CN112898570B - Sulfurized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt and preparation method and application thereof - Google Patents
Sulfurized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a sulfur-zinc-containing soap salt of sulfurized natural unsaturated phenol modified fatty acid and a preparation method thereof. The zinc soap salt can disperse white carbon black in vulcanized rubber, and the molecular structure of the zinc soap salt also contains a reactive sulfur-containing side chain and a phenolic hydroxyl group with higher activity, so that the mechanical property, wet gripping property and wear resistance of the rubber can be effectively improved. The invention also provides application of the zinc soap salt in rubber products such as tire treads, steel wire coating rubber, carcass cords and the like. The invention takes renewable, green and environment-friendly natural products with rich resources as raw materials, and conforms to the strategy of sustainable development.
Description
Technical Field
The invention relates to the field of rubber processing aids, in particular to a vulcanized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt and a preparation method and application thereof.
Background
White carbon black is a rubber reinforcing filler which has a great development prospect and is second to carbon black, but the surface of the white carbon black contains a large amount of hydroxyl, so that the white carbon black has high acidity, hygroscopicity and hydrophilicity; poor compatibility with rubber, high viscosity of a large amount of filling rubber materials, poor processability along with the prolonging of storage time, difficult hardening and extrusion of the rubber materials after storage, poor molding viscosity and the like, and easy generation of static accumulation of the filling rubber materials [ beauty and auspicious, rubber industry, 2004,51(6):376 and 378 ]. Therefore, in the processing of various rubbers, some processing aids are required to improve the processability of the compounds.
The processing aids commonly used at present comprise fatty acid metal soaps, fatty acid alcohols, fatty acid amides, fatty acid esters and other fatty acid derivatives, wherein the fatty acid metal soaps are most commonly used and are composed of longer fatty carbon chains and metal ions, the long carbon chain structure enables the fatty acid soaps to be easily dissolved in a rubber matrix, and the polar metal ions have good affinity with white carbon black, so that the dispersion of the white carbon black in the rubber matrix is favorably improved [ Von Kunhao et al, Guangdong rubber, 2018,10:21-26 ]. Research shows that when the unsaturated fatty acid zinc soap processing aid is added, the Mooney viscosity of the NR sizing material is obviously reduced, and along with the increase of the unsaturation degree of the unsaturated fatty acid zinc soap processing aid, the Mooney viscosity of the NR sizing material is greatly reduced, the dispersion performance of carbon black is improved, the reversion resistance performance is improved, and the heat aging resistance performance is reduced [ Lixibo et al, rubber science and technology, 2015,5:15-18 ].
Meanwhile, Liuyansheng and the like carry out application research on unsaturated fatty acid zinc soap salt processing aids DR and Z210 and a plasticizer A in NR and NR/BR blend rubber, and research shows that the unsaturated fatty acid zinc soap salt plays a role in internal lubrication in rubber, namely a role in a physical peptizer which does not damage a rubber macromolecular chain, improves the dynamic performance of vulcanized rubber, but has no significant influence on the physical and mechanical properties of the rubber [ Liuyansheng and the like, tire industry, 2001,21(8): 475-.
Because the existing fatty acid zinc soap salt does not react with rubber molecules, a strong polar force is formed between a polar functional group and the rubber molecules to play an internal plasticization role, if the fatty acid zinc soap salt is not well dissolved in the rubber, the use performance of the rubber product is reduced, and the service life of the rubber product is shortened.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a vulcanized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt capable of being used as a rubber processing aid and a preparation method thereof. The side chain of the natural unsaturated phenol generally contains more than one unsaturated double bond, the natural unsaturated phenol and unsaturated fatty acid are firstly subjected to a vulcanization reaction with sulfur under the protection of nitrogen, then a certain amount of fatty acid is added, and the mixture is mixed and then reacts with zinc oxide to prepare the zinc soap salt containing sulfur and phenolic hydroxyl. The prepared sulfur-containing zinc soap salt of the vulcanized natural unsaturated phenol modified fatty acid can disperse white carbon black, the sulfur-containing side chain can participate in rubber vulcanization, and the phenolic hydroxyl can also react with the white carbon black, so that the mechanical property, wet gripping property and wear resistance of the rubber material can be effectively improved, and the sulfur-containing zinc soap salt can be used as a rubber processing aid to be applied to rubber and products thereof. The invention takes renewable, green and environment-friendly natural products with rich resources as raw materials, and conforms to the strategy of sustainable development.
