CN107189059A - A kind of polyamide solid phase thickening control ball and application - Google Patents
A kind of polyamide solid phase thickening control ball and application Download PDFInfo
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- CN107189059A CN107189059A CN201710469698.5A CN201710469698A CN107189059A CN 107189059 A CN107189059 A CN 107189059A CN 201710469698 A CN201710469698 A CN 201710469698A CN 107189059 A CN107189059 A CN 107189059A
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- polyamide
- control ball
- blade
- solid phase
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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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
- C08G69/06—Solid state polycondensation
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- 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
- Y02P20/141—Feedstock
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Polyamides (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to technical field of polymer preparation, a kind of polyamide solid phase thickening control ball and application are disclosed.The control ball is linked together by one end, the other end is constituted in three dimensions in the blade of spherical diverging, the blade with mesh-structured top layer, inner filter screen layer and inner space from outside to inside successively by constituting, the inner space loads inorganic particle, the seepage that the achievable gas of inner filter screen layer passes through prevention inorganic particle simultaneously.The control ball blade of the present invention can be that solid-state polyamide or copolyamide section provide separate layer, and promote the polyamide or copolyamide that stir in energy, control ball of section to cut into slices along blade movement in dynamic, so as to strengthen the upset of section；It can be adsorbed simultaneously by the inorganic particle in blade, beneficial to the spilling of steam in polyamide or copolyamide section, realize the effect of reinforcing stirring, and then slowly release sour gas, so as to promote the progress of solid-phase tack producing process.
Description
Technical field
The invention belongs to technical field of polymer preparation, and in particular to a kind of polyamide solid phase thickening control ball and application.
Background technology
Polyamide (PA is commonly called as nylon), since being developed by du pont company from 1930s and realize industrialization,
Existing more than 70 years history.There is hydrogen bond between polyamide molecule, imparting polyamide has preferably affine make to numerous materials
With and good cohesive force act on, it is high-strength wearable, self-lubricating, oil resistant, resistance to while polyamide also has an excellent mechanical property
The premium properties such as chemicals, therefore polyamide can be used as fiber, it is also possible to make engineering plastics, be industrially widely used
Prospect.In order to obtain more preferable mechanical performance, generally require to increase the molecular weight of polymer by certain mode, so as to the greatest extent may be used
Polymer molecular chain tail end ratio can be reduced, so as to realize the acquisition of HMW (high viscosity) polyamide raw materials.
In the polycondensation process of polyamide, the dwell time in extension polymerization later stage can be directly realized by carrying for polymer molecular weight
Rise, but cause the discharge of high bondable polyamide in the molten state difficult.Accordingly, it would be desirable to realize high viscosity by other approach
The preparation of polyamide section.Solid phase polycondensation is conventional effective ways.
Solid phase polycondensation (SSP) is the polycondensation reaction carried out in the solid state, early in the 1930s, Flory is just sent out
The polyamide now obtained by melt polycondensation maintains certain temperature to may continue to occur polycondensation reaction in the solid state.With research
Deepen continuously, people have been able to by solid phase polycondensation obtain high-quality, high-performance, high relative molecular mass polymer, especially
It is the polycondensation process for very high or easily decomposes more than the fusing point monomer of those fusing points, and heat-resistant polymer, Gu
Phase polycondensation is even more important polymerization.Solid phase polycondensation is that the relatively low performed polymer of monomer or molecular weight is heated into glass transition
More than temperature, the process of polycondensation reaction is carried out below fusing point.Now macromolecular chain is still in by fixed state, and end function
Group then obtains enough activity, and by spreading adjacent to each other and reacting, the small molecule by-product of generation is then by means of true
Empty or inert gas takes reaction system out of, so as to promote polycondensation reaction forward direction progress, improves constantly molecular weight of product, finally obtains
Obtain highly viscous copolymer.The characteristics of solid phase polycondensation, is as follows：(1) reaction temperature is substantially reduced, and accessory substance and degradation reaction are obvious
Reduce.(2) relative molecular mass of polymer can be significantly improved, so as to improve its mechanical property.(3) solid phase polycondensation temperature compared with
It is low, and avoid the stirring of high viscous melt so that whole polycondensation process energy consumption reduction.(4) solid phase polycondensation need not use molten
Agent, is a kind of environment-friendly polymerisation.(5) polymerization technique is simple, flexible；Polymerization methodses can be operated continuously, also can between
Have a rest operation.(6) reacting balance, and high pressure is not required, low is required to equipment and materials.
