CN109265738A - A kind of environmental friendly regenerated glue and preparation method thereof - Google Patents
A kind of environmental friendly regenerated glue and preparation method thereof Download PDFInfo
- Publication number
- CN109265738A CN109265738A CN201811134562.XA CN201811134562A CN109265738A CN 109265738 A CN109265738 A CN 109265738A CN 201811134562 A CN201811134562 A CN 201811134562A CN 109265738 A CN109265738 A CN 109265738A
- Authority
- CN
- China
- Prior art keywords
- added
- mass ratio
- takes
- take
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08J11/22—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 oxygen-containing compounds
- C08J11/26—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 oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
-
- 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
- C08J11/20—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 hydrocarbons or halogenated hydrocarbons
-
- 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
-
- 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
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- 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
Abstract
The invention discloses a kind of environmental friendly regenerated glue and preparation method thereof, belong to technical field of rubber preparation.The present invention forms bridge ligand with m-terephthal aldehyde and malonic acid, coordination assembling is carried out with metallic cobalt again, the molecular skeleton of formation has rigidity, and the addition of the conjugation allyl of extension makes carboxyl and phenyl ring bond length from elongated, and the form for enhancing reclaimed rubber is kept and the raising of mechanical property；The present invention, through alpha-amylase, alkali protease enzymatic hydrolysis again through beta amylase mixed enzymolysis, is conducive to the raising of rubber elongation at break, increases the elasticity of rubber using waste swill and pig manure as raw material；The present invention opens waste rubber powder internal gutter during preparing reclaimed rubber, first with pillared additive, promotes cross-bond fracture, enhances internal combustion performance, improve the performance of reclaimed rubber.The present invention, which solves in current reclaimed rubber regenerative process, to be polluted greatly, and regeneration efficiency is low, the low problem of reclaimed rubber tensile strength obtained.
Description
Technical field
The invention belongs to technical field of rubber preparation, and in particular to a kind of environmental friendly regenerated glue and preparation method thereof.
Background technique
The quantity of waste old material is only second to waste plastics in spent high molecular material.The recycling of waste old with
Based on waste tire, other further includes waste rubber shoe and inner tube of a tyre etc., and the utilization of scrap rubber is conducive to protect environment, realizes resource
It recycles, is conducive to the sustainable development of social economy.It is usually original with leftover bits or product cured in rubber product
Material, there is certain plasticity, is processed into the rubber that can be reused by desulfurization and is just known as reclaimed rubber.It is different by scrap rubber used, then
Raw rubber is divided into cover tire class, inner tube of a tyre class and rubber overshoes class etc..Reclaimed rubber be always rubber industry, the important raw material of building materials industry it
One, it not only largely saves rubber, reduces rubber product cost, and can guarantee resource regeneration, protects environment, eliminates dirty
Dye, is to turn harm into good, turns waste into wealth, be a kind of environmental protection industry benefited the nation and the people.
Currently, conventional regeneration glue needs to carry out in regenerating tank in regenerative process, heating stirring, cleaning and dewatering essence are needed
The processes such as refining, equipment and process are more complex, and investment is big.In regenerative process, larger amount of softening agent coal tar, pine joined
Tar, petroleum extract etc. make reclaimed rubber have very niff, and there are biggish pollutions, also containing many toxic
Carcinogenic chemical substance.The conventional regeneration glue current regeneration technology time, steam pressure was in 1MPa or so, time mostly in 4h or so
It is long, low efficiency.Conventional regeneration glue cannot add in many rubber products, and enterprise is badly in need of environmentally-friendly reclaimed rubber and occurs.
It needs to carry out in high temperature desulfurizing tank in regenerative process, it usually needs a large amount of water is added, it is heated to stir, is clear
It the processes such as washes, be dehydrated, refining to obtain, equipment and process are more complex, and investment is big, in addition, the regeneration technology time is long, low efficiency,
Reclaimed rubber physical mechanical property obtained is poor, and tensile strength is mostly only 7 ~ 8MPa generally in 3 ~ 14MPa.For some
To the more demanding application demand of the tensile strength of reclaimed rubber, the tensile strength of above-mentioned reclaimed rubber is obviously unable to satisfy demand.
Therefore, developing environmentally protective, high-tenacity the reclaimed rubber of one kind becomes urgent problem to be solved in the industry.
Summary of the invention
The technical problems to be solved by the invention: big for pollution in current reclaimed rubber regenerative process, regeneration efficiency is low, system
The low problem of reclaimed rubber tensile strength, a kind of environmental friendly regenerated glue and preparation method thereof is provided.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of environmental friendly regenerated glue, including softening additive, pillared additive, interface modifier, filler additive；
It is described softening additive the preparation method comprises the following steps:
Take swill 2 ~ 5:1 in mass ratio ~ 3:10 ~ 30 that pig manure, distilled water mixing is added, homogenate obtains homogenate, takes homogenate by matter
Corn flour, water mixing is added than 15 ~ 20:2 ~ 5:4 ~ 6 in amount, obtains mixture a, takes alpha-amylase 2 ~ 5:1 in mass ratio ~ 3 that alkali is added
Property protease mixing, obtain mixture b, mixture b taken to be seeded in mixture a by 5 ~ 9% inoculum concentration, in 80 ~ 85 DEG C keep the temperature 2 ~
4h adds the beta amylase of mixture a mass 3 ~ 5%, in 40 ~ 45 DEG C of 30 ~ 50min of heat preservation, stands, enzyme deactivation takes upper liquid to subtract
Pressure distillation is to get softening additive.
