CN105733021A - Reclaiming activator for rubber and preparation method of reclaiming activator - Google Patents
Reclaiming activator for rubber and preparation method of reclaiming activator Download PDFInfo
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- CN105733021A CN105733021A CN201610130260.XA CN201610130260A CN105733021A CN 105733021 A CN105733021 A CN 105733021A CN 201610130260 A CN201610130260 A CN 201610130260A CN 105733021 A CN105733021 A CN 105733021A
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- activator
- rubber
- reclaiming
- solvent
- phenolic compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2317/00—Characterised by the use of reclaimed rubber
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a reclaiming activator for rubber and a preparation method of the reclaiming activator. The activator is alkylphenol disulphide modified based on natural phenolic compounds. The reclaiming activator has the following advantages: firstly, the activator contains no cancerogenic substances, namely polycyclic aromatic hydrocarbon (anthracene, naphthalene and the like), and is compliant with the REACH (registration, evaluation, authorization and restriction of chemicals) laws of the European union; secondly, natural phenolic compounds are creatively synthesized and modified, and an obtained additive has effects of a softener and the activator at the same time, so that multifunction of the additive is achieved; thirdly, mechanical performance of the reclaimed rubber can be improved; fourthly, the reclaiming reaction temperature can be effectively lowered, and the reclaiming efficiency can be improved.
Description
Technical field
The present invention relates to a kind of rubber regenerative activating agent and preparation method thereof, particularly relate to the preparation method of key assistant in the process preparing reclaimed rubber with waste or used vulcanized rubber for raw material, belong to reclaimed rubber technical field.
Background technology
Rubber is important strategic materials, the situation according to domestic rubber sources, China after reclaimed rubber being listed in natural rubber, synthetic rubber the third-largest rubber sources developed.China's reclaimed rubber consumption in 2014 reaches 4,000,000 tons, is the big reclaimed rubber manufacturing country of the first in the world, and the utilization of reclaimed rubber is made that tremendous contribution to alleviating China's rubber sources shortage.
The regeneration of waste old refers to that utilization either physically or chemically makes the netted construction recovery of rubber cross for line style state, namely sulfur-sulfur (S-S) key is switched on again, and do not destroy carbon-to-carbon (C-C) key as far as possible, make rubber have can processability again, and make every effort to the original physical property keeping or recovering rubber.Prepare reclaimed rubber at present, widely used in industry is high-temperature dynamic desulfurization and normal pressure continuous desulfurization method, both sulfur removal technologies belong to pyrochemical process desulfurization, technical process needs use regenerative agent to include regeneration activator, regeneration softening agent, application regeneration activator can reduce rubber regeneration time and softening agent consumption, improves reclaimed rubber processing characteristics and physical and mechanical properties simultaneously.The regeneration activator that domestic and international rubber uses mainly has mercaptan (aliphatic mercaptan and aromatic mercaptans), unsaturated compound, amino-compound, alkylphenol monosulfide and disulphide etc., wherein alkyl phenol disulfide class regeneration activator due to preparation technology simple, less costly, activity is higher, storage stability is better, develop at home quickly in recent years, widely used in the industry at present.
Various regeneration activators on domestic market are mostly with the by-product of rubber chemicals production for raw material, and material composition is complicated, it is easy to cause that product is unstable;It mostly is dark thick liquid under room temperature, all has denseer penetrating odor, not environmentally, significantly limit the application market of environmental friendly regenerated rubber and value of the product.
Summary of the invention
In order to solve regeneration activator unstable properties and problem not environmentally in prior art, the present invention provides a kind of environmental protection and the waste or used vulcanized rubber regeneration activator of excellent performance and preparation method.
The technical scheme is that
A kind of rubber regenerative activating agent, described activator is the alkyl phenol disulfide modified based on natural phenolic compound.
The Main Ingredients and Appearance of the rubber regenerative activating agent provided of the present invention is the compound of alkyl-(phenoxy group) disulphide, containing being provided with attack free radical, terminating the disulphide of the function such as macromolecular radical, peroxynitrite decomposition free radical.Containing hydrogen chloride in the waste gas that the compound of alkyl-(phenoxy group) disulphide is discharged in preparation process, introducing exhaust gas into purifying processing device, it is possible to reclaim hydrochloric acid, this compound discharges without waste water and gas in process of production.
Preferably: described activator is pure substance or the mixture of following general formula of molecular structure:
R is the hydrocarbon compound at least provided with a carbon-carbon double bond.
