CN116535641A - Block type polyester amide and preparation method thereof - Google Patents
Block type polyester amide and preparation method thereof Download PDFInfo
- Publication number
- CN116535641A CN116535641A CN202310508935.XA CN202310508935A CN116535641A CN 116535641 A CN116535641 A CN 116535641A CN 202310508935 A CN202310508935 A CN 202310508935A CN 116535641 A CN116535641 A CN 116535641A
- Authority
- CN
- China
- Prior art keywords
- epsilon
- polyester amide
- nylon
- caprolactone
- block type
- 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.)
- Granted
Links
- 229920006149 polyester-amide block copolymer Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 97
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 30
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229960002684 aminocaproic acid Drugs 0.000 claims abstract description 27
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 50
- 230000003197 catalytic effect Effects 0.000 claims description 34
- 239000004677 Nylon Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 28
- 229920001778 nylon Polymers 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims description 6
- 235000013847 iso-butane Nutrition 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical group [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-AZXPZELESA-N 2-methylpropane Chemical group C[13CH](C)C NNPPMTNAJDCUHE-AZXPZELESA-N 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 239000012974 tin catalyst Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- 230000001105 regulatory effect Effects 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 238000010926 purge Methods 0.000 description 23
- 238000001291 vacuum drying Methods 0.000 description 23
- 230000003068 static effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 229920001610 polycaprolactone Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000004632 polycaprolactone Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012661 block copolymerization Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- -1 aryl tin Chemical compound 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000000685 Carr-Purcell-Meiboom-Gill pulse sequence Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- 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
- C08G69/44—Polyester-amides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a block type polyester amide and a preparation method thereof, wherein epsilon-caprolactam and 6-aminocaproic acid are subjected to a prepolymerization reaction to obtain a Pre-PA6 prepolymer; then, dropwise adding epsilon-caprolactone into Pre-PA6 to carry out ring-opening polyaddition polymerization reaction to obtain PEA prepolymer; then adding a tetraphenyl tin catalyst into the PEA prepolymer to carry out coordination ring-opening reaction to obtain the block type polyester amide copolymer. The block type polyester amide material prepared by the invention has the characteristics of stable melting point, low oligomer content and controllable water absorption.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a block type polyester amide and a preparation method thereof
Background
Polyamide (PA), commonly known as Nylon (Nylon), is called Nylon when used as a fiber, and is a polymer having amide bonds in the main chain molecule. Since the last century, the preparation level of polyamide has been rapidly developed, the market demand has been growing, and the polyamide exceeds other five engineering plastics in terms of yield, and the polyamide is an important polymer material essential for our daily life. The polyamide 6 (PA 6) molecular main chain contains repeated amide bonds, has excellent performances of high mechanical strength, good thermal performance, chemical corrosion resistance, easy molding and processing and the like, is an important synthetic fiber and engineering plastic raw material, and has been widely applied to the fields of chemistry and chemical engineering, in particular to the fields of textile or light industry. However, PA6 is easy to absorb water due to the existence of a large number of highly polar amide groups in the molecular main chain, and PA6 has a high melting point, and is insufficient in fluidity and easy to generate warping behavior when preparing a precision electronic device. In addition, PA6 is a petroleum-based polymer material, which is difficult to degrade in natural environment, thus causing serious environmental pollution.
Polycaprolactone (PCL), also known as poly epsilon-caprolactone, is a semi-crystalline, opaque, odorless polymeric material at room temperature. The melting temperature (Tm) is between 50 and 64 ℃, the glass transition temperature (Tg) is near-60 ℃, and the glass transition temperature (Tg) has the advantages of no toxicity, small irritation, good biocompatibility of biology or materials, low-temperature molding processing, biodegradability and the like. Meanwhile, the PCL is hydrophobic aliphatic polyester, and 5 nonpolar methylene and polar ester groups in the repeating units enable the PCL to have a high crystallization rate and a high crystallinity, high elongation at break and good flexibility, and has excellent biocompatibility and biodegradability.
Therefore, the copolyamide (Poly (esteramide), PEA) prepared by copolymerization of caprolactone and caprolactam can combine the advantages and disadvantages of the caprolactone and the caprolactam, improve the fluidity of PA6, reduce the hygroscopicity, effectively improve the water absorbability and the melting point of PCL, endow the material with excellent biocompatibility and degradability, enable the material to have wider and adjustable range performance, expand the application field and the development direction of the material, and be one of the hot fields of polymer chemistry research.
The block copolymers can better retain the characteristics of each block than random copolymers, and their unique inherent properties and combination of properties are of great concern. However, in the process of preparing polyesteramide by the existing method, ester-amide exchange is easy to occur between ester groups and amide groups on a molecular main chain, and polyester amide with regular two-block and three-block structures is difficult to obtain, so that complex microphase separation is caused, and the melting crystallization behavior of a polymer is influenced.
