CN107325291A - A kind of method of continuous production polyetheramide elastomeric body - Google Patents
A kind of method of continuous production polyetheramide elastomeric body Download PDFInfo
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- CN107325291A CN107325291A CN201710674755.3A CN201710674755A CN107325291A CN 107325291 A CN107325291 A CN 107325291A CN 201710674755 A CN201710674755 A CN 201710674755A CN 107325291 A CN107325291 A CN 107325291A
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- elastomeric body
- continuous production
- polyetheramide elastomeric
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to a kind of method of continuous production polyetheramide elastomeric body, pre-polymerization and the polymerisation of continuous production polyetheramide elastomeric body are carried out using the prepolymerization kettle and several disk reactors of series connection, by low molecular polyamides, polyethers, catalyst in mass ratio 100:20~600:0.1 ~ 0.5 is continuously introduced into prepolymerization kettle and is well mixed, and is then polymerize again in disk reactor, and the pressure in disk reactor is 0.09Mpa ~ 0.1Mpa, and polymerization reaction time is 1 ~ 4h, and reaction temperature is 220 ~ 260 DEG C.Present invention process method is simple, and step is easily operated, and polyetheramide elastomeric body is produced using continuous process, and production efficiency is high, and the reaction time is short, and product quality is stable, and the polyetheramide elastomeric body of production has a wide range of application.
Description
Technical field
The present invention relates to a kind of method of continuous production polyetheramide elastomeric body, belong to technical field of polymer preparation.
Background technology
Polyetheramides analog thermoplastic elastomer is a kind of block copolymer, be by dystectic crystallinity polyamide hard section and
Amorphism or amorphous polyester or polyester soft segment composition.Their chemical composition, fragment length and between ratio determine
The physics and chemical property of such material.Polyamide elastomer intensity is high, high, the elastic good, proportion of toughness is low, resist bending is tired
Performance is good, anti-wear performance is good, low temperature performance well, can be widely applied to automobile, sporting goods, medical supplies, seal, machine
In terms of tool parts.
The production method of current polyetheramide elastomeric body is largely Batch Process.No matter one-step method or two-step method, all
It is that material is placed in batch reactor, polyetheramide elastomeric body is obtained by certain reaction time.In industrialized production
In, the shortcoming of Batch Process is it is clear that the production efficiency such as Batch Process is relatively low, and quality fluctuation is larger between batch.Poly-
Need to try one's best the small molecule in system in ether amide production process and remove clean and obtain HMW.The reactor of batch (-type)
Gas liquid interfacial area is smaller, and the removing of small molecule is difficult, in order to obtain the polyetheramide elastomeric body of HMW, it is necessary to for a long time
Reaction time, which increase the possibility of material thermal degradation in reactor, cause the property of the polyetheramide elastomeric body obtained by production
Can reduction.In order to obtain higher production efficiency and stable quality, it is necessary to develop the production technology of serialization.
The content of the invention
The invention aims to solve the above problems, there is provided a kind of side of continuous production polyetheramide elastomeric body
Method, shortens the production time, improves the quality of product.
The present invention is adopted the following technical scheme that：A kind of method of continuous production polyetheramide elastomeric body, using series connection
Prepolymerization kettle and several disk reactors carry out pre-polymerization and the polymerisation of continuous production polyetheramide elastomeric body, including as follows
Step：
（1）Pre-polymerization：By low molecular polyamides, polyethers, catalyst in mass ratio 100:20~600 : 0.1:0.5 is continuously introduced into
In prepolymerization kettle and it is well mixed, prepolymerization kettle is heated up, and carry out preliminary polymerization, the reaction time of material is 30 ~ 60min, instead
200 ~ 230 DEG C of temperature is answered, reaction pressure is 0 ~ -0.08Pa；
（2）Polymerization：The material pump for completing mixing is sent out from prepolymerization kettle, polymerize in feeding disk reactor, disk
Pressure in reactor is -0.09Mpa ~ -0.1Mpa, and polymerization reaction time is 1 ~ 4h, and reaction temperature is 220 ~ 260
℃。
Further, the Versamid is the g/mol of molecular weight 200 ~ 3000 AABB types polyamide or AB types
Polyamide.
