CN111303480B - Vulcanization-promoted comprehensive protective material and preparation method thereof - Google Patents

Vulcanization-promoted comprehensive protective material and preparation method thereof Download PDF

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CN111303480B
CN111303480B CN202010336203.3A CN202010336203A CN111303480B CN 111303480 B CN111303480 B CN 111303480B CN 202010336203 A CN202010336203 A CN 202010336203A CN 111303480 B CN111303480 B CN 111303480B
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antioxidant
protective material
vulcanization
acetone
emulsifier
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CN111303480A (en
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唐英俊
张莉娜
张小丽
陆唯一
方韬
方春平
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Changzhou Wuzhou Chemical Co ltd
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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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a vulcanization-accelerated comprehensive protective material and a preparation method thereof. The protective material consists of an anti-aging agent RD, an anti-aging agent 4020, an anti-aging agent 4030 and zinc terephthalate, and the proportion is (by weight) 25-30: 20-25: 20-35. The preparation method of the protective material comprises the following steps: (1) adding the anti-aging agents RD, 4020 and 4030 and an emulsifier into acetone, and stirring to obtain an emulsion system A; (2) dispersing zinc terephthalate and an emulsifier in acetone to obtain an emulsion system B; (3) and mixing the system A and the system B in a homogenizer, distilling to recover acetone, cooling the residual substance, and granulating to obtain the target product. The protective material has excellent protective effects of thermal oxygen resistance, dynamic and static ozone resistance, metal poison resistance and the like, and can promote the rubber vulcanization process.

