CN104356507A - Hindered phenol type polypropylene composite antioxidant - Google Patents
Hindered phenol type polypropylene composite antioxidant Download PDFInfo
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- CN104356507A CN104356507A CN201410616966.8A CN201410616966A CN104356507A CN 104356507 A CN104356507 A CN 104356507A CN 201410616966 A CN201410616966 A CN 201410616966A CN 104356507 A CN104356507 A CN 104356507A
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- butyl
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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
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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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
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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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
- C08K5/49—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
Abstract
The invention discloses a hindered phenol type polypropylene composite antioxidant which is formed by compounding the following components in parts by weight: 2-12 parts of a main antioxidant and 1-5 parts of an auxiliary antioxidant, wherein according to 100 percent of the main antioxidant, the mass percentage of N,N-di[3-(3,5-di-tert-butyl-4-hydroxy phenyl) propionyl] hexamethylene diamine is 2-30 percent; the mass content of alpha-vitamin E is 5-75 percent of N,N-di[3-(3,5-di-tert-butyl-4-hydroxy phenyl) propionyl] hexamethylene diamine, and the balance is tetra-{beta-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid} pentaerythritol ester; the auxiliary antioxidant is tri(2,4-tert-butyl-phenyl) phosphite ester. The preparation method of the composite antioxidant comprises the steps of mixing N,N-di[3-(3,5-di-tert-butyl-4-hydroxy phenyl) propionyl] hexamethylene diamine, alpha-vitamin E and tetra-{beta-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid} pentaerythritol ester to obtain a mixture, granulating the mixture, mixing the mixture with tri(2,4-tert-butyl-phenyl) phosphite ester to obtain another mixture, and granulating the second mixture to obtain the hindered phenol type polypropylene composite antioxidant. The hindered phenol type polypropylene composite antioxidant can better meet the requirement for the multi-aspect comprehensiveness of polypropylene, and the antioxidant performance can be improved, and the cost is lowered.
Description
Technical field
The present invention relates to a kind of polypropylene oxidation inhibitor, be a kind of Hinered phenols polypropylene complex type antioxidant specifically, belong to polypropylene admixture field and anti-oxidation field.
Background technology
At present, polypropylene oxidation inhibitor mostly is Hinered phenols antioxidant, phosphite ester kind antioxidant, sulphur ester antioxidant and complex class oxidation inhibitor.Be used alone a kind antioxidant technique allotment simple, easy to use, can antioxidant effect be played, but all have some limitations, be difficult to meet the many-sided performance requriements of macromolecule organic.Wherein easily to produce yellow look dirty for hindered phenol anti-oxidants, phosphite ester kind antioxidant facile hydrolysis, sulphur ester antioxidant and polypropylene compatible poor.
There is synergistic effect between different oxidation inhibitor, the compound system be made up of the primary antioxidant and auxiliary antioxidant that can produce synergistic effect is the system the most effectively preventing polymer thermo-oxidative ageing.Compound product has that the construction cycle is short, effective, over-all properties is good, multiple auxiliary agent gives full play to synergy, the advantage such as to be user-friendly to.Along with the expansion of the multifunction of resins for universal use in plastics industry, high added value and matrix material and engineering plastics range of application, require the performances such as oxidation inhibitor has efficiently, low toxicity, consistency are good, do not separate out.
Alpha-tocopherol is a kind of novel antioxidant, has that environmental protection, volume are few, antioxygen property advantages of higher; If be used alone, the shortcoming that yellowing is serious can be there is.So at present to the application of alpha-tocopherol oxidation inhibitor mainly through with phosphite ester kind antioxidant with polyvalent alcohol is composite realizes, existing trade names are that Ronntec 201 (U.S.), Uvinul 2003 AO(U.S. vapour bar are meticulous) and Irganox E 201 (German BASF) etc., be foreign products; The domestic research backwardness relatively to mixing alpha-tocopherol composite antioxidant, does not also form Industrial products.The important factor that the development of alpha-tocopherol composite antioxidant is mixed in impact is that the cost of alpha-tocopherol is very high, and the cost of composite antioxidant is high, and the market competitiveness is not enough.Finding one and have good synergistic oxidation inhibitor with alpha-tocopherol, improve antioxygen property, reduce alpha-tocopherol volume simultaneously by the effect of compound, is reduce a kind of method of mixing alpha-tocopherol composite antioxidant cost.
Summary of the invention
The object of this invention is to provide the Hinered phenols polypropylene complex type antioxidant that a kind of compound cost is low, antioxidant property is effective.