The invention provides a sulfurized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt, wherein natural unsaturated phenols in molecules of the sulfurized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt include but are not limited to urushiol and cardanol.
The invention also provides a preparation method of the sulfur-containing zinc soap salt of sulfurized natural unsaturated phenol modified fatty acid, which comprises the following steps:
(1) and (3) vulcanization reaction: and carrying out vulcanization reaction on the natural unsaturated phenol, the unsaturated fatty acid and sulfur to obtain the vulcanized natural unsaturated phenol modified unsaturated fatty acid sulfur-containing resin.
(2) And (3) saponification reaction: the first stage, adding fatty acid and a certain amount of zinc oxide into the sulfurated natural unsaturated phenol modified unsaturated fatty acid sulfur-containing resin obtained in the step (1) to carry out saponification reaction for a period of time; and in the second stage, adding a certain amount of zinc oxide for saponification reaction to obtain the sulfur-zinc-containing soap salt of the sulfurized natural unsaturated phenol modified fatty acid.
The invention also comprises a granulation step after the step (2): pouring out the sulfur-containing zinc soap salt of the sulfurized natural unsaturated phenol modified fatty acid prepared in the step (2), cooling to obtain solid sulfur-containing zinc soap salt of the sulfurized natural unsaturated phenol modified fatty acid, bagging and granulating to finish.
In the step (1), the natural unsaturated phenol is any one of urushiol and cardanol or a combination of two of urushiol and cardanol in any molar ratio.
In the step (1), the unsaturated fatty acid is one or more of oleic acid, linoleic acid, ricinoleic acid, eleostearic acid, arachidonic acid, tall oil fatty acid, palm oil fatty acid, soybean oil fatty acid and the like; preferably, oleic acid.
In the step (1), the molar ratio of the natural unsaturated phenol to the unsaturated fatty acid to the sulfur in the sulfuration reaction is (0.1-1) to 1 (0.1-4); preferably, it is 1: 1: 1.
in the step (1), the temperature of the vulcanization reaction is 140-180 ℃; preferably, it is 160 ℃.
In the step (1), the time of the vulcanization reaction is 3-6 h; preferably, it is 4 h.
In the step (1), the sulfurization reaction is preferably carried out under the protection of nitrogen.
In the step (2), the fatty acid is one or more of oleic acid, linoleic acid, ricinoleic acid, eleostearic acid, arachidonic acid, tall oil fatty acid, palm oil fatty acid, soybean oil fatty acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, pearlescent fatty acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, lacceric acid and the like; preferably, stearic acid.
In the step (2), the molar ratio of the added fatty acid to the unsaturated fatty acid added in the vulcanization reaction is 1 (0.01-1); preferably, it is 1: 1.
in the first stage, 2/3 is added, wherein the amount of zinc oxide accounts for the total molar amount of zinc oxide.
In the step (2), in the first stage, the temperature of the saponification reaction is 120-140 ℃; preferably, it is 130 ℃.
In the step (2), in the first stage, the saponification reaction time is 0.5-1.5 h; preferably, it is 1.0 h.
In the second stage, 1/3, which is the total molar weight of zinc oxide, is added into the solution in step (2).
In the step (2), in the second stage, the saponification reaction temperature is 120-140 ℃; preferably 130 deg.c.
In the step (2), in the second stage, the saponification reaction time is 0.5-1.5 h; preferably, it is 1.5 h.
In the step (2), the total molar amount of the zinc oxide is 0.5-0.6 times of the total molar amount of the carboxylic acid; preferably 0.5 times.
In one embodiment, the preparation method of the sulfurized natural unsaturated phenol modified fatty acid zinc sulfate-containing soap salt comprises the following steps:
the first step is as follows: firstly, under the protection of nitrogen, carrying out a vulcanization reaction on cardanol, unsaturated fatty acid and sulfur to synthesize vulcanized cardanol modified unsaturated fatty acid sulfur-containing resin shown as a structural formula (I):
wherein x is in the range of 1-4; preferably, it is 1.
