CN1715316A - Polypropylene nucleating agent and its preparing method - Google Patents
Polypropylene nucleating agent and its preparing method Download PDFInfo
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- CN1715316A CN1715316A CN 200510021265 CN200510021265A CN1715316A CN 1715316 A CN1715316 A CN 1715316A CN 200510021265 CN200510021265 CN 200510021265 CN 200510021265 A CN200510021265 A CN 200510021265A CN 1715316 A CN1715316 A CN 1715316A
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- xylitol
- phenyl aldehyde
- clean
- acetone
- out system
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Abstract
The present invention relates to a new kind of polypropylene nucleating agent with structural general expression as shown and its preparation process. The polypropylene nucleating agent can improve the transparency property of polypropylene, raise its tensile strength, bending strength, impact strength and other physical performance, and raise the crystallization temperature greatly. In addition, the nucleating agent of the present invention may be used also for other polyolefin material, such as polyethylene, polyvinyl chloride, etc.
Description
One, technical field
The invention belongs to high molecule plastic auxiliary agent and preparing technical field thereof, be specifically related to a kind of polypropylene nucleater that has higher melt, has good stability and preparation method thereof.
Two, background technology
Polypropylene (PP) is though with its good mechanical property, nontoxic, good characteristic such as relative density is low, chemical-resistant resistance and inexpensive, easy machine-shaping, become one of kind that rate of growth is the fastest in the synthetic resins, new product development is the most active, but, because some defectives that self also exist, poor as the transparency, impact property is bad, and the tensile strength of material, thermotolerance etc. are resisted the ability of external force effect, has still limited the range of application of polypropylene material to a great extent.
Thereby the development research modified polypropene becomes the main direction of polypropylene development, wherein adds nucleator and be to make one of the most economical of modified polypropene and effective ways that technical difficulty is low.Japanese hamad finds that sorbyl alcohol contracts behind the nucleating effect of two phenyl aldehydes (DBS) from the seventies, the one-tenth nuclear technique of this class material has obtained general application in worldwide, comprising the application in polypropylene, make mechanical propertys such as the polyacrylic transparency, transmittance and the tensile strength of having added nucleator, flexural strength, shock strength all obtain remarkable improvement.Its mechanism of action is: when melt polypropylene cools off, nucleator is dispersed in the melt polypropylene as the out-phase nucleus with extremely small solid particulate form on the one hand, reduce polypropylene and become the needed interfacial free energy of crystalline nucleation, promoted that the polypropylene segment is center crystallization simultaneously with this kind nucleus, on the other hand, because increasing of nucleation centre number, nucleus growth leeway is diminished, when crystal growth stops crystallization when running into another crystal, thereby make the polypropylene crystal become tiny, make polyacrylic degree of crystallinity, Tc improves, physicals is also corresponding to be improved, and when polyacrylic spherulite size during less than light wavelength, its transparency also just is improved.
Being used for polypropylene nucleating agent in the market mainly is glucitols and organic phosphate two big classes.Wherein nucleator in organic phosphate class (U.S.Pat.No.5,342,868) because of its fusing point than higher, all poor generally all greater than 300 ℃, thereby limited the application of this nucleator with polyacrylic consistency and dispersiveness; Glucitols nucleator (U.S.Pat.No.5,574,174) is though can significantly improve polyacrylic physical and chemical performance and optical property, and it is more to exist bubble, the problem that smell is bigger.Document such as U.S.Pat.No.4419473 and U.S.Pat.No.5001174 has proposed and can improve these weak points by the method for adding deodovization agent or stablizer, and has obtained certain effect.
Three, summary of the invention
The object of the present invention is to provide a kind of new ethylidene ether structure that has, the polypropylene nucleater that can improve the polyacrylic transparency, tensile strength, impact property.
Another object of the present invention provides a kind of method for preparing above-mentioned nucleator with Xylitol and phenyl aldehyde compounds through catalyzed reaction.
The general structure of new polypropylene nucleater provided by the invention is as follows:
R wherein
1, R
2Represent hydrogen, chlorine, C respectively
1～C
4Alkyl or C
3～C
4The alkyl isomers, R
1And R
2Can be identical, also can be inequality.
