CN115197529A - Anti-aging composition and application thereof in ABS - Google Patents
Anti-aging composition and application thereof in ABS Download PDFInfo
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- CN115197529A CN115197529A CN202211032605.XA CN202211032605A CN115197529A CN 115197529 A CN115197529 A CN 115197529A CN 202211032605 A CN202211032605 A CN 202211032605A CN 115197529 A CN115197529 A CN 115197529A
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
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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
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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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
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- 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
Abstract
The invention provides an anti-aging composition for ABS, which comprises 10-40% of hindered phenol antioxidant by weight percentage; 10-45% of phosphite ester antioxidant; 5-40% of thioester antioxidant; 5-60% of lubricant. The invention also provides an ABS material containing the anti-aging composition. The anti-aging composition can improve the whiteness of ABS materials and reduce the yellow index in the production, storage, transportation and use processes of ABS.
Description
Technical Field
The invention relates to the field of general plastics, in particular to an anti-aging composition and application thereof in ABS materials.
Background
In the field of high polymer materials, ABS is a graft copolymer of three monomers of butadiene, styrene and acrylonitrile, has the characteristics of high strength, good toughness, excellent processing performance, good mechanical performance, good chemical stability resistance, good surface gloss and the like, is widely applied in the fields of automobiles, household appliances, office equipment, building material industry and the like, and is one of five indispensable synthetic resins in social life. However, polybutadiene in ABS contains a large number of double bonds which are easy to break, so that butylene rubber particles in the copolymer are firstly degraded in the aging process, the toughness is reduced, the rigidity is improved, the appearance color gradually turns yellow and deepens, and the whiteness is gradually reduced, thereby limiting the application of the copolymer.
In the prior art, the most common method for improving the whiteness of ABS and reducing the yellow index is to add a whitening agent, an anti-yellowing agent or add other additives such as toner pigment, titanium dioxide, metal passivator and the like. For example, in patent CN109942976B, the whiteness of ABS products is improved by adding a metal passivator; in patent CN105038096A, the whiteness of ABS products is improved by adding fluorescent whitening agent and titanium dioxide. The method has relatively large addition amount, increases the production cost of the ABS, and cannot directly inhibit the fracture of polybutadiene double bonds in the ABS by adding the additives.
In order to better inhibit the double bond fracture of polybutadiene in ABS, improve the whiteness of ABS and reduce the yellow index, the method commonly used in the art is to add an antioxidant into ABS. Typical natural antioxidants, such as small molecular weight phenolic antioxidants like vitamin E or ascorbic acid, are difficult to meet antioxidant requirements during high temperature processing. In the prior art, the addition of phosphite antioxidants and hindered phenol antioxidants has the problems of unsatisfactory physical properties, initial whiteness and yellow index for a long time, or reduction of whiteness and gradual increase of yellow value along with the prolonging of service time, thus affecting the appearance and use of ABS. In addition, the addition of the antioxidant is generally added to an ABS resin blending unit in the form of solid powder in industry, which causes a great amount of dust pollution in the addition process and has the risk of dust explosion, and simultaneously, the problems of material blockage and difficult metering are easy to occur in the addition process of the solid powder.
Therefore, it is necessary to develop an anti-aging agent which is environmentally friendly and has more excellent performance, and can improve the whiteness of ABS and reduce the yellow index.
Disclosure of Invention
The invention aims to provide an environment-friendly anti-aging composition, which can be used for obtaining an ABS material with high initial whiteness and yellowing resistance after being used for ABS resin; the anti-aging composition can also solve the problems of reduction of whiteness value and increase of yellowness index of ABS materials in the processes of storage, transportation and use.
The invention provides a composition, which comprises a high polymer material and an anti-aging auxiliary composition, wherein the high polymer material is ABS resin, and the anti-aging composition comprises the following components in percentage by weight:
10-40% of hindered phenol antioxidant;
10-45% of phosphite ester antioxidant;
5-40% of thioester antioxidant;
5-60% of lubricant.
