CN102850577A - Nucleating agent composition and preparation method thereof, and polypropylene material - Google Patents
Nucleating agent composition and preparation method thereof, and polypropylene material Download PDFInfo
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- CN102850577A CN102850577A CN2011101846108A CN201110184610A CN102850577A CN 102850577 A CN102850577 A CN 102850577A CN 2011101846108 A CN2011101846108 A CN 2011101846108A CN 201110184610 A CN201110184610 A CN 201110184610A CN 102850577 A CN102850577 A CN 102850577A
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Abstract
The invention relates to a nucleating agent composition and preparation method thereof, and a polypropylene material. The nucleating agent composition contains an A type compound represented by a formula (I) and/or (II) and a B type compound represented by a formula (III), wherein in the formula (I), R1, R2, R3 and R4 represent a hydrogen atom or an alkyl group, respectively, and M1 represents an alkali metal cation; in the formula (II), R5, R6, R7 and R8 represent an alkyl group, respectively, and M2 represents an alkali metal cation; and in the formula (III), M3 is an alkali metal cation, and R9 is a C6-C29 alkyl or alkenyl group. The inventive nucleating agent composition can significantly improve rigidity, toughness and heat resistance of resin.
Description
Technical field
The present invention relates to nucleating agent compositions and preparation method thereof and polypropylene material, be specifically related to organic phosphate nucleating agent composition and method of making the same and the polypropylene material that contains this nucleating agent compositions.
Background technology
The substituted diaryl organophosphate is widely used as the nucleation improving agent of acrylic resin, is applied to the modification of acrylic resin, and organic phosphate nucleating agent and fluoropolymer resin have good consistency, can significantly improve the transparency and the surface luster of goods.Be characterized in that fusing point is high, thermostability is outstanding, and the nucleation ability is strong, can improve goods transparency rigidity.Such as two (4,6-di-t-butyl phenoxy group) sodium phosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) sodium phosphate etc. can improve the processing characteristics of these resins significantly.Document " polyacrylic high performance-nucleator " (" chemical industry ", 1999 (8), p11), " impact of Nucleating Agent On The Polypropylene Property " (" synthetic resins and plastics ", and 2001,18 (4), 39-41) report is arranged all.
Such as German Patent 3,940,765A1 and " the synthetic and application of PP nucleator " (" plastics industry ", 1999 (5)) reported the synthetic of polypropylene nucleater in, substituted aryl organic phosphoric acid metal-salt synthetic is by making diaryl organic metal phosphate behind substituted aryl phenol and phosphorylation agent reaction, hydrolysis, the salify.
Wherein, 2,2 '-methylene radical-two (4,6-di-tert-butyl-phenyl) sodium phosphate is new aryl phosphoric acid ester nucleator, is characterized in that fusing point is high, and thermostability is outstanding, and the nucleation ability is strong, can improve the goods transparency and rigidity.Wherein, substituted diaryl organic metal phosphate such as two (4,6-di-t-butyl phenoxy group) sodium phosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) sodium phosphate etc., can improve significantly the processing characteristics of these resins, but this nucleator can not there be to rigidity, the toughness agent thermotolerance of acrylic resin whole raising.
Summary of the invention
In order to overcome the deficiencies in the prior art, the purpose of this invention is to provide a kind of polypropylene material that can improve the preparation method of polyolefinic rigidity, toughness and stable on heating nucleating agent compositions and nucleating agent compositions and contain this nucleating agent compositions.
In order to achieve the above object, the invention provides a kind of nucleating agent compositions, this nucleating agent compositions contain by formula (I) and/or (II) representative the category-A compound and by the category-B compound of formula (III) representative,
R in the formula (I)
1, R
2, R
3And R
4Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched, M
1Represent alkali metal cation; R in the formula (II)
5, R
6, R
7And R
8Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched, M
2Represent alkali metal cation;
In the formula (III), M
3Be alkali metal cation, R
9Be C
6-C
29Replacement or alkyl or the thiazolinyl of unsubstituted straight or branched.
In addition, the present invention also provides a kind of preparation method of nucleating agent compositions, the method comprises: under the salt-forming reaction condition, with following formula (VI) and/or the substituted diaryl organophosphate (VII) with contacted with the alkali metal hydroxide salt forming agent becoming in the presence of the salt solvent by longer chain fatty acid shown in (VIII) of following formula
R in the formula (VI)
1, R
2, R
3And R
4Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched; R in the formula (VII)
5, R
6, R
7And R
8Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched,
In the formula (VIII), R
9Be C
6-C
29Replacement or alkyl or the thiazolinyl of unsubstituted straight or branched.