The second step: and then reacting the vulcanized cardanol modified unsaturated fatty acid sulfur-containing resin shown in the formula (I) with zinc oxide to obtain vulcanized cardanol modified fatty acid sulfur-containing zinc soap salt shown in the structural formula (II):
wherein x ranges from 1 to 4; preferably, it is 1.
The third step: pouring out the hot sulfurized cardanol modified fatty acid sulfur-containing zinc soap salt, cooling to obtain sulfurized cardanol modified fatty acid sulfur-containing zinc soap salt solid, bagging, and granulating.
In another embodiment, the preparation method of the sulfurized natural unsaturated phenol modified fatty acid zinc sulfate-containing soap salt comprises the following steps:
the first step is as follows: firstly, under the protection of nitrogen, carrying out a vulcanization reaction on urushiol, unsaturated fatty acid and sulfur to synthesize a sulfurized urushiol modified unsaturated fatty acid sulfur-containing resin shown as a structural formula (III):
wherein x is in the range of 1-4; preferably, it is 1.
The second step is that: and then reacting the urushiol sulfide modified unsaturated fatty acid sulfur-containing resin shown as the formula (III) with zinc oxide to obtain a zinc soap salt shown as a structural formula (IV):
wherein x ranges from 1 to 4; preferably, it is 1.
The third step: pouring out the hot sulfur zinc soap salt of the urushiol sulfide modified fatty acid, cooling to obtain a solid sulfur zinc soap salt of the urushiol sulfide modified fatty acid, bagging and granulating.
In another embodiment, the preparation method of the sulfurized natural unsaturated phenol modified fatty acid zinc sulfate soap salt comprises the following steps:
the first step is as follows: firstly, under the protection of nitrogen, performing a vulcanization reaction on cardanol, urushiol, unsaturated fatty acid and sulfur to synthesize a vulcanized natural unsaturated phenol modified unsaturated fatty acid sulfur-containing resin shown as a structural formula (V):
wherein x ranges from 1 to 4; preferably, it is 1.
The second step: and then reacting the sulfurized natural unsaturated phenol modified unsaturated fatty acid sulfur-containing resin shown in the formula (V) with zinc oxide to obtain sulfurized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt with the structural formula (VI):
wherein x is in the range of 1-4; preferably, it is 1.
The third step: pouring out the hot vulcanized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt, cooling to obtain a vulcanized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt solid, bagging, and granulating.
The invention also provides the sulfur-containing zinc soap salt of the sulfurized natural unsaturated phenol modified fatty acid prepared by the method.
The invention also provides application of the sulfur-containing zinc soap salt of the vulcanized natural unsaturated phenol modified fatty acid as a processing aid in rubber and products thereof.
The invention also provides application of the sulfur-containing zinc soap salt of the sulfurized natural unsaturated phenol modified fatty acid in rubber compounds containing white carbon black formulas.
Wherein, the rubber and the products thereof comprise tire treads, steel wire coating, tire carcass cords and the like.
The invention has the beneficial effects that: 1) natural unsaturated phenol is adopted as a basic raw material, and is firstly mixed with unsaturated fatty acid, then the mixture is subjected to a vulcanization reaction with sulfur, and finally the mixture is subjected to a saponification reaction with zinc oxide to prepare the vulcanized natural unsaturated phenol modified fatty acid zinc-sulfur-containing soap salt, wherein the unsaturated side chain is grafted with sulfur elements, and active phenolic hydroxyl groups are reserved, so that the vulcanized natural unsaturated phenol modified fatty acid zinc-sulfur-containing soap salt is a multifunctional rubber processing aid. 2) The prepared sulfur-zinc-containing soap salt of the vulcanized natural unsaturated phenol modified fatty acid can disperse white carbon black, can vulcanize rubber by reactive sulfur side chains contained in the molecular structure of the soap salt, can couple white carbon black by phenolic hydroxyl with higher activity, can effectively improve the mechanical property, wet grip performance and wear resistance of rubber materials, and can be used as a rubber processing aid to be applied to rubber and products thereof. The conventional fatty acid zinc soap salt does not react with rubber molecules, and only forms stronger polar force between polar functional groups and the rubber molecules, thereby playing an internal plasticizing role. 3) The method adopts natural unsaturated phenol and fatty acid as basic raw materials to prepare the sulfur-containing zinc soap salt of sulfurized natural unsaturated phenol modified fatty acid, has simple process flow, takes natural products with rich resources as raw materials, has wide raw material sources, is green and environment-friendly, and has renewability.
