CN112552694A - Novel protective wax and application thereof in diene rubber field - Google Patents

Novel protective wax and application thereof in diene rubber field Download PDF

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Publication number
CN112552694A
CN112552694A CN201910915428.1A CN201910915428A CN112552694A CN 112552694 A CN112552694 A CN 112552694A CN 201910915428 A CN201910915428 A CN 201910915428A CN 112552694 A CN112552694 A CN 112552694A
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China
Prior art keywords
wax
protective
fatty alcohol
microcrystalline
coal
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CN112552694B (en
Inventor
谢治国
范汝良
董栋
张宁
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Tongcheng Chemical China Co ltd
Red Avenue New Materials Group Co Ltd
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Tongcheng Chemical China Co ltd
Red Avenue New Materials Group Co Ltd
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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
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a novel protective wax and application thereof in the field of diene rubber. The weight percentages of the components are as follows: 10-50% of fully refined paraffin, 1-40% of mixed crystal wax, 10-50% of microcrystalline wax, 1-10% of coal-based wax, 1-10% of bio-based wax, 1-30% of fatty alcohol-polyoxyethylene ether and 1-30% of fatty alcohol-polyoxypropylene ether. The protective wax has the advantage of bright appearance, is applied to the field of diene rubber, and can form an ozone protective film on the surface of rubber to be transparent and bright, effectively improve the appearance quality of rubber products, reduce the phenomenon of whitening on the surface of the rubber products, improve the free flowing characteristic of the protective wax, and avoid the caking phenomenon of the protective wax in the high-temperature storage or transportation process.

Description

Novel protective wax and application thereof in diene rubber field
Technical Field
The invention belongs to the technical field of rubber, and relates to novel protective wax and application thereof in the field of diene rubber.
Background
In modern society, with the progress of science and technology and the improvement of consciousness of human beings on environmental protection, green tires are rapidly developed. The preparation of novel protective wax to improve the ozone aging resistance of rubber materials has become the research direction of the rubber industry. Rubber products are attacked by ozone during use, especially unsaturated rubbers containing C ═ C double bonds, such as NR, SBR, BR, and the like; after being attacked by ozone, cracks can be generated on the surface, and the cracks gradually increase and deepen along with the deepening of the aging degree, so that the physical and mechanical properties of the rubber are influenced. The rubber protective wax can stably migrate to the surface of a rubber product, and a layer of compact protective film is formed on the surface, so that the ozone molecules in the air are prevented from reacting with diene rubber macromolecules, the rubber protective wax is used for blocking the attack of ozone on the rubber macromolecules, the unsaturated double bonds in the rubber macromolecules and the ozone in the air are prevented from undergoing an addition reaction, and the rubber protective wax is aged under the action of light and oxygen, the rubber macromolecules are prevented from being broken at the double bond positions and losing elasticity, the cracking on the surface of a tire or other rubber products is avoided, and the purpose of improving the service life of the rubber products is finally achieved. In the modern tire industry, particularly for 'green' tires, new formulations need to be researched to meet higher requirements of low rolling resistance, wet skid resistance, low noise performance and wear resistance improvement of the green tires, higher requirements are also put forward for rubber protective wax, the stability of a film of the original rubber protective wax which is migrated to the surface of rubber is poorer, the toughness is lower, the rubber protective wax can only be suitable for ozone protection in a narrower temperature range and a shorter time range, and the appearance of the tire is whitish, so that tire products need ozone protection in all-weather temperature change range and atmospheric weather environment, the endurance time of the protective effect is prolonged, and the appearance quality of the tire is improved. Meanwhile, higher requirements are also put forward on the raw materials of the wax, and biodegradable and sustainable raw materials become a new research direction of protective wax.
The rubber protective wax on the current market has the following problems:
1. the appearance of the commercial protective wax in the market is whitish and opaque, so that the wax film formed on the surface of the rubber is influenced on the appearance quality of the surface of the tire.