The pillared additive the preparation method comprises the following steps:
(1) take pyridine 10 ~ 15:1 in mass ratio ~ 4 be added piperidines mixing, obtain mixture, take m-terephthal aldehyde in mass ratio 0.2 ~
Malonic acid is added in 0.3:100 ~ 200, adds 3 ~ 9 times of malonic acid quality of mixture, it is stirred 18 in 75 ~ 80 DEG C ~ for 24 hours,
It is cooled to room temperature, adjusts pH to 1 ~ 1.5, filtering takes filter residue to wash through deionized water, is dried in vacuo, obtains vacuum drying object, takes true
Distilled water is added in empty dried object 1 ~ 3:100 in mass ratio ~ 150, and 20 ~ 30min is stirred in 50 ~ 60 DEG C, and vacuum drying is added
The sodium hydroxide of amount of substance 20 ~ 30% is stirred, and is filtered, is taken pumping filter residue and drying, obtain dried object；
(2) take dried object 1 ~ 3:10 in mass ratio ~ 30 be added water mixing, obtain mixed liquor a, take dehydrated alcohol 1 ~ 3:1 in mass ratio ~
4 are added water mixing, obtain mixed liquor b, 1 ~ 3:8 ~ 10 in mass ratio mixed liquor b is taken to be added dropwise in mixed liquor a, score layer liquid takes six
Nitric hydrate cobalt 1 ~ 3:80 ~ 100 in mass ratio are added to absolute ethanol, and obtain mixed liquor c, take mixed liquor c 1 ~ 5:20 in mass ratio ~
40 instill in layering liquid, stand 5 ~ 7 days, filtering, take precipitating through distillation water washing to get pillared additive.
The sodium hydroxide of vacuum drying amount of substance 20 ~ 30% is added in the step (1) is stirred condition are as follows: in 50 ~
60 DEG C are stirred 1 ~ 3h.
A kind of preparation method of environmental friendly regenerated glue, includes the following steps:
S1. it takes waste tire film to be cut into 5cm × 5cm fritter, is broken into the micelle that diameter grain is 2cm through boulder crusher, goes to clean
Matter ground 50 ~ 60 meshes, collected sieving particle, took sieving particle 30 ~ 50:3 in mass ratio ~ 8 that pillared addition is added
Agent, 3 ~ 5min of homogeneous, ultraviolet light irradiation, roll-in obtain matrix object；
S2. it takes matrix object 200 ~ 300:40 in mass ratio ~ 60:10 ~ 15 that softening additive, glycerol mixing is added, is warming up to 75 ~ 80
DEG C, in 800r/min, 15MPa through supercritical CO220 ~ 40min of processing is cooled to then at 2450MHz, 800W 5 ~ 8min of microwave
Room temperature obtains cooled material, takes cooled material to be warming up to 160 ~ 190 DEG C of 5 ~ 10min of heat preservation, must pre-process matrix object, according to the mass fraction,
Take 300 ~ 500 parts of pretreatment matrix objects, 20 ~ 40 parts of interface modifiers, 80 ~ 100 parts of filler additives, 2 ~ 6 parts of N- tert-butyls-bis-
The mixing of (2-[4-morpholinodithio) sulfenamide, is kneaded, and bottom sheet, compression molding is cooled to room temperature to get environmental friendly regenerated glue.
Ultraviolet lamp irradiation condition in the step S1 are as follows: through the ultraviolet 36 ~ 48h of light irradiation of 125W in fully sheathed case.
Interface modifier in the step S2 are as follows: take apple polyphenol 3 ~ 8:2 in mass ratio ~ 5 that tannic acid mixing is added, i.e.,
?.
Filler additive in the step S2 are as follows: take SILICA FUME in 600 ~ 700 DEG C of 2 ~ 4h of activation, be cooled to room temperature, obtain work
Compound takes 30 ~ 80 parts of activators, 30 ~ 50 parts of white carbon blacks, 20 ~ 40 parts of magnesium borate crystal whiskers, 1 ~ 5 part of dodecane according to the mass fraction
Base benzene sulfonic acid sodium salt, 100 ~ 150 parts of dehydrated alcohol mixing, are stirred 1 ~ 3h in 35 ~ 40 DEG C to get filler additive.
