CN105623080A - Nucleating agent composition and polypropylene material - Google Patents
Nucleating agent composition and polypropylene material Download PDFInfo
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- CN105623080A CN105623080A CN201410614426.6A CN201410614426A CN105623080A CN 105623080 A CN105623080 A CN 105623080A CN 201410614426 A CN201410614426 A CN 201410614426A CN 105623080 A CN105623080 A CN 105623080A
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- 0 Cc1cc(*)cc(Cc2cc(*)cc(*)c2O2)c1*P2(OC(*)(*)*)=O Chemical compound Cc1cc(*)cc(Cc2cc(*)cc(*)c2O2)c1*P2(OC(*)(*)*)=O 0.000 description 2
Abstract
The present invention relates to a nucleating agent composition and a polypropylene material, the nucleating agent composition contains a diaryl-substituted organic phosphate shown in following formula (I), an aliphatic monocarboxylic acid metal salt and magnesium hydroxide, wherein in formula (I), R1, R2, R3 and R4 are same or different, are each independently a hydrogen atom or a substituted or unsubstituted C1-C6 straight or branched chain alkyl group; M is a metal cation, the valence of M is = m + n; m is the coordination number of an organic phosphorus group, m is greater than or equal to 1; n is the number of hydroxyl groups, and n is less than or equal to 3. The nucleating agent composition comprehensively improves polypropylene product transparency, rigidity, heat resistance and impact resistance.
Description
Technical field
The present invention relates to a kind of nucleating agent compositions and the polypropylene material containing this nucleating agent compositions.
Background technology
Polypropylene as in current five big general synthetic resins the fastest kind of concerned growth rate, not only cheap but also there is many good characteristics, but polypropylene exists the shortcomings such as poor rigidity, poor toughness, transparency be low. Nucleator can promote non-crystalline type or imperfect crystal type polymer crystallization and make grainiess miniaturization, thus improving the degree of crystallinity of polymer. It is greatly improved the stretching of polypropylene articles, bending and shock resistance by adding the method for nucleator. Additionally, nucleator can also make polypropylene crystals size diminish, thus the scattering decreased on the crystalline portion of crystal and amorphous fraction interface, thus make the polyacrylic transparency significantly improve.
Polypropylene nucleater chemically forms can be divided into two classes inorganic, organic.
Organic nucleator mainly has substituted aryl organic phosphate, glucitol derivative, metal salt of organic carboxylic acid, dehydrogenated metallic abietate and high score subclass etc. Organic nucleating agent and fluoropolymer resin have the good compatibility, it is possible to significantly improve the transparency and the lustrous surface of goods. Wherein, 2,2 '-methylene-bis-(4,6-di-t-butyl phenoxy group) aluminum phosphate is third generation aryl phosphoric acids esters nucleator, and the transparency for improving goods has extremely prominent effect, but the shock resistance of goods can be made to significantly reduce.
Mineral-type nucleator mainly has Pulvis Talci, silicate, titanium dioxide, aluminium oxide, nano silicon etc. Although titanium dioxide abundance conventional at present, cheap and easy to get, but the transparency and lustrous surface to goods has a certain impact, and result of use is poor, and range of application is limited to.
CN102850595A discloses a kind of nucleating agent compositions, and said composition contains substituted diaryl organic phosphate and rutile type nano titanic oxide simultaneously, can improve polyacrylic rigidity, the transparency and thermostability simultaneously. But, said composition is relatively limited to the raising of polypropylene transparent, and polyacrylic shock resistance can be made to reduce.
Summary of the invention
It is an object of the invention to solve the disadvantages mentioned above of prior art, it is provided that a kind of organic phosphate nucleating agent composition and method of making the same that can simultaneously improve the transparency of resin, rigidity, impact resistance and thermostability and the acrylic resin containing said composition.
To achieve these goals, the present inventor has done big quantity research and has had been surprisingly found that, specific substituted diaryl organic phosphate, aliphatic monocarboxylic acid slaine and magnesium hydroxide are coordinated and is used as nucleator, it is possible not only to significantly improve polyacrylic rigidity, the transparency and thermostability, and polyacrylic impact resistance can be significantly improved.
