CN107778526A - A kind of polypropene composition based on organic hydrazide compound nucleator - Google Patents

A kind of polypropene composition based on organic hydrazide compound nucleator Download PDF

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Publication number
CN107778526A
CN107778526A CN201711156100.3A CN201711156100A CN107778526A CN 107778526 A CN107778526 A CN 107778526A CN 201711156100 A CN201711156100 A CN 201711156100A CN 107778526 A CN107778526 A CN 107778526A
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China
Prior art keywords
polypropylene
carbon number
nucleator
polypropene composition
organic
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Pending
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CN201711156100.3A
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Chinese (zh)
Inventor
张跃飞
周培章
林祥凤
毛静静
李涛
夏民强
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Changsha University of Science and Technology
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Changsha University of Science and Technology
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Priority to CN201711156100.3A priority Critical patent/CN107778526A/en
Publication of CN107778526A publication Critical patent/CN107778526A/en
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    • 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
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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

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  • 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)

Abstract

The invention discloses a kind of polypropene composition based on organic hydrazide compound nucleator.It is based on parts by weight of raw materials including following component：100 parts of polypropylene, organic 0.001 10 parts of hydrazides class nucleator, 0.001 5 parts of antioxidant.The performance of polypropylene material is greatly improved by introducing the preferable modifying agent of high temperature resistant in polypropene composition in the present invention.The present invention is by adjusting each raw material components and its proportioning so that polypropene composition has good heat resistance and lower temperature resistance, excellent mechanical property；And there is antioxidant, service life length.There is good application prospect in polypropylene application field, the exploitation to high-performance polypropylene material is significant.

