CN105602115A - Polypropylene nucleator composition and preparation method thereof - Google Patents
Polypropylene nucleator composition and preparation method thereof Download PDFInfo
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- CN105602115A CN105602115A CN201610174573.5A CN201610174573A CN105602115A CN 105602115 A CN105602115 A CN 105602115A CN 201610174573 A CN201610174573 A CN 201610174573A CN 105602115 A CN105602115 A CN 105602115A
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- nucleator
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- polypropylene
- preparation
- nucleating agent
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- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 27
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 27
- -1 Polypropylene Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 5
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000002667 nucleating agent Substances 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical class ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003595 mist Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses a polypropylene nucleator composition and a preparation method thereof. The nucleator composition is composed of an organic nucleator 1,3,5-phenyltrimethamide nucleator and a nano graphene material in a weight ratio of 5:1-1:5. The nucleator composition is in a microemulsion state. The preparation method of the nucleator comprises the following steps: (1) dispersing the nano graphene material in deionized water, and dissolving the 1,3,5-phenyltrimethamide nucleator in N,N-dimethylformamide; and (2) uniformly mixing the nano graphene material water-phase dispersion solution and the 1,3,5-phenyltrimethamide-nucleator-dissolved N,N-dimethylformamide with a surfactant to form the microemulsion. The nucleator has the advantages of high efficiency, simple preparation technique and the like, obviously improves the mechanical properties of the polypropylene and enhances the transparency of the polypropylene.
Description
Technical field
The present invention relates to a kind of polypropylene nucleater composition, specifically, relate to the composite nucleating agent of a kind of organic nucleating agent and inorganic nano grapheme material, belong to field of novel.
Background technology
Polypropylene (PP) is a kind of widely used general-purpose thermoplastic plastic, although it has lot of advantages, the part that also comes with some shortcomings, such as shortcomings such as crystallization rate are slow, the transparency is poor. In PP, adding nucleator and improve PP mechanical property and optical property, accelerate PP crystallization rate, shorten the product molding cycle etc., is current most widely used method of modifying.
Polyacrylic nucleator can improve crystalling propylene behavior, thereby improves its physical and mechanical properties and thermodynamic property. Nucleator can be divided into mineral-type, phosphate metal salt, carboxylic acid metal's salt, glucitols high score subclass nucleator. Rapidly, the efficient nucleator of extensive use at present mainly comprises aryl-heterocyclic phosphate and the large class of glucitol derivative two, but also has its defect, such as rigidity poor with the compatibility of PP, PP is improved DeGrain etc. in nucleator development in recent years.
Organic nucleating agent 1,3,5-benzene trimethamide class Nucleating Agent on Pp hot property and mechanical property have very large improvement, and especially the lifting of rigidity clearly, and can make polyacrylic mist degree significantly decline. nano-graphene material can largely improve the mechanical performance (yield strength of PP, Young's modulus etc.), but the dispersiveness of nano-graphene material in PP limited its large-scale application, by 1, 3, 5-benzene trimethamide class nucleator and nano-graphene material are prepared nucleating agent compositions by the method for microemulsion, not only can improve the dispersiveness of nano-graphene material in polypropylene, make nucleating effect more obvious, and because 1, 3, the existence of 5-benzene trimethamide class nucleator can make its mist degree significantly reduce, the mechanical property of two kinds of Nucleating Agent on Pps also has obvious improvement simultaneously.
Summary of the invention
The invention provides a kind of novel, efficient, simple polypropylene nucleating agent compositions of preparation technology. Adopt organic nucleating agent 1,3,5-benzene trimethamide class nucleator and the blend of inorganic nano grapheme material form the method for microemulsion and prepare nucleator, and both have cooperative effect, and method is simple, good dispersion, nucleating effect are good, improve mechanical property, reduce the advantages such as mist degree.
Organic nucleating agent 1 of the present invention, 3,5-benzenetricarboxylic acid three (cyclohexylamine) is synthesized by following steps: cyclohexylamine and dry lithium chloride add 1-METHYLPYRROLIDONE and pyridine after stirring, constant temperature to 5 DEG C in ice-water bath, then add 1 in system, 3,5-benzene three formyl chlorides, are increased to reaction temperature 75 DEG C rapidly, constantly stir and make mixture fully react 2.5h, finally reflection product is poured in frozen water and separated out precipitation, after filtration, be recrystallized. Wherein cyclohexylamine, the weight ratio of lithium chloride and 1,3,5-benzene, three formyl chlorides is 8.9 ~ 9.2:0.9 ~ 1.1:8.0 ~ 8.2, the portion rate that adds 1-METHYLPYRROLIDONE and pyridine and lithium chloride is 290 ~ 310:45 ~ 55:0.9 ~ 1.1. This product is white crystal.