The invention provides a kind of nucleating agent compositions, said composition contains the substituted diaryl organic phosphate shown in following chemical formula (I), aliphatic monocarboxylic acid slaine and magnesium hydroxide,
In formula (I), R1��R2��R3And R4Identical or differ; R1��R2��R3And R4It is respectively hydrogen atom or C1-C6The alkyl of substituted or unsubstituted straight or branched; M is metal cation, the valence mumber=m+n of M; M is the ligancy of organophosphorous groups (i.e. part in bracket), m >=1; N is hydroxyl number, n��3.
Separately, present invention also offers a kind of polypropylene material, this polypropylene material contains acrylic resin and above-mentioned nucleating agent compositions.
The present invention makes full use of nucleator in the different guiding function of polyolefin crystallization process, and the nucleating agent compositions prepared comprehensively improves the transparency of polypropylene articles, rigidity, thermostability and impact resistance.
Detailed description of the invention
The invention provides a kind of nucleating agent compositions, said composition contains the substituted diaryl organic phosphate shown in following chemical formula (I), aliphatic monocarboxylic acid slaine and magnesium hydroxide,
In formula (I), R1��R2��R3And R4Identical or differ; R1��R2��R3And R4It is respectively hydrogen atom or C1-C6The alkyl of substituted or unsubstituted straight or branched; M is metal cation, the valence mumber=m+n of M; M is the ligancy of organophosphorous groups (i.e. part in bracket), m >=1; N is 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, with the gross weight of nucleating agent compositions for benchmark, described substituted diaryl organic phosphate accounts for 10-70 weight %, and described aliphatic monocarboxylic acid slaine accounts for 10-70 weight %, and described magnesium hydroxide accounts for 5-80 weight %; It is highly preferred that with the gross weight of nucleating agent compositions for benchmark, described substituted diaryl organic phosphate accounts for 30-70 weight %, and described aliphatic monocarboxylic acid slaine accounts for 15-50 weight %, and described magnesium hydroxide accounts for 5-50 weight %.
Nucleating agent compositions according to the present invention, it is preferable that the mean diameter of described nucleating agent compositions less than 10 microns, it is more preferred to, less than 5 microns. In the present invention, the implication of the mean diameter of described nucleating agent compositions be the homogenous spheres (or combination) when certain physical characteristic of tested granule or physical behavio(u)r and a certain diameter the most close time, just using the diameter of this spheroid (or combination) equivalent grain size as tested granule.
Nucleating agent compositions according to the present invention, in formula (I), R1��R2��R3And R4Can be each methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 2, one in 3-dimethylbutyl and 2,2 '-dimethylbutyl.
Nucleating agent compositions according to the present invention, in formula (I), the metal cation representated by M can be a kind of metal cation in Na (sodium), Li (lithium), Mg (magnesium), Ca (calcium), Zn (zinc) and Al (aluminum); Preferably, the metal cation representated by M is a kind of metal cation in Mg (magnesium), Ca (calcium), Zn (zinc) and Al (aluminum); It is highly preferred that the metal cation representated by M is Mg (magnesium) or Al (aluminum).
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, preferably, described substituted diaryl organic phosphate is one or more in following compounds: two [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] magnesium, two [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] magnesium, two [2, 2 '-methylene-bis-(6-methyl-4-tert-butyl group phenoxy group) phosphoric acid] magnesium, two [2, 2 '-methylene-bis-(4-ethyl-6-tert-butyl group phenoxy group) phosphoric acid] magnesium, two [2, 2 '-methylene-bis-(4-propyl group-6-tert-butyl group phenoxy group) phosphoric acid] magnesium, two [2, 2 '-methylene-bis-(4-butyl-6-tert-butyl group phenoxy group) phosphoric acid] magnesium, two [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] hydroxy Al, two [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] hydroxy Al, two [2, 2 '-methylene-bis-(6-methyl-4-tert-butyl group phenoxy group) phosphoric acid] hydroxy Al, two [2, 2 '-methylene-bis-(4-ethyl-6-tert-butyl group phenoxy group) phosphoric acid] hydroxy Al, two [2, 2 '-methylene-bis-(4-propyl group-6-tert-butyl group phenoxy group) phosphoric acid] hydroxy Al, two [2, 2 '-methylene-bis-(4-butyl-6-tert-butyl group phenoxy group) phosphoric acid] hydroxy Al, three [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] aluminum and three [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] aluminum.