In addition, the present invention also provides a kind of polypropylene material, and this polypropylene material contains acrylic resin and above-mentioned nucleating agent compositions.
Polypropylene anti-reflection nucleating agent of the present invention takes full advantage of nucleator in the guiding function of polyolefine crystallisation process owing to containing two kinds of above-mentioned compounds, can significantly improve rigidity, toughness and the thermotolerance of resin.Reason may be because the bootable polypropylene of category-A compound substituted diaryl phosphoric acid salt forms alpha-crystal form polypropylene actually, can significantly improve polyolefinic rigidity; Category-B long-chain fat carboxylate salt helps to improve polyacrylic toughness, can also significantly improve polyacrylic thermotolerance after A and the B mating reaction.
Embodiment
According to nucleating agent compositions provided by the invention, wherein, the content of described category-A compound and described category-B compound can change within a large range; Preferably, described category-A compound accounts for the 10-80 % by weight, and described category-B compound accounts for the 20-90 % by weight; More preferably, described category-A compound accounts for the 20-70 % by weight, and described category-B compound accounts for the 30-80 % by weight; Most preferably, described category-A compound accounts for the 30-60 % by weight, and described category-B compound accounts for the 40-70 % by weight.
According to nucleating agent compositions of the present invention, the R in the formula (I)
1, R
2, R
3And R
4And the R in the formula (II)
5, R
6, R
7And R
8Can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 2 separately, 3-dimethylbutyl and 2, a kind of in 2 '-dimethylbutyl.
On the basis of technique scheme, in formula (I) and the formula (II), M
1And M
2The alkali metal cation of representative is respectively a kind of metallic cation among Na (sodium), Li (lithium) and the K (potassium).
On the basis of technique scheme, preferred, M
1And M
2Be identical metallic cation.
Preferably, described category-A compound is one or more in the following compounds: 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) sodium phosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) sodium phosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) potassiumphosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) potassiumphosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) Trilithium phosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) Trilithium phosphate, two (2-methyl-4-tertiary butyl phenoxy group) sodium phosphate, two (2-methyl-4-tertiary butyl phenoxy group) potassiumphosphate, two (2-methyl-4-tertiary butyl phenoxy group) Trilithium phosphate, two (2,4-di-t-butyl phenoxy group) sodium phosphate, two (2,4-di-t-butyl phenoxy group) potassiumphosphate, two (2,4-di-t-butyl phenoxy group) Trilithium phosphate.
Most preferably, described category-A compound is 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) sodium phosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) sodium phosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) potassiumphosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) Trilithium phosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) potassiumphosphate, two (2-methyl-4-tertiary butyl phenoxy group) sodium phosphate, in two (2,4-di-t-butyl phenoxy group) Trilithium phosphate one or more.
Described category-A compound can be obtained by the whole bag of tricks; for example can be commercially available; also can prepare according to existing preparation method; for example can adopt the method that comprises the steps to prepare: with substituted aryl phenol raw material in the presence of toluene and triethylamine; carry out phosphorus acylation reaction with phosphorus oxychloride; then with product in the mixing solutions of acetone and water; carry out salt-forming reaction with the salt forming agent aqueous solution; count in molar ratio; the substituted diaryl organophosphate: salt forming agent=about 0.8: 1.2; and be that the metal hydroxide solutions of 10-30 % by weight is regulated pH with for example concentration; steam solvent; after the drying, obtain the substituted diaryl organophosphate, and; employed substituted aryl phenol raw material is following formula (III) and/or (IV) compound of representative
Wherein, the R in the formula (IV)
1, R
2, R
3And R
4Identical or not identical, R
1, R
2, R
3And R
4Hydrogen atom or C respectively do for oneself
1-C
6Replacement or unsubstituted straight or branched alkyl; R in the formula (V)
5And R
6Identical or not identical, R
5And R
6Hydrogen atom or C respectively do for oneself
1-C
6Replacement or unsubstituted straight or branched alkyl.C
1-C
6Replacement or unsubstituted straight or branched alkyl can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 2,3-dimethylbutyl and 2, a kind of in 2 '-dimethylbutyl.