Further, the polyethers is the g/mol of molecular weight 200 ~ 3000 hydroxy-end capped polyethers or amino-terminated
Polyethers.
Further, the catalyst is titanium, zirconium, the metal derivative of hafnium or phosphorous atomic compound.
Further, the disk reactor includes two.
Further, the top of the prepolymerization kettle sets exhaust outlet and condensing reflux pipe respectively.
Further, the bottom of the prepolymerization kettle is connected with Melt Pump.
Further, it is provided with 5-10 disk in the disk reactor.
Further, the outside of the prepolymerization kettle and reactor is respectively arranged with chuck, the chuck and is connected with conduction oil.
Pre-polymerization:Prepolymerization kettle is the reactor stirred with high shear ability, and the material that can be will be fed into is mixed in a short time
Close uniform.Material heats up and is sufficiently mixed in prepolymerization kettle, and carries out preliminary polymerization, to improve the compatibility between material.
Polymerization：The material pump for completing to be mixed and heated reaction temperature is sent out from blender, is carried out in feeding reactor
Polymerization.5-10 disk is provided with disk reactor disk, material is divided into cell one by one, phase by two adjacent disks
When in complete mixing flow reactor small one by one, each small chamber lower part is material pond, and top half is gas-phase space.In disk
In rotation process, disk constantly takes the material in the material pond of bottom to upper space, and material forms liquid film on disk, increases
Big gas liquid interfacial area, the resistance of reduction small molecule removing has higher gas liquid interfacial area, and Surface Renewal speed is fast, energy
It is enough readily to discharge the accessory substance of course of reaction, while the equipment of high-viscosity material can be handled.In the course of the polymerization process with
Continue polycondensation reaction between the discharge of small molecule, the polyetheramides of low molecular polyamides, polyethers and low polymerization degree, finally give
Highly viscous polyetheramides, its performance disclosure satisfy that materials'use requirement.
Present invention process method is simple, and step is easily operated, and polyetheramide elastomeric body, production effect are produced using continuous process
Rate is high, and the reaction time is short, and product quality is stable, and the polyetheramide elastomeric body of production has a wide range of application.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
（1）Relative viscosity
Accurate weighing 1g polyamides, are added in 100ml 96% sulfuric acid, in 20-30 DEG C of stirring and dissolving.Completely
After dissolving, take solution to be placed in Ubbelohde viscometer, after 25 DEG C of thermostats are placed 10 minutes, determine decrease speed
(t).In addition, decrease speed (the t of the same sulfuric acid of measure 96%0).According to the following formula by t and t0Calculate relative
Viscosity.
Relative viscosity=t/t0
（2）Mechanical performance
Melted in injection (mo(u)lding) machine, at a temperature of 30 DEG C of the fusing point higher than polyamide, in injection pressure 600kgf/
Obtain being injected into matrix under conditions of cm2, injection time 1.0sec, 40 DEG C of mold temperature.What is obtained is injected into matrix 25
After the annealing that 24 hours are implemented at DEG C, tests below has been carried out in the state of adiabatic drying.
Tensile strength, elongation at break are determined by ISO527-2 methods.
Embodiment 1：
A kind of method of continuous production polyetheramide elastomeric body, is connected using the prepolymerization kettle of series connection and two disk reactors
The pre-polymerization of continuous metaplasia production polyetheramide elastomeric body and polymerisation；
Low molecular polyamides PA610, molecular weight 1000, the kg/hr of flow 10；Polytetrahydrofuran diol, molecular weight 600, flow
6 kg/hr；Catalyst butyl titanate, the g/hr of flow 20.
Reactor operating condition：
Prepolymerization kettle：220 DEG C of reaction temperature, pressure normal pressure, 1 hour residence time.
First disk reactor：8 disks, 240 DEG C of reaction temperature, pressure 2000Pa, during stop are provided with reactor
Between 1 hour.