Nucleating agent compositions according to the present invention, most preferably, described substituted diaryl organic phosphate is one or more in following compounds: two [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] hydroxy Al, two [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] hydroxy Al, three [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] aluminum, three [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] aluminum, two [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] magnesium and two [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] magnesium.
Nucleating agent compositions according to the present invention, substituted diaryl organic phosphate representated by formula (I) can be obtained by various methods, such as it is commercially available, can also prepare according to existing preparation method, the method comprised the steps such as can be adopted to prepare: by substituted diaryl phenol raw material under the existence of toluene and triethylamine, phosphorus acylation reaction is carried out with phosphorus oxychloride, then by product in the mixed solution of acetone and water, salt-forming reaction is carried out with the aqueous solution of salt forming agent such as magnesium chloride and/or aluminum chloride, ratio, substituted diaryl organophosphorus ester: salt forming agent=1.8-2.2:1, and regulate pH to neutral with the sodium hydroxide solution that such as concentration is 10-30 weight %, steam solvent, after drying, obtain substituted diaryl organic phosphate, and, the substituted diaryl phenol raw material used is the compound representated by following chemical formula (II),
Wherein, the R in formula (II)1��R2��R3And R4Identical or differ; R1��R2��R3And R4It is respectively hydrogen atom or C1-C6Substituted or unsubstituted straight or branched alkyl. The substituted or unsubstituted straight or branched alkyl of C1-C6 can be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 2, one in 3-dimethylbutyl and 2,2 '-dimethylbutyl.
Nucleating agent compositions according to the present invention, described aliphatic monocarboxylic acid slaine is by one or more in alkali metal, alkaline-earth metal, transition metal and C6-C29Aliphatic monocarboxylic acid formed salt, preferably, described aliphatic monocarboxylic acid slaine is one or more in following compounds: the salt formed with lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, heptadecanoic acid, stearic acid, cis-4-nonendioic acid, dodecylic acid, palmitoleic acid, petroselic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolelaidic acid, gamma-Linolenic acid, linolenic acid, castor oil acid, 12-hydroxy stearic acid or aphthenic acids by alkali metal.
Nucleating agent compositions according to the present invention, it is preferable that described aliphatic monocarboxylic acid slaine is one or more in the lithium salts of lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, heptadecanoic acid, stearic acid and 12-hydroxy stearic acid.
Nucleating agent compositions according to the present invention, it is preferable that the mean diameter of described magnesium hydroxide is 10nm-10 ��m; It is highly preferred that the mean diameter of described magnesium hydroxide is 50-500nm.
Nucleating agent compositions according to the present invention, described magnesium hydroxide is commercially available or is prepared by known method, but the present invention is prepared preferably by the method comprised the following steps:
1) when stirring, magnesium chloride brine is mixed with magnesium oxide powder, until magnesium oxide powder is completely dissolved;
2) by step 1) in the magnesium oxide powder that obtains dissolve after solution left standstill, after solid precipitate out, be sequentially carried out filtration and washing, obtain solid intermediate product;
3) under the existence of deionized water, by step 2) solid intermediate product that obtains reacts in a kettle., and then it is sequentially carried out cooling, filtration, washing and dry, obtains magnesium hydroxide product;
Wherein, in step 1) in, in molar ratio, magnesium chloride: magnesium oxide=5-15:1; Preferably, in molar ratio, magnesium chloride: magnesium oxide=10-12:1;
Wherein, in step 2) in, the time of described standing can be 10-50 hour, it is preferred to 20-30 hour;
Wherein, in step 3) in, the described temperature reacted in a kettle. can be 100-200 DEG C, and the time can be 1-10 hour; Preferably, the temperature reacted in a kettle. is 120-180 DEG C, and the time is 5-8 hour.
