CN105001480A - Complex antioxidant for polyolefin and preparing method of complex antioxidant - Google Patents

Complex antioxidant for polyolefin and preparing method of complex antioxidant Download PDF

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Publication number
CN105001480A
CN105001480A CN201510446650.3A CN201510446650A CN105001480A CN 105001480 A CN105001480 A CN 105001480A CN 201510446650 A CN201510446650 A CN 201510446650A CN 105001480 A CN105001480 A CN 105001480A
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China
Prior art keywords
antioxidant
composite antioxidant
polyolefinic
weight percent
aperture
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CN201510446650.3A
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Chinese (zh)
Inventor
朱浩良
潘勇
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Wuhan Sanyou Petrochemical Co Ltd
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Wuhan Sanyou Petrochemical Co Ltd
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Priority to CN201510446650.3A priority Critical patent/CN105001480A/en
Publication of CN105001480A publication Critical patent/CN105001480A/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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • 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

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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 complex antioxidant for polyolefin and a preparing method of the complex antioxidant. The complex antioxidant comprises, by weight, 30-70% of antioxidant 1010, 15-50% of antioxidant 626, 2-15% of DHT-4A, 1-5% of di-(3,5-tert-butyl-4-hydroxy phenyl) thioether and 1-5% of thiodipropionic acid diester. The antioxidant 1010 is tetra- [beta-(3,5-di-tertiary butyl-4--hydroxy phenyl) propionic acid] pentaerythritol ester, the antioxidant 626 is di-(2,4- di-tertiary butylphenol) pentaerythritol diphosphite, and the DHT-4A is (Mg6A12(OH)16CO34H2O). The complex antioxidant for polyolefin can obviously improve the processing stability and the color improvement of polyolefin under high temperatures, and is simple in formula, low in cost, convenient to use and capable of being widely applied in industrialization production.

