CN109749123A - A kind of rubber powder and preparation method with vulcanization facilitation - Google Patents
A kind of rubber powder and preparation method with vulcanization facilitation Download PDFInfo
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- CN109749123A CN109749123A CN201910126567.6A CN201910126567A CN109749123A CN 109749123 A CN109749123 A CN 109749123A CN 201910126567 A CN201910126567 A CN 201910126567A CN 109749123 A CN109749123 A CN 109749123A
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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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
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Abstract
The invention discloses a kind of modified glue powders and preparation method with vulcanization facilitation.The preparation method obtains the rubber powder of dense sulfuric acid treatment the following steps are included: take rubber powder dense sulfuric acid treatment；In deionized water by the rubber powder dispersion of dense sulfuric acid treatment, rubber powder suspension is obtained, chlorine-containing silane coupling agent is added in suspension, obtains the activated rubber powder of coupling agent treatment；Vulcanization accelerator is added in activated rubber powder, further after reaction, vulcanization accelerator is supported on vulcanized rubber powder, and the modified glue powder with vulcanization facilitation is prepared.By the way that promotor is supported on vulcanized rubber powder, to assign rubber powder vulcanization facilitation, the rubber powder for loading vulcanization accelerator is applied in rubber, it can promote the vulcanization of rubber powder Yu rubber matrix interface, promote interfacial interaction, to make rubber/rubber powder composite material be enhanced, modified glue powder plays a dual role of vulcanization promotion and filler reinforcement.
Description
Technical field
The present invention relates to rubber powder functional modification field more particularly to a kind of preparation sides with vulcanization accelerator modified glue powder
Method and its application.
Background technique
China is the first big rubber-consumer state in the world, while being the relatively deficient country nearly 80% of rubber sources again
Natural rubber and 40% synthetic rubber depend on import, wherein the import dependency degree of natural rubber be higher than petroleum, iron ore and
Grain etc., ranks first place, and the consumption of tire accounts for 70% or more rubber total amount.Not with the price of natural rubber and synthetic rubber
It is disconnected to go up, it makes full use of waste tire and is applied to rubber material, for alleviating the pressure of China's rubber sources scarcity, reduce ring
Border pollution is of great significance.Currently, waste old utilizes based on reclaimed rubber, account for about the 71% of total amount.Compared to reclaimed rubber,
The comparision of production environmental protection of rubber powder, waste old production rubber powder are to integrate environmentally friendly rising with resource regeneration
Way of recycling, and advocate the optimum utilization form developed a circular economy, application prospect is very wide.Rubber powder can be applied
It in rubber, plastics, pitch, cellulose etc., also can be applied in inorganic matter, such as cement, and achieve certain effect.
Rubber powder is a kind of material containing cross-linked structure being made of rubber, carbon black etc..The surface-active of rubber powder is low, works as addition
It is weaker with the interaction force of basis material when in basis material, cause the performance of material to decline, therefore need when in use
It is modified.Be mainly the following mode at present: rubber powder desulfurization is modified, in CN201610054645.2, by micro-
Wave handles rubber powder and carries out desulfurization, is applied in natural gum；Mechanical-chemical modification, such as document [woods very [J] specific rubber system
Product, 2013 (1): 62-65.] in, regenerant consumption, regeneration temperature and time, mill temperature are had studied using mechanochemical method
The influence of degree and time to crumb rubber activation effect；Grafting or interpenetrating polymer networks are modified, such as patent CN201710707103.5
In, by reacting for ethyl orthosilicate and n-butylamine, in-situ preparation silica is grafted on vulcanized rubber powder, and modified glue powder is used for day
Right rubber, and pass through interpenetrating polymer networks in [Yang Li etc. [J] Environmental science and technology, 2012,35 (3): 63-67.]
Technology modified glue powder is prepared for natural rubber/public network/shoddy and is conjugated three components；These method of modifying achieve one
Fixed effect, but by dense sulfuric acid treatment rubber powder, increase the active group of vulcanized rubber powder, then will be vulcanized by coupling agent again
Promotor is connect with the active group on rubber powder, so that vulcanization accelerator is supported on rubber powder, assign rubber powder filler reinforcement and
The technology of vulcanization double action is promoted to there are no patent and non-patent literature report.