When substituted aryl phenol raw material is a kind of compound shown in the formula (V), can obtain R
5And R
7Identical, R
6And R
8Identical category-A compound; When substituted aryl phenol raw material is two kinds of compounds shown in the formula (V), can obtain R
5, R
6, R
7And R
8Different compound.
On the basis of technique scheme, in the formula (III), M
3The alkali metal cation of representative is respectively a kind of metallic cation among Na (sodium), Li (lithium), the K (potassium).
On the basis of technique scheme, in formula (III), R
9Be C
6-C
29Replacement or the alkyl or alkenyl of unsubstituted straight or branched, the example of the described category-B compound that satisfies condition has: caproic acid, sad, 2 ethyl hexanoic acid, the n-nonanoic acid capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, margaric acid, stearic acid, nondecylic acid, eicosanoic acid, docosoic acid, Lignoceric acid, cerinic acid, montanic acid, cis-4-nonene diacid, dodecylic acid, Zoomeric acid, petroselinic acid, oleic acid, elaidic acid, isooleic acid, linolic acid, trans,trans-Linoleic acid, gamma-linolenic acid, linolenic acid, ricinolic acid, the an alkali metal salt of one or more in 12-oxystearic acid or the sylvic acid.
More preferably, R
9Be C
12-C
18Straight chained alkyl, the described category-B compound that satisfies condition is one or more an alkali metal salt in lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, margaric acid, stearic acid, cis-4-nonene diacid, dodecylic acid, Zoomeric acid, petroselinic acid, oleic acid, elaidic acid, isooleic acid, linolic acid, trans,trans-Linoleic acid, gamma-linolenic acid, linolenic acid, ricinolic acid or the 12-oxystearic acid.
On the basis of technique scheme, most preferably, described category-B compound is a kind of in sodium laurate, potassium stearate, lithium laurate or the lithium stearate.
According to the present invention, described category-B compound can be commercially available also and can be prepared by a conventional method to obtain, have no particular limits for the preparation method, can prepare by following steps: longer chain fatty acid is dissolved in the ethanol, contact with the ethanolic soln of metal hydroxides, obtain described category-B compound.
Nucleating agent compositions of the present invention also can further contain other nucleators and additive as required.
Nucleator as beyond the nucleator of the present invention can list: the carboxylate salt metal-salts such as lithium benzoate, Sodium Benzoate, aluminum benzoate, 4-tertiary butyl M-nitro benzoic acid aluminium salt, hexanodioic acid sodium; The polyol derivatives such as two (4-tert-butyl-phenyl) sodium phosphate, Sorbitol dibenzal, two (methyl benzylidene) sorbyl alcohol, two (dimethyl benzylidene) sorbyl alcohol etc.
In addition, the additive as using as required can list: the additive of the known normal operations such as hyte amine photostabilizer, UV light absorber, Phosphorus antioxidant, phenol antioxidant, sulphur class antioxidant.
Aforesaid nucleating agent compositions can mix or prepare respectively to mix after each component by the category-A compound that will be commercially available and category-B compound and obtains; Preferably, by method preparation of the present invention.
Preparation method according to nucleating agent compositions of the present invention, there is no particular limitation for the feed ratio of described substituted diaryl organophosphate and longer chain fatty acid, the category-A compound accounts for 10-80% described in the nucleating agent compositions that finally makes as long as satisfy, and described category-B compound accounts for 20-90% and gets final product; Preferably, count in molar ratio substituted aryl organophosphate: longer chain fatty acid=1: 0.2-3; More preferably, count in molar ratio substituted aryl organophosphate: longer chain fatty acid=1: 1-2.
According to the preparation method of nucleating agent compositions of the present invention, described one-tenth salt solvent is preferably water and is selected from mixture at least a in the following material: acetone, ethanol, propyl alcohol, methyl alcohol, ethyl acetate, benzene, tetrahydrofuran (THF), hexanaphthene, normal hexane, butanols; More preferably, at least a mixture in water and the following material: acetone, ethanol, propyl alcohol, methyl alcohol; Most preferably, the mixture of water and acetone.
According to the preparation method of nucleating agent compositions of the present invention, the content of water 10-90 % by weight preferably in the described one-tenth salt solvent; More preferably, 30-50 % by weight; Most preferably, 35-45 % by weight.