The present invention is compared with other methods, and advantageous effects are:
(1) pillared additive prepared by the present invention be bridge ligand is formed with m-terephthal aldehyde and malonic acid, then with metallic cobalt into
Row coordination assembling, obtains the coordination polymer of organic carboxyl acid class ligand generation, the metal framework structure with intercal type can be
Three-dimensional structure is formed inside scrap rubber, the molecular skeleton of formation not only has rigidity, but also the addition of the conjugation allyl extended
Make carboxyl and phenyl ring bond length from elongated, waste rubber inside formed and is supported, oxide catalyst is had in the multi-pore channel of formation,
Through ultraviolet light, the cross-bond in scrap rubber is interrupted without destroying main chain through catalysis oxidation, is that scrap rubber reply plasticity reaches
Regenerated purpose, while the structure of similar intercalation enhances the form of reclaimed rubber and keeps and the raising of mechanical property；
(2) softening additive prepared by the present invention is using waste swill and pig manure as raw material, first through alpha-amylase, alkali protease
Enzymatic hydrolysis obtains again through beta amylase mixed enzymolysis containing the small-molecule substances such as bion grease and protein, grease type therein
Substance flexibility with higher has preferable lubricating action to rubber macromolecule, this oleic acid contained and palmitinic acid are conducive to again
Raw reaction, containing a large amount of fatty acid, fatty acid plays the role of vulcanization accelerator in sulfidation, penetrates into inside rubber
Softening agent encirclement barrier action can be played to macromolecular chain segment, increase the distance between macromolecular chain segment, reduce macromolecular
Between interaction force, improve the motility of macromolecular chain segment, accelerate the regeneration event of rubber, be conducive to rubber and pull apart elongation
The raising of rate, while protein small-molecule substance enters rubber powder and is supplemented, and increases the elasticity of rubber；
(3) present invention opens waste rubber powder internal gutter first with pillared additive, promotes during preparing reclaimed rubber
Cross-bond fracture adds softening agent through supercritical carbon dioxide, microwave, heating mixed processing method, handles rubber powder,
Increase so that softening regenerated active material diffusion value in micelle, improves regeneration efficiency, add interface modifier apple
It is more uniform that the addition of fruit polyphenol and tannic acid is distributed regeneration glue additive in rubber matrix, and section hole is less, interface
Effect is enhanced, while complexing of the filler through interface modifier is added, and is enhanced internal combustion performance, is improved reclaimed rubber
Performance.
Specific embodiment
Pillared additive the preparation method comprises the following steps:
(1) take pyridine 10 ~ 15:1 in mass ratio ~ 4 be added piperidines mixing, obtain mixture, take m-terephthal aldehyde in mass ratio 0.2 ~
Malonic acid is added in 0.3:100 ~ 200, adds 3 ~ 9 times of malonic acid quality of mixture, it is stirred 18 in 75 ~ 80 DEG C ~ for 24 hours,
It is cooled to room temperature, adjusts pH to 1 ~ 1.5, filtering takes filter residue to wash through deionized water, is dried in vacuo, obtains vacuum drying object, takes true
Distilled water is added in empty dried object 1 ~ 3:100 in mass ratio ~ 150, and 20 ~ 30min is stirred in 50 ~ 60 DEG C, and vacuum drying is added
The sodium hydroxide of amount of substance 20 ~ 30% is stirred 1 ~ 3h in 50 ~ 60 DEG C, filters, takes pumping filter residue and drying, obtain dried object；
(2) take dried object 1 ~ 3:10 in mass ratio ~ 30 be added water mixing, obtain mixed liquor a, take dehydrated alcohol 1 ~ 3:1 in mass ratio ~
4 are added water mixing, obtain mixed liquor b, 1 ~ 3:8 ~ 10 in mass ratio mixed liquor b is taken to be added dropwise in mixed liquor a, score layer liquid takes six
Nitric hydrate cobalt 1 ~ 3:80 ~ 100 in mass ratio are added to absolute ethanol, and obtain mixed liquor c, take mixed liquor c 1 ~ 5:20 in mass ratio ~
40 instill in layering liquid, stand 5 ~ 7 days, filtering, take precipitating through distillation water washing to get pillared additive.
Soften additive the preparation method comprises the following steps:
Take swill 2 ~ 5:1 in mass ratio ~ 3:10 ~ 30 that pig manure, distilled water mixing is added, homogenate obtains homogenate, takes homogenate by matter
Corn flour, water mixing is added than 15 ~ 20:2 ~ 5:4 ~ 6 in amount, obtains mixture a, takes alpha-amylase 2 ~ 5:1 in mass ratio ~ 3 that alkali is added
Property protease mixing, obtain mixture b, mixture b taken to be seeded in mixture a by 5 ~ 9% inoculum concentration, in 80 ~ 85 DEG C keep the temperature 2 ~
4h adds the beta amylase of mixture a mass 3 ~ 5%, in 40 ~ 45 DEG C of 30 ~ 50min of heat preservation, stands 2 ~ 4h, enzyme deactivation takes upper layer
Liquid vacuum distillation is to get softening additive.
Interface modifier are as follows: take apple polyphenol 3 ~ 8:2 in mass ratio ~ 5 be added tannic acid mixing to get.