A kind of Hinered phenols polypropylene complex type antioxidant provided by the invention, it is composited by the primary antioxidant of 2 ~ 12 weight parts and the auxiliary antioxidant of 1 ~ 5 weight part:
Primary antioxidant is by total mass 100%, N, two [the 3-(3 of N-, 5-di-tert-butyl-hydroxy phenyl) propionyl] mass content of hexanediamine is 2% ~ 30%, the mass content of alpha-tocopherol is 5% ~ 75% of two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of N, N-, surplus is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester;
Auxiliary antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester;
The preparation method of this complex type antioxidant is first by N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, alpha-tocopherol and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester mixing; and granulating, then mix with three (2,4-di-tert-butyl-phenyl) phosphorous acid ester; and granulating, to obtain final product.
The key of above-mentioned formula is, be main antioxygen component with four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, volume is maximum; Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is color and luster conditioning agent, prevents the aberration situations such as yellowing; Alpha-tocopherol is as efficient antioxygen component, and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine compound use two with N, N-, volume is few.
The feature of above-mentioned formula is, due to the efficient antioxygen component of compound use and color and luster conditioning agent, its excellent combination property, especially on antioxidant capacity; Due to compound use alpha-tocopherol and two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of N, N-, both have good synergy, therefore the volume of alpha-tocopherol is little, and the cost of composite antioxidant is low.
Proportion relation in above-mentioned is through that a large amount of tests gets, in described scope, over-all properties can be obtained good, the complex type antioxidant that resistance of oxidation is outstanding, especially in primary antioxidant, alpha-tocopherol and N, two [the 3-(3 of N-, 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine is in described scope, both have good synergy, and preferably, primary antioxidant is by total mass 100%, N, two [the 3-(3 of N-, 5-di-tert-butyl-hydroxy phenyl) propionyl] mass content of hexanediamine is 2% ~ 10%, the mass content of alpha-tocopherol is N, two [the 3-(3 of N-, 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 20% ~ 70%.
Two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of the antioxygen recombiner N that searching of the present invention and alpha-tocopherol act synergistically good, N-, to reduce alpha-tocopherol consumption in composite antioxidant, reaches the object reduced the cost; Utilize four (β-(3 simultaneously, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, alpha-tocopherol and N, two [the 3-(3 of N-, 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine mixture is primary antioxidant, with three (2,4-di-tert-butyl-phenyl) to be that auxiliary antioxidant carries out composite for other oxidation inhibitor such as phosphorous acid ester, study its synergistic effect, through ratio modulation, acquisition over-all properties is good, the compound Hinered phenols antioxidant product innovation that resistance of oxidation is outstanding.
The invention has the beneficial effects as follows, obtain over-all properties good, resistance of oxidation is outstanding, low cost mix the compound Hinered phenols antioxidant product innovation of alpha-tocopherol.
Embodiment
Embodiment one:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 4.5Kg, alpha-tocopherol 2.0Kg and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 93.5Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment two:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 4.5Kg, alpha-tocopherol 2.5Kg and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 93.0Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment three:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 4.5Kg, alpha-tocopherol 2.9Kg and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 92.5Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment four:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 6.5Kg, alpha-tocopherol 2.9Kg and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 90.6Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment five:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 6.5Kg, alpha-tocopherol 3.6Kg and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 90.0Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment six:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 6.5Kg, alpha-tocopherol 4.2Kg and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 89.3Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment seven:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 8.5Kg, alpha-tocopherol 3.8g and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 87.7Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment eight:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 8.5Kg, alpha-tocopherol 4.7g and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 86.8Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
Embodiment nine:
By N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 8.5Kg, alpha-tocopherol 5.5g and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 85.9Kg mixes, and granulating, obtain primary antioxidant; by primary antioxidant 20Kg and three (2; 4-di-tert-butyl-phenyl) phosphorous acid ester 50Kg mixes, and granulating, obtain this complex type antioxidant.
By the compound Hinered phenols polypropylene oxidation inhibitor obtained by 0.15% volume mix in mixer with polypropylene powder, then the melt flow rate (MFR) (MFR) of composite antioxidant is detected according to " GB 3682-2000 ", the oxidation induction period of composite antioxidant is detected according to " GB 19466.6-2009 ", detect the yellowness index of composite antioxidant according to " GB-T 240-1980 ", comprehensive three Testing index judge the antioxidant property of compound Hinered phenols polypropylene oxidation inhibitor.
