CN111777635B - Chloropropyl tri-p-phenylamine oxy silane and preparation method and application thereof - Google Patents
Chloropropyl tri-p-phenylamine oxy silane and preparation method and application thereof Download PDFInfo
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- CN111777635B CN111777635B CN202010690771.3A CN202010690771A CN111777635B CN 111777635 B CN111777635 B CN 111777635B CN 202010690771 A CN202010690771 A CN 202010690771A CN 111777635 B CN111777635 B CN 111777635B
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- -1 Chloropropyl Chemical group 0.000 title claims abstract description 57
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 30
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 9
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical group [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 4
- PHEXXGCUKSJMBJ-UHFFFAOYSA-N [O].[SiH4] Chemical compound [O].[SiH4] PHEXXGCUKSJMBJ-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 18
- 230000035484 reaction time Effects 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 150000003512 tertiary amines Chemical group 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses chloropropyl tri-p-phenylamine oxy silane, a preparation method and application thereof, wherein N, N-dimethyl-4-hydroxyaniline is used as a raw material to react with gamma-chloropropyl trichlorosilane to prepare the chloropropyl tri-p-phenylamine oxy silane. The high activity of N, N-dimethyl-4-hydroxy aniline in the reaction obviously shortens the reaction time, and in addition, because the N, N-dimethyl-4-hydroxy aniline has a tertiary amine structure, the N, N-dimethyl-4-hydroxy aniline can be used as an acid binding agent to capture by-product hydrogen chloride so as to promote the forward progress of the reaction. In addition, the introduction of the N, N-dimethyl-4-hydroxyanilino group can decompose the obtained silane coupling agent in rubber to generate a phenol structure, and meanwhile, the para amino group has a certain activation effect on the phenolic hydroxyl group, so that free radicals can be captured, and the effect of delaying the aging of the rubber is achieved in the rubber.
Description
Technical Field
The invention relates to an intermediate of a silane coupling agent and a novel silane coupling agent, in particular to chloropropyl tri-p-phenylamine oxy silane, a preparation method thereof and application of the intermediate of the silane coupling agent, and also relates to the novel silane coupling agent prepared by taking the chloropropyl tri-p-phenylamine oxy silane as the intermediate, belonging to the technical field of organosilicon synthesis.
Background
The silane coupling agent is used as a molecular bridge for connecting inorganic materials and organic materials, and has wide application in the fields of automobiles, aviation, medical treatment, construction, electronics and the like. For example, in the field of automobile tires, white carbon black can be used as a reinforcing agent and a filler of rubber, but the white carbon black has poor dispersibility in the rubber due to a large physical and chemical property difference between the reinforcing agent and the filler, and the problem of poor dispersibility is well solved by introducing a silane coupling agent, so that the processing and the service performance of the tire are obviously improved.
In addition, the silane coupling agent is widely used for surface modification of various materials as a bridge for taking up inorganic matters and organic matters. In recent years, the effect of the silane coupling agent in the pretreatment of the metal surface is gradually focused by students at home and abroad, and compared with the traditional phosphating process, the silane coupling agent has the advantages of no pollution of heavy metal ions, no phosphorus, low consumption, excellent anti-corrosion effect, simple treatment process and the like.
Bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (also known as Si-69) is a commonly used silane coupling agent, and can be used as a reinforcing agent, a coupling agent and a plasticizer for processing due to its multifunctional effect on rubber, so that the bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide is widely applied to various rubber industries. At present, the preparation method of Si-69 generally takes gamma-chloropropyl trichlorosilane as a raw material, the gamma-chloropropyl trichlorosilane reacts with ethanol to form a chloropropyl triethoxysilane intermediate, and then the intermediate reacts with disodium tetrasulfide under the condition of a phase transfer catalyst to obtain Si-69. In the reaction process, the reaction time of the gamma-chloropropyl trichlorosilane and ethanol is long, and in addition, byproduct hydrogen chloride is generated, and the byproduct hydrogen chloride needs to be removed in time to promote the forward progress of the reaction. Two modes of removing the hydrogen chloride are adopted, one is to decompress and extract the gaseous hydrogen chloride, which requires an additional hydrogen chloride absorption device, and the other is to add an acid binding agent, but the addition of the acid binding agent improves the production cost on one hand and increases the post-treatment difficulty on the other hand.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides chloropropyl tri-p-phenylamine oxy silane, the product can be used as a silane coupling agent intermediate, has similar effect with a silane coupling agent synthesized by the chloropropyl triethoxy silane intermediate, and can be used as a substitute of chloropropyl triethoxy silane.