According to the preparation method of nucleating agent compositions of the present invention, raw material substituted diaryl organophosphate with longer chain fatty acid with the feed ratio that becomes salt solvent is, by mass, and substituted diaryl organophosphate and longer chain fatty acid: become salt solvent=1: 5-80; Preferably, substituted diaryl organophosphate and longer chain fatty acid: become salt solvent=1: 15-60; More preferably, substituted diaryl organophosphate and longer chain fatty acid: become salt solvent=1: 35-50.
According to the preparation method of nucleating agent compositions of the present invention, under the preferable case, described salt-forming reaction condition comprises: temperature is 10 ℃-90 ℃, is preferably 40-80 ℃, and the time is 0.1-10 hour, is preferably 4-8 hour.
According to the preparation method of nucleating agent compositions of the present invention, preferred, described salt forming agent is selected from a kind of in sodium hydroxide, potassium hydroxide and the lithium hydroxide.
According to the preparation method of nucleating agent compositions of the present invention, the add-on of described salt forming agent is to count in molar ratio substituted diaryl organophosphate and longer chain fatty acid: salt forming agent=0.2-4: 1; Preferably, substituted diaryl organophosphate and longer chain fatty acid: salt forming agent=0.5-2: 1; More preferably, substituted diaryl organophosphate and longer chain fatty acid: salt forming agent=1-1.5: 1.
According to the preparation method of nucleating agent compositions of the present invention, products therefrom is preferably further through distilling, filter, be washed to neutrality, drying.
The advantage of utilizing aforesaid method to prepare nucleating agent compositions is that technique is simple, preparation process is short, and the nucleating agent compositions for preparing is mixed evenly, better melting disperses under the acrylic resin processing temperature, dispersiveness in resin and consistency are also better, can obtain better nucleating effect.
In addition, according to the polypropylene material that contains above-mentioned organic phosphate nucleating agent composition of the present invention, with respect to the acrylic resin of 100 weight parts, the content of nucleating agent compositions is the 0.1-04 weight part.
Below with preparation example, embodiment and application examples the present invention is described in more detail.But the present invention is not subject to any restriction of following examples.
Preparation example 1
In reaction flask, add 2,2 '-methylene radical-two (4-methyl-6-tert-butylphenol) 34g, toluene 160ml and triethylamine 50ml, being stirred to solid fully dissolves, nitrogen is passed in the solution, flow velocity 80ml/min, and under room temperature condition, in 0.5 hours, add phosphorus oxychloride 20ml with uniform speed, reacted again after dropwising 12 hours; Add water 150ml in reaction flask, 75 ℃ of temperature stirred 0.5 hour, then steamed toluene, filtered, and got solid product after the washing, were intermediate product 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid ester crude product; With described substituted diaryl organophosphate crude product, add in the solvent that is formed by ethanol 200ml and Virahol 50ml, stir, water 36ml is added carry out dispersing and settling again.After filtration, drying obtains intermediate product 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid ester 38.6g;
With gained 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid ester is dissolved in in the salt solvent, described one-tenth salt solvent is comprised of acetone and water, wherein the content of water is into 35 % by weight of salt solvent, stir, being heated to 60 ℃, then is that 30 % by weight potassium hydroxide aqueous solutions join in the solution of gained and carry out salt-forming reaction, 2 with concentration, the mol ratio of 2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid ester and calcium hydroxide is 1: 1, reacted 6 hours, reaction distills out acetone after finishing, and obtains white solid product, after the filtration, be washed with water to neutrality, filter, get white solid product behind the heat drying.Determine that through mass spectrum and infrared analysis described product is 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) potassiumphosphate confirms that through high-efficient liquid phase chromatogram technique analysis purity is 99.1%.
