CN106398073B - A kind of optical grade PMMA continuous bulk polymerization process and its production system - Google Patents
A kind of optical grade PMMA continuous bulk polymerization process and its production system Download PDFInfo
- Publication number
- CN106398073B CN106398073B CN201610905726.9A CN201610905726A CN106398073B CN 106398073 B CN106398073 B CN 106398073B CN 201610905726 A CN201610905726 A CN 201610905726A CN 106398073 B CN106398073 B CN 106398073B
- Authority
- CN
- China
- Prior art keywords
- continuous
- pmma
- reaction
- optical grade
- polymerization reactor
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of optical grade PMMA continuous bulk polymerization process and its production system, this method comprises the following steps: reaction raw materials methyl methacrylate, initiator, auxiliary agent are mixed to get mixed solution according to the ratio, it is injected after metering in continuous polymerization reactor and carries out polymerization reaction and continuously squeeze out, devolatilization is handled after extrusion, and PMMA solid material is made.The present invention is rotated material dispersion and is sheared by screw axis body, thins, keep material molecular weight distribution reasonable, improve the mixing uniformity between reactive component, it is set to carry out heat exchange with barrel wall, axis outer wall in time, while whole process is continuous, reduces residence time of material, and then reduce the possibility of heat localization, the temperature gradient for reducing storeroom solves the reaction heat control problem of bulk polymerization, finally realizes product and continuously squeezes out during the reaction.
Description
Technical field
The present invention relates to the preparation method of polymer, more particularly to a kind of optical grade PMMA continuous bulk polymerization process and
Its production system.
Background technique
Polymethyl methacrylate is the homopolymer or copolymer of methyl methacrylate, and abbreviation PMMA is a kind of synthesis
The transparent material haveing excellent performance.It has fabulous translucency, apparent glossiness, excellent weather resistance and it is good after plus
Work performance.Due to raw material and technology etc. are many, existing PMMA product quality and performances are not good enough, and single variety, it is difficult to
Meet the market demand.
The synthesis of industrial methyl methacrylate mainly has suspension polymerization, solution polymerization process, emulsion polymerization at present,
Wherein emulsion polymerization is more universal, but lotion, three kinds of suspension, solution methods all suffer from a series of problems, such as a large amount of solvents or
Water needs to be recycled, and synthesis technology is complicated, and the auxiliary agent remained in the polymer is also made troubles to the processing and utilization in later period, raw
The PMMA degree of purity of output is not high, it is necessary to is just able to achieve using bulk polymerization.
But there are many defects for the mode of existing bulk polymerization, for example, Auto-acceleration is big, system is sticky, relatively
Molecular mass adjusts difficulty, and relative molecular mass distribution is wide；Heat of polymerization is not easy to spread, and polymerization temperature is difficult to control, easily part mistake
Heat can lead to sudden and violent poly- when serious；Unreacted monomer is not easy to eliminate, so as to cause products machinery degradation.
Conventional bulk polymerization causes Methyl Methacrylate Bulk Polymerization manufacture high-quality because there are above-mentioned problems
It measures, the industrialized production of the PMMA of high cleanliness is difficult to realize.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of optical grade PMMA continuous bulks
Polymerization and its production system, for solving the synthetic method complexity of polymethyl methacrylate in the prior art, being also easy to produce
A large amount of solvents and water and need to be recycled, the auxiliary agent of residual in the polymer is also made troubles etc. to the processing and utilization in later period and is asked
Topic.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of optical grade PMMA continuous bulk
Polymerization includes the following steps: to mix reaction raw materials, obtains mixed solution, injects in continuous polymerization reactor after metering
It carries out polymerization reaction and continuously squeezes out, devolatilization is handled after extrusion, and PMMA solid material is made.
Further, screw speed≤120rpm of the continuous polymerization reactor.
Further, the conversion zone temperature of the continuous polymerization reactor is 90 DEG C~240 DEG C, and extruding zone temperature is 90 DEG C
~240 DEG C.The biography that temperature control in reactor cavity room passes through the uniaxially or biaxially heat-conducting medium of continuous polymerization reactor interlayer
Heat is realized, achievees the purpose that efficiently controlling temperature.
Further, the cavity indoor pressure of the continuous polymerization reactor is 0-3MPa.
Further, the reaction raw materials include methyl methacrylate, initiator and auxiliary agent.
Further, by weight, the reaction raw materials include: 100 parts of methyl methacrylate, initiator 0.01~3
Part, 0~3 part of auxiliary agent；The initiator is di-t-butyl peroxide, and the auxiliary agent is lauryl mercaptan.
