CN112062948A - Preparation process of polybutyrolactam block copolymer - Google Patents
Preparation process of polybutyrolactam block copolymer Download PDFInfo
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- polybutyrolactam
- block copolymer
- butyrolactam
- chloride
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000003213 activating effect Effects 0.000 claims abstract description 32
- -1 butyrolactam anion Chemical class 0.000 claims abstract description 23
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000012190 activator Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 5
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- LCPNYLRZLNERIG-ZETCQYMHSA-N (2S)-6-amino-2-[2-(oxomethylidene)hydrazinyl]hexanoyl isocyanate Chemical compound NCCCC[C@H](NN=C=O)C(=O)N=C=O LCPNYLRZLNERIG-ZETCQYMHSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012346 acetyl chloride Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 claims description 2
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims 1
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims 1
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 13
- 230000008018 melting Effects 0.000 abstract description 13
- 229920001007 Nylon 4 Polymers 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- KMLPEYHLAKSCGX-UHFFFAOYSA-N 2-aminocyclohexan-1-one Chemical compound NC1CCCCC1=O KMLPEYHLAKSCGX-UHFFFAOYSA-N 0.000 description 1
- UNSAJINGUOTTRA-UHFFFAOYSA-N 3-(3-bromophenyl)prop-2-yn-1-ol Chemical compound OCC#CC1=CC=CC(Br)=C1 UNSAJINGUOTTRA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- C08G69/02—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
- C08G69/24—Pyrrolidones or piperidones
-
- 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
- C08G69/18—Anionic polymerisation
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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)
- Polyamides (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a preparation process of a polybutyrolactam block copolymer, which comprises the following steps: mixing and polymerizing butyrolactam anion activating solution and a macromolecular activating agent to obtain a crude product, removing monomers and oligomers in the crude product, and drying to obtain a polybutyrolactam block copolymer, wherein the butyrolactam anion activating solution is obtained by reacting butyrolactam and a catalyst; the macromolecular activator is prepared from an acylating agent and a polymer polyol. Compared with the prior art, the polybutyrolactam block copolymer obtained by the preparation process has the viscosity average molecular weight of more than 30000 and the melting point of the polybutyrolactam block copolymer is obviously reduced compared with that of polybutyrolactam (PA 4). Meanwhile, the mechanical property and the barrier property of the obtained polybutyrolactam block copolymer are obviously improved compared with PA4 by adopting the preparation process.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and relates to a preparation process of a polybutyrolactam (PA4) block copolymer.
Background
Polybutyrolactam (PA4), also known as Polyamide (4), is a white crystalline polymer. Generally by ring-opening polymerization of butyrolactam anions, wherein butyrolactam can be obtained from petroleum products or extracted from biomass by fermentation. Compared with other nylons, the polybutyrolactam molecular chain has high amido bond density and strong water absorption, has hydrophilicity close to that of natural fiber cotton and silk, can replace cotton fiber, and has long-standing attention on application research in the fiber field. In addition, the polybutyrolactam (PA4) can be effectively degraded in activated sludge, seawater and organisms, and is a bio-based degradable material with high application value. The melting point of the polybutyrolactam is 260-265 ℃, the polybutyrolactam has excellent heat resistance, but the thermal decomposition temperature is 260-285 ℃, so that the polybutyrolactam is difficult to process in the traditional forms of melt extrusion, injection molding and the like, and the development and the application of the polybutyrolactam are greatly limited.
Due to the specificity of the molecular structure of the polybutyrolactam and the presence of lactam groups at the molecular chain ends of PA4 obtained by anionic ring-opening polymerization, the thermal decomposition temperature of PA4 is very low. In recent years, a great deal of research has been conducted on the thermal stability of PA4, and the main methods include copolymerization modification with different monomers, end group modification of PA4, addition of inorganic particles, and the like.
