CN108659261A - A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material - Google Patents
A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material Download PDFInfo
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- CN108659261A CN108659261A CN201810405227.2A CN201810405227A CN108659261A CN 108659261 A CN108659261 A CN 108659261A CN 201810405227 A CN201810405227 A CN 201810405227A CN 108659261 A CN108659261 A CN 108659261A
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- makrolon
- catalysis
- molecular sieves
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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
- C08J11/16—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 inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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 present invention relates to field of new material preparation, particularly with regard to a kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material；Its technical solution is：By polyethylene oxide polypropylene oxide polyethylene oxide triblock copolymer, poly- dodecane amide triazine stilbenesulphonic acid ammonium, polyoxyethylene cetyl base stearyl bis ether, the homopolymer of 4 vinylphenol of bromination, hydrochloric acid solution is added in reaction kettle, 40 50 DEG C of temperature control, stirs 60 80min, then ethyl orthosilicate is added in reaction kettle, cooled to room temperature after reacting is completed, is then filtered, is washed, calcining, you can obtain a kind of catalysis makrolon degradation Molecular Sieves as Template material.
Description
Technical field
The present invention relates to field of material preparation, particularly with regard to a kind of catalysis makrolon degradation Molecular Sieves as Template material
Preparation method.
Background technology
There are close contact, polyester material between polyester material itself and petrochemical industry and organic chemistry industry
Production and demand is increasing in addition, domestic PC consumption figures have also been up to 900,000 t/a or more.It is a large amount of waste and old poly-
The generation of ester material brings very big burden to environment and leads to some relevant social concerns.Therefore, makrolon material
Recovery technology receives the extensive concern of people.
CN104877168A provides a kind of recovery method of makrolon.The solvent that this method selects solubility property good is made
For reaction medium, makrolon and solvent are added in there-necked flask, after makrolon is completely dissolved, by catalyst, alcoholysis agent
It is added in reaction system, carries out alcoholysis reaction, wait for after reaction, reaction solution is washed, suction filtration is dried process, obtains
To alcoholysis product of the end with hydroxyl and different viscosity numbers identical from makrolon repeating segment structure.After reaction, instead
The last handling processes such as system is washed, filters, is dry are answered to obtain alcoholysis product.The recovery method is under mild conditions to poly- carbon
Acid esters is degraded；The product of different chain links is obtained by the reaction condition for setting different；Because its product both ends carries hydroxyl energy
Polycondensation reaction is carried out with other proper monomers, to recycling for the makrolon of realization truly.
CN106432797A discloses a kind of recovery process of waste and old cross-linked polycarbonate, and steps are as follows：Step 1) is waste and old
The pretreatment of cross-linked polycarbonate：Waste and old cross-linked polycarbonate is subjected to surface spraying cleaning and ultraviolet sterilization；Step 2) is useless
The depolymerization of old cross-linked polycarbonate is recycled：After crushed by step 1) treated waste and old cross-linked polycarbonate, extruder is added,
Under high temperature and alternating shear effect so that depolymerization occurs for the strand of cross-linked polycarbonate, realizes and recycles.The invention
Advantageous effect is：It can with environment-friendly high-efficiency depolymerization cross-linked polycarbonate so that the makrolon after depolymerization has temperature flowing
And machinability, the production of articles in downstream is directly applied to, pollution and the low efficiency problem of traditional treatment method are solved.
CN101665584A provides a kind of recovery method of makrolon, includes the following steps：Recycle the plastic cement of PC compositions
Part->Cleaning->Cleaning->Cooling broken->Clean again->Dewatered drying->Add additive extrusion molding；Wherein add
Doping extrusion molding specifically includes, and is equipped with again using extruder as capital equipment and adds additivated auxiliary device in temperature
MBS series toughener, the 1%- of ABS, 3-10% of 10-85% are added at a temperature of 240 DEG C -300 DEG C by weight percentage
The lubricant of 10%SMA phase solvents and 0.1-0.5%, surplus are that PC plastic cement is stirred simultaneously extrusion molding.Added using above-mentioned
Add formula that can produce not flame retardant series PC/ABS alloy materials of substitution import performance completely, is widely used in mobile phone electricity
Brain shell electron-like electricity.
Currently, scholars study PC chemistry deagglomeration problems when, mainly by thermal cracking, hydrolysis, alcoholysis and surpass
（It is sub-）The methods of depolymerization under critical depolymerization and ionic liquid environment realization, but during depolymerization, it cannot be to catalyst
It is recycled, this results in will produce a large amount of waste residue in depolymehzation process, and is brought seriously to the equipment that depolymerization uses
Corrosive effect.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of systems of catalysis makrolon degradation Molecular Sieves as Template material
Preparation Method.