The structural formula of the chloropropyl tri-p-phenylamine oxy silane provided by the invention is as follows:
the synthesis method of the chloropropyl tri-p-phenylamine oxy silane is simple, and the preparation method is obtained by taking gamma-chloropropyl trichlorosilane and N, N-dimethyl-4-hydroxyaniline as raw materials and reacting the gamma-chloropropyl trichlorosilane and the N, N-dimethyl-4-hydroxyaniline.
Furthermore, the invention uses N, N-dimethyl-4-hydroxyaniline to replace ethanol to react with gamma-chloropropyl trichlorosilane to form a novel silane coupling agent intermediate. The molar ratio of the N, N-dimethyl-4-hydroxyaniline to the gamma-chloropropyl trichlorosilane is 3.0-3.2:1, preferably 3.0-3.1:1. Compared with ethanol, the N, N-dimethyl-4-hydroxyaniline has higher reactivity in the reaction, the reason is that the essence of the first step of reaction is nucleophilic substitution reaction, hydroxyl oxygen on the N, N-dimethyl-4-hydroxyaniline attacks silicon lacking electrons, the reaction is completed by removing hydrogen chloride, and the nucleophilicity of the hydroxyl oxygen is enhanced due to the electron conjugated activation of the N, N-dimethyl, so that the reaction time is shortened. On the other hand, the nitrogen-containing group in the N, N-dimethyl-4-hydroxyaniline is tertiary amine, which can play a role of an acid binding agent in the reaction process to promote the forward progress of the reaction. The invention does not need to increase a hydrogen chloride absorption device to decompress and extract hydrogen chloride, and does not need to introduce a new acid-binding agent, and N, N-dimethyl-4-hydroxyaniline is not only used as a reaction raw material but also used as an acid-binding agent, and excessive addition is not needed, thereby avoiding the conditions of increased cost and difficult post-treatment implementation, improving the reaction operability, having the advantages of short reaction time, simple post-treatment, green and environment-friendly performance and the like, and effectively improving the economic benefit.
Further, the reaction temperature of gamma-chloropropyl trichlorosilane and N, N-dimethyl-4-hydroxyaniline is 60-100 ℃, preferably 60-80 ℃. At this temperature, the reaction is carried out to an end point, which can be determined by detecting the content of the starting materials, and the reaction time is generally 2 to 4 hours, preferably 2 to 3 hours.
Further, after the gamma-chloropropyl trichlorosilane reacts with N, N-dimethyl-4-hydroxyaniline, chloropropyl tri-p-phenylaminoxysilane hydrochloride is formed, and the reaction product is subjected to alkali washing and post-treatment after the alkali washing to obtain the chloropropyl tri-p-phenylaminoxysilane.
Further, alkali washing is carried out until the pH value of the system is neutral, unreacted raw materials and solvents are removed by means of distillation and the like after alkali washing, inorganic salts are removed by filtration, and the remainder is the chloropropyl tri-p-anilinoxysilane.
Further, the product may be subjected to alkali washing by an ethanol solution of sodium ethoxide. The ethanol solution can avoid the hydrolysis of the product, and the produced salt can be separated out in a precipitation form and is easy to collect.
The chloropropyl tri-p-phenylamine oxy silane can be used as an intermediate of a silane coupling agent and is used for preparing the silane coupling agent. The chloropropyl tri-p-phenylamine oxy silane can replace chloropropyl triethoxy silane, and can be further reacted with other components reported in the prior art to prepare a silane coupling agent. For example, the silane coupling agent can be prepared by further reacting with a sulfur-containing, mercapto-containing, thiocarboxylate-containing substance such as disodium tetrasulfide, sodium hydrosulfide, allyl thiocarboxylate or the like.