2. The protective effect of wax against ozone aging of rubber depends on its mobility in the rubber, the crystalline state of the wax in the protective film, the adhesion strength of the protective film to the rubber and the flexibility. In order to ensure that the wax migrates continuously to the surface to form a film throughout the life of the rubber article, it is necessary to use different forms of wax. The rubber protective wax commonly used at present is a mixed wax prepared by blending paraffin wax and microcrystalline wax. The molecular weight is small, the content of the different carbon is low, the mobility or the ejection speed is high due to low solubility in a rubber matrix, and an ozone protection film formed on the outer surface of the tire is not compact and stable enough, so that the appearance quality of the surface of the tire is influenced, and the ozone protection effect on the surface of the tire is reduced;
3. the free flowing property is poor, and the blocking phenomenon of the protective wax is easy to occur in the high-temperature storage or transportation process.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a novel protective wax.
The novel protective wax comprises a mixture of seven components, namely fully refined paraffin, mixed crystal wax, microcrystalline wax, coal-based wax, bio-based wax, fatty alcohol-polyoxyethylene ether and fatty alcohol-polyoxypropylene ether. The novel protective wax has the characteristics of bright appearance, better adhesion of a formed wax film, better anti-caking performance and the like.
In the invention, the components of the protective wax and the weight percentages of the components are respectively as follows: 10-50% of fully refined paraffin, 1-40% of mixed crystal wax, 10-50% of microcrystalline wax, 1-10% of coal-based wax, 1-10% of bio-based wax, 1-30% of fatty alcohol-polyoxyethylene ether and 1-30% of fatty alcohol-polyoxypropylene ether.
Preferably, the protective wax comprises the following components in percentage by weight: 12-45% of fully refined paraffin, 1-35% of mixed crystal wax, 15-45% of microcrystalline wax, 1-10% of coal-based wax, 1-10% of bio-based wax, 1-20% of fatty alcohol-polyoxyethylene ether and 1-20% of fatty alcohol-polyoxypropylene ether.
Wherein the melting point of the fully refined paraffin is 52-70 ℃; preferably, from 54 ℃ to 66 ℃.
Wherein the melting point of the mixed crystal wax is 70-80 ℃; preferably, from 72 ℃ to 80 ℃.
Wherein the melting point of the microcrystalline wax is 70-95 ℃; preferably, from 70 ℃ to 90 ℃.
Wherein the melting point of the coal-based wax is 70-120 ℃; preferably, it is from 80 ℃ to 115 ℃.
Wherein the melting point of the bio-based wax is 80-100 ℃; preferably, from 85 ℃ to 100 ℃.
Wherein the fully refined paraffin wax is one or more of fully refined petroleum wax with the grade number of 52# -70 #; preferably, 54# -68# of fully refined paraffin.
Wherein the mixed crystal wax is synthetic wax with non-normal alkane content of 35-45%; preferably, the wax is a synthetic wax with a non-normal alkane content of 38% -45%.
Wherein the microcrystalline wax is one or more of microcrystalline petroleum wax with the grade number of 70# -95 #; preferably microcrystalline petroleum wax, brand 70# -90 #.
Wherein the molecular weight of the coal-based wax is 300-1200; preferably, the molecular weight is 300-1000.
Wherein the bio-based wax is one or more of carnauba wax, rice bran wax, candelilla wax, sugar cane wax, bay wax, castor bean wax, jojoba wax, lacquer wax, pine wax, beeswax, insect wax, spermaceti wax, etc.; preferably, carnauba wax, rice bran wax, candelilla wax, lacquer wax, beeswax.
Wherein the structural formula of the fatty alcohol-polyoxyethylene ether is as follows: R-O- (C2H4O) m-H, wherein R is a saturated or unsaturated C12-18 alkyl group, m is the addition number of ethylene oxide, namely the number of oxyethylene groups in the molecule, and m is preferably 3-100.
Wherein the structural formula of the fatty alcohol polyoxypropylene ether is as follows: R-O- (C3H6O) n-H, wherein R is a saturated or unsaturated C12-18 alkyl group, n is the addition number of propylene oxide, i.e. the number of oxypropylene groups in the molecule, and n is preferably 3-70.
The n-alkane content of the novel protective wax is 30-60 percent; preferably, it is 35-55%.
Compared with the existing known protective wax, the novel protective wax has reasonable carbon number distribution, higher freezing point and better free flow characteristic, and the substantial differences enable the protective wax to provide long-term effective ozone protection for rubber products, improve the appearance quality of the rubber products, enable the rubber products to be bright and black in appearance, and simultaneously enable the prepared protective wax to have better anti-caking performance.