Further, the hindered phenol antioxidant is selected from one or more of polyphenol type hindered phenol with a hindered phenol unit of more than or equal to 2 or monophenol type hindered phenol containing a lactone group;
preferably, the polyphenol type hindered phenol is selected from one or more of tetrakis [ β - (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, 1,3,5-trimethyl-2,4,6-tris (3,5, -di-t-butyl-4-hydroxybenzyl) benzene, 4,4 '-thiobis (6-t-butyl-3-methylphenol), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione, 2,2' -thiodiglycol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], triglycidiobis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ], bis (3434 zxft-butyl-4-hydroxy-propylhydrazine), p-butylcresol, and p-butylcresol; more preferably one or more of tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the monophenol hindered phenol is selected from octadecyl beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or 3,5-di-tert-butyl-4-hydroxyphenyl iso-octyl propionate.
Further, the phosphite antioxidant is selected from one or more of a phosphite antioxidant containing 2,4-di-tert-butylphenyl groups or a phosphite antioxidant containing a phosphorus ester group with more than 12 carbon atoms;
preferably, the phosphite antioxidant is selected from one or more of bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenol) 4,4' -biphenyl diphosphite, and dioctadecyl pentaerythritol diphosphite.
Further, the thioester antioxidant is selected from one or more of didodecyl thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate and pentaerythritol tetrakis (3-lauryl thiopropionate); and/or the lubricant is selected from one or more of ethylene bis stearamide, magnesium stearate and calcium stearate.
Further, the anti-aging composition also comprises one or more of an acid scavenger, a colorant, a whitening agent and a toner pigment.
Further, the anti-aging composition comprises the following components in percentage by weight:
15-35% of hindered phenol antioxidant;
15-40% of phosphite ester antioxidant;
15-40% of thioester antioxidant;
20-50% of a lubricant;
preferably, the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant to the thioester antioxidant in the anti-aging composition is (2-4) to (1-3) to (2-4).
Further, the addition amount of the anti-aging composition is 0.1-10%, preferably 0.1-5%, and more preferably 0.1-1% of the weight of the ABS resin.
The invention provides an anti-aging composition, which comprises the following components in percentage by weight:
15-35% of hindered phenol antioxidant;
15-40% of phosphite ester antioxidant;
15-40% of thioester antioxidant;
20-50% of a lubricant;
the hindered phenol antioxidant is selected from one or more of polyphenol type hindered phenols with hindered phenol units more than or equal to 2 or monophenol type hindered phenols with lactone groups; the phosphite antioxidant is selected from one or more of a phosphite antioxidant containing 2,4-di-tert-butylphenyl groups or a phosphite antioxidant containing a phosphorus ester group with more than 12 carbon atoms; the thioester antioxidant is selected from one or more of didodecyl thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate and pentaerythritol tetrakis (3-lauryl thiopropionate); the lubricant is selected from one or more of ethylene bis stearamide, magnesium stearate and calcium stearate.
The anti-aging composition is in the form of solid particles, and is prepared by granulating at the temperature of 150-250 ℃ after being melted and mixed.
The invention also provides the application of the anti-aging composition in the production, processing, use, storage and transportation of ABS materials, wherein the anti-aging composition can be the anti-aging composition in the composition of the first aspect of the invention, and can also be the anti-aging composition of the second aspect of the invention.
The invention has the beneficial effects that:
1. the invention utilizes the synergistic antioxidant effect among specific antioxidants, selects the antioxidant combination with a specific proportion as the anti-aging agent, is applied to ABS resin, and can obtain the ABS material with higher initial whiteness and yellowing resistance.
2. The powdery antioxidant in the prior art is granulated into granular materials, so that dust pollution in the using process of the antioxidant is reduced, and the granular material has good environmental protection property.
