CN107189102B - A kind of hydridization filler support type anti-aging agent and the preparation method and application thereof - Google Patents
A kind of hydridization filler support type anti-aging agent and the preparation method and application thereof Download PDFInfo
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- CN107189102B CN107189102B CN201710497838.XA CN201710497838A CN107189102B CN 107189102 B CN107189102 B CN 107189102B CN 201710497838 A CN201710497838 A CN 201710497838A CN 107189102 B CN107189102 B CN 107189102B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of hydridization filler support type anti-aging agents and the preparation method and application thereof.This method comprises the following steps: (1) hydridization filler with silane coupling agent is mixed, is stirred to react 10 at 70 ~ 90 DEG C~for 24 hours, it is dry after intermediate product；(2) intermediate product of step (1) is mixed with 4-aminodiphenylamine (RT), 8~12h is stirred to react at 50~70 DEG C, obtains hydridization filler support type anti-aging agent after dry.The hydridization filler support type anti-aging agent can significantly reduce volatilization transport phenomena of the small molecule anti-aging agent in rubber matrix, have than general Ammonia antioxidant 4010NA and more effectively prevent old effect, be with a wide range of applications in rubber materials.
Description
Technical field
The invention belongs to rubber antioxidant and application fields, and in particular to a kind of hydridization filler support type anti-aging agent and its system
Preparation Method and application.
Background technique
The development of rubber composite material and the extensive use of inorganic filler and rubber chemicals are closely related.Nano hybridization filler
Be two or more inorganic nano-particle is combined by modes such as hydrogen bond, Electrostatic Absorption, chemical bonds it is new
Type nanofiller.Compared with common single filler, hydridization filler has unique appearance structure, usually to macromolecule composite wood
Material generates more significant synergy.In the early-stage study of applicant, by sol-gal process in galapectite surface in situ
One layer of nano-silicon dioxide particle is generated, a kind of novel hydridization filler has been obtained.It is this to receive compared with halloysite nanotubes
Rice hydridization packing specific area significantly improves, and surface has more activity hydroxies, is a kind of excellent nano-carrier.
Rubber antioxidant is component part important in rubber product, generally gives to the excellent heat oxygen aging resistance of rubber product
Performance, but common commercialization anti-aging agent there is also it is easy to migrate, move out the shortcomings that, therefore, develop it is resistance to move out it is novel prevent
Old agent is always the research emphasis of rubber materials.The present invention is using coupling agent as bridge, by Ammonia anti-aging agent (4010NA, 4020)
Intermediate N diphenyl-para-phenylene diamine (RT) load to the surface of hydridization filler, it is anti-that a kind of hydridization filler support type has been prepared
Old agent.This support type anti-aging agent is that small molecule anti-aging agent or anti-aging agent intermediate are tightly secured in hydridization by chemical bond
The surface of filler significantly reduces volatilization and migration of the small molecule anti-aging agent in rubber matrix, improves rubber composite wood
The anti-old effect of material, has a good application prospect in rubber industry.Such anti-aging agent has not been reported so far.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention is first modified hydridization filler using a kind of silane coupling agent,
Then intermediate product is reacted with RT again and prepares support type anti-aging agent, solved the disadvantage that Ammonia anti-aging agent is easy to migrate and move out.
The purpose of the invention is achieved by the following technical solution.
A kind of preparation method of hydridization filler support type anti-aging agent, comprises the following steps:
(1) hydridization filler is mixed with silane coupling agent, is stirred to react at 70~90 DEG C, obtain intermediate product after dry
(m-HS)；
(2) intermediate product of step (1) is mixed with 4-aminodiphenylamine, is stirred to react at 50~70 DEG C, it is dry
Hydridization filler support type anti-aging agent is obtained afterwards.
Preferably, silane coupling agent described in step (1) be γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane,
Gamma-aminopropyl-triethoxy-silane, γ-methacryloxypropyl trimethoxy silane, γ-r-chloropropyl trimethoxyl silicon
Alkane, bis- (γ-triethoxy silicon substrate propyl) one of tetrasulfides and 3- (trimethoxysilyl) -1- propanethiol with
On, further preferably γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH560).