Summary of the invention
The present invention problem weaker in conjunction with rubber interface for current rubber powder, using dense sulfuric acid treatment rubber powder, then again
Using chlorine-containing silane coupling agent and vulcanization accelerator modified glue powder, vulcanization accelerator is supported on vulcanized rubber powder, preparation has
Vulcanization promotes and the modified glue powder of filler reinforcement double action.
Technical solution of the present invention is as follows.
A kind of preparation method of the modified glue powder with vulcanization facilitation, comprising the following steps:
(1) rubber powder is added in the concentrated sulfuric acid, Quick mechanical stirs 5-60min at room temperature, obtains the rubber powder of dense sulfuric acid treatment；
(2) it disperses the rubber powder of dense sulfuric acid treatment in deionized water, addition chlorine-containing silane coupling agent, at 25~100 DEG C
Quick mechanical stirring 1~obtain activated rubber powder for 24 hours；
(3) in activated rubber powder, vulcanization accelerator is added, nitrogen atmosphere reaction 1 at 60~100 DEG C~for 24 hours, product is through washing
It washs, filter, dry, obtain the modified glue powder with vulcanization facilitation.
In the above method, in step (1), the mass ratio of the concentrated sulfuric acid and rubber powder is 0.01-0.05:1.
In the above method, in step (2), the mass ratio of the deionized water and rubber powder is 1~2:1, coupling agent and rubber powder
Mass ratio be 0.03~0.12:1.
In the above method, in step (3), the mass ratio of the promotor and rubber powder is 0.01~0.1:1.
In the above method, the chlorine-containing silane coupling agent includes r-chloropropyl trimethoxyl silane, chloropropyl triethoxy silicon
Alkane, chloromethyl trimethoxy silane, chloromethyl triethoxysilane, chloroethyl trimethoxy silane, chloroethene ethyl triethoxy silicane
On one of alkane, chloropropyl trichloro-silane, chloropropyl dimethoxy monosilane, chloroethyl dimethoxy monosilane.
In the above method, the vulcanization accelerator includes 2-mercaptobenzothiazole, dibenzothiazyl disulfide, dimethyl two
Thioamido zinc formate, dibutyl dithio amidocarbonic acid zinc, diethyl-dithio amidocarbonic acid zinc, the thio amine of ethylphenyl two
Base zinc formate, dibenzyl dithio amidocarbonic acid zinc, dibutyl dithio amidocarbonic acid iron, dibutyl dithio amidocarbonic acid copper
One or more of.
The present invention provides a kind of specific reaction mechanism, but not limited to this, when coupling agent is chloropropyl triethoxysilane
(CTS), when vulcanization accelerator is 2-mercaptobenzothiazole, it is shown that the reaction mechanism is as follows:
Compared with prior art, present invention has an advantage that
(1) present invention loads vulcanization accelerator on rubber powder, assigns rubber powder and vulcanizes facilitation；
(2) present invention load vulcanization promote agent in vulcanized rubber powder, modified glue powder application is filled in rubber, promote rubber powder with
Vulcanization time is shortened in the vulcanization of rubber matrix interface, improves rate of cure；
(3) interfacial interaction for promoting rubber powder and rubber matrix, so that rubber/rubber powder composite material be made to obtain reinforcement；
(4) modified glue powder with vulcanization facilitation of preparation, plays filler reinforcement in rubber/rubber powder composite material
And the double action that vulcanization promotes, effectively improve the comprehensive performance of composite material.
Detailed description of the invention
Fig. 1 is the water contact angle figure of unmodified rubber powder in embodiment 1, comparison rubber powder 1, modified glue powder 1.
Fig. 2 be butadiene-styrene rubber, butadiene-styrene rubber in example 2/unmodified rubber powder, butadiene-styrene rubber/comparison rubber powder 2, butadiene-styrene rubber/
The DSC test chart of modified glue powder 2.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Rubber powder in the embodiment of the present invention, which is bought, likes its Science and Technology Co., Ltd. in Guangzhou.
