CN102532623B - Renewable bundled and crosslinked rubber material - Google Patents
Renewable bundled and crosslinked rubber material Download PDFInfo
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- CN102532623B CN102532623B CN201110451114.4A CN201110451114A CN102532623B CN 102532623 B CN102532623 B CN 102532623B CN 201110451114 A CN201110451114 A CN 201110451114A CN 102532623 B CN102532623 B CN 102532623B
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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 renewable bundled and crosslinked rubber material. The renewable bundled and crosslinked rubber material is in a three-dimensional net structure which is formed by bundling and crosslinking of rubber molecules formed by dehydration of dicarboxylic acid, and consists of the following components in percent by weight: 5wt%-30wt% of acid anhydride and 70wt%-95wt% of saturated or unsaturated rubber diad components. The renewable bundled and crosslinked rubber material comprises the main components in parts by mass: 100 parts of rubber, 5-40 parts of dicarboxylic acid and 2.5-20 parts of dehydrating agent; and all the components are mixed for 10 minutes at the temperature of 40-55 DEG C, and are molded for 5-60 minutes at the temperature of 150-200 DEG C. According to the renewable bundled and crosslinked rubber material, in a mixed solvent of water and an organic solvent, the ring acid anhydride opens the ring to form acid, the acid anhydride component is removed by extraction to obtain pure rubber components, so that the recycling of the rubber material is realized.
Description
Technical field
The present invention relates to a kind of renewable binding cross-linked rubber masses, particularly in rubber matrix, utilize dewatering agent that di-carboxylic acid is dehydrated into ring, realize the crosslinked elastomeric material of binding.
Background technology
Rubber molecule obtains tridimensional network by crosslinked, thereby makes material obtain good physical and chemical performance.Traditional crosslinking method is covalent cross-linking, but because bond energy of covalent bond is large, is difficult to recycle by its crosslinked rubber forming, therefore the application of restriction elastomeric material.Therefore, the crosslinking method of research novel environment friendly becomes the urgent problem in the whole world.
The today constantly strengthening in environmental consciousness, non covalent bond cross-linked network structure has the reversibility of physics or chemistry, can greatly improve the recovery utilization rate of its cross-linked rubber, is deeply subject to for many years extensive concern.As the people such as P.Antony (Polymer, 2000,41:787-793) report a kind of ionomer rubber/inorganic filler plastic blending material, by carboxyl and zinc oxide reacting forming ion dipole in carboxylated nitrile rubber (XNBR) and polyethylene acrylic acid (PEA), make ionic crosslinking thermoplastic elastic body; K.Chino and M.Ashiura (Macromolecules, 2001,34 (26): 9201) reported a kind of cross-linked rubber masses with reversible supramolecule hydrogen bond network structure.The reactive force of these non-covalent cross-link bonds is all more weak, and mechanical property, thermotolerance and the solvent stability etc. of its cross-linked rubber are often all very poor.
Patent " ZL 200410025013.0 " has reported that the metal ion and the paracril Semi-polarity group itrile group generation coordination reaction that utilize in transition metal salt form coordination crosslinking rubber, but because limitation and the cross-linking efficiency of glue kind are not high, restricting the application of coordination crosslinking rubber.
Summary of the invention
The object of the invention is to, a kind of renewable binding cross-linked rubber masses is provided, overcome the deficiency of the existing crosslinking method of rubber.The present invention bundlees cross-linked rubber masses and has good mechanical property, preparation process environmental protection, and technique is simple, and recyclable recycling, is a kind of environment-friendly novel cross-linked rubber masses.
For achieving the above object, the present invention adopts following technical measures: in rubber matrix, introduce di-carboxylic acid and dewatering agent, in hot-forming process, di-carboxylic acid is dehydrated into ring under the effect of dewatering agent, rubber molecule is tied up, thereby it is crosslinked to realize rubber binding.
The renewable binding cross-linked rubber masses of one of the present invention, it is characterized in that, the structure of described renewable binding cross-linked rubber masses is: by the dewater ring that forms of di-carboxylic acid, rubber molecule binding is cross-linked into tridimensional network, is made up of the acid anhydrides of 5wt%-30 wt% and saturated or unsaturated rubber diad part of 70 wt%-95 wt%.See accompanying drawing 1.
Described renewable binding cross-linked rubber masses, be characterised in that: in the mixed solvent of water and organic solvent, cyclic acid anhydride in renewable binding cross-linked rubber masses is met water and the acid of open loop one-tenth, can remove small molecular organic acid composition through extracting, thereby obtain pure rubber components, realize the recycling of elastomeric material.