The catalysis makrolon degradation is prepared with Molecular Sieves as Template material according to following scheme：
According to mass fraction：By 40-50 partsPolyethylene oxide-Polypropylene oxidePolyethylene oxideTriblock copolymer, 0.4-
0.8 part of poly- dodecane amide triazine stilbenesulphonic acid ammonium, 0.5-0.9 parts of polyoxyethylene cetyl base stearyl bis ether,
The homopolymer of 0.1-0.6 parts of bromination -4- vinyl-phenol, 800-1000 parts of hydrochloric acid solution are added in reaction kettle, temperature control
40-50 DEG C, 60-80min is stirred, then 85-95 parts of ethyl orthosilicate is added in reaction kettle, is slowly added to, in 70-
It is added in 90min；Then 45-55 DEG C of temperature control reacts 18-24h；Reaction temperature is raised to 95-105 DEG C after the completion, the reaction was continued
20-26h；Cooled to room temperature after reacting is completed, is then filtered, washs, is caught up in 70-80 DEG C of baking oven after 3-7h in horse
It is not calcined in stove, you can obtain a kind of catalysis makrolon degradation Molecular Sieves as Template material.
Further, according to mass fraction, auxiliary agent containing strontium and 100-150 parts of deionized water are added in reaction kettle,
50-60 DEG C is heated to, 60-80 parts of catalysis makrolon degradation Molecular Sieves as Template material is then added, keeps temperature,
Continue to stir 8-12h, then stop stirring, stand 2-6h, then filter, molecular sieve is done under 50-60 DEG C of water bath condition
Dry 120-180min is then transferred in 60-70 DEG C of baking oven dry 150-210min；After completing drying, you can obtain one kind
Makrolon degradation catalyst.
The calcium nitrate that the auxiliary agent containing strontium is 2.8-3.5 parts, 0.4-0.8 parts of poly- (3- dodecyls thiophene -2,5- bis-
Base), 0.04-0.08 parts (1,10- Phen) dinitric acid copper, the poly- ammonia third of 1.1-1.6 parts of strontium nitrate and 1.8-2.6 part
The mixture of base biguanides stearate composition.
A concentration of 2.0-2.5mol/L of the hydrochloric acid solution.
The calcination condition is to be warming up to 550-650 DEG C with the heating rate of 2-5 DEG C/min to calcine 4- in Muffle furnace
8h。
A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material, this programme disclosed in the method for the present invention
The catalyst of the catalysis makrolon degradation of preparation, pore passage structure, aperture size with high-sequential, mesoporous complexion are more
The composition and property that becomes, may be selected hole wall, have extraordinary thermal stability and hydrothermal stability, can recycle, and solve
Traditional catalyst cannot be reused, waste residue amount is big problem.
Specific implementation mode
The invention is described further below by specific embodiment：
Embodiment 1
A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material, technology of preparing scheme are as follows：
According to mass fraction：By 45 partsPolyethylene oxide-Polypropylene oxidePolyethylene oxideTriblock copolymer, 0.6 part
Poly- dodecane amide triazine stilbenesulphonic acid ammonium, 0.6 part of polyoxyethylene cetyl base stearyl bis ether, 0.3 part of bromination -4-
The homopolymer of vinyl-phenol, 900 parts of hydrochloric acid solution are added in reaction kettle, 45 DEG C of temperature control, stir 60-80min, then
90 parts of ethyl orthosilicate is added in reaction kettle, is slowly added to, is added in 60min；Then 50 DEG C of temperature control react 22h；
Reaction temperature is raised to 100 DEG C after the completion, the reaction was continued 23h；Cooled to room temperature after reacting is completed, is then filtered, is washed,
It catches up in 75 DEG C of baking oven and is calcined in Muffle furnace after 5h, you can obtain a kind of catalysis makrolon degradation molecular sieve
Mould material.