Provided by the inventionly prepare the method for above-mentioned nucleator with Xylitol and phenyl aldehyde compounds through catalyzed reaction, this method adopts following steps and condition:
1) Xylitol and phenyl aldehyde compounds are joined in the reactor that is placed with cyclohexane solvent by 1: 1.9～3 mol ratio, stir and be heated to boiling;
2) adding with the Xylitol mol ratio is 0.1～0.05 an acidic catalyst, react that the removal solvent promptly gets product after 3.5～6 hours;
3) adding volume ratio in product is 1: 1～3 hexanaphthene: acetone mixings clean-out system, and after being 8～10 with pH regulator agent adjusting pH value, heat, stirring and washing is 1～3 hour under the boiling condition, suction filtration;
4) in the suction filtration products therefrom, continue to add clean-out system and clean suction filtration, vacuum drying then at normal temperatures.
The described phenyl aldehyde compounds of step 1) is one or both in phenyl aldehyde, p-tolyl aldehyde, the 4-chloro-benzaldehyde in aforesaid method.
When described phenyl aldehyde compounds is selected two kinds for use, in order to suppress the too much generation of side reaction, should add reaction step by step, the step that adds reaction is:
1) Xylitol and a kind of phenyl aldehyde compounds are wherein joined in the reactor that is placed with cyclohexane solvent, stir and be heated to boiling;
2) adding and Xylitol mol ratio are 0.1～0.05 an acidic catalyst, react to add another kind of phenyl aldehyde compounds after 2～3 hours again, continue to react under the boiling condition 2～3 hours, remove solvent and promptly get product.
It is the same that products therefrom is carried out follow-up cleaning, suction filtration, drying and other steps and condition, and the mol ratio of added two kinds of phenyl aldehyde compounds and Xylitol still is 1.9～3: 1.
Step 2 in aforesaid method) described an acidic catalyst is tosic acid or dilute sulphuric acid; The described pH regulator agent of step 3) is sodium hydroxide or potassium hydroxide solution; The described clean-out system of step 4) is methyl alcohol or acetone.
Four, embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above still belong to protection scope of the present invention.
Embodiment 1
Present embodiment is the synthetic of diphenylmethylene Xylitol, and its reaction formula is:
In a reactor that thermometer, agitator and water trap be housed, add 0.1mol Xylitol, 0.198mol phenyl aldehyde and 350ml solvent hexanaphthene, mix also being warming up to boiling through abundant stirring and dissolving; Add the 0.005mol tosic acid again, steam solvent with ordinary method and promptly get product after 4 hours in reaction under the boiling condition; The adding volume ratio is 1: 1 a hexanaphthene in product: acetone mixing clean-out system 300ml, and behind the ethanolic soln regulation system pH value to 9 with 1M sodium hydroxide, heating, stirring and washing is 3 hours under the boiling condition, suction filtration; Products therefrom is continued at normal temperatures with behind the cleaning of 100ml acetone, the suction filtration, and vacuum drying promptly obtains the white powder solid.196～197 ℃ of this white powder solid fusing points; Proton nmr spectra (δ ppm) 5.7
7.38,7.48
Do not go out near the 10ppm peak (do not have-CHO): carbon-13 nmr spectra (δ ppm): 128.0
Infrared spectra (cm
-1): 1168
3320 (OH).
Embodiment 2
Present embodiment is the synthetic of two (to the methylbenzene methylene radical) Xylitol, and its reaction formula is:
In a reaction flask that thermometer, agitator and branch water still be housed, add 0.05mol Xylitol, 0.15mol p-tolyl aldehyde and 300ml solvent hexanaphthene, mix also being warming up to boiling through abundant stirring and dissolving; Add the 0.0028mol tosic acid again, steam solvent with ordinary method and promptly get product after 3.5 hours in reaction under the boiling condition; The adding volume ratio is 1: 1 a hexanaphthene in product: acetone mixing clean-out system 200ml, and behind the ethanolic soln regulation system pH value to 8 with 1M potassium hydroxide, heating, stirring and washing is 3 hours under the boiling condition, suction filtration; Products therefrom is continued at normal temperatures with behind the cleaning of 50ml acetone, the suction filtration, and vacuum drying promptly obtains the white powder solid.238～239 ℃ of this white powder solid fusing points. proton nmr spectra (δ ppm) 2.3 (6H;-CH
3) 5.6
7.35 (8H; ), do not go out near the 10ppm peak (do not have-CHO): carbon-13 nmr spectra (δ ppm): 128.0,128.6
Infrared spectra (cm
-1): 1168
3394 (OH).