The invention also provides a preparation method of the novel protective wax, which comprises the following specific steps:
(1) weighing the fully refined paraffin, the mixed crystal wax, the microcrystalline wax, the fatty alcohol-polyoxyethylene ether, the fatty alcohol-polyoxypropylene ether, the bio-based wax and the coal-based wax according to the proportion;
(2) melting pot N2Replacing, adding weighed fully refined paraffin, mixed crystal wax, microcrystalline wax, fatty alcohol-polyoxyethylene ether, fatty alcohol-polyoxypropylene ether, bio-based wax and coal-based wax into a melting tank, heating to 80-150 ℃, melting for 10-60 minutes, entering a stirring tank after complete melting, heating to 80-120 ℃, and stirring for 10-60 minutes at constant temperature; and filtering the obtained product, cooling to about 80 ℃, transferring to granulation equipment, and granulating and forming to obtain the novel protective wax.
In the step (1), the fully refined paraffin wax is one or more of fully refined petroleum wax with the grade number of 52# -70 #; preferably, 54# -68# of fully refined paraffin.
In the step (1), the mixed crystal wax is synthetic wax with non-normal alkane content of 35-45%; preferably, the wax is a synthetic wax with a non-normal alkane content of 38% -45%.
In the step (1), the microcrystalline wax is one or more of microcrystalline petroleum waxes with the grades of 70# -95 #; preferably microcrystalline petroleum wax, brand 70# -90 #.
In the step (1), the molecular weight of the coal-based wax is 300-1200; preferably, the molecular weight is 300-1000.
In the step (1), the bio-based wax is one or more of carnauba wax, rice bran wax, candelilla wax, sugar cane wax, bay wax, castor bean wax, jojoba wax, lacquer wax, pine wax, beeswax, insect wax, spermaceti wax and the like; preferably, carnauba wax, rice bran wax, candelilla wax, lacquer wax.
In the step (1), the structural formula of the fatty alcohol-polyoxyethylene ether is as follows: R-O- (C2H4O) m-H, wherein R is a saturated or unsaturated C12-18 alkyl group, m is the addition number of ethylene oxide, namely the number of oxyethylene groups in the molecule, and m is preferably 3-100.
In the step (1), the structural formula of the fatty alcohol polyoxypropylene ether is as follows: R-O- (C3H6O) n-H, wherein R is a saturated or unsaturated C12-18 alkyl group, n is the addition number of propylene oxide, i.e. the number of oxypropylene groups in the molecule, and n is preferably 3-70.
In the step (1), the weight percentages of the fully refined paraffin wax, the mixed crystal wax, the microcrystalline wax, the fatty alcohol-polyoxyethylene ether, the fatty alcohol-polyoxypropylene ether, the bio-based wax and the coal-based wax are (10-50%): (1% -40%): (10% -50%): (1% -30%): (1% -30%): (1% -10%): (1% -10%); preferably, it is (12% -45%): (1% -35%): (15% -45%): (1% -20%): (1% -20%): (1% -10%): (1% -10%).
In the step (2), after the mixture is added into a melting tank, the temperature is preferably raised to 110-140 ℃, the melting time is preferably 20-50 min, after the mixture is completely melted, the mixture enters a stirring tank, the temperature is preferably raised to 85-115 ℃, and the constant-temperature stirring time is preferably 20-50 min.
And (2) granulating by cooling a steel belt.
The invention also provides the protective wax prepared by the method.
The invention also provides application of the protective wax in the field of diene rubber.
The fatty alcohol-polyoxyethylene ether, the fatty alcohol-polyoxypropylene ether, the bio-based wax and the coal-based wax used in the invention have the following advantages:
patent document CN107868479A discloses that the migration speed of the wax film is controlled by the proper normal/iso carbon content, the wax film for preventing the wax from migrating to the tire surface does not turn white, and the appearance quality can be improved, but during the long-term use of the tire, the wax may crystallize, resulting in the wax film migration speed being too fast and the tire surface appearance turning white. The fatty alcohol-polyoxyethylene ether and the fatty alcohol-polyoxypropylene ether used in the invention can effectively prevent the crystallization phenomenon of paraffin, so that the prepared protective wax has transparent appearance, and can form a transparent and bright wax film layer after migrating to the surface of rubber, thereby being capable of improving the appearance quality of tire products for a long time.
