CN102746577A - Organic ammonium phosphate nucleating agent for polypropylene transparency and preparation method thereof - Google Patents
Organic ammonium phosphate nucleating agent for polypropylene transparency and preparation method thereof Download PDFInfo
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- CN102746577A CN102746577A CN2012102524110A CN201210252411A CN102746577A CN 102746577 A CN102746577 A CN 102746577A CN 2012102524110 A CN2012102524110 A CN 2012102524110A CN 201210252411 A CN201210252411 A CN 201210252411A CN 102746577 A CN102746577 A CN 102746577A
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Abstract
The invention discloses an organic ammonium phosphate nucleating agent for polypropylene transparency and a preparation method of the organic ammonium phosphate nucleating agent. The molecular formula of the organic ammonium phosphate nucleating agent is shown in the description, wherein R1, R2, R3 and R4 are all hydrogen atoms or C1-C4 alkyl or branched alkyl; R1, R2, R3 and R4 are completely the same, completely different or partly same. The organic ammonium phosphate can be used as a nucleating agent for polypropylene transparency and has the advantages of low melting temperature, good dispersing effect, high nucleating efficiency and significant antireflection effect. The method is simple in operation and the yield is more than 85%.
Description
Technical field
The present invention relates to material science, especially a kind of organic phosphoric acid ammonium salt class polypropylene transparent nucleater and preparation method thereof.
Background technology
At present, Vestolen PP 7052 (PP) is one type of excellent property, low price, of many uses, translucent half hitch crystal formation resin, can improve its crystallinity, the transparency, the better transparent polypropylene plastics of obtained performance through adding nucleator.The polypropylene nucleater of selling in the market mainly contains sorbyl alcohol type and organophosphate two big classes.In recent years, nucleator in organic phosphate class was used day by day extensive, and this type of nucleator improves performances such as polyacrylic rigidity, heat-drawn wire when significantly improving polypropylene transparent property.Existing organophosphate series nucleator is mainly metallic salt; Product with the electrochemical company of the Japanese rising sun is representative, has successively experienced three generation products, is respectively NA-10, NA-11, NA-21; Dispersiveness in Vestolen PP 7052 is relatively poor relatively, and generally to recommend consumption be about 0.3% of base resin.
Summary of the invention
The objective of the invention is: a kind of organic phosphoric acid ammonium salt class polypropylene transparent nucleater and preparation method thereof is provided, and its fusing point obviously reduces, and dispersion effect is good; Nucleation efficient is high; Antireflective effect is remarkable, and the preparation method is simple, has the homophase nucleating effect of fitting mutually with NA-11.
The present invention is achieved in that organic phosphoric acid ammonium salt class polypropylene transparent nucleater, and its structural formula is:
Wherein R1, R2, R3 and R4 are alkyl or the branched-chain alkyl of Wasserstoffatoms or C1 ~ C4; R1, R2, R3 and R4 are identical, part is identical or complete difference.It can be symmetrical structure that identical structure is divided in the center, and promptly R1 is identical with R4, and R2 is identical with R3, but R1 is different with R2.
The alkyl of described C1 ~ C4 or branched-chain alkyl are the hexyl of amyl group, n-hexyl or the side chain of methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, side chain.
The preparation method of organic phosphoric acid ammonium salt class polypropylene transparent nucleater gets 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER; Add in the alcoholic solvent and disperse, heat to 40～90 ℃ dispersed with stirring; Keep 40～90 ℃ of following constant temperature, add mass percent concentration again and be 15～30% NaOH solution, reaction 0.5～3h; Add mass percent concentration then and be 20～30% ammonium salt solution, continue isothermal reaction 2～5h after, after behind the suction filtration, washing, drying finished product; 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER, alcoholic solvent, the mol ratio of NaOH and ammonium salt is 1:50:1:1; Perhaps, get 2,2 '-methylene-bis (4; The 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER adds in the alcoholic solvent and disperses, and heats to 40～90 ℃; Dispersed with stirring keeps 40～90 ℃ of following constant temperature, adds mass percent concentration again and be 25～35% ammoniacal liquor; Behind reaction 2～5h, after behind the suction filtration, washing, drying finished product; 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER, alcoholic solvent, the mol ratio of a hydration ammonia is 1:50:1.5.
Described ammonium salt solution is an ammonium chloride solution, a kind of in ammoniumsulphate soln or the sal volatile.
Described alcoholic solvent is one or more combination in methyl alcohol, ethanol, Virahol, propyl carbinol, terepthaloyl moietie, USP Kosher or the phenylcarbinol.