In order to raise the thermal decomposition temperature of PA4, there is a prior art scheme of copolymerizing 2-pyrrolidone with other monomers, and the purpose is to increase-CH in the molecular chain by copolymerization2And the number of the amide bonds is increased, so that the disorder of the molecules is improved, the crystallinity is reduced, the melting point is further reduced, the density of the amide bonds is reduced, the thermal degradation temperature is increased, and the processing performance is enhanced. The main comonomers at present are caprolactam, 2-aminocaprone, -caprolactone, lactide and the like. Nam and the like use 2-pyrrolidone and caprolactam as raw materials to obtain polyamide 46 copolymers through anion ring-opening polymerization, and authors explore the influences of copolymer molecular weights and copolymer thermal stability such as different polymerization temperatures (50-100 ℃), monomer ratios and the like. The authors found that the copolymers obtained by polymerization at 70 ℃ had the best thermal stability and the highest molecular weight, that the melting point was the lowest when the 2-pyrrolidone content was around 40%, and that the thermal stability was not significantly affected by the molecular weight of the copolymer. Kang et alBy varying the comonomer content, catalyst content, temperature, initiator content and reaction temperature, polyamides 45 of different structures were obtained, and the results of the study showed that the melting point of the copolymer decreased significantly with increasing proportion of 2-aminocyclohexanone in the charge, which means that the melting point of the copolymer could be controlled by the charge ratio.
Nor1oki et al initiate the polymerization of 2-pyrrolidone to PA4 using an acid chloride bearing an azo group as initiator. Naoko et al also synthesized a block copolymer PA4-b-PVAc with a weight average molecular weight of 46800-163700 g/mol by the same method, and the molecular weight linearly changed with the molar ratio of ethyl acetate (VAc) to PA 4-azo, and the thermal and mechanical properties of the copolymer were studied at the same time, and found that the melting point of the copolymer is improved compared with that of PA4 homopolymer, the tensile strength is increased with the increase of the content of PA4 block, and the elongation at break is increased with the increase of the content of VAc.
Since the heat stability of acylbutyrolactams is more easily decomposed than other groups on the molecular chain of PA4, the improvement of the heat stability of PA4 by chemical modification of the terminal group is expected. Kazuhiko et al reported a method for modifying the end groups of PA4, the authors first synthesized PA4 with acyllactam end groups, then chemically changed the end groups into carbonyl, amino and alkyl groups and studied the thermal properties of the different end groups of PA4, and the authors found that the thermal decomposition temperature of PA4 after end group change was higher than the original one and the thermal degradation temperature was the highest when the end group was amino, but the improvement of the thermal properties of PA4 was limited.
In the prior art, heat resistance modification is carried out on PA4 by copolymerization modification, end group change, blending modification and other modes, but the improvement effect is limited.
Disclosure of Invention
The invention aims to provide a preparation process of a polybutyrolactam block copolymer, which is used for improving the thermal property, the mechanical property and the barrier property of PA 4.
According to the invention, from the block copolymerization angle, a macroinitiator is synthesized according to the butyrolactam anion ring-opening polymerization principle to prepare a polybutyrolactam (PA4) block copolymer, and a polymer with a relatively low melting point is introduced into a molecular chain to reduce the melting point of a PA4 product and improve the mechanical property and the barrier property of PA 4.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a preparation process of a polybutyrolactam block copolymer, which comprises the following steps:
mixing the butyrolactam anion activating solution and the macromolecular activating agent, polymerizing to obtain a crude product, removing monomers and oligomers in the crude product, drying to obtain a polybutyrolactam block copolymer,
the butyrolactam anion activating solution is obtained by reacting butyrolactam with a catalyst;
the macromolecular activator is prepared from an acylating agent and a polymer polyol.
In one embodiment of the invention, the conditions for reacting butyrolactams with a catalyst to obtain a butyrolactam anion activating solution are as follows: the mol ratio of butyrolactam to the catalyst is 100: 10-1000: 1; the reaction temperature of the butyrolactam and the catalyst is 60-110 ℃, the reaction time is 0.5-12h, and the reaction environment of the butyrolactam and the catalyst is a reaction under the vacuum condition.