After the bio-based wax used by the invention is combined with other waxes used by the invention in a compatible manner, the protective wax has the properties of fine texture, permeability, toughness, smoothness and the like, can endow the product with a glossy feeling, can improve the appearance quality of a rubber product to a certain extent, increases the adhesive force of the protective wax on the surface of the rubber product, effectively prevents the wax film from falling off, and can provide long-lasting and long-acting ozone protection for the rubber product.
The coal-based wax used in the invention has a more obvious advantage than petroleum wax in price, can reduce the cost of the protective wax, is beneficial to improving the oxidation resistance of the protective wax and improving the weather resistance of the protective wax product; meanwhile, the coal-based wax is hard in texture and high in melting point, can improve the characteristics of the protective wax such as flexibility, viscosity and toughness, improves the free flowing characteristic of the protective wax, and avoids the caking phenomenon of the protective wax in the high-temperature storage or transportation process.
Compared with the prior art, the invention has the beneficial effects that:
(1) the protective wax prepared by the invention has the advantage of bright appearance, so that a wax film formed on the surface of the rubber is transparent and bright, and the appearance quality of a tire product can be effectively improved for a long time;
(2) the protective wax has higher adhesive force on the surface of a rubber product, effectively prevents the wax film from falling off on the surface of the rubber product, and can provide long-lasting and long-acting ozone protection for the rubber product;
(3) the protective wax improves the free flowing characteristic of the protective wax, and avoids the caking phenomenon of the protective wax in the high-temperature storage or transportation process;
(4) the protective wax of the invention has better weather resistance when being used for ozone protection of diene rubber.
Detailed Description
The present invention is further described in detail with reference to the following specific embodiments, and all changes and advantages that can be made by those skilled in the art without departing from the spirit and scope of the inventive concept are intended to be embraced therein. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
The novel protective wax comprises the following components in percentage by weight: 28% of fully refined paraffin, 18% of mixed crystal wax, 30% of microcrystalline wax, 4% of coal-based wax, 5% of bio-based wax, 10% of fatty alcohol-polyoxyethylene ether and 5% of fatty alcohol-polyoxypropylene ether. The freezing point of the product is 72 ℃, the normal carbon structure content is 47.9 percent, and the isoparaffin content is 52.1 percent.
Example 2
The novel protective wax comprises the following components in percentage by weight: 30% of fully refined paraffin, 21% of mixed crystal wax, 25% of microcrystalline wax, 5% of coal-based wax, 6% of bio-based wax, 8% of fatty alcohol-polyoxyethylene ether and 5% of fatty alcohol-polyoxypropylene ether. The freezing point of the product is 71 ℃, the normal carbon structure content is 47.7 percent, and the isoparaffin content is 52.3 percent.
Example 3
The novel protective wax comprises the following components in percentage by weight: 45% of fully refined paraffin, 9% of mixed crystal wax, 25% of microcrystalline wax, 5% of coal-based wax, 5% of bio-based wax, 6% of fatty alcohol-polyoxyethylene ether and 5% of fatty alcohol-polyoxypropylene ether. The freezing point of the product is 75 ℃, the normal carbon structure content is 53.9 percent, and the isoparaffin content is 46.1 percent.
Example 4
The novel protective wax comprises the following components in percentage by weight: 22% of fully refined paraffin, 22% of mixed crystal wax, 30% of microcrystalline wax, 6% of coal-based wax, 4% of bio-based wax, 8% of fatty alcohol-polyoxyethylene ether and 8% of fatty alcohol-polyoxypropylene ether. The freezing point of the product is 72 ℃, the normal carbon structure content is 49.7%, and the isoparaffin content is 50.3%.
Example 5
The novel protective wax comprises the following components in percentage by weight: 45% of fully refined paraffin, 1% of mixed crystal wax, 25% of microcrystalline wax, 10% of coal-based wax, 4% of bio-based wax, 7% of fatty alcohol-polyoxyethylene ether and 8% of fatty alcohol-polyoxypropylene ether. The freezing point of the product is 72 ℃, the normal carbon structure content is 46.7 percent, and the isoparaffin content is 53.3 percent.
