WO2020130326A1 - Procédé de préparation d'un polyamide par polymérisation par ouverture de cycle anionique-par coordination au moyen d'un catalyseur à base de silice, et cyclisation anionique et polyamide ainsi obtenu - Google Patents

Procédé de préparation d'un polyamide par polymérisation par ouverture de cycle anionique-par coordination au moyen d'un catalyseur à base de silice, et cyclisation anionique et polyamide ainsi obtenu Download PDF

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Publication number
WO2020130326A1
WO2020130326A1 PCT/KR2019/014572 KR2019014572W WO2020130326A1 WO 2020130326 A1 WO2020130326 A1 WO 2020130326A1 KR 2019014572 W KR2019014572 W KR 2019014572W WO 2020130326 A1 WO2020130326 A1 WO 2020130326A1
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polyamide
coordination
opening polymerization
group
polymerization reaction
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PCT/KR2019/014572
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English (en)
Korean (ko)
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이진서
이혜연
도승회
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한화솔루션 주식회사
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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
    • 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
    • C08G69/20—Anionic polymerisation characterised by the catalysts used

Definitions

  • the present invention relates to a method for producing polyamide by coordination-anion ring-opening polymerization and a polyamide prepared thereby, in particular, as a coordination polymerization catalyst, a silica-based catalyst is used to improve molecular weight and PDI, and the polymerization rate is fast. It relates to a method for producing a polyamide of a polymer having no color change.
  • Polyamide resin is a linear polymer bound by amide (-NHCO-) bonds. It is tough and has excellent properties such as friction resistance, abrasion resistance, oil resistance and solvent resistance, and is easily melt-molded. Textiles for clothing materials and industrial materials It is widely used as engineering plastics. Polyamides can be classified into aliphatic polyamides, aromatic polyamides, and aliphatic cyclic polyamides according to the molecular structure, and double aliphatic polyamides are called nylon and aromatic polyamides are called aramids. Also.
  • polyamides are produced 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, It can be largely divided into those obtained by polycondensation of aminocarboxylic acids such as nylon 11 and nylon 12.
  • so-called hybrid polymerized nylons such as hybrid condensates of caprolactam and 6, 10-nylon salts (hexamethylenediamine and sebacate), are produced industrially, and in the molecule, functional groups such as side chains and hydroxyl groups, aromatic rings And polyamides, including heterocycles, have been studied.
  • Lactams such as caprolactam
  • This method generally uses a catalyst and also an initiator (also known as an active agent) (activated anionic polymerization).
  • an initiator also known as an active agent
  • Diisocyanates or derivatives thereof have been used as initiators or active agents frequently used so far.
  • polyamide 12 is produced by ring-opening polymerization of laurolactam, and at this time, a polymerization initiator is required to activate the catalyst and polymerization reaction with the monomer laurolactam to initiate polymerization. In addition, it affects the thermal properties, polymerization rate, reaction conversion rate, etc. of the polyamide obtained according to the type of polymerization initiator selected during polymerization of polyamide 12.
  • Polyamide 12 has low strength and is difficult to apply to high-load equipment materials. However, it has a wide range of applications due to its low water absorption, excellent weather resistance, and excellent chemical resistance. However, anionic polymerization of polyamides is difficult to produce high molecular weight polyamides with a narrow molecular weight distribution (PDI) due to side reactions such as branching and back biting, and color changes occur during polymerization. There is a problem.
  • PDI molecular weight distribution
  • United States Patent Registration No. US 4719285 discloses a method of producing polyamide by using a silicone compound as a catalyst for diamine and diamide in nylon form polyamide. However, this is a difference in producing a polyamide from diamine and diamide, not an anionic polymerization method.
  • Korean Patent Publication No. 10-20040030642 provides a method for producing nylon 6 by supplying a feed stream containing caprolactam, nylon 6 prepolymer and a small amount of aminocapronitrile to a multi-stage reactive distillation column as a method for producing nylon 6. Is disclosed. This provides a method that does not require the additional purification step of the intermediate product, and has a low contribution to the improvement of molecular weight and PDI in the production of polyamide.
  • the present invention was completed to prepare a polyamide without improvement in polymerization speed, molecular weight, and PDI by preparing polyamide by coordination-anion ring-opening polymerization.
  • Patent Document 1 U.S. Patent No. 4719285 (Jan. 12, 1988)
  • Patent Document 2 Chinese Patent Publication No. 001853778 (Nov. 2006)
  • Patent Document 3 Korean Patent Publication No. 10-2004-0030642 (2004.04.09)