Filler additive are as follows: take SILICA FUME in 600 ~ 700 DEG C of 2 ~ 4h of activation, be cooled to room temperature, obtain activator, by mass parts
Number meter, take 30 ~ 80 parts of activators, 30 ~ 50 parts of white carbon blacks, 20 ~ 40 parts of magnesium borate crystal whiskers, 1 ~ 5 part of neopelex,
100 ~ 150 parts of dehydrated alcohol mixing, are stirred 1 ~ 3h in 35 ~ 40 DEG C to get filler additive.
A kind of preparation method of environmental friendly regenerated glue, includes the following steps:
S1. it takes waste tire film to be cut into 5cm × 5cm fritter, is broken into the micelle that diameter grain is 2cm through boulder crusher, successively passes through
Magnetic separator, winnowing machine remove impurity, grind 50 ~ 60 meshes, collect sieving particle, take sieving particle in mass ratio 30 ~
Pillared additive, 3 ~ 5min of homogeneous, through the ultraviolet 36 ~ 48h of light irradiation of 125W in fully sheathed case, on open mill is added in 50:3 ~ 8
Roll-in obtains matrix object；
S2. it takes matrix object 200 ~ 300:40 in mass ratio ~ 60:10 ~ 15 that softening additive, glycerol mixing is added, is warming up to 75 ~ 80
DEG C, in 800r/min, 15MPa through supercritical CO220 ~ 40min of processing is cooled to then at 2450MHz, 800W 5 ~ 8min of microwave
Room temperature obtains cooled material, takes cooled material to be warming up to 160 ~ 190 DEG C of 5 ~ 10min of heat preservation, must pre-process matrix object, according to the mass fraction,
Take 300 ~ 500 parts of pretreatment matrix objects, 20 ~ 40 parts of interface modifiers, 80 ~ 100 parts of filler additives, 2 ~ 6 parts of N- tert-butyls-bis-
The mixing of (2-[4-morpholinodithio) sulfenamide, is kneaded 3 ~ 5min, and bottom sheet is cold through 140 ~ 145 DEG C, 10MPa compression molding 10 ~ 15min
But to room temperature to get environmental friendly regenerated glue.
Pillared additive the preparation method comprises the following steps:
(1) it takes pyridine 10:1 in mass ratio that piperidines mixing is added, obtains mixture, m-terephthal aldehyde 0.2:100 in mass ratio is taken to add
Enter malonic acid, add 3 times of malonic acid quality of mixture, be stirred 18h in 75 DEG C, be cooled to room temperature, adjusts pH to 1,
Filtering, takes filter residue to wash through deionized water, is dried in vacuo, obtains vacuum drying object, and vacuum drying object 1:100 in mass ratio is taken to be added
Distilled water is stirred 20min in 50 DEG C, and the sodium hydroxide of vacuum drying amount of substance 20% is added, is stirred 1h in 50 DEG C,
It filters, takes pumping filter residue and drying, obtain dried object；
(2) it takes dried object 1:10 in mass ratio that water mixing is added, obtains mixed liquor a, take dehydrated alcohol 1:1 in mass ratio that water is added mixed
It closes, obtains mixed liquor b, mixed liquor b 1:8 in mass ratio is taken to be added dropwise in mixed liquor a, score layer liquid takes cabaltous nitrate hexahydrate by matter
Amount is added to absolute ethanol than 1:80, obtains mixed liquor c, is taken mixed liquor c 1:20 in mass ratio to instill in layering liquid, is stood 5 days, mistake
Filter takes precipitating through distillation water washing to get pillared additive.
Soften additive the preparation method comprises the following steps:
Take swill 2:1:10 in mass ratio that pig manure, distilled water mixing is added, homogenate obtains homogenate, takes homogenate in mass ratio 15:
Corn flour, water mixing is added in 2:4, obtains mixture a, takes alpha-amylase 2:1 in mass ratio that alkali protease mixing is added, must mix
Object b takes mixture b to be seeded in mixture a by 5% inoculum concentration, in 80 DEG C of heat preservation 2h, adds the β-of mixture a mass 3%
Amylase stands 2h in 40 DEG C of heat preservation 30min, and enzyme deactivation takes upper liquid to be evaporated under reduced pressure to get softening additive.
Interface modifier are as follows: take apple polyphenol 3:2 in mass ratio be added tannic acid mixing to get.
Filler additive are as follows: it takes SILICA FUME in 600 DEG C of activation 2h, is cooled to room temperature, obtains activator, according to the mass fraction,
30 parts of activators, 30 parts of white carbon blacks, 20 parts of magnesium borate crystal whiskers, 1 part of neopelex, 100 parts of dehydrated alcohol mixing are taken,
1h is stirred in 35 DEG C to get filler additive.