Embodiment 1
It weighs 80 mesh rubber powder of 100g, the concentrated sulfuric acid is added, Quick mechanical stirs 60min at room temperature, the concentrated sulfuric acid and rubber powder
Mass ratio is 0.01:1, obtains the rubber powder of dense sulfuric acid treatment；It disperses the rubber powder of dense sulfuric acid treatment in deionized water, is added even
Join agent chloropropyl triethoxysilane, wherein the mass ratio of deionized water and rubber powder is 1:1, and the mass ratio of coupling agent and rubber powder is
0.03:1, Quick mechanical stirs 12h at 50 DEG C, and reaction obtains activated rubber powder, adds promotor 2-mercaptobenzothiazole, promotes
The mass ratio of agent and rubber powder is 0.1:1, and for 24 hours, product is washed, filters, is dry for nitrogen atmosphere reaction at 60 DEG C, is obtained with sulphur
Change the modified glue powder 1 of facilitation.
To compare influence of the modifying process to rubber powder structure and performance, by activated rubber powder obtained in above-mentioned preparation process into
After row washing, filtering, drying, comparison rubber powder 1 is obtained.Water contact is carried out to unmodified rubber powder, comparison rubber powder 1 and modified glue powder 1
Angle test, experimental result such as Fig. 1.The water contact angle of unmodified rubber powder is 116.0 °, the comparison glue after sulfuric acid and coupling agent activation
Powder 1 is 133.1 °, and further increasing for promotor modified glue powder 1 is 147.2 °, illustrates that promotor has successfully been grafted to rubber powder table
Face.
Embodiment 2
It weighs 105g rubber powder and the concentrated sulfuric acid is added, Quick mechanical stirs 5min, the mass ratio of the concentrated sulfuric acid and rubber powder at room temperature
For 0.05:1, the rubber powder of dense sulfuric acid treatment is obtained；It disperses the rubber powder of dense sulfuric acid treatment in deionized water, coupling agent is added
Chloroethyl trimethoxy silane, wherein the mass ratio of deionized water and rubber powder is 2:1, and the mass ratio of coupling agent and rubber powder is
0.12:1, Quick mechanical stirring for 24 hours, obtains activated rubber powder at 25 DEG C, and the promotor diethyl that mass ratio is 2:1 is wherein being added
The mass ratio of base dithiocarbamate zinc, ethylphenyl dithiocarbamate zinc, promotor and rubber powder be 0.01:1,100
Nitrogen atmosphere reacts 1h at DEG C, and product is washed, filters, is dry, obtains modified glue powder 2.
Influence for more each rubber powder to rubber/rubber powder composite material performance, will be living obtained in above-mentioned preparation process
After change rubber powder is washed, filtered, dried, comparison rubber powder 2 is obtained.
By modified glue powder 2 and butadiene-styrene rubber and each rubber chemicals mill on a mill, butadiene-styrene rubber/modified adhesive is obtained
Powder composite material, same method obtain butadiene-styrene rubber/2 material of comparison rubber powder, butadiene-styrene rubber/unmodified glue powder material, are not filled by
Styrene-butadiene rubber, by styrene-butadiene rubber, butadiene-styrene rubber/unmodified glue powder material, butadiene-styrene rubber/2 material of comparison rubber powder,
2 material of butadiene-styrene rubber/modified glue powder is vulcanized, and takes vulcanizate to do DSC test, as a result as shown in Figure 2.Be calculated rubber by
The mass fraction (χ im) for limiting molecular layer is respectively 0,5.2%, 9.3%, 16.9%, and 2 material of butadiene-styrene rubber/modified glue powder has
Highest restrained molecular quality amount score shows that modified glue powder 2 and the interfacial interaction of rubber matrix are most strong.
Embodiment 3
It weighs 110g rubber powder and the concentrated sulfuric acid is added, Quick mechanical stirs 25min, the mass ratio of the concentrated sulfuric acid and rubber powder at room temperature
For 0.04:1, the rubber powder of dense sulfuric acid treatment is obtained；It disperses the rubber powder of dense sulfuric acid treatment in deionized water, mass ratio is added
For the coupling agent chloromethyl triethoxysilane and chloroethyl trimethoxy silane of 1:1, the wherein quality of deionized water and rubber powder
Than for 1.2:1, the mass ratio of coupling agent and rubber powder is 0.10:1, Quick mechanical stirs 18h at 60 DEG C, and reaction obtains activity gel
Powder adds accelerator dibenzothiazyl disulfide, and wherein the mass ratio of accelerator dibenzothiazyl disulfide and rubber powder is
0.08:1, nitrogen atmosphere reacts 18h at 70 DEG C, and product is washed, filtering, dry, obtains modified glue powder 3.