Further, chloropropyl tri-p-phenylamine oxy silane can be reacted with disodium tetrasulfide, sodium hydrosulfide, allyl thiocarboxylate and the like to prepare a silane coupling agent. In the preparation of the silane coupling agent, the reaction conditions used may be selected and adjusted with reference to the conditions disclosed in the prior art.
In the present invention, a specific silane coupling agent is provided, which has the following structural formula:
in the silane coupling agent, R is a group such as-S4-, -SH or a thiocarboxylate group.
In a specific embodiment of the invention, chloropropyl tri-p-aminooxy silane reacts with disodium tetrasulfide to prepare the silane coupling agent bis- [ gamma- (tri-p-aminooxy) propyl ] tetrasulfide, and the product is light yellow transparent liquid with the impurity content less than or equal to 4.0 percent. Disodium tetrasulfide may be obtained by reacting sodium hydroxide solution with sulfur, or may be obtained according to other methods disclosed in the prior art. The reaction formula is as follows:
further, the reaction of chloropropyl tri-p-anilinoxysilane with disodium tetrasulfide is carried out in the presence of a phase transfer catalyst, which may be a phase transfer catalyst disclosed in the art, such as tetrabutylammonium bromide and the like. The molar ratio of the disodium tetrasulfide to the chloropropyl tri-p-anilinoxysilane to the phase transfer catalyst is 0.5-0.6:1:0.01-0.02, the reaction temperature is 90-120 ℃, preferably 100-120 ℃, and the reaction time is generally 2-5 hours, preferably 3-5 hours.
The invention has the following advantages:
1. in the reaction, N, N-dimethyl-4-hydroxyaniline is adopted to replace ethanol to react with gamma-chloropropyl trichlorosilane, the high activity of the N, N-dimethyl-4-hydroxyaniline in the reaction obviously shortens the reaction time, and in addition, the N, N-dimethyl-4-hydroxyaniline has a tertiary amine structure and can be used as an acid binding agent to capture by-product hydrogen chloride so as to promote the forward progress of the reaction.
2. The preparation method has the advantages of short reaction time, simple post-treatment, green environment protection and strong operability, the obtained chloropropyl tri-p-anilinoxy silane can be used as an intermediate of a silane coupling agent, and the introduction of N, N-dimethyl-4-hydroxyanilino groups can decompose the obtained silane coupling agent in rubber to generate a phenol structure, and meanwhile, the para-amino groups have a certain activation effect on phenolic hydroxyl groups, so that free radicals can be captured to play a role in delaying rubber aging in rubber, and thus, certain ageing resistance of the rubber is endowed.
Detailed Description
The invention will now be further illustrated with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
In the following examples, the yield was calculated as: the obtained product quality/theoretical product quality. The impurity content was measured by HPLC.
Example 1
182.67g of gamma-chloropropyl trichlorosilane is added into a 1L reaction kettle, 366.48g of N, N-dimethyl-4-hydroxyaniline is added, the temperature is slowly raised to 80 ℃, the reaction is carried out for 3 hours under stirring, 280g of ethanol solution containing 177.23g of sodium ethoxide is added after the reaction is finished, the mixture is stirred for 0.5 hour, reduced pressure distillation is carried out to remove a small amount of unreacted N, N-dimethyl-4-hydroxyaniline and ethanol, then suction filtration is carried out to remove sodium chloride, 420.83g of chloropropyl tri-p-phenylaminoxysilane is obtained, and the yield is 95.0% and the impurity content is 1.28% based on the gamma-chloropropyl trichlorosilane.
