CN102382139A - Preparation method of organic phosphate polypropylene nucleating agent - Google Patents
Preparation method of organic phosphate polypropylene nucleating agent Download PDFInfo
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- CN102382139A CN102382139A CN2010102678622A CN201010267862A CN102382139A CN 102382139 A CN102382139 A CN 102382139A CN 2010102678622 A CN2010102678622 A CN 2010102678622A CN 201010267862 A CN201010267862 A CN 201010267862A CN 102382139 A CN102382139 A CN 102382139A
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Abstract
The invention discloses a preparation method of an organic phosphate polypropylene nucleating agent. In the method, only a single reactor is used as a reactor for reaction, and at the same time, the following reactions are carried out continuously in one reactor: bridging reaction to synthesize an intermediate product substituted diaryl phenol, aromatization to synthesize diaryl organic phosphoric acyl chloride, hydrolysis to produce substituted diaryl organic phosphate and final salt formation reaction to synthesize a substituted diaryl organic phosphate nucleating agent. A suction type filtration pipe with a filter screen is inserted into the reactor to reduce pressure in solid-liquid separation of each step so as to extract filtrate out of the reactor for solid-liquid separation. The multiple steps of reaction operations can be avoided, and the defects of the prior art such as multiple devices, large investment, complex reaction, troublesome operation and the like can be overcome. The operation can be simplified, the cost can be reduced, the reaction yield is high, the operation is safe, no combustion is needed, and the environmental protection can be facilitated.
Description
Technical field
The present invention relates to the petrochemical technology field, particularly relate to a kind of preparation method of organic phosphate polypropylene nucleating agent.
Background technology
Substituted aryl organic phosphoric acid metal-salt is widely used as the nucleation improving agent of acrylic resin, is applied to the modification of acrylic resin, wherein substituted diaryl organic metal phosphate such as two (2; 4-di-t-butyl phenoxy) sodium phosphate, 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) sodium phosphate etc.; The processing characteristics that can improve these resins significantly is (referring to " polyacrylic high performance-nucleator "; " chemical industry ", 1999 (8), p11); " nucleator is to the influence of Properties of Polypropylene ", " synthetic resins and plastics ", 2001,18 (4), 39-41).
At present, substituted diaryl organic metal phosphate synthetic is the substituted diaryl organic metal phosphate that makes by behind substituted aryl phenol and phosphorylation agent reaction in organic solvent, hydrolysis, the salify." the synthetic and application of PP nucleator " (plastics industry, Vol.27, No.5,29-31; 1999) reported in PP nucleator 2,2 '-methylene radical-two (2,4-di-t-butyl phenoxy) sodium phosphate synthetic, it is through 2; 2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) is a raw material, is dissolved in the organic solvent, with phosphorus oxychloride reaction; Add triethylamine simultaneously as acid binding agent, the hcl reaction with producing in the reaction generates triethylamine salt in reaction system; The hydrolysis preparation 2 then, 2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) SULPHOSUCCINIC ACID ESTER.Products obtained therefrom behind the recrystallization, is neutralized into reactant salt with sodium hydroxide in the mixed solution of acetone and water in ethanol, prepare 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) sodium phosphate after steaming acetone again.This technology shortcoming is in the reaction of producing nucleator, and operation must the branch multistep carry out, and equipment is many, and investment is big, complex operation, and intermediate material must repeatedly be carried, and it is big to produce the waste gas smell, is unfavorable for environment protection.
Disclose a kind of technology of one-stage synthesizing substituted diaryl organic metal phosphate in the Chinese patent 01132065.6, the technology that this invention proposes is: begin from raw material fortified phenol or substituted diaryl bis-phenol, through closed loop condensation, hydrolysis, in and the fabricating technology accomplished in a still of salify three-step reaction; Make the processing unit of synthesizing substituted diaryl organic metal phosphate simplify; Shorten man-hour, and yield improves, and the three wastes reduce; Energy consumption reduces, and cost descends.But owing to exist the complex system of multiple reactant and product in the ring structureization of this technology and the hydrolysis reaction, comprising the SULPHOSUCCINIC ACID ESTER of replacement being arranged, replace single phenol, replacing diphenol, phosphoric acid, triethylamine, triethylamine hydrochloride, hydrochloric acid, toluene etc.Each step of this technology is not all adopted separating step, causes obtaining more purified organophosphate, has influenced the quality of nucleator product.