Preferably, the temperature of step (1) described drying is 50~70 DEG C.
Preferably, silane coupling agent described in step (1) is γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane.
Preferably, hydridization filler described in step (1) is prepared for halloysite nanotubes by sol-gal process inorganic
Filler, surface contain active hydroxyl.This method specific steps are as follows: the 5g halloysite nanotubes purified are distributed to 100ml
In 95% dehydrated alcohol, and the ammonium hydroxide of 5ml 25wt% is added, then 0.2ml bis- is added dropwise in the ultrasonic disperse 20min at 30 DEG C
Dibutyl tin laurate stirs 0.5 hour at 40 DEG C, the ethyl orthosilicate of 2.5g is then added dropwise, after being added dropwise, 40
It DEG C is stirred to react 3 hours, product is centrifugated and uses ethanol washing five times, is put into 80 DEG C of vacuum drying ovens and dries 10 hours, obtains
Hydridization filler, i.e. halloysite nanotubes-SiO 2 hybrid filler.
Preferably, the time being stirred to react described in step (1) be 10~for 24 hours.
Preferably, silane coupling agent described in step (1) is 8wt%~10wt% of hydridization filler.
Preferably, the silane coupling agent is the 9wt% of hydridization filler.
Preferably, in step (2), the mass ratio 10:(0.5 of hydridization filler and 4-aminodiphenylamine in intermediate product
~2), further preferably 8:1.
Preferably, the time being stirred to react described in step (2) is 8~12h.
Preferably, the temperature of drying described in step (2) is 50~70 DEG C.
Preferably, the mass ratio of the hydridization filler in intermediate product described in step (2) and 4-aminodiphenylamine is 10:
1。
A kind of hydridization filler support type anti-aging agent being prepared by the process described above, the hydridization filler support type are anti-
Old agent is preparing the application in rubber composite material.
Preferably, the matrix of the rubber composite material is natural rubber, butadiene-styrene rubber (SBR) or other synthetic rubber.
The principle of the present invention: hydridization filler HNTs-g-SiO is prepared first in situ synthesis2(HS), it then to it carries out
Coupling agent treatment obtains intermediate product m-HS, and intermediate product and RT reaction are then prepared support type antioxidant H S-s-RT.
Compared with prior art, the invention has the following advantages that
1, support type anti-aging agent of the invention is uniformly dispersed in rubber matrix, can preferably play and prevent old effect, extends
The service life of rubber product；
2, support type anti-aging agent of the invention is not easy to migrate in rubber matrix, has excellent solvent resistant, heat-resisting oxygen old
The effect of change.
Detailed description of the invention
Fig. 1 is the preparation principle schematic diagram of hydridization filler support type anti-aging agent of the present invention.
The infrared spectrogram for the HS-s-RT that Fig. 2 is HS and prepared by embodiment 1.
Fig. 3 is the thermal gravimetric analysis curve figure of the HS-s-RT of HS, m-HS and the preparation of embodiment 1.
Fig. 4 is the oxidation induction period curve graph of styrene-butadiene rubber composite material prepared by embodiment 2.
Fig. 5 is the stretching strength retentivity curve graph after styrene-butadiene rubber composite material aging prepared by embodiment 2.
Fig. 6 is the styrene-butadiene rubber composite material oxidation induction period of the preparation of embodiment 2 with extraction times variation diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Wherein, hydridization filler HNTs-g-SiO used in following embodiment2Preparation method be detailed in that application No. is 2016107406975
Patent application.
The preparation principle schematic diagram of hydridization filler support type anti-aging agent of the present invention is as shown in Figure 1.
Embodiment 1
By 10g HNTs-g-SiO2(HS) and 0.8g silane coupling agent γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicon
Alkane is added in the three-necked flask of 500mL, reacts 10 hours, is cooled to room temperature at 70 DEG C, obtains centre after dry at 50 DEG C
Product (m-HS).0.5g RT (4-aminodiphenylamine) is added, 8h is reacted at 50 DEG C, is then obtained after drying at 60 DEG C
To support type anti-aging agent, it is labeled as HS-s-RT.