During solid-phase tack producing, effective abjection of small molecule can be such that polycondensation reaction is carried out to the direction of polymerization, therefore, more
Beneficial to the lifting for promoting solid-phase tack producing effect.Therefore in actual industrialization production, polyamide section to be viscosified often is in one
Fixed motion state.In addition, according to polyamide Condensation polymerization mechanism, sour environment is beneficial to the progress of polycondensation, therefore, suitably improves polycondensation
The pH value atmosphere of environment is also beneficial to the lifting of solid-phase tack producing effect.
The industrial solid-phase tack producing process that carries out often is carried out in rotatory vacuum rotary drum (vacuum drier), with vacuum drum
Rotation, realize section turns motion, beneficial to the abjection of the small molecule produced by polycondensation, so as to realize thickening process.But only
Only by the turning effort of vacuum drum, the eliminating efficiency and Efficient Adhesive Promotion of small molecule are needed to be further improved.
The content of the invention
In place of the shortcoming and defect existed for above prior art, primary and foremost purpose of the invention is to provide a kind of polyamides
Amine solid-phase tack producing control ball.
Another object of the present invention is to provide above-mentioned solid phase to viscosify control ball in polyamide or copolyamide solid-phase tack producing
In application.
The object of the invention is achieved through the following technical solutions：
A kind of polyamide solid phase viscosifies control ball, is linked together by one end, and the other end is in spherical hair in three dimensions
Scattered blade is constituted, and the blade is from outside to inside successively by with mesh-structured top layer, inner filter screen layer and inner space structure
Into the inner space loads inorganic particle, the seepage that the achievable gas of inner filter screen layer passes through prevention inorganic particle simultaneously.
Preferably, the quantity of the blade is 3~12.
Preferably, the blade is willow foliation structure, and length of blade a is not less than width b, and wherein a, b span are
0.5~20mm, blade twist angular range is 10~65 °.
Preferably, it is described have mesh-structured top layer be that mesh density is 50 with mesh-structured stainless steel layer~
800 mesh, mesh is circular, ellipse or rectangle, and mesh diameter or length and width scope are 0.2~2.0mm.The stainless steel includes
But be not limited to 301 stainless steels, it is 302 stainless steels, 304 stainless steels, 309 stainless steels, 316 stainless steels, 321 stainless steels, 440 stainless
Steel.
Preferably, inner filter screen layer is heat-resistant polymer filter mesh layer, and heat-resistant polymer filter mesh layer is included but not
The grammes per square metre for being limited to individual layer or two layers and the above is 40g/m2~300g/m2Polyphenylene sulfide non-woven fabrics or woven cloth, polyacrylonitrile
Non-woven fabrics or woven cloth.
Preferably, the inorganic particle includes but is not limited to citric anhydride, disodium hydrogen phosphate, sodium dihydrogen phosphate.Inorganic particulate
Grain realizes that the slow release of acid ingredient overflows after moisture is absorbed with the evaporation of moisture.
Above-mentioned solid phase viscosifies application of the control ball in polyamide or copolyamide solid-phase tack producing, and the application process is：
After control ball is directly mixed with polyamide or the copolyamide section for needing to viscosify, enter into batch (-type) solid-phase tack producing device
Row solid state polycondensation, obtains high bondable polyamide or copolyamide.
The control ball of the present invention has the following advantages that and beneficial effect：
The control ball blade of the present invention can be that solid-state polyamide or copolyamide section provide separate layer, and promote in dynamic
Polyamide or the copolyamide section entered in the upset of section, control ball are moved along blade, so as to strengthen the upset of section；
It can be adsorbed simultaneously by the inorganic particle in blade, it is real beneficial to the spilling of steam in polyamide or copolyamide section
Now strengthen the effect of stirring, and then slowly release sour gas, so as to promote the progress of solid-phase tack producing process.