Description

A kind of for polyolefinic composite antioxidant and preparation method thereof
Technical field
The present invention and a kind of composite antioxidant, espespecially a kind of for polyolefinic composite antioxidant and preparation method thereof.
Background technology
In each stage of polymkeric substance life cycle, namely in its production, storage, processing, use procedure, all because of self or extraneous factor, oxygenizement can occur, cause decline or the loss of polymkeric substance and product properties thereof, this is also referred to as the aging of macromolecular material.Add oxidation inhibitor and effectively can delay material aging, improve its color and luster and use properties.Current much oxidation inhibitor is that one-component adds, and non-refractory has obvious decline to processing stability polyolefinic under high temperature and color and luster improvement.
Therefore, be necessary design one at high temperature, polyolefinic processing stability and color and luster improvement are all had clear improvement, and formula is simple, cost is lower, easy to use for polyolefinic composite antioxidant, to overcome the problems referred to above.
Summary of the invention
For background technology institute problems faced, the object of the present invention is to provide a kind of under high temperature and ultrahigh-temperature, polyolefinic processing stability and color and luster improvement all to be had clear improvement, and stable performance, cost lower, easy to use for polyolefinic composite antioxidant.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of for polyolefinic composite antioxidant, composed as follows by weight percentage:
Described antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and described oxidation inhibitor 626 is two (2,4 ?DI-tert-butylphenol compounds) pentaerythritol diphosphites, described DHT ?4A be [Mg 6al 2(OH) 16cO 34H 2o].
Preferably, the weight percent of described antioxidant 1010 is 40 ~ 60%.
Preferably, the weight percent of described antioxidant 1010 is 45 ~ 50%.
Preferably, the weight percent of described oxidation inhibitor 626 is 25 ~ 45%.
Preferably, the weight percent of described oxidation inhibitor 626 is 33 ~ 37%.
Preferably, the weight percent of described DHT-4A is 7 ~ 9%.
Preferably, the weight percent of described two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether is 2 ~ 4%.
Preferably, the weight percent of described thio-2 acid dibasic acid esters is 3 ~ 4%.
Preferably, composed as follows by weight percentage:
For a preparation method for polyolefinic composite antioxidant, comprise the steps:
(1) each component mixing, under temperature is 25 DEG C of conditions, is that the speed of 1000rpm stirs 60 seconds with stirring velocity;
(2) get each component after stirring to knock down in Squeezinggranulator and carry out granulation, the heating zone temperature of Squeezinggranulator is 50 DEG C, the temperature of head section is 60 DEG C, obtains particle by being extruded the billot obtained by head by air-cooled travelling belt by its natural fracture;
(3) particle obtained is crossed 3 layers of sieve, the aperture of particle be more than 4mm be finished product, the aperture of particle is less than the recycling of 4mm;
In described step (3), the particle obtained is crossed 3 layers of sieve, the aperture of the first layer sieve is 8mm, the aperture 6mm of second layer sieve, and the aperture of third layer sieve is 4mm.
Described antioxidant 1010 chemistry four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester by name is white crystalline powder, chemical property is stablized, general-purpose plastics can be widely used in, engineering plastics, synthetic rubber, fiber, hot melt adhesive, resin, oil product, ink, in the industries such as coating; And in the hot-work of polypropylene, polyethylene, polyoxymethylene, ABS resin etc., can extend the work-ing life of plastics.
Described oxidation inhibitor 626 chemistry two (2,4-DTBP) pentaerythritol diphosphites by name, the external trade mark is Antioxidant 626, Antioxidant 24, and the call of the domestic trade mark is oxidation inhibitor 626.Oxidation inhibitor 626 1 kinds of phosphorous acid esters auxiliary type oxidation inhibitor, feature is anti-yellowing change, high transparent, it is the agent of a kind of low volatility organic synthesis resistance to the oxygen inhibiting polymerization, polypropylene, polyethylene, ABS, the synthesis gathering all types of plastic such as carbonic acid fiber and vibrin and processing can be applied to, and effectively improve processing stability and the color and luster improvement of resin.
Described DHT-4A is hydration talcum powder, chemistry [Mg by name 6al 2(OH) 16cO 34H 2o].It is the suction acid stablizer that Japanese Kyowa Chemical Industry Co., Ltd (Kyowa Chemical) produces.Described suction sour stablizer DHT-4A is used for absorbing free acid ion in material, effectively can improve thermotolerance and the water resistance of goods, prevent product to turn to be yellow, ensure the color and luster of polyolefin products.
Described two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether is Hinered phenols antioxidant, has the phenolic compound of steric restriction, their thermal oxidation resistance Be very effective, and can not pollute goods.
Described thio-2 acid dibasic acid esters is a class auxiliary antioxidant, with two (3,5-, the tri-grades of butyl-4-hydroxy phenyls) thioether of oxidation inhibitor and use, and Be very effective.
Compared with prior art, the present invention has following beneficial effect: the oxidation inhibitor antioxidant capacity of above-mentioned raw materials composition is outstanding, heat resistanceheat resistant is functional, synergy reaches maximum, described for polyolefinic composite antioxidant, at high temperature, polyolefinic processing stability and color and luster improvement are all had clear improvement, simultaneously described simple for polyolefinic composite antioxidant formula used, cost is lower, easy to use, can be able to be used widely in suitability for industrialized production.
[embodiment]
Object for a better understanding of the present invention, feature and effect etc., be described further technical scheme of the present invention below in conjunction with specific embodiment.
The formula for polyolefinic composite antioxidant of embodiment 1-10 is in table 1.
Table 1
1, for a preparation method for polyolefinic composite antioxidant, it comprises the following steps:
(1) by each component mixing for polyolefinic composite antioxidant of embodiment 1-10 formula, under temperature is 25 DEG C of conditions, be that the speed of 1000rpm stirs 60 seconds with stirring velocity;
(2) get each component after stirring to knock down in Squeezinggranulator and carry out granulation, the heating zone temperature of Squeezinggranulator is 50 DEG C, the temperature of head section is 60 DEG C, obtains particle by being extruded the billot obtained by head by air-cooled travelling belt by its natural fracture;
(3) particle obtained is crossed 3 layers of sieve, the aperture of particle be more than 4mm be finished product, the aperture of particle is less than the recycling of 4mm.
In described step (3), the particle obtained is crossed 3 layers of sieve, the aperture of the first layer sieve is 8mm, the aperture 6mm of second layer sieve, and the aperture of third layer sieve is 4mm.
2, melting index and isotactic index evaluation:
In above-described embodiment 1-10 formulated for polyolefinic composite antioxidant in 1% ratio add in polyacrylic production, the polypropylene produced is carried out to the evaluation of melting index (MFR) and isotactic index, evaluation result is as table 2
Table 2
As can be seen from the above table: what embodiment 1-10 filled a prescription all can as industrialization product for polyolefinic composite antioxidant; And the melting index that embodiment 5 is filled a prescription is minimum, isotactic index is the highest, is the first-selection formula of industrialization product.
One of the present invention is outstanding for polyolefinic composite antioxidant antioxidant capacity, heat resistanceheat resistant is functional, synergy reaches maximum, simultaneously under high temperature and ultrahigh-temperature, positive effect is had to polyolefinic processing stability and color and luster improvement, and formula is simple, cost is lower, easy to use, can be able to be used widely in suitability for industrialized production.
More than describe in detail and be only the explanation of the preferred embodiment of the present invention, non-ly therefore limit to the scope of the claims of the present invention, so the equivalence techniques that all this creation of utilization specification sheetss and diagramatic content are done changes, and is all contained in the scope of the claims of the present invention.