The antioxidant property of table one compound Hinered phenols polypropylene oxidation inhibitor:
| Composite antioxidant | Melt flow rate (MFR) (g/10min) | Oxidation induction period/min | Yellowness index |
| Blank | 6.20 | 0.4 | 6.40 |
| Embodiment one | 3.56 | 3.9 | 3.35 |
| Embodiment two | 3.51 | 4.8 | 3.37 |
| Embodiment three | 3.67 | 4.2 | 3.46 |
| Embodiment four | 3.63 | 3.9 | 3.65 |
| Embodiment five | 3.51 | 4.5 | 3.57 |
| Embodiment six | 3.56 | 4.6 | 3.59 |
| Embodiment seven | 3.45 | 4.9 | 4.83 |
| Embodiment eight | 3.42 | 4.6 | 4.87 |
| Embodiment nine | 3.32 | 4.7 | 4.85 |
Table two compound Hinered phenols polypropylene oxidation inhibitor physical index:
Claims (3)
1. a Hinered phenols polypropylene complex type antioxidant, is characterized in that, it is composited by the primary antioxidant of 2 ~ 12 weight parts and the auxiliary antioxidant of 1 ~ 5 weight part:
Primary antioxidant is by total mass 100%, N, two [the 3-(3 of N-, 5-di-tert-butyl-hydroxy phenyl) propionyl] mass content of hexanediamine is 2% ~ 30%, the mass content of alpha-tocopherol is 5% ~ 75% of two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of N, N-, surplus is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester;
Auxiliary antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester;
The preparation method of this complex type antioxidant is first by N; two [the 3-(3 of N-; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, alpha-tocopherol and four (β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester mixing; and granulating, then with three (2,4-di-tert-butyl-phenyl) phosphorous acid ester compound; and granulating, to obtain final product.
2. a kind of Hinered phenols polypropylene complex type antioxidant as claimed in claim 1, it is characterized in that, primary antioxidant is by total mass 100%, N, the mass content of two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of N-is 2% ~ 10%, and the mass content of alpha-tocopherol is N, 30% ~ 70% of two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of N-.
3. a kind of Hinered phenols polypropylene complex type antioxidant as claimed in claim 2, it is characterized in that, primary antioxidant is by total mass 100%, N, the mass content of two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of N-is 4.5%, and the mass content of alpha-tocopherol is N, 55% of two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine of N-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410616966.8A CN104356507A (en) | 2014-11-06 | 2014-11-06 | Hindered phenol type polypropylene composite antioxidant |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410616966.8A CN104356507A (en) | 2014-11-06 | 2014-11-06 | Hindered phenol type polypropylene composite antioxidant |
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| CN104356507A true CN104356507A (en) | 2015-02-18 |
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| CN201410616966.8A Pending CN104356507A (en) | 2014-11-06 | 2014-11-06 | Hindered phenol type polypropylene composite antioxidant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017766A (en) * | 2016-11-01 | 2018-05-11 | 中国石油化工集团公司 | It is a kind of to be used to preventing or mitigating composite antioxidant and its application that soft polyurethane foam reddens |
| CN111472095A (en) * | 2020-05-07 | 2020-07-31 | 常熟市恒运无纺制品有限公司 | High-permeability mask non-woven fabric and manufacturing method thereof |
| CN112266534A (en) * | 2020-10-26 | 2021-01-26 | 刘城 | Ultra-transparent polypropylene compound agent, preparation method thereof and ultra-transparent polypropylene composition |
| CN113621202A (en) * | 2021-07-08 | 2021-11-09 | 无锡市恒龙电缆材料有限公司 | Anti-oxidation filling rope |
-
2014
- 2014-11-06 CN CN201410616966.8A patent/CN104356507A/en active Pending
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| 李德忠，刘庆民: ""酚类抗氧剂在聚合物中的应用"", 《科技创新导报》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017766A (en) * | 2016-11-01 | 2018-05-11 | 中国石油化工集团公司 | It is a kind of to be used to preventing or mitigating composite antioxidant and its application that soft polyurethane foam reddens |
| CN108017766B (en) * | 2016-11-01 | 2020-12-01 | 中国石油化工集团公司 | Composite antioxidant for preventing or reducing reddening of polyurethane soft foam and application thereof |
| CN111472095A (en) * | 2020-05-07 | 2020-07-31 | 常熟市恒运无纺制品有限公司 | High-permeability mask non-woven fabric and manufacturing method thereof |
| CN112266534A (en) * | 2020-10-26 | 2021-01-26 | 刘城 | Ultra-transparent polypropylene compound agent, preparation method thereof and ultra-transparent polypropylene composition |
| CN113621202A (en) * | 2021-07-08 | 2021-11-09 | 无锡市恒龙电缆材料有限公司 | Anti-oxidation filling rope |
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Application publication date: 20150218 |