Further, it is first passed through nitrogen into the continuous polymerization reactor before reaction or argon gas carries out deoxygenation, the company
Continuous polymer reactor is uniaxially or biaxially continuous polymerization reactor.Prepare the blending tank of mixed solution, storage tank, metering device,
Continuous polymerization reactor, Devolatilization device internal chamber pass through nitrogen displacement, in closed nitrogen protection environment, system
The indoor gas of chamber is after analysis detection is qualified, then starts to feed, and is filled with nitrogen into system with starvation, effectively avoids firing
Decrepitate is fried.
Further, the temperature of mixed solution is controlled at 90 DEG C hereinafter, devolatilization temperature is controlled at 160-180 DEG C.It is obtained
PMMA solid material can enter the processes such as granulation.
Second aspect of the present invention provides the production system of above-mentioned optical grade PMMA continuous bulk polymerization, including sequentially connected
Blending tank, continuous polymerization reactor, Devolatilization device.
The continuous polymerization reactor is uniaxially or biaxially continuous polymerization reactor.
Further, storage tank and metering device are successively arranged between the blending tank and continuous polymerization reactor.Specifically
Ground, the material of blending tank are temporarily stored after fully mixed, into storage tank, and the material of storage tank enters metering device
It is measured, metering device is mass flowmenter or volume flowmeter, and metering can be into continuous polymerization reactor after terminating
Charging.
Further, the blending tank is atomizing or stirring-type blending tank.
Further, the Devolatilization device is uniaxial evaporator, twin shaft evaporator, single screw extrusion machine, twin-screw extrusion
Any one of machine.
As described above, optical grade PMMA continuous bulk polymerization process of the invention and its production system, have beneficial below
Effect: the present invention synthesizes PMMA moulding compound using this polymerization technique of continuous bulk, provides skill for PMMA industrial production equipment
Art is supported.The bulk polymerization mode that the present invention uses has that polymer is very pure, free from admixture, solvent-free recycling, low energy consumption, without dirt
The advantages that dye, this method are rotated material dispersion and are sheared by screw axis body, thin, and make it in time and outside barrel wall, axis
Wall carries out heat exchange, while having self-cleaning function, and entire reaction process can be made to be carried out continuously, reduce residence time of material,
And then reduce the possibility of heat localization.Present invention process is simple, the polymer of synthesis is pure, replacement product is flexible, material high temperature
Residence time is short, process environments are friendly, cost of investment is low, residence time of the material in uniaxially or biaxially continuous polymerization reactor
Within 50min, material residence time in a high temperauture environment is effectively shortened.
The present invention is turned using the uniaxially or biaxially continuous polymerization reactor with self-cleaning function as consersion unit by screw rod
The control of speed, temperature condition and pressure provides reaction compartment appropriate and residence time for synthetic reaction, and then solves reaction
Conversion ratio is low and the disengaging problem of reactive component.In addition, under the action of the axis body with self-cleaning function, using reactor outside
The methods of circulatory mediator forced heat-exchanging, solves the problems, such as mass-and heat-transfer, to solve the problems, such as cruelly poly-.
The present invention is rotated material dispersion and is sheared by screw axis body, thins, and is kept material molecular weight distribution reasonable, is mentioned
Mixing uniformity between high reactive component makes it carry out heat exchange with barrel wall, axis outer wall in time, while whole process connects
It is continuous, reduce residence time of material, and then reduce the possibility of heat localization, reduce the temperature gradient of storeroom, solves this
The reaction heat control problem of body polymerization, finally realizes product and continuously squeezes out during the reaction and produce high cleanliness
PMMA。
Detailed description of the invention
Fig. 1 is shown as the structural schematic diagram of production system of the present invention.
Fig. 2 is shown as the graph of relation of PMMA sample delivery time and voltage output value made from the embodiment of the present invention 1.
Fig. 3 is shown as PMMA molecular weight analyte test result figure made from the embodiment of the present invention 1.
Fig. 4 is shown as the graph of relation of PMMA sample delivery time and voltage output value made from the embodiment of the present invention 2.
Fig. 5 is shown as PMMA molecular weight analyte test result figure made from the embodiment of the present invention 2.
Fig. 6 is shown as the graph of relation of PMMA sample delivery time and voltage output value made from the embodiment of the present invention 3.
Fig. 7 is shown as PMMA molecular weight analyte test result figure made from the embodiment of the present invention 3.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
As shown in Figure 1, a kind of optical grade PMMA continuous bulk polymerization production system, including sequentially connected blending tank, list
Axis or twin shaft continuous polymerization reactor, Devolatilization device.
