WO2019093729A2 - Procédé de préparation d'un polyamide par décyclisation anionique et polyamide ainsi obtenu - Google Patents

Procédé de préparation d'un polyamide par décyclisation anionique et polyamide ainsi obtenu Download PDF

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WO2019093729A2
WO2019093729A2 PCT/KR2018/013328 KR2018013328W WO2019093729A2 WO 2019093729 A2 WO2019093729 A2 WO 2019093729A2 KR 2018013328 W KR2018013328 W KR 2018013328W WO 2019093729 A2 WO2019093729 A2 WO 2019093729A2
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polyamide
polymerization
weight
group
parts
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PCT/KR2018/013328
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Korean (ko)
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WO2019093729A3 (fr
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도승회
이진서
권경호
김두경
이혜연
임경원
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한화케미칼 주식회사
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Priority claimed from KR1020180133921A external-priority patent/KR102287634B1/ko
Application filed by 한화케미칼 주식회사 filed Critical 한화케미칼 주식회사
Priority to EP18875580.5A priority Critical patent/EP3708604A4/fr
Priority to US16/762,725 priority patent/US20200270397A1/en
Priority to CN201880070855.8A priority patent/CN111295410B/zh
Priority to JP2020525933A priority patent/JP7084478B2/ja
Publication of WO2019093729A2 publication Critical patent/WO2019093729A2/fr
Publication of WO2019093729A3 publication Critical patent/WO2019093729A3/fr

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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
    • C08G69/08—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/12—Hydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a process for producing polyamides by anion ring-opening polymerization and a polyamide produced by the process, and more particularly to a process for producing a polyamide by an anion ring-
  • the present invention relates to a process for producing a polyamide by anion ring-opening polymerization which enables a high-molecular-weight polymerization with a high conversion ratio within a short period of time, and a polyamide produced thereby.
  • the polyamide resin is a linear polymer bonded by an amide (-NHCO-) bond and is strong and has excellent properties such as abrasion resistance, abrasion resistance, oil resistance and solvent resistance, and is easily melt-molded. , Engineering plastics, and the like.
  • Polyamides can be classified into aliphatic polyamides, aromatic polyamides and aliphatic cyclic polyamides depending on the molecular structure.
  • Nylon is referred to as an aliphatic polyamide, and aramid as an aromatic polyamide. do.
  • Such polyamides are prepared by various polymerization methods, such as by ring-opening polymerization of lactams such as nylon 6, by polycondensation of diamines and dibasic acids such as nylon 6,6, nylon 6,10 and nylon 4,6, Such as nylon 11 and nylon 12, by the polycondensation of aminocarboxylic acid.
  • lactams such as nylon 6,
  • diamines and dibasic acids such as nylon 6,6, nylon 6,10 and nylon 4,6,
  • nylon 11 and nylon 12 by the polycondensation of aminocarboxylic acid.
  • So-called hybridized nylon such as a condensation product of caprolactam and 6,10-nylon salt (hexamethylenediamine and sebacate) is industrially produced.
  • functional groups such as a side chain and a hydroxyl group, And various types of polyamides including heterocyclic rings have been studied.
  • the lactam such as caprolactam
  • the lactam may be anionic polymerized.
  • This method generally uses a catalyst, and also an initiator (also referred to as an activator) (activated anion polymerization).
  • an initiator also referred to as an activator
  • activator activated anion polymerization
  • EP 1091991 discloses compositions comprising as component A polyisocyanurate having an average of more than 3.5 NCO functional groups, and also a method of making a surface coating composition using the compositions described.
  • US 3423372 uses a non-capped polyisocyanate (thus significantly reducing reactivity) and the concentration of activator in that example is very low (1/200 to 1/50 moles). Polymerization takes more than three minutes for the concentration used in this US patent.
  • EP 0156129 uses rubber (i.e., an elastomer) as a precursor of a multifunctional activator, and thus the resulting PA is not as hard as a maximum of 1.12 GPa.
  • the active agent has a high Mw, wherein a large amount of activator is required (20% or more).
  • a mixture of a bifunctional activator and a multifunctional activator is used; Thus, the resulting polyamide is not a crosslinked material.
  • U.S. Patent No. 4,067,861 (1978) discloses an anionic polymerization technique of lactam through an extruder in which a metering pump is provided between an extruder body and an extruder die to obtain a constant output, uniform viscosity, (metering pump) was installed to solve the viscosity non-uniformity mechanically, but it is not a fundamental solution.
  • U.S. Patent 5,747,634 (1998) introduces a solution liquid system that simultaneously contains a catalyst and an initiator (reaction promoter) to obtain a more uniform product.
  • a solution system is introduced to obtain a uniform product having a uniform quality and a reproducible result is described.
  • it is not efficient due to a solvent removal problem in applying to the reaction extrusion method.
