CN100400577C - Organophosphate polypropylene nucleation agent and its preparation method - Google Patents
Organophosphate polypropylene nucleation agent and its preparation method Download PDFInfo
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- CN100400577C CN100400577C CNB2004100863873A CN200410086387A CN100400577C CN 100400577 C CN100400577 C CN 100400577C CN B2004100863873 A CNB2004100863873 A CN B2004100863873A CN 200410086387 A CN200410086387 A CN 200410086387A CN 100400577 C CN100400577 C CN 100400577C
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Abstract
The present invention discloses an organophosphate polypropylene nucleating agent and a preparation method thereof. The nucleating agent of the present invention is obtained by the preparation method which comprises the following steps that substituted diaryl phosphoric acid and alcohol are used as reactants; water, organic solvent and the alcohol as the reactant are sprayed in the substituted diaryl phosphoric acid; the moisture content of materials is controlled to be 3 to 22%, and the materials are stirred for reaction when esterifying catalysts exist under a dry condition. The substituted diaryl organophosphate of the present invention is used as a nucleation modifying agent of polypropylene resin, which can obviously improve various processing properties of the polypropylene resin.
Description
Technical field
The present invention relates to a kind of polypropylene nucleater and preparation method thereof.
Background technology
Diaryl organic phosphoric acid compound 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 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.Above content can referring to scientific and technical literature " 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).
DE3940765A1 discloses a kind of preparation method of diaryl organic phosphoric acid compound.This method adopts substituted aryl phosphoric acid to react in the aqueous solution of acetone-alkali 2 hours, and distillation removes and desolvates then, crystallization, filtration, washing, drying, pulverizes and produces." the synthetic and application of PP nucleator " (" plastics industry ", 1999 (5)) a kind of preparation method of diaryl organophosphate is disclosed, this method adopts substituted aryl phosphoric acid being hydrolyzed and solvolytic reaction in a large amount of solvents, and is dry then, pulverize, and obtains product.
Prior preparation method all is to adopt wet processing to prepare diaryl organic phosphoric acid compound, and mostly uses the diaryl organophosphate as nucleator.Wet processing is complicated operation not only, but also must use a large amount of water and organic solvent, exists and cause environmental pollution, increases shortcomings such as manufacturing expense.
In order to solve the shortcoming that exists in the existing organic phosphoric acid compound polypropylene nucleater technology of preparing, the present invention adopts dry process reaction technology to prepare polypropylene nucleater, obtains a kind of novel organophosphate polypropylene nucleation agent.
Summary of the invention
An object of the present invention is to provide a kind of organophosphorus polypropylene nucleater, concrete provide a kind of substituted diaryl phosphoric acid ester polypropylene nucleater.
Organophosphate polypropylene nucleation agent of the present invention, prepare by the method that may further comprise the steps: with substituted diaryl phosphoric acid and alcohols is reactant, in mixing agitator, add substituted diaryl phosphoric acid earlier, respectively water, organic solvent and reactant alcohols are sprayed into then, control material moisture content is 3-22%, in the presence of dry conditions, esterifying catalyst, stirs material, reaction.
Substituted diaryl organophosphate polypropylene nucleation agent of the present invention is directly to add substituted diaryl phosphoric acid earlier in reactor, sprays into a spot of aqueous catalyst solution then, and spray into a spot of organic solvent gradually, and the reactant alcohols, under dry conditions, stir material, mixing; Then at a certain temperature, react, after reaction finishes, carry out dry and pulverize to handle obtaining.
Preferred described method is to react under 80-250 ℃ the condition in temperature of reaction.
The add-on of preferred described reaction raw materials is respectively: to add the reaction raw materials gross weight is 100 parts, substituted diaryl phosphoric acid 58-85 part, water 2-10 part, organic solvent 1-12 part, reactant alcohols 10-39 part.
Described catalyzer can be a general esterification catalyzer commonly used, is preferably to be selected from a kind of in urea, methyl urea, acetyl urea, acrylamide and the trolamine; The add-on of described catalyzer is the 0.3%-6% (wt) of reaction raw materials gross weight.
The general structure of preferred described reactant substituted diaryl phosphoric acid is shown in (I), (II):
R wherein
1, R
2Represent C
1-C
6Alkyl, R
1, R
2Can be identical or inequality; Preferred R
1, R
2Represent methylidene, ethyl, n-propyl, sec.-propyl, isobutyl-or the tertiary butyl; More preferably R
1, R
2Represent identical alkyl.