Drawings
FIG. 1 is an infrared spectrum of cardanol, oleic acid and sulfurized cardanol modified fatty acid resin; 3009cm -1 The absorption peak is the absorption peak of carbon-hydrogen vibration of the unsaturated double bond of the cardanol side chain, and is 3008cm -1 The absorption peak is the hydrocarbon vibration absorption peak of the oleic acid unsaturated double bond, and the absorption peak on the spectrum of the sulfurized cardanol modified fatty acid resin almost disappears, which indicates that the sulfurization reaction occurs, and the unsaturated double bond on the side chain of cardanol completely reacts with sulfur.
FIG. 2 is an infrared spectrum of a urushiol, oleic acid and sulfurized urushiol modified fatty acid resin; 3011cm -1 The absorption peak is the absorption peak of carbon-hydrogen vibration of urushiol side chain unsaturated double bond, 3008cm -1 The absorption peak is the carbon-hydrogen vibration absorption peak of the oleic acid unsaturated double bond, and the absorption peak on the spectrum of the sulfurized urushiol modified fatty acid resin almost disappears, which indicates that the sulfurization reaction occurs, and the unsaturated double bond on the urushiol side chain is completely reacted with sulfur.
FIG. 3 is a gel permeation chromatogram of cardanol, oleic acid and sulfurized cardanol modified fatty acid resin, in a GPC spectrum of cardanol, the number of the first peak is the relative molecular mass (M) n ) 484% at 93.8%, the number of the second minor peak is relative to the molecular mass (M) n ) 641 in a ratio of 4.59%; number average relative molecular mass (M) in GPC spectra of sulfurized cardanol modified fatty acid resins n ) 53.62%, 21.12%, 10.03% and 15.24% respectively at about 470, 1252, 1665 and 2888; therefore, the experiment is carried out according to the design thought, and the target product is successfully synthesized.
FIG. 4 is a gel permeation chromatogram of urushiol, oleic acid, and sulfurized urushiol modified fatty acid resin, in which the GPC spectra of urushiol are the number average relative molecular mass (M) n ) About 564, 677, 1443 and 2578, respectively, account for 21.19%, 58.63%, 12.62% and 7.14%; number average relative molecular mass (M) in GPC chart of sulfurized urushiol modified fatty acid resin n ) At 494, 675, 1281, 1889. 2524, 3196, 5579 and 18367 account for 24.25%, 10.74%, 13.95%, 8.10%, 6.14%, 4.02%, 17.43% and 15.37% respectively. Therefore, the experiment is carried out according to the design idea, and the target product is successfully synthesized.
FIG. 5 is a Payne effect graph showing that the dynamic modulus of each group decreases sharply with increasing stress; the weaker the Payne effect, the better the dispersion of the reinforcement system. In fig. 5, the curves from top to bottom are comparative example 1, comparative example 2 and examples 1 to 5 in sequence, and compared with comparative examples 1 to 2, the modulus of examples 1 to 5 of the present invention is greatly reduced, which indicates that the sulfurized natural unsaturated phenol modified fatty acid zinc sulfate soap salt prepared in examples 1 to 5 of the present invention can effectively promote the dispersion of white carbon black and has the function of dispersing white carbon black.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be determined by the appended claims. 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.
In the experiment of the invention, sulfur, zinc oxide and cardanol are of industrial grade, oleic acid and stearic acid are analytically pure, urushiol, zinc fatty acid and zinc sulfurized fatty acid are prepared by the laboratory, and the iodine value of cardanol is 156.33gI 2 100g, iodine value of urushiol 167.64gI 2 100g, oleic acid iodine value of 118gI 2 /100g。
Example 1
Adding 30.0g of cardanol, 28.2g of oleic acid and 3.2g of sulfur into a 500ml round-bottom flask provided with a stirring device, a temperature control device, a reflux condenser and a dropping funnel, reacting for 4 hours at 165 ℃ under the protection of nitrogen, absorbing tail gas with distilled water, and enabling a sample to be black viscous liquid; cooling, adding 28.4g of stearic acid, mixing, adding 5.4g of zinc oxide, and reacting for 1 hour at 135 ℃; adding 2.7g of zinc oxide, reacting at 135 ℃ for 2.5h, and stopping the reaction to obtain the sulfurized cardanol modified fatty acid zinc sulfate-containing soap salt; pouring out the hot vulcanized cardanol modified fatty acid sulfur-containing zinc soap salt, cooling to obtain a sulfur-containing zinc soap salt solid, bagging, and granulating to finish.