  • Patent Document 1 US 2016-0102175
  • Patent Document 2 US 5,519,097
  • Patent Document 3 US 3,883,608
  • Patent Document 4 US 7,135,428
  • Patent Document 5 US 5,362,448
  • the present invention has been made to solve the above-mentioned problems of the prior art and the technical problems required from the past.
  • the present invention provides a process for producing polyamide by anion polymerization, which process comprises reacting 100 parts by weight of lactam and the lactam in an amount of 0.01 to 20 parts by weight of an alkali metal as an initiator, 0.3 to 10 parts by weight of a molecular weight modifier, and 0.002 to 1.0 part by weight of carbon dioxide as an activator.
  • the lactam is at least one selected from the group consisting of caprolactam, laurolactam, pyrrolidone and piperidinone. And a manufacturing method thereof.
  • the lactam is composed of two kinds, and at least one lactam is contained in an amount of not less than 50 parts by weight based on 100 parts by weight of the total lactam.
  • a process for preparing polyamide by polymerization is provided.
  • a polyamide having a polydispersity index (PDI) having a narrow molecular weight distribution through an appropriate amount of a molecular weight modifier during polymerization by using carbon dioxide as an activator without using a solvent as a catalyst, it is possible to produce a polyamide having a polydispersity index (PDI) having a narrow molecular weight distribution through an appropriate amount of a molecular weight modifier during polymerization.
  • PDI polydispersity index
  • the alkali metal may include at least one selected from the group consisting of a metal hydride, a metal hydroxide, and a metal alkoxide, , But is not limited thereto.
  • the molecular weight modifier is selected from the group consisting of ethylene-bis-stearamide (EBS), amine compounds, urea compounds and di- And at least one compound selected from the group consisting of compounds.
  • EBS ethylene-bis-stearamide
  • amine compounds amine compounds
  • urea compounds urea compounds
  • the polymerization reaction may be carried out at a temperature range of 180 to 250 ° C for 0.5 to 120 minutes based on the laboratory reactor.
  • the polymerization reaction time is not particularly limited and may be appropriately adjusted depending on the weight of the compound to be charged or the size and type of the reactor.
  • the lactam in the polymerization reaction may have a conversion of at least 95% to polyamide.
  • the present invention provides a polyamide produced by the above polyamide production method.
  • the polyamide may have a molecular weight distribution value of 3.0 or less.
  • the weight average molecular weight (Mw) of the polyamide may range from 40,000 to less than 80,000.
  • the polyamide may be a linear, branched, polybranched having a hyperbranched or dendritic structure.
  • the present invention relates to a polyamide resin composition for a vehicle, a material for an electronic device, an industrial pipe material, an architectural civil engineering material, a 3D printer material, a fiber material, a cladding material, It provides parts materials selected from the group consisting of materials for aviation, materials for solar cells, materials for batteries, materials for sports, materials for home appliances, household materials and cosmetics.
  • the product comprising the component material is selected from the group consisting of automotive air ducts, plastic / rubber compounds, adhesives, lights, polymer optical fibers, fuel filter caps, line systems, cables of electronics, reflectors, Wire protection tube, control unit, light tube, pipe tube, liner, pipe coating agent, oilfield hose, 3D printer, multifilament, spray hose, valve, duct, pulp, gear, medical catheter, aircraft fire retardant, , High hardness film, ski boots, headset, eyeglass frame, toothbrush, water bottle or outsole.
  • the present invention is an eco-friendly process which does not use a solvent as a catalyst, and has a high conversion ratio at a low temperature in a short polymerization time and can produce a polymer having a uniform molecular weight.
  • FIG. 1 is a graph showing the results of GPC analysis of polymerized samples prepared according to the present invention.
  • 3 is a graph showing the results of TGA analysis of the polymerization samples prepared according to the present invention.
  • substituted to “substituted” means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (-F, -Cl, -Br or -I)
  • a halogen atom (-F, -Cl, -Br or -I)
  • substituted means an aryl group substituted with a substituent such as a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, .
  • hydrocarbon group means a linear, branched or cyclic saturated or unsaturated hydrocarbon group unless otherwise specified, and the alkyl group, alkenyl group, alkynyl group and the like may be linear, branched or cyclic.
  • alkyl group means C1 to C30 alkyl group
  • aryl group means C6 to C30 aryl group.
  • heterocyclic group refers to a group containing 1 to 3 hetero atoms selected from the group consisting of O, S, N, P, Si and combinations thereof in one ring. Examples thereof include pyridine, Thiophene, pyrazine, and the like, but is not limited thereto.
  • a process for producing polyamide by anionic polymerization comprising reacting 0.01 to 20 parts by weight of an alkali metal as an initiator, 0.3 to 10 parts by weight of a molecular weight adjuster, 0.002 To 1.0 part by weight of anionic ring-opening polymerization.
