CN101418083B - Polypropylene nucleater and preparation method thereof - Google Patents
Polypropylene nucleater and preparation method thereof Download PDFInfo
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- CN101418083B CN101418083B CN2008100799894A CN200810079989A CN101418083B CN 101418083 B CN101418083 B CN 101418083B CN 2008100799894 A CN2008100799894 A CN 2008100799894A CN 200810079989 A CN200810079989 A CN 200810079989A CN 101418083 B CN101418083 B CN 101418083B
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- polypropylene
- titanium isopropylate
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- polypropylene nucleater
- hydrolysis
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Abstract
The invention provides a polypropylene nucleating agent and a preparation method thereof, which belongs to the research field of polypropylene nucleation and in particular relates to an aromatic acyl titanic acid, as well as a saline polypropylene nucleating agent and a preparation method thereof. The structural formula of the nucleating agent is as above, wherein in the formula, n can be equal to 1, 2, 3 or 4; M is H, Na or Li; and R is H, methyl, ethyl or p-tert-butyl. When the addition amount of polypropylene is 0.15 to 0.6 percent of the mass of the polypropylene, the crystallization temperature and crystallinity degree of the polypropylene are effectively raised, and various mechanical properties of the polypropylene are improved. The nucleating agent has the advantages that the nucleating agent can remarkably raise the crystallization temperature of the polypropylene and copolymer thereof, and can optimize the mechanical properties of the polypropylene.
Description
Technical field
A kind of polypropylene nucleater of the present invention and preparation method thereof belongs to polypropylene nucleation research field, is specifically related to a kind of aromaticacyl radical metatitanic acid and salt polypropylene nucleater thereof and preparation method thereof.
Background technology
Utilize polypropylene nucleater can change the degree of crystallinity of acrylic resin, accelerate its crystallization rate, improve the polyacrylic transparency, improve heat-drawn wire, improve performances such as product surface smooth finish.It is a kind of simple and effective polypropylene modification method.US.PAT.NO.5574174 has invented the glucitols polypropylene nucleater, can to a certain degree improve polyacrylic physical and chemical performance, but have the problem that bubble is more, smell is bigger.US.PAT.NO.4419473 and US.PAT.NO.5001174 propose to improve to the problems referred to above, obtain certain effect.US.PAT.NO.5342868 has invented organophosphorus acids nucleator, and to improving polyacrylic Tc, improving polyacrylic rigidity has obvious effects.Its fusing point is higher, generally greater than 300 ℃, with polyacrylic consistency and dispersiveness is all relatively poor and price is higher.CN1769329A discloses a kind of organophosphate polypropylene nucleation agent and preparation method thereof, and this nucleator is by substituted diaryl phosphoric acid, alcohols, and water and organic solvent and esterifying catalyst make, and above weak point is arranged equally.CN1803900A discloses a kind of mixing organic phosphate polypropylene nucleating agent and preparation method thereof, changes nucleator and is mixed by several organophosphates, and is more quite a lot of than single phosphoric acid salt nucleator effect, but still has above weak point.Two p-tert-butyl benzoic acid oxyaluminum are cheap nucleators that polypropylene increases firm type, are being used widely aspect the polypropylene enhancing modified at present.
Summary of the invention
The invention provides a kind of polypropylene nucleater and preparation method thereof, aim to provide a kind of can significantly improve polyacrylic Tc and improve the polypropylene mechanical property and the preparation method simple, and the technical scheme of nucleator of the preferable cheapness of nucleation effect and preparation method thereof.
The structure of above-mentioned polypropylene nucleater is:
N can equal 1,2,3 or 4 in the formula, and M is H, Na or Li, and R is H, methyl, ethyl or to the tertiary butyl.
Above-mentioned polypropylene nucleater is characterized in that it being the mixture that n equals several structures of 1,2,3,4 o'clock.
The method of above-mentioned a kind of polypropylene nucleater is characterized in that this method adopts following steps and condition:
Get titanium isopropylate and aromatic acid: phenylformic acid or p-methylbenzoic acid or to ethyl benzoate or p-tert-butyl benzoic acid, feed intake than for titanium isopropylate/aromatic acid=1/x by amount of substance, in temperature of reaction is 60～130 ℃, react, to deviate from pure amount as reaction end, after reacting completely, the adding mole number is that the concentration of 5 times of titanium isopropylate mole numbers is 95% alcohol, the unreacted titanium isopropylate of hydrolysis, hydrolysis is the back direct filtration fully, wash with water, oven dry, obtain product after the grinding, or in hydrolysis fully to add concentration be that 10% NaOH or the LiOH pH that neutralizes is 8 in the back, filter then, wash with water, oven dry, grind product.