Second disk reactor：5 disks, 250 DEG C of reaction temperature, pressure 200Pa, during stop are provided with reactor
Between 1 hour.
The relative viscosity 1.2 of polyetheramide elastomeric body.Tensile strength 30Mpa, elongation at break 500%.
Embodiment 2：
A kind of method of continuous production polyetheramide elastomeric body, is connected using the prepolymerization kettle of series connection and two disk reactors
The pre-polymerization of continuous metaplasia production polyetheramide elastomeric body and polymerisation；
Low molecular polyamides PA1010, molecular weight 1000, the kg/hr of flow 10；Polytetrahydrofuran diol, molecular weight 1000, stream
Measure 10 kg/hr；Catalyst butyl titanate, the g/hr of flow 20.
Prepolymerization kettle：220 DEG C of reaction temperature, pressure normal pressure, 1 hour residence time.
First disk reactor：8 disks, 240 DEG C of reaction temperature, pressure 2000Pa, during stop are provided with reactor
Between 1 hour.
Second disk reactor：5 disks, 250 DEG C of reaction temperature, pressure 200Pa, during stop are provided with reactor
Between 1 hour.
The relative viscosity 1.4 of obtained polyetheramide elastomeric body.Tensile strength 30Mpa, elongation at break 600%.
Embodiment 3：
A kind of method of continuous production polyetheramide elastomeric body, is connected using the prepolymerization kettle of series connection and two disk reactors
The pre-polymerization of continuous metaplasia production polyetheramide elastomeric body and polymerisation；
Low molecular polyamides PA610, molecular weight 1000, the kg/hr of flow 10；Polytetrahydrofuran diol, molecular weight 600, flow
2 kg/hr；Catalyst butyl titanate, flow 10g/hr.
Reactor operating condition：
Prepolymerization kettle：200 DEG C of reaction temperature, pressure is -0.05Mpa, 1 hour residence time.
First disk reactor：8 disks, 220 DEG C of reaction temperature, pressure 2000Pa, during stop are provided with reactor
Between 1 hour.
Second disk reactor：5 disks, 260 DEG C of reaction temperature, pressure 200Pa, during stop are provided with reactor
Between 4 hours.
The relative viscosity 1.5 of polyetheramide elastomeric body.Tensile strength 30Mpa, elongation at break 500%.
Embodiment 4：
A kind of method of continuous production polyetheramide elastomeric body, is connected using the prepolymerization kettle of series connection and two disk reactors
The pre-polymerization of continuous metaplasia production polyetheramide elastomeric body and polymerisation；
Low molecular polyamides PA1010, molecular weight 1000, the kg/hr of flow 10；Polytetrahydrofuran diol, molecular weight 1000, stream
Measure 60 kg/hr；Catalyst butyl titanate, the g/hr of flow 50.
Prepolymerization kettle：230 DEG C of reaction temperature, pressure is -0.08Mpa, residence time 30min.
First disk reactor：8 disks, 220 DEG C of reaction temperature, pressure 2000Pa, during stop are provided with reactor
Between 4 hours.
Second disk reactor：5 disks, 260 DEG C of reaction temperature, pressure 200Pa, during stop are provided with reactor
Between 1 hour.
The relative viscosity 1.2 of polyetheramide elastomeric body.Tensile strength 26Mpa, elongation at break 1000%.
Claims (9)
1. a kind of method of continuous production polyetheramide elastomeric body, it is characterised in that：Using the prepolymerization kettle of series connection and several
Disk reactor carries out pre-polymerization and the polymerisation of continuous production polyetheramide elastomeric body, comprises the following steps：
（1）Pre-polymerization：By low molecular polyamides, polyethers, catalyst in mass ratio 100:20 ~ 600 :0.1 ~ 0.5 continuously send
Enter in prepolymerization kettle and be well mixed, prepolymerization kettle is heated up, and carry out preliminary polymerization, the reaction time of material is 30 ~ 60min,
200 ~ 230 DEG C of reaction temperature, reaction pressure is 0 ~ -0.08Mpa；
（2）Polymerization：The material pump for completing mixing is sent out from prepolymerization kettle, polymerize in feeding disk reactor, disk
Pressure in reactor is -0.09Mpa ~ -0.1Mpa, and polymerization reaction time is 1 ~ 4h, and reaction temperature is 220 ~ 260
℃。
2. the method for continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The low molecular weight polycaprolactone
Acid amides is the g/mol of molecular weight 200 ~ 3000 AABB types polyamide or AB type polyamide.