  • Patent Document 4 Japanese Patent Registration No. 08-259806 (2003.04.14)
  • the present invention aims to solve the problems of the prior art as described above and the technical problems requested from the past.
  • the object of the present invention is to improve the molecular weight and PDI by reducing the side reaction of the polymerization reaction by adding the silica-based catalyst as the coordination polymerization catalyst and the alkali metal as the anionic polymerization catalyst during coordination-anion polymerization of the amide. In providing.
  • the object of the present invention is to provide the polyamide without color change in the polymerization process, as well as improving the molecular weight and PDI, and also increasing the polymerization rate by adding the catalysts.
  • the method for producing polyamide by coordination-anionic ring-opening polymerization according to the present invention for achieving the above object is lactam, 0.001 to 20 parts by weight of silica-based catalyst as a coordination polymerization catalyst, and anionic polymerization catalyst with respect to 100 parts by weight of the entire lactam.
  • the alkali metal may include 0.01 to 20 parts by weight.
  • the silica-based catalyst is a method for producing polyamide by coordination-anion ring-opening polymerization reaction, characterized in that it comprises at least one or more selected from the group consisting of compounds represented by the following formula: Is provided.
  • n means a natural number of 1 to 4
  • R is any one or more selected from hydrogen, alkyl, alkoxy and aromatic, and the alkyl and the alkoxy have 1 to 12 carbons.
  • the alkali metal may include at least one selected from the group consisting of metal hydride, metal hydroxide and metal alkoxide, It is not limited to this.
  • the molecular weight modifiers are ethylene-bis-stearamide (EBS), amine compound, urea compound, and di-urea compound. It may further include at least one or more selected from the group consisting of.
  • the activator may further include carbon dioxide (CO 2 ), but is not limited thereto, such as benzoyl chloride, N-acetyl caprolactam, From the group consisting of N-acetyl laurolactam, octadecyl isocyanate (SIC), toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) It may include at least one selected.
  • CO 2 carbon dioxide
  • CO 2 carbon dioxide
  • benzoyl chloride such as benzoyl chloride, N-acetyl caprolactam, From the group consisting of N-acetyl laurolactam, octadecyl isocyanate (SIC), toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) It may include at least one selected.
  • the polymerization reaction can be carried out within a range of 0.5 to 180 minutes.
  • the polymerization reaction time is not particularly limited, of course, can be appropriately adjusted according to the weight of the compound to be added or the size and type of the reactor.
  • the polymerization reaction can be carried out at 180 to 300 °C.
  • the present invention provides a polyamide prepared by the above manufacturing method, wherein the polyamide may have a molecular weight distribution range (PDI: polydispersity index) of 4.0 or less.
  • PDI molecular weight distribution range
  • the present invention has an effect of providing a polyamide having improved molecular weight and PDI by reducing side reactions by adding a silica-based catalyst together during coordination of an amide-anionic polymerization.
  • the object of the present invention is to improve the molecular weight and PDI by adding the catalysts, the reaction rate is also fast, there is an effect of providing a polyamide without color change in the polymerization process.
  • substituted to “substituted” means that at least one hydrogen atom in the functional group of the present invention is a halogen atom (-F, -Cl, -Br or -I), a hydroxyl group, Nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group, ester group, ketone group, substituted or unsubstituted alkyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group , Substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted heteroaryl group, and substituted or unsubstituted heterocyclic group means one or more substituents selected from the group consisting of , The substituents may be connected to each other to form
  • substitution is a hydrogen atom is 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, or an aryloxy group having 6 to 20 carbon atoms, unless otherwise specified.
  • 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, or an aryloxy group having 6 to 20 carbon atoms, unless otherwise specified.
  • 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 a C1 to C30 alkyl group
  • aryl group means a C6 to C30 aryl group.
  • heterocyclic group refers to a group containing 1 to 3 heteroatoms in one ring selected from the group consisting of O, S, N, P, Si and combinations thereof, such as pyridine, Thiophene, pyrazine, and the like, but is not limited thereto.
  • the anionic polymerization of the conventional lactam is a side reaction, for example, due to the occurrence of side reactions such as branching and bact biting, there was a problem in manufacturing a high molecular weight polyamide having a narrow PDI. .
  • lactam as a method for producing polyamide by coordination-anion ring-opening polymerization reaction, lactam, 0.001 to 20 parts by weight of silica catalyst as a coordination polymerization catalyst, and alkali metal 0.01 as anionic polymerization catalyst It provides a method for producing a polyamide by coordination-anion ring-opening polymerization reaction comprising 20 parts by weight.
