CN105602115B - Polypropylene nucleating agent composition and preparation method thereof - Google Patents
Polypropylene nucleating agent composition and preparation method thereof Download PDFInfo
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- CN105602115B CN105602115B CN201610174573.5A CN201610174573A CN105602115B CN 105602115 B CN105602115 B CN 105602115B CN 201610174573 A CN201610174573 A CN 201610174573A CN 105602115 B CN105602115 B CN 105602115B
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- nucleating agent
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- 239000002667 nucleating agent Substances 0.000 title claims abstract description 32
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 24
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- -1 Polypropylene Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 7
- 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 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 26
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical group OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000006911 nucleation Effects 0.000 claims 1
- 238000010899 nucleation Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 abstract 1
- WXWQVSOHWXJBDF-UHFFFAOYSA-N benzene-1,3,5-tricarboxamide Chemical compound NC(=O)C1=CC(C(N)=O)=CC(C(N)=O)=C1 WXWQVSOHWXJBDF-UHFFFAOYSA-N 0.000 abstract 1
- 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 compound 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
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 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
- 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
- 238000003756 stirring Methods 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 238000000593 microemulsion method 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
- 235000009566 rice Nutrition 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a polypropylene nucleating agent composition and a preparation method thereof. The nucleating agent composition is composed of an organic nucleating agent 1,3, 5-benzene tricarbonamide nucleating agent and a nano graphene material, the weight ratio of the organic nucleating agent 1,3, 5-benzene tricarbonamide nucleating agent to the nano graphene material is 5: 1-1: 5, and the nucleating agent composition is in a micro-emulsion state. The preparation method of the nucleating agent comprises the following steps: (1) dispersing a nano graphene material in deionized water, and dissolving a 1,3, 5-benzene trimethyl amide nucleating agent in N, N-dimethylformamide; (2) and (3) uniformly mixing the nano graphene material aqueous dispersion liquid obtained in the step (A) and the N, N-dimethylformamide dissolved with the 1,3, 5-benzene tricarboxamide nucleating agent with a surfactant to form a microemulsion. The nucleating agent has the advantages of high efficiency, simple preparation process, obvious improvement on the mechanical property of polypropylene, improvement on the transparency of polypropylene and the like.
Description
Technical field
The present invention relates to a kind of polypropylene nucleater composition, it particularly relates to which a kind of organic nucleating agent is received with inorganic
The composite nucleating agent of rice grapheme material, belongs to field of novel.
Background technology
Polypropylene (PP) is a kind of widely used general-purpose thermoplastic plastic, although it has lot of advantages, is also deposited
In place of some shortcomings, such as crystallization rate is slower, it is transparent poor the shortcomings of.Nucleator is added in PP improves PP mechanics
Performance and optical property, accelerate PP crystallization rates, shorten product molding cycle etc., are current most widely used method of modifying.
Polyacrylic nucleator can improve crystalling propylene behavior, so as to improve its physical and mechanical properties and thermodynamics
Energy.Nucleator can be divided into inorganic, phosphate metal salt, carboxylic acid metal's salt, glucitols high score subclass nucleator.In recent years
Take nucleator to quickly grow, the efficient nucleation agent being widely used at present mainly includes aryl-heterocyclic phosphate and glucitol derivative
Two major classes, but also have its defect, such as the compatibility with PP is poor, PP rigid improvement is not obvious etc..
Organic nucleating agent 1,3,5- benzene trimethamide class Nucleating Agent on Pp hot propertys and mechanical property have very big
Improve, especially rigid lifting is it is obvious that and can make polyacrylic mist degree significantly decline.Nano-graphene material can be with
Largely improve PP mechanical performance（Yield strength, Young's modulus etc.）, but nano-graphene material is scattered in PP
Property limit its large-scale application, the side that 1,3,5- benzene trimethamide class nucleator and nano-graphene material are passed through into microemulsion
Method prepares nucleating agent compositions, can not only improve dispersiveness of the nano-graphene material in polypropylene, make nucleating effect more
Plus substantially, and because the presence of 1,3,5- benzene trimethamide class nucleators can be greatly lowered its mist degree, while two kinds
The mechanical property of Nucleating Agent on Pp also has obvious improvement.