A kind of preparation method of environmental friendly regenerated glue, includes the following steps:
S1. it takes waste tire film to be cut into 5cm × 5cm fritter, is broken into the micelle that diameter grain is 2cm through boulder crusher, successively passes through
Magnetic separator, winnowing machine remove impurity, grind 50 meshes, collect sieving particle, and sieving particle 30:3 in mass ratio is taken to add
Enter pillared additive, homogeneous 3min, through the ultraviolet light irradiation 36h of 125W in fully sheathed case, the roll-in on open mill obtains matrix
Object；
S2. it takes matrix object 200:40:10 in mass ratio that softening additive, glycerol mixing is added, 75 DEG C is warming up to, in 800r/
Min, 15MPa are through supercritical CO2Processing 20min is cooled to room temperature then at 2450MHz, 800W microwave 5min, obtains cooled material, take
Cooled material is warming up to 160 DEG C of heat preservation 5min, must pre-process matrix object, according to the mass fraction, takes 300 parts of pretreatment matrix objects, 20
Part interface modifier, 80 parts of filler additives, 2 parts of N- tert-butyls-bis- (2-[4-morpholinodithio) sulfenamides mixing, are kneaded 3min,
Bottom sheet is cooled to room temperature through 140 DEG C, 10MPa compression molding 10min to get environmental friendly regenerated glue.
Pillared additive the preparation method comprises the following steps:
(1) it takes pyridine 13:3 in mass ratio that piperidines mixing is added, obtains mixture, take m-terephthal aldehyde 0.2.5:150 in mass ratio
Be added malonic acid, add 7 times of malonic acid quality of mixture, be stirred 22h in 78 DEG C, be cooled to room temperature, adjust pH to
1.3, filtering takes filter residue to wash through deionized water, is dried in vacuo, obtains vacuum drying object, takes vacuum drying object 2:130 in mass ratio
Distilled water is added, 25min is stirred in 55 DEG C, the sodium hydroxide of vacuum drying amount of substance 25% is added, is stirred in 55 DEG C
2h is filtered, is taken pumping filter residue and drying, obtain dried object；
(2) it takes dried object 2:20 in mass ratio that water mixing is added, obtains mixed liquor a, take dehydrated alcohol 2:3 in mass ratio that water is added mixed
It closes, obtains mixed liquor b, mixed liquor b 2:9 in mass ratio is taken to be added dropwise in mixed liquor a, score layer liquid takes cabaltous nitrate hexahydrate by matter
Amount is added to absolute ethanol than 2:90, obtains mixed liquor c, is taken mixed liquor c 4:30 in mass ratio to instill in layering liquid, is stood 6 days, mistake
Filter takes precipitating through distillation water washing to get pillared additive.
Soften additive the preparation method comprises the following steps:
Take swill 4:2:20 in mass ratio that pig manure, distilled water mixing is added, homogenate obtains homogenate, takes homogenate in mass ratio 18:
Corn flour, water mixing is added in 4:5, obtains mixture a, takes alpha-amylase 4:2 in mass ratio that alkali protease mixing is added, must mix
Object b takes mixture b to be seeded in mixture a by 4% inoculum concentration, in 83 DEG C of heat preservation 3h, adds the β-of mixture a mass 4%
Amylase stands 3h in 43 DEG C of heat preservation 40min, and enzyme deactivation takes upper liquid to be evaporated under reduced pressure to get softening additive.
Interface modifier are as follows: take apple polyphenol 6:4 in mass ratio be added tannic acid mixing to get.
Filler additive are as follows: it takes SILICA FUME in 650 DEG C of activation 3h, is cooled to room temperature, obtains activator, according to the mass fraction,
60 parts of activators, 40 parts of white carbon blacks, 30 parts of magnesium borate crystal whiskers, 3 parts of neopelexes, 130 parts of dehydrated alcohol mixing are taken,
2h is stirred in 38 DEG C to get filler additive.
A kind of preparation method of environmental friendly regenerated glue, includes the following steps:
S1. it takes waste tire film to be cut into 5cm × 5cm fritter, is broken into the micelle that diameter grain is 2cm through boulder crusher, successively passes through
Magnetic separator, winnowing machine remove impurity, grind 55 meshes, collect sieving particle, and sieving particle 40:6 in mass ratio is taken to add
Enter pillared additive, homogeneous 4min, through the ultraviolet light irradiation 40h of 125W in fully sheathed case, the roll-in on open mill obtains matrix
Object；
S2. it takes matrix object 250:50:13 in mass ratio that softening additive, glycerol mixing is added, 78 DEG C is warming up to, in 800r/
Min, 15MPa are through supercritical CO2Processing 30min is cooled to room temperature then at 2450MHz, 800W microwave 6min, obtains cooled material, take
Cooled material is warming up to 180 DEG C of heat preservation 8min, must pre-process matrix object, according to the mass fraction, takes 400 parts of pretreatment matrix objects, 30
Part interface modifier, 90 parts of filler additives, 5 parts of N- tert-butyls-bis- (2-[4-morpholinodithio) sulfenamides mixing, are kneaded 4min,
Bottom sheet is cooled to room temperature through 143 DEG C, 10MPa compression molding 13min to get environmental friendly regenerated glue.