Infrared spectroscopy of the support type anti-aging agent manufactured in the present embodiment after ethanolic extraction as shown in the curve b in Fig. 2,
2946cm-1And 2875cm-1Place is the stretching vibration absworption peak of methylene, while in 1521cm-1There are the carbon skeleton C=C of aromatic ring
Bending vibration absorption peak.The thermogravimetric analysis figure of the present embodiment synthetic product is as shown in Figure 3.In conjunction with infrared spectrum and thermogravimetric analysis figure
It is found that RT is successfully grafted on hydridization filler.
Embodiment 2
By 10g HNTs-g-SiO2(HS) and 1g silane coupling agent γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
It is added in the three-necked flask of 500mL, reacts 12 hours, be cooled to room temperature at 80 DEG C, obtain intermediate product after dry at 70 DEG C
(m-HS).It adds 1g RT (4-aminodiphenylamine) and reacts 12h at 60 DEG C, it is anti-to obtain support type after dry at 50 DEG C
Old agent is labeled as HS-s-RT.
Fourth is prepared using the support type antioxidant H S-s-RT of γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane preparation
The basic recipe of benzene rubber composite material is as shown in table 1.The preparation detailed process of styrene-butadiene rubber composite material: by addition rubber
(SBR), the sequence of activator (ZnO+St), filler, promotor, anti-aging agent and Sulfur, successively mixes on the double roll mill
Uniformly, then vulcanization obtains styrene-butadiene rubber composite material at 160 DEG C.
Table 1
Unit in table 1 is mass parts (phr)；Wherein St is stearic acid；CZ is rubber accelerator N- cyclohexyl -2- benzene a pair of horses going side by side
Thiazolesulfenamide；4010NA indicates anti-aging agent N- isopropyl-N'- diphenyl-para-phenylene diamine；S is Sulfur.
The oxidation induction period test curve figure of gained styrene-butadiene rubber composite material as shown in figure 4, rubber composite material oxygen
Change induction period size and be followed successively by SBR/HS-s-RT > SBR/m-HS/4010NA > SBR/HS/4010NA, prevents in SBR/HS-s-RT old
Agent is supported on filler, as filler glue is evenly dispersed in rubber matrix, compared to the anti-aging agent in other composite materials, with
Rubber contact chance greatly increases, so its oxidation induction period highest.
Fig. 5 is the stretching strength retentivity of styrene-butadiene rubber composite material with the variation diagram of days of ageing, it is seen that
Stretching strength retentivity is apparently higher than the rubber composite material of small molecule anti-aging agent filling, prevents old excellent effect.Fig. 6 is butylbenzene rubber
Glue composite material oxidation induction period with extraction times variation diagram, there it can be seen that addition support type anti-aging agent of the invention
The oxidation induction period of the styrene-butadiene rubber composite material of HS-s-RT reduces smaller, resistance to effect of moving out with the extension of extraction times
It is substantially better than common small molecule anti-aging agent.
Embodiment 3
By 10g HNTs-g-SiO2(HS) and 0.9g silane coupling agent γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicon
Alkane is added in the three-necked flask of 500mL, reacts 24 hours, is cooled to room temperature at 90 DEG C, obtains centre after dry at 60 DEG C
Product (m-HS).It adds 2g RT (4-aminodiphenylamine) and reacts 10h at 70 DEG C, be dried to obtain support type at 70 DEG C
Anti-aging agent is labeled as HS-s-RT.
Table 2
According to the formula of table 2, after in the anti-aging agent addition butadiene-styrene rubber of preparation, survey its oxidation induction period it is found that with
SBR/m-HS/4010NA is compared, and the oxidation induction period of SBR/HS-s-RT composite material is increased to by 109.45min
The ageing-resistant performance of 122.73min, styrene-butadiene rubber composite material significantly improve.
Claims (9)
1. a kind of preparation method of hydridization filler support type anti-aging agent, which is characterized in that comprise the following steps:
(1) hydridization filler is mixed with silane coupling agent, is stirred to react at 70 ~ 90 DEG C, obtain intermediate product after dry；Described
Hydridization filler is HNTs-g-SiO2；
(2) intermediate product of step (1) is mixed with 4-aminodiphenylamine, is stirred to react at 50~70 DEG C, obtained after dry
Hydridization filler support type anti-aging agent.