Description

Vulcanization-promoted comprehensive protective material and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a vulcanization-promoted type comprehensive protection material for rubber and a preparation method thereof.
Background
During the processing, storage and use of the rubber and the products thereof, the aging symptoms such as cracking, stickiness, hardening, softening, powdering, discoloration, mold growth and the like can occur due to the combined action of internal and external factors, and finally the use value is lost. The rubber anti-aging agent is a product capable of preventing or delaying rubber aging. Different anti-aging materials have different protection emphasis points, and engineers generally match and use the materials according to the characteristics of each material to achieve the best effect.
Rubber antioxidant RD [2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (C)12H15N)n，n＝2～4]Is the most widely usedThe quinoline anti-aging agent has good protection effect on rubber thermo-oxidative aging, has a certain inhibition effect on metal catalytic aging, has low toxicity, and is the most common anti-thermo-oxidative aging agent at present. RD is composed of monomers and multimers (dimers, trimers, tetramers) of 2,2, 4-trimethyl-1, 2-dihydroquinoline, wherein the effective component is multimer. The trimer and the tetramer have large molecular weight, are not easy to migrate, have excellent thermal oxidation aging resistance under a static condition, but have insufficient dynamic performance; the dimer has good thermal oxidation aging resistance under dynamic and static conditions, but has certain mobility due to small molecular weight.
The rubber antioxidant 4020[ N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine ] is a universal variety with excellent performance in amine antioxidants, has excellent ozone aging cracking and flex cracking resistance, has a certain passivation effect on variable-valence metals, is the most commonly used dynamic ozone aging inhibitor at present, and is often used together with RD (RD). However, because of its small molecular weight, it is easy to migrate and precipitate particularly in high temperature rubber products such as tires, which not only affects the long-term protection effect, but also makes the products turn reddish and affects the appearance.
The static ozone aging resistant effect of the rubber antioxidant 4030[ N-N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine ] is the most excellent in the p-phenylenediamine antioxidants, but the dynamic protection effect is almost not.
The invention aims to combine the advantages and disadvantages of various important anti-aging agents and obtain a protective material with excellent comprehensive protection effect through improvement.
Disclosure of Invention
The invention aims to provide a vulcanization-accelerated comprehensive protective material and a preparation method thereof. The protective material prepared by the method has excellent effects of resisting thermal oxygen, static ozone, dynamic ozone and heavy metal ion toxicity, and has a certain promotion effect on rubber vulcanization, so that the use of a vulcanization activator is reduced.
In order to achieve the purpose, the invention is realized by the following technical scheme: the vulcanization-promoted comprehensive protection material consists of an anti-aging agent RD, an anti-aging agent 4020, an anti-aging agent 4030 and zinc terephthalate.
The method for preparing the vulcanization-promoted comprehensive protective material comprises the following steps:
(1) adding the antioxidant RD, the antioxidant 4020 and the antioxidant 4030 into acetone in proportion, stirring until the mixture is dissolved, and adding an emulsifier to obtain an emulsion system A;
(2) dispersing zinc terephthalate in acetone, and adding an emulsifier to obtain an emulsion system B;
(3) and (3) fully mixing the system A in the step (1) and the system B in the step (2) in a homogenizer, recovering acetone through distillation, conveying the rest substances into a storage tank in a heat preservation state, cooling to a proper temperature, and granulating through a steel belt cooling granulator to obtain a final granular finished product.
Furthermore, the proportion of the antioxidant RD, the antioxidant 4020, the antioxidant 4030 and the zinc terephthalate is (by weight parts) 25-30: 20-25: 20-35.
Further, the emulsifier is at least one selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium palmitate, OP-10, OP-20 and OP-50.
Further, the particle diameter D of zinc terephthalate is preferable97Less than 3 microns, and BET specific surface area greater than 80m2/g。
Has the advantages that:
(1) the preparation method can ensure that all the components can be fully and uniformly mixed, and coordination bonds are formed between various anti-aging agents and zinc terephthalate; in addition, zinc terephthalate forms salt cross-linking bonds with rubber molecules during rubber vulcanization. Therefore, the target product overcomes the defect that the raw material anti-aging agent is easy to migrate and frost in rubber, thereby relieving the defects of insufficient long-term aging performance and easy reddening of rubber products.
(2) The target product of the invention has the following effects: the product has excellent thermal oxidation aging resistance of RD, dynamic ozone resistance of 4020 and static ozone resistance of 4030; in addition, the zinc terephthalate has good complexing effect on heavy metals, can stabilize heavy metal ions, and improves the effect of preventing metal poisoning. Therefore, the synergistic effect among the components ensures that the target product prepared by the invention has excellent comprehensive protection effect.
(3) The zinc terephthalate has certain vulcanization activity in rubber, can promote the vulcanization crosslinking process, shorten the vulcanization time and improve the crosslinking density, so that the use of the traditional activator zinc oxide can be properly reduced in the formula of the product, thereby reducing the zinc content in the rubber material and the volume cost of the product.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The invention will be better understood from the following examples. The examples are not intended to limit the scope of the present invention.
Example 1
The vulcanization-promoted comprehensive protective material comprises the following components: antioxidant RD, antioxidant 4020, antioxidant 4030 and zinc terephthalate.
The method for preparing the vulcanization-promoted comprehensive protective material comprises the following steps:
(1) adding the antioxidant RD, the antioxidant 4020 and the antioxidant 4030 into acetone in proportion, stirring until the mixture is dissolved, and adding an emulsifier to obtain an emulsion system A;
(2) dispersing zinc terephthalate in acetone, and adding an emulsifier to obtain an emulsion system B;
(3) and (3) fully mixing the system A in the step (1) and the system B in the step (2) in a homogenizer, recovering acetone through distillation, conveying the rest substances into a storage tank in a heat preservation state, cooling to a proper temperature, and granulating through a steel belt cooling granulator to obtain a final granular finished product.
Further, the proportion of the antioxidant RD, the antioxidant 4020, the antioxidant 4030 and the zinc terephthalate (by weight parts) is 25: 20: 35.
Further, the emulsifier is selected from sodium lauryl sulfate.
Further, the particle diameter D97 of zinc terephthalate was 2.5 μm, and the BET specific surface area was 85m 2/g.
Example 2
Example 2 differs from example 1 in that:
further, the ratio of the antioxidant RD, the antioxidant 4020, the antioxidant 4030 and the zinc terephthalate (by weight parts) is 30: 25: 20.
Further, the emulsifier is selected from OP-10.
Further, the particle diameter D97 of zinc terephthalate was 1.5. mu.m, and the BET specific surface area was 100m 2/g.
Example 3
Example 3 differs from example 1 in that:
further, the proportion of the antioxidant RD, the antioxidant 4020, the antioxidant 4030 and the zinc terephthalate (by weight) is 28: 23: 26.
Further, the emulsifier is selected from a mixture of sodium palmitate and OP-20.
Further, the particle diameter D97 of zinc terephthalate was 0.8. mu.m, and the BET specific surface area was 150m 2/g.
Comparative example 1
Comparative example 1 differs from example 1 in that:
adding antiager RD, antiager 4020 and antiager 4030 into acetone at a ratio (by weight) of 38.46: 30.77, stirring for dissolving, recovering acetone by distillation, cooling the rest substances to appropriate temperature, and crushing to obtain the final product.
Comparative example 2
Comparative example 2 differs from example 1 in that:
the antioxidant RD, the antioxidant 4020, the antioxidant 4030 and the zinc terephthalate are uniformly mixed in a high-speed mixer according to the proportion (by weight) of 25: 20: 35.
Application test:
comparative tests for the application of anti-aging agents were carried out in the following manner.
1. Formulation of
Various protective materials are applied to a tire tread formula, and the formula is as follows: NR 100, stearic acid 2, zinc oxide (variable), sulfur 1.2, NOBS 1.6, N22045, aromatic oil 5, protective wax 2 and anti-aging agent (variable and variable), and the specific formula arrangement is shown in Table 1. In addition, copper in an amount of 0.005% by mass of the rubber compound was additionally added to the formulation, formulation 3 and formulation 5.
Table 1 test formulations
Item Formulation 1 Formulation 2 Formulation 3 Formulation 4 Formulation 5
NR 100 100 100 100 100
Stearic acid 2 2 2 2 2
Sulfur 1.2 1.2 1.2 1.2 1.2
NOBS 1.6 1.6 1.6 1.6 1.6
N220 45 45 45 45 45
Aromatic oil 5 5 5 5 5
Protective wax 2 2 2 2 2
Zinc oxide 4 3 4 3 4
Example 1 anti-aging agent 2 2
Comparative example 1 antioxidant 2 2
Comparative example 2 antioxidant 2
2. Mechanical property test
On a double-roller open mill, firstly plasticating the natural rubber, then adding various auxiliary agents to obtain mixed rubber, and then vulcanizing at 151 ℃ for normal vulcanization time to obtain vulcanized rubber. Aging test conditions: 48 hours at 100 ℃, 72 hours at 100 ℃ and 144 hours at 100 ℃. The test was carried out according to the national standard and the properties obtained are shown in Table 2.
Table 2 performance test data
Figure GDA0003014142480000041
Figure GDA0003014142480000051
3. Static ozone aging resistance test
The formula 1, formula 3 and formula 5 rubber materials are subjected to static ozone aging resistance, and the test piece is aged after being stretched by 60%.
The test was carried out in hot summer with a temperature above 30 ℃ during the day. After one and a half month, no breach was observed for formulas 1,3 and 5; after two and a half months, the formulas 1 and 3 still have no crack, and the formula 5 has tiny cracks; after three months, minor cracks appeared in formulations 1 and 3, with the most severe cracks in formulation 5; after four months, it is clear that the split was most severe for formula 5, 3 times for formula 1, and relatively minimal for formula 1.
Comparing the performance data of table 2 with the static ozone aging resistance test results, it can be seen that: the target product prepared by the invention has the most excellent hot oxygen resistance and ozone resistance under dynamic and static conditions, and can still maintain the performance of vulcanized rubber under the condition of reduction of zinc oxide serving as an activating agent.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the foregoing description only for the purpose of illustrating the principles of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims, specification, and equivalents thereof.