Owing to adopted technique scheme, compared with prior art, the present invention adopts organic phosphoric acid ammonium salt class as polypropylene transparent nucleater; Its fusing point is low, and dispersion effect is good, and nucleation efficient is high; Antireflective effect is remarkable, and the preparation method is simple, and productive rate can reach more than 85%.Material source of the present invention is extensive, is easy to obtain, and is with low cost, and result of use is good.
Description of drawings
Accompanying drawing 1 is the TG curve of the product of embodiments of the invention 1;
Accompanying drawing 2 is the DSC curve of the product of embodiments of the invention 1.
Embodiment
Embodiments of the invention 1: the preparation of organic phosphoric acid ammonium salt class polypropylene transparent nucleater, with 0.1mol 2,2 '-methylene-bis (4; The 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER adds in the 5mol methyl alcohol and disperses, and heats to 40 ℃; Dispersed with stirring keeps 40 ℃ of following constant temperature, and it is 20% NaOH solution that 0.1mol NaOH is mixed with mass percent concentration; Add the NaOH solution prepare and also react 0.5h, add mass percent concentration then and be 27% ammonium salt solution, continue isothermal reaction 3h after; After behind the suction filtration, washing, drying finished product, its productive rate is 89.41%.
For further checking effect of the present invention, the product of embodiment 1 is carried out following experimental analysis:
KBr compressing tablet IR analyzes: 2958cm
-1Absorption peak be that saturated C-H stretching vibration absorbs; 1606cm
-1, 1479cm
-1For the phenyl ring skeletal vibration absorbs; 1363cm
-1For-CH
3Flexural vibration absorb; 1178cm
-1, 1158cm
-1, 1126cm
-1Stretching vibration absorption for the C-O key; 1230cm
-1Strong absorption peak be that the stretching vibration of P=O key absorbs, 1080cm
-1, 1022cm
-1Absorption peak do
In the P-O stretching vibration absorb 918cm
-1, 887cm
-1Be the P-O stretching vibration.822cm
-1, 784cm
-1, 698cm
-1For phenyl ring C-H flexural vibration absorb.
Get the product of embodiment 1, adopt TQ-50 type thermogravimetric analyzer and Q10 type differential thermal analyzer at N
2Measure its thermal property under the atmosphere.Temperature rise rate is 10 ℃/min.As depicted in figs. 1 and 2 respectively, be 326.6 ℃ by the maximum decomposition temperature that can find out this nucleator among Fig. 1, and as can be seen from Figure 2 the fusing point of this nucleator is 275.5 ℃.
Embodiments of the invention 2: the preparation of organic phosphoric acid ammonium salt class polypropylene transparent nucleater, with 0.1mol 2,2 '-methylene-bis (4; The 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER; Add in the 5mol methyl alcohol and disperse, heat to 40 ℃ dispersed with stirring; Keep 40 ℃ of following constant temperature, add the ammoniacal liquor (NH that wherein adds of 30% mass percent concentration
3H
2The total amount of O is 0.15mol) behind the reaction 3h, after behind the suction filtration, washing, drying finished product, its productive rate is 92.45%.
The product of embodiment 2 is carried out following experimental analysis:
KBr compressing tablet IR analyzes: 3680cm
-1～3080cm
-1Tangible broad peak appears in the place, and this is due to the intramolecular hydrogen bond effect; 2958cm
-1Absorption peak be that saturated C-H stretching vibration absorbs; 1606cm
-1, 1479cm
-1For the phenyl ring skeletal vibration absorbs; 1363cm
-1For-CH
3Flexural vibration absorb; 1178cm
-1, 1158cm
-1, 1126cm
-1Stretching vibration absorption for the C-O key; 1230cm
-1Strong absorption peak be that the stretching vibration of P=O key absorbs, 1085cm
-1, 918cm
-1, 894cm
-1Be the P-O stretching vibration.819cm
-1, 781cm
-1, 700cm
-1For phenyl ring C-H flexural vibration absorb.
Measure 324.26 ℃ of the maximum decomposition temperatures of embodiment 2 nucleators by TG, it is 263.75 ℃ that DSC records its fusing point.
The prepared product that obtains of the foregoing description joined extrude injection moulding processing among the PP (T30S), NA-11 is applied among the PP under similarity condition, example 1 as a comparison is with not handling through same with the PP of nucleator, as check sample.Table 1 is listed in influence to crystal property.Influence to mechanical property is as shown in table 2.Improvement to optical property is as shown in table 3.The result shows, product of the present invention is to PP Crystal Physics mechanical property, nucleogenesis, and all there is good improvement aspects such as optical property.Wherein extrusion temperature is 220 ℃, 210 ℃ of injection temperatures.