The renewable binding cross-linked rubber masses of one of the present invention, its chief component, mass fraction are as follows:
100 parts of rubber;
Di-carboxylic acid 5-40 part;
Dewatering agent 2.5-20 part;
At 40 DEG C-50 DEG C mixing 10 minutes, then mold pressing 5-60 minute at 150 DEG C-200 DEG C.
Elastomeric material of the present invention is selected from: paracril, hydrogenated nitrile-butadiene rubber, natural rubber, chloroprene rubber, isoprene-isobutylene rubber, styrene-butadiene rubber(SBR) or cis-1,4-polybutadiene rubber.
Di-carboxylic acid of the present invention is selected from saturated dicarboxylic acid and/or unsaturated dicarboxylic acid, and the di-carboxylic acid of recommendation is toxilic acid, succinic acid, pentanedioic acid, oxysuccinic acid.
Dewatering agent of the present invention is selected from: calcium chloride, zinc chloride, zinc oxide, calcium oxide, magnesium sulfate, Vanadium Pentoxide in FLAKES.
In addition, in preparation renewable binding cross-linked rubber masses of the present invention, can also add parts by weight is the antiaging agent (as amine protective agent, ketoamine class protective agent or diaryl secondary amine antioxidant etc.) of 0.5-3 part, parts by weight are the strengthening agent (as the carbon black of various models or white carbon black) of 40-80 part, to improve Drawing abillity and anti ageing property, and reduce the production cost of material.Add above-mentioned various auxiliary agent, can make the tensile strength of matrix material at least reach 15MPa, elongation rate of tensile failure at least reaches 300%, and hardness (Shao A) at least reaches 60, at 150 DEG C, places 48h, and the stretching strength retentivity of material is 95%.
Compared with the existing, its advantage is renewable binding cross-linked rubber masses of the present invention, utilizes this novel crosslinking method of binding to realize material crosslinked; Formula, mainly taking di-carboxylic acid as binding linking agent, taking metal oxide or metal-salt as dewatering agent, is cross-linked into three-dimensional net structure, the simple environmental protection of filling a prescription by rubber binding; Due in the mixed solvent of water and organic solvent, the cyclic acid anhydride in renewable binding cross-linked rubber masses is met water and the acid of open loop one-tenth, can remove acid anhydrides composition, thereby obtain pure rubber components through extracting, realizes the recycling of elastomeric material.Belong to a kind of environment-friendly novel cross-linked rubber masses.
Brief description of the drawings
Fig. 1 is cross-linked into three-dimensional netted of the present invention renewable binding cross-linked rubber masses structural representation by the dewater ring that forms of di-carboxylic acid by rubber molecule binding.
Embodiment
Below by embodiment, the present invention is further illustrated, its objective is in order better to understand content of the present invention.Therefore, the cited case does not limit the scope of the invention.
The renewable binding cross-linked rubber masses of one of the present invention, it is characterized in that, the structure of described renewable binding cross-linked rubber masses is: by the dewater ring that forms of di-carboxylic acid, rubber molecule binding is cross-linked into tridimensional network, is made up of saturated or unsaturated rubber 2 diad parts of the acid anhydrides 1 and 70 wt%-95 wt% of 5wt%-30 wt%.See accompanying drawing 1.
Embodiment 1
100 parts of cis-1,4-polybutadiene rubbers, 18 parts of succinic acid, 9 parts, calcium oxide, on 45 DEG C of two rod mills or Banbury mixer mixing evenly, then on compression molding instrument in 200 DEG C, under 10Mpa, hot pressing 30 minutes, can obtain bundling cross-linked rubber masses.Bundling crosslinked elastomeric material tensile strength is 6MPa, and fault growth rate is 550%, hardness (Shao A) 45.At 150 DEG C, place 48h, the stretching strength retentivity of material is 95%.
Embodiment 2
100 parts of cis-1,4-polybutadiene rubbers, 18 parts of succinic acid, 9 parts, calcium oxide, 50 parts of carbon blacks, on 45 DEG C of two rod mills or Banbury mixer mixing evenly, then on compression molding instrument in 200 DEG C, under 10Mpa, hot pressing 30 minutes, can obtain bundling cross-linked rubber masses.Bundling crosslinked elastomeric material tensile strength is 15MPa, and fault growth rate is 400%, hardness (Shao A) 60.At 150 DEG C, place 48h, the stretching strength retentivity of material is 95%.