Preparation example 2
In reaction flask, add 2,2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) 42.4g, toluene 160ml and triethylamine 50ml, being stirred to solid fully dissolves, nitrogen is passed in the solution, flow velocity 80ml/min, and under room temperature condition, in 0.5 hours, add phosphorus oxychloride 20ml with uniform speed, reacted again after dropwising 12 hours; Add water 150ml in reaction flask, 75 ℃ of temperature stirred 0.5 hour, then steamed toluene, filtered, and got solid product after the washing, were intermediate product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester crude product; With described substituted diaryl organophosphate crude product, add in the solvent that is formed by ethanol 200ml and Virahol 50ml, stir, water 36ml is added carry out dispersing and settling again.After filtration, drying obtains intermediate product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester 46.8g;
Gained obtained intermediate product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester is dissolved in in the salt solvent, described one-tenth salt solvent is comprised of acetone and water, and wherein the content of water is into 40 % by weight of salt solvent, stirs, be heated to 75 ℃, then be that the salify neutralization reaction is carried out in the adding of 30 % by weight lithium hydroxide aqueous solutions with concentration, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) mol ratio of phosphoric acid ester and lithium hydroxide is 1: 1, reacted 5 hours, reaction distills out acetone after finishing, and obtains white solid product, after the filtration, be washed with water to neutrality, filter, get white solid product behind the heat drying.Determine that through mass spectrum and infrared analysis described product is 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) Trilithium phosphate confirms that through high-efficient liquid phase chromatogram technique analysis purity is 99.5%.
Preparation example 3
In reaction flask, add 2,4-DI-tert-butylphenol compounds 20.6g, toluene 160ml and triethylamine 50ml, being stirred to solid fully dissolves, nitrogen is passed in the solution, flow velocity 80ml/min, and under room temperature condition, in 0.5 hours, add phosphorus oxychloride 20ml with uniform speed, reacted again after dropwising 12 hours; Add water 150ml in reaction flask, 75 ℃ of temperature stirred 0.5 hour, then steamed toluene, filtered, and got solid product after the washing, were intermediate product two (2,4-di-t-butyl phenoxy group) phosphoric acid ester crude product; With described substituted diaryl organophosphate crude product, add in the solvent that is formed by ethanol 200ml and Virahol 50ml, stir, water 36ml is added carry out dispersing and settling again.After filtration, drying obtains intermediate product two (2,4-di-t-butyl phenoxy group) phosphoric acid ester 23.7g;
With gained two (2,4-di-t-butyl phenoxy group) phosphoric acid ester is dissolved in in the salt solvent, described one-tenth salt solvent is comprised of acetone and water, wherein the content of water is into 45 % by weight of salt solvent, stir, being heated to 40 ℃, then is that 30 % by weight potassium hydroxide aqueous solutions join and carry out salt-forming reaction, two (2 in the gained solution with concentration, 4-di-t-butyl phenoxy group) mol ratio of phosphoric acid ester and potassium hydroxide is 1: 1, reacted 8 hours, reaction distills out acetone after finishing, and obtains white solid product, after the filtration, be washed with water to neutrality, filter, get white solid product behind the heat drying.Determine that through mass spectrum and infrared analysis described product is two (2,4-di-t-butyl phenoxy group) Trilithium phosphate, confirm that through high-efficient liquid phase chromatogram technique analysis purity is 99.0%.
Preparation example 4
Lauric acid is dissolved in the ethanol, and the concentration that drips lithium hydroxide is the ethanolic soln of 15 % by weight, stirs, and reacts after one hour, filters and obtains the solid product lithium laurate.
Preparation example 5
Stearic acid is dissolved in the ethanol, and the concentration that drips lithium hydroxide is the ethanolic soln of 15 % by weight, stirs, and reacts after one hour, filters and obtains the solid product lithium stearate.
Embodiment 1
The method identical with preparation example 2 prepares 2, product 46.8g after 2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester is purified;
With gained 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester adds in the salt solvent with lauric acid 32g, become salt solvent to be comprised of acetone and water, wherein the content of water is into 45 % by weight of salt solvent, stirs, be heated to 60 ℃, then be that the salify neutralization reaction is carried out in the adding of 30 % by weight aqueous sodium hydroxide solutions with concentration, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) mol ratio of phosphoric acid ester and lauric acid and sodium hydroxide is 1: 1, reacted 6 hours, reaction distills out acetone after finishing, obtain white solid product, after the filtration, be washed with water to neutrality, filter, obtain 2 behind the heat drying, 2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) sodium phosphate and sodium laurate determine that through efficient liquid phase chromatographic analysis the content in gross product is respectively 57.8 % by weight and 42.2 % by weight.
Final product is uniformly dispersed in cyclohexane solution, then adopts spray-drier dry, make uniform nucleating agent compositions powder, the median size of composition is below 5 μ m in the nucleating agent compositions.