Embodiment 3
Present embodiment is the synthetic of two (to the chlorobenzene methylene radical) Xylitol, and its reaction formula is:
In a reactor that thermometer, agitator and water trap be housed, add 0.05mol Xylitol, 0.145mol 4-chloro-benzaldehyde and 300ml solvent hexanaphthene, mix also being warming up to boiling through abundant stirring and dissolving; Add the 0.0032mol dilute sulphuric acid again, steam solvent with ordinary method and promptly get product after 3.5 hours in reaction under the boiling condition; The adding volume ratio is 1: 2 a hexanaphthene in product: acetone mixing clean-out system 150ml, and behind the ethanolic soln regulation system pH value to 9 with 1M potassium hydroxide, heating, stirring and washing is 1 hour under the boiling condition, suction filtration; Products therefrom is continued at normal temperatures with behind 75ml washed with methanol, the suction filtration, and vacuum drying promptly obtains the white powder solid.240～241 ℃ of this white powder solid fusing points. proton nmr spectra (δ ppm) 5.7
7.46 (8H; ), do not go out near the 10ppm peak (do not have-CHO): carbon-13 nmr spectra (δ ppm): 127.8
Infrared spectra (cm
-1): 1166
3404 (OH).
Embodiment 4
What present embodiment was a Ben Yajiaji to methylbenzene methylene radical Xylitol is synthetic, and its reaction formula is:
Main reaction:
Side reaction:
In a reactor that thermometer, agitator and water trap be housed, add 0.1mol Xylitol, 0.09mol phenyl aldehyde and 400ml solvent hexanaphthene, mix also being warming up to boiling through abundant stirring and dissolving; Add the 0.098mol tosic acid again, reaction is 2.5 hours under the boiling condition, adds the 0.1mol p-tolyl aldehyde again, reacts after 3 hours, steams solvent with ordinary method and promptly gets product; The adding volume ratio is 1: 1 a hexanaphthene in product: acetone mixing clean-out system 200ml, and behind the ethanolic soln regulation system pH value to 9 with 1M sodium hydroxide, heating, stirring and washing is 2.5 hours under the boiling condition, suction filtration; Products therefrom is continued at normal temperatures with behind the cleaning of 100ml acetone, the suction filtration, and vacuum drying promptly obtains the white powder solid.215～217 ℃ of this white powder solid fusing points. proton nmr spectra (δ ppm): 2.3,2.5 (6H;-CH
3) 5.6
7.38 (8H; ), do not go out near the 10ppm peak (do not have-CHO): carbon-13 nmr spectra (δ ppm): 125.8,128.0
Or
Infrared spectra (cm
-1): 1168
3414 (OH).
Embodiment 5
What present embodiment was a Ben Yajiaji to chlorobenzene methylene radical Xylitol is synthetic, and its reaction formula is:
Main reaction:
Side reaction:
In a reactor that thermometer, agitator and water trap be housed, add 0.1mol Xylitol, 0.1mol phenyl aldehyde and 400ml solvent hexanaphthene, mix also being warming up to boiling through abundant stirring and dissolving; Add the 0.0042mol dilute sulphuric acid again, reaction is 2 hours under the boiling condition, adds the 0.108mol 4-chloro-benzaldehyde again, reacts after 2 hours, steams solvent with ordinary method and promptly gets product; The adding volume ratio is 1: 3 a hexanaphthene in product: acetone mixing clean-out system 250ml, and behind the acetone soln regulation system pH value to 9 with 1M sodium hydroxide, heating, stirring and washing is 2 hours under the boiling condition, suction filtration; Products therefrom is continued at normal temperatures with behind 100ml washed with methanol, the suction filtration, and vacuum drying promptly obtains the white powder solid.210～211 ℃ of this white powder solid fusing points. proton nmr spectra (δ ppm): 2.3 (6H;-CH
3) 5.7
7.38 (8H; ), do not go out near the 10ppm peak (do not have-CHO): carbon-13 nmr spectra (δ ppm): 128.0
Or
Infrared spectra (cm
-1): 1168
3418 (OH).
