CN106397635A - Biobased silicon-containing alternating EP rubber and preparation method thereof - Google Patents
Biobased silicon-containing alternating EP rubber and preparation method thereof Download PDFInfo
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- CN106397635A CN106397635A CN201610791622.XA CN201610791622A CN106397635A CN 106397635 A CN106397635 A CN 106397635A CN 201610791622 A CN201610791622 A CN 201610791622A CN 106397635 A CN106397635 A CN 106397635A
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- percha
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
TThe invention relates to a preparation method of biobased silicon-containing alternating EP rubber. Triethylsilane is used as a modifier, and a hydrosilation reaction is carried out for modification of gutta-percha. The triethylsilane modification reaction is carried out for modification of gutta-percha, the method can be carried out in a solution at a normal pressure, the operation is simple, the method has low requirements for equipment, and the method is easy to amplified and promoted. The modified rubber has strictly alternative ethylene and propylene, in the prerequisite that aging resistance and weatherability are not reduced, a reactive group is introduced to a gutta-percha main chain, and possibilities are provided for further modification. Compared with original gutta-percha elastomer, the structure has excellent interface compatibility as well as high moisture and slip resistance.
Description
Technical field
The present invention relates to field of rubber materials, the siliceous alternately EP rubbers of more particularly, to a kind of bio-based.
Background technology
EP rubbers is the third-largest synthetic rubber kind in the world after butadiene-styrene rubber and butadiene rubber, excellent with it
The features such as resistance to ag(e)ing, heat-resisting, tolerance to cold, is widely used in the fields such as auto industry, electric, building.With modified second
Being continuously increased of third rubber clone, the application of EP rubbers is more and more wider, and controlled long chain branching EP rubbers solves it
Processing characteristics and the conflicting problem of physical property, EP rubbers is carried out bromination, chlorination, sulfonation etc. process can improve its with
The compatibility of other glue kinds, introduces conjugated diene or vinyl monomer makes ethylene propylene diene rubber as third component, significantly carries
Rise its shock resistance.With the blending such as polyamide, NR, BR, SBR, NBR, IIR can comprehensive rubber performance, overcome each not
Foot.But industrialized EP rubbers, is prepared by ziegler-natta catalyst coordination polymerization, it be unable to do without ethylene propylene all the time
The petroleum resources such as alkene, petroleum resources belong to non-renewable resources, and just in increasingly depleted, and the demand of EP rubbers is increasingly
Increase, the preparation method seeking bio-based green EP rubbers becomes extremely urgent problem.Only document report is with sweet at present
The ethanol extracting in sugarcane prepares ethylene for EP rubbers, but the method ethanol extraction, ethylene complicated process of preparation, and
Propylene still relies on petroleum resources.And gutta-percha is a kind of natural resources, wide material sources, Guangdong and Guangxi Provinces are arrived in south, and Jilin, west to west are arrived in north
Gutta-percha tree can be planted in Tibetan, and planting range alreadys exceed 3,000,000 considerably beyond natural rubber, the plantation amount of current gutta-percha tree
Mu.Because in gutta-percha strand, strict transconfiguration leads to crystallization under its room temperature, existed with hard state it is impossible to play rubber
Glue characteristic.
Researcher is studying the elastomer how being changed into gutta-percha under room temperature always for a long time, and Yan Ruifang exists
Trans- Isosorbide-5-Nitrae-polyisoprene is made for gum elastic during the eighties by eighties of last century first, and subsequently in Chinese Academy of Sciences's work
Gutta-percha is modified as gum elastic, thus changing gutta-percha to cannot function as gum elastic using " three sections of sulfuration methods " by period
Present situation.Huang Bao treasure seminar once adopted the method for halogenation to destroy the crystallization of gutta-percha.Yang Feng et al. is also destroyed using epoxidation
The crystallization of gutta-percha.The method that this laboratory also once passes through hydrogenation successfully destroyed gutta-percha crystallization so as at normal temperatures by moulding
Material is changed into elastomeric material.
Therefore seek a kind of low cost, easily preparation, propagable gutta-percha multifunction method of modifying becomes Du
Secondary glue research direction highly significant.The silane with correctability functional group can be connected to Du by silicon hydrogenation at ambient pressure
On secondary glue main chain, both made to be changed into rubber from plastics under gutta-percha room temperature, again be its further modification provide possibility, silane simultaneously
Side base also advantageously improves the interface performance of strand and inorganic filler, and the weatherability to rubber for the moderate silane of reactivity
Have no significant effect with resistance to ag(e)ing, prepare the siliceous alternately EP rubbers of bio-based, broken EP rubbers and depended on oil
The limitation of resource, prepares a kind of alternately EP rubbers elastomer of novel siliceous again.