Preferred described reactant alcohols is selected from least a in n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ethylene glycol, Pentyl alcohol, primary isoamyl alcohol, neopentyl alcohol, glycerol and the phenylcarbinol.
Preferred described organic solvent is selected from acetone, tetrahydrofuran (THF), ethyl acetate, normal hexane, Skellysolve A, benzene, toluene He one or more in the diox.
Another object of the present invention provides a kind of preparation method and application thereof of substituted diaryl phosphoric acid ester polypropylene nucleater.
The preparation method of organophosphate polypropylene nucleation agent of the present invention comprises the steps:
1) be reactant with substituted diaryl phosphoric acid and alcohols, to add the reaction raw materials gross weight is 100 parts, in mixing agitator, add earlier substituted diaryl phosphoric acid 58-85 part with the general structure shown in (I), (II), then respectively with water 2-10 part, organic solvent 1-12 part, and reactant alcohols 10-39 part spray into;
2) in the presence of esterifying catalyst, stir material, heating, control material moisture content is in the 3-22% scope, wherein said catalyzer is selected from a kind of in urea, methyl urea, acetyl urea, acrylamide and the trolamine, and the add-on of described catalyzer is the 0.3%-6% (wt) of reaction raw materials gross weight;
3) under being 80-250 ℃ condition, temperature proceeds to stir material, mixing, reaction;
4) after reaction finishes, reaction product is carried out drying, pulverizing, obtain described organophosphate polypropylene nucleation agent.
Described mixing agitator can be various types of agitators, is preferably selected from a kind of in kneader, ebullated dryer, oar formula mixing drier, rake formula mixing drier, extrusion machine, ball mill and the blending machine etc.
Substituted diaryl phosphoric acid ester polypropylene nucleater of the present invention is applied in the acrylic resin processing, and the polypropylene processing characteristics is significantly improved.
The beneficial effect that polypropylene nucleater of the present invention has is as follows:
1, because organophosphate polypropylene nucleation agent of the present invention adopts dry process reaction technology to make, and reaction mass reacts under the dry state condition, therefore saves the use of solvent and reagent, and shortened the exsiccant time, reduced energy consumption.
2, use organophosphate polypropylene nucleation agent of the present invention, can improve the processing characteristicies such as modulus in flexure, heat-drawn wire and notched Izod impact strength of acrylic resin significantly.
Embodiment
The preparation of embodiment 1-3 nucleator of the present invention
Embodiment 1
In the dry type mixing agitator, add two (2,4-di-t-butyl phenoxy group) phosphoric acid 53.88 grams, its structural formula shown in (II), R
1, R
2Be the tertiary butyl.Under agitation, 1.8 gram catalyzer urea are dissolved in the 3 gram water, respectively the aqueous solution, acetone 2.5 grams, isopropylcarbinol 36.2 grams of urea are sprayed into atomizer, at room temperature mixing then 1 hour, elevated temperature to 40～50 ℃ maintenance is 1.5 hours then, surveying its material moisture content with quick humidometer is 13 ± 2%, elevated temperature to 135 ℃ then, continue to stir 2.5 hours, dry then, carry out pulverization process, obtain two (2,4-di-t-butyl phenoxy group) phosphoric acid tert-butyl ester, fusing point is greater than 270 ℃.
Embodiment 2
In the dry type mixing agitator, add 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid 70.2 grams, its structural formula shown in (I), R
1, R
2Be the tertiary butyl.Under agitation, 1.8 gram catalyzer urea are dissolved in the 3 gram water, spray into the aqueous solution, acetone 2.5 grams of urea respectively with atomizer, isopropylcarbinol 37.8 grams, at room temperature mixing then 1 hour, elevated temperature to 40～50 ℃ maintenance is 1.5 hours then, surveying its material moisture content with quick humidometer is 13 ± 2%, and elevated temperature to 138 ℃ continues to stir 2.5 hours then, dry then, carry out pulverization process, obtain 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid tert-butyl ester, fusing point is greater than 270 ℃.