On the other hand, polymers prepared from caprolactam and caprolactone ROP contain active groups at their ends, which "bite" into the ester or amide groups in the middle of the molecular chain, which in turn produces cyclic dimers, cyclic trimers. Fluctuations in the residual oligomer content can even affect the rheological behavior of the polymer during the molding process, resulting in unstable molding processes. Particularly, the aggregation characteristic of the oligomer can induce induced crystallization, a special crystal point is formed in the material, stress concentration easily occurs when the material is stressed, a cracking phenomenon occurs, and the service performance of the material, particularly a precision electronic device, is seriously affected. When used as a separator, dissolution and migration of the oligomer also cause instability of important properties such as conductivity.
Disclosure of Invention
The invention discloses a block type polyester amide and a preparation method thereof, which are used for solving the problems of the existing gear contact fatigue life prediction method.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for preparing block type polyesteramide, comprising the following steps:
step one, carrying out prepolymerization reaction on epsilon-caprolactam and 6-aminocaproic acid to obtain nylon prepolymer;
step two, adding a catalyst into the nylon prepolymer under the anaerobic condition to obtain a double-end catalytic nylon 6 block; the catalyst is phenyltin;
step three, adding epsilon-caprolactone, and carrying out copolymerization reaction on epsilon-caprolactone and a double-end catalytic nylon 6 block to obtain block polyester amide;
the mass ratio of the epsilon-caprolactam to the epsilon-caprolactone is 2-9:1-8; the mass ratio of the 6-aminocaproic acid to the epsilon-caprolactone is 0.2-0.9: 1 to 8.
In the first step, the prepolymerization reaction temperature is 240-250 ℃ and the time is 1-3 h.
In the second step, the copolymerization reaction temperature is 240-250 ℃ and the time is 1-7 h.
Further improving, wherein the addition amount of the catalyst is 1-6wt% of the mass of the nylon prepolymer, and the catalyst is added with the nylon prepolymer and then maintains the prepolymerization reaction temperature for 15-30 min to obtain a double-end catalytic nylon 6 block; the phenyl tin is one or any combination of tetraphenyl tin, triphenyltin and Salen tin, and the structural formula of the Salen tin is as follows:
wherein R is 1 Is 2-methylpropane, R2 is 2-methylpropane or pyridine, and R is phenyl.
The water absorption of the obtained polyester amide gradually decreases with the increase of the mass ratio of epsilon-caprolactone to epsilon-caprolactam, and the water absorption of the polyester amide gradually increases with the decrease of the mass ratio of epsilon-caprolactone to epsilon-caprolactam
Further improvement, the mass ratio of epsilon-caprolactone to epsilon-caprolactam is adjusted according to the water absorption required by the polyester amide, when the polyester amide with lower water absorption is required, the mass ratio of epsilon-caprolactone to epsilon-caprolactam is increased, and when the polyester amide with higher water absorption is required, the mass ratio of epsilon-caprolactone to epsilon-caprolactam is reduced.
Further improvement, the reaction temperature of the prepolymerization reaction is 240-245 ℃, and the prepolymerization reaction time is 2h; the copolymerization reaction temperature is 240-245 ℃ and the time is 1-7 h; the catalyst is tetraphenyl tin, and the addition amount of the catalyst is 1-6wt% of the mass of the nylon prepolymer.
Further improvement, the mass ratio of epsilon-caprolactam, 6-aminocaproic acid and epsilon-caprolactone is 3:0.3:7, preparing a base material; the reaction temperature of the prepolymerization reaction is 240 ℃, and the prepolymerization reaction time is 2 hours; the copolymerization reaction temperature is 240 ℃ and the time is 1h; the catalyst is tetraphenyl tin, and the addition amount of the catalyst is 5 wt% of the mass of the nylon prepolymer.
Further improved, the molecular weight of the nylon 6 prepolymer ranges from 5000 to 8000.
A block type polyester amide prepared by the preparation method of the block type polyester amide according to any one of claims 1 to 8.
Further improved, the melting point of the block type polyester amide is 204-217 ℃, the mass content of the oligomer is 0.5-3.5%, and the water absorption is 2.62-32.23%.
The invention has the advantages that:
the invention provides a preparation method of polyester amide, which comprises the following steps: pre-polymerizing epsilon-caprolactam and 6-aminocaproic acid to obtain nylon 6 prepolymer; adding a catalyst into the prepolymer melt to generate a double-end catalytic nylon 6 block, and then adding epsilon-caprolactone for copolymerization to obtain a block type polyester amide copolymer; the catalyst is aryl tin and Salen tin; the mass ratio of the epsilon-caprolactone to the caprolactam is 1-8:2-9; the temperature of the copolymerization reaction is 240-250 ℃ and the time is 1-7 h. The method provided by the invention effectively improves the conversion rate of the raw materials, prevents the back biting of the functional groups at the tail end of the molecular chain and reduces the content of the oligomer by controlling the reaction raw materials and the reaction conditions. The example results show that the melting point of the polyesteramide prepared by the method provided by the invention is 204-217 ℃, the mass content of the oligomer is 0.5-3.5%, and the water absorption is 2.62-32.23%.