  • compositions included in the polyamide production by anion ring-opening polymerization according to the present invention will be described below.
  • the lactam according to the present invention can be preferably used as a monomer for producing a polyamide.
  • the lactam according to the present invention is not limited thereto, and includes 4 to 12 carbon atoms in the ring. Examples thereof include caprolactam, Propiolactam, 2-pyrrolidone, valerolactam, caprolactam, caprolactam, caprolactam, caprolactam, caprolactam, caprolactam, caprolactam, May include caprolactam, heptanolactam, octanolactam, nonanolactam, decanolactam, undecanolactam, and dodecanolactam. have.
  • the lactam according to the present invention may comprise at least one or more selected from the group consisting of caprolactam, laurolactam, pyrrolidone and piperidone.
  • a mixture of caprolactam and laurolactam can be used, but is not limited thereto.
  • the lactam is composed of two kinds, and at least one lactam may include at least 50 parts by weight based on 100 parts by weight of the total lactam.
  • the lactam may be of two kinds, and the two lactams may be caprolactam and laurolactam. Any one of them may contain 50 parts by weight or more of lactam, for example, 90 parts by weight and 10 parts by weight of caprolactam and laurolactam.
  • the present invention is not limited thereto.
  • the alkali metal catalyst according to the present invention is an initiator for producing a polyamide and is a compound which permits the formation of the lactam anion, and is a metal hydride, a metal hydroxide and a metal alkoxide And at least one selected from the group consisting of
  • alkali metals such as sodium or potassium, alkali metal bases
  • sodium hydride, sodium hydride, sodium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate or sodium butanolate or potassium base such as potassium hydride, potassium, potassium hydroxide, potassium methanolate, Potassium ethanolate, potassium propanolate, potassium butanolate, or a mixture thereof, preferably sodium caprolactamate, potassium caprolactamate, magnesium bromide caprolactamate, magnesium Sodium hydroxide, sodium hydroxide, sodium methanolate, sodium propanolate, sodium butanolate, potassium hydroxide, potassium hydroxide, potassium methanolate, potassium ethanolate, potassium carbonate, , Potassium propanolate, potassium butano
  • Such metal catalysts can be used in solid form or as a solution, and it is preferable to use the catalyst in the form of a solid.
  • the catalyst is preferably added to the laurolactam melt, in which the catalyst can be dissolved.
  • the alkali metal catalyst may be contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the total lactam. Preferably 0.03 to 10 parts by weight, and more preferably 0.05 to 5.0 parts by weight.
  • the alkali metal catalyst is added in an amount of less than 0.01 part by weight, there may be a problem of unreacted or reduced reaction rate. If the alkali metal catalyst is more than 20 parts by weight, there may be a problem of generating a low molecular weight polymer The above range is good.
  • the molecular weight modifier according to the present invention may be ethylene-bis-stearamide (EBS), but is not limited thereto, and may be an amine compound, a urea compound And a di-urea compound.
  • EBS ethylene-bis-stearamide
  • the molecular weight modifier may be contained in an amount of 0.3 to 10 parts by weight based on 100 parts by weight of the total lactam. Preferably 0.4 to 7.0 parts by weight, and more preferably 0.5 to 3.0 parts by weight.
  • the molecular weight modifier When the molecular weight modifier is added in an amount of less than 0.3 part by weight, there may be a problem of a high molecular weight polymer or gelation. If the molecular weight adjuster is more than 10 parts by weight, there may be a problem of low molecular weight polymer formation or non- The above range is good.
  • the activator may be preferably carbon dioxide (CO2), but is not limited thereto.
  • CO2 carbon dioxide
  • SIC octadecyl isocyanate
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • the carbon dioxide may be contained in an amount of 0.002 to 1.0 part by weight based on 100 parts by weight of the total lactam. Preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 0.1 part by weight.
  • carbon dioxide is added in an amount of less than 0.002 parts by weight, there may be a problem of unreacted or slowed reaction rate. If the amount of carbon dioxide exceeds 1.0 part by weight, gelation may occur.
  • Example 1 Laurolactam 20 0.02 0.15 1.7
  • Example 2 Laurolactam 20 0.04 0.30 3.4
  • Example 3 Laurolactam 20 0.002 0.15 1.7
  • Example 4 Laurolactam 20 0.05 0.15 1.7
  • Example 5 Laurolactam 20 0.09 0.15 1.7
  • Example 6 Laurolactam 20 0.02 0.05 1.7
  • Example 7 Laurolactam 20 0.02 0.6 1.7
  • Example 8 Laurolactam 20 0.02 0.9 1.7
  • Example 9 Laurolactam 20 0.02 0.15 0.2
  • Example 10 Laurolactam 20 0.02 0.15 6
  • Example 11 Laurolactam 20 0.02 0.15 100
  • Example 12 Laurolactam 2 Caprolactam 18 0.04 0.30 3.4 Comparative Example 1 20 0.02 - 1.7 Comparative Example 2 20 0.02 0.15 - Comparative Example 3 20 - 0.15 1.7
  • a polymerization sample was prepared in the same manner as in Example 1 except that 0.30 g of EBS and 0.04 g of NaH were added.
