CN115716819A - Rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium and preparation method and application thereof - Google Patents
Rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium and preparation method and application thereof Download PDFInfo
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- -1 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium Chemical compound 0.000 title claims abstract description 66
- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000005060 rubber Substances 0.000 title claims abstract description 65
- 239000000654 additive Substances 0.000 title claims abstract description 32
- 230000000996 additive effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 104
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019441 ethanol Nutrition 0.000 claims abstract description 31
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 21
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 12
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 9
- 230000022244 formylation Effects 0.000 claims abstract description 4
- 238000006170 formylation reaction Methods 0.000 claims abstract description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 15
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- 239000002244 precipitate Substances 0.000 claims description 8
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 claims description 7
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 claims description 7
- 229960003495 thiamine Drugs 0.000 claims description 7
- 235000019157 thiamine Nutrition 0.000 claims description 7
- 239000011721 thiamine Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- HDOWRFHMPULYOA-UHFFFAOYSA-N piperidin-4-ol Chemical compound OC1CCNCC1 HDOWRFHMPULYOA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 abstract description 26
- 230000003712 anti-aging effect Effects 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052711 selenium Inorganic materials 0.000 abstract description 4
- 239000011669 selenium Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 abstract 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002174 Styrene-butadiene Substances 0.000 description 14
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 230000003679 aging effect Effects 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
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- 238000005580 one pot reaction Methods 0.000 description 4
- RVRYQLNRLHTHSZ-UHFFFAOYSA-N (4-methylpiperidin-1-yl)carbamodithioic acid Chemical compound CC1CCN(NC(S)=S)CC1 RVRYQLNRLHTHSZ-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 150000004005 nitrosamines Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KSAPYRIVHFAQGR-UHFFFAOYSA-N 1-sulfanylbenzimidazole Chemical compound C1=CC=C2N(S)C=NC2=C1 KSAPYRIVHFAQGR-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a preparation method and application of a rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium. The method comprises the following steps: (1) Respectively dissolving selenium dioxide and 2-mercaptobenzimidazole in absolute ethyl alcohol, then dropwise adding an ethanol solution of the selenium dioxide into an ethanol solution of the 2-mercaptobenzimidazole under the conditions of heating and stirring, and continuously reacting to prepare an intermediate ligand, namely mercaptobenzimidazole selenium; (2) After the sulfenamide formylation, the sulfhydrylazole selenium is oxidized and coupled with piperidine ligand to obtain the 4-methylpiperidinyl dithiocarbamic acid sulfhydrylazole selenium. The prepared multifunctional rubber additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium can obviously improve the heat-oxygen aging resistance of rubber materials, can stably exert an anti-aging effect for a long time, has a better vulcanization promoting effect than other dithiocarbamate accelerators, has the advantage of reducing the use amount of other additives, and is environment-friendly and pollution-free.
Description
Technical Field
The invention relates to the field of multifunctional rubber additives, in particular to a multifunctional rubber additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium and a preparation method and application thereof.
Background
As a material having high elasticity at normal temperature, rubber has special elasticity which is not possessed by other materials. With the development of the last hundred years, the synthesis and processing technology of modern rubber is greatly improved, and correspondingly, a plurality of new problems are always met and need to be solved. At present, the rubber material mainly takes the aspects of high performance, functionalization, automation, green, energy conservation and the like as the development direction.
The rubber raw material for producing the product needs to be matched with other auxiliary agents besides the matrix rubber material so as to meet the performance requirement of the rubber product. The rubber auxiliary agents commonly used at present mainly comprise the following types: vulcanizing agent, vulcanization accelerator, vulcanization activator, reinforcing agent, filler, anti-aging agent, plasticizer and the like.
With the development of recent years, rubber materials face several difficulties, the most important of which is environmental protection, energy consumption, pollution and the like. In the vulcanization process, a vulcanization accelerator containing secondary amine groups (such as secondary sulfenamides, thiurams, dithiocarbamate accelerators and the like) and nitrogen oxides in air or in auxiliaries generate stable nitrosamines with carcinogenicity under certain conditions, so that the nitrosamines are harmful to human bodies in use. As for the anti-aging agent, the commonly used amine anti-aging agents for rubber mainly comprise p-phenylenediamine, diphenylamine and the like, and the anti-aging agent has anti-aging and anti-ozone properties, but has pollution and can pollute the environment.