In the present embodiment, it is equipped with storage tank between blending tank and uniaxially or biaxially continuous polymerization reactor, is made in blending tank
The material obtained enters storage tank and is stored, and guarantees that production is carried out continuously, is not in the situation of upstream material insufficient supply.
Metering device is equipped between storage tank and uniaxially or biaxially continuous polymerization reactor, metering device can be quality stream
Meter, volume flowmeter etc., metering device are connect with uniaxially or biaxially continuous polymerization reactor, realize the accurate conveying of material,
So that stable production process carries out, product quality is influenced due to will not be excessive or too small because of inlet amount.
Blending tank is that atomizing or stirring-type blending tank, blending tank are sufficiently mixed material, is stirred material mixed
It is even, it is convenient for subsequent polymerization process.
Devolatilization device is specifically as follows uniaxial evaporator, twin shaft evaporator, single screw extrusion machine, double screw extruder etc.,
Realize that the devolatilization to material is handled.
The embodiment for carrying out PMMA production using above-mentioned production system is as follows:
Embodiment 1
A kind of production optical grade PMMA continuous bulk polymerization process, includes the following steps: reactive component methacrylic acid
Methyl esters (i.e. MMA), initiator, auxiliary agent are mixed into mixed solution according to the ratio, and the raw material of mixed solution includes (by weight): methyl
100 parts of methyl acrylate, 1 part of di-t-butyl peroxide, 1 part of lauryl mercaptan.When mixing, temperature control is at 87 DEG C hereinafter, by each raw material
It being sufficiently mixed in investment atomizing blending tank, mixed solution is directed into material storage kettle by blending tank and is stored, then passes through metering device,
Mixed solution is injected into have been subjected in the qualified uniaxial continuous polymerization reactor system of nitrogen displacement and carries out polymerization reaction and company
Continuous to squeeze out, in reaction process, the screw speed of uniaxial continuous polymerization reactor is 60rpm, uniaxial continuous polymerization reactor it is anti-
Answer the indoor pressure control of chamber in 3.0MPa, at 90 DEG C~100 DEG C, extruding zone temperature is controlled in 120- the control of conversion zone temperature
135 DEG C, the PMMA material of extrusion passes through a twin shaft evaporator devolatilization, the control of devolatilization temperature at 160 DEG C, pressure control-
0.099MPa obtains PMMA glue material after extrusion, closed can be granulated into granulating working procedure.The present embodiment devolatilization is made
Conversion rate of products be 87%, conversion ratio refers to that the weight of PMMA material made from devolatilization accounts for the percentage of raw material MMA weight.
Embodiment 2
A kind of production optical grade PMMA continuous bulk polymerization process, includes the following steps: reactive component methacrylic acid
Methyl esters (i.e. MMA), initiator, auxiliary agent are mixed into mixed solution according to the ratio, and the raw material of mixed solution includes (by weight): methyl
100 parts of methyl acrylate, 1/2 part of di-t-butyl peroxide, 1/2 part of lauryl mercaptan.When mixing, temperature control is at 80 DEG C hereinafter, by each
It is sufficiently mixed in raw material investment atomizing blending tank, mixed solution is directed into material storage kettle by blending tank and is stored, then passes through metering
Mixed solution is injected into the uniaxial continuous polymerization reactor system for having been subjected to nitrogen displacement qualification and carries out polymerization reaction by device
And continuously squeeze out, in reaction process, the screw speed of uniaxial continuous polymerization reactor is 45rpm, uniaxial continuous polymerization reactor
The control of reaction chamber indoor pressure in 0.3MPa, at 120~130 DEG C, extruding zone temperature is controlled 130 the control of conversion zone temperature
~140 DEG C, the PMMA material of extrusion passes through a twin shaft evaporator devolatilization, the control of devolatilization temperature at 160 DEG C, pressure control-
0.099MPa obtains PMMA glue material after extrusion, closed can be granulated into granulating working procedure.The present embodiment devolatilization is made
Conversion rate of products be 90%.