The concrete preparation process of nucleating agent compositions of the present invention is: nano-graphene dispersion of materials, in deionized water, ultrasonic 30 minutes, is obtained to homodisperse nano-graphene dispersion of materials liquid. Supersonic frequency is 70kHz ~ 90kHz, ultrasonic number of times 1 time ~ 2 times, ultrasonic time 15min ~ 30min.
1,3,5-benzene trimethamide class nucleator is dissolved in DMF, is then jointly mixed into microemulsion with above-mentioned nano-graphene dispersion of materials liquid, add surfactant. Wherein 1,3,5-benzene trimethamide class nucleator with nano-graphene material weight than being 5:1 ~ 1:5.
Above-mentioned prepared nucleating agent compositions state is microemulsion, adds polypropylene powder to mix nucleating agent compositions, after being dried, adds antioxidant 1010 and 168 simultaneously, carries out processing and forming, extrudes, is injection molded into standard batten. It specifically consists of: 100 parts of polypropylene, 0.05 ~ 0.2 part of nucleating agent compositions, 0.1 part, antioxidant.
Detailed description of the invention
Embodiment 1
Preparation 1,3,5-benzenetricarboxylic acid three (cyclohexylamine) is (BTCA-TCHA): cyclohexylamine and dry lithium chloride add 1-METHYLPYRROLIDONE and pyridine after stirring, constant temperature to 5 DEG C in ice-water bath, then add 1 in system, 3,5-benzene three formyl chlorides, are increased to reaction temperature 75 DEG C rapidly, constantly stir and make mixture fully react 2.5h, finally reflection product is poured in frozen water and separated out precipitation, after filtration, be recrystallized. Wherein cyclohexylamine, the weight ratio of lithium chloride and 1,3,5-benzene, three formyl chlorides is 9.1:1:8.1, adds the portion rate 300:50:1 of 1-METHYLPYRROLIDONE and pyridine and lithium chloride, and the BTCA-TCHA preparing is dissolved in DMF.
Nano-graphene dispersion of materials, in deionized water, ultrasonic 30 minutes, is obtained to homodisperse nano-graphene dispersion of materials liquid. Supersonic frequency is 80kHz, ultrasonic number of times 1 time, ultrasonic time 20min.
To be dissolved with 1,3, the DMF of 5-benzenetricarboxylic acid three (cyclohexylamine) mixes jointly with nano-graphene dispersion of materials liquid, adds surfactant, wherein 1,3,5-benzenetricarboxylic acid three (cyclohexylamine) than being 5:1, adopts magnetic stirrer 10min after mixing with nano-graphene material weight, then ultrasonic 10min, obtains nucleating agent compositions dispersion liquid.
Add polypropylene powder to mix nucleating agent compositions, add antioxidant 1010 and 168 simultaneously, after being dried, carry out processing and forming, extrude, be injection molded into standard batten. It specifically consists of: 100 parts of polypropylene, and 0.06 part of nucleating agent compositions, 0.1 part, antioxidant, obtains standard batten 1.
Embodiment 2
The present embodiment as different from Example 11,3,5-benzenetricarboxylic acid three (cyclohexylamine) than being 4:2, obtains standard batten 2 with nano-graphene material weight, and all the other are identical with embodiment 1.
Embodiment 3
The present embodiment as different from Example 11,3,5-benzenetricarboxylic acid three (cyclohexylamine) than being 3:3, obtains standard batten 3 with nano-graphene material weight, and all the other are identical with embodiment 1.
Embodiment 4
The present embodiment as different from Example 11,3,5-benzenetricarboxylic acid three (cyclohexylamine) than being 2:4, obtains standard batten 4 with nano-graphene material weight, and all the other are identical with embodiment 1.
Embodiment 5
The present embodiment as different from Example 11,3,5-benzenetricarboxylic acid three (cyclohexylamine) than being 1:5, obtains standard batten 5 with nano-graphene material weight, and all the other are identical with embodiment 1.