According to mass fraction, by 3.2 parts of calcium nitrate, 0.6 part of poly- (3- dodecyl thiophene -2,5- diyl), 0.05 part
(1,10- Phen) dinitric acid copper, 1.3 parts of strontium nitrate, 2.2 parts of polyaminopropyl biguanide stearate and 120 parts
Deionized water is added in reaction kettle, heats to 55 DEG C, and 70 parts of catalysis makrolon degradation molecular sieve is then added
Mould material keeps temperature, continues to stir 10h, then stops stirring, stands 4h, then filter, the water by molecular sieve at 55 DEG C
Dry 150min under the conditions of bath, is then transferred in 65 DEG C of baking oven dry 180min；After completing drying, you can obtain a kind of poly-
Carbonic ester degradation catalyst.
A concentration of 2.3mol/L of the hydrochloric acid solution.
The calcination condition is to be warming up to 600 DEG C with the heating rate of 3 DEG C/min to calcine 6h in Muffle furnace.
Embodiment 2
A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material, technology of preparing scheme are as follows：
According to mass fraction：By 40 partsPolyethylene oxide-Polypropylene oxidePolyethylene oxideTriblock copolymer, 0.4 part
Poly- dodecane amide triazine stilbenesulphonic acid ammonium, 0.5 part of polyoxyethylene cetyl base stearyl bis ether, 0.1 part of bromination -4-
The homopolymer of vinyl-phenol, 800 parts of hydrochloric acid solution are added in reaction kettle, 40 DEG C of temperature control, 60min are stirred, then by 85
The ethyl orthosilicate of part is added in reaction kettle, is slowly added to, is added in 70min；Then 45 DEG C of temperature control react 18h；It completes
Reaction temperature is raised to 95 DEG C afterwards, the reaction was continued 20h；Cooled to room temperature after reacting is completed, is then filtered, is washed, 70
DEG C baking oven in catch up with and calcined in Muffle furnace after 3h, you can obtain a kind of catalysis makrolon degradation Molecular Sieves as Template
Material.
According to mass fraction, by 2.8 parts of calcium nitrate, 0.4 part of poly- (3- dodecyl thiophene -2,5- diyl), 0.04 part
(1,10- Phen) dinitric acid copper, 1.1 parts of strontium nitrate, 1.8 parts of polyaminopropyl biguanide stearate and 100 parts
Deionized water is added in reaction kettle, heats to 50 DEG C, and 60 parts of catalysis makrolon degradation molecular sieve is then added
Mould material keeps temperature, continues to stir 8h, then stops stirring, stands 2h, then filter, the water by molecular sieve at 50 DEG C
Dry 120min under the conditions of bath, is then transferred in 60 DEG C of baking oven dry 150min；After completing drying, you can obtain a kind of poly-
Carbonic ester degradation catalyst.
A concentration of 2.0mol/L of the hydrochloric acid solution.
The calcination condition is to be warming up to 550 DEG C with the heating rate of 2 DEG C/min to calcine 4h in Muffle furnace.
Embodiment 3
A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material, technology of preparing scheme are as follows：
According to mass fraction：By 50 partsPolyethylene oxide-Polypropylene oxidePolyethylene oxideTriblock copolymer, 0.8 part
Poly- dodecane amide triazine stilbenesulphonic acid ammonium, 0.9 part of polyoxyethylene cetyl base stearyl bis ether, 0.6 part of bromination -4-
The homopolymer of vinyl-phenol, 1000 parts of hydrochloric acid solution are added in reaction kettle, 50 DEG C of temperature control, stir 680min, then will
95 parts of ethyl orthosilicate is added in reaction kettle, is slowly added to, and is added in 90min；Then 55 DEG C of temperature control, reaction is for 24 hours；It is complete
Reaction temperature is raised to 105 DEG C after, the reaction was continued 26h；Cooled to room temperature after reacting is completed, is then filtered, is washed,
It catches up in 80 DEG C of baking oven and is calcined in Muffle furnace after 7h, you can obtain a kind of catalysis makrolon degradation molecular sieve mould
Plate material.
According to mass fraction, by 3.5 parts of calcium nitrate, 0.8 part of poly- (3- dodecyl thiophene -2,5- diyl), 0.08 part
(1,10- Phen) dinitric acid copper, 1.6 parts of strontium nitrate, 2.6 parts of polyaminopropyl biguanide stearate and 150 parts
Deionized water is added in reaction kettle, heats to 60 DEG C, and 80 parts of catalysis makrolon degradation molecular sieve is then added
Mould material keeps temperature, continues to stir 12h, then stops stirring, stands 6h, then filter, the water by molecular sieve at 60 DEG C
Dry 180min under the conditions of bath, is then transferred in 70 DEG C of baking oven dry 150-210min；After completing drying, you can obtain one
Kind makrolon degradation catalyst.