The preparation method that the present invention also provides for above-mentioned rubber regenerative activating agent, its synthetic reaction molecular structure schematically as follows shown in:
Further, as preferably: with natural phenolic compound for body material, it is added reactor with solvent and acid binding agent and stirs, disulphur dichloride is added at-30 DEG C to 30 DEG C, react 1-12 hour in the scope of 0-100 DEG C, after solvent being distilled off by reducing pressure, obtain modified alkyl phenol disulphide rubber regenerative activating agent.
Further, as preferably: described natural phenolic compound raw material: solvent: acid binding agent: the mass ratio of disulphur dichloride is 5-10: 5-10: 1-3: 3-5.
Further, as preferably: described natural phenolic compound be in natural fruits, seed, shell, timber extract one or more.
Further, as preferably: described solvent is one or more in toluene, dichloromethane, chloroform, petroleum ether 60-90, petroleum ether 90-120, acetone, benzene.
Further, as preferably: described acid binding agent is one or more in triethylamine, ethylenediamine, pyridine, carbonate.
Product of the present invention is applied in the middle of the production of reclaimed rubber as waste or used vulcanized rubber regeneration activator, owing to products material of the present invention is with natural phenolic compound for reaction substrate, containing longer alkyl chain in its molecular structure, improve with the basis of the compatibility of rubber on, show environment friendly.
The present invention is with natural phenolic compound for raw material, it is provided that the preparation method of a kind of environmental protection regenerating waste or used rubber activator.The Main Ingredients and Appearance of activator is modified alkyl phenol disulphide, containing longer alkyl chain in its molecular structure, it is possible to being effectively improved and the compatibility of various scrap rubbers, this environmental friendly regenerated activator has the advantage that in addition
1, do not contain carcinogen condensed-nuclei aromatics (anthracene, naphthalene etc.), meet EU REACH Legislation;
2, novelty natural phenolic compound is carried out synthesis modification, the auxiliary agent obtained has the effect of softening agent and activator concurrently, it is achieved that the multifunctionality of auxiliary agent;
3, remaining the long alkyl chain with alkene on the aromatic rings of this product, the reclaimed rubber prepared with this product has more sulfurate activity point, can improve reclaimed rubber mechanical mechanics property;
4, this product can be effectively reduced regenerative response temperature, improves regeneration efficiency, and consumption is little, reduces reclaimed rubber production cost.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained activator Y-1 and cashew nut shell liquid1H-NMR comparison diagram.
Detailed description of the invention
The following examples can make professional within the scope of this area be more completely understood by the present invention, but does not limit the present invention in any way.
Embodiment 1
In the 250mL there-necked flask equipped with stirring, thermometer and constant pressure funnel, add cashew nut shell liquid 40g, dichloromethane 30mL and triethylamine 5g, disulphur dichloride 2mL is dissolved in 15mL dichloromethane and then passes through constant pressure funnel dropping, controlling reaction temperature is 0 DEG C, rate of addition is about 1 drop/sec, tail gas sig water absorbs, and after continuing reaction 1h, adds distilled water 5mL and terminates reaction after dropwising.Using petroleum ether/distilled water that system is extracted, the oil phase obtained removes after solvent through Rotary Evaporators, obtains bronzing oily liquids, called after Y-1.Yield is 95%.
Embodiment 2
In the 250mL there-necked flask equipped with stirring, thermometer and constant pressure funnel, add Cardanol 40g, disulphur dichloride 1mL be dissolved in 15mL dichloromethane and then pass through constant pressure funnel dropping, controlling reaction temperature is 0 DEG C, rate of addition is about 1 drop/sec, tail gas sig water absorbs, after continuing reaction 1h after dropwising, add distilled water 5mL and terminate reaction.Using petroleum ether/distilled water that system is extracted, the oil phase obtained removes after solvent through Rotary Evaporators, obtains bronzing oily liquids, called after Y-2.Yield is 96%.
Embodiment 3
In the 1000mL there-necked flask equipped with stirring, thermometer and constant pressure funnel, add cashew nut shell liquid 200g, Cardanol 200g, disulphur dichloride 10mL is dissolved in 100mL dichloromethane and then passes through constant pressure funnel dropping, controlling reaction temperature is 0 DEG C, rate of addition is about 1 drop/sec, tail gas sig water absorbs, and after continuing reaction 1h, adds distilled water 5mL and terminates reaction after dropwising.Using petroleum ether/distilled water that system is extracted, the oil phase obtained removes after solvent through Rotary Evaporators, obtains bronzing oily liquids, called after Y-3.Yield is 97%.