Embodiment 3
A kind of production optical grade PMMA continuous bulk polymerization process, includes the following steps: reactive component methacrylic acid
Methyl esters (i.e. MMA), initiator, auxiliary agent are mixed into mixed solution according to the ratio, and the raw material of mixed solution includes (by weight): methyl
100 parts of methyl acrylate, 1/2 part of di-t-butyl peroxide.When mixing, temperature control is at 85 DEG C hereinafter, each raw material is put into atomizing
It is sufficiently mixed in blending tank, mixed solution is directed into material storage kettle by blending tank and is stored, then by metering device, by mixed solution
It is injected into have been subjected to and carries out polymerization reaction in the qualified uniaxial continuous polymerization reactor system of nitrogen displacement and continuously squeeze out, react
In the process, the screw speed of uniaxial continuous polymerization reactor is 50rpm, the indoor pressure of the reaction chamber of uniaxial continuous polymerization reactor
Power control is in 0.95MPa, and at 230 DEG C~240 DEG C, extruding zone temperature is controlled at 220 DEG C~240 DEG C the control of conversion zone temperature, squeezes
PMMA material out passes through a twin shaft evaporator devolatilization, and the control of devolatilization temperature at 180 DEG C, squeeze in -0.099MPa by pressure control
PMMA glue material is obtained after out, closed can be granulated into granulating working procedure.The conversion of product made from the present embodiment devolatilization
Rate is 92%.
The present invention uses high-purity MMA, such as MMA used to be not up to purity requirement, should purify in advance through rectification and purification device
After use, MMA material purity of the invention be 99.995%.
The following table 1 is the datagram for extracting sample from the product after devolatilization in three embodiments and being detected.
Table 1
In conjunction with table 1, Fig. 2 to Fig. 7, it can be seen that comparative example 1 and 2, as initiator and promoter addition are reduced,
Melt mass flow rate reduces, and weight average molecular weight increases to 105093g/mol from 48966g/mol；Comparative example 2 and 3,
With the reduction of auxiliary agent, weight average molecular weight, which increases to 165810g/mol, initiator and auxiliary agent, has direct shadow to weight average molecular weight
It rings.
Abscissa, the ordinate of Fig. 2, Fig. 4, Fig. 6 respectively represent time (min), voltage output value (mV), indicate material from
Delivery time and corresponding voltage in pillar, transverse and longitudinal coordinate pass through Logarithmic calculation again and obtain molecular weight Mn, Mw, Mz.
In conclusion the bulk polymerization mode that uses of the present invention have very pure polymer, free from admixture, solvent-free recycling,
The advantages that low energy consumption, pollution-free, for this method by the axis body of a screw with self-cleaning function element, rotation and shearing will
Material dispersion thins, and so that it is carried out heat exchange with barrel wall, axis outer wall in time, while entire reaction process is carried out continuously, and is reduced
Residence time of material, and then reduce the possibility of heat localization.Present invention process is simple, the polymer of synthesis is pure, replacement produces
Product are flexibly, material high-temperature residence time is short, process environments are friendly, cost of investment is low, and material is anti-in uniaxially or biaxially continuous polymerization
It answers the residence time in device within 50min, effectively shortens material residence time in a high temperauture environment.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (5)
1. a kind of optical grade PMMA continuous bulk polymerization process, which comprises the steps of: reaction raw materials are mixed,
Mixed solution is obtained, is injected after metering in continuous polymerization reactor and is carried out polymerization reaction and continuously squeeze out, devolatilization is handled after extrusion,
PMMA solid material is made, the continuous polymerization reactor is rotated material dispersion and sheared by screw axis body, thins, described
Screw speed≤120rpm of continuous polymerization reactor；By weight, the composition of the reaction raw materials are as follows: methyl methacrylate
100 parts, 0.5~1 part of initiator, 0.5~1 part of auxiliary agent；The initiator is di-t-butyl peroxide, and the auxiliary agent is 12 sulphur
Alcohol.
2. optical grade PMMA continuous bulk polymerization process according to claim 1, it is characterised in that: the continuous polymerization is anti-
The conversion zone temperature for answering device is 90 DEG C~240 DEG C, and extruding zone temperature is 90 DEG C~240 DEG C.
3. optical grade PMMA continuous bulk polymerization process according to claim 1, it is characterised in that: the continuous polymerization is anti-
The cavity indoor pressure for answering device is 0-3MPa.
4. optical grade PMMA continuous bulk polymerization process according to claim 1, it is characterised in that: first to described before reaction
It is passed through nitrogen in continuous polymerization reactor or argon gas carries out deoxygenation, the continuous polymerization reactor is uniaxially or biaxially continuous polymerization
Reactor.