Influence for more each rubber powder to rubber/rubber powder composite material performance, will be living obtained in above-mentioned preparation process
After change rubber powder is washed, filtered, dried, comparison rubber powder 3 is obtained.
Embodiment 4
It weighs 115g rubber powder and the concentrated sulfuric acid is added, Quick mechanical stirs 40min, the mass ratio of the concentrated sulfuric acid and rubber powder at room temperature
For 0.03:1, the rubber powder of dense sulfuric acid treatment is obtained；It disperses the rubber powder of dense sulfuric acid treatment in deionized water, coupling agent is added
Chloroethyl dimethoxy monosilane, wherein the mass ratio of deionized water and rubber powder is 1.5:1, and the mass ratio of coupling agent and rubber powder is
0.08:1, Quick mechanical stirs 12h at 80 DEG C, obtains activated rubber powder, adds promotor dibutyl dithio amidocarbonic acid iron,
Wherein the mass ratio of promotor and rubber powder is 0.05:1, and nitrogen atmosphere reacts 8h at 60 DEG C, and product is washed, filters, is dry, is obtained
To modified glue powder 4.
Influence for more each rubber powder to rubber/rubber powder composite material performance, will be living obtained in above-mentioned preparation process
After change rubber powder is washed, filtered, dried, comparison rubber powder 4 is obtained.
Embodiment 5
It weighs 120g rubber powder and the concentrated sulfuric acid is added, Quick mechanical stirs 50min, the mass ratio of the concentrated sulfuric acid and rubber powder at room temperature
For 0.02:1, the rubber powder of dense sulfuric acid treatment is obtained；It disperses the rubber powder of dense sulfuric acid treatment in deionized water, coupling agent chlorine is added
Ethyl triethoxysilane, wherein the mass ratio of deionized water and rubber powder is 1.8:1, and the mass ratio of coupling agent and rubber powder is
0.06:1, Quick mechanical stirs 1h at 100 DEG C, obtains activated rubber powder, adds promotor diethyl-dithio amidocarbonic acid
Zinc, wherein the mass ratio of promotor and rubber powder is 0.03:1, and nitrogen atmosphere reacts 6h at 90 DEG C, and product is washed, filtering, does
It is dry, obtain modified glue powder 5.
Influence for more each rubber powder to rubber/rubber powder composite material performance, will be living obtained in above-mentioned preparation process
After change rubber powder is washed, filtered, dried, comparison rubber powder 5 is obtained.
Comparison rubber powder 2-5, modified glue powder 2-5 in unmodified rubber powder and above-described embodiment 2-5 is respectively applied to butylbenzene
Rubber, butadiene rubber, nitrile rubber, natural rubber, the rubber powder of addition are 40 parts, test the curing curve of rubber compound, and root
The performance of material is measured according to standard GB/T/T 528-2009, test result is as shown in table 1.
1 rubber material the performance test results of table
It can be obtained by above embodiments, the rubber powder for loading vulcanization accelerator is added in rubbery system, can not only promote rubber
Glue/rubber powder composite material curingprocess rate shortens vulcanization time, while playing filling effect, and makes rubber/rubber powder composite wood
The tensile strength of material gets a promotion.
Claims (7)
1. a kind of preparation method of the modified glue powder with vulcanization facilitation, which comprises the following steps:
(1) rubber powder is added in the concentrated sulfuric acid, Quick mechanical stirs 5-60min at room temperature, obtains the rubber powder of dense sulfuric acid treatment；
(2) it disperses the rubber powder of dense sulfuric acid treatment in deionized water, chlorine-containing silane coupling agent, quick machine at 25 ~ 100 DEG C is added
Tool stirs 1 ~ 24 h and obtains activated rubber powder；
(3) in activated rubber powder, vulcanization accelerator is added, nitrogen atmosphere reacts 1 ~ 24 h at 60 ~ 100 DEG C, and product is washed, mistake
Filter, drying, obtain the modified glue powder with vulcanization facilitation.