Example 6
The novel protective wax comprises the following components in percentage by weight: 30% of fully refined paraffin, 15% of mixed crystal wax, 33% of microcrystalline wax, 8% of coal-based wax, 4% of bio-based wax, 5% of fatty alcohol-polyoxyethylene ether and 5% of fatty alcohol-polyoxypropylene ether. The freezing point of the product is 73 ℃, the normal carbon structure content is 41.2 percent, and the isoparaffin content is 55.8 percent.
The above examples are preferred embodiments of the present invention, and in order to illustrate the advantages of the present invention, commercial rubber protective wax is purchased from the market, and compared with the rubber protective wax obtained in examples 1 to 6 of the present invention, the influence of the product of the present invention on the physical properties of the tire and the protective effect are verified by comparing each item through the application experiment, and the experimental results are shown in the following table 1.
The specific sample preparation and the specific experimental procedure were as follows:
the preparation of the sample is strictly in accordance with GB/T6038-
1. Preparation of formula and sample:
NR (SCR 10): 40; BR 9000: 60, adding a solvent to the mixture; carbon black N550: 50; a process oil 12; chemical anti-aging agent: 5.0; protective wax: 2; and (3) sulfur: 1.5; other accelerators, etc.: 1.
2. experimental equipment and methods:
the 3L kneader, 6 inch open mill, Alpha rubber rotorless sulfur variation apparatus MDR2000, Alpha Mooney viscometer MV2000, Instron tensile machine 3365, and other equipment were used normally.
3. Mixing process:
7 different rubber protective waxes are subjected to the same-quantity variety-changing test of the formula. The same 2-stage mixing process was used, and mixing was carried out in a 3L kneader at 45r/min for one stage. The sulfur and accelerator were added at 25r/min in the second stage using the same equipment, and the sheet was taken off on a 6-inch open mill.
4. Ozone aging static and dynamic test method:
adopting ASTM D1149 GB7762 standard
Sample conditioning:
stretching 10%, or 20%, or 35%, or 50%, or others, standing at room temperature 23 ℃ for 0 hour, 24 hours, 48 hours, 72 hours, or more, standing for conditioning in the stretched state to allow the "wax film" that has broken in the stretched state to reform, the higher the congealing point, or the higher the iso-carbon content, or the higher the molecular weight of the protective wax, the longer the standing conditioning time is required to form a stable "protective film".
Ozone aging conditions:
ozone concentration: 50pphm, 100pphm, 200pphm, 300pphm, or others, selected from one of;
aging temperature: 40 + -2 deg.C, 0 + -2 deg.C, 20 + -2 deg.C, 50 + -2 deg.C, or others;
aging time: 24h, 36h, 48h, 60h, 72h, 96h or others, and one of them is selected.
TABLE 1 comparison of physical Properties of seven protective waxes in the same formulation
Detecting items Commercial protective wax Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
ML(dNm) 1.58 1.57 1.57 1.54 1.56 1.53 1.58
MH(dNm) 11.95 12.00 12.04 12.07 12.12 12.03 12.07
T90(s) 11.90 12.00 12.07 11.95 11.95 12.02 12.02
ts2(s) 6.80 6.87 6.90 6.82 6.82 6.89 6.89
ML1+4(100℃) 40 39 39 40 39 41 40
Scorch time TS5(127 ℃ C.) min 29.3 29.4 29.7 29.4 29.4 29.5 29.5
Shore A hardness 53 53 53 53 53 53 53
Tensile strength MPa 15.8 15.8 16.1 16.0 16.0 16.0 15.8
Elongation at break% 845 849 850 853 855 858 838
300% stress at definite elongation MPa 6.4 6.3 6.4 6.3 6.4 6.5 6.3
Tear Strength KN/m 58 58 56 58 57 58 57
As can be seen from Table 1, the seven rubber protective waxes have no obvious influence on the physical and mechanical properties of the rubber material, and the physical and mechanical properties are relatively close to each other.