3. The anti-aging agent composition disclosed by the invention is simple in component, and can be used for obviously improving the whiteness of ABS and reducing the yellow index without adding a whitening agent, an anti-yellowing agent and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In order to solve the technical problems of low whiteness and reduced yellow index of ABS resin materials in the background art, the invention adopts the following technical scheme:
in a first aspect, the invention provides an anti-aging composition, which comprises the following components in percentage by weight:
10-40% of hindered phenol antioxidant;
10-45% of phosphite ester antioxidant;
5-40% of thioester antioxidant;
5-60% of lubricant.
According to some embodiments of the invention, the anti-aging composition comprises the following components in percentage by weight:
15-35% of hindered phenol antioxidant;
15-40% of phosphite ester antioxidant;
15-40% of thioester antioxidant;
20 to 50 percent of lubricant.
The anti-aging composition has good synergistic effect among the components, wherein the hindered phenol antioxidant has long-term protective effect on the material and relatively slow effect, and the phosphite antioxidant is added on the basis, so that the protective effect of the material can be exerted in a short period, and the anti-discoloration effect of the material is obviously improved; the thioester antioxidant is added, which greatly contributes to the long-acting stability of the material; the lubricant can uniformly disperse the three antioxidants into the resin matrix material to better play an anti-aging role. The four components are matched with each other, so that alkyl free radicals, alkyl oxygen free radicals and hydroperoxide generated by aging of the material can be effectively inhibited, and after the four components are mixed according to a specific proportion, the anti-aging effect realizes the synergistic effect. In addition, the lubricant mainly improves the processability of the ABS material, particularly the melt mass flow rate, and can improve the long-term physical stability of the ABS material when used together with the three antioxidants.
In some embodiments, the hindered phenolic antioxidant is present in the anti-aging composition in an amount of 15%, 18%, 20%, 25%, 28%, 30%, 32%, or 35% by weight.
In some embodiments, the antioxidant is present in the antiaging composition in an amount of 15%, 18%, 20%, 25%, 28%, 30%, 32%, 35%, 38%, or 40% by weight.
In some embodiments, the weight percent content of thioester antioxidants in the anti-aging composition is 15%, 18%, 20%, 25%, 28%, 30%, 32%, 35%, 38%, or 40%.
In some embodiments, the lubricant is present in the anti-aging composition in an amount of 20%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, or 50% by weight.
In order to further improve the stability of the ABS material, ensure the initial color of the material and improve the yellowing resistance of the material, and enable the three antioxidants to play the optimal synergistic effect, the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant to the thioester antioxidant is (2-4) to (1-3) to (2-4).
The hindered phenol antioxidant in the anti-aging composition can provide basic comprehensive protection for materials, inhibit the aging degradation of the materials in the whole life cycle during processing, storage and use, and particularly can remarkably improve the long-term whiteness and yellowing resistance of ABS materials.
According to some embodiments of the invention, the hindered phenolic antioxidant is a polyphenol type hindered phenol having a hindered phenol unit of 2 or more, such as antioxidant 1010 (tetra [ β - (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol), antioxidant 330 (1,3,5-trimethyl-2,4,6-tris (3,5, -di-tert-butyl-4-hydroxybenzyl) benzene), antioxidant 300 (4,4 '-thiobis (6-tert-butyl-3-methylphenol)), antioxidant 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1h, 3h, 5h) trione), antioxidant 1035 (2,2' -thiolene glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ]), antioxidant 245 (triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]), antioxidant 1024 (bis (3,5-di-tert-butyl-4-hydroxybenzoyl) hydrazine), antioxidant CPL (butyl of p-cresol and dicyclopentadiene), or a mixture thereof.
According to some embodiments of the present invention, the hindered phenolic antioxidant is a monophenol-type hindered phenol containing lactone groups, such as antioxidant 1076 (octadecyl beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and antioxidant 1135 (3,5-di-tert-butyl-4-hydroxyphenyl iso-octyl propionate).