Summary of the invention
The present invention provides a kind of preparation method of organic phosphate polypropylene nucleating agent, exists operation the branch multistep to carry out in order to solve in the prior art, and equipment is many; Investment is big, complex operation, and intermediate material must repeatedly be carried; It is big to produce the waste gas smell, is unfavorable for the problem of environment protection.
For reaching above-mentioned purpose, the present invention provides a kind of preparation method of organic phosphate polypropylene nucleating agent, and said method adopts single still to do reactor drum, carries out following steps continuously at a reactor drum simultaneously:
Wherein, the general structure of said substituted aryl phenol is shown in (I) formula:
Wherein, (I) R in the formula
1Represent Wasserstoffatoms or C
1～C
6Alkyl, R
2Represent Wasserstoffatoms or C
1～C
6Alkyl, R
1With R
2Identical or inequality.
Wherein, the general structure of said substituted diaryl phenol is shown in (II) formula;
Wherein, (II) R in the formula
1Represent Wasserstoffatoms or C
1～C
6Alkyl, R
2Represent Wasserstoffatoms or C
1～C
6Alkyl, R
1With R
2Identical or inequality.
Wherein, the general structure of said substituted diaryl organic metal phosphate is shown in (III) formula:
(III)
Wherein: (III) R in the formula
1Represent hydrogen or C
1～C
6Alkyl, R
2Represent hydrogen or C
1～C
6Alkyl, R
1With R
2Identical or inequality; M represents one of following metal: potassium, sodium, lithium, calcium, magnesium, aluminium, zinc, barium or copper.
Wherein, in molar ratio, substituted aryl phenol: bridging agent=1: 1～3; Substituted aryl phenol: tensio-active agent=1: 0.0005～0.5; Substituted aryl phenol: souring agent=1: 1～2.5.
Wherein, in molar ratio: substituted diaryl phenol: phosphoric acid agent=1: 1～2.5, phosphoric acid agent: triethylamine=1: 1～3.
Wherein, quality meter: substituted diaryl organophosphate: become salt solvent=1: 2～50; Substituted diaryl organophosphate: the aqueous solution of salt forming agent=1: 0.01～100.
Wherein, in the step 1, temperature of reaction is 5 ℃ of boiling points to reaction soln.
Wherein, in the step 2, temperature of reaction is-25 ℃ of boiling points to reaction soln.
Wherein, in the step 4, temperature of reaction is 16 ℃～100 ℃.
Beneficial effect of the present invention is following:
The present invention has avoided operation the branch multistep to carry out, and the equipment that has overcome the prior art existence is many, and investment is big, and reaction process is complicated, shortcomings such as complex operation.Not only make processing ease, and can reduce cost that reaction yield is high, operational safety is not burnt, and is beneficial to environmental protection.
Description of drawings
Fig. 1 is a kind of structural representation that is used as single still of reactor drum of the embodiment of the invention;
Wherein, 1: filtering net; 2: the suction filtration pipe; 3: stirring arm; 4: chuck.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, does not limit the present invention.
The four step rule preparation method who the purpose of this invention is to provide a kind of organic phosphate polypropylene nucleating agent.This method only adopts single still to do reactor drum in reaction, and is as shown in Figure 1, and reactor drum stirs through the mixture in 3 pairs of chucks of stirring arm 4.In reaction process, adopt in the solid-liquid separation process in each step and be equipped with in the suction filtration pipe 2 insertion reaction stills of filtering net 1, the decompression extraction reaction kettle of will filtrate carries out solid-liquid separation.So carry out following reaction continuously at a reactor drum simultaneously: at first carry out the bridging reaction, synthetic mesophase product disubstituted aryl phenol; Encircle the structure reaction then, synthetic substituted diaryl organic phosphoric acid acyl chlorides; Generate the substituted diaryl organophosphate through hydrolysis reaction again; The synthetic substituted diaryl organic phosphate nucleating agent of last salt-forming reaction.