Content of the invention
First purpose of the present invention is to provide a kind of preparation method of the siliceous alternately EP rubbers of bio-based, and it is：
With triethyl silicane as modifying agent, by silicon hydrogenation, gutta-percha is modified, obtains final product.
Preferably, its preparation method comprises the steps：Under the protection of noble gases, described gutta-percha and described three second
The catalytic action by Wilkinson catalyst for the base silane, reacts 1～48 hour at 40 DEG C～120 DEG C, obtains final product.
Preferably, the reaction of described gutta-percha and described triethyl silicane is carried out in solution system, and solvent is toluene, ring
Hexane, chloroform or petroleum ether.
Preferably, also include hydrogenation is carried out to the modified rubber obtaining step.If the double bond in rubber after reaction
Content is higher, can control double bond content therein by hydrogenation.
Preferably, described triethyl silicane consumption is the 5%～80% of described gutta-percha quality；Preferably 30～50%.
Preferably, the consumption of described Wilkinson catalyst is the 0.5%～10% of dry glue quality；Preferably 3～7%.
Preferably, in described solution, the concentration of gutta-percha is 1%～6%.
Preferably, method of the present invention comprises the steps：
1) gutta-percha is made in toluene the solution that concentration is 1%～6%；
2) Wilkinson catalyst and triethyl silicane are added in the solution of described gutta-percha, in temperature 80～110
8～24h is reacted under conditions of DEG C；The addition of described Wilkinson catalyst is the 3～7% of gutta-percha dry glue quality, described
The addition of triethyl silicane is the 30～50% of gutta-percha dry glue quality.
Further preferably, method of the present invention comprises the steps：
1) gutta-percha is made in toluene the solution that concentration is 2%～4%；
2) Wilkinson catalyst and triethyl silicane are added in the solution of described gutta-percha, in temperature 80～110
8～24h is reacted under conditions of DEG C；The addition of described Wilkinson catalyst is the 5% of gutta-percha dry glue quality, described three second
The addition of base silane is the 40% of gutta-percha dry glue quality.
Above-mentioned gutta-percha dry glue is the quality that in Cortex Eucommiae sol solution, Du promotees glue.
Method of the present invention, also can carry out vulcanizing treatment to described modified rubber according to demand.
It is another object of the present invention to the siliceous alternately EP rubbers of bio-based that protection the method for the invention prepares.
The content being connected to silane side base on described modified rubber main chain is 5～60%, and/or remaining double bond content is 0%
～70%, and/or its residual crystallinity be 0～30%.
Final object of the present invention is to protect modified rubber of the present invention in the tread rubber preparing tire
Application.
Technical solutions according to the invention have the advantages that：
The present invention is modified to gutta-percha using the reaction of silicon hydrogenation modification, can carry out in solution at ambient pressure, operate
Simply, low for equipment requirements, easily expansion and popularization.
By gutta-percha, the plastics under room temperature are changed into elastomeric material to the present invention, and for preparing a kind of bio-based contains silane
Side base, second third strictly alternate EP rubbers, its structure is as follows：
Simultaneously on the premise of not reducing its resistance to ag(e)ing and weatherability, reactive base is introduced on gutta-percha main chain
Group, for its further modification provide possibility.
Modified rubber of the present invention has second third structure of silane side base, and this structure makes itself and original Cortex Eucommiae glue elasticity
The body phase interface compatibility more excellent than having and higher resistance to wet skidding performance energy.
, compared with original ethylene propylene diene rubber, its tensile strength and elastic modelling quantity are all for modified rubber of the present invention
Lifting.
Modified rubber of the present invention can be provided commonly for the tread rubber of tire with other rubber, lifts the anti-slippery of tire
Performance.Make the application of Cortex Eucommiae glue elastomer more extensive, be conducive to the exploitation of the peculiar resource of this China.
Modified rubber of the present invention, with gutta-percha as raw material, has been broken original EP rubbers industry and has been relied on oil money
The present situation in source, is conducive to EP rubbers industry to develop towards green, environmental friendliness direction.
Brief description
Fig. 1 is the H-NMR spectrum contrast of different silicon hydrogenation degree gutta-percha；
Fig. 2 is the DSC spectrogram contrast of different silicon hydrogenation degree gutta-percha；
Fig. 3 is the XRD spectra contrast of different silicon hydrogenation degree gutta-percha；
Fig. 4 is the SEM spectrogram contrast of the siliceous alternately EP rubbers of bio-based and original Cortex Eucommiae glue elastomer；
Fig. 5 is the DMA spectrogram contrast of the siliceous alternately EP rubbers of bio-based and original Cortex Eucommiae glue elastomer；
Fig. 6 is the tensile property contrast of the siliceous alternately EP rubbers of bio-based and original Cortex Eucommiae glue elastomer；
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention.