5. optical grade PMMA continuous bulk polymerization process according to claim 1, it is characterised in that: the temperature of mixed solution
Control is at 90 DEG C hereinafter, the control of devolatilization temperature is at 160-180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610905726.9A CN106398073B (en) | 2016-10-18 | 2016-10-18 | A kind of optical grade PMMA continuous bulk polymerization process and its production system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610905726.9A CN106398073B (en) | 2016-10-18 | 2016-10-18 | A kind of optical grade PMMA continuous bulk polymerization process and its production system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106398073A CN106398073A (en) | 2017-02-15 |
| CN106398073B true CN106398073B (en) | 2019-02-05 |
Family
ID=58013517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610905726.9A Expired - Fee Related CN106398073B (en) | 2016-10-18 | 2016-10-18 | A kind of optical grade PMMA continuous bulk polymerization process and its production system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106398073B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023564B (en) * | 2022-12-30 | 2024-06-04 | 南京大学 | Continuous bulk polymerization method of polymethyl methacrylate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751070A (en) * | 2003-02-14 | 2006-03-22 | 利斯特股份公司 | Method for carrying out a mass polymerisation |
| CN101031592A (en) * | 2004-09-30 | 2007-09-05 | 利斯特股份公司 | Method for the continuous implementation of polymerisation processes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3395291B2 (en) * | 1993-11-05 | 2003-04-07 | 住友化学工業株式会社 | Method for producing methacrylic polymer |
| JP3289627B2 (en) * | 1996-12-26 | 2002-06-10 | 住友化学工業株式会社 | Method for producing methyl methacrylate polymer |
| CN102336864B (en) * | 2011-06-16 | 2013-03-20 | 中国科学院长春应用化学研究所 | Preparation method for polymethyl methacrylate (PMMA) resin with high thermal stability |
| CN206089531U (en) * | 2016-10-18 | 2017-04-12 | 重庆世纪之光科技实业有限公司 | Continuous bulk polymerization production system of optics level PMMA |
-
2016
- 2016-10-18 CN CN201610905726.9A patent/CN106398073B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751070A (en) * | 2003-02-14 | 2006-03-22 | 利斯特股份公司 | Method for carrying out a mass polymerisation |
| CN101031592A (en) * | 2004-09-30 | 2007-09-05 | 利斯特股份公司 | Method for the continuous implementation of polymerisation processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106398073A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100547022C (en) | The preparation method of starch and polyvinyl alcohol thermoplastic material | |
| CN100402567C (en) | Preparation method of graft starch | |
| WO2020143208A1 (en) | Method and device for directly preparing foamed polylactic acid article using polylactic acid polymer melt | |
| CN102702661B (en) | Antioxidant polypropylene compatilizer and preparation method and application thereof | |
| CN102152568B (en) | Non-adhesive polyethylene protective film and preparation method thereof | |
| CN104356640B (en) | The preparation method of polyacrylate compound particle for nylon 6 low temperature toughening modifyings | |
| CN103570881A (en) | Polyacrylate grafted vinyl chloride composite resin and preparation method thereof | |
| CN103540020B (en) | A kind of Production method of lithium ion battery barrier membrane homo-polypropylene special material | |
| CN104693636A (en) | A polymerization method capable of increasing an ABS grafted copolymer conversion ratio | |
| CN106398073B (en) | A kind of optical grade PMMA continuous bulk polymerization process and its production system | |
| CN115646395B (en) | System and method for producing aramid fiber slurry by multi-device combined continuous polymerization | |
| CA2661231C (en) | Recirculation loop reactor bulk polymerization process | |
| CN105622850A (en) | Efficient and environment-friendly preparation method of double-monomer solid-phase grafted PP (polypropylene) | |
| CN109316979B (en) | Continuous preparation method of high-compactness polystyrene cation exchange membrane | |
| CN110055030A (en) | A kind of preparation method of hot melt adhesive | |
| CN201960730U (en) | Serial type extruder | |
| CN104448112B (en) | The nylon 6 low temperature toughening modifying preparation method of functionalization poly acrylate composite emulsion | |
| CN104817793B (en) | A kind of PVC base wood-plastic composite material and preparation method thereof | |
| CN206089531U (en) | Continuous bulk polymerization production system of optics level PMMA | |
| CN104559846A (en) | Normal-temperature non-viscous sealing adhesive for lithium battery and preparation method for sealing adhesive | |
| CN105670524B (en) | The preparation method of high quality heat melten gel breathable films | |
| CN105126630B (en) | The preparation method of the homogeneous anions and canons exchange membrane of continuous production polyvinyl chloride half | |
| CN103223305A (en) | Polystyrene/polyvinylidene fluoride quaternary ammonium type anion exchange alloy film preparation method | |
| CN109289547A (en) | A kind of continuous preparation method of polystyrene/Kynoar amberplex | |
| CN104558388B (en) | Continuous bulk polymerization method of medicinal polyacrylic resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190205 Termination date: 20211018 |