Drawings
FIG. 1 is a GPC chart of polyesteramides prepared in different proportions of Caprolactam (CPL) and Caprolactone (CL);
FIG. 2 is a low field nuclear magnetic spectrum of a polyesteramide of Caprolactam (CPL) and Caprolactone (CL).
In the figure, a represents a macromolecular chain signal peak, B represents an oligomer small molecular signal peak, A represents a hard-segment relaxation time signal peak, B represents a soft-segment relaxation time signal peak, C represents an oligomer relaxation time signal peak, and D represents an oligomer relaxation time signal peak.
FIG. 3 is a PDI profile of the polyesteramide prepared in comparative example 1 and comparative example 2.
Detailed Description
The invention will now be described in more detail with reference to the drawings and examples.
The invention provides a preparation method for preparing polyesteramide by a stepwise method, which comprises the following steps:
(1) Pre-polymerizing epsilon-caprolactam and 6-aminocaproic acid to obtain nylon prepolymer;
(2) Adding a catalyst into the nylon prepolymer to obtain a double-end catalytic nylon 6 block;
(3) Adding epsilon-caprolactone, and carrying out block copolymerization on the epsilon-caprolactone and double-end catalytic nylon 6 to obtain block polyester amide;
the catalyst is aryl tin (tetraphenyl tin, triphenyltin) or Salen tin;
the mass ratio of the epsilon-caprolactone monomer to the caprolactam monomer is 2-9:8-1;
the reaction temperature is 240 ℃, the prepolymerization time is 1-3 h, the copolymerization time is 1-7 h, and the three steps can be carried out under normal pressure or vacuum condition.
In the present invention, the addition amount of 6-aminocaproic acid is preferably 10% when epsilon-caprolactam and 6-aminocaproic acid are prepolymerized. The 6-aminocaproic acid used was previously dried in vacuo.
Mixing epsilon-caprolactam and 6-aminocaproic acid, and then carrying out a prepolymerization reaction, wherein the temperature of the prepolymerization reaction is preferably 240 ℃, and the time is preferably 1-3 h, and more preferably 2h; the prepolymerization is preferably carried out under nitrogen protection. In the process of the prepolymerization reaction, epsilon-caprolactam and 6-aminocaproic acid undergo a ring-opening reaction to form nylon 6 prepolymer. In the present invention, the nylon 6 prepolymer formed contains terminal amino groups and terminal carboxyl groups for later coordination with the catalyst to form a double ended catalytic nylon 6 block (i.e., a truly active catalyst). The invention controls the prepolymerization reaction time and the raw material consumption, and the number average molecular weight of the prepared nylon 6 prepolymer is preferably controlled within the range of 5000-8000, which is favorable for the coordination reaction.
The invention preferably adds catalyst after the prepolymerization reaction is finished, then adds epsilon-caprolactone, takes care of anaerobic operation in the whole process, preferably takes copolymerization time of 1-7 h, further preferably takes 1-4 h, most preferably takes 2h, copolymerization temperature of 240-250 ℃ and takes place in the whole process under the protection of nitrogen, thus obtaining the copolyester amide. The number average molecular weight of the copolyester amide obtained by the invention is 25000-39000. The epsilon-caprolactone and epsilon-caprolactam used in the invention all need to be dried in vacuum in advance to remove water.
In the invention, after adding 1-6wt.permillage of catalyst, the time for generating the double-end catalytic nylon 6 block by the coordination reaction is preferably 10min, 15min, 20min, 25min and 30min, and the catalytic time after further optimization is 15min.
The melting point of the polyesteramide provided by the invention is 167-216 ℃, the mass content of the oligomer is 0.5-3.5%, and the water absorption is 2.62-32.23%. In the present invention, the oligomer is caused by back biting of the molecular segments during the reaction.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
900 parts by mass of epsilon-caprolactam and 90 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 2h of prepolymerization.
Adding 1wt. -% tetraphenyltin into a nylon prepolymer, reacting for 15min at 240 ℃ to obtain a double-end catalytic nylon 6 block, adding 100 parts by mass of epsilon-caprolactone which is dehydrated by vacuum drying in advance into a four-neck flask, and performing block copolymerization with the double-end catalytic nylon 6, wherein the rotating speed is 80rpm, nitrogen purging and the temperature is 240 ℃, and reacting for 4h to obtain the block type copolyester amide.
The polyester amide prepared in example 1 had a melting point of 208 ℃.