Pillared additive the preparation method comprises the following steps:
(1) it takes pyridine 15:4 in mass ratio that piperidines mixing is added, obtains mixture, m-terephthal aldehyde 0.3:200 in mass ratio is taken to add
Enter malonic acid, add 9 times of malonic acid quality of mixture, be stirred for 24 hours, be cooled to room temperature in 80 DEG C, adjust pH to
1.5, filtering takes filter residue to wash through deionized water, is dried in vacuo, obtains vacuum drying object, takes vacuum drying object 3:150 in mass ratio
Distilled water is added, 30min is stirred in 60 DEG C, the sodium hydroxide of vacuum drying amount of substance 30% is added, is stirred in 60 DEG C
3h is filtered, is taken pumping filter residue and drying, obtain dried object；
(2) it takes dried object 3:30 in mass ratio that water mixing is added, obtains mixed liquor a, take dehydrated alcohol 3:4 in mass ratio that water is added mixed
It closes, obtains mixed liquor b, mixed liquor b 3:10 in mass ratio is taken to be added dropwise in mixed liquor a, score layer liquid takes cabaltous nitrate hexahydrate by matter
Amount is added to absolute ethanol than 3:100, obtains mixed liquor c, is taken mixed liquor c 5:40 in mass ratio to instill in layering liquid, is stood 7 days,
Filtering takes precipitating through distillation water washing to get pillared additive.
Soften additive the preparation method comprises the following steps:
Take swill 5:3:30 in mass ratio that pig manure, distilled water mixing is added, homogenate obtains homogenate, takes homogenate in mass ratio 20:
Corn flour, water mixing is added in 5:6, obtains mixture a, takes alpha-amylase 5:3 in mass ratio that alkali protease mixing is added, must mix
Object b takes mixture b to be seeded in mixture a by 9% inoculum concentration, in 85 DEG C of heat preservation 4h, adds the β-of mixture a mass 5%
Amylase stands 4h in 45 DEG C of heat preservation 50min, and enzyme deactivation takes upper liquid to be evaporated under reduced pressure to get softening additive.
Interface modifier are as follows: take apple polyphenol 8:5 in mass ratio be added tannic acid mixing to get.
Filler additive are as follows: it takes SILICA FUME in 700 DEG C of activation 4h, is cooled to room temperature, obtains activator, according to the mass fraction,
80 parts of activators, 50 parts of white carbon blacks, 40 parts of magnesium borate crystal whiskers, 5 parts of neopelexes, 150 parts of dehydrated alcohol mixing are taken,
3h is stirred in 40 DEG C to get filler additive.
A kind of preparation method of environmental friendly regenerated glue, includes the following steps:
S1. it takes waste tire film to be cut into 5cm × 5cm fritter, is broken into the micelle that diameter grain is 2cm through boulder crusher, successively passes through
Magnetic separator, winnowing machine remove impurity, grind 60 meshes, collect sieving particle, and sieving particle 50:8 in mass ratio is taken to add
Enter pillared additive, homogeneous 5min, through the ultraviolet light irradiation 48h of 125W in fully sheathed case, the roll-in on open mill obtains matrix
Object；
S2. it takes matrix object 300:60:15 in mass ratio that softening additive, glycerol mixing is added, 80 DEG C is warming up to, in 800r/
Min, 15MPa are through supercritical CO2Processing 40min is cooled to room temperature then at 2450MHz, 800W microwave 8min, obtains cooled material, take
Cooled material is warming up to 190 DEG C of heat preservation 10min, must pre-process matrix object, according to the mass fraction, takes 500 parts of pretreatment matrix objects, 40
Part interface modifier, 100 parts of filler additives, 6 parts of N- tert-butyls-bis- (2-[4-morpholinodithio) sulfenamides mixing, are kneaded 5min,
Bottom sheet is cooled to room temperature through 145 DEG C, 10MPa compression molding 15min to get environmental friendly regenerated glue.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking softening additive.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking pillared additive.
Comparative example 3: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking interface modifier.
Comparative example 4: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking filler additive.
Comparative example 5: the environmental friendly regenerated glue of company of Jinan City production.
Embodiment and comparative example are tested according to GB/T13460-2008, GB/T 1232.1-2000 standard, tested
The results are shown in Table 1.
Table 1:
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Elongation at break (%) | 589 | 580 | 585 | 576 | 578 | 575 | 571 | 410 |
| Tensile strength (MPa) | 20.5 | 20.1 | 20.4 | 19.6 | 19.8 | 19.5 | 19.1 | 10.5 |
| 100% stress at definite elongation (MPa) | 3.54 | 3.51 | 3.53 | 3.47 | 3.49 | 3.45 | 3.39 | 1.74 |
| Mooney viscosity (Pa s) | 53 | 57 | 55 | 64 | 61 | 66 | 68 | 78 |
In conclusion the environmental friendly regenerated glue of technical solution of the present invention preparation has both the spy of excellent mechanical performance and processing performance
Point has broad prospects in the development of reclaimed rubber industry, is worth promoting.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of environmental friendly regenerated glue, which is characterized in that including softening additive, pillared additive, interface modifier, filler addition
Agent；
It is described softening additive the preparation method comprises the following steps:
Take swill 2 ~ 5:1 in mass ratio ~ 3:10 ~ 30 that pig manure, distilled water mixing is added, homogenate obtains homogenate, takes homogenate by matter
Corn flour, water mixing is added than 15 ~ 20:2 ~ 5:4 ~ 6 in amount, obtains mixture a, takes alpha-amylase 2 ~ 5:1 in mass ratio ~ 3 that alkali is added
Property protease mixing, obtain mixture b, mixture b taken to be seeded in mixture a by 5 ~ 9% inoculum concentration, in 80 ~ 85 DEG C keep the temperature 2 ~
4h adds the beta amylase of mixture a mass 3 ~ 5%, in 40 ~ 45 DEG C of 30 ~ 50min of heat preservation, stands, enzyme deactivation takes upper liquid to subtract
Pressure distillation is to get softening additive.