Following examples are all carried out in accordance with the following steps：Gutta-percha is made in advance the gutta-percha first that mass fraction is 2%
Benzole soln.Wilkinson catalyst and silicon hydrogen alkane are sequentially added in reaction bulb, pump drainage air, heat up and carry out silicon hydrogenation,
Reaction terminates the heavy glue of rear ethanol, and is dried at 50 DEG C 24 hours, kneads, vulcanizes.Proton nmr spectra characterizes its silicon hydrogenation journey
Degree, DSC and XRD characterizes its crystalline fracture situation, DMA table levies its dynamic mechanical, SEM observes section microstructure, omnipotent
Testing machine characterizes its tensile property.
Embodiment 1
Take as above step, control triethyl silicane consumption for the 40% of gutta-percha, Wilkinson catalyst consumption is Du
The 5% of secondary glue, reaction temperature is 100 DEG C, and the response time is 8 hours, and the silicon hydrogenation degree reacting the gutta-percha obtaining is
57.33%.
Implement row 2～5
Compared with Example 1, its difference is, Wilkinson catalyst consumption is respectively gutta-percha dry glue quality
0.5%th, 3%, 7%, 9%.The silicon hydrogenation degree of obtained gutta-percha is as shown in table 1：
Table 1
| Catalyst concn (%) | Silicon hydrogenation degree (%) | |
| Embodiment 2 | 0.5 | 35.73 |
| Embodiment 3 | 3 | 50.20 |
| Embodiment 4 | 7 | 50.72 |
| Embodiment 5 | 9 | 43.28 |
Embodiment 6～9
Compared with embodiment 1, its difference is, the addition of triethyl silicane is respectively gutta-percha dry glue quality
5%th, 15%, 60%, 80%.The silicon hydrogenation degree of obtained gutta-percha is as shown in table 2.
Table 2
| Triethyl silicane consumption (%) | Silicon hydrogenation degree (%) | |
| Embodiment 6 | 5% | 28.97 |
| Embodiment 7 | 15% | 43.14 |
| Embodiment 8 | 60% | 32.33 |
| Embodiment 9 | 80% | 30.25 |
Embodiment 10～13
Compared with embodiment 1, its difference is, reaction temperature is respectively 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C.Institute
The silicon hydrogenation degree obtaining gutta-percha is as shown in table 3.
Table 3
| Reaction temperature (DEG C) | Silicon hydrogenation degree (%) | |
| Embodiment 10 | 40 | 16.25 |
| Embodiment 11 | 60 | 17.12 |
| Embodiment 12 | 80 | 27.28 |
| Embodiment 13 | 110 | 45.16 |
Embodiment 14～23
Compared with embodiment 1, its difference is, the response time be respectively 1h, 3h, 10h, 12h, 14h, 16h, 20h, 24h,
30h、36h.The silicon hydrogenation degree obtaining gutta-percha is as shown in table 4.
Table 4
Embodiment 24
Wilkinson catalyst consumption is the 5% of dry glue quality, and triethyl silicane consumption is 5mL, and reaction temperature is 65 DEG C,
Response time is 8h, prepares the silicon hydrogutta-percha that silicon hydrogenation degree is 19.72%.Silicon hydrogutta-percha is carried out hydrogenation
Prepare the siliceous alternately EP rubbers that residual double bonds content is 14.22%.
Being characterized by the HNMR of Fig. 1 proves that silicon hydrogenation successfully occurs.The XRD of Fig. 2 DSC and Fig. 3 characterizes explanation silicon hydrogen
Chemical conversion work(destroys the crystalline texture of gutta-percha, and is progressively destroyed with the raising crystallization of silicon hydrogenation degree, until disappearing completely
Lose.
Fig. 4 can be seen that in original Cortex Eucommiae glue elastomer that white carbon dispersion is very uneven, white carbon and colloid median surface performance
Very poor.And the white carbon dispersion in the siliceous alternately EP rubbers of bio-based is very uniform, with colloid, there is good interface performance.
The resistance to wet skidding performance of the siliceous alternately EP rubbers of the DMA comparative illustration bio-based in Fig. 5 can increase significantly.
The siliceous alternately EP rubbers of performance comparison explanation bio-based of Fig. 6 has more excellent tensile strength and springform
Amount.