In the face of the environmental protection problem brought by rubber, researchers combine various additives required to be added into rubber materials into a whole, put forward the concept of multifunctional additives with multiple functions, and provide a new thought for the multifunction, high performance, environmental protection and compounding of the rubber additives. The multifunctional rubber auxiliary agent has the functions of a single auxiliary agent (such as vulcanization, promotion, aging prevention and the like), can improve the performance of rubber, and has the characteristics of environmental protection and low consumption. Compared with the existing common multifunctional rubber additive which is added with various additives, the multifunctional rubber additive with one dosage and multiple functions can achieve the effect of single use of various additives only by using the same or less amount, thereby achieving the purposes of reducing the use of harmful additives, reducing environmental pollution and reducing the complexity of mixing operation during processing production. Therefore, the multifunctional auxiliary agent with one agent and multiple functions has excellent development prospect.
The multifunctional rubber auxiliary agent can be realized in various ways, and not only the existing common accelerant is connected with a filler or a carrier, but also the accelerant group can be combined with other substances. However, in general, the idea of realizing the multifunctional rubber auxiliary agent is to combine related groups with the functions of vulcanization, promotion and aging resistance together to form a single substance, so that the multifunctional rubber auxiliary agent has multiple functions.
In the preparation of the dithiocarbamic acid rubber accelerator mentioned in the prior art, the performance requirements are relatively single, for example, in patent CN112062701a, "a rubber accelerator diethyl dithiocarbamic acid sulfone and its preparation method and application", sodium diethyldithiocarbamate is dispersed in an organic solvent with polarity less than 0.2 under the stirring condition, and then sulfuryl chloride is added, and the mixture is stirred for reaction to obtain light yellow solid a; and (3) carrying out suction filtration, washing, drying, crushing and sieving on the light yellow solid A to obtain the rubber accelerator diethyl dithiocarbamate sulfone. The vulcanization accelerating effect of the accelerator is better than that of a dithiocarbamate accelerator and a thiuram accelerator which have the same side group, but the accelerator only aims at accelerating and vulcanizing effects and does not achieve the effect of one dose and multiple functions.
Disclosure of Invention
In order to overcome the defects and shortcomings of the technology and synthesize a novel multifunctional rubber additive, the invention aims to provide a multifunctional rubber additive 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium comprises the following steps:
(1) Respectively dissolving selenium dioxide and 2-mercaptobenzimidazole in absolute ethyl alcohol, then dropwise adding the ethanol solution of the selenium dioxide into the ethanol solution of the 2-mercaptobenzimidazole under heating and stirring, and continuously reacting to obtain solid precipitate; carrying out suction filtration, washing and drying on the product to obtain the intermediate ligand mercaptobenzimidazole selenium;
(2) In an alkaline medium, oxidizing coupling mercaptobenzimidazole selenium after thiamine formylation with piperidine ligand, adding potassium iodide solution for continuous reaction, then carrying out suction filtration, filtering and washing with water until no alkali exists, and carrying out vacuum drying to obtain the 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium.
Further, the selenium dioxide in the step (1) is obtained from commercial selenium dioxide with the purity of 99 wt%; the 2-mercaptobenzimidazole in the step (1) is sourced from commercial 2-mercaptobenzimidazole with the purity of 97-98 wt%.
Further, the molar ratio of the selenium dioxide to the 2-mercaptobenzimidazole in the step (1) is 1 (4.0-4.2).
Further, the concentration of the ethanol solution of the selenium dioxide in the step (1) is 0.02 g/mL-0.04 g/mL; the concentration of the ethanol solution of the 2-mercaptobenzimidazole in the step (1) is 0.035 g/mL-0.055 g/mL.
Further, the volume ratio of the ethanol solution of the selenium dioxide to the ethanol solution of the 2-mercaptobenzimidazole in the step (1) is 1 (4.0-4.2).
Further, the continuous reaction in the step (1) is carried out for 1-3h under the conditions that the heating temperature is 50-60 ℃ and the stirring speed is 450-500 rpm.
Further, the piperidine ligand in the step (2) comprises more than one of piperidine, 4-methylpiperidine and 4-hydroxypiperidine.