Embodiment 2
The method identical with preparation example 1 prepares 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid ester 38.6g, use 2-methyl-4-TBP 16.4g to replace 2,4-DI-tert-butylphenol compounds 20.6g prepares two (2-methyl-4-tertiary butyl phenoxy group) phosphoric acid ester 23.7g according to the method identical with preparation example 3;
With obtained above 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid ester, two (2-methyl-4-tertiary butyl phenoxy group) phosphoric acid ester is dissolved in in the salt solvent with lauric acid 40g, described one-tenth salt solvent is comprised of acetone and water, wherein the content of water is into 35 % by weight of salt solvent, stir, be heated to 80 ℃, then be that 30 % by weight aqueous sodium hydroxide solutions join and carry out salt-forming reaction in the resulting solution with concentration, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid ester, the mol ratio of two (2-methyl-4-tertiary butyl phenoxy group) phosphoric acid ester and lauric acid and sodium hydroxide is 1: 1, reacted 4 hours, reaction distills out acetone after finishing, obtain white solid product, after the filtration, be washed with water to neutrality, filter, obtain 2 behind the heat drying, 2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) sodium phosphate, two (2-methyl-4-tertiary butyl phenoxy group) sodium phosphate and sodium laurate determines that through efficient liquid phase chromatographic analysis the content in gross product is respectively 41.3 % by weight, 21.2 % by weight and 37.5 % by weight.
Final product is uniformly dispersed in cyclohexane solution, then adopts spray-drier dry, make uniform nucleating agent compositions powder, the median size of composition is below 5 μ m in the nucleating agent compositions.
Embodiment 3
The method identical with preparation example 2 prepares 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester 46.8g;
With obtain 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester adds in the salt solvent with stearic acid 32g, become salt solvent to be formed by acetone and water, wherein the content of water is into 45 % by weight of salt solvent, stir, be heated to 75 ℃, then be that 30 % by weight potassium hydroxide aqueous solutions join in the solution of gained and carry out salt-forming reaction with concentration, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) mol ratio of phosphoric acid ester and stearic acid and potassium hydroxide is 1: 1, reacted 5 hours, reaction distills out acetone after finishing, obtain white solid product, after the filtration, be washed with water to neutrality, filter, obtain 2 behind the heat drying, 2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) potassiumphosphate and potassium stearate determine that through efficient liquid phase chromatographic analysis the content in gross product is respectively 58.7 % by weight and 41.3 % by weight.
Final product is uniformly dispersed in cyclohexane solution, then adopts spray-drier dry, make uniform nucleating agent compositions powder, the median size of composition is below 5 μ m in the nucleating agent compositions.
Embodiment 4
The method identical with preparation example 3 prepares two (2,4-di-t-butyl phenoxy group) phosphoric acid ester 23.7g;
With resulting two (2,4-di-t-butyl phenoxy group) phosphoric acid ester adds in the salt solvent with stearic acid 20g, become salt solvent to be formed by acetone and water, wherein the content of water is into 40 % by weight of salt solvent, stir, be heated to 50 ℃, then be that salt-forming reaction is carried out in the adding of 30 % by weight lithium hydroxide aqueous solutions with concentration, the mol ratio of two (2,4-di-t-butyl phenoxy group) phosphoric acid ester and stearic acid and lithium hydroxide is 1: 1, reacts 7 hours, reaction distills out acetone after finishing, obtain white solid product, after the filtration, be washed with water to neutrality, filter, obtain two (2,4-di-t-butyl phenoxy group) Trilithium phosphate and lithium stearate behind the heat drying, determine that through efficient liquid phase chromatographic analysis the content in gross product is respectively 54.2 % by weight and 45.8 % by weight.
Final product is uniformly dispersed in cyclohexane solution, then adopts spray-drier dry, make uniform nucleating agent compositions powder, the median size of composition is below 5 μ m in the nucleating agent compositions.