2. environmental friendly regenerated glue according to claim 1, which is characterized in that the pillared additive the preparation method comprises the following steps:
(1) take pyridine 10 ~ 15:1 in mass ratio ~ 4 be added piperidines mixing, obtain mixture, take m-terephthal aldehyde in mass ratio 0.2 ~
Malonic acid is added in 0.3:100 ~ 200, adds 3 ~ 9 times of malonic acid quality of mixture, it is stirred 18 in 75 ~ 80 DEG C ~ for 24 hours,
It is cooled to room temperature, adjusts pH to 1 ~ 1.5, filtering takes filter residue to wash through deionized water, is dried in vacuo, obtains vacuum drying object, takes true
Distilled water is added in empty dried object 1 ~ 3:100 in mass ratio ~ 150, and 20 ~ 30min is stirred in 50 ~ 60 DEG C, and vacuum drying is added
The sodium hydroxide of amount of substance 20 ~ 30% is stirred, and is filtered, is taken pumping filter residue and drying, obtain dried object；
(2) take dried object 1 ~ 3:10 in mass ratio ~ 30 be added water mixing, obtain mixed liquor a, take dehydrated alcohol 1 ~ 3:1 in mass ratio ~
4 are added water mixing, obtain mixed liquor b, 1 ~ 3:8 ~ 10 in mass ratio mixed liquor b is taken to be added dropwise in mixed liquor a, score layer liquid takes six
Nitric hydrate cobalt 1 ~ 3:80 ~ 100 in mass ratio are added to absolute ethanol, and obtain mixed liquor c, take mixed liquor c 1 ~ 5:20 in mass ratio ~
40 instill in layering liquid, stand 5 ~ 7 days, filtering, take precipitating through distillation water washing to get pillared additive.
3. environmental friendly regenerated glue according to claim 1, which is characterized in that vacuum drying substance is added in the step (1)
The sodium hydroxide of amount 20 ~ 30% is stirred condition are as follows: is stirred 1 ~ 3h in 50 ~ 60 DEG C.
4. a kind of preparation method of the environmental friendly regenerated glue as described in claim 1 ~ 3 any one, which is characterized in that the preparation side
Method includes the following steps:
S1. it takes waste tire film to be cut into 5cm × 5cm fritter, is broken into the micelle that diameter grain is 2cm through boulder crusher, goes to clean
Matter ground 50 ~ 60 meshes, collected sieving particle, took sieving particle 30 ~ 50:3 in mass ratio ~ 8 that pillared addition is added
Agent, 3 ~ 5min of homogeneous, ultraviolet light irradiation, roll-in obtain matrix object；
S2. it takes matrix object 200 ~ 300:40 in mass ratio ~ 60:10 ~ 15 that softening additive, glycerol mixing is added, is warming up to 75 ~ 80
DEG C, in 800r/min, 15MPa through supercritical CO220 ~ 40min of processing is cooled to then at 2450MHz, 800W 5 ~ 8min of microwave
Room temperature obtains cooled material, takes cooled material to be warming up to 160 ~ 190 DEG C of 5 ~ 10min of heat preservation, must pre-process matrix object, according to the mass fraction,
Take 300 ~ 500 parts of pretreatment matrix objects, 20 ~ 40 parts of interface modifiers, 80 ~ 100 parts of filler additives, 2 ~ 6 parts of N- tert-butyls-bis-
The mixing of (2-[4-morpholinodithio) sulfenamide, is kneaded, and bottom sheet, compression molding is cooled to room temperature to get environmental friendly regenerated glue.
5. the preparation method of environmental friendly regenerated glue according to claim 4, which is characterized in that ultraviolet lamp shines in the step S1
Penetrate condition are as follows: through the ultraviolet 36 ~ 48h of light irradiation of 125W in fully sheathed case.
6. the preparation method of environmental friendly regenerated glue according to claim 4, which is characterized in that the interface in the step S2 changes
Property agent are as follows: take apple polyphenol 3 ~ 8:2 in mass ratio ~ 5 be added tannic acid mixing to get.