In reclaimed rubber produces, using activator 480, cashew nut shell liquid, Cardanol, Y-1, Y-2, Y-3 and blank sample as activator respectively, reclaimed rubber performance is detected, the reclaimed rubber performance indications of production are as shown in table 1:
Table 1 adopts synthesis activator to produce the index of reclaimed rubber
Table 1 is it can be seen that the activation effect synthesizing the raw material of activator is consistent with blank formula (1#) effect, it was demonstrated that substantially without activation effect;And the Y-1/Y-2/Y-3 activation effect that the present invention prepares is with industry regeneration activator 480 quite, even better than 480, there is the activation of excellence.
Embodiment 1 gained activator Y-1 and cashew nut shell liquid1H-NMR comparison diagram is shown in Fig. 1, it can be seen that compared to cashew nut shell liquid, the activator Y-1 formant at 6.25ppm place disappears, this be due on cashew nut shell liquid phenolic hydroxyl group ortho-hydrogens by caused by sulphur atom replaces;Activator Y-1 is that within the scope of 6.5-7.5ppm, the hydrogen chemical shifts on phenyl ring generally slightly moves to low field direction in chemical shift simultaneously, the hydrogen proved on phenolic hydroxyl group ortho position is replaced by S--S, inducing action makes cloud density on phenyl ring change, causing relevant position to be deshielded declines, chemical shift is moved to low field.Thus prove, by the synthetic method of the present invention, prepare target double sulfide activator.
Claims (10)
1. a rubber regenerative activating agent, it is characterised in that: described activator is the alkyl phenol disulfide modified based on natural phenolic compound.
2. it is rubber regenerative activating agent as claimed in claim 1, it is characterised in that: described activator is pure substance or the mixture of following general formula of molecular structure:
;R is the hydrocarbon compound at least provided with a carbon-carbon double bond.
3. the method preparing rubber regenerative activating agent as claimed in claim 2, it is characterised in that: the reaction equation of the synthetic reaction of described activator is as follows:
。
4. method according to claim 3, it is characterized in that: with natural phenolic compound for body material, it is mixed and stirred for solvent and acid binding agent, disulphur dichloride is added at-30 DEG C to 30 DEG C, react 1-12 hour in the scope of 0-100 DEG C, after removing solvent, obtain modified alkyl phenol disulphide rubber regenerative activating agent.
5. method according to claim 3, it is characterised in that: described natural phenolic compound raw material: solvent: acid binding agent: the mass ratio of disulphur dichloride is 5-10:5-10:1-3:3-5.
6. method according to claim 3, it is characterised in that: described natural phenolic compound is one or more that extract in natural fruits, seed, shell, timber.
7. method according to claim 5, it is characterised in that: described natural phenolic compound be Cardanol, cashew nut shell liquid one or more.
8. method according to claim 3, it is characterised in that: described solvent is one or more in toluene, dichloromethane, chloroform, petroleum ether 60-90, petroleum ether 90-120, acetone, benzene.
9. method according to claim 3, it is characterised in that: described acid binding agent is one or more in triethylamine, ethylenediamine, pyridine, carbonate.
10. method according to claim 3, it is characterised in that: solvent is distilled off by reducing pressure.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107759714A (en) * | 2017-11-01 | 2018-03-06 | 青岛科技大学 | A kind of environment-friendly type softening agent grafting reclaimed rubber and preparation method thereof |
US11713362B2 (en) | 2020-12-28 | 2023-08-01 | Industrial Technology Research Institute | Depolymerizer and recycled rubber |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101113140A (en) * | 2006-07-26 | 2008-01-30 | 宋同银 | Vulcanized rubber regeneration activator and preparation method and uses thereof |
CN102050960A (en) * | 2010-11-30 | 2011-05-11 | 胥乾 | Efficient scrap rubber regeneration activator and preparation method thereof |
CN104520369A (en) * | 2013-07-12 | 2015-04-15 | (株)Mnb绿地公司 | Novel cardanol-based organic vulcanizing agent, production method for same and blended rubber composition for tyres using same |
-
2016
- 2016-03-09 CN CN201610130260.XA patent/CN105733021B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101113140A (en) * | 2006-07-26 | 2008-01-30 | 宋同银 | Vulcanized rubber regeneration activator and preparation method and uses thereof |
CN102050960A (en) * | 2010-11-30 | 2011-05-11 | 胥乾 | Efficient scrap rubber regeneration activator and preparation method thereof |
CN104520369A (en) * | 2013-07-12 | 2015-04-15 | (株)Mnb绿地公司 | Novel cardanol-based organic vulcanizing agent, production method for same and blended rubber composition for tyres using same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107759714A (en) * | 2017-11-01 | 2018-03-06 | 青岛科技大学 | A kind of environment-friendly type softening agent grafting reclaimed rubber and preparation method thereof |
US11713362B2 (en) | 2020-12-28 | 2023-08-01 | Industrial Technology Research Institute | Depolymerizer and recycled rubber |
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