The low field nuclear magnetic test was performed on the content of oligomers in the polyesteramide prepared in example 1 by placing 3-5mg of the sample in a low field nuclear magnetic tube. Determination of T of target samples under CPMG sequence using low field nuclear magnetism from Neuman analytical instruments, st 2 Relaxation time. After multicomponent inversion, the "polymeric segment" and "small molecule segment" in the polymer are calculated from the ratio of the different peak areas. The test frequency was 21MHz, the magnet strength was 0.5T, and the contents of all samples were measured on a VTMR20-010V-I spectrometer with a 10mm hydrogen test probe at a magnet temperature of 35.+ -. 0.01 ℃. The oligomer content was measured to be 3.5%.
The polyesteramide prepared in example 1 was subjected to static contact angle test and water absorption test. The test method adopts GB-1034-70 to manufacture a block target sample with the size of 60mm multiplied by 1mm, fully dries for 24 hours, and then weighs (m 1). Immersing it in distilled water at 23 ℃, measuring its mass (m 2) for 24 hours, 48 hours, 72 hours, 96 hours, 120 hours, 148 hours, 172 hours, 30 days, 33 days and 35 days, respectively, and recording the weight of the immersed sample when dried as m0;
the nylon 6 prepolymer in the polyesteramide prepared in example 1 had a molecular weight of 5200, a melting point of 208℃and an oligomer content of 3.5%, a static contact angle of 50.3℃and a water absorption of 32.23% and a number average molecular weight of 39000.
The oligomer content test methods in examples 2 to 8 and comparative examples 1 and 2 were the same as that in example 1.
Example 2
800 parts by mass of epsilon-caprolactam and 80 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 250 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 3h of prepolymerization.
Adding 1 wt%tetraphenyltin into nylon prepolymer, reacting for 15min at 250 ℃, obtaining double-end catalytic nylon 6 block, adding 200 parts by mass of epsilon-caprolactone which is dehydrated by vacuum drying in advance into a four-neck flask, and carrying out block copolymerization with the double-end catalytic nylon 6, wherein the rotating speed is 80rpm, nitrogen purging and the temperature is 230 ℃, and reacting for 3h, thus obtaining the polyesteramide.
The nylon 6 prepolymer in the polyesteramide prepared in example 2 had a molecular weight of 5100 and a melting point of 204 ℃. The oligomer had a mass content of 1.7%, a static contact angle of 52.5 °, a water absorption of 26.54% and a number average molecular weight of 32000.
Example 3
700 parts by mass of epsilon-caprolactam and 70 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 245 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after the prepolymerization reaction for 1 h.
Adding 1wt.% > of tetraphenyltin into a nylon prepolymer, reacting for 30min at 245 ℃ to obtain a double-end catalytic nylon 6 block, then adding 300 parts by mass of epsilon-caprolactone which is dehydrated by vacuum drying in advance into a four-neck flask dropwise to block-react with the double-end catalytic nylon 6, wherein the rotating speed is 80rpm, the nitrogen purging is carried out, the temperature is 220 ℃, and the reaction is carried out for 6h to obtain the copolyester amide.
The nylon 6 prepolymer in the polyesteramide prepared in example 3 had a molecular weight of 5300 and a melting point of 204 ℃. The oligomer had a mass content of 2.1%, a static contact angle of 57.8 °, a water absorption of 20.44% and a number average molecular weight of 33000.
Example 4
600 parts by mass of epsilon-caprolactam and 60 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 2h of prepolymerization.
Adding 1wt.% tetraphenyltin into a nylon prepolymer, reacting for 15min at 240 ℃ to obtain a double-end catalytic nylon 6 block, adding 400 parts by mass of epsilon-caprolactone which is dehydrated by vacuum drying in advance into a four-neck flask, and performing block copolymerization with the double-end catalytic nylon 6, wherein the rotating speed is 80rpm, nitrogen purging and the temperature is 240 ℃, and reacting for 7h to obtain the polyesteramide.
The nylon 6 prepolymer in the polyesteramide prepared in example 4 had a molecular weight of 5100 and a melting point of 208 ℃. The oligomer had a mass content of 2.9%, a static contact angle of 59 °, a water absorption of 11.02% and a number average molecular weight of 36300.
Example 5
500 parts by mass of epsilon-caprolactam and 50 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 2h of prepolymerization.
5 wt.% > of tetraphenyltin is added into a nylon prepolymer to react for 20min at 240 ℃ to obtain a double-end catalytic nylon 6 block, then 500 parts by mass of epsilon-caprolactone which is dried in vacuum in advance and dehydrated are added into a four-neck flask drop by drop to block with the double-end catalytic nylon 6, the rotating speed is 80rpm, nitrogen purging is carried out, the temperature is 230 ℃, and the reaction is carried out for 3h to obtain the copolyester amide.