7. the preparation method of environmental friendly regenerated glue according to claim 4, which is characterized in that filler adds in the step S2
Agent are as follows: take SILICA FUME in 600 ~ 700 DEG C of 2 ~ 4h of activation, be cooled to room temperature, obtain activator, according to the mass fraction, take 30 ~ 80 parts of work
Compound, 30 ~ 50 parts of white carbon blacks, 20 ~ 40 parts of magnesium borate crystal whiskers, 1 ~ 5 part of neopelex, 100 ~ 150 parts of dehydrated alcohols
Mixing, is stirred 1 ~ 3h in 35 ~ 40 DEG C to get filler additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811134562.XA CN109265738A (en) | 2018-09-28 | 2018-09-28 | A kind of environmental friendly regenerated glue and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811134562.XA CN109265738A (en) | 2018-09-28 | 2018-09-28 | A kind of environmental friendly regenerated glue and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109265738A true CN109265738A (en) | 2019-01-25 |
Family
ID=65199067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811134562.XA Pending CN109265738A (en) | 2018-09-28 | 2018-09-28 | A kind of environmental friendly regenerated glue and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109265738A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4031039A (en) * | 1975-09-02 | 1977-06-21 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for treating waste high-polymer mixture |
| CN101473069A (en) * | 2006-05-16 | 2009-07-01 | 巴斯夫欧洲公司 | Process for preparing porous metal organic frameworks |
| CN103694282A (en) * | 2013-11-28 | 2014-04-02 | 浙江大学 | Synthetic method of Tenuifoliside B |
| CN107216659A (en) * | 2017-06-17 | 2017-09-29 | 常州市玉宇化工有限公司 | A kind of preparation method of reclaimed rubber |
| CN107308975A (en) * | 2017-07-07 | 2017-11-03 | 江南大学 | A kind of preparation method of nitrogen-doped carbon package metals oxide catalyst |
| CN108373557A (en) * | 2017-12-29 | 2018-08-07 | 天台坤荣橡胶有限公司 | A kind of preparation method of high-performance reclaimed rubber |
-
2018
- 2018-09-28 CN CN201811134562.XA patent/CN109265738A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4031039A (en) * | 1975-09-02 | 1977-06-21 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for treating waste high-polymer mixture |
| CN101473069A (en) * | 2006-05-16 | 2009-07-01 | 巴斯夫欧洲公司 | Process for preparing porous metal organic frameworks |
| CN103694282A (en) * | 2013-11-28 | 2014-04-02 | 浙江大学 | Synthetic method of Tenuifoliside B |
| CN107216659A (en) * | 2017-06-17 | 2017-09-29 | 常州市玉宇化工有限公司 | A kind of preparation method of reclaimed rubber |
| CN107308975A (en) * | 2017-07-07 | 2017-11-03 | 江南大学 | A kind of preparation method of nitrogen-doped carbon package metals oxide catalyst |
| CN108373557A (en) * | 2017-12-29 | 2018-08-07 | 天台坤荣橡胶有限公司 | A kind of preparation method of high-performance reclaimed rubber |
Non-Patent Citations (1)
| Title |
|---|
| 肖刚: "《能源工程技术丛书 CO2减排技术》", 31 August 2015 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102634062B (en) | Method for preparing high-tenacity reclaimed rubber by adding coupling agent | |
| CN105694962B (en) | A kind of regeneration technology of waste mineral oil | |
| CN105461956A (en) | Production technique of green environment-friendly tire reclaimed rubber | |
| CN102179239A (en) | Method for recycling carclazyte used for refining petroleum | |
| CN103435843A (en) | Reclaiming agent, reclaimed rubber prepared therefrom, and preparation method of reclaimed rubber | |
| CN102786713A (en) | Resource treating method for oil field and oil sludge | |
| CN103484158B (en) | Method for preparing chemicals containing phenols and aromatic hydrocarbons from bio-oil pyrolysis lignin through catalysis | |
| CN104745251B (en) | A kind of preparation method of energy-saving agent for biomass fuel oil | |
| CN109265738A (en) | A kind of environmental friendly regenerated glue and preparation method thereof | |
| CN103980720B (en) | A kind of environment-friendly type compounded rubber regenerator and preparation method thereof | |
| Singhal et al. | Chemical recycling of waste clothes: a smarter approach to sustainable development | |
| CN102766285A (en) | Production process for preparing reclaimed rubber through sewage oil sludge | |
| CN110373257A (en) | A method of tail seal grease of shield is produced with used oil | |
| CN105772113B (en) | A kind of additive for recovering activity of hydrocatalyst | |
| CN104017223A (en) | Preparation method of sulfydryl lignin for regenerating waste rubber | |
| CN201442321U (en) | Polystyrene waste plastic recycling equipment | |
| CN105837829B (en) | The preparation method of the low super tackifying resin of ash content alkyl phenol acetylene | |
| CN111925558A (en) | Normal-temperature regeneration method of waste rubber | |
| CN104479884A (en) | Method for preparing diesel from illegal cooking oil | |
| CN109054921A (en) | Waste mineral oil refining methd | |
| CN104017239B (en) | A kind of preparation method of sulfhydryl modified activated carbon for regenerating waste or used rubber | |
| CN109232924A (en) | A kind of preparation method of environmental friendly regenerated glue | |
| CN103981292A (en) | Resource utilization method of wax-containing waste paper | |
| CN104194035B (en) | Degradation agent and method for making waste circuit boards and waste resin plates into plates | |
| CN108285563A (en) | A kind of preparation method of compliant rubber powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190125 |
|
| WD01 | Invention patent application deemed withdrawn after publication |