Embodiment 3
In the dry type mixing agitator, add 2,2 '-methylene radical-two (4-methyl, 6-tertiary butyl phenoxy group) phosphoric acid 66.8 grams, its structural formula shown in (I), R
1Be the tertiary butyl, R
2Be methyl.Under agitation, 1.8 gram catalyzer urea are dissolved in the 3 gram water, spray into the aqueous solution, isopropylcarbinol 36.2 grams, acetone 2.5 grams of urea respectively with atomizer, at room temperature mixing then 1 hour, elevated temperature to 40～50 ℃ maintenance is 1.5 hours then, surveying its material moisture content with quick humidometer is 13 ± 2%, elevated temperature to 135 ℃ then, continue to stir 2.5 hours, dry then, carry out pulverization process, obtain 2,2 '-methylene radical-two (4-methyl, 6-tertiary butyl phenoxy group) phosphoric acid tert-butyl ester, fusing point is greater than 270 ℃.
Embodiment 4 application of nucleator of the present invention in polymer processing
Get 100 parts of weight of polypropylene (trade mark K8303), get 0.2 part of weight of nucleator that embodiment 1-3 makes, 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 polypropylene that does not add nucleator is handled through same, as check sample.
The batten that obtains is carried out modulus in flexure test (press the ASTMD790 testing standard), and socle girder notched Izod impact strength test (by the ASTMD256 testing standard) and heat-drawn wire are tested the table 1 that the results are shown in that (by the ASTMD648 testing standard) obtain.
Table 1
| The nucleator that uses | Sample modulus in flexure Gpa | Breach resistance to impact shock J/m | Heat-drawn wire ℃ |
| Embodiment 1 | 1.587 | 244.95 | 124.8 |
| Embodiment 2 | 1.604 | 257.04 | 126.1 |
| Embodiment 3 | 1.613 | 260.25 | 128.2 |
| Do not add | 1.270 | 153.00 | 100.1 |
As can be seen from Table 1, phosphoric acid tert-butyl ester is as nucleator in two (2,4-di-t-butyl phenoxy group) that use embodiments of the invention 1 obtain, and the polymer-modified modulus in flexure that obtains can improve 25%, and the breach resistance to impact shock improves 60.1%; Use that embodiments of the invention 2 obtain 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy group) phosphoric acid tert-butyl ester is as nucleator, the polymer-modified modulus in flexure that obtains improves 26.3%, the breach resistance to impact shock improves 68%; Use in the embodiments of the invention 32,2 '-methylene radical-two (4-methyl, 6-tertiary butyl phenoxy group) phosphoric acid tert-butyl ester is as nucleator, and the polymer-modified modulus in flexure that obtains improves 27%, and the breach resistance to impact shock improves 70.1%.
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.
Claims (8)
1. the preparation method of an organophosphate polypropylene nucleation agent, it may further comprise the steps: with substituted diaryl phosphoric acid and alcohols is reactant, in mixing agitator, add substituted diaryl phosphoric acid earlier, respectively aqueous catalyst solution, organic solvent and reactant alcohols are sprayed into then, control material moisture content is 3-22%, in the presence of dry conditions, esterifying catalyst, stirs material, reaction; To add the reaction raw materials gross weight is 100 parts, and the add-on of described reaction raw materials is respectively: substituted diaryl phosphoric acid 58-85 part, water 2-10 part, organic solvent 1-12 part, reactant alcohols 10-39 part; And the add-on of described esterifying catalyst is the 0.3%-6% (wt) of reaction raw materials gross weight.
2. the preparation method of polypropylene nucleater as claimed in claim 1 is characterized in that described method is to carry out under 80-250 ℃ the condition in temperature of reaction; Described esterifying catalyst is selected from a kind of in urea, methyl urea, acetyl urea, acrylamide and the trolamine.
3. the preparation method of polypropylene nucleater as claimed in claim 1, the general structure that it is characterized in that described reactant substituted diaryl phosphoric acid is shown in (I), (II):
R wherein
1, R
2Represent C
1-C
6Alkyl, R
1, R
2Can be identical or inequality.
4. the preparation method of polypropylene nucleater as claimed in claim 3 is characterized in that the R in the described substituted diaryl phosphoric acid
1, R
2Represent methylidene, ethyl, n-propyl, sec.-propyl, isobutyl-or the tertiary butyl.
5. the preparation method of polypropylene nucleater as claimed in claim 1 is characterized in that described reactant alcohols is selected from least a in n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ethylene glycol, Pentyl alcohol, primary isoamyl alcohol, neopentyl alcohol, glycerol and the phenylcarbinol.