Table 1 DSC data results
Table 2 nucleator is to the improvement of PP physical and mechanical property
Table 3 nucleator is to the improvement of the optical property of PP
The present invention prepared 2, (4,6-di-tert-butyl-phenyl ammonium phosphate salt can be used as the nucleator of homopolymerization, atactic copolymerized polypropene to 2 '-methylene-bis, and the consumption of nucleator is 0.05～0.2%.Preparing method of the present invention is simple; The nucleator product yield is high, and this nucleator fusing point is low, good dispersivity in polymkeric substance; In melt extruding process, there is not agglomeration; Can improve polyacrylic Tc, percent crystallinity, flexural strength, modulus in flexure and tensile strength, improve properties of transparency, be a kind of good polypropylene nucleater.
According to embodiment 1; In the scope of claims, change processing parameter and also realize technical scheme of the present invention, the temperature rising can make productive rate descend, when product purity was lower than 3h when the reaction times was 2h; Reaction times is little above model change behind the 3h, and productive rate slightly raises.
According to embodiment 2, it is also feasible to change processing parameter at claims, and temperature raises the reaction generation comparatively fast, and productive rate decreases, and productive rate changes little behind the reaction times 3h.
Claims (5)
1. organic phosphoric acid ammonium salt class polypropylene transparent nucleater, it is characterized in that: its structural formula is:
Wherein R1, R2, R3 and R4 are alkyl or the branched-chain alkyl of Wasserstoffatoms or C1 ~ C4; R1, R2, R3 and R4 are identical, part is identical or complete difference.
2. organic phosphoric acid ammonium salt class polypropylene transparent nucleater according to claim 1 is characterized in that: the alkyl of described C1 ~ C4 or branched-chain alkyl are the hexyl of amyl group, n-hexyl or the side chain of methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, side chain.
3. the preparation method of an organic phosphoric acid ammonium salt class polypropylene transparent nucleater is characterized in that: get 2,2 '-methylene-bis (4; The 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER adds in the alcoholic solvent and disperses, and heats to 40～90 ℃; Dispersed with stirring keeps 40～90 ℃ of following constant temperature, adds mass percent concentration again and be 15～30% NaOH solution; Reaction 0.5～3h; Add mass percent concentration then and be 20～30% ammonium salt solution, continue isothermal reaction 2～5h after, after behind the suction filtration, washing, drying finished product; 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER, alcoholic solvent, the mol ratio of NaOH and ammonium salt is 1:50:1:1; Perhaps, get 2,2 '-methylene-bis (4; The 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER adds in the alcoholic solvent and disperses, and heats to 40～90 ℃; Dispersed with stirring keeps 40～90 ℃ of following constant temperature, adds mass percent concentration again and be 25～35% ammoniacal liquor; Behind reaction 2～5h, after behind the suction filtration, washing, drying finished product; 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) SULPHOSUCCINIC ACID ESTER, alcoholic solvent, the mol ratio of a hydration ammonia is 1:50:1.5.
4. the preparation method of organic phosphoric acid ammonium salt class polypropylene transparent nucleater according to claim 3 is characterized in that: described ammonium salt solution is an ammonium chloride solution, a kind of in ammoniumsulphate soln or the sal volatile.
5. the preparation method of organic phosphoric acid ammonium salt class polypropylene transparent nucleater according to claim 3 is characterized in that: described alcoholic solvent is one or more combination in methyl alcohol, ethanol, Virahol, propyl carbinol, terepthaloyl moietie, USP Kosher or the phenylcarbinol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019041961A1 (en) * | 2017-08-29 | 2019-03-07 | 孙志强 | Transparent nucleating agent, preparation method therefor and use thereof |
| CN114410132A (en) * | 2021-12-27 | 2022-04-29 | 江西隆源化工股份有限公司 | Preparation method of easily-dispersible pigment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311296A (en) * | 1995-05-22 | 1996-11-26 | Tonen Chem Corp | Polypropylene resin composition |
| JPH093294A (en) * | 1995-06-15 | 1997-01-07 | Tonen Chem Corp | Polypropylene resin composition |
| CN101665586A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Method for preparing organic phosphate nucleating agent through ultrasonic sedimentation |
-
2012
- 2012-07-20 CN CN2012102524110A patent/CN102746577A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311296A (en) * | 1995-05-22 | 1996-11-26 | Tonen Chem Corp | Polypropylene resin composition |
| JPH093294A (en) * | 1995-06-15 | 1997-01-07 | Tonen Chem Corp | Polypropylene resin composition |
| CN101665586A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Method for preparing organic phosphate nucleating agent through ultrasonic sedimentation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019041961A1 (en) * | 2017-08-29 | 2019-03-07 | 孙志强 | Transparent nucleating agent, preparation method therefor and use thereof |
| CN114410132A (en) * | 2021-12-27 | 2022-04-29 | 江西隆源化工股份有限公司 | Preparation method of easily-dispersible pigment |
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Application publication date: 20121024 |