  • a polymerized sample was prepared in the same manner as in Example 1 except that the content ratio of the composition was changed as shown in Table 1.
  • a polymerization sample was prepared in the same manner as in Example 2, except that 2 g and 18 g of laurolactam and caprolactam, respectively, were added as monomers.
  • a polymerization sample was prepared in the same manner as in Example 1, except that EBS was not used.
  • a polymerized sample was prepared in the same manner as in Example 1, except that the reaction was carried out for 30 minutes without carbon dioxide injection.
  • a polymerization sample was prepared in the same manner as in Example 1 except that NaH was added.
  • Example 5 containing NaH as 0.09 as the Laurolactam was found to have a somewhat lower molecular weight as compared to Examples 1 to 4.
  • Example 8 containing 0.9 of EBS showed a lower molecular weight as compared to Examples 6 to 7
  • carbon dioxide (CO 2 ) in 12 ml was shown to have a higher molecular weight as compared to Examples 9 to 10.
  • Comparative Example 1 which does not contain EBS as a molecular weight modifier
  • the molecular weight distribution was extremely broad as compared with Examples 1 to 11.
  • Comparative Example 3 in which NaH, which is an alkali metal, was not included
  • Comparative Example 2 which was not included, the results showed that polymerization did not proceed.
  • Example 12 it was confirmed that even when a mixture of laurolactam and caprolactam was used as a monomer, the polymerization proceeded to a satisfactory level of molecular weight and PDI.
  • the weight average molecular weight (Mw) was 73,500 and the polydispersity index (PDI) was 2.5 as determined by GPC analysis of the polymer samples prepared as described above.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne un procédé de préparation d'un polyamide par polymérisation par décyclisation anionique et le polyamide ainsi obtenu et, plus spécifiquement, un procédé de préparation d'un polyamide par polymérisation par décyclisation anionique et le polyamide ainsi obtenu, où le procédé est un procédé de traitement écologique n'utilisant pas de solvant à titre de catalyseur et qui permet une polymérisation à un poids moléculaire uniforme, à un taux de conversion élevé en un temps de réaction de polymérisation court, à basse température, comparativement à un procédé de polymérisation existant. Pour ce faire, le procédé de préparation d'un polyamide par polymérisation par décyclisation anionique selon la présente invention est un procédé de préparation d'un polyamide par une réaction de polymérisation anionique, où un lactame, et pour 100 parties en poids de lactame total, 0,01 à 20 parties en poids d'un métal alcalin à titre d'initiateur, 0,3 à 10 parties en poids d'un ajusteur de poids moléculaire, et 0,002 à 1,0 partie en poids de dioxyde de carbone à titre d'activateur peuvent être ajoutés. Comme décrit ci-dessus, la présente invention concerne un procédé de traitement écologique n'utilisant pas de solvant à titre de catalyseur et ayant pour effet de permettre une polymérisation à un poids moléculaire uniforme, à un taux de conversion élevé en un temps de réaction de polymérisation court, à basse température, comparativement à un procédé de polymérisation existant.
PCT/KR2018/013328 2017-11-08 2018-11-05 Procédé de préparation d'un polyamide par décyclisation anionique et polyamide ainsi obtenu WO2019093729A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18875580.5A EP3708604A4 (fr) 2017-11-08 2018-11-05 Procédé de préparation d'un polyamide par décyclisation anionique et polyamide ainsi obtenu
US16/762,725 US20200270397A1 (en) 2017-11-08 2018-11-05 Method for preparing polyamide by anion ring-opening polymerization and polyamide prepared thereby
CN201880070855.8A CN111295410B (zh) 2017-11-08 2018-11-05 通过阴离子开环聚合制备聚酰胺的方法及由此制备的聚酰胺
JP2020525933A JP7084478B2 (ja) 2017-11-08 2018-11-05 陰イオン開環重合によるポリアマイドの無溶媒製造方法及びそれにより製造されたポリアマイド

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KR10-2017-0148304 2017-11-08
KR20170148304 2017-11-08
KR1020180133921A KR102287634B1 (ko) 2017-11-08 2018-11-02 음이온 개환 중합에 의한 폴리아마이드의 제조 방법 및 이에 의해 제조된 폴리아마이드
KR10-2018-0133921 2018-11-02

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EP1091991A1 (fr) 1998-06-29 2001-04-18 Basf Aktiengesellschaft Compositions contenant des polyisocyanates tres visqueux
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