6. the preparation method of polypropylene nucleater as claimed in claim 1 is characterized in that described organic solvent is selected from acetone, tetrahydrofuran (THF), ethyl acetate, normal hexane, Skellysolve A, benzene, toluene He one or more in the diox.
7. the preparation method of the described organophosphate polypropylene nucleation agent of one of claim 1-6 comprises the steps:
1) be reactant with substituted diaryl phosphoric acid and alcohols, to add the reaction raw materials gross weight is 100 parts, in mixing agitator, add earlier substituted diaryl phosphoric acid 58-85 part with the general structure shown in (I), (II), then respectively with water 2-10 part, organic solvent 1-12 part, and reactant alcohols 10-39 part spray into;
2) in the presence of esterifying catalyst, stir material, heating, control material moisture content is in the 3-22% scope, wherein said esterifying catalyst is selected from a kind of in urea, methyl urea, acetyl urea, acrylamide and the trolamine, and the add-on of described esterifying catalyst is the 0.3%-6% (wt) of reaction raw materials gross weight;
3) under being 80-250 ℃ condition, temperature proceeds to stir material, mixing, reaction;
4) after reaction finishes, reaction product is carried out drying, pulverizing, obtain described organophosphate polypropylene nucleation agent.
8. according to the described preparation method of claim 7, it is characterized in that described mixing agitator is selected from a kind of in kneader, ebullated dryer, oar formula mixing drier, rake formula mixing drier, extrusion machine, ball mill and the blending machine.
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| CNB2004100863873A CN100400577C (en) | 2004-10-27 | 2004-10-27 | Organophosphate polypropylene nucleation agent and its preparation method |
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| CN1769329A CN1769329A (en) | 2006-05-10 |
| CN100400577C true CN100400577C (en) | 2008-07-09 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423636B (en) * | 2007-10-31 | 2011-08-03 | 中国石油化工股份有限公司 | High rigid and high heat tolerant polypropylene composition and preparation method thereof |
| CN101423624B (en) * | 2007-10-31 | 2011-05-04 | 中国石油化工股份有限公司 | Miniaturization organic phoshate nucleating agent and preparation method thereof |
| CN101591455B (en) * | 2008-05-29 | 2011-05-04 | 中国石油化工股份有限公司 | Ultrafine organic phosphate nucleating agent and preparation method thereof |
| CN102382134B (en) * | 2010-08-30 | 2014-07-09 | 中国石油化工股份有限公司 | Preparation method of polypropylene nucleating agent |
| CN102382328B (en) * | 2011-08-25 | 2013-04-10 | 贵州省复合改性聚合物材料工程技术研究中心 | Preparation method of silica sol-modified organophosphate nucleating agent |
| CN105733092B (en) * | 2016-03-09 | 2018-05-15 | 贵州省材料产业技术研究院 | A kind of binary composite transparent polypropylene nucleater |
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| JP2002348421A (en) * | 2001-05-24 | 2002-12-04 | Chisso Corp | Polypropylene resin composition and transparent sheet |
| 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 |
| JP2004115570A (en) * | 2002-09-24 | 2004-04-15 | Sumitomo Chem Co Ltd | Polypropylene resin composition |
| US20040197584A1 (en) * | 2000-11-09 | 2004-10-07 | Michael Jeschke | Highly crystalline polypropylene film for packaging purposes |
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2004
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040197584A1 (en) * | 2000-11-09 | 2004-10-07 | Michael Jeschke | Highly crystalline polypropylene film for packaging purposes |
| JP2002348421A (en) * | 2001-05-24 | 2002-12-04 | Chisso Corp | Polypropylene resin composition and transparent sheet |
| 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 |
| JP2004115570A (en) * | 2002-09-24 | 2004-04-15 | Sumitomo Chem Co Ltd | Polypropylene resin composition |
Non-Patent Citations (4)
| Title |
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| PP成核剂的合成及应用. 王一中.塑料工业，第27卷第5期. 1999 |
| PP成核剂的合成及应用. 王一中.塑料工业，第27卷第5期. 1999 * |
| 有机磷酸酯成核剂在聚丙烯中成核的有效性. 张广平等.石油化工，第32卷第9期. 2003 |
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