  • compositions included in the preparation of polyamide by coordination-anion ring-opening polymerization according to the present invention will be described.
  • the lactam according to the present invention can be preferably used as a monomer for preparing polyamide.
  • the present invention is not limited thereto, and may include, for example, laurolactam, caprolactam, piperidone, pyrrolidone, enantolactam, and caprylactam, and in some cases propiolactam, 2 -Pyrrolidone (2-pyrrolidone), valerolactam, caprolactam, heptanolactam, octanolactam, nonanolactam, decanolactam , Undecanolactam and dodecanolactam.
  • the silica-based catalyst may include 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight. In the above range, it is possible to manufacture a polyamide with improved molecular weight and PDI without changing color while simultaneously reducing the occurrence of side reactions.
  • the silica-based catalyst may include at least one selected from the group consisting of compounds represented by the following formula, but is not limited thereto.
  • n means a natural number of 1 to 4
  • R is any one or more selected from hydrogen, alkyl, alkoxy and aromatic, and the alkyl and the alkoxy have 1 to 12 carbons.
  • the catalyst is, for example, an alkali metal, in order to solve the problem of lowering the polymerization rate due to weak base amine formation occurring during the conventional lactam polymerization, the catalyst relative to 100 parts by weight of the entire lactam Phosphorus alkali metal may be included in 0.01 to 20 parts by weight. Preferably it may contain 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.
  • the catalyst is added in an amount of less than 0.01 part by weight, there may be a problem of unpolymerization or a reduction in reaction rate, and when the catalyst exceeds 20 parts by weight, there may be a problem of generating a low molecular weight polymer.
  • the range is preferred.
  • Such a metal catalyst can be used in the form of a solid or a solution, and it is preferred 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.
  • a molecular weight modifier may be included, and preferably, it may be ethylene-bis-stearamide (EBS), but is not limited thereto. It may include at least one selected from the group consisting of a compound, a urea (urea) compound and a diurea (di-urea) compound.
  • EBS ethylene-bis-stearamide
  • the molecular weight modifier may include 0.3 to 10 parts by weight based on 100 parts by weight of the entire lactam. Preferably it may contain 0.4 to 7.0 parts by weight, more preferably 0.5 to 3.0 parts by weight.
  • the molecular weight modifier when added in an amount of less than 0.3 parts by weight, there may be a high molecular weight polymer or gelation problem, and when the molecular weight modifier exceeds 10 parts by weight, there may be a problem of generating a low molecular weight polymer or non-polymerization.
  • the above range is preferred.
  • the activator may be preferably carbon dioxide (CO 2 ), but is not limited thereto, for example, benzoyl chloride, N-acetyl caprolactam, From the group consisting of N-acetyl laurolactam, octadecyl isocyanate (SIC), toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) It may include one or more selected.
  • CO 2 carbon dioxide
  • benzoyl chloride N-acetyl caprolactam
  • N-acetyl caprolactam N-acetyl caprolactam
  • SIC octadecyl isocyanate
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • the activator may include 0.002 to 20 parts by weight based on 100 parts by weight of the entire lactam. Preferably it may contain from 0.005 to 5 parts by weight, more preferably from 0.01 to 1 part by weight. In this case, when the activator is added in an amount of less than 0.002 parts by weight, a polymer having a low molecular weight due to non-polymerization may be produced or a reaction rate may be reduced. The above range is preferable because there may be.
  • compositions included in the preparation of polyamide by coordination-anion ring-opening polymerization according to the present invention have been described above, and the synthesis of polyamide is described below.
  • the polymerization reaction can be carried out within a range of 0.5 to 180 minutes.
  • the polymerization reaction time is not particularly limited, of course, can be appropriately adjusted according to the weight of the compound to be added or the size and type of the reactor.
  • the polymerization reaction can be carried out at 180 to 300 °C. Preferably it can be carried out at 200 to 280 °C.
  • the present invention provides a polyamide prepared by the above manufacturing method, wherein the polyamide may have a molecular weight distribution range (PDI: polydispersity index) of 4.0 or less.
  • PDI molecular weight distribution range
  • Polyamide 12 was prepared in the same manner as in Example 1, except that the polymerization temperature was 230°C.
  • Polyamide 12 was prepared in the same manner as in Example 1, except that 1.14 ml of Tetraethyl orthosilicate was injected.
  • Polyamide 12 was prepared in the same manner as in Example 1, except that Tetraethyl orthosilicat was not used.
  • Polyamide 12 was prepared in the same manner as in Example 2, except that Tetraethyl orthosilicat was not used.