Example 2
Adding 15.0g of cardanol, 28.2g of oleic acid and 3.2g of sulfur into a 500ml round-bottom flask provided with a stirring device, a temperature control device, a reflux condenser and a dropping funnel, reacting for 4 hours at 165 ℃ under the protection of nitrogen, absorbing tail gas with distilled water, and enabling a sample to be black viscous liquid; cooling, adding 28.4g of stearic acid, mixing, adding 5.4g of zinc oxide, and reacting for 1 hour at 135 ℃; adding 2.7g of zinc oxide, reacting at 135 ℃ for 1.5h, and stopping the reaction to obtain the sulfurized cardanol modified fatty acid zinc-sulfur-containing soap salt; pouring out the hot vulcanized cardanol modified fatty acid sulfur-containing zinc soap salt, cooling to obtain a sulfur-containing zinc soap salt solid, bagging, and granulating to finish.
Example 3
Adding 33.0g of urushiol, 28.2g of oleic acid and 3.2g of sulfur into a 500ml round-bottom flask provided with a stirring device, a temperature control device, a reflux condenser and a dropping funnel, reacting for 4 hours at 165 ℃ under the protection of nitrogen, absorbing tail gas with distilled water, and enabling a sample to be black viscous liquid; after cooling, 28.4g of stearic acid is added and mixed, 5.4g of zinc oxide is added, and the mixture reacts for 1 hour at 135 ℃; adding 2.7g of zinc oxide, reacting at 135 ℃ for 1.5h, and stopping the reaction to obtain the urushiol sulfide modified fatty acid zinc sulfate-containing soap salt; pouring out the hot sulfur-containing zinc soap salt of the urushiol sulfide modified fatty acid, cooling to obtain a sulfur-containing zinc soap salt solid, bagging, and granulating.
Example 4
Adding 16.5g urushiol, 28.2g oleic acid and 3.2g sulfur into a 500ml round-bottom flask provided with a stirring device, a temperature control device, a reflux condenser and a dropping funnel, reacting for 4 hours at 165 ℃ under the protection of nitrogen, absorbing tail gas by distilled water, and enabling a sample to be black viscous liquid; cooling, adding 28.4g of fatty acid, mixing, adding 5.4g of zinc oxide, and reacting at 135 ℃ for 1 h; adding 2.7g of zinc oxide, reacting at 135 ℃ for 2.5h, and stopping the reaction to obtain the sulfur zinc soap salt of the urushiol-sulfide modified fatty acid; pouring out the hot sulfur-containing zinc soap salt of the urushiol sulfide modified fatty acid, cooling to obtain a sulfur-containing zinc soap salt solid, bagging, and granulating.
Example 5
Adding 15.0g of cardanol, 16.5g of urushiol, 28.2g of oleic acid and 3.2g of sulfur into a 500ml round-bottom flask provided with a stirring device, a temperature control device, a reflux condenser and a dropping funnel, reacting for 4 hours at 165 ℃ under the protection of nitrogen, absorbing tail gas with distilled water, and enabling a sample to be black sticky liquid; after cooling, 28.2g of stearic acid is added and mixed, 5.4g of zinc oxide is added, and the mixture reacts for 1 hour at 135 ℃; adding 2.7g of zinc oxide, reacting at 135 ℃ for 3.0h, and stopping the reaction to obtain sulfurized natural unsaturated phenol modified fatty acid zinc sulfate-containing soap salt; pouring out the hot sulfurized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt, cooling to obtain sulfur-containing zinc soap salt solid, bagging and granulating.
Comparative example 1
Adding 28.2g of oleic acid and 28.4g of stearic acid into a 250ml round-bottom flask provided with a stirring device, a temperature control device, a reflux condenser and a dropping funnel, mixing, heating to 135 ℃, adding 5.4g of zinc oxide, and reacting for 1 hour; adding 2.7g of zinc oxide, reacting at 135 ℃ for 2.0h, and stopping the reaction to obtain fatty acid zinc soap salt; pouring out hot fatty acid zinc soap salt, cooling, bagging and granulating.