The nylon 6 prepolymer in the polyesteramide prepared in example 5 had a molecular weight of 5100 and a melting point of 209 ℃. The mass content of the oligomer was 0.8%, the static contact angle was 63.8 °, the water absorption was 9.53% and the number average molecular weight was 25000.
Example 6
400 parts by mass of epsilon-caprolactam and 40 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 245 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 3h of prepolymerization.
Adding 6 wt%tetraphenyltin into nylon prepolymer, reacting for 10min at 245 ℃ to obtain double-end catalytic nylon 6 block, then adding 600 parts by mass of epsilon-caprolactone which is dehydrated by vacuum drying in advance into a four-neck flask dropwise to block-react with double-end catalytic nylon 6, wherein the rotating speed is 80rpm, nitrogen purging is carried out, the temperature is 230 ℃, and reacting for 7h to obtain the polyesteramide.
The polyester amide prepared in example 6 had a melting point of 211 ℃. The mass content of the oligomer was 0.9%, the static contact angle was 65.2 °, the water absorption was 4.05% and the number average molecular weight was 26000.
Example 7
300 parts by mass of epsilon-caprolactam and 30 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 2h of prepolymerization.
Adding 5 wt%tetraphenyltin into nylon prepolymer, reacting for 15min at 240 ℃ to obtain double-end catalytic nylon 6 block, then adding 700 parts by mass of epsilon-caprolactone which is dried in vacuum in advance and dehydrated into a four-neck flask dropwise to block copolymer with double-end catalytic nylon 6, wherein the rotating speed is 80rpm, nitrogen purging is carried out, the temperature is 240 ℃, and the reaction is carried out for 1h to obtain the polyesteramide.
The melting point of the polyesteramide prepared in example 7 was 212 ℃. The oligomer had a mass content of 0.5%, a static contact angle of 66.8 °, a water absorption of 3.76% and a number average molecular weight of 27100.
Example 8
200 parts by mass of epsilon-caprolactam and 20 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 2h of prepolymerization.
Adding 1wt.% > of tetraphenyltin into a nylon prepolymer, reacting for 15min at 240 ℃ to obtain a double-end catalytic nylon 6 block, dropwise adding 800 parts by mass of epsilon-caprolactone which is dehydrated by vacuum drying into a four-neck flask, and reacting with the double-end catalytic nylon 6 block at the speed of 80rpm and the temperature of 240 ℃ for 4h to obtain the polyesteramide.
The melting point of the polyesteramide prepared in example 8 was 217 ℃. The mass content of the oligomer was 1.2%, the static contact angle was 71.3 °, the water absorption was 2.62% and the number average molecular weight was 27300.
Example 9
200 parts by mass of epsilon-caprolactam and 20 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 2h of prepolymerization.
Adding 2 wt%triphenyltin into nylon prepolymer, reacting for 15min at 245 ℃ to obtain double-end catalytic nylon 6 block, dropwise adding 800 parts of epsilon-caprolactone which is dehydrated by vacuum drying into a four-neck flask, reacting with the double-end catalytic nylon 6 block at the speed of 80rpm and the temperature of 240 ℃ for 4h, and obtaining the polyesteramide.
The polyester amide prepared in example 9 had a melting point of 215 ℃. The oligomer had a mass content of 1.4%, a static contact angle of 69.5, a water absorption of 2.83% and a number average molecular weight of 24400.
Example 10
300 parts by mass of epsilon-caprolactam and 30 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 250 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 3h of prepolymerization.
3 wt.% > Salen tin (R 1 And R is 2 2-methylpropane) is added into nylon prepolymer at 250 ℃ for reaction for 10min to obtain double-end catalytic nylon 6 block, 800 parts of epsilon-caprolactone which is dehydrated by vacuum drying in advance is added into a four-neck flask drop by drop to react with the double-end catalytic nylon 6 block at the rotating speed of 80rpm and the temperature of 230 ℃ by nitrogen purging, and the polyesteramide is obtained after reaction for 3h.
The polyester amide prepared in example 10 had a melting point of 215 ℃. The mass content of the oligomer was 1.1%, the static contact angle was 69.5 °, the water absorption was 2.96%, and the number average molecular weight was 21600.
Example 11
300 parts by mass of epsilon-caprolactam and 30 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask, the rotating speed is regulated to 80rpm, the temperature is regulated to 250 ℃ after nitrogen purging for 0.5h, and the prepolymerization stage is completed after 3h of prepolymerization.
6 wt.% > Salen tin (R 1 Is 2-methylpropane, R 2 Pyridine) is added into nylon prepolymer to react for 10min at 240 ℃ to obtain double-end catalytic nylon 6 block, and 800 mass percent of water is removed by vacuum drying in advanceAnd (3) dropwise adding the epsilon-caprolactone into a four-necked flask, reacting with the double-end catalytic nylon 6 block at the speed of 80rpm and the temperature of 235 ℃ under nitrogen purging for 2 hours to obtain the polyesteramide.