2. having the preparation method of the modified glue powder of vulcanization facilitation according to claim 1, which is characterized in that step
(1) in, the mass ratio of the concentrated sulfuric acid and rubber powder is 0.01-0.05:1.
3. having the preparation method of the modified glue powder of vulcanization facilitation according to claim 1, which is characterized in that step
(2) in, the mass ratio of the deionized water and rubber powder is 1 ~ 2:1, and the mass ratio of coupling agent and rubber powder is 0.03 ~ 0.12:1.
4. having the preparation method of the modified glue powder of vulcanization facilitation according to claim 1, which is characterized in that step
(3) in, the mass ratio of the promotor and rubber powder is 0.01 ~ 0.1:1.
5. having the preparation method of the modified glue powder of vulcanization facilitation according to claim 1, which is characterized in that described to contain
Chlorosilane coupling agent includes r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, chloromethyl trimethoxy silane, chloromethane
Ethyl triethoxy silicane alkane, chloroethyl trimethoxy silane, chloroethyl triethoxysilane, chloropropyl trichloro-silane, chloropropyl two
On one of methoxy methyl silane, chloroethyl dimethoxy monosilane.
6. having the preparation method of the modified glue powder of vulcanization facilitation according to claim 1, which is characterized in that the sulphur
Changing promotor includes 2-mercaptobenzothiazole, dibenzothiazyl disulfide, dimethyl disulfide for amidocarbonic acid zinc, two sulphur of dibutyl
For amidocarbonic acid zinc, diethyl-dithio amidocarbonic acid zinc, ethylphenyl dithiocarbamate zinc, dibenzyl dithio amido
One or more of zinc formate, dibutyl dithio amidocarbonic acid iron, dibutyl dithio amidocarbonic acid copper.
7. the modified glue powder with vulcanization facilitation is prepared by any one of claim 1 ~ 6 preparation method.
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| CN201910126567.6A CN109749123B (en) | 2019-02-20 | 2019-02-20 | Rubber powder with vulcanization promoting effect and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7092233B1 (en) | 2021-04-19 | 2022-06-28 | 住友ゴム工業株式会社 | tire |
| WO2022234443A1 (en) * | 2021-05-04 | 2022-11-10 | Rubber Nano Products (Proprietary) Limited | Method of functionalising an elastomeric material and the use thereof in rubber formulations |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5817130A (en) * | 1981-07-24 | 1983-02-01 | Hayakawa Rubber Co Ltd | Reclamation of vulcanized rubber |
| CN101631829A (en) * | 2007-09-10 | 2010-01-20 | 住友橡胶工业株式会社 | Vulcanized rubber composition, pneumatic tire, and their production methods |
| CN103736465A (en) * | 2013-12-12 | 2014-04-23 | 华中科技大学 | Modified waste rubber powder for absorbing heavy metals and preparation method thereof |
| CN109320799A (en) * | 2017-08-01 | 2019-02-12 | 住友橡胶工业株式会社 | Rubber composition and pneumatic tire |
-
2019
- 2019-02-20 CN CN201910126567.6A patent/CN109749123B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5817130A (en) * | 1981-07-24 | 1983-02-01 | Hayakawa Rubber Co Ltd | Reclamation of vulcanized rubber |
| CN101631829A (en) * | 2007-09-10 | 2010-01-20 | 住友橡胶工业株式会社 | Vulcanized rubber composition, pneumatic tire, and their production methods |
| CN103736465A (en) * | 2013-12-12 | 2014-04-23 | 华中科技大学 | Modified waste rubber powder for absorbing heavy metals and preparation method thereof |
| CN109320799A (en) * | 2017-08-01 | 2019-02-12 | 住友橡胶工业株式会社 | Rubber composition and pneumatic tire |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7092233B1 (en) | 2021-04-19 | 2022-06-28 | 住友ゴム工業株式会社 | tire |
| WO2022224538A1 (en) * | 2021-04-19 | 2022-10-27 | 住友ゴム工業株式会社 | Tire |
| JP2022165291A (en) * | 2021-04-19 | 2022-10-31 | 住友ゴム工業株式会社 | tire |
| WO2022234443A1 (en) * | 2021-05-04 | 2022-11-10 | Rubber Nano Products (Proprietary) Limited | Method of functionalising an elastomeric material and the use thereof in rubber formulations |
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