Comparative example 2
Adding 56.4g of oleic acid and 3.2g of sulfur into a 500ml round-bottom flask provided with a stirring device, a temperature control device, a reflux condenser and a dropping funnel, reacting for 4 hours at 165 ℃ under the protection of nitrogen, absorbing tail gas by distilled water, and enabling a sample to be black viscous liquid; cooling, adding 28.4g of stearic acid, mixing, adding 8.1g of zinc oxide, and reacting for 1 hour at 135 ℃; adding 4.0g of zinc oxide, reacting at 135 ℃ for 2.0h, and stopping the reaction to obtain the sulfur-zinc-containing soap salt of the sulfurized fatty acid; pouring out the hot sulfur-containing zinc soap salt of the sulfurized fatty acid, cooling to obtain solid sulfur-containing zinc soap salt, bagging and granulating.
TABLE 1 rubber application test formulation
Example 6 rubber article applications
In the first step, the rubber components are mixed and kneaded at about 155 ℃ using a Banbury mixer to prepare a master batch.
In the second step, the zinc soap salt and the powder prepared in example 1, example 2, example 3, example 4, example 5, comparative example 1 and comparative example 2 were mixed into a master batch obtained by kneading in a Banbury mixer at a temperature of about 155 ℃.
Thirdly, adding the vulcanizing agent and the accelerator CBS listed in the table 1 at 60-80 ℃ for mixing, and placing the product obtained by mixing in an environment with a constant temperature of about 23 ℃ and a relative humidity of 50% overnight. Then, the sulfur rheometer vulcanization, shape, and optimum vulcanization degree were measured at 160 ℃ to obtain test data on the modified vulcanized rubber compositions shown in tables 2, 3, and 4. Wherein, the tensile property is tested by GB/T528-2009, and the vulcanization condition of the rubber material is 160 ℃ for 30 min; the hardness is tested by GB/T531.1-2008; DMA test is carried out by adopting a METTLER TOLEDO instrument; the DIN abrasion adopts a drum type abrasion tester, and refers to the standards GB/T9867-2008 and GB/T533-2008; Payne-G' using an RPA2000 rubber processing Analyzer, according to the standard ASTM 6601.
TABLE 2 mechanical Properties
TABLE 3 DMA test
TABLE 4 DIN abrasion
As can be seen from the data in tables 2, 3 and 4, compared with the data in comparative examples 1-2, the mechanical properties of the rubber compound modified by the sulfurized natural unsaturated phenol modified fatty acid sulfur-containing zinc soap salt prepared by the invention in examples 1-5 are improved to different degrees, the tensile strength and the tensile elongation are obviously increased, and the 100 percent definite elongation (MPa), the 300 percent definite elongation (MPa), the tear strength and the hardness are increased, which shows that the mechanical properties of the rubber compound modified by the natural unsaturated phenol are improved. DMA test results show that compared with comparative examples 1-2, Tan sigma (0 ℃) values of rubber compounds modified by vulcanized natural unsaturated phenol modified fatty acid sulfur-zinc-containing soap salts prepared in examples 1-5 of the invention are obviously increased, which shows that wet grip performance of cardanol and urushiol modified fatty acid zinc soap salt rubber compounds is greatly improved; DIN abrasion shows that the abrasion index of the rubber material modified by the sulfurized natural unsaturated phenol modified fatty acid containing zinc sulfate soap salt prepared in examples 1-5 of the invention is obviously increased compared with that of comparative examples 1-2, which shows that the modified fatty acid zinc sulfate soap salt can effectively improve the abrasion resistance.
Therefore, the natural unsaturated phenol modified fatty acid zinc soap salt prepared by the embodiment of the invention can improve the physical and mechanical properties of rubber materials, can be used as a white carbon black dispersing agent to be applied to rubber and products thereof, and can replace or partially replace the existing fatty acid zinc soap salt.