Make the magnesium hydroxide prepared in aforementioned manners compared with the magnesium hydroxide of prior art or the magnesium hydroxide that is purchased, the performance improving polypropylene material is more favourable.
Nucleating agent compositions according to the present invention, can also contain other nucleators and additive as required further. As the nucleator beyond the nucleator of the present invention, can list: carboxylate metal's salt such as lithium benzoate, sodium benzoate, aluminum benzoate, 4-tert-butyl group benzoic acid aluminium salt, adipic acid sodium; The polyol derivatives etc. such as two (4-tert-butyl-phenyl) sodium phosphate, dibenzyl sorbitol, two (methylbenzilidene) sorbitol and two (dimethyl benzylidene) sorbitol. It addition, as the additive used as required, can list: the known additives generally used such as steric hindrance amine light stabilizer, UV absorbent, phosphorus antioxidants, phenol antioxidant and sulfur class antioxidants.
The preparation method of above-mentioned nucleating agent compositions provided by the invention is fairly simple, for instance can by being mixed to get with aliphatic monocarboxylic acid slaine and magnesium hydroxide by the substituted diaryl organic phosphate shown in above-mentioned formula (I).
According to the present invention, with the gross weight of nucleating agent compositions for benchmark, the consumption of described substituted diaryl organic phosphate can be 10-70 weight %, and the consumption of described aliphatic monocarboxylic acid slaine can be 10-70 weight %, and the consumption of described magnesium hydroxide can be 5-80 weight %; Preferably, with the gross weight of nucleating agent compositions for benchmark, described substituted diaryl organic phosphate accounts for 30-70 weight %, and described aliphatic monocarboxylic acid slaine accounts for 15-50 weight %, and described magnesium hydroxide accounts for 5-50 weight %.
According to the present invention, described mixed method has a variety of, as long as mixed method commonly used in the art is all unrestricted, it is preferable that mixed grinding in ball mill. The grinder that mixed grinding uses, it can be mortar, ball mill, rod mill, tube mill, taper grinding machine, vibrator, Hai Siwen ball mill, roller mill, vial-type grinding machine, hammer mill, mill, injector-type mill, jet-O-Mizer, ultra tiny metal grinding machine, nanocone drill bit, fine grinding machine, colloidal mill, general class mayer colloidal mill, micron grinding machine, charlotte colloid mill machine and rotation stage property etc., it is preferred to ball mill. The mixed grinding time according to use the kind of grinder, model, severity of grind, material powder kind etc. select, be generally 5 minutes-10 hours, it is preferable that 0.5-4 hour, it is most preferred that 1 hour.
According to the invention, it is further possible to by further mixed mixture being disperseed in a solvent, be then dried, to obtain particle diameter and the better nucleating agent compositions of uniformity. Described solvent is solvent commonly used in the art, it is possible to for one or more in water, methanol, ethanol, propanol, butanol, acetone, ethyl acetate, benzene, toluene, oxolane, hexamethylene and normal hexane, it is preferred to hexamethylene. What described scattered method was known to the skilled person by solid finely dispersed method in a liquid, can not repeat them here. Described dry can use commonly used in the art for dry method and apparatus, it is preferred to use spray dryer dries.
Selection according to raw materials such as the present invention, described substituted diaryl organic phosphate, aliphatic monocarboxylic acid slaine and magnesium hydroxide can be identical with nucleating agent compositions provided by the invention, does not repeat them here.
Present invention also offers a kind of polypropylene material, this polypropylene material contains acrylic resin and above-mentioned nucleating agent compositions.
Polypropylene material according to the present invention, relative to the acrylic resin of 100 weight portions, the content of nucleating agent compositions can be 0.1-1 weight portion, it is preferred to 0.1-0.4 weight portion.
Hereinafter it is more fully described the present invention by preparation example, embodiment and application examples. But the present invention is not exposed to any restriction of following example.