Preferably, the reaction of butyrolactams with the catalyst is carried out under vacuum at-0.010. + -. 0.05 MPa.
In one embodiment of the invention, the catalyst can be organic or inorganic base, and is selected from one or more of potassium tert-butoxide, sodium ethoxide, potassium ethoxide, sodium hydroxide, potassium hydroxide, tert-butyllithium, urea, 1, 8-diazabicycloundecen-7-ene or thiourea.
In one embodiment of the invention, the reaction conditions for reacting the acylating agent with the polymer polyol to produce the macromolecular activator are: the mol ratio of the acylating agent to the polymer polyol is 4:1-1:4, preferably 1: 2-2: 1, the reaction temperature of the acylating agent and the polymer polyol is 25-100 ℃, the reaction time is 0.5-5 h, preferably 50-100 ℃, and the reaction time is 0.5-3 h.
In one embodiment of the invention, the acylating agent is selected from one or more of benzoyl chloride, terephthaloyl chloride, valeryl chloride, oxalyl chloride, acetyl chloride, stearoyl chloride, myristoyl chloride, caprylyl chloride, terephthaloyl chloride, meta-phenylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate or L-lysine diisocyanate.
In one embodiment of the invention, the polymer polyol is selected from one or more of polypropylene glycol (PPG), Polycaprolactone (PCL), Polylactide (PLA), hydroxyl-terminated polybutadiene (HTPB), or hydroxyl silicone oil; the molecular weight of the polymer polyol is 500-5000 g/mol.
In one embodiment of the invention, the reaction temperature is 20-90 ℃, preferably 40-80 ℃ and the reaction time is 0.5-7 days during the mixing process of the butyrolactam anion activating solution and the macromolecular activating agent.
In one embodiment of the present invention, the reaction conditions during the mixing of the butyrolactam anion activating solution and the macromolecular activating agent are preferably carried out under an inert gas atmosphere.
In one embodiment of the invention, the molar ratio of the butyrolactam anion activating solution to the macromolecular activating agent is 1000: 1-10: 1.
In one embodiment of the invention, the removal of monomers and oligomers in the crude product is: washing with water at 50-80 deg.c to eliminate impurity and obtain polybutyrolactam block copolymer.
Compared with the prior art, the polybutyrolactam block copolymer obtained by the preparation process has the viscosity average molecular weight of more than 30000 and the melting point ratio PA4 which is obviously reduced. Meanwhile, the mechanical property and the barrier property of the obtained polybutyrolactam block copolymer are obviously improved compared with PA4 by adopting the preparation process. The invention realizes the reduction of the melting point of the PA4 product by introducing the polymer with relatively low melting point into the molecular chain, and improves the mechanical property and the barrier property of PA 4.
Drawings
FIG. 1: an infrared image of the polybutyrolactam block copolymer (PA4-b-PPG) obtained in example 2;
FIG. 2: GPC analysis charts of the polybutyrolactam block copolymers obtained in examples 1 to 4;
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A polybutyrolactam block copolymer (PA4-b-HTPB) was prepared by the following steps:
step 1: preparation of butyrolactam anion activating solution
Weighing 20g of butyrolactam, pouring the weighed butyrolactam into a three-neck flask, heating the mixture to 70 ℃, adding 1.1g of lithium tert-butoxide and 1.0g of potassium tert-butoxide, reacting the mixture for 3 hours under the condition of 70 ℃ and the stirring speed of 120r/min and then cooling the mixture to 48 ℃.