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 (10)
1. A preparation method of sulfur-containing zinc soap salt of sulfurized natural unsaturated phenol modified fatty acid is characterized by comprising the following steps:
in the first step, a vulcanization reaction: carrying out vulcanization reaction on natural unsaturated phenol, unsaturated fatty acid and sulfur to obtain vulcanized natural unsaturated phenol modified unsaturated fatty acid sulfur-containing resin; the natural unsaturated phenol is any one of urushiol and cardanol or the combination of two of urushiol and cardanol in any molar ratio; the unsaturated fatty acid is oleic acid;
step two, saponification: a first stage, adding fatty acid and a certain amount of zinc oxide into the vulcanized natural unsaturated phenol modified unsaturated fatty acid sulfur-containing resin obtained in the first step to carry out saponification reaction for a period of time; in the second stage, a certain amount of zinc oxide is added for saponification reaction to obtain the sulfur-zinc-containing soap salt of the sulfurized natural unsaturated phenol modified fatty acid;
the fatty acid is stearic acid;
the first stage, adding 2/3 of zinc oxide with the amount accounting for the total molar weight of the zinc oxide; the second stage, 1/3 of the total molar quantity of zinc oxide is added;
in the first stage, the saponification reaction time is 0.5-1.5 h.
2. The method according to claim 1, wherein in the first step, the natural unsaturated phenol, the unsaturated fatty acid and the sulfur are subjected to the sulfurization reaction at a molar ratio of (0.1-1): 1 (0.1-4).
3. The method according to claim 1, wherein in the first step, the temperature of the vulcanization reaction is 140 to 180 ℃; and/or the time of the vulcanization reaction is 3-6 h.
4. The method according to claim 1, wherein the molar ratio of the fatty acid to the unsaturated fatty acid in the first sulfurization reaction in the second step is 1 (0.01-1).
5. The method of claim 1, wherein in the second step, the total molar amount of zinc oxide added is 0.5 to 0.6 times the total molar amount of carboxylic acid.
6. The method according to claim 1, wherein in the second step, the saponification reaction is carried out at a temperature of 120 to 140 ℃ in the first step; in the second stage, the temperature of the saponification reaction is 120-140 ℃; the saponification reaction time is 0.5-1.5 h.
7. Sulfurized zinc sulfate-containing soap salt of a naturally unsaturated phenol-modified fatty acid prepared by the method as defined in any one of claims 1 to 6.
8. Use of the sulfur-containing zinc soap salt of sulfurized natural unsaturated phenolic modified fatty acid as claimed in claim 7 as a processing aid in rubber and its products.
9. The use according to claim 8, wherein the rubber and its articles are prepared from a rubber compound containing a white carbon formulation.
10. The use of claim 8 wherein the rubber and its articles include tire treads, wire skim and tire carcass cords.
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|---|---|---|---|---|
| CN103333378A (en) * | 2013-05-23 | 2013-10-02 | 青岛福凯橡塑新材料有限公司 | White carbon black dispersant and preparation method thereof |
| CN103387695A (en) * | 2013-08-06 | 2013-11-13 | 山东阳谷华泰化工股份有限公司 | White carbon black dispersing agent and preparation method thereof |
| JP2015110750A (en) * | 2013-11-01 | 2015-06-18 | 荒川化学工業株式会社 | Rosin-modified phenolic resin, binder for offset printing ink, varnish for offset printing ink, and offset printing ink |
| CN106397865A (en) * | 2016-10-21 | 2017-02-15 | 北京彤程创展科技有限公司 | Rubber composition for tread and tire tread prepared from rubber composition |
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2019
- 2019-12-04 CN CN201911225681.0A patent/CN112898570B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333378A (en) * | 2013-05-23 | 2013-10-02 | 青岛福凯橡塑新材料有限公司 | White carbon black dispersant and preparation method thereof |
| CN103387695A (en) * | 2013-08-06 | 2013-11-13 | 山东阳谷华泰化工股份有限公司 | White carbon black dispersing agent and preparation method thereof |
| JP2015110750A (en) * | 2013-11-01 | 2015-06-18 | 荒川化学工業株式会社 | Rosin-modified phenolic resin, binder for offset printing ink, varnish for offset printing ink, and offset printing ink |
| CN106397865A (en) * | 2016-10-21 | 2017-02-15 | 北京彤程创展科技有限公司 | Rubber composition for tread and tire tread prepared from rubber composition |
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