Preparation example 1 prepares substituted diaryl organic phosphate
Reaction bulb adds 2,2 '-methylene-bis-(4,6-DI-tert-butylphenol compounds) (Shanghai Taurus Chemical Co., Ltd. produces, the trade mark is 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid and fully dissolves, nitrogen is passed in solution, flow velocity 80ml/min, and under room temperature condition, in 0.5 hours, add phosphorus oxychloride 20ml with uniform speed, react again after dropwising 12 hours, add water 150ml in reaction bulb, under 75 DEG C of conditions of temperature, stirs 0.5 hour, then under 85 DEG C of conditions, steam solvent toluene, filter remaining solidliquid mixture, after washing, obtain solid product, it is intermediate product 2,2 '-methylene-bis-(4,6-di-t-butyl phenoxy group) phosphate ester, by gained intermediate product 2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphate ester is dissolved in in the mixed liquor of salt solvent acetone and water, becoming the mass ratio of acetone and water in salt solvent is 4:6, organophosphorus ester is 1:30 with the mass ratio becoming salt solvent, it is that the substituted diaryl organophosphorus ester described in 30% weight aluminum chloride aqueous solution adds carries out into salt by concentration, aluminum chloride and 2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) mol ratio of phosphate ester is 1:2, dropping concentration is that 10 weight % sodium hydrate regulator solution pH value are to neutral, steam acetone, obtain white solid product, after filtration, with deionized water wash to pH=7-8, after heat drying, the fusing point of described product is more than 300 DEG C, product two [2 is confirmed as to obtain through mass spectrum and infrared analysis, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] hydroxy Al No.1, confirm that purity is 99% through high performance liquid chromatography.
Preparation example 2 prepares substituted diaryl organic phosphate
Reaction bulb adds 2, (Shanghai Taurus Chemical Co., Ltd. produces 2 '-methylene-bis-(4-methyl-6-tert-butylphenol), the trade mark is 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid fully to dissolve, nitrogen is passed in solution, flow velocity 80ml/min, and under room temperature condition, in 0.5 hours, add phosphorus oxychloride 20ml with uniform speed, react again after dropwising 12 hours. add water 150ml in reaction bulb, temperature 75 DEG C, stirs 0.5 hour, then steams solvent, filters, and obtains solid product, be intermediate product 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphate ester after washing, by gained intermediate product 2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphate ester is dissolved in in the mixed liquor of salt solvent acetone and water, becoming the mass ratio of acetone and water in salt solvent is 4:6, organophosphorus ester is 1:30 with the mass ratio becoming salt solvent, it is that 30% weight aluminum chloride aqueous solution adds described 2 by concentration, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphate ester carries out into salt, aluminum chloride and 2, the mol ratio of 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphate ester is 1:2, dropping concentration is that 10 weight % sodium hydrate regulator solution pH value are to neutral, steam acetone, obtain white solid product, after filtration, with deionized water wash to pH=7-8, heat drying, the fusing point of described product is more than 300 DEG C, two [2 are confirmed as through mass spectrum and infrared analysis, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] hydroxy Al No.2, confirm that purity is 99.1% through high performance liquid chromatography.
Preparation example 3 prepares substituted diaryl organic phosphate
Reaction bulb adds 2, 2 '-methylene-bis-(4, 6-DI-tert-butylphenol compounds) (Shanghai Taurus Chemical Co., Ltd. produces, the trade mark is 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid and fully dissolves, nitrogen is passed in solution, flow velocity 80ml/min, and under room temperature condition, in 0.5 hour, add phosphorus oxychloride 20ml with uniform speed, react again after dropwising 12 hours. add water 150ml in reaction bulb, under 75 DEG C of conditions of temperature, stirs 0.5 hour, then under 85 DEG C of conditions, steam solvent toluene, filter remaining solidliquid mixture, after washing, obtain solid product, it is intermediate product 2,2 '-methylene-bis-(4,6-di-t-butyl phenoxy group) phosphate ester. by intermediate product 2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphate ester is dissolved in in the mixed liquor of salt solvent acetone and water, becoming the mass ratio of acetone and water in salt solvent is 4:6, organophosphorus ester is 1:30 with the mass ratio becoming salt solvent, the aluminum chloride aqueous solution that concentration is 30 weight % is joined 2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphate ester solution carries out into salt, aluminum chloride and 2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) mol ratio of phosphate ester is 1:3.5, dropping concentration is that the sodium hydrate regulator solution pH value of 10 weight % is to neutral, steam acetone, obtain white solid product, after filtration, with deionized water wash to pH=7-8, solid product is obtained after heat drying, described solid product is added in solvent methanol, in gained solution, the concentration of product is 30 weight %, will be equivalent to the water of 50 volume % of methanol again join in gained solution to precipitate out sedimentation, filter and product No.3 will be obtained after solid drying, described solid product fusing point is more than 300 DEG C, it is three [2 through mass spectrum and infrared analysis results verification, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] aluminum No.3, it is 90% by high effective liquid chromatography for measuring purity.