Step 2: preparation of macromolecular activators
Weighing 4.70g of hydroxyl-terminated polybutadiene (HTPB) with the molecular weight of 4000 into a flask, heating to 70 ℃, adding 0.52g of isophorone diisocyanate under the condition of nitrogen, reacting for 60min, cooling to 48 DEG C
And step 3: preparation of polybutyrolactam block copolymer (PA4-b-HTPB)
The macromolecule activating agent is added into the butyrolactam anion activating solution, and the preparation of the polybutyrolactam (PA4) block copolymer is obtained by reaction at 80 ℃, the molecular weight is 35000, and the product yield is 95%.
The GPC analysis chart of the polybutyrolactam block copolymer (PA4-b-HTPB) obtained in this example is shown in FIG. 2.
Example 2
A polybutyrolactam block copolymer (PA4-b-PPG) was prepared by the following steps:
step 1: preparation of butyrolactam anion activating solution
Weighing 20g of butyrolactam, pouring the butyrolactam into a three-neck flask, heating the temperature to 60 ℃, adding 2.1g of potassium tert-butoxide and 0.06g of urea, stirring the mixture at the temperature of 60 ℃ at the speed of 120r/min, reacting the mixture for 3 hours under the vacuum condition, and then cooling the mixture to 52 ℃.
Step 2: preparation of macromolecular activators
Weighing 2.35g PPG with molecular weight of 2000 in a flask, heating to 80 deg.C, adding 0.33g benzoyl chloride under nitrogen, reacting for 30min, cooling to 52 deg.C
And step 3: preparation of polybutyrolactam (PA4) Block copolymer
Adding a macromolecular activator into the butyrolactam anion activating solution, and reacting at 52 ℃ for 12h to obtain the preparation of the polybutyrolactam (PA4) block copolymer, wherein the molecular weight is 38000 and the product yield is 85%.
The IR spectrum of the polybutyrolactam block copolymer (PA4-b-PPG) obtained in this example is shown in FIG. 1.
The GPC analysis chart of the polybutyrolactam block copolymer (PA4-b-PPG) obtained in this example is shown in FIG. 2.
Example 3
A polybutyrolactam block copolymer (PA4-b-PLA) was prepared by the following steps:
step 1: preparation of butyrolactam anion activating solution
Weighing 20g of butyrolactam, pouring the butyrolactam into a three-neck flask, heating to 80 ℃, adding 2.1g of sodium tert-butoxide, stirring at the temperature of 80 ℃ at the speed of 120r/min, reacting for 3h under the vacuum condition, and then cooling to 53 ℃.
Step 2: preparation of macromolecular activators
Weighing 2.35g PLA with molecular weight of 2000 in a flask, heating to 100 deg.C, adding 0.49g terephthaloyl chloride under nitrogen condition, reacting for 30min, cooling to 53 deg.C
And step 3: preparation of a Polybutyrolactam Block copolymer (PA4-b-PLA)
Adding a macromolecular activator into butyrolactam anion activating solution, and reacting at 53 ℃ to obtain the polybutyrolactam (PA4) block copolymer, wherein the molecular weight is 41000, and the product yield is 87%.
The GPC analysis chart of the polybutyrolactam block copolymer (PA4-b-PLA) obtained in this example is shown in FIG. 2.
Example 4
A polybutyrolactam block copolymer (PA4-b-PCL) was prepared by the following steps:
step 1: preparation of butyrolactam anion activating solution
Weighing 20g of butyrolactam, pouring the butyrolactam into a three-neck flask, heating the temperature to 80 ℃, adding 2.1g of lithium tert-butoxide, stirring the mixture at the temperature of 80 ℃ at the speed of 120r/min, reacting the mixture for 3 hours under the vacuum condition, and then cooling the mixture to 52 ℃.
Step 2: preparation of macromolecular activators
Weighing 4.70g of PCL with molecular weight of 4000 into a flask, heating to 80 ℃, adding 0.58g of p-phenylene diisocyanate under the condition of nitrogen, reacting for 30min, cooling to 52 DEG C
And step 3: preparation of polybutyrolactam Block copolymer (PA4-b-PCL)
Adding a macromolecular activator into butyrolactam anion activating solution, and reacting at 80 ℃ to obtain the preparation of polybutyrolactam (PA4) block copolymer, wherein the molecular weight is 32000 and the product yield is 91%.