Above step is specific as follows:
The first step, the bridging reaction;
The structure of raw material substituted aryl phenol is shown in (I) formula:
(I) R in the formula
1Represent Wasserstoffatoms or C
1～C
6Alkyl, R
2Represent Wasserstoffatoms or C
1～C
6Alkyl, R
1With R
2Identical or inequality;
Substituted aryl phenol is a kind of in following: p-methyl phenol, Resorcinol, p-ethyl phenol, p-tert-butylphenol, 2; 4-xylenol, 2; 4-DI-tert-butylphenol compounds, 4-methyl-2-tert.-butyl phenol, phenol, the 4-tertiary butyl-2-methylphenol, australol, to acetylamino phenol, 2-methyl hydroquinone, 2; 2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 2; 2 '-methylene radical-two (6-methyl-4-tert.-butyl phenol), 2; 2 '-methylene radical-two (4-ethyl-6-tert.-butyl phenol), 2,2 '-methylene radical-two (4-propyl group-6-tert.-butyl phenol) or 2,2 '-methylene radical-two (4-butyl-6-tert.-butyl phenol).
At first; With substituted aryl phenol, bridging agent and tensio-active agent; And the bridging solvent, being stirred to dissolving in the adding reaction kettle, the mass concentration of substituted aryl phenol is 10%～60% in the gained solution; Through the add-on of control bridging solvent, the mass concentration of controlling substituted aryl phenol is 10%～60%.Preferred 10%～30%.In the above-mentioned raw materials, in molar ratio, substituted aryl phenol: bridging agent=1: 1～3; Substituted aryl phenol: tensio-active agent=1: 0.0005～0.5; For obtaining effect more, substituted aryl phenol: tensio-active agent=1: 0.02～0.06;
The bridging agent is at least a in following: acetaldehyde, formaldehyde.Tensio-active agent is at least a in following: sodium lauryl sulphate, sodium laurylsulfonate, X 2073, OTAC, octadecyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, polyoxyethylene glycol or polyoxyethylene octyl phenyl ether, T 46155 nonylplenyl ether, C
18Polyoxyethylenated alcohol, Ucar 35 Soxylat A 25-7, USP Kosher Soxylat A 25-7 and ethoxylated dodecyl alcohol.The bridging solvent is at least a in following: water, ethanol, methyl alcohol.
Then, in above-mentioned gained solution, add souring agent, in molar ratio, substituted aryl phenol: souring agent=1: 1～2.5.Souring agent is at least a in following: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
Temperature of reaction is 5 ℃ of boiling points to reaction soln, and preferred temperature is 10 ℃～50 ℃; In 1 hour～36 hours reaction times, the preferred reaction time is 6 hours～16 hours; Obtain substituted diaryl phenol, structure is shown in (II) formula;
(II) R in the formula
1Represent Wasserstoffatoms or C
1～C
6Alkyl, R
2Represent Wasserstoffatoms or C
1～C
6Alkyl, R
1With R
2Identical or inequality;
After reaction finished, in a suction filtration pipe insertion reaction still that filtering net is housed, decompression was extracted water out reaction kettle, drains.In reaction kettle, inject water again, agitator treating, with being equipped with in the suction filtration pipe insertion reaction still of filtering net, decompression is extracted filtrate water out reaction kettle again.Repeated multiple times is neutral until pH.Be warming up to 70 ℃～100 ℃ dryings under stirring.
Second step, phosphorylation reaction:
At first, substituted diaryl phenol and triethylamine with the last step obtains join in the phosphorylation solvent, are stirred to dissolving, and the mass concentration of substituted diaryl phenol is 10%～60% in the gained solution, and preferred 10%～30%.
Then, in above-mentioned gained solution, add phosphoric acid agent, in molar ratio: substituted diaryl phenol: phosphoric acid agent=1: 1～2.5, phosphoric acid agent: triethylamine=1: 1～3; Temperature of reaction is-25 ℃ of boiling points to reaction soln, preferred 10 ℃～50 ℃; 1 hour～36 hours reaction times, preferred 6 hours～16 hours; Generate substituted diaryl organic phosphoric acid acyl chlorides.