Preferred hindered phenolic antioxidants of the present invention are one or more of antioxidant 1010 (tetrakis [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol), antioxidant 245 (triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate ]), antioxidant 1076 (β - (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid octadecyl ester).
The phosphite antioxidant can improve the high-temperature processing stability in the ABS blending granulation stage, especially can ensure the initial whiteness of ABS, reduce the yellow index of ABS and play a good role in protecting ABS.
According to some embodiments of the invention, the phosphite antioxidant is selected from one or more of a phosphite antioxidant containing 2,4-di-tert-butylphenyl groups or a phosphite antioxidant containing a phosphorus ester group with more than 12 carbon atoms. 2,4-di-tert-butylphenol containing such as 626 (bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite), 168 (tris (2,4-di-tert-butylphenyl) phosphite), PEPQ (tetrakis (2,4-di-tert-butylphenyl) -4,4' biphenylbisphosphite), long carbon chain such as antioxidant 618 (pentaerythrityl dioctadecyl diphosphite).
Preferably, the combination of the phosphite ester containing 2,4-di-tert-butyl phenol and a long carbon chain structure containing more than 12 carbon atoms is more effective; such as antioxidant 626 in combination with antioxidant 168, and antioxidant 618 in combination with antioxidant 168.
Preferably, the ratio (by weight) of the phosphite containing 2,4-di-tert-butylphenol to the phosphite containing a long carbon chain structure containing more than 12 carbon atoms is (0.5-9) 1, 0.8.
The thioester antioxidant disclosed by the invention can play a role in long-acting thermal stability in an ABS material.
According to some embodiments of the present invention, the thioester antioxidant is selected from one or more of DLTP (didodecanediol thiodipropionate), DSTP (dioctadecyl thiodipropionate), DMTDP (dimyristyl thiodipropionate), 412S (pentaerythritol tetrakis (3-laurylthiopropionate)).
The lubricant can meet the requirement of the processability of ABS materials, is more favorable for ensuring the requirement of melt mass flow rate, and controls the melt mass flow rate (g/10 min) to be 16-24.
According to some embodiments of the invention, the lubricant is selected from one or more of EBS (ethylene bis stearamide), magnesium stearate, calcium stearate.
According to some embodiments of the present invention, the anti-aging composition may further comprise corresponding additives, such as one or more of an acid scavenger, a colorant, a whitening agent, and a toner pigment, according to the requirements of the processing or application scenario, and in further specific examples, the additives may be selected from one or more of magnesium oxide, titanium dioxide, and a fluorescent whitening agent.
According to some embodiments of the invention, the anti-aging composition is in solid particulate form.
In a second aspect, the present invention provides a method for granulating the anti-aging composition of the first aspect of the present invention.
The granulation process comprises the steps of uniformly mixing the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant, the lubricant and optional additives in a mixing tank, and granulating at the temperature of 150-250 ℃, preferably 180-220 ℃ to obtain anti-aging composition solid particles;
preferably, the components of the anti-aging composition are uniformly mixed by a high-speed mixer according to the proportion, and solid particles are prepared by adopting dry extrusion granulation technologies such as flat grinding, ring die, double-roll, double-screw and the like, wherein the solid particles comprise but are not limited to amorphous particles, columnar particles, hemispherical particles and spheroidal particles.
In a third aspect, the present invention provides the use of the anti-aging composition according to the first aspect of the present invention in ABS materials, in particular in the production, processing, use, storage and transportation of ABS materials, in particular for increasing the whiteness and/or reducing the yellowness index of ABS materials.
The anti-aging composition is in a solid granular shape, can reduce dust pollution and explosion risks caused by powdery materials in the using process, has good environmental protection performance, and avoids the risk of pipe blockage caused by materials in the adding process because the flowability of a granulated product is superior to that of the powdery materials.