Further, the step (2) of performing thiamine formylation on the selenium mercaptobenzimidazole comprises the following steps: putting mercaptobenzimidazole selenium and ethanol into a three-neck flask, adding an ethanol-water mixture containing caustic soda as a solution of mercaptobenzimidazole selenium ligand, stirring at room temperature, performing suction filtration if necessary to obtain a clear solution, then cooling the solution to 0 ℃, adding carbon disulfide into the solution, and continuing stirring for 25-35 min to mature the dithiocarbamate solution.
Further, the temperature of the oxidative coupling in the step (2) is 15-25 ℃, and the time is 15-25 min.
Further, the continuous reaction in the step (2) is carried out for 1-3h under the conditions that the heating temperature is 20-50 ℃ and the stirring speed is 450-500 rpm.
The invention provides a rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium prepared by the preparation method.
The invention combines related groups with the functions of vulcanization, promotion and anti-aging to synthesize a single substance, so that the single substance has multiple functions. And the related groups do not influence the performance of the compound, so that the effect of 1+1 > 2 is realized.
The multifunctional rubber assistant 4-methylpiperidinyl dithiocarbamic acid thiobenzidine selenium series vulcanization accelerator for styrene butadiene rubber is also an antioxidant for styrene butadiene rubber. Preferably, the composition comprises the following components in parts by weight: 100 parts of styrene butadiene rubber, 50 parts of carbon black N-550, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of sulfur and 1 part of rubber multifunctional additive 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium. The performance of the catalyst is superior to that of common vulcanization accelerators M (benzothiazole), NS (N-tertiary butyl-2-benzothiazole sulfonamide) and ZDC (zinc diethyl dithiocarbamate), and no waste gas is generated in the production process, and no hazardous chemical raw materials such as toxic gas, virulent substances or carcinogens are used.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the preparation method provided by the invention, absolute ethyl alcohol is used as a solvent in the first step of reaction, the absolute ethyl alcohol can be recycled after the reaction is finished, and only water is generated as a byproduct in the reaction process, so that the preparation method is environment-friendly and pollution-free.
(2) The invention adopts an organic solvent in the first step of reaction, synthesizes the product by a one-pot method, and has simple operation and high yield.
(3) The multifunctional rubber additive 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium prepared by the invention can obviously improve the heat-oxygen aging resistance of a rubber material, can stably exert an anti-aging effect for a long time, and has the heat-oxygen aging resistance effect superior to that of common comprehensive anti-aging agents 4010NA, MB and RD. The vulcanization accelerating effect is better than that of other dithiocarbamate accelerators such as commonly used vulcanization accelerators M, NS and ZDC. And has the advantage of reducing the use amount of other auxiliary agents.
Drawings
FIG. 1 is a vulcanization curve of the rubber mixtures obtained in example 4 and comparative example 1.
FIG. 2 is a stress-strain diagram of the rubber mixtures obtained in example 4 and comparative example 1.
FIG. 3 is a graph showing the tensile strength retention ratio of the rubber mixtures obtained in example 5 and comparative example 2.
FIG. 4 is a graph showing the retention of elongation at break of the mixes obtained in example 5 and comparative example 2.
FIG. 5 is an infrared spectrum of the selenium mercaptobenzimidazole prepared in example 1, 4-methylpiperidinyldithiocarbamate, and 2-mercaptobenzimidazole.
FIG. 6 is a DSC thermogram of the selenium mercaptobenzimidazole prepared in example 1, 4-methylpiperidyldithiocarbamate, and 2-mercaptobenzimidazole.
FIG. 7 is a TG thermal analysis plot of the selenium mercaptobenzimidazole prepared in example 1 and 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated by the manufacturer, and are regarded as conventional products commercially available.
Example 1
(1) The product of the mercaptobenzimidazole selenium is obtained by a one-pot reaction in an ethanol solution: dissolving 1g of selenium dioxide (0.009 mol) in 25mL of absolute ethanol, and then dissolving 5.44g of 2-mercaptobenzimidazole (0.036 mol) in 100mL of absolute ethanol; then dropwise adding the ethanol solution of selenium dioxide into the ethanol solution of 2-mercaptobenzimidazole, and continuously reacting for 2h under the conditions of heating at 50 ℃ and stirring at 500 rpm; after the reaction is finished, carrying out suction filtration, drying and crushing to generate green precipitate, thus obtaining the intermediate ligand thiobendazole selenium (MBSe). The yield of the product obtained is 83%.