The phosphorylation solvent is at least a in following: benzene,toluene,xylene, trimethylbenzene, methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride, methylene bromide, methenyl bromide, monobromethane and glycol dibromide;
Phosphoric acid agent is at least a in following: phosphorus trichloride and POCl3;
In the 3rd step, hydrolysis substituted diaryl organic phosphoric acid acyl chlorides obtains the substituted diaryl organophosphate;
At first, in the second step gains (being meant the reactant that contains substituted diaryl organic phosphoric acid acyl chlorides), add entry, by the quality of substituted aryl phenol in the raw material, substituted aryl phenol: water=1: 1～40; Preferably, substituted aryl phenol: water=1: 20～40; Under 15 ℃～75 ℃ conditions of temperature, stir reaction down 0.1 hour～6 hours; Reaction finishes the back desolventizing: 40 ℃～150 ℃ distillations, steam organic solvent, separate out solid; Remaining water is extracted decompression in the suction filtration pipe insertion reaction still that filtering net is housed out reaction kettle again, drain.In reaction kettle, inject water again, agitator treating is extracted filtrate water out reaction kettle with decompression in the suction filtration pipe insertion reaction still that filtering net is housed again.Repeated multiple times is neutral until pH.Be warming up to 70 ℃～100 ℃ drying solid things under stirring, promptly obtain the substituted diaryl organophosphate.
The 4th step, salt-forming reaction:
At first, with described substituted diaryl organophosphate, add in the salt solvent.Wherein, press mass ratio, the substituted diaryl organophosphate: become salt solvent=1: 2～50;
Then, the aqueous solution with salt forming agent adds again, in pH=7～13, reacts under 16 ℃～100 ℃ conditions of temperature; Reaction times: 0.5～10 hour; After reaction finished, products therefrom filtered, washes to pH through distillation, product and is neutral, heat drying;
Obtain the substituted diaryl organic metal phosphate of general structure like (III) formula:
(III) in the formula: R
1Represent hydrogen or C
1～C
6Alkyl, R
2Represent hydrogen or C
1～C
6Alkyl, R
1With R
2Identical or inequality; M represents one of following metal: potassium, sodium, lithium, calcium, magnesium, aluminium, zinc, barium or copper;
Becoming salt solvent is at least a mixture in water and the following material: acetone, ethanol, propyl alcohol, methyl alcohol, ETHYLE ACETATE, benzene, THF, hexanaphthene, normal hexane and butanols, and the mass ratio of water is 10%～90% in this mixture;
Become the quality of the add-on of salt solvent: the substituted diaryl organophosphate: become salt solvent=1: 2～50 by intermediate product substituted diaryl organophosphate;
Salt forming agent is at least a in following: Pottasium Hydroxide, sodium hydroxide, Lithium Hydroxide MonoHydrate, calcium hydroxide, Marinco H, white lake, zinc hydroxide, hydrated barta and verditer; In the aqueous solution of said salt forming agent, the mass concentration of salt forming agent: 10%～60%, preferred 25%～35%;
Press mass ratio, the substituted diaryl organophosphate: the aqueous solution of salt forming agent=1: 0.01～100; Preferably, substituted diaryl organophosphate: the aqueous solution of salt forming agent=1: 0.1～0.8.
Through above-mentioned four steps, the substituted diaryl organic metal phosphate that obtains is the polypropylene nucleater product.
In the above-mentioned steps, in the insertion reaction still decompression will filtrate the extraction reaction kettle the suction filtration pipe comprise stainless steel cartridge filter, carbon steel cartridge filter, vacuum plastics chimney filter or taper filter cylinder.The filtering net that the suction filtration pipe adopts comprises: Stainless Steel Cloth, copper wire gauze, stainless steel punching net, stainless steel mesh grid or filter cloth.The mesh diameter of the filtering net that the suction filtration pipe adopts is 1 μ m～250 μ m, preferred 10 μ m～150 μ m.
Be elaborated with specific embodiment below:
In reaction kettle, add 250ml water, 2; 4-DI-tert-butylphenol compounds 41.27 gram and 37% formaldehyde 20ml are stirred to solid and fully dissolve, and add sodium laurylsulfonate 0.5 gram at ambient temperature; Slowly add 98% sulfuric acid 5ml, at room temperature reacted after dropwising 2 hours; Stirred then 1.5 hours, and then one was equipped with to reduce pressure in the suction filtration pipe insertion reaction still that mesh is 80 μ m filtering nets and extracts water out reaction kettle, drain.In reaction kettle, inject water again, agitator treating will be equipped with in the suction filtration pipe insertion reaction still of filtering net decompression again and extract filtrate water out reaction kettle.Repeated multiple times is neutral until pH.It is dry to be warming up to 80 degree under stirring.