Preparation example 4 prepares substituted diaryl organic phosphate
Reaction bulb adds 2, 2 '-methylene-bis-(4, 6-DI-tert-butylphenol compounds) (Shanghai Taurus Chemical Co., Ltd. produces, the trade mark is 2246) 42.4g, toluene 160ml and triethylamine 50ml, it is stirred to solid and fully dissolves, nitrogen is passed in solution, flow velocity 80ml/min, and under room temperature condition, in 0.5 hour, add phosphorus oxychloride 20ml with uniform speed, react again after dropwising 12 hours. add water 150ml in reaction bulb, temperature 75 DEG C, stirs 0.5 hour, then steams solvent, filters, and obtains solid product, be intermediate product 2,2 '-methylene-bis-(4,6-di-t-butyl phenoxy group) phosphate ester after washing, by gained intermediate product 2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphate ester is dissolved in in the mixed liquor of salt solvent acetone and water, becoming the mass ratio of acetone and water in salt solvent is 4:6, organophosphorus ester is 1:30 with the mass ratio becoming salt solvent, it is that 30% weight magnesium chloride brine joins described 2 by concentration, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphate ester solution carries out into salt, magnesium chloride and 2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) mol ratio of phosphate ester is 1:2, dropping concentration is that 10% weight sodium hydroxide regulates solution ph to neutral, steam acetone, obtain white solid product, after filtration, with deionized water wash to pH=7-8, solid product No.4 is obtained after heat drying, the fusing point of described product is more than 300 DEG C, [2 are confirmed as through mass spectrum and infrared analysis, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] magnesium No.4, confirm that purity is 99.5% through high performance liquid chromatography.
Preparation example 5 prepares magnesium hydroxide
Adding 500mL2M magnesium chloride brine in reaction bulb, stirring is lower adds 0.1mol magnesium oxide powder, stirs and is completely dissolved to magnesium oxide, stops stirring; Solution stands 24 hours in room temperature, has Precipitation; Precipitation is filtered, washes with water; Above-mentioned precipitation is added in reactor, add deionized water, react 6 hours at 180 DEG C; After cooling, product filters, and washes with water, prepares magnesium hydroxide after drying. Being defined as magnesium hydroxide No.5 through X-ray diffractometer, it is 127nm that laser particle analyzer measures mean diameter.
Preparation example 6 prepares magnesium hydroxide
Adding 500mL2M magnesium chloride brine in reaction bulb, stirring is lower adds 0.1mol magnesium oxide powder, stirs and is completely dissolved to magnesium oxide, stops stirring; Solution stands 24 hours in room temperature, has Precipitation; Precipitation is filtered, washes with water; Above-mentioned precipitation is added in reactor, add deionized water, react 5 hours at 160 DEG C; After cooling, product filters, and washes with water, prepares magnesium hydroxide after drying. Being defined as magnesium hydroxide No.6 through X-ray diffractometer, it is 235nm that laser particle analyzer measures mean diameter.
Preparation example 7 prepares magnesium hydroxide
Adding 500mL2M magnesium chloride brine in reaction bulb, stirring lower addition 0.1mol magnesium oxide powder stirring is completely dissolved to magnesium oxide, stops stirring; Solution stands 24 hours in room temperature, has Precipitation; Precipitation is filtered, washes with water; Above-mentioned precipitation is added in reactor, add deionized water, react 8 hours at 120 DEG C; After cooling, product filters, and washes with water, prepares magnesium hydroxide after drying. Being defined as magnesium hydroxide No.7 through X-ray diffractometer, it is 472nm that laser particle analyzer measures mean diameter.