(2) Formylating mercaptobenzimidazole selenium by thiamine: 0.01mol of selenium mercaptobenzimidazole and 30mL of ethanol were taken in a three-necked flask, and 20mL of an ethanol-water mixture containing 0.8g (0.02 mol) of caustic soda was added thereto, and stirred at room temperature, and suction-filtered if necessary to obtain a clear solution. The solution was then cooled to 0 ℃ and 0.76mL (0.01 mol) of carbon disulfide (in 5mL of ethanol) was added thereto at a controlled rate and stirring was continued for 30min to mature the dithiocarbamate solution.
(3) Preparation of 4-methylpiperidinyldithiocarbamic acid mercaptophenylimidazole selenium: 4-methylpiperidine (dissolved in 5mL of deionized water) was then added (0.04 mol) to the flask and the contents allowed to stand for 5-10min to reach ambient temperature. Finally, 50mL of potassium iodide solution (0.01 mol of iodine and 0.03mol of potassium iodide in water) was added, the reaction was continued for 1 hour with heating at 50 ℃ and stirring at 500rpm to obtain a pale yellow precipitate, which was further stirred for about 1.5 hours, filtered with suction and washed with water until free of alkali, and finally dried under vacuum at 50 ℃. 5.63g of selenium 4-methylpiperidinyldithiocarbamate mercaptobenzimidazole were obtained in a yield of 75.1%.
Example 2
(1) The product of the mercaptobenzimidazole selenium is obtained by a one-pot reaction in an ethanol solution: dissolving 1g of selenium dioxide (0.009 mol) in 40mL of absolute ethanol, and then dissolving 5.44g of 2-mercaptobenzimidazole (0.036 mol) in 150mL of absolute ethanol; then dropwise adding the ethanol solution of selenium dioxide into the ethanol solution of 2-mercaptobenzimidazole, and continuously reacting for 2 hours under the conditions of heating at 55 ℃ and stirring at 500 rpm; after the reaction is finished, carrying out suction filtration, drying and crushing to generate green precipitate, thus obtaining the intermediate ligand thiobenzimidazole selenium (MBSe). The product yield was 92.4%.
(2) Formylating mercaptobenzimidazole selenium by thiamine: 0.01mol of selenium mercaptobenzimidazole and 30mL of ethanol were taken in a three-necked flask, and 20mL of an ethanol-water mixture containing 0.8g (0.02 mol) of caustic soda was added thereto, stirred at room temperature, and filtered with suction as necessary to obtain a clear solution. The solution was then cooled to 0 ℃ and 0.76mL (0.01 mol) of carbon disulfide (in 5mL of ethanol) was added thereto at a controlled rate and stirring was continued for 35min to mature the dithiocarbamate solution.
(3) Preparation of 4-methylpiperidinyldithiocarbamic acid mercaptophenylimidazole selenium: 4-methylpiperidine (dissolved in 5mL of deionized water) was then added (0.04 mol) to the flask and the contents allowed to stand for 5-10min to reach ambient temperature. Finally, 50mL of potassium iodide solution (0.01 mol of iodine and 0.03mol of potassium iodide in water) was added, the reaction was continued for 1 hour with heating at 30 ℃ and stirring at 500rpm to obtain a pale yellow precipitate, which was further stirred for about 1.5 hours, filtered with suction and washed with water until free of alkali, and finally dried under vacuum at 50 ℃. 4.86g of selenium 4-methylpiperidyldithiocarbamate mercaptobenzimidazole was obtained in a yield of 64.8%.
Example 3
(1) The product of the mercaptobenzimidazole selenium is obtained by a one-pot reaction in an ethanol solution: dissolving 1g of selenium dioxide (0.009 mol) in 40mL of absolute ethanol, and then dissolving 5.44g of 2-mercaptobenzimidazole (0.036 mol) in 150mL of absolute ethanol; then dropwise adding the ethanol solution of selenium dioxide into the ethanol solution of 2-mercaptobenzimidazole, and continuously reacting for 2h under the conditions of heating at 55 ℃ and stirring at 500 rpm; after the reaction is finished, carrying out suction filtration, drying and crushing to generate green precipitate, thus obtaining the intermediate ligand thiobendazole selenium (MBSe). The product yield was 92.4%.