2. a kind of preparation method of hydridization filler support type anti-aging agent according to claim 1, which is characterized in that step
(1) silane coupling agent described in is γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy silicon
Alkane, γ-methacryloxypropyl trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, bis- (γ-triethoxy silicon substrate
Propyl) one or more of tetrasulfide and 3- (trimethoxysilyl) -1- propanethiol.
3. a kind of preparation method of hydridization filler support type anti-aging agent according to claim 1, which is characterized in that step
(1) time being stirred to react described in be 10~for 24 hours.
4. a kind of preparation method of hydridization filler support type anti-aging agent according to claim 1, which is characterized in that step
(1) silane coupling agent described in is 8wt% ~ 10wt% of hydridization filler.
5. a kind of preparation method of hydridization filler support type anti-aging agent according to claim 4, which is characterized in that described
Silane coupling agent is the 9wt% of hydridization filler.
6. a kind of preparation method of hydridization filler support type anti-aging agent according to claim 1, which is characterized in that step
(2) in, the mass ratio of hydridization filler and 4-aminodiphenylamine in intermediate product is 10:(0.5~2).
7. a kind of preparation method of hydridization filler support type anti-aging agent according to claim 1, which is characterized in that step
(2) time being stirred to react described in is 8~12h.
8. a kind of hydridization filler support type anti-aging agent being prepared by the described in any item methods of claim 1 ~ 7.
9. a kind of hydridization filler support type anti-aging agent according to any one of claims 8 is preparing the application in rubber composite material.
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| CN106854387A (en) * | 2017-01-04 | 2017-06-16 | 华南理工大学 | A kind of rubber antioxidant reduction and modified graphene oxide and preparation method and application |
| CN110734581A (en) * | 2018-07-18 | 2020-01-31 | 北京化工大学 | halloysite nanotube grafted with antioxidant as well as preparation method and application thereof |
| CN111825898B (en) * | 2019-04-18 | 2022-06-28 | 北京化工大学 | Rubber anti-aging agent and preparation method thereof |
| CN110564072B (en) * | 2019-10-25 | 2021-12-21 | 长春工业大学 | Preparation method of high-rigidity, high-toughness and aging-resistant ABS resin |
| CN115403680B (en) * | 2022-08-24 | 2023-03-21 | 华南理工大学 | Nano silicon dioxide/chitosan hybrid material loaded anti-aging agent and preparation and application thereof |
| CN115536913B (en) * | 2022-10-12 | 2024-04-16 | 科迈特新材料有限公司 | Heat-resistant and aging-resistant modifier for rubber and preparation method thereof |
| CN115612191B (en) * | 2022-10-17 | 2023-08-22 | 太原理工大学 | High-temperature-resistant aging-resistant flame-retardant rubber material, rubberizing, high-temperature-resistant high-adhesion-resistant flame-retardant rubber conveyer belt and preparation method thereof |
| CN115536914B (en) * | 2022-10-17 | 2023-06-09 | 山西浙大新材料与化工研究院 | Composite anti-aging agent, preparation method thereof and heat-resistant rubber material |
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| CN101372620B (en) * | 2008-09-25 | 2011-05-18 | 河南省科学院 | Galapectite load antimony pentoxide nano complex and preparation thereof |
| CN103396592B (en) * | 2013-07-11 | 2015-09-16 | 华南理工大学 | Loading type rubber antioxidant and preparation method thereof and application |
| CN105670040A (en) * | 2016-02-25 | 2016-06-15 | 华南理工大学 | Loaded rubber anti-aging agent and preparation method and application thereof |
| CN106279772B (en) * | 2016-08-26 | 2019-05-14 | 华南理工大学 | A kind of method of halloysite nanotubes surface in situ growth silica preparation hydridization filler |
| CN106349505A (en) * | 2016-08-26 | 2017-01-25 | 华南理工大学 | Reinforcing and anti-aging environment-friendly rubber aging inhibitor and preparation method and application thereof |
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