Claims (10)

1., for a polyolefinic composite antioxidant, it is characterized in that, composed as follows by weight percentage:
Described antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and described oxidation inhibitor 626 is two (2,4 ?DI-tert-butylphenol compounds) pentaerythritol diphosphites, described DHT ?4A be [Mg 6al 2(OH) 16cO 34H 2o].
2. as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that: the weight percent of described antioxidant 1010 is 40 ~ 60%.
3. as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that: the weight percent of described antioxidant 1010 is 45 ~ 50%.
4. as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that: the weight percent of described oxidation inhibitor 626 is 25 ~ 45%.
5. as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that: the weight percent of described oxidation inhibitor 626 is 33 ~ 37%.
6. as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that: the weight percent of described DHT-4A is 7 ~ 9%.
7. as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that: the weight percent of described two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether is 2 ~ 4%.
8. as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that: the weight percent of described thio-2 acid dibasic acid esters is 3 ~ 4%.
9., as claimed in claim 1 for polyolefinic composite antioxidant, it is characterized in that, composed as follows by weight percentage:
10., as claimed in claim 1 for a preparation method for polyolefinic composite antioxidant, it is characterized in that, comprise the steps:
(1) each component mixing, under temperature is 25 DEG C of conditions, is that the speed of 1000rpm stirs 60 seconds with stirring velocity;
(2) get each component after stirring to knock down in Squeezinggranulator and carry out granulation, the heating zone temperature of Squeezinggranulator is 50 DEG C, the temperature of head section is 60 DEG C, obtains particle by being extruded the billot obtained by head by air-cooled travelling belt by its natural fracture;
(3) particle obtained is crossed 3 layers of sieve, the aperture of particle be more than 4mm be finished product, the aperture of particle is less than the recycling of 4mm;
In described step (3), the particle obtained is crossed 3 layers of sieve, the aperture of the first layer sieve is 8mm, the aperture 6mm of second layer sieve, and the aperture of third layer sieve is 4mm.
CN201510446650.3A 2015-07-27 2015-07-27 Complex antioxidant for polyolefin and preparing method of complex antioxidant Pending CN105001480A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108329517A (en) * 2018-02-09 2018-07-27 江苏汉光实业股份有限公司 A kind of novel plastic processing emulsion composite antioxidant and preparation method thereof
CN111454517A (en) * 2020-05-13 2020-07-28 东华能源(宁波)新材料有限公司 Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101701084A (en) * 2009-11-22 2010-05-05 李庆民 Improved high-pressure polyethylene transparency complex additive and preparation method thereof
CN101701075A (en) * 2009-11-22 2010-05-05 李庆民 Linear metallocene PE modified compound additive
CN104558826A (en) * 2014-05-26 2015-04-29 江苏汉光实业股份有限公司 Formula and preparation method of special compound additive for polypropylene film material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101701084A (en) * 2009-11-22 2010-05-05 李庆民 Improved high-pressure polyethylene transparency complex additive and preparation method thereof
CN101701075A (en) * 2009-11-22 2010-05-05 李庆民 Linear metallocene PE modified compound additive
CN104558826A (en) * 2014-05-26 2015-04-29 江苏汉光实业股份有限公司 Formula and preparation method of special compound additive for polypropylene film material

Non-Patent Citations (1)

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Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108329517A (en) * 2018-02-09 2018-07-27 江苏汉光实业股份有限公司 A kind of novel plastic processing emulsion composite antioxidant and preparation method thereof
CN111454517A (en) * 2020-05-13 2020-07-28 东华能源(宁波)新材料有限公司 Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof
CN111454517B (en) * 2020-05-13 2021-09-10 东华能源(宁波)新材料有限公司 Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof

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Application publication date: 20151028