The melting point of the polyesteramide prepared in example 11 was 217 ℃. The mass content of the oligomer was 1.2%, the static contact angle was 70.5 °, the water absorption was 3.01% and the number average molecular weight was 21500.
As can be seen from examples 1-8 above, the water absorption of the polyesteramide gradually decreases with increasing amount of epsilon-caprolactone, more specifically with increasing mass ratio of epsilon-caprolactone to epsilon-caprolactam, and the water absorption of the polyesteramide gradually decreases and increases with decreasing mass ratio of epsilon-caprolactone to epsilon-caprolactam. Wherein the catalyst dosage of examples 1-4 and 8 is 1% and the catalyst dosage of examples 5-7 is 5-6%, all follow the above rule, which shows that the catalyst dosage does not affect the water absorption of the product basically. The melting point is 204-217 ℃, and the difference is very small, so that the melting point of the prepared product is relatively stable.
Comparative example 1
500 parts by mass of epsilon-caprolactam, 500 parts by mass of epsilon-caprolactone, 1wt. per mill of tetraphenyltin and 50 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask by adopting a one-pot method, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the product is taken out after the reaction for 6 h.
The caprolactam polymer prepared in comparative example 1 was tested for number average molecular weight 6000, melting point 103 deg.c, soft texture, oil stain on the surface, difficult hot press molding and oligomer content of 60.5%.
Comparative example 2
500 parts by mass of epsilon-caprolactam and 50 parts by mass of 6-aminocaproic acid which are dehydrated by vacuum drying in advance are added into a four-necked flask by adopting a fractional step method, the rotating speed is regulated to 80rpm, the temperature is regulated to 240 ℃ after nitrogen purging for 0.5h, and the product is taken out after 2h of reaction, so that the prepolymerization stage is completed.
500 parts by mass of epsilon-caprolactone which is dehydrated by vacuum drying in advance is dropwise added into a four-necked flask to be subjected to addition polymerization with Pre-PA6, the rotating speed is 80rpm, nitrogen purging is carried out, the temperature is 240 ℃, and the reaction is carried out for 4 hours, so that the product is obtained.
The caprolactam polymer prepared in comparative example 2 was tested for a number average molecular weight of 11000, a melting point of 192℃and an oligomer content of 7.2%.
Comparative example 1 and comparative example 2 illustrate that PEA prepared by the one-pot and no-catalyst step method is inferior to PEA prepared by the step method with respect to molecular weight, oligomer content, etc. added with tetraphenyltin.
Claims (10)
1. A preparation method of block type polyester amide is characterized by comprising the following steps:
step one, carrying out prepolymerization reaction on epsilon-caprolactam and 6-aminocaproic acid to obtain nylon prepolymer;
step two, adding a catalyst into the nylon prepolymer under the anaerobic condition to obtain a double-end catalytic nylon 6 block; the catalyst is phenyltin;
step three, adding epsilon-caprolactone, and carrying out copolymerization reaction on epsilon-caprolactone and a double-end catalytic nylon 6 block to obtain block polyester amide;
the mass ratio of the epsilon-caprolactam to the epsilon-caprolactone is 2-9:1-8; the mass ratio of the 6-aminocaproic acid to the epsilon-caprolactone is 0.2-0.9: 1 to 8.
2. The method for preparing a block type polyesteramide according to claim 1, wherein in the first step, the prepolymerization reaction temperature is 240-250 ℃ and the time is 1-3 h.
3. The process for preparing a block type polyesteramide according to claim 1, wherein in the second step, the copolymerization reaction temperature is 240 to 250 ℃ and the time is 1 to 7 hours.
4. The preparation method of the block type polyester amide according to claim 1, wherein the addition amount of the catalyst is 1-6wt% of the mass of the nylon prepolymer, and the pre-polymerization temperature is maintained for 15-30 min after the nylon prepolymer is added to the catalyst, so that a double-ended catalytic nylon 6 block is obtained; the phenyl tin is one or any combination of tetraphenyl tin, triphenyltin and Salen tin, and the structural formula of the Salen tin is as follows:
wherein R is 1 Is 2-methylpropane, R2 is 2-methylpropane or pyridine, and R is phenyl.
The water absorption of the obtained polyester amide gradually decreases with the increase of the mass ratio of epsilon-caprolactone to epsilon-caprolactam, and the water absorption of the polyester amide gradually increases with the decrease of the mass ratio of epsilon-caprolactone to epsilon-caprolactam.
5. The process for preparing a block type polyester amide according to claim 1, wherein the mass ratio of epsilon-caprolactone to epsilon-caprolactam is adjusted according to the water absorption required for the polyester amide, and when a polyester amide having a lower water absorption is required, the mass ratio of epsilon-caprolactone to epsilon-caprolactam is increased, and when a polyester amide having a higher water absorption is required, the mass ratio of epsilon-caprolactone to epsilon-caprolactam is decreased.