Brief description of the drawings
Fig. 1 is the three-view diagram (a of polyamide solid phase thickening control ball in embodiment 5：Front view；B left views；c：Overlook
Figure)；
Fig. 2 is the structural representation (a of polyamide solid phase thickening control ball willow leaf shape structure blade in embodiment 5：Profile
Figure；b：Internal structure schematic diagram).
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of polyamide solid phase thickening control ball of the present embodiment, is linked together by one end by center spheroid, another
Hold and constituted in three dimensions in 3 willow leaf shape structure blades of spherical diverging, length of blade a is 20mm, width b is 10mm,
Blade twist angle is 30 °.The blade and center spheroid are by with mesh-structured top layer, inner filter screen layer and inner space
Constitute.Top layer is using No. 301 stainless steel layers, and mesh density is 800 mesh, and the diameter of circular mesh is 0.2mm.Blade it is interior
Layer uses polyphenylene sulfide non-woven fabrics as high temperature resistant non-woven fabrics filter mesh layer, and the grammes per square metre of nonwoven cloth material is 300g/m2；The inside
Space uses sodium dihydrogen phosphate as inorganic particle, absorbs the slow release for realizing acid ingredient after moisture with the evaporation of moisture
Overflow.The seepage that the achievable gas of inner filter screen layer passes through prevention inorganic particle simultaneously.
The control ball of the present embodiment is used for batch process and prepares high viscous copolyamide 6/66, by control ball directly with needing thickening
Copolyamide 6/66 section mixing after, carry out solid state polycondensation into batch (-type) solid-phase tack producing device, obtain high adhesive aggregation
Acid amides or copolyamide.As a result the viscosity of copolyamide 6/66 relative viscosity in 165 DEG C of vacuum rotating dryer drums is shown
It it is 16~24 hours from 2.8 times for increasing to 4.0.Control ball is not added to realize under same dried equipment, drying temperature together
The time of sample Efficient Adhesive Promotion is 32~40 hours.
Embodiment 2
A kind of polyamide solid phase thickening control ball of the present embodiment, is linked together by one end by center spheroid, another
Hold and constituted in three dimensions in 12 willow leaf shape structure blades of spherical diverging, length of blade a is 0.5mm, and width b is
0.5mm, blade twist angle is 10 °.The blade and center spheroid are by with mesh-structured top layer, inner filter screen layer and interior
Portion space is constituted.Top layer is using No. 304 stainless steel layers, and mesh density is 50 mesh, and the major diameter of oval mesh is 1.0mm,
Minor axis diameter is 0.4mm.The internal layer of blade uses two layers of polypropylene nitrile non-woven fabrics as high temperature resistant nonwoven layer filter screen, non-woven fabrics
The grammes per square metre of material is 40g/m2；Using disodium hydrogen phosphate and sodium dihydrogen phosphate, (quality proportioning is 1 for the inner space:1) conduct
Inorganic particle, absorbs and realizes that the slow release of acid ingredient overflows after moisture with the evaporation of moisture.Inner filter screen layer can be achieved
The seepage that gas passes through prevention inorganic particle simultaneously.
The control ball of the present embodiment prepares high bondable polyamide 66 for batch process, by control ball directly with needing what is viscosified to gather
After the section mixing of acid amides 66, solid state polycondensation is carried out into batch (-type) solid-phase tack producing device, high bondable polyamide is obtained or common
Polyamide.As a result show that the viscosity of the polyamide 66 relative viscosity in 245 DEG C of vacuum rotating dryer drums increases to from 2.8
4.0 time is 18~24 hours.Control ball is not added, and same Efficient Adhesive Promotion is realized under same dried equipment, drying temperature
Time is 32~40 hours.