Embodiment 1-8 and comparative example 1-5
Three kinds of materials are mixed in following ratio, by various component composition mixed grinding 1 hour in ball mill, sample is uniformly dispersed in cyclohexane solution, spray dryer is then adopted to dry, prepare uniform nucleating agent compositions powder, the mean diameter of nucleating agent compositions is below 5 ��m, the magnesium hydroxide of embodiment 8 is purchased from Jin Haohui Sociedad De Desarrollo Minero Limitada "Sodemi Ltda" of Shenzhen, the trade mark is JLH-QD2, the magnesium oxide of comparative example 5 is purchased from Hangzhou Wanjing New Material Co., Ltd., the trade mark is VK-Mg50D, and concrete composition and ratio are as shown in table 1.
Application examples
Take polypropylene and (raise sub-petrochemical iy produced, the trade mark is F401) 100 parts of weight, 0.2 part of weight of nucleating agent compositions that Example 1-8 and comparative example 1-3 prepares respectively, extrude in TE-34 type double screw extruder after mixing in super mixer, extrusion temperature 220 DEG C, then becomes sample standard batten through injector (ST125 type) injection moulding (injection temperature 230 DEG C); The polypropylene being added without nucleating agent compositions is processed through same, as blank sample.
The batten obtained is curved modulus test (by GB/T9341-2008 testing standard), Izod notched impact strength test (by GB/T1843-2008 testing standard), mist degree test (by GB/T2410-2008 testing standard) and heat distortion temperature test (by GB/T1634.2-2004 testing standard) result of obtaining and be listed in table 2.
Table 1
Table 2 nucleating agent compositions application effect in Polymer Processing
As can be seen from Table 2, use nucleating agent compositions in embodiments of the invention 1-8, the nucleating agent compositions of the compositions (comparative example 1 and comparative example 2) comparing individually each component of employing (comparative example 3 and comparative example 4) or two of which component or the comparative example 5 using magnesium oxide to obtain, significantly improves the bending modulus of polypropylene articles, impact strength and heat distortion temperature and reduces mist degree. Wherein, compared with the polypropylene of comparative example 1, the polypropylene of embodiment 1 only more contains magnesium hydroxide, but the polyacrylic notch impact strength of embodiment 1 significantly improves, and mist degree, bending modulus and heat distortion temperature are more preferably or similar. And, the magnesium hydroxide prepared containing method produced according to the present invention in nucleating agent compositions is compared containing the magnesium hydroxide being purchased, it is possible to increase the bending modulus of polypropylene articles, impact strength and heat distortion temperature also reduce mist degree. Therefore the nucleating agent compositions of the present invention can improve the transparency of acrylic resin, rigidity, toughness and thermostability, can meet polymer completely and propose high performance requirement in application.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
Claims (10)
1. a nucleating agent compositions, it is characterised in that said composition contains the substituted diaryl organic phosphate shown in following chemical formula (I), aliphatic monocarboxylic acid slaine and magnesium hydroxide,
In formula (I), R1��R2��R3And R4Identical or differ, it is each independently hydrogen atom or C1-C6The alkyl of substituted or unsubstituted straight or branched; M is metal cation, the valence mumber=m+n of M; M is the ligancy of organophosphorous groups, m >=1; N is hydroxyl number, n��3.
2. compositions according to claim 1, wherein, the mean diameter of described nucleating agent compositions is less than 10 ��m, it is preferred to less than 5 ��m.
3. compositions according to claim 1 and 2, wherein, with the gross weight of nucleating agent compositions for benchmark, described substituted diaryl organic phosphate accounts for 10-70 weight %, described aliphatic monocarboxylic acid slaine accounts for 10-70 weight %, and described magnesium hydroxide accounts for 5-80 weight %.
4. the compositions according to any one in claim 1-3, wherein, the metal cation representated by M is a kind of metal cation in Mg, Ca, Zn and Al.