A concentration of 2.5mol/L of the hydrochloric acid solution.
The calcination condition is to be warming up to 650 DEG C with the heating rate of 5 DEG C/min to calcine 8h in Muffle furnace.
Comparative example 1
It is not added with (1,10- Phen) dinitric acid copper, the other the same as in Example 1.
Comparative example 2
Not addition polymerization (3- dodecyl thiophene -2,5- diyl), the other the same as in Example 1.
Comparative example 3
It is not added with polyaminopropyl biguanide stearate, the other the same as in Example 1.
Comparative example 4
It is not added withPolyethylene oxide-Polypropylene oxidePolyethylene oxideTriblock copolymer, the other the same as in Example 1.
Comparative example 5
Not addition polymerization dodecanoyl amine triazine stilbenesulphonic acid ammonium, the other the same as in Example 1.
Comparative example 6
It is not added with the homopolymer of bromination -4- vinyl-phenol, the other the same as in Example 1.
Table：The performance for the test specimen that different process is made compares.
| Number | Porosity（cm3/g） | PC degradation rates（%） |
| Embodiment 1 | 0.93 | 96.8 |
| Embodiment 2 | 0.91 | 96.4 |
| Embodiment 3 | 0.94 | 97.3 |
| Comparative example 1 | 0.88 | 94.3 |
| Comparative example 2 | 0.84 | 94.6 |
| Comparative example 3 | 0.82 | 93.2 |
| Comparative example 4 | 0.74 | 92.0 |
| Comparative example 5 | 0.89 | 95.1 |
| Comparative example 6 | 0.89 | 95.5 |
Claims (3)
1. a kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material according to claim 1, special
Sign is：The catalysis makrolon degradation is prepared with Molecular Sieves as Template material according to following scheme：
According to mass fraction：By 40-50 parts of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, 0.4-
0.8 part of poly- dodecane amide triazine stilbenesulphonic acid ammonium, 0.5-0.9 parts of polyoxyethylene cetyl base stearyl bis ether,
The homopolymer of 0.1-0.6 parts of bromination -4- vinyl-phenol, 800-1000 parts of hydrochloric acid solution are added in reaction kettle, temperature control
40-50 DEG C, 60-80min is stirred, then 85-95 parts of ethyl orthosilicate is added in reaction kettle, is slowly added to, in 70-
It is added in 90min；Then 45-55 DEG C of temperature control reacts 18-24h；Reaction temperature is raised to 95-105 DEG C after the completion, the reaction was continued
20-26h；Cooled to room temperature after reacting is completed, is then filtered, washs, is caught up in 70-80 DEG C of baking oven after 3-7h in horse
It is not calcined in stove, you can obtain a kind of catalysis makrolon degradation Molecular Sieves as Template material.
2. a kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material according to claim 3, special
Sign is：A concentration of 2.0-2.5mol/L of the hydrochloric acid solution.
3. a kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material according to claim 3, special
Sign is：The calcination condition is to be warming up to 550-650 DEG C with the heating rate of 2-5 DEG C/min to calcine 4- in Muffle furnace
8h。
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| CN201810405227.2A CN108659261A (en) | 2018-04-29 | 2018-04-29 | A kind of preparation method of catalysis makrolon degradation Molecular Sieves as Template material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723396A (en) * | 2009-11-26 | 2010-06-09 | 上海大学 | Hexagonal flaky sequential silicon-based mesoporous material SBA-15 and preparation method thereof |
| CN110408076A (en) * | 2018-04-29 | 2019-11-05 | 王金桢 | A kind of preparation method of the catalysis material of polycarbonate degradation |
-
2018
- 2018-04-29 CN CN201810405227.2A patent/CN108659261A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723396A (en) * | 2009-11-26 | 2010-06-09 | 上海大学 | Hexagonal flaky sequential silicon-based mesoporous material SBA-15 and preparation method thereof |
| CN110408076A (en) * | 2018-04-29 | 2019-11-05 | 王金桢 | A kind of preparation method of the catalysis material of polycarbonate degradation |
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Effective date of registration: 20190920 Address after: Yiwu City, the new town hospital in Zhejiang province Jinhua city 5 District 322009 Building 1 unit 201 room Applicant after: Yiwu Ce New Material Co., Ltd. Address before: Yiwu City, the new town hospital in Zhejiang province Jinhua city 5 District 322009 Building 1 unit 201 room Applicant before: Wang Jin Zhen |
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Application publication date: 20181016 |