The content of the invention
The invention provides a kind of simple polypropylene nucleating agent compositions of new, efficient, preparation technology.Using organic
Nucleator 1,3,5- benzene trimethamide class nucleator is blended to form the method for microemulsion to prepare with inorganic nano grapheme material
Nucleator, both have cooperative effect, and method is simple, good dispersion, excellent nucleating effect, improvement mechanical property, reduction mist degree
The advantages of.
Organic nucleating agent 1,3,5- benzenetricarboxylic acids three (cyclohexylamine) of the present invention are synthesized by following steps：Cyclohexylamine is with doing
1-METHYLPYRROLIDONE and pyridine are added after the stirring of dry lithium chloride, constant temperature is to 5 DEG C in ice-water bath, then adds into system 1,3,
The formyl chloride of 5- benzene three, is increased to 75 DEG C by reaction temperature rapidly, and being stirred continuously makes mixture fully react 2.5h, finally will reflection
Product, which is poured into, separates out precipitation in frozen water, recrystallized after filtering.Wherein cyclohexylamine, lithium chloride and 1, the formyl chloride of 3,5- benzene three
Weight ratio is 8.9 ~ 9.2:0.9~1.1:8.0 ~ 8.2, the portion rate for adding 1-METHYLPYRROLIDONE and pyridine and lithium chloride is 290
~310:45~55:0.9~1.1.The product is white crystal.
The specific preparation process of nucleating agent compositions of the present invention is：Nano-graphene material is scattered in deionized water
In, ultrasound 30 minutes obtains dispersed nano-graphene material dispersion liquid.Supersonic frequency is 70kHz ~ 90kHz, ultrasound time
Number 1 time ~ 2 times, ultrasonic time 15min ~ 30min.
1,3,5- benzene trimethamide class nucleator is dissolved in DMF, then with above-mentioned nano-graphene
Material dispersion liquid is mixed into microemulsion jointly, adds surfactant.Wherein 1,3,5- benzene trimethamide class nucleator and nanometer
Grapheme material weight ratio is 5:1~1:5.
Above-mentioned prepared nucleating agent compositions state is microemulsion, and nucleating agent compositions addition polypropylene powder is mixed
Close, add antioxidant 1010 and 168 after drying simultaneously, carry out processing and forming, extrude, be molded into standard batten.Its concrete composition
For：100 parts of polypropylene, 0.05 ~ 0.2 part of nucleating agent compositions, 0.1 part of antioxidant.
Embodiment
Embodiment 1
Prepare 1,3,5- benzenetricarboxylic acids three (cyclohexylamine) (BTCA-TCHA)：Cyclohexylamine after drying lithium chloride stirring with adding
1-METHYLPYRROLIDONE and pyridine, constant temperature adds the formyl chloride of 1,3,5- benzene three to 5 DEG C, then into system in ice-water bath, rapidly
Reaction temperature is increased to 75 DEG C, being stirred continuously makes mixture fully react 2.5h, finally reflection product is poured into frozen water and analysed
Go out precipitation, recrystallized after filtering.Wherein cyclohexylamine, lithium chloride and 1, the weight ratio of the formyl chloride of 3,5- benzene three is 9.1:1:
8.1, add the portion rate 300 of 1-METHYLPYRROLIDONE and pyridine and lithium chloride:50:1, the BTCA-TCHA prepared is dissolved in
In N,N-dimethylformamide.
Nano-graphene material is scattered in deionized water, ultrasound 30 minutes obtains dispersed nano-graphene
Material dispersion liquid.Supersonic frequency is 80kHz, ultrasonic number of times 1 time, ultrasonic time 20min.