200g of aqueous solution containing 52.38g of sodium hydroxide is added into another 1L reaction kettle, 64.17g of sulfur is added, the temperature of the system is controlled to be 100 ℃, the reaction time is 2 hours, then 2.64g of tetrabutylammonium bromide is added, 420.83g of chloropropyl tri-p-anilinoxysilane is fully added, the temperature of the system is controlled to be 110 ℃, the reaction is carried out for 3 hours under the stirring state, water washing, liquid separation, drying and active carbon decoloration post-treatment are carried out after the reaction is finished, 441.37g of light yellow transparent liquid is finally obtained, namely the bis- [ gamma- (tri-p-anilinoxy) propyl ] tetrasulfide, the calculated yield is 94.4% by gamma-chloropropyl trichlorosilane, and the impurity content is 2.57%.
Example 2
157.47g of gamma-chloropropyl trichlorosilane is added into a 1L reaction kettle, then 305.83g of N, N-dimethyl-4-hydroxyaniline is added, the temperature is slowly raised to 100 ℃, the reaction is carried out for 3 hours under stirring, 250g of ethanol solution containing 153.27g of sodium ethoxide is added after the reaction is finished, the mixture is stirred for 0.5 hour, reduced pressure distillation is carried out to remove a small amount of unreacted N, N-dimethyl-4-hydroxyaniline and ethanol, then suction filtration is carried out to remove sodium chloride, 351.39g of chloropropyl tri-p-phenylaminoxysilane is obtained, the yield is 92.0% based on the gamma-chloropropyl trichlorosilane, and the impurity content is 1.57%.
180g of aqueous solution containing 41g of sodium hydroxide is added into another 1L reaction kettle, 51.83g of sulfur is added, the system temperature is controlled to be 100 ℃, the reaction time is 2h, then 2.2g of tetrabutylammonium bromide is added, 351.39g of chloropropyl tri-p-anilinoxy silane is added, the system temperature is controlled to be 100 ℃, the reaction is carried out for 4h under a stirring state, water washing, liquid separation, drying and active carbon decoloration post-treatment are carried out after the reaction is finished, 367.59g of light yellow transparent liquid is finally obtained, the calculated yield of gamma-chloropropyl trichlorosilane is 91.2%, and the impurity content is 3.26%.
Example 3
173.26g of gamma-chloropropyl trichlorosilane is added into a 1L reaction kettle, 358.81g of N, N-dimethyl-4-hydroxyaniline is added, the temperature is slowly raised to 70 ℃ for reaction for 3 hours under stirring, 280g of ethanol solution containing 168.87g of sodium ethoxide is added after the reaction is finished, the mixture is stirred for 0.5 hour, a small amount of unreacted N, N-dimethyl-4-hydroxyaniline and ethanol are removed by reduced pressure distillation, then sodium chloride is removed by suction filtration, and 399.24g of chloropropyl tri-p-phenylamine oxy silane is obtained, wherein the yield is 95.0% and the impurity content is 1.31% based on the gamma-chloropropyl trichlorosilane.
Adding 200g of water solution containing 49.7g of sodium hydroxide into another 1L reaction kettle, adding 60.88g of sulfur, controlling the temperature of the system to be 100 ℃, reacting for 2 hours, adding 2.5g of tetrabutylammonium bromide, adding 399.24g of chloropropyl tri-p-anilinoxy silane, controlling the temperature of the system to be 120 ℃, reacting for 3 hours in a stirring state, washing, separating liquid, drying and decolorizing with active carbon after the reaction is finished, and finally obtaining 417.36g of light yellow transparent liquid, wherein the calculated yield of the gamma-chloropropyl trichlorosilane is 94.1%, and the impurity content is 2.68%.
Example 4
112.6g of gamma-chloropropyl trichlorosilane is added into a 1L reaction kettle, 225.9g of N, N-dimethyl-4-hydroxyaniline is added, the temperature is slowly raised to 60 ℃, the reaction is carried out for 4 hours under stirring, 220g of ethanol solution containing 110.45g of sodium ethoxide is added after the reaction is finished, the mixture is stirred for 0.5 hour, a small amount of unreacted N, N-dimethyl-4-hydroxyaniline and ethanol are removed through reduced pressure distillation, then the suction filtration is carried out to remove sodium chloride, 259.46g of chloropropyl tri-p-phenylaminoxysilane is obtained, and the yield is 95.0% and the impurity content is 1.27% based on the gamma-chloropropyl trichlorosilane.