6. The method for preparing the block type polyesteramide according to claim 1, wherein the reaction temperature of the prepolymerization is 240-245 ℃ and the prepolymerization time is 2h; the copolymerization reaction temperature is 240-245 ℃ and the time is 1-7 h; the catalyst is tetraphenyl tin, and the addition amount of the catalyst is 1-6wt% of the mass of the nylon prepolymer.
7. The method for preparing the block type polyester amide according to claim 6, wherein the mass ratio of epsilon-caprolactam, 6-aminocaproic acid and epsilon-caprolactone is 3:0.3:7, preparing a base material; the reaction temperature of the prepolymerization reaction is 240 ℃, and the prepolymerization reaction time is 2 hours; the copolymerization reaction temperature is 240 ℃ and the time is 1h; the catalyst is tetraphenyl tin, and the addition amount of the catalyst is 5 wt% of the mass of the nylon prepolymer.
8. The method for producing a block type polyesteramide according to claim 1, wherein the molecular weight of the nylon 6 prepolymer is in the range of 5000 to 8000.
9. A block type polyester amide, which is characterized in that the block type polyester amide is prepared by the preparation method of the block type polyester amide according to any one of claims 1 to 8.
10. The block type polyester amide as claimed in claim 8, wherein the melting point of the block type polyester amide is 204-217 ℃, the mass content of the oligomer is 0.5-3.5%, and the water absorption is 2.62-32.23%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310508935.XA CN116535641B (en) | 2023-05-08 | 2023-05-08 | Block type polyester amide and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310508935.XA CN116535641B (en) | 2023-05-08 | 2023-05-08 | Block type polyester amide and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116535641A true CN116535641A (en) | 2023-08-04 |
CN116535641B CN116535641B (en) | 2024-06-11 |
Family
ID=87446563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310508935.XA Active CN116535641B (en) | 2023-05-08 | 2023-05-08 | Block type polyester amide and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116535641B (en) |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3160609A (en) * | 1962-03-12 | 1964-12-08 | Monsanto Co | Preparation of polyesteramides with tetraphenyl tin catalyst |
GB1099184A (en) * | 1965-04-06 | 1968-01-17 | Ici Ltd | Polyesteramides |
US3979479A (en) * | 1973-12-28 | 1976-09-07 | Societa' Italiana Resine S.I.R. S.P.A. | Block copolymers |
US4101524A (en) * | 1975-09-24 | 1978-07-18 | Chemische Werke Huls Aktiengesellschaft | Method for the production of colorless polyester amides |
JPH06192417A (en) * | 1992-12-25 | 1994-07-12 | Agency Of Ind Science & Technol | Biodegradable plastic |
JPH06200016A (en) * | 1992-12-28 | 1994-07-19 | Sekisui Plastics Co Ltd | Production of biodegradable plastic |
US6172167B1 (en) * | 1996-06-28 | 2001-01-09 | Universiteit Twente | Copoly(ester-amides) and copoly(ester-urethanes) |
CN102015842A (en) * | 2008-04-29 | 2011-04-13 | 阿肯马法国公司 | Method for increasing the difference between the melting temperature and the crystallization temperature of a polyamide powder |
CN105646876A (en) * | 2016-04-08 | 2016-06-08 | 南京工业大学 | Method for preparing polyesteramide |
CN111217997A (en) * | 2020-03-26 | 2020-06-02 | 湖南师范大学 | Polycaprolactone-based polyamide composite material and preparation method thereof |
CN112029077A (en) * | 2019-06-03 | 2020-12-04 | 北京化工大学 | Polyamide-b-polyester block copolymer, and preparation method and application thereof |
CN115044035A (en) * | 2022-06-08 | 2022-09-13 | 东华大学 | Sequence-regular polyesteramide and one-pot preparation method thereof |
CN116063673A (en) * | 2023-03-07 | 2023-05-05 | 苏州大学 | Polyamide elastomer and preparation method and application thereof |
-
2023
- 2023-05-08 CN CN202310508935.XA patent/CN116535641B/en active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3160609A (en) * | 1962-03-12 | 1964-12-08 | Monsanto Co | Preparation of polyesteramides with tetraphenyl tin catalyst |
GB1099184A (en) * | 1965-04-06 | 1968-01-17 | Ici Ltd | Polyesteramides |
US3979479A (en) * | 1973-12-28 | 1976-09-07 | Societa' Italiana Resine S.I.R. S.P.A. | Block copolymers |
US4101524A (en) * | 1975-09-24 | 1978-07-18 | Chemische Werke Huls Aktiengesellschaft | Method for the production of colorless polyester amides |