Description

A kind of polypropene composition based on organic hydrazide compound nucleator
Technical field
It is more particularly to a kind of poly- based on organic hydrazide compound nucleator the invention belongs to polymer modification field Propylene compositions.
Background technology
Polypropylene has low relative density, nontoxic, heat resistance, corrosion resistance, electrical insulating property as general thermoplastic resin It is excellent, heat distortion temperature is high, easy processing and it is inexpensive the advantages that, have been widely used for numerous areas, and also constantly expanding New application.But the shortcomings that its some performance also limit its application, for example its transparency is bad, intensity is undesirable, conductive Poor performance etc..It is modified for disadvantage mentioned above, becomes the focus of Recent study.Polypropylene nucleater species is numerous More, the action effect of different types of Nucleating Agent on Pp is different.Certain form of nucleator such as aryl carboxylic acid salt is to change It is apt to the nucleator of polyacrylic mechanical property, it is possible to increase polyacrylic rigidity；Dibenzal sorbitol class nucleator is to improve to gather The nucleator of the transparent performance of propylene；And some nucleators such as substituted aromatic heterocyclic phosphate class is can both to significantly improve poly- third The rigidity of alkene, the nucleator of polyacrylic transparent performance can also be obviously improved.Organic carboxylate and derivative species nucleator are A kind of polypropylene reinforced modifier, its main function are to improve polyacrylic rigidity, improve polyacrylic crystallization peak temperature.But All with a common feature, they can be significantly improved all nucleators with good nucleating effect in polypropylene Polyacrylic crystallization peak temperature, accelerate polyacrylic crystalline rate, shorten molding cycle, refine polyacrylic spherulite size.This Invention provides brand-new application scheme of a kind of α nucleators in polypropylene, using organic hydrazide kind compound as raw material, passes through extrusion It is granulated, prepares high-performance polypropylene product.
The content of the invention
It is an object of the invention to provide a kind of polypropene composition based on organic hydrazide compound nucleator.
The present invention adopts the following technical scheme that：
The new application of organic hydrazides class nucleator, specifically, application of organic hydrazides class nucleator in polypropylene.
Preferably, organic hydrazides class nucleator of 0.001-10 parts by weight is mixed in the polypropylene of 100 parts by weight, 0.001-5 parts by weight antioxidant.
Preferably, polypropylene uses isotactic polypropylene.
Preferably, antioxidant uses the compound that antioxidant 1010 mixes with irgasfos 168.
Organic hydrazide compound nucleator has following formulas（1）,（2）The compound of expression：
（1）
R in formula1Represent saturation either unsaturated fatty chain, unsaturated finger ring or the aromatic ring that carbon number is 2-30.R2Represent Hydrogen atom, carbon number 1-30 alkyl, carbon number 2-30 alkenyl, carbon number 3-12 cycloalkyl, phenyl, naphthyl, Anthryl or following formula（a）-（d）In any one represent group.More than one hydrogen atom can use methyl, alkyl etc. Can also be the substituents such as hydroxyl, nitro, amino, halogen atom, alkoxy, its substituent can be the same or different.
(a)
（R in formula3Represent carbon number 1-30 alkyl, alkoxy, carbon number 2-30 alkenyl, carbon number 3-12 ring Alkyl, phenyl, naphthyl, anthryl, halogen atom.L represents 1-5 integer.）
(b)
（R in formula5With above-mentioned R3It is synonymous.R5Represent carbon number 1-30 straight-chain or the alkylidene of branched.M represents 0- 5 integer.）
(c)
（R in formula6With above-mentioned R3It is synonymous.N represents 1-5 integer.）
（d）
（R in formula7With above-mentioned R3It is synonymous.R8With above-mentioned R5It is synonymous.O represents 1-5 integer.）
(2)
R in formula9Represent saturation either unsaturated fatty chain, unsaturated finger ring or the aromatic ring that carbon number is 0-30.R10、R11 With above-mentioned R2It is synonymous.
As formula（1）-（2）Represented particular compound, such as adipic acid dibenzoyl hydrazine, suberic acid can be enumerated Dibenzoyl hydrazine, decanedioic acid dibenzoyl hydrazine, adipic dihydrazide, the hydrazides of suberic acid two, sebacic dihydrazide, benzoyl hydrazine, To ethoxybenzene formylhydrazine, 4- amino benzoyl hydrazines, to tert-butyl benzoyl hydrazine.
Preferably, organic hydrazide compound nucleator uses decanedioic acid dibenzoyl hydrazine
Preferably, polypropylene uses common mechanical mixture with organic hydrazide compound nucleator, the hybrid mode of antioxidant.
In summary, the present invention has advantages below：
Present invention raw material based on polypropylene, by adding organic hydrazide compound nucleator, antioxidant, improve poly- third property heat Mechanical property；With excellent mechanical property；And there is antioxidant, service life length.
Embodiment
Embodiment of the present invention is described in further detail with reference to specific embodiment.
Embodiment 1：A kind of polypropene composition based on organic hydrazide compound nucleator in the present embodiment, be by with What lower step was carried out.
By 100g polypropylene, decanedioic acid dibenzoyl hydrazine 0.06g, antioxidant（1010 and 168）0.1g is in high-speed mixer Uniformly mixing 3-8min, obtains mixed material.Mixed material is put into extruding pelletization in double screw extruder, finally combined Thing.
Embodiment 2：As different from Example 1, quality used in decanedioic acid dibenzoyl hydrazine is 0.1g.
Embodiment 3：As different from Example 1, quality used in decanedioic acid dibenzoyl hydrazine is 0.15g.
Embodiment 4：As different from Example 1, quality used in decanedioic acid dibenzoyl hydrazine is 0.2g.
Embodiment 5：As different from Example 1, quality used in decanedioic acid dibenzoyl hydrazine is 0.25g.
Embodiment 6：As different from Example 1, quality used in decanedioic acid dibenzoyl hydrazine is 0.3g.
Embodiment 7：As different from Example 1, quality used in decanedioic acid dibenzoyl hydrazine is 0.4g.
Embodiment 8：As different from Example 1, quality used in decanedioic acid dibenzoyl hydrazine is 0.5g.
Comparative example 1：By 100g polypropylene, antioxidant（1010 and 168）0.1g uniformly mixes 3-8min in high-speed mixer, Obtain mixed material.Mixed material is put into extruding pelletization in double screw extruder, obtains final composition.
The crystallization behavior test result of prepared polypropylene material is as shown in table 1.
The crystallization peak temperature of modified polypropene obtained by the different embodiments of table 1
Above is illustrating for possible embodiments of the invention, but the embodiment and the patent for being not used to the limitation present invention Scope, all equivalence enforcements or change without departing from the present invention, it is intended to be limited solely by the scope of the claims of the present invention.

Claims (5)