It will disperse dissolved with the N,N-dimethylformamide of 1,3,5- benzenetricarboxylic acids three (cyclohexylamine) with nano-graphene material
Liquid is mixed jointly, adds surfactant, wherein 1,3,5- benzenetricarboxylic acid three (cyclohexylamine) and nano-graphene material weight ratio
For 5:1, magnetic stirrer 10min is used after mixing, then ultrasound 10min, obtains nucleating agent compositions dispersion liquid.
Nucleating agent compositions are added into polypropylene powder to mix, while adding antioxidant 1010 and 168, carried out into after drying
Type is processed, and is extruded, is molded into standard batten.It is specifically comprised：100 parts of polypropylene, 0.06 part of nucleating agent compositions, antioxidant
0.1 part, obtain standard batten 1.
Embodiment 2
The present embodiment 1,3,5- benzenetricarboxylic acids three (cyclohexylamine) and nano-graphene material weight as different from Example 1
Than for 4:2, standard batten 2 is obtained, remaining is same as Example 1.
Embodiment 3
The present embodiment 1,3,5- benzenetricarboxylic acids three (cyclohexylamine) and nano-graphene material weight as different from Example 1
Than for 3:3, standard batten 3 is obtained, remaining is same as Example 1.
Embodiment 4
The present embodiment 1,3,5- benzenetricarboxylic acids three (cyclohexylamine) and nano-graphene material weight as different from Example 1
Than for 2:4, standard batten 4 is obtained, remaining is same as Example 1.
Embodiment 5
The present embodiment 1,3,5- benzenetricarboxylic acids three (cyclohexylamine) and nano-graphene material weight as different from Example 1
Than for 1:5, standard batten 5 is obtained, remaining is same as Example 1.
Claims (2)
1. a kind of polypropylene nucleater composition, it is characterised in that the nucleating agent compositions are by the benzene three of organic nucleating agent 1,3,5-
Benzamide type nucleator, nano-graphene material, deionized water, DMF and surfactant are constituted, its
The weight ratio of middle 1,3,5- benzene trimethamide class nucleator and nano-graphene material is 5:1~1:5；
The preparation method of above-mentioned polypropylene nucleater composition comprises the following steps：
(1) nano-graphene material is scattered in deionized water, 1,3,5- benzene trimethamide class nucleator is dissolved in N, N- bis-
In NMF；
(2) the nano-graphene material aqueous dispersion liquid that obtains above-mentioned steps and dissolved with 1,3,5- benzene trimethamide class nucleation
The DMF of agent is uniformly mixed with surfactant, forms microemulsion；
The nano-graphene material is graphene oxide or graphene；
The organic nucleating agent 1,3,5- benzene trimethamide class nucleator is 1,3,5- benzenetricarboxylic acids three (cyclohexylamine)；
The surfactant is glycerin monostearate.
2. polypropylene nucleater composition according to claim 1, it is characterised in that the nucleating agent compositions are micro emulsion
Liquid status.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610174573.5A CN105602115B (en) | 2016-03-25 | 2016-03-25 | Polypropylene nucleating agent composition and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610174573.5A CN105602115B (en) | 2016-03-25 | 2016-03-25 | Polypropylene nucleating agent composition and preparation method thereof |
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| Publication Number | Publication Date |
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| CN105602115A CN105602115A (en) | 2016-05-25 |
| CN105602115B true CN105602115B (en) | 2017-09-08 |
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| CN106750909A (en) * | 2016-12-01 | 2017-05-31 | 长沙理工大学 | Composite nucleating agent based on trimesoyl triamide and polypropylene composition |
| CN106750910A (en) * | 2016-12-01 | 2017-05-31 | 长沙理工大学 | Polypropylene composite nucleating agent 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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| CN102731832B (en) * | 2012-07-05 | 2013-11-06 | 四川大学 | Graphene-loaded beta nucleating agent, preparation method and application thereof |
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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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