Ozone aging according to GB7762 under the experimental conditions of 50pphm ozone concentration and 40 + -2 deg.C temperature, the experimental results are shown in the following table 2:
TABLE 2 comparison results of ozone accelerated tests in laboratory for seven protective waxes
Experimental protocol Commercial protective wax Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
24 hours Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks
36 hours Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks
48 hours Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks
60 hours Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks
72 hours Has cracks Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks
96 hours Has cracks Without cracks Without cracks Without cracks Without cracks Without cracks Without cracks
As can be seen from the comparison of the experimental results with Table 2, the ozone aging performance of the rubber protective wax prepared according to the examples 1-6 of the present invention is superior to that of the commercial protective wax product, so that the protective wax prepared according to the examples 1-6 of the present invention can provide long-term effective ozone protection for tires and rubber products.
TABLE 3 comparison of appearance quality of seven protective wax ozone accelerated test sizing materials
Experimental protocol Commercial protective wax Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
24 hours Blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair
48 hours Blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair
72 hours Slight white Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair
96 hours Whitening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair
128 hours Whitening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair Brightening and blackening hair
As can be seen from the comparison of the experimental results with Table 3, the rubber protective waxes prepared in examples 1-6 according to the present invention have better improvement in the appearance quality of tires than commercial protective wax products, so that the novel protective waxes prepared in examples 1-6 according to the present invention can effectively improve the appearance quality of tires and rubber products.
TABLE 4 comparison of the results of the anti-caking Performance of seven protective waxes at room temperature
Experimental protocol Commercial protective wax Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
6 months old Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate
12 months old Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate
18 months old Agglomeration of Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate
24 months Agglomeration of Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate Does not agglomerate
As can be seen from the comparison of the experimental results with Table 4, the anti-caking properties of the rubber protective waxes prepared according to examples 1-6 of the present invention are superior to those of the commercial protective wax products, so that the protective waxes prepared according to examples 1-6 of the present invention can prevent the caking phenomenon during storage or transportation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (12)

1. The protective wax is characterized by comprising the following components in percentage by weight: 10-50% of fully refined paraffin, 1-40% of mixed crystal wax, 10-50% of microcrystalline wax, 1-10% of coal-based wax, 1-10% of bio-based wax, 1-30% of fatty alcohol-polyoxyethylene ether and 1-30% of fatty alcohol-polyoxypropylene ether.
2. The protective wax of claim 1, wherein the fully refined paraffin wax has a melting point of 52 ℃ to 70 ℃; and/or the melting point of the mixed crystal wax is 70-80 ℃; and/or the melting point of the microcrystalline wax is 70-95 ℃; and/or the melting point of the coal-based wax is 70-120 ℃; and/or the melting point of the bio-based wax is 80-100 ℃.
3. The protective wax of claim 1, wherein the fully refined paraffin wax is one or more of fully refined petroleum waxes having a designation number of 52# -70 #; and/or the microcrystalline wax is one or more of microcrystalline petroleum wax with the grade number of 70-95 #.
4. The protective wax according to claim 1, wherein the mixed crystal wax is a synthetic wax having a non-normal paraffin content of 35 to 45%; and/or the molecular weight of the coal-based wax is 300-1200.
5. The protective wax of claim 1 wherein the fatty alcohol-polyoxyethylene ether has the formula: R-O- (C2H4O) m-H, wherein R is a saturated or unsaturated C12-18 alkyl group, and m is the addition number of ethylene oxide and is 3-100; and/or the structural formula of the fatty alcohol polyoxypropylene ether is as follows: R-O- (C3H6O) n-H, wherein R is a saturated or unsaturated C12-18 alkyl group, and n is the addition number of propylene oxide and is 3-70.
6. The protective wax of claim 1, wherein the bio-based wax is one or more of carnauba wax, rice bran wax, candelilla wax, sugarcane wax, bay wax, castor bean wax, jojoba wax, sumac wax, pine wax, beeswax, insect wax, spermaceti wax.