Embodiment 6
Present embodiment is that its reaction formula is to methylbenzene methylene radical synthetic to chlorobenzene methylene radical Xylitol:
Main reaction:
Side reaction:
In a reactor that thermometer, agitator and water trap be housed, add 0.1mol Xylitol, 0.15mol p-tolyl aldehyde and 400ml solvent hexanaphthene, mix also being warming up to boiling through abundant stirring and dissolving; Add the 0.008mol tosic acid again, reaction is 3 hours under the boiling condition, adds the 0.15mol 4-chloro-benzaldehyde again, reacts after 3 hours, steams solvent with ordinary method and promptly gets product; The adding volume ratio is 1: 2 a hexanaphthene in product: acetone mixing clean-out system 200ml, and behind the ethanolic soln regulation system pH value to 10 with 1M sodium hydroxide, heating, stirring and washing is 2.5 hours under the boiling condition, suction filtration; Products therefrom is continued at normal temperatures with behind the cleaning of 100ml acetone, the suction filtration, and vacuum drying promptly obtains the white powder solid.212～213 ℃ of this white powder solid fusing points. proton nmr spectra (δ ppm) 2.3 (6H;-CH
3) 5.7
7.38 (8H; ), do not go out near the 10ppm peak (do not have-CHO): carbon-13 nmr spectra (δ ppm): 127.8,128.0
Or
Infrared spectra (cm
-1): 1168
3418 (OH).
For some physico-chemical properties and its effect of using in polypropylene material of the nucleator product of understanding the present invention preparation, the present invention has also done following test respectively with products obtained therefrom:
(1) in 0.1～0.5% ratio above embodiment products therefrom is extruded as nucleator and dried PP blend, pelletizing after dry 48 hours, is made DSC with differential scanning calorimeter NETZSCH DSC 204 and is detected, and tests its Tc.Test result sees Table 1.
(2) polypropylene that will be added with nucleator is after dry 48 hours, and it is thick to be injection molded into 1mm, and the twin polishing thin plate that 5cm is square is tested its mist degree and transmittance by GB2410.Test result sees Table 1.
(3) the nucleation polypropylene specimen of granulation is injection molded into the standard batten after dry 48 hours, does the test of mechanical property by GB1040, GB1042, GB1843.Test result sees Table 1.
Table 1
Can see that from above test data polypropylene nucleater provided by the invention has not only improved the transparency of polypropylene material, improve the tensile strength of polypropylene material, flexural strength, physicalies such as shock strength simultaneously, also make polyacrylic Tc obtain bigger raising.Preparation method provided by the invention is also very simple, and technology also is easy to control.Because known acetals nucleator is α type nucleator, infers that thus nucleator of the present invention also belongs to α type nucleator.In view of α type nucleator can be widely used in polyolefinic modification, thereby gained nucleator of the present invention also can be applicable to other polyolefine material, as polyethylene, and polyvinyl chloride etc.
Claims (10)
1, a kind of polypropylene nucleater, the general structure of this nucleator is as follows:
R wherein
1, R
2Represent hydrogen, chlorine, C respectively
1～C
4Alkyl or C
3～C
4The alkyl isomers, R
1And R
2Can be identical, also can be inequality.