Embodiment 3
A kind of polyamide solid phase thickening control ball of the present embodiment, is linked together by one end by center spheroid, another
Hold and constituted in three dimensions in 12 willow leaf shape structure blades of spherical diverging, length of blade a is 20mm, width b is 15mm,
Blade twist angle is 45 °.The blade and center spheroid are by with mesh-structured top layer, inner filter screen layer and inner space
Constitute.Top layer is 600 mesh using No. 302 stainless steel layers, mesh density, and the length and width of quadratic mesh is divided into 2.0mm and 0.5mm.Leaf
The internal layer of piece uses polyphenylene sulfide longitude and latitude woven cloth as high temperature resistant filter mesh layer, and the grammes per square metre of braiding cloth material is 250g/m2；It is described
Inner space uses sodium dihydrogen phosphate as inorganic particle, absorbs and realizes the slow of acid ingredient after moisture with the evaporation of moisture
The property released is overflowed.The seepage that the achievable gas of inner filter screen layer passes through prevention inorganic particle simultaneously.
The control ball of the present embodiment is used for batch process and prepares high viscous copolyamide 6/66/10, by control ball directly with needs
After the section mixing of copolyamide 6/66/10 of thickening, solid state polycondensation is carried out into batch (-type) solid-phase tack producing device, is obtained
High bondable polyamide or copolyamide.As a result show the viscosity of copolyamide 6/66/10 in 230 DEG C of vacuum rotating dryer drums
Relative viscosity is 16~24 hours from 2.8 times for increasing to 4.0.Control ball is not added in same dried equipment, drying temperature
The lower time for realizing same Efficient Adhesive Promotion will be 32~40 hours.
Embodiment 4
A kind of polyamide solid phase thickening control ball of the present embodiment, is linked together by one end by center spheroid, another
Hold and constituted in three dimensions in 8 willow leaf shape structure blades of spherical diverging, length of blade a is 16mm, and width b is
10.8mm, blade twist angle is 60 °.The blade and center spheroid by with mesh-structured top layer, inner filter screen layer and
Inner space is constituted.Top layer is using No. 309 stainless steel layers, and mesh density is 400 mesh, and the diameter of circular mesh is 0.8mm.
The internal layer of blade uses two layers of polyphenylene sulfide non-woven fabrics as high temperature resistant nonwoven layer filter screen, and the grammes per square metre of Single layer nonwoven cloth material is
100g/m2；The inner space uses citric anhydride as inorganic particle, and acid is realized with the evaporation of moisture after absorbing moisture
Property composition slow release overflow.The seepage that the achievable gas of inner filter screen layer passes through prevention inorganic particle simultaneously.
The control ball of the present embodiment is used for batch process and prepares high viscous copolyamide 6/12, by control ball directly with needing thickening
Copolyamide 6/12 section mixing after, carry out solid state polycondensation into batch (-type) solid-phase tack producing device, obtain high adhesive aggregation
Acid amides or copolyamide.As a result the viscosity of copolyamide 6/12 relative viscosity in 140 DEG C of vacuum rotating dryer drums is shown
It it is 20~28 hours from 2.8 times for increasing to 4.0.Control ball is not added to realize under same dried equipment, drying temperature together
The time of sample Efficient Adhesive Promotion is 32~40 hours.
Embodiment 5
A kind of polyamide solid phase thickening control ball of the present embodiment, its three-view diagram (a as shown in Figure 1：Front view；B left views
Figure；c：Top view), linked together by one end by center spheroid, the other end is in 10 of spherical diverging in three dimensions
Willow leaf shape structure blade is constituted.The structural representation of the willow leaf shape structure blade (a as shown in Figure 2：Profile diagram；b：Internal junction
Structure schematic diagram), length of blade a is 20mm, and width b is 8mm, and the θ of blade twist angle 2 is 65 °.The blade and center spheroid by
Constituted with mesh-structured top layer, inner filter screen layer and inner space.Top layer is using No. 440 stainless steel layers, mesh density
600 mesh, the diameter of circular mesh is 0.4mm.The internal layer of blade is filtered using polyacrylonitrile longitude and latitude woven cloth as high temperature resistant
Stratum reticulare, the grammes per square metre of braiding cloth material is 240g/m2；The inner space uses sodium dihydrogen phosphate as inorganic particle, absorbs water
Realize that the slow release of acid ingredient overflows after point with the evaporation of moisture.The achievable gas of inner filter screen layer is by preventing simultaneously
The seepage of inorganic particle.