(2) Formylating mercaptobenzimidazole selenium by thiamine: 0.01mol of selenium mercaptobenzimidazole and 30mL of ethanol were taken in a three-necked flask, and 20mL of an ethanol-water mixture containing 0.8g (0.02 mol) of caustic soda was added thereto, stirred at room temperature, and filtered with suction as necessary to obtain a clear solution. The solution was then cooled to 0 ℃ and 0.76mL (0.01 mol) of carbon disulfide (in 5mL of ethanol) was added thereto at a controlled rate and stirring was continued for 30min to mature the dithiocarbamate solution.
(3) Preparation of 4-hydroxypiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium: then 4-hydroxypiperidine (0.04 mol) is added to the flask (dissolved in 5mL of deionized water) and the contents are allowed to stand for 5-10min to reach ambient temperature. Finally, 50mL of potassium iodide solution (0.01 mol of iodine and 0.03mol of potassium iodide in water) was added, the reaction was continued for 1 hour with heating at 50 ℃ and stirring at 500rpm to obtain a pale yellow precipitate, which was further stirred for about 1.5 hours, filtered with suction and washed with water until free of alkali, and finally dried under vacuum at 50 ℃. 6.74g of selenium 4-methylpiperidyldithiocarbamate mercaptobenzimidazole was obtained in 86.1% yield.
Example 4
A neat rubber mix, designated SBR 4-PDMBSe, was prepared by adding 2g of sulfur, 1g of the selenium mercaptobenzimidazole 4-methylpiperidyl dithiocarbamate (prepared in example 1), 5g of zinc oxide, and 2g of stearic acid to 100g of styrene butadiene rubber in an open mill. The sulfur evolution was carried out at 160 ℃ and the vulcanization curve is shown in FIG. 1, with the vulcanization parameters shown in Table 1.
Example 5
A carbon black rubber mixture, designated SBR/N5504-PDMBSe, was prepared by adding 2g of sulfur, 2g of 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium (prepared in example 1), 5g of zinc oxide, 2g of stearic acid, and 50g of carbon black N550 to 100g of styrene-butadiene rubber by means of an open mill. The aging property retention rate curves of the tablets are shown in figures 3 and 4 and the aging parameters are shown in table 2 when the tablets are pressed at 160 ℃ and tested according to the GB/T3512-2014 standard.
Comparative example 1
100g of styrene-butadiene rubber was mixed with 2g of sulfur, 1g of an accelerator M (available from Siqi rubber technology Co., ltd., dongguan) or 1g of an accelerator NS (available from Siqi rubber technology Co., ltd., dongguan) or 1g of an accelerator ZDC (available from Siqi rubber technology Co., ltd., dongguan), 5g of zinc oxide and 2g of stearic acid by means of an open mill to obtain a pure rubber compound, which was referred to as SBR/M, SBR/NS and SBR/ZDC, respectively. The vulcanization was carried out at 160 ℃ and the vulcanization curve is shown in FIG. 1 and the vulcanization parameters are shown in Table 1.
Comparative example 2
100g of styrene butadiene rubber was mixed with 2g of sulfur, 1g of an accelerator ZDC (available from Siqi rubber technology Co., ltd., dongguan), 5g of zinc oxide, 2g of stearic acid, 1g of an antioxidant MB (available from Siqi rubber technology Co., ltd., dongguan) or 1g of an antioxidant RD (available from Siqi rubber technology Co., ltd., dongguan) or 1g of an antioxidant 4010NA (available from Siqi rubber technology Co., ltd., dongguan) and 50g of carbon black N550 by an open mill to obtain carbon black rubber mixtures respectively named ZDC/MB, ZDC/RD and ZDC4010NA. The aging property retention rate curves of the tablets are shown in figures 3 and 4 and the aging parameters are shown in table 2 when the tablets are pressed at 160 ℃ and tested according to the GB/T3512-2014 standard.