7. The protective wax of claim 1, wherein the protective wax has an n-alkane content of 30% to 60%.
8. The preparation method of the protective wax is characterized by comprising the following steps:
(1) weighing the fully refined paraffin, the mixed crystal wax, the microcrystalline wax, the fatty alcohol-polyoxyethylene ether, the fatty alcohol-polyoxypropylene ether, the bio-based wax and the coal-based wax according to the proportion;
(2) melting pot N2Replacing, adding the fully refined paraffin wax, the mixed crystal wax, the microcrystalline wax, the fatty alcohol-polyoxyethylene ether, the fatty alcohol-polyoxypropylene ether, the bio-based wax and the coal-based wax weighed in the step (1) into a melting tank, heating to 80-150 ℃, melting for 10-60 minutes, after complete melting, entering a stirring tank, heating to 80-120 ℃, and stirring for 10-60 minutes at constant temperature; and filtering the obtained product, cooling to 80 ℃, transferring to granulation equipment, and granulating and forming to obtain the protective wax.
9. The method of claim 8, wherein the fully refined paraffin wax is one or more of fully refined petroleum waxes having a designation number of 52# -70 #; and/or the microcrystalline wax is one or more of microcrystalline petroleum wax with the grade number of 70-95 #; and/or the mixed crystal wax is synthetic wax with non-normal alkane content of 35-45%; and/or the molecular weight of the coal-based wax is 300-1200; and/or the structural formula of the fatty alcohol-polyoxyethylene ether is as follows: R-O- (C2H4O) m-H, wherein R is a saturated or unsaturated C12-18 alkyl group, and m is the addition number of ethylene oxide and is 3-100; and/or the structural formula of the fatty alcohol polyoxypropylene ether is as follows: R-O- (C3H6O) n-H, wherein R is a saturated or unsaturated C12-18 alkyl group, and n is the addition number of propylene oxide and is 3-70; and/or the bio-based wax is one or more of carnauba wax, rice bran wax, candelilla wax, sugar cane wax, bay wax, castor bean wax, jojoba wax, sumac wax, pine wax, beeswax, insect wax and spermaceti wax.
10. The preparation method of claim 8, wherein the mass ratio of the fully refined paraffin wax, the mixed crystal wax, the microcrystalline wax, the fatty alcohol-polyoxyethylene ether, the fatty alcohol-polyoxypropylene ether, the bio-based wax and the coal-based wax is (10% -50%): (1% -40%): (10% -50%): (1% -30%): (1% -30%): (1% -10%): (1% -10%).
11. Protective wax prepared according to the process of any one of claims 8 to 10.
12. Use of the protective wax according to claim 1 in the field of diene rubbers.
CN201910915428.1A 2019-09-26 2019-09-26 Novel protective wax and application thereof in diene rubber field Active CN112552694B (en)

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0145448B1 (en) * 1983-12-06 1989-05-24 Nippon Oil Co. Ltd. Method for surface treatment of powdery and granular material stored in open air
JP3759284B2 (en) * 1997-05-19 2006-03-22 帝人株式会社 Integral molded body of thermoplastic resin and silicone rubber
CN101649119A (en) * 2009-03-20 2010-02-17 上海绿菱特种蜡制品厂 Novel rubber protective wax
WO2012061579A1 (en) * 2010-11-03 2012-05-10 Saudi Arabian Oil Company Sulfur modified asphalt for warm mix applications
CN102822262A (en) * 2010-08-25 2012-12-12 Nok株式会社 Nbr composition and rubber material for sealing
CN103665897A (en) * 2013-11-29 2014-03-26 山东永泰化工有限公司 Rubber protective agent
CN104059271A (en) * 2014-06-26 2014-09-24 青岛博洋生物技术有限公司 Light/heat-resistant rubber protective agent and preparation method thereof