2, a kind of method for preparing the described polypropylene nucleater of claim 1, this method adopts following steps and condition:
1) Xylitol and phenyl aldehyde compounds are joined in the reactor that is placed with cyclohexane solvent by 1: 1.9～3 mol ratio, stir and be heated to boiling;
2) adding with the Xylitol mol ratio is 0.1～0.05 an acidic catalyst, react that the removal solvent promptly gets product after 3.5～6 hours;
3) adding volume ratio in product is 1: 1～3 hexanaphthene: acetone mixings clean-out system, and after being 8～10 with pH regulator agent adjusting pH value, heat, stirring and washing is 1～3 hour under the boiling condition, suction filtration;
4) in the suction filtration products therefrom, continue to add clean-out system and clean suction filtration, vacuum drying then at normal temperatures.
3, according to the method for claim 2, wherein the described phenyl aldehyde compounds of step 1) is one or both in phenyl aldehyde, p-tolyl aldehyde, the 4-chloro-benzaldehyde.
4, according to the method for claim 3, when wherein said phenyl aldehyde compounds is selected two kinds for use, should add reaction step by step, the step that adds reaction is:
1) Xylitol and a kind of phenyl aldehyde compounds are wherein joined in the reactor that is placed with cyclohexane solvent, stir and be heated to boiling;
2) adding and Xylitol mol ratio are 0.1～0.05 an acidic catalyst, react to add another kind of phenyl aldehyde compounds after 2～3 hours again, continue to react under the boiling condition 2～3 hours, remove solvent and promptly get product.
5, according to the method for claim 2 or 3 or 4, step 2 wherein) described an acidic catalyst is tosic acid or dilute sulphuric acid.
6, according to the method for claim 2 or 3 or 4, wherein the described pH regulator agent of step 3) is sodium hydroxide or potassium hydroxide solution.
7, according to the method for claim 5, wherein the described pH regulator agent of step 3) is sodium hydroxide or potassium hydroxide solution.
8, according to the method for claim 2 or 3 or 4, wherein the described clean-out system of step 4) is methyl alcohol or acetone.
9, according to the method for claim 5, wherein the described clean-out system of step 4) is methyl alcohol or acetone.
10, according to the method for claim 7, wherein the described clean-out system of step 4) is methyl alcohol or acetone.
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|---|---|---|---|
| CN 200510021265 CN1715316A (en) | 2005-07-15 | 2005-07-15 | Polypropylene nucleating agent and its preparing method |
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|---|---|---|---|
| CN 200510021265 CN1715316A (en) | 2005-07-15 | 2005-07-15 | Polypropylene nucleating agent and its preparing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434607B (en) * | 2008-12-12 | 2010-12-29 | 深圳大学 | Method for synthesizing polyolefin nucleating agent aldehyde alcohol compound |
| CN101475704B (en) * | 2009-01-06 | 2011-06-08 | 华东理工大学 | Polyolefin nucleating agent, and preparation and use thereof |
| CN105061888A (en) * | 2015-08-04 | 2015-11-18 | 天津大学 | Polyhedral oligomeric silsesquioxane-polypropylene nucleating agent and preparation method thereof |
| CN111303098A (en) * | 2018-12-12 | 2020-06-19 | 天津尚德药缘科技股份有限公司 | Sphaelactone dimethylamine fumarate crystal form E and preparation method thereof |
-
2005
- 2005-07-15 CN CN 200510021265 patent/CN1715316A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434607B (en) * | 2008-12-12 | 2010-12-29 | 深圳大学 | Method for synthesizing polyolefin nucleating agent aldehyde alcohol compound |
| CN101475704B (en) * | 2009-01-06 | 2011-06-08 | 华东理工大学 | Polyolefin nucleating agent, and preparation and use thereof |
| CN105061888A (en) * | 2015-08-04 | 2015-11-18 | 天津大学 | Polyhedral oligomeric silsesquioxane-polypropylene nucleating agent and preparation method thereof |
| CN111303098A (en) * | 2018-12-12 | 2020-06-19 | 天津尚德药缘科技股份有限公司 | Sphaelactone dimethylamine fumarate crystal form E and preparation method thereof |
| CN111303098B (en) * | 2018-12-12 | 2022-10-04 | 天津尚德药缘科技股份有限公司 | Sphaelactone dimethylamine fumarate crystal form E and preparation method thereof |
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