In a fourth aspect, the present invention provides an ABS material, which comprises an ABS resin and the anti-aging composition of the first aspect of the present invention.
According to some embodiments of the invention, the anti-aging composition is added in an amount of 0.1 to 10%, such as 0.1%,0.2%,0.3%,0.4%,0.5%,0.6%,0.7%,0.8%,0.9%, 1%, 2%, 3%, 4% or 5% by weight of the ABS resin. The amount added is preferably 0.1 to 5%, more preferably 0.1 to 1% by weight of the ABS resin.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and do not constitute any limitation on the invention.
Examples
Examples 1-7 and comparative examples 1-5 of the present application each provide an ABS material comprising an ABS resin and an anti-aging composition, wherein the components and weight percentages of the anti-aging compositions in each of the examples and comparative examples are shown in table 1.
To illustrate the difference in the effect of the age resister composition between different polymeric materials, the present application also tried to use the age resister composition of example 1 in a polypropylene-based low-tack hot melt adhesive, see comparative example 6.
TABLE 1
And (3) performance testing:
mixing and granulating the components of the anti-aging compositions in examples 1-7 and comparative examples 1-5 according to a specific ratio, then respectively blending and granulating with ABS resin, and carrying out melt flow rate test, notch impact test and tensile property test on the ABS material; and testing the initial whiteness and the initial yellow index, and the whiteness value and the yellow index value change after the mixture is placed for different times. Since the hot-melt adhesive of comparative example 6 does not require the determination of processability and mechanical properties, only whiteness test and yellowness index test at room temperature and heat aging were tested.
1. Preparation of anti-aging composition granules
The components of the anti-aging compositions in examples 1-7 and comparative examples 1-5 were mixed uniformly in a mixing tank, and then delivered to a transition bin under negative pressure, the magnetic separator, the vibrating screen, the shaping machine, the granulator, the feeder and the feed screw were started in sequence, and the bottom valve of the transition bin was opened to granulate in a granulation device. The speed of the granulator is adjusted to obtain the anti-aging composition particles with the specified particle size.
ABS blending granulation
Uniformly mixing high rubber powder, SAN granules (general ABS brand composition: A/B/S = 0.25/0.15/0.60) and an anti-aging composition granule product according to a ratio of 1.04, extruding and granulating in a double-screw extruder, controlling the temperature (first-stage 180 ℃, second-stage 190 ℃, third-stage 190 ℃, fourth-stage 200 ℃ and neck mold 215 ℃) and performing fixed injection molding to obtain standard mechanical test sample bars and sample pieces.
3. Performance detection
The melt flow rate of the extruded and granulated ABS is tested according to the GB/T3682 standard, the test condition is 220 ℃,10kg, and the result is shown in Table 2; performing notch impact test and tensile property test on the mechanical test sample strip, and the results are shown in table 2; the mechanical test piece was subjected to initial whiteness and initial yellow index tests, and whiteness tests were performed after being left at room temperature for 2 days, 4 days, 6 days, and 8 days, with the results shown in table 3, and yellow index tests were performed after oven heat aging at 170 ℃ with the results shown in table 4.
TABLE 2
TABLE 3
TABLE 4
| YI-0 day | YI-2 days | YI-4 days | YI-6 days | YI-8 days | |
| Example 1 | 3.8 | 12.1 | 24.5 | 51.1 | 83.1 |
| Example 2 | 3.5 | 11.9 | 24.1 | 50.2 | 79.6 |
| Example 3 | 3.6 | 12.6 | 25.3 | 53.4 | 85.4 |
| Example 4 | 5.3 | 13.8 | 27.3 | 69.7 | 99.6 |
| Example 5 | 3.5 | 11.8 | 24 | 50.8 | 81.1 |
| Example 6 | 7.3 | 17.1 | 35.3 | 76.1 | 110.5 |
| Example 7 | 8.5 | 18.3 | 36.7 | 77.3 | 113.2 |
| Comparative example 1 | 8.2 | 18.2 | 38.9 | 77.8 | 124.5 |
| Comparative example 2 | 10.6 | 19.8 | 39.5 | 78.3 | 126.8 |
| Comparative example 3 | 8.3 | 20.3 | 41.1 | 79.8 | 129.6 |
| Comparative example 4 | 8.1 | 21.6 | 43.2 | 93.8 | 136.5 |
| Comparative example 5 | 9.1 | 19.5 | 38.1 | 77.9 | 114.1 |
| Comparative example 6 | 21.7 | 40.5 | 63.1 | 95.6 | 152.3 |
As can be seen from Table 2, by the synergistic effect between the antioxidant and the lubricant, the melt flow rate, the impact strength and the tensile strength can be well controlled, so that the numerical values are kept in a reasonable range, and the condition that the flow property and the mechanical property are unstable is avoided.