The preparation method of above-mentioned polypropylene nucleater is characterized in that described titanium isopropylate and aromatic acid feed intake than 1/x by amount of substance, and the span of x is 3≤x≤4.
The addition of above-mentioned a kind of polypropylene nucleater is 0.01%～5% of a polypropylene quality, preferable range 0.15～0.6%.
The advantage that the invention provides a kind of polypropylene nucleater and preparation method thereof is: improve polyacrylic Tc, degree of crystallinity effectively, improve various mechanical properties.Can significantly improve the Tc of polypropylene or its multipolymer and optimize the nucleator of its mechanical property.
Embodiment
Below further specify the present invention by example.Composition umber wherein by weight.It is important to point out that just the invention will be further described for following embodiment, can not be interpreted as limiting the scope of the invention.
Embodiment 1
Get 0.1mol titanium isopropylate and 0.3mol p-tert-butyl benzoic acid, react, to deviate from pure amount as reaction end at 60 ℃.After reacting completely, add 95% the alcohol of 0.5mol, the unreacted titanium isopropylate of hydrolysis.Fully to add the 10%NaOH solution pH that neutralizes be 8 in the back in hydrolysis, filter then, wash with water, dry, grind get final product nucleator.
Get iPP100 part (trade mark is PPH-XD-045), get 0.3 part of above-mentioned prepared nucleator, behind the thorough mixing, on vulcanizing press, be heated to 210 ℃, be molded into the thick sheet material of 2mm, cool off fast with cold water.Get a fritter sample and on the DSC200PC differential scanning calorimeter, do the DSC test.After the result shows the adding nucleator, Tc T
c=127 ℃.
Embodiment 2
Get 0.1mol titanium isopropylate and 0.4mol p-tert-butyl benzoic acid, react, to deviate from pure amount as reaction end at 130 ℃.After reacting completely, add 95% the alcohol of 0.5mol, the unreacted titanium isopropylate of hydrolysis.Fully to add the 10%NaOH solution pH that neutralizes be 8 in the back in hydrolysis, filter then, wash with water, dry, grind get final product nucleator.
Get iPP100 part (trade mark is PPH-XD-045), get 0.3 part of above-mentioned prepared nucleator nucleator, behind the thorough mixing, by real mode 1 sample preparation and do DSC test.After the result shows the adding nucleator, Tc T
C=130 ℃.
Embodiment 3
Get 0.1mol titanium isopropylate and 0.4mol phenylformic acid, react, to deviate from pure amount as reaction end at 70 ℃.After reacting completely, add the alcohol of 0.5mol95%, the unreacted isopropyl titanate of hydrolysis.Fully to add the 10%LiOH solution pH that neutralizes be 8 in the back in hydrolysis, filter then, wash with water, dry, grind get final product nucleator.
Get iPP100 part (trade mark is PPH-XD-045), get 0.6 part of above-mentioned prepared nucleator, behind the thorough mixing, by real mode 1 sample preparation and do DSC test.After the result shows the adding nucleator, Tc T
c=126 ℃.
Embodiment 4
Get 0.1mol titanium isopropylate and 0.4mol p-tert-butyl benzoic acid, react, to deviate from pure amount as reaction end at 80 ℃.After reacting completely, add 95% the alcohol of 0.5mol, the unreacted titanium isopropylate of hydrolysis.Fully to add the 10%LiOH solution pH that neutralizes be 8 in the back in hydrolysis, filter then, wash with water, dry, grind get final product nucleator.
Get 100 parts of iPP (trade mark is PPH-XD-045A), get 0.15 part of above-mentioned preparation nucleator.In single screw extrusion machine, extrude preparation standard batten and its stretching of test, counter-bending, erosion-resisting characteristics on CMT4204 type microcomputer control electronics universal testing machine, XCJ-500 impact experiment machine; Get a fritter sample and on the DSC200PC differential scanning calorimeter, do the DSC test.
Embodiment 5
Get 100 parts of iPP (trade mark is PPH-XD-045A), get in the embodiment 2 0.3 part of prepared nucleator. by embodiment 4 preparation battens and test its stretching, anti-impact, bending resistance; Get a fritter sample and on the DSC200PC differential scanning calorimeter, do the DSC test.