3. the device of continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The polyethers is to divide
200 ~ 3000 g/mol of son amount hydroxy-end capped polyethers or amino-terminated polyethers.
4. the device of continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The catalyst is
Titanium, zirconium, the metal derivative of hafnium or phosphorous atomic compound.
5. a kind of method of continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The disk
Reactor includes two.
6. a kind of method of continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The pre-polymerization
The top of kettle sets exhaust outlet and condensing reflux pipe respectively.
7. a kind of method of continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The pre-polymerization
The bottom of kettle is connected with Melt Pump.
8. a kind of method of continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The disk
5-10 disk is provided with reactor.
9. the device of continuous production polyetheramide elastomeric body as claimed in claim 1, it is characterised in that：The prepolymerization kettle and
The outside of reactor is respectively arranged with chuck, the chuck and is connected with conduction oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710674755.3A CN107325291A (en) | 2017-08-09 | 2017-08-09 | A kind of method of continuous production polyetheramide elastomeric body |
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| CN201710674755.3A CN107325291A (en) | 2017-08-09 | 2017-08-09 | A kind of method of continuous production polyetheramide elastomeric body |
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| CN107325291A true CN107325291A (en) | 2017-11-07 |
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| CN201710674755.3A Pending CN107325291A (en) | 2017-08-09 | 2017-08-09 | A kind of method of continuous production polyetheramide elastomeric body |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210076A (en) * | 2019-07-11 | 2021-01-12 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN114149590A (en) * | 2021-12-28 | 2022-03-08 | 无锡殷达尼龙有限公司 | Production process of polyether amide elastomer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208493A (en) * | 1977-12-30 | 1980-06-17 | Ato Chimie | Process for continuous synthesis of poly (ether-ester-amide) sequence copolycondensates |
| US5917000A (en) * | 1998-04-29 | 1999-06-29 | Tsai; J. H. | Manufacturing process of polyether-ester amide elastomer and elastic fiber |
| CN101426833A (en) * | 2006-02-16 | 2009-05-06 | 阿克马法国公司 | Copolymers comprising polyamide blocks and polyether blocks and having improved optical properties |
| CN105175703A (en) * | 2015-10-15 | 2015-12-23 | 宁波浙铁大风化工有限公司 | Equipment for preparing polycarbonate |
-
2017
- 2017-08-09 CN CN201710674755.3A patent/CN107325291A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208493A (en) * | 1977-12-30 | 1980-06-17 | Ato Chimie | Process for continuous synthesis of poly (ether-ester-amide) sequence copolycondensates |
| US5917000A (en) * | 1998-04-29 | 1999-06-29 | Tsai; J. H. | Manufacturing process of polyether-ester amide elastomer and elastic fiber |
| CN101426833A (en) * | 2006-02-16 | 2009-05-06 | 阿克马法国公司 | Copolymers comprising polyamide blocks and polyether blocks and having improved optical properties |
| CN105175703A (en) * | 2015-10-15 | 2015-12-23 | 宁波浙铁大风化工有限公司 | Equipment for preparing polycarbonate |
Non-Patent Citations (2)
| Title |
|---|
| 张洪沅，等: "《化工原理》", 31 August 1991, 成都科技大学出版社 * |
| 张瑞平，等: "《聚酯生产设备》", 31 May 1991, 东南大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210076A (en) * | 2019-07-11 | 2021-01-12 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN112210076B (en) * | 2019-07-11 | 2023-08-15 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN114149590A (en) * | 2021-12-28 | 2022-03-08 | 无锡殷达尼龙有限公司 | Production process of polyether amide elastomer |
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Application publication date: 20171107 |