The vulcanization parameters of the mixes obtained in example 4 and comparative example 1 are shown in Table 1, and FIG. 1 is a vulcanization curve of the mixes obtained in example 4 and comparative example 1. As can be seen from table 1 and fig. 1: the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium has a faster vulcanization speed than the accelerators M and NS, and the maximum torque is higher than the accelerators M, NS and ZDC. From the results, the 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium prepared by the invention has good vulcanization acceleration efficiency, has the vulcanization characteristic of shorter positive vulcanization time, and has the overall vulcanization performance superior to the accelerators M, NS and ZDC.
Table 1 shows the vulcanization parameters of the mixtures obtained in example 4 and comparative example 1
Physical property parameters of the mixes obtained in example 4 and comparative example 1 are shown in Table 2, and FIG. 2 is a graph showing the tensile characteristics of the mixes obtained in example 4 and comparative example 1. As can be seen from table 2 and fig. 2: the tensile strength of the SBR/4-PDMBSe vulcanized rubber is enhanced compared with SBR/M, SBR/NS and SBR/ZDC, and is respectively improved by 18.1%, 29.4% and 25.4%. The elongation at break of the SBR/4-PDMBSe vulcanized rubber is reduced compared with that of SBR/M, but is higher than that of SBR/NS and SBR/ZDC. The results show that the multifunctional rubber additive 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium prepared by the invention can effectively improve the mechanical property of rubber.
TABLE 2 physical Properties of the mixes obtained in example 4 and comparative example 1
The thermal oxidative aging properties of the mixes obtained in example 5 and comparative example 2 are shown in Table 3, FIG. 3 is a graph showing the retention rate of tensile strength of the mixes obtained in example 5 and comparative example 2, and FIG. 4 is a graph showing the retention rate of elongation at break of the mixes obtained in example 5 and comparative example 2. As can be seen from table 3, fig. 3 and fig. 4: the tensile strength retention rate and the breaking elongation retention rate of SBR/N550-PDMBSe are all superior to ZDC/MB, ZDC/RD and ZDC4010NA when the vulcanized rubber is aged for the same time, namely the heat-oxygen aging resistance of the vulcanized rubber of the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium is superior to that of the vulcanized rubber containing the antioxidant 4010NA or MB or RD. From the results, the 4-methylpiperidyl dithiocarbamic acid mercapto benzimidazole selenium prepared by the invention can stably exert the anti-aging effect in rubber for a long time.
TABLE 3 thermo-oxidative ageing Properties of the mixtures obtained in example 5 and comparative example 2
The infrared spectra of the selenium mercaptobenzimidazole (MBSe) prepared in example 1 of the present invention and the selenium mercaptobenzimidazole 4-methylpiperidinyl dithiocarbamate (4-PDMBSe) are shown in FIG. 5. As can be seen from fig. 5: 3070cm for MBSe -1 Is an absorption peak of v (N-H) bond, 1460cm -1 Is a resonance absorption peak of nu (N = C-S) exocyclic sulfur atom and imidazole ring, 1357cm -1 Is the absorption peak of v (C-N) bond, 1015cm -1 Is an absorption peak of ν (C-S) bond, and 2448cm -1 The absorption peak at ν (S-H) bond disappears. 2922cm for 4-PDMBSe -1 Is v (-CH) 2 -) peak of stretching vibration, 2866cm -1 Is a stretching vibration peak of v (-CH 3-), 1479cm -1 Is a resonance absorption peak of v (N = C-S) exocyclic sulfur atom and imidazole ring, 1357cm -1 Is an absorption peak of v (C-N) bond of 1013cm -1 Is the absorption peak of the ν (C-S) bond. The above data demonstrate that the present invention synthesizes a product having a target structure.