Embodiment 5
The method identical with preparation example 2 prepares 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester 46.8g, and the method identical with preparation example 3 prepares two (2,4-di-t-butyl phenoxy group) phosphoric acid ester 23.7g;
With resulting 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester, two (2,4-di-t-butyl phenoxy group) phosphoric acid ester adds in the salt solvent with stearic acid 50g, become salt solvent to be formed by acetone and water, wherein the content of water is into 35 % by weight of salt solvent, stir, be heated to 60 ℃, then be that the salify neutralization reaction is carried out in the adding of 30 % by weight aqueous sodium hydroxide solutions with concentration, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid ester, two (2,4-di-t-butyl phenoxy group) mol ratio of phosphoric acid ester and stearic acid and sodium hydroxide is 1: 1, reacted 6 hours, after reaction finishes, distill out acetone, obtain white solid product, after the filtration, be washed with water to neutrality, filter, obtain 2 behind the heat drying, 2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) Trilithium phosphate, two (2,4-di-t-butyl phenoxy group) Trilithium phosphate and lithium stearate are determined content 38.6 % by weight respectively in gross product through efficient liquid phase chromatographic analysis, 19.6 % by weight and 41.8 % by weight.
Final product is uniformly dispersed in cyclohexane solution, then adopts spray-drier dry, make uniform nucleating agent compositions powder, the median size of composition is below 5 μ m in the nucleating agent compositions.
Embodiment 6-8
With the compound of preparation example 1-5 according to the composition shown in the table 1 and ratio mixed grinding 1 hour in ball mill, sample is uniformly dispersed in cyclohexane solution, then adopt spray-drier dry, make uniform nucleating agent compositions powder, the median size of composition is below 5 μ m in the nucleating agent compositions.
Comparative Examples 1-6
Adopt the method identical with embodiment 6-8 to prepare nucleating agent compositions according to the composition shown in the table 1 and ratio.
Table 1
The application of application examples nucleator of the present invention in polymer processing
Get polypropylene (raising sub-petrochemical iy produced F401) 100 mass fractions, get respectively each 0.1 mass fraction of nucleator that embodiment 1-8 and Comparative Examples 1-6 make, respectively with nucleator and polypropylene in super mixer behind the mixing, extrude with TE-34 type twin screw extruder, 220 ℃ of extrusion temperatures, then through the injection moulding of ST125 type injector, 230 ℃ of injection temperatures are made sample standard batten; The polypropylene that does not add nucleator is processed through same, as check sample.
The batten that obtains is carried out the modulus in flexure test by the ASTMD790 testing standard, carry out the test of socle girder notched Izod impact strength by the ASTMD256 testing standard, carry out the heat-drawn wire test by the ASTMD648 testing standard.What obtain the results are shown in table 2.
Table 2
| The nucleator that uses | Sample modulus in flexure GPa | Breach resistance to impact shock MPa | Heat-drawn wire ℃ |
| Embodiment 1 | 1.55 | 686.0 | 146.2 |
| Embodiment 2 | 1.50 | 660.2 | 142.5 |
| Embodiment 3 | 1.52 | 658.1 | 140.8 |
| Embodiment 4 | 1.47 | 576.8 | 139.8 |
| Embodiment 5 | 1.49 | 570.5 | 145.2 |
| Embodiment 6 | 1.48 | 568.9 | 142.3 |
| Comparative Examples 1 | 1.42 | 442.8 | 134.2 |
| Comparative Examples 2 | 1.41 | 428.1 | 137.8 |
| Embodiment 7 | 1.47 | 508.4 | 140.1 |
| Comparative Examples 3 | 1.40 | 398.2 | 132.4 |
| Comparative Examples 4 | 1.38 | 345.0 | 130.2 |
| Embodiment 8 | 1.49 | 580.7 | 144.2 |
| Comparative Examples 5 | 1.35 | 327.9 | 132.7 |
| Comparative Examples 6 | 1.39 | 322.6 | 134.6 |
| Added Nucleating Agents not | 1.14 | 312.0 | 116.0 |
Can clearly find out from table 2 data, use nucleating agent compositions of the present invention, can significantly improve the multiple processing characteristics of polymkeric substance, increase substantially modulus in flexure, breach resistance to impact shock and the heat-drawn wire of acrylic resin; Compare when using category-A compound or category-B compound separately among the nucleating agent compositions of embodiment of the invention 1-8 and the Comparative Examples 1-6, significantly improved modulus in flexure, breach resistance to impact shock and heat-drawn wire; And the nucleating agent compositions of the embodiment 1-5 of preparation in accordance with the present invention preparation and method with prior art prepare respectively that category-A compound or category-B compound mix afterwards and must embodiment 6-8 nucleating agent compositions, all have some improvement in modulus in flexure, breach resistance to impact shock and heat-drawn wire, illustrate that nucleating agent compositions of the present invention has improved the rigidity of acrylic resin, toughness and thermotolerance well.