As can be seen from the results of tables 3 and 4, the ABS materials in examples 1-7 had higher initial whiteness values and lower initial yellow index values than the ABS materials in comparative examples 1-5; and the change of the whiteness values is small after the mixture is placed for 2 days, 4 days, 6 days and 8 days at room temperature, which shows that the whiteness attenuation is small along with the increase of time, the stability of the whiteness can be well kept, and the increase value of the yellow index of the mixture is relatively small after the mixture is subjected to heat aging in an oven at the temperature of 170 ℃. Therefore, the antioxidant is applied to the ABS resin material as an anti-aging agent by combining the specific antioxidants and utilizing the synergistic effect of the antioxidants, and has excellent effects on improving the whiteness value of the ABS material and reducing the yellow index value.
In addition, the effect test data of comparative example 6 shows that the anti-tarnishing effect of the inventive anti-aging composition is not as good in hot melt adhesives as in ABS materials.
The anti-aging composition is prepared into a granulated compound product, so that the dust pollution and explosion risks in the using process can be reduced, and the anti-aging composition has good environmental protection property. In addition, the components selected by the invention are all environment-friendly products, are harmless to human bodies and organisms, conform to the certification of REACH, FDA and other regulations, and are not listed in the list of high concerns such as SVHC and the like.
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims (10)
1. The composition comprises a high polymer material and an anti-aging composition, wherein the high polymer material is ABS resin, and the anti-aging composition comprises the following components in percentage by weight:
10-40% of hindered phenol antioxidant;
10-45% of phosphite ester antioxidant;
5-40% of thioester antioxidant;
5-60% of lubricant.
2. The composition as claimed in claim 1, wherein the hindered phenolic antioxidant is selected from one or more of polyphenol type hindered phenols with hindered phenol unit not less than 2, or monophenol type hindered phenols with lactone group;
preferably, the polyphenol type hindered phenol is selected from one or more of tetrakis [ β - (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, 1,3,5-trimethyl-2,4,6-tris (3,5, -di-t-butyl-4-hydroxybenzyl) benzene, 4,4 '-thiobis (6-t-butyl-3-methylphenol), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione, 2,2' -thiodiglycol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], triglycidiobis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ], bis (3434 zxft-butyl-4-hydroxy-propylhydrazine), p-butylcresol, and p-butylcresol; more preferably one or more of tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]; the monophenol hindered phenol is selected from octadecyl beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or 3,5-di-tert-butyl-4-hydroxyphenyl iso-octyl propionate.
3. The composition of claim 1, wherein the phosphite antioxidant is selected from one or more of a phosphite antioxidant containing 2,4-di-tert-butylphenyl groups or a phosphite antioxidant containing a phosphorus ester group with 12 or more carbon atoms;
preferably, the phosphite antioxidant is selected from one or more of bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenol) 4,4' -biphenyl diphosphite, and dioctadecyl pentaerythritol diphosphite.
4. The composition according to claim 1, wherein the thioester antioxidant is selected from one or more of didodecanediol thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate); and/or the lubricant is selected from one or more of ethylene bis stearamide, magnesium stearate and calcium stearate.