Dry back adds toluene 160ml and triethylamine 60ml in original reactor, be stirred to solid and fully dissolve, and slowly adds POCl3 20ml at ambient temperature, at room temperature reacts after dropwising 12 hours; Add water 150ml then and stirred 1.5 hours, steam toluene then, with one the water extraction reaction kettle that reduces pressure and will filtrate and be left in the suction filtration pipe insertion reaction still of filtering net is housed then, drain.In reaction kettle, inject water again, stir, washing reduces pressure to filtrate in the suction filtration pipe insertion reaction still that filtering net will be housed after finishing extracts reaction kettle out, drains.Repeated multiple times is neutral until pH.It is dry to be warming up to 80 degree under stirring.
In the white solid of dry afterreaction still, add in the 200ml water, add acetone 300ml again, dispersed with stirring is even, and controlled temperature is 45 ℃; Drip 30% aqueous sodium hydroxide solution 18ml and carry out the salify neutralization, the pH value is 8.5, drips off continued and stirs 2.5 hours, steams acetone; Filter,, use deionized water wash to pH value to be neutrality, get 2 behind the heat drying the white solid product filter cake that obtains; 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) sodium phosphate 47.09 grams, yield 98%.Fusing point＞400 ℃, product through mass spectrum and infrared analysis result and 2,2 '-expected structure of methylene radical-two (4,6-di-t-butyl phenoxy) sodium phosphate is consistent, the high-pressure liquid chromatography product purity is 97.0%.
In reaction kettle, add 250ml water, 4-methyl-6-tert butyl phenol 41.27 gram and 37% formaldehyde 20ml; Being stirred to solid fully dissolves; Add sodium laurylsulfonate 0.5 gram at ambient temperature, slowly add 98% sulfuric acid 5ml, at room temperature reacted after dropwising 2 hours; Stirred then 1.5 hours, and with one the extraction reaction kettle of will filtrating that reduces pressure in the suction filtration pipe insertion reaction still that mesh is 80 μ m filtering nets was housed then, drain.In reaction kettle, inject water again, stir, extract filtrate water out reaction kettle with decompression in the suction filtration pipe insertion reaction still that filtering net will be housed again.Repeated multiple times is neutral until pH.It is dry to be warming up to 80 degree under stirring.
Dry back adds toluene 160ml and triethylamine 60ml in original reactor, be stirred to solid and fully dissolve, and slowly adds POCl3 20ml at ambient temperature, at room temperature reacts after dropwising 12 hours; Add water 150ml then and stirred 1.5 hours, steam toluene then, remaining water is extracted decompression in the suction filtration pipe insertion reaction still that filtering net is housed out reaction kettle then, drain.In reaction kettle, inject water again, stir, washing reduces pressure to filtrate in the suction filtration pipe insertion reaction still that filtering net will be housed after finishing extracts reaction kettle out, drains.Repeated multiple times is neutral until pH.It is dry to be warming up to 80 degree under stirring.
In the white solid of dry afterreaction still, add in the 200ml water, add acetone 300ml again, dispersed with stirring is even; Controlled temperature is 45 ℃, drips 30% aqueous sodium hydroxide solution 18ml and carries out the salify neutralization, and the pH value is 8.5; Drip off continued and stirred 2.5 hours, steam acetone, filter; With the white solid product filter cake that obtains, use deionized water wash to pH value to be neutrality, get 2 behind the heat drying; 2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) hexameta phosphoric acid sodium 46.1 grams, yield 95.1%.Fusing point＞400 ℃, product through mass spectrum and infrared analysis result and 2,2 '-expected structure of methylene radical-two (4-methyl-6-tert butyl phenoxy) sodium phosphate is consistent, the high-pressure liquid chromatography product purity is 96.5%.