Embodiment 3
100 parts of cis-1,4-polybutadiene rubbers, 30 parts of toxilic acids, 15 parts, calcium oxide, 50 parts of carbon blacks, on 45 DEG C of two rod mills or Banbury mixer mixing evenly, then on compression molding instrument in 180 DEG C, under 10Mpa, hot pressing 15 minutes, can obtain bundling cross-linked rubber masses.Bundling crosslinked elastomeric material tensile strength is 30MPa, and fault growth rate is 350%, hardness (Shao A) 70.At 150 DEG C, place 48h, the stretching strength retentivity of material is 95%.
Embodiment 4
100 parts of cis-1,4-polybutadiene rubbers, 30 parts of toxilic acids, 15 parts, calcium oxide, anti-aging agent RD (2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer), 50 parts of carbon blacks, mixing even on 45 DEG C of two rod mills or Banbury mixer, then on compression molding instrument in 180 DEG C, under 10Mpa, hot pressing 15 minutes, can obtain bundling cross-linked rubber masses.Bundling crosslinked elastomeric material tensile strength is 33MPa, and fault growth rate is 300%, hardness (Shao A) 72.At 150 DEG C, place 48h, the stretching strength retentivity of material is 98%.
Claims (3)
1. the preparation method of a renewable binding cross-linked rubber masses, the chief component, the mass fraction that comprise the steps: described renewable binding cross-linked rubber masses are as follows: 100 parts of cis-1,4-polybutadiene rubbers, 18 parts of succinic acid, 9 parts, calcium oxide, mixing even on 45 DEG C of two roller mills or Banbury mixer, then on compression molding instrument in 200 DEG C, under 10MPa, hot pressing 30 minutes, can obtain bundling cross-linked rubber masses; Bundling crosslinked elastomeric material tensile strength is 6MPa, and fault growth rate is 550%, and hardness Shao A is 45, at 150 DEG C, places 48h, and the stretching strength retentivity of material is 95%.
2. the preparation method of a renewable binding cross-linked rubber masses, the chief component, the mass fraction that comprise the steps: described renewable binding cross-linked rubber masses are as follows: 100 parts of cis-1,4-polybutadiene rubbers, 18 parts of succinic acid, 9 parts, calcium oxide, 50 parts of carbon blacks, on 45 DEG C of two roller mills or Banbury mixer mixing evenly, then on compression molding instrument in 200 DEG C, under 10MPa, hot pressing 30 minutes, can obtain bundling cross-linked rubber masses; Bundling crosslinked elastomeric material tensile strength is 15MPa, and fault growth rate is 400%, and hardness Shao A is 60, at 150 DEG C, places 48h, and the stretching strength retentivity of material is 95%.
3. a preparation method for renewable binding cross-linked rubber masses, comprises the steps: that chief component, the mass fraction of described renewable binding cross-linked rubber masses is as follows: 100 parts of cis-1,4-polybutadiene rubbers, 30 parts of toxilic acids, 15 parts, calcium oxide, anti-aging agent 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, 50 parts of carbon blacks, on 45 DEG C of two roller mills or Banbury mixer mixing evenly, then on compression molding instrument in 180 DEG C, under 10MPa, hot pressing 15 minutes, can obtain bundling cross-linked rubber masses; Bundling crosslinked elastomeric material tensile strength is 33MPa, and fault growth rate is 300%, and hardness Shao A is 72; At 150 DEG C, place 48h, the stretching strength retentivity of material is 98%.
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| CN201110451114.4A CN102532623B (en) | 2011-12-29 | 2011-12-29 | Renewable bundled and crosslinked rubber material |
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| CN201110451114.4A CN102532623B (en) | 2011-12-29 | 2011-12-29 | Renewable bundled and crosslinked rubber material |
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| CN102532623A CN102532623A (en) | 2012-07-04 |
| CN102532623B true CN102532623B (en) | 2014-09-03 |
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| CN103980578B (en) * | 2014-05-06 | 2015-10-14 | 徐州工业职业技术学院 | A kind of regenerative vulcanized hydrogenated nitrile-butadiene rubber and preparation method thereof |
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Effective date of registration: 20190225 Address after: 518000 Nanhu Street Guest Road, Luohu District, Shenzhen City, Guangdong Province, 3567 Pengnian Square, 2002 Patentee after: SHENZHEN XUJING LIBO ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Address before: 350108 Fujian province Fuzhou County Minhou County Town Street School Park Road Fujian Normal University Qishan campus Science Research Division Fujian Normal University Patentee before: Fujian Normal University |
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