The control ball of the present embodiment prepares high bondable polyamide 6 for batch process, by control ball directly with needing what is viscosified to gather
After the section mixing of acid amides 6, solid state polycondensation is carried out into batch (-type) solid-phase tack producing device, high bondable polyamide or copolymerization is obtained
Acid amides.As a result show that the viscosity of the polyamide 6 relative viscosity in 210 DEG C of vacuum rotating dryer drums increases to 4.0 from 2.8
Time is 16~24 hours.The time that control ball realizes same Efficient Adhesive Promotion under same dried equipment, drying temperature is not added
For 32~40 hours.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of polyamide solid phase viscosifies control ball, it is characterised in that：The control ball is linked together by one end, and the other end exists
Constituted in three dimensions in the blade of spherical diverging, the blade is from outside to inside successively by with mesh-structured top layer, internal layer
Filter mesh layer and inner space are constituted, and the inner space loads inorganic particle, and the achievable gas of inner filter screen layer is by hindering simultaneously
The only seepage of inorganic particle.
2. a kind of polyamide solid phase thickening control ball according to claim 1, it is characterised in that：The quantity of the blade is
3~12.
3. a kind of polyamide solid phase thickening control ball according to claim 1, it is characterised in that：The blade is willow leaf shape
Structure, length of blade a be not less than width b, wherein a, b span be 0.5~20mm, blade twist angular range be 10~
65°。
4. a kind of polyamide solid phase thickening control ball according to claim 1, it is characterised in that：It is described have it is mesh-structured
Top layer be that with mesh-structured stainless steel layer, mesh density is 50~800 mesh, mesh is circular, ellipse or rectangle, net
Bore dia or length and width scope are 0.2~2.0mm.
5. a kind of polyamide solid phase thickening control ball according to claim 1, it is characterised in that：Inner filter screen layer is
The grammes per square metre of individual layer or two layers and the above is 40g/m2~300g/m2Polyphenylene sulfide non-woven fabrics or woven cloth, polyacrylonitrile nonwoven
Cloth or woven cloth.
6. a kind of polyamide solid phase thickening control ball according to claim 1, it is characterised in that：The inorganic particle is lemon
Lemon acid anhydrides, disodium hydrogen phosphate or sodium dihydrogen phosphate.
7. a kind of polyamide solid phase described in any one of claim 1~6 viscosifies control ball in polyamide or copolyamide solid phase
Application in thickening, it is characterised in that the application process is：Polyamide or copolymerization acyl by control ball directly with needing to viscosify
After amine section mixing, solid state polycondensation is carried out into batch (-type) solid-phase tack producing device, high bondable polyamide or copolymerization acyl is obtained
Amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710469698.5A CN107189059B (en) | 2017-06-20 | 2017-06-20 | Polyamide solid-phase tackifying control ball and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710469698.5A CN107189059B (en) | 2017-06-20 | 2017-06-20 | Polyamide solid-phase tackifying control ball and application thereof |
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| Publication Number | Publication Date |
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| CN107189059A true CN107189059A (en) | 2017-09-22 |
| CN107189059B CN107189059B (en) | 2023-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710469698.5A Active CN107189059B (en) | 2017-06-20 | 2017-06-20 | Polyamide solid-phase tackifying control ball and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293915A (en) * | 2018-10-25 | 2019-02-01 | 广东新会美达锦纶股份有限公司 | A kind of high viscous copolymer nylon and preparation method thereof |
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| CN102391489A (en) * | 2011-09-01 | 2012-03-28 | 大连海新工程技术有限公司 | Reactor integrating stirring, preheating and solid-phase viscosity increasing of polyester |
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| CN207031319U (en) * | 2017-06-20 | 2018-02-23 | 华南理工大学 | A kind of polyamide solid phase viscosifies control ball |
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| US3816369A (en) * | 1971-11-08 | 1974-06-11 | Ici Ltd | Process for the preparation of polyamides with alkali metal dihydrogen orthophosphate as catalyst |
| JP2010215682A (en) * | 2009-03-13 | 2010-09-30 | Mitsubishi Gas Chemical Co Inc | Method for solid state polymerization of polyamide |
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| CN109293915B (en) * | 2018-10-25 | 2020-12-11 | 广东新会美达锦纶股份有限公司 | High-viscosity copolymerized nylon and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN107189059B (en) | 2023-05-09 |
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