Claims (12)
1. nucleating agent compositions, this nucleating agent compositions contain by formula (I) and/or (II) representative the category-A compound and by the category-B compound of formula (III) representative,
R in the formula (I)
1, R
2, R
3And R
4Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched, M
1Represent alkali metal cation; R in the formula (II)
5, R
6, R
7And R
8Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched, M
2Represent alkali metal cation;
In the formula (III), M
3Be alkali metal cation, R
9Be C
6-C
29Replacement or alkyl or the thiazolinyl of unsubstituted straight or branched.
2. nucleating agent compositions according to claim 1, wherein, take the gross weight of composition as benchmark, described category-A compound accounts for the 10-80 % by weight, and described category-B compound accounts for the 20-90 % by weight.
3. nucleating agent compositions according to claim 1 and 2, wherein, described category-A compound is one or more in the following compounds: 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) sodium phosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) sodium phosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) potassiumphosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) potassiumphosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) Trilithium phosphate, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) Trilithium phosphate, two (2-methyl-4-tertiary butyl phenoxy group) sodium phosphate, two (2-methyl-4-tertiary butyl phenoxy group) potassiumphosphate, two (2-methyl-4-tertiary butyl phenoxy group) Trilithium phosphate, two (2,4-di-t-butyl phenoxy group) sodium phosphate, two (2,4-di-t-butyl phenoxy group) potassiumphosphate, two (2,4-di-t-butyl phenoxy group) Trilithium phosphate.
4. nucleating agent compositions according to claim 1 and 2, wherein, described category-B compound is one or more an alkali metal salt in lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, margaric acid, stearic acid, cis-4-nonene diacid, dodecylic acid, Zoomeric acid, petroselinic acid, oleic acid, elaidic acid, isooleic acid, linolic acid, trans,trans-Linoleic acid, gamma-linolenic acid, linolenic acid, ricinolic acid and the 12-oxystearic acid.
5. the preparation method of a nucleating agent compositions, the method comprises: under the salt-forming reaction condition, with following formula (VI) and/or the substituted diaryl organophosphate (VII) with contacted with the alkali metal hydroxide salt forming agent becoming in the presence of the salt solvent by the longer chain fatty acid shown in the following formula (VIII)
R in the formula (VI)
1, R
2, R
3And R
4Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched; R in the formula (VII)
5, R
6, R
7And R
8Identical or not identical, represent respectively hydrogen atom or C
1-C
6Replacement or the alkyl of unsubstituted straight or branched,
In the formula (VIII), R
9Be C
6-C
29Replacement or alkyl or the thiazolinyl of unsubstituted straight or branched.
6. method according to claim 5, wherein, count in molar ratio, substituted diaryl organophosphate and longer chain fatty acid: salt forming agent=0.2-4: 1, the feed ratio of described substituted diaryl organophosphate and longer chain fatty acid is, count in molar ratio substituted diaryl organophosphate: longer chain fatty acid=1: 0.2-3.
7. method according to claim 5, wherein, described one-tenth salt solvent is mixture at least a in water and the following material: acetone, ethanol, propyl alcohol, methyl alcohol, ethyl acetate, benzene, tetrahydrofuran (THF), hexanaphthene, normal hexane, butanols.
8. method according to claim 5, wherein, becoming the content of water in the salt solvent is the 10-90 % by weight.
9. method according to claim 5, wherein, described substituted diaryl organophosphate and longer chain fatty acid and the feed ratio that becomes salt solvent, meter in mass ratio, substituted diaryl organophosphate and longer chain fatty acid: become salt solvent=1: 5-80.
10. method according to claim 5, wherein, described salt-forming reaction condition comprises: temperature is 10-90 ℃, the time is 0.1-10 hour.
11. a polypropylene material, this polypropylene material contains acrylic resin and nucleating agent compositions, it is characterized in that, described nucleating agent compositions is the described nucleating agent compositions of any one among the claim 1-4.
12. polypropylene material according to claim 11, wherein, with respect to the acrylic resin of 100 weight parts, the content of nucleator is the 0.1-0.4 weight part.
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| CN109438753A (en) * | 2018-10-17 | 2019-03-08 | 山西省化工研究所（有限公司） | A kind of α nucleating agent compositions and the preparation method and application thereof |
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