Application examples
The application of nucleator of the present invention in polymer processing; Get 100 parts of weight of Vestolen PP 7052 (trade mark K8303); Get 0.2 part of weight of nucleator that embodiment 1～3 makes respectively; In super mixer, extrude in TE-34 type twin screw extruder behind the mixing, 220 ℃ of extrusion temperatures become sample standard batten through injector (ST125 type) injection moulding (230 ℃ of injection temperatures) then; The Vestolen PP 7052 that does not add nucleator is handled through same, as check sample.
The batten that obtains is carried out modulus in flexure test (pressing the ASTMD790 testing standard), and the result that socle girder notched Izod impact strength test (by the ASTMD256 testing standard) and heat-drawn wire test (by the ASTMD648 testing standard) obtain lists in table 1.
Table 1
| The nucleator that uses | The sample modulus in flexure | The breach resistance to impact shock | Heat-drawn |
| Embodiment | |||
| 1 | 1.614 | 313.91 | 122.0 |
| |
1.598 | 304.54 | 117.8 |
| Comparative Examples | 1.592 | 298.35 | 116.3 |
| Not with nucleator | 1.186 | 151.84 | 100.5 |
Can find out that from table 1 substituted diaryl organic metal phosphate that use embodiments of the invention 1 obtain is as nucleator, the polymer-modified modulus in flexure that obtains can improve 36.0%, and the breach resistance to impact shock improves 106.7%; The substituted diaryl organic metal phosphate that use embodiments of the invention 2 obtain is as nucleator, and the polymer-modified modulus in flexure that obtains improves 34.7%, and the breach resistance to impact shock improves 100.2%.Compare and adopt the effect of the substituted diaryl organophosphate that Comparative Examples (being to add the substituted diaryl organic metal phosphate that obtains through prior art as nucleator in the Comparative Examples) obtains making all to increase.Can satisfy polymkeric substance fully and improve performance demands in Application Areas.
Can clearly find out from table 1 data, use nucleator of the present invention, can significantly improve the multiple processing characteristics of polymkeric substance, and when improving modulus in flexure, resistance to impact shock also is significantly increased.
The present invention provides a kind of preparation method of polypropylene nucleater, and this method only adopts single still to do reactor drum in reaction, carries out following reaction continuously at a reactor drum simultaneously: at first carry out the bridging reaction, synthetic mesophase product substituted diaryl phenol.Encircle the structure reaction then, synthetic substituted diaryl organic phosphoric acid acyl chlorides.Generate the substituted diaryl organophosphate through hydrolysis reaction again.The synthetic substituted diaryl organic phosphate nucleating agent of last salt-forming reaction.In the solid-liquid separation process in each step, adopt in the suction filtration pipe insertion reaction still that filtering net is housed the decompression extraction reaction kettle of will filtrate to carry out solid-liquid separation.Avoided operation the branch multistep to carry out, the equipment that has overcome the prior art existence is many, and investment is big, and reaction process is complicated, shortcomings such as complex operation.Not only make processing ease, and can reduce cost that reaction yield is high, operational safety is not burnt, and is beneficial to environmental protection.
Obviously, those skilled in the art can carry out various changes and modification to the present invention and not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. the preparation method of an organic phosphate polypropylene nucleating agent is characterized in that, said method adopts single still to do reactor drum, carries out following steps continuously at a reactor drum simultaneously:
Step 1; With substituted aryl phenol, bridging agent and tensio-active agent; And the bridging solvent, be stirred to dissolving in the adding reaction kettle, in above-mentioned gained solution, add souring agent; Obtain substituted diaryl phenol after reaction finishes, and adopt in the suction filtration pipe insertion reaction still that filtering net is housed the decompression extraction reaction kettle of will filtrate to carry out solid-liquid separation;
Step 2 with said substituted diaryl phenol and triethylamine, joins in the phosphorylation solvent, is stirred to dissolving, then, in above-mentioned gained solution, adds phosphoric acid agent, and reaction obtains substituted diaryl organic phosphoric acid acyl chlorides after finishing;
Step 3, the said substituted diaryl organic phosphoric acid of hydrolysis acyl chlorides obtains the substituted diaryl organophosphate, and adopts in the suction filtration pipe insertion reaction still that filtering net is housed the decompression extraction reaction kettle of will filtrate to carry out solid-liquid separation;
Step 4 with described substituted diaryl organophosphate, adds in the salt solvent, and the aqueous solution with salt forming agent adds then, and reaction obtains substituted diaryl organic metal phosphate after finishing.
2. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, the general structure of said substituted aryl phenol is shown in (I) formula:
Wherein, (I) R in the formula
1Represent Wasserstoffatoms or C
1～C
6Alkyl, R
2Represent Wasserstoffatoms or C
1～C
6Alkyl, R
1With R
2Identical or inequality.
3. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, the general structure of said substituted diaryl phenol is shown in (II) formula;
Wherein, (II) R in the formula
1Represent Wasserstoffatoms or C
1～C
6Alkyl, R
2Represent Wasserstoffatoms or C
1～C
6Alkyl, R
1With R
2Identical or inequality.
4. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, the general structure of said substituted diaryl organic metal phosphate is shown in (III) formula:
Wherein: (III) R in the formula
1Represent hydrogen or C
1～C
6Alkyl, R
2Represent hydrogen or C
1～C
6Alkyl, R
1With R
2Identical or inequality; M represents one of following metal: potassium, sodium, lithium, calcium, magnesium, aluminium, zinc, barium or copper.
5. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, in molar ratio, and substituted aryl phenol: bridging agent=1: 1～3; Substituted aryl phenol: tensio-active agent=1: 0.0005～0.5; Substituted aryl phenol: souring agent=1: 1～2.5.
6. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, in molar ratio: substituted diaryl phenol: phosphoric acid agent=1: 1～2.5, phosphoric acid agent: triethylamine=1: 1～3.
7. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, by quality: the substituted diaryl organophosphate: become salt solvent=1: 2～50; Substituted diaryl organophosphate: the aqueous solution of salt forming agent=1: 0.01～100.
8. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, in the step 1, temperature of reaction is 5 ℃ of boiling points to reaction soln.
9. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, in the step 2, temperature of reaction is-25 ℃ of boiling points to reaction soln.
10. the preparation method of organic phosphate polypropylene nucleating agent as claimed in claim 1 is characterized in that, in the step 4, temperature of reaction is 16 ℃～100 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111712539A (en) * | 2018-02-13 | 2020-09-25 | 株式会社Adeka | Nucleating agent, polyolefin resin composition using same, and molded article thereof |
| CN112852138A (en) * | 2020-12-31 | 2021-05-28 | 深圳烯湾科技有限公司 | Thermoplastic resin-based conductive composite material and preparation method thereof |
| CN113214324A (en) * | 2021-04-14 | 2021-08-06 | 漯河市新旺化工有限公司 | Preparation method of substituted aryl organic phosphate nucleating agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1432594A (en) * | 2002-01-17 | 2003-07-30 | 扬子石油化工股份有限公司 | Polypropylene nucleator and its prepn process |
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| CN101367833A (en) * | 2007-08-17 | 2009-02-18 | 中国石油化工股份有限公司 | Preparation method for organic phosphate nucleating agent |
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| CN1432594A (en) * | 2002-01-17 | 2003-07-30 | 扬子石油化工股份有限公司 | Polypropylene nucleator and its prepn process |
| CN1857767A (en) * | 2005-11-02 | 2006-11-08 | 中国科学院过程工程研究所 | Multifunctional reactor for preparing ionic liquid |
| CN101367833A (en) * | 2007-08-17 | 2009-02-18 | 中国石油化工股份有限公司 | Preparation method for organic phosphate nucleating agent |
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| CN111712539A (en) * | 2018-02-13 | 2020-09-25 | 株式会社Adeka | Nucleating agent, polyolefin resin composition using same, and molded article thereof |
| US11306194B2 (en) | 2018-02-13 | 2022-04-19 | Adeka Corporation | Nucleating agent, polyolefin-based resin composition containing same, and molded article thereof |
| CN112852138A (en) * | 2020-12-31 | 2021-05-28 | 深圳烯湾科技有限公司 | Thermoplastic resin-based conductive composite material and preparation method thereof |
| CN113214324A (en) * | 2021-04-14 | 2021-08-06 | 漯河市新旺化工有限公司 | Preparation method of substituted aryl organic phosphate nucleating agent |
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