Embodiments of the invention in order to example and description for the sake of and be given, and be not exhaustively or by this
Bright it is limited to disclosed form.Many modifications and variations are obvious for the ordinary skill in the art.Choosing
Selecting and describe embodiment is in order to the principle of the present invention and practical application are more preferably described, and makes those of ordinary skill in the art
It will be appreciated that the present invention is thus design is suitable to the various embodiments with various modifications of special-purpose.
Claims (10)
1. a kind of preparation method of the siliceous alternately EP rubbers of bio-based is it is characterised in that with triethyl silicane as modifying agent, lead to
Cross silicon hydrogenation gutta-percha is modified, obtain final product.
2. preparation method according to claim 1 is it is characterised in that comprise the steps：Under the protection of noble gases,
The catalytic action by Wilkinson catalyst of described gutta-percha and described triethyl silicane, at 40 DEG C～120 DEG C reaction 1～
48 hours, obtain final product.
3. preparation method according to claim 2 is it is characterised in that the reaction of described gutta-percha and described triethyl silicane
Solution system is carried out, solvent is toluene, hexamethylene, chloroform or petroleum ether.
4. the preparation method according to any one of claims 1 to 3 is it is characterised in that also include to the modified rubber obtaining
The step carrying out hydrogenation.
5. the preparation method according to any one of claims 1 to 3 is it is characterised in that the consumption of described triethyl silicane is
The 5%～80% of described gutta-percha quality；Preferably 30～50%.
6. the preparation method according to any one of claims 1 to 3 is it is characterised in that the use of described Wilkinson catalyst
Measure 0.5%～10% for described gutta-percha quality；Preferably 3～7%.
7. preparation method according to claim 3 it is characterised in that in described solution gutta-percha concentration be 1%～
6%.
8. the siliceous alternately EP rubbers of bio-based that any one of claim 1～7 methods described prepares.
9. modified rubber according to claim 8 is it is characterised in that be connected to silane side base on described modified rubber main chain
Content is 5～60%, and/or remaining double bond content is 0%～70%, and/or its residual crystallinity is 0～30%.
10. application in the tread rubber preparing tire for the modified rubber described in claim 8 or 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615901A (en) * | 2019-09-20 | 2019-12-27 | 北京化工大学 | Self-crosslinking shape memory gutta-percha composite material and preparation method and application thereof |
| CN115109561A (en) * | 2022-07-21 | 2022-09-27 | 深圳市华思电子科技有限公司 | Organic silicon gel and preparation method applying IGBT packaging |
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| JP2001139695A (en) * | 1999-09-03 | 2001-05-22 | Shin Etsu Polymer Co Ltd | Olefine based thermoplastic elastomer composition and its preparation method |
| JP2001342294A (en) * | 2000-06-01 | 2001-12-11 | Tokai Rubber Ind Ltd | Liquid rubber composition and electrophotographic member using the same |
| CN103804603A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Solution polymerized styrene-butadiene rubber, synthetic method thereof, and applications of acid anhydride |
| CN104053676A (en) * | 2011-04-15 | 2014-09-17 | 米其林集团总公司 | Method for preparing masterbatch of elastomer and inorganic reinforcing filler |
| CN105273106A (en) * | 2015-09-24 | 2016-01-27 | 北京化工大学 | Low temperature resistance-controllable modified nitrile butadiene rubber and preparation method thereof |
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2016
- 2016-08-31 CN CN201610791622.XA patent/CN106397635B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001139695A (en) * | 1999-09-03 | 2001-05-22 | Shin Etsu Polymer Co Ltd | Olefine based thermoplastic elastomer composition and its preparation method |
| JP2001342294A (en) * | 2000-06-01 | 2001-12-11 | Tokai Rubber Ind Ltd | Liquid rubber composition and electrophotographic member using the same |
| CN104053676A (en) * | 2011-04-15 | 2014-09-17 | 米其林集团总公司 | Method for preparing masterbatch of elastomer and inorganic reinforcing filler |
| CN103804603A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Solution polymerized styrene-butadiene rubber, synthetic method thereof, and applications of acid anhydride |
| CN105273106A (en) * | 2015-09-24 | 2016-01-27 | 北京化工大学 | Low temperature resistance-controllable modified nitrile butadiene rubber and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615901A (en) * | 2019-09-20 | 2019-12-27 | 北京化工大学 | Self-crosslinking shape memory gutta-percha composite material and preparation method and application thereof |
| CN115109561A (en) * | 2022-07-21 | 2022-09-27 | 深圳市华思电子科技有限公司 | Organic silicon gel and preparation method applying IGBT packaging |
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| CN106397635B (en) | 2018-05-01 |
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