Claims (4)

1. A vulcanization-accelerated comprehensive protective material is characterized by consisting of an anti-aging agent RD, an anti-aging agent 4020, an anti-aging agent 4030 and zinc terephthalate; the ratio of the antioxidant RD to the antioxidant 4020 to the antioxidant 4030 to the zinc terephthalate is 25-30: 20-25: 20-35 in parts by weight;
the preparation method of the vulcanization-accelerated comprehensive protective material comprises the following steps:
(1) adding the antioxidant RD, the antioxidant 4020 and the antioxidant 4030 into acetone in proportion, stirring until the mixture is dissolved, and adding an emulsifier to obtain an emulsion system A;
(2) dispersing zinc terephthalate in acetone, and adding an emulsifier to obtain an emulsion system B;
(3) and (3) fully mixing the system A in the step (1) and the system B in the step (2) in a homogenizer, recovering acetone through distillation, conveying the rest substances into a storage tank in a heat preservation state, cooling to a proper temperature, and granulating through a steel belt cooling granulator to obtain a final granular finished product.
2. The method for preparing the vulcanization-accelerating type composite protective material as set forth in claim 1, characterized by comprising the steps of:
(1) adding the antioxidant RD, the antioxidant 4020 and the antioxidant 4030 into acetone in proportion, stirring until the mixture is dissolved, and adding an emulsifier to obtain an emulsion system A;
(2) dispersing zinc terephthalate in acetone, and adding an emulsifier to obtain an emulsion system B;
(3) and (3) fully mixing the system A in the step (1) and the system B in the step (2) in a homogenizer, recovering acetone through distillation, conveying the rest substances into a storage tank in a heat preservation state, cooling to a proper temperature, and granulating through a steel belt cooling granulator to obtain a final granular finished product.
3. The method for preparing a vulcanization accelerating type composite protective material according to claim 2, wherein the emulsifier is at least one selected from the group consisting of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium palmitate, OP-10, OP-20 and OP-50.
4. The method for producing a vulcanization-accelerating type composite protective material as claimed in claim 2, wherein the particle diameter D of zinc terephthalate is97Less than 3 microns, and BET specific surface area greater than 80m2/g。
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