CN104946134A (en) * 2015-07-08 2015-09-30 江苏四新科技应用研究所股份有限公司 Preparation method of stable oil-in-water emulsion with high solid content
CN106751940A (en) * 2017-01-17 2017-05-31 江苏卡欧化工股份有限公司 A kind of efficient rubber cracking preventing agent
CN108080564A (en) * 2017-12-29 2018-05-29 广州市德隆化工贸易有限公司 A kind of hot investment casting Wax particles mould material and preparation method and application
CN109777128A (en) * 2019-01-31 2019-05-21 青岛福凯橡塑新材料有限公司 A kind of high isoparaffin Wax-for preventing rubber and preparation method thereof
CN111212872A (en) * 2017-10-17 2020-05-29 日本精蜡株式会社 Surface modifier for rubber composition and rubber composition containing the same

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0145448B1 (en) * 1983-12-06 1989-05-24 Nippon Oil Co. Ltd. Method for surface treatment of powdery and granular material stored in open air
JP3759284B2 (en) * 1997-05-19 2006-03-22 帝人株式会社 Integral molded body of thermoplastic resin and silicone rubber
CN101649119A (en) * 2009-03-20 2010-02-17 上海绿菱特种蜡制品厂 Novel rubber protective wax
CN102822262A (en) * 2010-08-25 2012-12-12 Nok株式会社 Nbr composition and rubber material for sealing
WO2012061579A1 (en) * 2010-11-03 2012-05-10 Saudi Arabian Oil Company Sulfur modified asphalt for warm mix applications
CN103665897A (en) * 2013-11-29 2014-03-26 山东永泰化工有限公司 Rubber protective agent
CN104059271A (en) * 2014-06-26 2014-09-24 青岛博洋生物技术有限公司 Light/heat-resistant rubber protective agent and preparation method thereof
CN104946134A (en) * 2015-07-08 2015-09-30 江苏四新科技应用研究所股份有限公司 Preparation method of stable oil-in-water emulsion with high solid content
CN106751940A (en) * 2017-01-17 2017-05-31 江苏卡欧化工股份有限公司 A kind of efficient rubber cracking preventing agent
CN111212872A (en) * 2017-10-17 2020-05-29 日本精蜡株式会社 Surface modifier for rubber composition and rubber composition containing the same
CN108080564A (en) * 2017-12-29 2018-05-29 广州市德隆化工贸易有限公司 A kind of hot investment casting Wax particles mould material and preparation method and application
CN109777128A (en) * 2019-01-31 2019-05-21 青岛福凯橡塑新材料有限公司 A kind of high isoparaffin Wax-for preventing rubber and preparation method thereof

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
PASTORBLAS, MM 等: "Weak boundary layers in styrene-butadiene rubber", 《JOURNAL OF ADHESION》 *
PASTORBLAS, MM 等: "Weak boundary layers in styrene-butadiene rubber", 《JOURNAL OF ADHESION》, vol. 50, no. 2, 31 December 1995 (1995-12-31), pages 191 - 210 *
SUARIA, GIUSEPPE 等: "The Occurrence of Paraffin and Other Petroleum Waxes in the Marine Environment: A Review of the Current Legislative Framework and Shipping Operational Practices", 《FRONTIERS IN MARINE SCIENCE》 *
SUARIA, GIUSEPPE 等: "The Occurrence of Paraffin and Other Petroleum Waxes in the Marine Environment: A Review of the Current Legislative Framework and Shipping Operational Practices", 《FRONTIERS IN MARINE SCIENCE》, vol. 05, 27 March 2018 (2018-03-27) *
刘炳义: "《中国石油化工商品手册》", 31 March 2000, 中国石化出版社, pages: 224 *
刘练 等: "不同碳数分布防护蜡对胶料性能影响探讨", 《中国橡胶》 *
刘练 等: "不同碳数分布防护蜡对胶料性能影响探讨", 《中国橡胶》, vol. 30, no. 17, 30 September 2014 (2014-09-30), pages 46 - 48 *
周秋成: "煤焦油制蜡技术的研究", 《石油炼制与化工》 *
周秋成: "煤焦油制蜡技术的研究", 《石油炼制与化工》, vol. 49, no. 12, 31 December 2018 (2018-12-31), pages 58 - 63 *
李凤艳 等: "分子筛吸附法测定微晶蜡正、异构烷烃含量", 《石油化工》 *
李凤艳 等: "分子筛吸附法测定微晶蜡正、异构烷烃含量", 《石油化工》, no. 04, 30 April 1997 (1997-04-30), pages 3 *
胡伟庆 等: "国内外橡胶防护蜡的研究进展与市场应用状况", 《合成橡胶工业》 *
胡伟庆 等: "国内外橡胶防护蜡的研究进展与市场应用状况", 《合成橡胶工业》, vol. 38, no. 06, 30 November 2015 (2015-11-30), pages 486 - 491 *

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