Claims (6)
1. a polypropylene nucleater composition, is characterized in that described nucleating agent compositions is by organic nucleating agent 1,3,5-benzene trimethamide class nucleator and nano-graphene material composition, and its weight ratio is 5:1 ~ 1:5.
2. polypropylene nucleater composition according to claim 1, is characterized in that described organic nucleating agent 1,3,5-benzene trimethamide class nucleator be 1,3,5-benzenetricarboxylic acid three (cyclohexylamine) (BTCA-TCHA).
3. polypropylene nucleater composition according to claim 1, is characterized in that described nano-graphene material is graphene oxide or Graphene.
4. polypropylene nucleater composition according to claim 1, its preparation method comprise the steps: (1) by nano-graphene dispersion of materials in deionized water, 1,3,5-benzene trimethamide class nucleator is dissolved in DMF; (2) nano-graphene material water phase dispersant liquid above-mentioned steps being obtained and the DMF that is dissolved with 1,3,5-benzene trimethamide class nucleator evenly mix with surfactant, form microemulsion.
5. the preparation method of polypropylene nucleater composition according to claim 4, is characterized in that described nucleating agent compositions is microemulsion state.
6. the preparation method of polypropylene nucleater composition according to claim 4, is characterized in that described surfactant is glycerin monostearate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610174573.5A CN105602115B (en) | 2016-03-25 | 2016-03-25 | A kind of polypropylene nucleater composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610174573.5A CN105602115B (en) | 2016-03-25 | 2016-03-25 | A kind of polypropylene nucleater composition and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN105602115A true CN105602115A (en) | 2016-05-25 |
| CN105602115B CN105602115B (en) | 2017-09-08 |
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| CN201610174573.5A Active CN105602115B (en) | 2016-03-25 | 2016-03-25 | A kind of polypropylene nucleater composition and preparation method thereof |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750909A (en) * | 2016-12-01 | 2017-05-31 | 长沙理工大学 | A kind of composite nucleating agent and polypropene composition based on equal benzene trimethamide |
| CN106750910A (en) * | 2016-12-01 | 2017-05-31 | 长沙理工大学 | A kind of polypropylene composite materials nucleator based on self assembly and preparation method thereof |
| CN107043475A (en) * | 2017-04-21 | 2017-08-15 | 厦门正新橡胶工业有限公司 | Graphene pickering emulsion optimization rubber composition and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN102731832A (en) * | 2012-07-05 | 2012-10-17 | 四川大学 | Graphene-loaded beta nucleating agent, preparation method and application thereof |
-
2016
- 2016-03-25 CN CN201610174573.5A patent/CN105602115B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731832A (en) * | 2012-07-05 | 2012-10-17 | 四川大学 | Graphene-loaded beta nucleating agent, preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 张跃飞 等: "1,3,5-苯三甲酸三（环己胺）在PP中的成核效应", 《工程塑料应用》 * |
| 张跃飞 等: "1,3,5-苯三甲酸衍生物类新型成核剂的合成及应用研究", 《中国塑料》 * |
| 张跃飞 等: "成核剂1,3,5-苯三甲酸三（环己胺）作用下聚丙烯的等温结晶动力学研究", 《塑料工业》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750909A (en) * | 2016-12-01 | 2017-05-31 | 长沙理工大学 | A kind of composite nucleating agent and polypropene composition based on equal benzene trimethamide |
| CN106750910A (en) * | 2016-12-01 | 2017-05-31 | 长沙理工大学 | A kind of polypropylene composite materials nucleator based on self assembly and preparation method thereof |
| CN107043475A (en) * | 2017-04-21 | 2017-08-15 | 厦门正新橡胶工业有限公司 | Graphene pickering emulsion optimization rubber composition and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN105602115B (en) | 2017-09-08 |
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Effective date of registration: 20221221 Address after: 410203 Building A1-1 and A1-2, Xinya Venture Park, Huashi Village, Tongguan Town, Wangcheng District, Changsha City, Hunan Province Patentee after: HUNAN SHENGYANG NEW MATERIAL Co.,Ltd. Address before: 410114 No. two, 960 Wan Li Li South Road, Yuhua District, Changsha, Hunan Patentee before: CHANGSHA University OF SCIENCE AND TECHNOLOGY |
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