150g of an aqueous solution containing 34.32g of sodium hydroxide is added into another 1L reaction kettle, 39.56g of sulfur is added, the temperature of the system is controlled to be 110 ℃, the reaction time is 2 hours, then 1.63g of tetrabutylammonium bromide is added, 259.46g of chloropropyl tri-p-anilinoxy silane is added, the temperature of the system is controlled to be 90 ℃, the reaction is carried out for 4 hours under a stirring state, water washing, liquid separation, drying and active carbon decoloration post-treatment are carried out after the reaction is finished, 265.72g of light yellow transparent liquid is finally obtained, the calculated yield of gamma-chloropropyl trichlorosilane is 92.2%, and the impurity content is 3.87%.
Comparative example 1
Chloropropyl tri-p-anilinoxysilane was synthesized as in example 1, except that: the synthesis process is controlled at 50 ℃ and the reaction time is 3h. The yield of the product obtained by counting gamma-chloropropyl trichlorosilane is 78.23 percent, and the impurity content is 7.45 percent.
Comparative example 2
Chloropropyl tri-p-anilinoxysilane was synthesized as in example 1, except that: the synthesis process is controlled at 120 ℃ and the reaction time is 1h. The yield of the product was 81.76% and the impurity content was 10.25% based on gamma-chloropropyl trichlorosilane.
Comparative example 3
Bis- [ gamma- (tri-p-aminoxy) propyl ] tetrasulfide was synthesized according to the procedure of example 1, except that: after the chloropropyl tri-p-phenylamine oxy silane is added, the temperature is controlled to be 80 ℃, and the reaction time is 5 hours. The yield of the product obtained by counting gamma-chloropropyl trichlorosilane is 75.31 percent, and the impurity content is 5.24 percent.
Comparative example 4
Bis- [ gamma- (tri-p-aminoxy) propyl ] tetrasulfide was synthesized according to the procedure of example 1, except that: after the chloropropyl tri-p-phenylamine oxy silane is added, the temperature is controlled to be 140 ℃, and the reaction time is 2 hours. The yield of the product was 81.94% and the impurity content was 6.34% based on gamma-chloropropyl trichlorosilane.
Performance verification
The bis- [ gamma- (tri-p-aminoxy) propyl ] tetrasulfide prepared in example 1 was used as a silane coupling agent with Si-69, and its properties in rubber compounds were verified.
1. Preparing sizing material
The raw materials were weighed according to the following table 1:
2. rubber mixing
One-stage banburying process (initial temperature 80 ℃ C., rotational speed 40 rpm): adding raw rubber for 20s, adding white carbon black into a pressing block for 30s, adding carbon black into a pressing block for 10s, adding carbon black into a pressing block for 60s, adding carbon black into a pressing block for 10s, lifting the pressing block, cleaning for 10s, mixing the pressing block for 50s, and discharging rubber (the rubber discharging temperature is 145+/-5 ℃). And packaging a section of master batch 3, and discharging the master batch for standby.
Two-stage open mill: the front roller is 50 ℃, the rear roller is 60 ℃, the roller spacing of 4mm is 1min, si-69 is added for 2min, S-80 and CZ-80 are added for 1min, 2 cutters are respectively arranged at left and right sides, the minimum roller spacing is divided into 4 triangular bags, and 4 rolls are divided into 4mm and then are cut into pieces to be measured.
3. Performance analysis
The vulcanization characteristics, processability, mechanical properties and aging properties of the obtained sizing material are detected by the following method:
3.1 detection of the vulcanization properties: the vulcanization performance is tested by using a GB/T16584 rubber rotor-free vulcanizing instrument, and the instrument meets the requirements of the standard GB/T16584 'rubber rotor-free vulcanizing instrument' and ISO 6502.