  1. A kind of 1. polypropene composition based on organic hydrazide compound nucleator, it is characterised in that the polypropene composition It is made up of polypropylene, organic hydrazide compound nucleator, antioxidant.
  2. 2. a kind of polypropene composition based on organic hydrazide compound nucleator according to claim 1, its feature exist Organic hydrazides class nucleator of 0.001-10 parts by weight is mixed in the polypropylene in 100 parts by weight, 0.001-5 parts by weight resist Oxygen agent.
  3. 3. a kind of polypropene composition based on organic hydrazide compound nucleator according to claim 1, its feature exist In polypropylene be isotactic polypropylene, syndiotactic polypropylene, random polypropylene.
  4. 4. a kind of polypropene composition based on organic hydrazide compound nucleator according to claim 1, its feature exist There are following formulas in organic hydrazides class nucleator（1）、（2）The compound of expression：
    （1）
    R in formula1Represent saturation either unsaturated fatty chain, unsaturated finger ring or the aromatic ring that carbon number is 2-30.R2Represent hydrogen Atom, carbon number 1-30 alkyl, carbon number 2-30 alkenyl, carbon number 3-12 cycloalkyl, phenyl, naphthyl, anthracene Base or following formula（a）-（d）In any one represent group；More than one hydrogen atom can use methyl, alkyl etc. Can be the substituents such as hydroxyl, nitro, amino, halogen atom, alkoxy, its substituent can be the same or different；
    (a)
    （R in formula3Represent carbon number 1-30 alkyl, alkoxy, carbon number 2-30 alkenyl, carbon number 3-12 cycloalkanes Base, phenyl, naphthyl, anthryl, halogen atom；L represents 1-5 integer）
    (b)
    （R in formula5With above-mentioned R3It is synonymous；R5Represent carbon number 1-30 straight-chain or the alkylidene of branched；M represents 0- 5 integer）
    (c)
    （R in formula6With above-mentioned R3It is synonymous；N represents 1-5 integer）
    (d)
    （R in formula7With above-mentioned R3It is synonymous；R8With above-mentioned R5It is synonymous；O represents 1-5 integer）
    (2)
    R in formula9Represent saturation either unsaturated fatty chain, unsaturated finger ring or the aromatic ring that carbon number is 0-30；R10、R11With Above-mentioned R2It is synonymous.
  5. 5. a kind of polypropene composition based on organic hydrazide compound nucleator according to claim 1, its feature exist In antioxidant be phenolic antioxidant or phenolic antioxidant and phosphoric acid ester antioxidant in mass ratio 1:The compound of 1 mixing, wherein Phenolic antioxidant is using four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 3- (3.5 couples of tertiary butyl -4- Hydroxy-cyclohexyl) propionic ester, 1,3,5, three (3,5- di-t-butyls, 4- hydroxybenzyls) s-triazine, 2,4,5- (1H, 3H, 5H) three Ketone or 3,3,3,5,5,5- six tert-butyl group-a, a, a- (bases of 1,3,5- trimethylbenzenes -2,4,6- three) three-p- cresols；Phosphorus system antioxygen Agent is using three (2,4- di-tert-butyl-phenyls) phosphite esters, double (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites or double (2,6- di-tert-butyl-phenyls) phosphite ester, double (2,4- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphites.
CN201711156100.3A 2017-11-20 2017-11-20 A kind of polypropene composition based on organic hydrazide compound nucleator Pending CN107778526A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424545A (en) * 2018-04-27 2018-08-21 长沙理工大学 A kind of composite nucleating agent and its polypropene composition replacing hydrazides based on phenyl
CN108440786A (en) * 2018-04-27 2018-08-24 长沙理工大学 A kind of composite nucleating agent and its polypropene composition replacing hydrazides based on alkyl
CN108517053A (en) * 2018-04-27 2018-09-11 长沙理工大学 A kind of composite nucleating agent and its polypropene composition replacing hydrazides based on cyclohexyl
CN109942887A (en) * 2019-03-18 2019-06-28 朴蓝聚烯烃科技发展（上海）有限公司 A kind of polypropene composition based on three hydrazide compound nucleating agents
CN117106237A (en) * 2023-07-05 2023-11-24 湖南联塑科技实业有限公司 Composite modifier and polypropylene composition thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102137893A (en) * 2008-08-28 2011-07-27 株式会社Adeka Polyolefin resin composition
CN102344389A (en) * 2011-10-17 2012-02-08 姚建文 Double-hindered phenol structure-contained hydrazides compound and preparation method thereof
CN102510877A (en) * 2009-10-23 2012-06-20 株式会社艾迪科 Polyolefin resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102137893A (en) * 2008-08-28 2011-07-27 株式会社Adeka Polyolefin resin composition
CN102977439A (en) * 2008-08-28 2013-03-20 株式会社Adeka Polyolefin resin composition
CN102510877A (en) * 2009-10-23 2012-06-20 株式会社艾迪科 Polyolefin resin composition
CN102344389A (en) * 2011-10-17 2012-02-08 姚建文 Double-hindered phenol structure-contained hydrazides compound and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424545A (en) * 2018-04-27 2018-08-21 长沙理工大学 A kind of composite nucleating agent and its polypropene composition replacing hydrazides based on phenyl
CN108440786A (en) * 2018-04-27 2018-08-24 长沙理工大学 A kind of composite nucleating agent and its polypropene composition replacing hydrazides based on alkyl
CN108517053A (en) * 2018-04-27 2018-09-11 长沙理工大学 A kind of composite nucleating agent and its polypropene composition replacing hydrazides based on cyclohexyl
CN109942887A (en) * 2019-03-18 2019-06-28 朴蓝聚烯烃科技发展（上海）有限公司 A kind of polypropene composition based on three hydrazide compound nucleating agents
CN117106237A (en) * 2023-07-05 2023-11-24 湖南联塑科技实业有限公司 Composite modifier and polypropylene composition thereof
CN117106237B (en) * 2023-07-05 2024-03-26 湖南联塑科技实业有限公司 Composite modifier and polypropylene composition thereof

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Application publication date: 20180309