The DSC thermal analysis curves of the selenium mercaptobenzimidazole (MBSe) prepared in example 1 of the present invention and the 4-methylpiperidinyldithiocarbamic acid selenium mercaptobenzimidazole (4-PDMBSe) are shown in FIG. 6, and the TG thermal analysis curves are shown in FIG. 7. As can be seen from fig. 6 and 7: the melting point of MBSe is 249.6 ℃, and the decomposition temperature is 311.1 ℃; the melting point of 4-PDMBSe is 199.6 ℃, and the decomposition temperature is 223.9 ℃. And the curves of the 4-methylpiperidinyl dithiocarbamic acid mercaptobenzimidazole selenium all have sharp endothermic peaks and a thermal weight loss step, which indicates that the prepared product has higher purity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a rubber multifunctional additive 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium is characterized by comprising the following steps:
(1) Respectively dissolving selenium dioxide and 2-mercaptobenzimidazole in absolute ethyl alcohol, then dropwise adding the ethanol solution of the selenium dioxide into the ethanol solution of the 2-mercaptobenzimidazole under heating and stirring, and continuously reacting to obtain solid precipitate; carrying out suction filtration, washing and drying on the product to obtain the intermediate ligand mercaptobenzimidazole selenium;
(2) In an alkaline medium, after being formylated by thiamine, the mercaptophenylimidazole selenium is oxidized and coupled with piperidine ligand, potassium iodide solution is added for continuous reaction, then the mixture is filtered and filtered by water until no alkali exists, and the mixture is dried in vacuum, so that the 4-methylpiperidyl dithiocarbamic acid mercaptophenylimidazole selenium is obtained.
2. The preparation method of the multifunctional rubber additive, namely the selenium 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole, according to claim 1, wherein the molar ratio of the selenium dioxide to the 2-mercaptobenzimidazole in the step (1) is 1 (4.0-4.2).
3. The preparation method of the multifunctional rubber additive, namely the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium, according to claim 1, wherein the concentration of the ethanol solution of the selenium dioxide in the step (1) is 0.02 g/mL-0.04 g/mL; the concentration of the ethanol solution of the 2-mercaptobenzimidazole in the step (1) is 0.035 g/mL-0.055 g/mL; the volume ratio of the ethanol solution of the selenium dioxide to the ethanol solution of the 2-mercaptobenzimidazole in the step (1) is 1 (4.0-4.2).
4. The preparation method of the multifunctional rubber additive, namely the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium, according to claim 1, characterized in that the continuous reaction in the step (1) is carried out for 1-3h under the conditions that the heating temperature is 50-60 ℃ and the stirring speed is 450-500 rpm.
5. The preparation method of the multifunctional rubber additive 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium according to claim 1, characterized in that the piperidine ligand in step (2) comprises one or more of piperidine, 4-methylpiperidine and 4-hydroxypiperidine.
6. The preparation method of the multifunctional rubber additive, namely the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium, according to claim 1, wherein the step (2) of performing thiamine formylation on the mercaptobenzimidazole selenium comprises the following steps: adding mercaptobenzimidazole selenium and ethanol into a three-neck flask, adding an ethanol-water mixture containing caustic soda, stirring at room temperature, performing suction filtration if necessary to obtain a clear solution, then cooling the solution to 0 ℃, adding carbon disulfide into the solution, and continuously stirring for 25-35 min to mature the dithiocarbamate solution.
7. The preparation method of the multifunctional rubber additive, namely the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium, according to claim 1, wherein the temperature of the oxidative coupling in the step (2) is 15-25 ℃, and the time is 15-25 min.
8. The preparation method of the multifunctional rubber additive, namely the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium, according to claim 1, characterized in that the continuous reaction in the step (2) is carried out for 1-3h under the conditions of a heating temperature of 20-50 ℃ and a stirring speed of 450-500 rpm.
9. The multifunctional rubber additive, namely the 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole selenium prepared by the preparation method of any one of claims 1 to 8.
10. The use of the multifunctional rubber additive, 4-methylpiperidyl dithiocarbamic acid mercaptobenzimidazole of claim 9 in rubber.
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| CN111943909A (en) * | 2020-08-31 | 2020-11-17 | 华南理工大学 | Rubber accelerator selenobenzothiazole and preparation method and application thereof |
| CN112062701A (en) * | 2020-08-31 | 2020-12-11 | 华南理工大学 | Rubber accelerator diethyl dithiocarbamate sulfone and preparation method and application thereof |
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| CN111943909A (en) * | 2020-08-31 | 2020-11-17 | 华南理工大学 | Rubber accelerator selenobenzothiazole and preparation method and application thereof |
| CN112062701A (en) * | 2020-08-31 | 2020-12-11 | 华南理工大学 | Rubber accelerator diethyl dithiocarbamate sulfone and preparation method and application thereof |
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