3.2, detecting the processing performance: the measurement was carried out according to the method of Standard GB/T1232.1-2016 disk shear viscometer for unvulcanized rubber.
3.3 mechanical property detection before and after aging: the measurement was carried out according to the method of Standard GB/T528-1998 "measurement of tensile stress Strain properties of vulcanized rubber or thermoplastic rubber".
4. Results and analysis
4.1 vulcanization Properties
4.2 processability of
4.3 ageing Properties
From the above results, it was found that the silane coupling agent of the present invention had a slightly increased Mooney viscosity compared with si69, and the scorch time and vulcanization rate were comparable. From the mechanical property, the performance before aging is equivalent, the tensile strength and modulus of the aged sizing material are slightly larger, the aging resistance is certain, and in addition, the heat and oxygen aging resistance is certain from the view of a combined structure.
Claims (12)
1. The chloropropyl tri-p-phenylamine oxy silane is characterized by having the following structural formula:
2. a process for the preparation of chloropropyl tri-p-anilinoxysilane as claimed in claim 1, characterised in that: comprises the step of preparing chloropropyl tri-p-phenylamine oxy silane by reacting gamma-chloropropyl trichlorosilane with N, N-dimethyl-4-hydroxyaniline.
3. The preparation method according to claim 2, characterized in that: and (3) after the gamma-chloropropyl trichlorosilane reacts with the N, N-dimethyl-4-hydroxyaniline, performing alkali washing on the reactant, and performing aftertreatment after the alkali washing to obtain the chloropropyl tri-p-phenylamine oxy silane.
4. A method of manufacture according to claim 3, characterized in that: and (3) performing alkali washing by adopting an ethanol solution of sodium ethoxide, and performing post-treatment of removing impurities by distillation and inorganic salts by filtration after alkali washing to obtain the chloropropyl tri-p-aniline oxy silane.
5. The method according to claim 2, 3 or 4, wherein: the molar ratio of the N, N-dimethyl-4-hydroxyaniline to the gamma-chloropropyl trichlorosilane is 3.0-3.2:1.
6. the preparation method according to claim 5, characterized in that: the molar ratio of the N, N-dimethyl-4-hydroxyaniline to the gamma-chloropropyl trichlorosilane is 3.0-3.1:1.
7. the method according to claim 2, 3 or 4, wherein: the reaction temperature is 60-100 ℃.
8. The method for preparing the composite material according to claim 7, wherein: the reaction temperature is 60-80 ℃.
9. The use of chloropropyl tri-p-anilinoxysilane according to claim 1 for the preparation of a silane coupling agent, characterized in that: reacting chloropropyl tri-p-phenylamine oxygen silane with a substrate to prepare a silane coupling agent; the substrate is a sulfur-containing material.
10. The use according to claim 9, characterized in that: the substrate is a substance containing sulfhydryl and thiocarboxylate.
11. The use according to claim 9, characterized in that: the substrate is disodium tetrasulfide, sodium hydrosulfide or allyl thiocarboxylate.
12. A silane coupling agent is characterized by having the following structural formula:
wherein R is S 4 。
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| CN102584886A (en) * | 2012-01-17 | 2012-07-18 | 华南理工大学 | Silane coupling agent and preparation method thereof |
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| CN103342716A (en) * | 2013-07-18 | 2013-10-09 | 招远市金鹏橡胶助剂有限公司 | Method for synthesizing bis-[propyl trimethoxysilane]-tetrasulfide silane coupling agent |
| CN104961760A (en) * | 2015-02-26 | 2015-10-07 | 菏泽学院 | Synthetic method for novel rubber sulfur-containing silane coupling agent--bis-[gamma-(trimethoxy)silylpropyl]tetrasulfide |
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| US4375420A (en) * | 1982-02-22 | 1983-03-01 | Olin Corporation | Selected 4-hydroxyphenyl anilino alkoxysilanes and their use as antioxidants |
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| CN102584886A (en) * | 2012-01-17 | 2012-07-18 | 华南理工大学 | Silane coupling agent and preparation method thereof |
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