5. The composition of any of claims 1-4, wherein the anti-aging composition further comprises one or more of an acid scavenger, a colorant, a whitening agent, a toner pigment.
6. The composition according to any one of claims 1 to 4, wherein the anti-aging composition comprises the following components in percentage by weight:
15-35% of hindered phenol antioxidant;
15-40% of phosphite ester antioxidant;
15-40% of thioester antioxidant;
20-50% of a lubricant;
preferably, the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant to the thioester antioxidant in the anti-aging composition is (2-4) to (1-3) to (2-4).
7. The composition according to any one of claims 1 to 6, characterized in that the anti-aging composition is added in an amount of 0.1 to 10%, preferably 0.1 to 5%, more preferably 0.1 to 1% by weight of the ABS resin.
8. The anti-aging composition is characterized by comprising the following components in percentage by weight:
15-35% of hindered phenol antioxidant;
15-40% of phosphite ester antioxidant;
15-40% of thioester antioxidant;
20-50% of a lubricant;
the hindered phenol antioxidant is selected from one or more of polyphenol type hindered phenols with hindered phenol units more than or equal to 2 or monophenol type hindered phenols with lactone groups; the phosphite ester antioxidant is selected from one or more of a phosphite ester antioxidant containing 2,4-di-tert-butylphenyl groups or a phosphite ester antioxidant containing a phosphorus ester group with more than 12 carbon atoms; the thioester antioxidant is selected from one or more of didodecyl thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate and pentaerythritol tetrakis (3-lauryl thiopropionate); the lubricant is selected from one or more of ethylene bis stearamide, magnesium stearate and calcium stearate.
9. The composition according to any one of claims 1 to 7 or the age resistor composition according to claim 8, wherein the age resistor composition is in the form of solid particles, and the age resistor composition is prepared by melt-mixing and granulating at a temperature of 150 to 250 ℃.
10. Use of an anti-aging composition for the production, processing, use, storage and transportation of ABS material, wherein the anti-aging composition is according to any one of claims 1 to 8.
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| CN202211032605.XA CN115197529A (en) | 2022-08-26 | 2022-08-26 | Anti-aging composition and application thereof in ABS |
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| CN202211032605.XA CN115197529A (en) | 2022-08-26 | 2022-08-26 | Anti-aging composition and application thereof in ABS |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023729A (en) * | 2023-01-09 | 2023-04-28 | 广州华新科智造技术有限公司 | Special master batch for PE white film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102746624A (en) * | 2012-07-24 | 2012-10-24 | 北京市化学工业研究院 | Preparation method for flame-retardant polybutylene terephthalate engineering plastic |
| CN106832744A (en) * | 2017-02-24 | 2017-06-13 | 合肥卡洛塑业科技有限公司 | A kind of ABS composite material of ageing-resistant discoloration and preparation method thereof |
| CN111320810A (en) * | 2018-12-14 | 2020-06-23 | 天津利安隆新材料股份有限公司 | Anti-aging agent composition for talcum powder filled polypropylene composite material |
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- 2022-08-26 CN CN202211032605.XA patent/CN115197529A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746624A (en) * | 2012-07-24 | 2012-10-24 | 北京市化学工业研究院 | Preparation method for flame-retardant polybutylene terephthalate engineering plastic |
| CN106832744A (en) * | 2017-02-24 | 2017-06-13 | 合肥卡洛塑业科技有限公司 | A kind of ABS composite material of ageing-resistant discoloration and preparation method thereof |
| CN111320810A (en) * | 2018-12-14 | 2020-06-23 | 天津利安隆新材料股份有限公司 | Anti-aging agent composition for talcum powder filled polypropylene composite material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116023729A (en) * | 2023-01-09 | 2023-04-28 | 广州华新科智造技术有限公司 | Special master batch for PE white film and preparation method thereof |
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