The GPC analysis chart of the polybutyrolactam block copolymer (PA4-b-PCL) obtained in this example is shown in FIG. 2.
In addition, the melting point, tensile strength, oxygen permeability coefficient and water vapor permeability coefficient data of the polybutyrolactam block copolymers PA4-b-HTPB, PA4-b-PPG, PA4-b-PLA and PA4-b-PCL obtained in examples 1 to 4 and polybutyrolactam PA4 are shown in Table 1.
TABLE 1 Performance Table of PA4, PA4-b-HTPB, PA4-b-PPG, PA4-b-PLA, PA4-b-PCL
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation process of a polybutyrolactam block copolymer is characterized by comprising the following steps:
mixing the butyrolactam anion activating solution and the macromolecular activating agent, polymerizing to obtain a crude product, removing monomers and oligomers in the crude product, drying to obtain a polybutyrolactam block copolymer,
the butyrolactam anion activating solution is obtained by reacting butyrolactam with a catalyst;
the macromolecular activator is prepared from an acylating agent and a polymer polyol.
2. The process for preparing polybutyrolactam block copolymer according to claim 1, wherein the conditions for reacting butyrolactams with a catalyst to obtain a butyrolactam anion activating solution are as follows: the mol ratio of butyrolactam to the catalyst is 100: 10-1000: 1; the reaction temperature of the butyrolactam and the catalyst is 60-110 ℃, the reaction time is 0.5-12h, and the reaction environment of the butyrolactam and the catalyst is a reaction under the vacuum condition.
3. The process for preparing polybutyrolactam block copolymer according to claim 1, wherein said catalyst is selected from one or more of potassium tert-butoxide, sodium ethoxide, potassium ethoxide, sodium hydroxide, potassium hydroxide, tert-butyllithium, urea, 1, 8-diazabicycloundecen-7-ene or thiourea.
4. The process of claim 1, wherein the acylating agent is reacted with the polymer polyol to produce the macromolecular activator under the conditions: the mol ratio of the acylating agent to the polymer polyol is 3:1-2:1, the reaction temperature of the acylating agent and the polymer polyol is 25-100 ℃, and the reaction time is 0.5-5 h.
5. The process for preparing polybutyrolactam block copolymer according to claim 1, wherein said acylating agent is selected from one or more of benzoyl chloride, terephthaloyl chloride, valeroyl chloride, oxalyl chloride, acetyl chloride, stearoyl chloride, myristyl chloride, capryloyl chloride, terephthaloyl chloride, m-phenylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate or L-lysine diisocyanate.
6. The process for preparing polybutyrolactam block copolymer according to claim 1, wherein said polymer polyol is one or more selected from the group consisting of polypropylene glycol, polycaprolactone, polylactide, hydroxyl-terminated polybutadiene, and hydroxyl silicone oil; the molecular weight of the polymer polyol is 500-5000 g/mol.
7. The process for preparing polybutyrolactam block copolymer according to claim 1, wherein the reaction temperature is 20 to 90 ℃ and the reaction time is 0.5 to 7 days in the process of mixing the polybutyrolactam anion activating solution and the macromolecular activating agent.
8. The process for preparing polybutyrolactam block copolymer according to claim 1, wherein the reaction conditions in the mixing of the butyrolactam anion activating solution and the macromolecular activating agent are carried out under an inert gas atmosphere.
9. The process for preparing a polybutyrolactam block copolymer according to claim 1, wherein the molar ratio of the butyrolactam anion activating solution to the macromolecular activating agent is 1000:1 to 10: 1.
10. A polybutyrolactam block copolymer obtained by the process according to any one of claims 1 to 9, characterized by a viscosity average molecular weight of more than 30000.
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