Embodiment 6
Get 0.1mol titanium isopropylate and 0.3mol p-tert-butyl benzoic acid, carry out dealcoholization, to deviate from pure amount as reaction end at 90 ℃.After reacting completely, add the alcohol of 0.5mol95%, the unreacted titanium isopropylate of hydrolysis.Fully to add the 10%LiOH solution pH that neutralizes be 8 in the back in hydrolysis, filter then, wash with water, dry, grind get final product nucleator.
Get 100 parts of iPP (trade mark is PPH-XD-045A), get 0.15 part of above-mentioned prepared nucleator, prepare battens and test its stretching, anti-impact, bending resistance by embodiment 4; Get a fritter sample and on the DSC200PC differential scanning calorimeter, do the DSC test.
Embodiment 7
Get 100 parts of iPP (trade mark is PPH-XD-045A), get 0.6 part of embodiment 6 prepared nucleator, prepare battens and test its stretching, anti-impact, bending resistance by embodiment 4; Get a fritter sample and on the DSC200PC differential scanning calorimeter, do the DSC test.
The contrast of each embodiment performance of table 1 and blank PP
Claims (4)
1. a polypropylene nucleater is characterized in that it being a kind of aromaticacyl radical titanate polypropylene nucleater, and its structural formula is:
N equals 1,2,3 or 4 in the formula, and M is Na or Li, and R is methyl, ethyl or the tertiary butyl.
2. according to the described a kind of polypropylene nucleater of claim 1, it is characterized in that it being that n equals 1,2,3 or the mixture of 4 o'clock four class formations.
3. the method for preparing the described a kind of polypropylene nucleater of claim 1, adopt following steps and condition: get titanium isopropylate and aromatic acid: p-methylbenzoic acid, to ethyl benzoate or p-tert-butyl benzoic acid, feed intake than for titanium isopropylate/aromatic acid=1/x by amount of substance, 60～130 ℃ of temperature of reaction, react, to deviate from pure amount as reaction end, after reacting completely, the adding mole number is that the concentration of 5 times of titanium isopropylate mole numbers is 95% alcohol, the unreacted titanium isopropylate of hydrolysis, it is characterized in that this method is that fully to add concentration be that 10% NaOH or the LiOH pH that neutralizes be=8 in the back in hydrolysis, filtration then, washing, oven dry, grind product.
4. by the preparation method of the described a kind of polypropylene nucleater of claim 3, it is characterized in that described titanium isopropylate and aromatic acid feed intake than 1/x by amount of substance, the span of x is 3≤x≤4.
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| CN2008100799894A CN101418083B (en) | 2008-11-28 | 2008-11-28 | Polypropylene nucleater and preparation method thereof |
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| CN2008100799894A CN101418083B (en) | 2008-11-28 | 2008-11-28 | Polypropylene nucleater and preparation method thereof |
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| CN101418083A CN101418083A (en) | 2009-04-29 |
| CN101418083B true CN101418083B (en) | 2011-06-22 |
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| CN105348310A (en) * | 2015-12-04 | 2016-02-24 | 广州呈和科技有限公司 | Preparation method for nucleating agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6551533B1 (en) * | 2000-11-28 | 2003-04-22 | Chemat Technology, Inc. | Method of forming fibrous materials and articles therefrom |
| CN1974611A (en) * | 2006-11-20 | 2007-06-06 | 华东理工大学 | Prepn and application of catalytic nucleating agent for polyolefin |
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2008
- 2008-11-28 CN CN2008100799894A patent/CN101418083B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6551533B1 (en) * | 2000-11-28 | 2003-04-22 | Chemat Technology, Inc. | Method of forming fibrous materials and articles therefrom |
| CN1974611A (en) * | 2006-11-20 | 2007-06-06 | 华东理工大学 | Prepn and application of catalytic nucleating agent for polyolefin |
Non-Patent Citations (3)
| Title |
|---|
| 万兆荣.铝系新型聚丙烯成核剂的制备及表征.《太原理工大学学报》.2009,第40卷(第5期),第476-478页. * |
| 乔志华.新型聚丙烯成核剂的制备及表征.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2008,(第10期),第37-38页. * |
| 公维光等.取代芳基钛酸钠在等规聚丙烯忠的成核作用研究.《中国塑料》.2007,第21卷(第6期),第79-78页. * |
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