5. the compositions according to any one in claim 1-4, wherein, described substituted diaryl organic phosphate is one or more in following compounds: two [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] hydroxy Al, two [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] hydroxy Al, three [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] aluminum, three [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] aluminum, two [2, 2 '-methylene-bis-(4, 6-di-t-butyl phenoxy group) phosphoric acid] magnesium and two [2, 2 '-methylene-bis-(4-methyl-6-tert butyl phenoxy) phosphoric acid] magnesium.
6. the compositions according to any one in claim 1-5, wherein, described aliphatic monocarboxylic acid slaine is by one or more in alkali metal, alkaline-earth metal, transition metal and C6-C29Aliphatic monocarboxylic acid formed salt, preferably, described aliphatic monocarboxylic acid slaine is one or more in following compounds: the salt formed with lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, heptadecanoic acid, stearic acid, cis-4-nonendioic acid, dodecylic acid, palmitoleic acid, petroselic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolelaidic acid, gamma-Linolenic acid, linolenic acid, castor oil acid, 12-hydroxy stearic acid or aphthenic acids by alkali metal.
7. the compositions according to any one in claim 1-6, wherein, the mean diameter of described magnesium hydroxide is 10nm-10 ��m.
8. the compositions according to any one in claim 1-7, wherein, described magnesium hydroxide is prepared by the method comprised the following steps:
1) when stirring, magnesium chloride brine is mixed with magnesium oxide powder, until magnesium oxide powder is completely dissolved;
2) by step 1) in the magnesium oxide powder that obtains dissolve after solution left standstill, after solid precipitate out, be sequentially carried out filtration and washing, obtain solid intermediate product;
3) under the existence of deionized water, by step 2) solid intermediate product that obtains keeps 1-10 hour in a kettle. at 100-200 DEG C;
Wherein, in step 1) in, in molar ratio, magnesium chloride: magnesium oxide=5-15:1.
9. a polypropylene material, this polypropylene material contains acrylic resin and nucleating agent compositions, it is characterised in that described nucleating agent compositions is the nucleating agent compositions in claim 1-8 described in any one.
10. polypropylene material according to claim 9, wherein, relative to the acrylic resin of 100 weight portions, the content of nucleating agent compositions is 0.1-1 weight portion.
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| CN110684049A (en) * | 2019-10-16 | 2020-01-14 | 山西省化工研究所（有限公司） | One-pot preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent |
| CN110734463A (en) * | 2019-10-16 | 2020-01-31 | 山西省化工研究所（有限公司） | Preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agents |
| TWI695859B (en) * | 2018-08-30 | 2020-06-11 | 日商Ａｄｅｋａ股份有限公司 | Composition, thermoplastic resin composition containing it and its molded product |
| CN113845698A (en) * | 2021-04-27 | 2021-12-28 | 朴蓝聚烯烃科技发展（上海）有限公司 | Polymer composite nucleating agent and polymer composition |
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| CN102408444A (en) * | 2010-09-25 | 2012-04-11 | 中国石油化工股份有限公司 | Ultrasonic preparation method of fine transparent nucleating agent |
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| CN102408444A (en) * | 2010-09-25 | 2012-04-11 | 中国石油化工股份有限公司 | Ultrasonic preparation method of fine transparent nucleating agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI695859B (en) * | 2018-08-30 | 2020-06-11 | 日商Ａｄｅｋａ股份有限公司 | Composition, thermoplastic resin composition containing it and its molded product |
| CN110684049A (en) * | 2019-10-16 | 2020-01-14 | 山西省化工研究所（有限公司） | One-pot preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent |
| CN110734463A (en) * | 2019-10-16 | 2020-01-31 | 山西省化工研究所（有限公司） | Preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agents |
| WO2021073070A1 (en) * | 2019-10-16 | 2021-04-22 | 山西省化工研究所（有限公司） | Preparation method for bisphenol phosphate hydroxyl aluminum salt nucleating agent |
| CN110734463B (en) * | 2019-10-16 | 2021-05-25 | 山西省化工研究所（有限公司） | Preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent |
| CN113845698A (en) * | 2021-04-27 | 2021-12-28 | 朴蓝聚烯烃科技发展（上海）有限公司 | Polymer composite nucleating agent and polymer composition |
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