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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)

Abstract

La présente invention concerne un procédé de préparation d'un polyamide par polymérisation par ouverture de cycle anionique-par coordination, et un polyamide préparé par procédé et, plus particulièrement, un procédé de préparation d'un polyamide d'un polymère à l'aide d'un catalyseur à base de silice en tant que catalyseur de polymérisation par coordination de sorte que le polyamide présente un poids moléculaire et un PDI améliorés, un taux de polymérisation rapide, et aucun changement de couleur. Par conséquent, la présente invention a pour effet de fournir un polyamide ayant un poids moléculaire amélioré et un PDI par l'ajout du catalyseur en même temps que la polymérisation anionique-par coordination, et la réduction d'une réaction latérale.
PCT/KR2019/014572 2018-12-18 2019-10-31 Procédé de préparation d'un polyamide par polymérisation par ouverture de cycle anionique-par coordination au moyen d'un catalyseur à base de silice, et cyclisation anionique et polyamide ainsi obtenu WO2020130326A1 (fr)

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KR10-2018-0164129 2018-12-18
KR1020180164129A KR102287645B1 (ko) 2018-12-18 2018-12-18 실리카계 촉매를 이용한 배위-음이온 개환 중합에 의한 폴리아마이드의 제조방법 및 이에 의해 제조된 폴리아마이드

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101531A (en) * 1976-05-19 1978-07-18 Chevron Research Company Anionic copolymerization of 2-pyrrolidone with caprolactam or piperidone
US4719285A (en) * 1986-09-17 1988-01-12 The Standard Oil Company Process for the manufacture of polyamide from diamines and diamides catalyzed by silicon compounds
KR20130118326A (ko) * 2010-10-07 2013-10-29 바스프 에스이 단량체 조성물을 제조하는 방법 및 몰딩된 폴리아미드 부품 제조를 위한 이의 용도
KR20140115171A (ko) * 2013-03-20 2014-09-30 한국화학연구원 바이오매스 기반의 나일론 6,5 랜덤 공중합체 및 이의 제조 방법
KR20150044786A (ko) * 2011-03-02 2015-04-27 바스프 에스이 락탐 조성물에서의 비닐방향족-디엔 공중합체의 용도

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69034146T2 (de) 1989-04-13 2005-07-14 Beecham Group P.L.C., Brentford Chemische Verbindungen
JP3396321B2 (ja) 1994-12-05 2003-04-14 三菱化学株式会社 ポリアミド樹脂組成物、その製造方法及びその用途
US6437089B1 (en) 2001-06-01 2002-08-20 E. I. Du Pont De Nemours And Company Process for the production of nylon 6

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101531A (en) * 1976-05-19 1978-07-18 Chevron Research Company Anionic copolymerization of 2-pyrrolidone with caprolactam or piperidone
US4719285A (en) * 1986-09-17 1988-01-12 The Standard Oil Company Process for the manufacture of polyamide from diamines and diamides catalyzed by silicon compounds
KR20130118326A (ko) * 2010-10-07 2013-10-29 바스프 에스이 단량체 조성물을 제조하는 방법 및 몰딩된 폴리아미드 부품 제조를 위한 이의 용도
KR20150044786A (ko) * 2011-03-02 2015-04-27 바스프 에스이 락탐 조성물에서의 비닐방향족-디엔 공중합체의 용도
KR20140115171A (ko) * 2013-03-20 2014-09-30 한국화학연구원 바이오매스 기반의 나일론 6,5 랜덤 공중합체 및 이의 제조 방법

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KR20200075449A (ko) 2020-06-26
KR102287645B1 (ko) 2021-08-06

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