three [2,2 '-methylene-bis- (4- methyl-6-terts butyl phenoxy) phosphoric acid] aluminium, two [2,2 '-
Methylene-bis- (4,6- di-t-butyls phenoxy group) phosphoric acid] magnesium and two [2,2 '-methylene-bis- (4- methyl-6-tert butyl benzene oxygen
Base) phosphoric acid] magnesium.
6. according to the composition described in any one in claim 1-3, wherein, the aliphatic monocarboxylic acid metal salt is by alkali
One or more and C in metal, alkaline-earth metal, transition metal6-C29Aliphatic monocarboxylic acid formed salt.
7. composition according to claim 6, wherein, the aliphatic monocarboxylic acid metal salt is one in following compounds
Kind is a variety of：By alkali metal and tridecanoic acid, tetradecanoic acid, pentadecanoic acid, Heptadecanoic acide, stearic acid, dodecanoic acid, palm oil
Acid, petroselic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolelaidic acid, leukotrienes, ricinoleic acid, 12- hydroxy stearic acids or
The salt that aphthenic acids is formed.
8. composition according to claim 7, wherein, the aliphatic monocarboxylic acid metal salt is following compounds：By alkali
The salt that metal is formed with gamma-Linolenic acid.
9. according to the composition described in any one in claim 1-3, wherein, the average grain diameter of the magnesium hydroxide is
10nm-10μm。
10. according to the composition described in any one in claim 1-3, wherein, the magnesium hydroxide is by including following step
It is prepared by rapid method：
1) under conditions of stirring, magnesium chloride brine is mixed with magnesium oxide powder, until magnesium oxide powder is completely dissolved；
2) the magnesium oxide powder dissolved solution obtained in step 1) is stood, is filtered and washes successively after solid precipitation
It washs, obtains solid intermediate product；
3) in the presence of deionized water, the solid intermediate product that step 2) is obtained is protected at 100-200 DEG C in a kettle
It holds 1-10 hours；
Wherein, in step 1), in molar ratio, magnesium chloride：Magnesia=5-15：1.
11. a kind of polypropylene material, which contains acrylic resin and nucleating agent compositions, which is characterized in that institute
Nucleating agent compositions are stated as the nucleating agent compositions described in any one in claim 1-10.
12. polypropylene material according to claim 11, wherein, relative to the acrylic resin of 100 parts by weight, nucleating agent
The content of composition is 0.1-1 parts by weight.
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