JPH06192417A (en) * | 1992-12-25 | 1994-07-12 | Agency Of Ind Science & Technol | Biodegradable plastic |
JPH06200016A (en) * | 1992-12-28 | 1994-07-19 | Sekisui Plastics Co Ltd | Production of biodegradable plastic |
US6172167B1 (en) * | 1996-06-28 | 2001-01-09 | Universiteit Twente | Copoly(ester-amides) and copoly(ester-urethanes) |
CN102015842A (en) * | 2008-04-29 | 2011-04-13 | 阿肯马法国公司 | Method for increasing the difference between the melting temperature and the crystallization temperature of a polyamide powder |
CN105646876A (en) * | 2016-04-08 | 2016-06-08 | 南京工业大学 | Method for preparing polyesteramide |
CN112029077A (en) * | 2019-06-03 | 2020-12-04 | 北京化工大学 | Polyamide-b-polyester block copolymer, and preparation method and application thereof |
CN111217997A (en) * | 2020-03-26 | 2020-06-02 | 湖南师范大学 | Polycaprolactone-based polyamide composite material and preparation method thereof |
CN115044035A (en) * | 2022-06-08 | 2022-09-13 | 东华大学 | Sequence-regular polyesteramide and one-pot preparation method thereof |
CN116063673A (en) * | 2023-03-07 | 2023-05-05 | 苏州大学 | Polyamide elastomer and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
DOU YUANYUAN: "Facile Method for the Synthesis of PCL-b-PA6-b-PCL Using Amino-Terminated PA6 as a Macroinitiator and Its Characterization", 《MACROMOLECULES》, vol. 55, no. 22, 31 October 2022 (2022-10-31), pages 10090 - 10099 * |
Also Published As
Publication number | Publication date |
---|---|
CN116535641B (en) | 2024-06-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Electroactive nanofibrous biomimetic scaffolds by thermally induced phase separation | |
US6099907A (en) | Stable, concentrated solutions of high molecular weight polyaniline and articles therefrom | |
EP1795631B1 (en) | High-strength fiber of biodegradable aliphatic polyester and process for producing the same | |
Graf et al. | β‐Lactams, Their Polymerization and Use as Raw Materials for Fibers | |
US3538058A (en) | Polyesteramides | |
Meng et al. | Synthesis of bio-based semi aromatic high temperature polyamide PA5T/56 and effect of benzene ring on non-isothermal crystallization kinetics | |
CN101547954A (en) | Polylactide-urethane copolymers | |
Gao et al. | Structure and properties of novel PMDA/ODA/PABZ polyimide fibers | |
CN116535641B (en) | Block type polyester amide and preparation method thereof | |
JPH0286623A (en) | Manufacture of thermotropic aromatic copolyester-amide | |
Qu et al. | Studies on isosorbide-enhanced biodegradable poly (ethylene succinate) | |
Agarwal et al. | Enhancement of polymerization rates for rigid rod-like molecules by shearing | |
Zhao et al. | Synthesis and properties of novel polyimide fibers containing phosphorus groups in the side chain (DATPPO) | |
CN113444348A (en) | Polylactic acid stereocomplex, preparation method and application | |
IL33634A (en) | Spinnable solutions of copolymers containing amide and imide groups and process for their preparation | |
CN107011516A (en) | Poly- pentanediamine binary acid block copolymer of polyester and preparation method thereof and fiber | |
NO152792B (en) | ELASTOMER, THERMOPLASTIC COPOLYESTERAMIDS | |
US3674752A (en) | Copolyamides from 1,6 or 2,6-naphthalene dicarboxylic acid | |
Xu et al. | Study on the preparation and properties of lactic acid based copolymer | |
CN114702638B (en) | Polypropylene carbonate chain-extended copolymer and preparation method thereof | |
US3247168A (en) | Polyoxamides | |
Huang et al. | Poly (amide‐ester) s from p‐aminobenzoic acid | |
CN114213653B (en) | Polyamide and preparation method thereof | |
US3684775A (en) | Chain terminated polyhexamethylene adipamide | |
Shang et al. | Synthesis and Properties of High-Performance Thermoplastic Poly (ester-ether) Elastomers Reinforced by N, N′-Bis (2-carboxyethyl) Pyromellitimide Moieties |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information |
Country or region after: China Address after: 424000 Hunan Juren Chemical New Material Technology Co., Ltd., Green Chemical Industry Park, Yunxi District, Yueyang City, Hunan Province Applicant after: Hunan Juren New Materials Co. Address before: 424000 Hunan Juren Chemical New Material Technology Co., Ltd., Green Chemical Industry Park, Yunxi District, Yueyang City, Hunan Province Applicant before: HUNAN JUREN CHEMICAL NEW MATERIAL TECHNOLOGY CO.,LTD. Country or region before: China |
|
CB02 | Change of applicant information | ||
GR01 | Patent grant |