WO2014104483A1 - Résine polyamide, son procédé de préparation et produit moulé la comprenant - Google Patents

Résine polyamide, son procédé de préparation et produit moulé la comprenant Download PDF

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Publication number
WO2014104483A1
WO2014104483A1 PCT/KR2013/002532 KR2013002532W WO2014104483A1 WO 2014104483 A1 WO2014104483 A1 WO 2014104483A1 KR 2013002532 W KR2013002532 W KR 2013002532W WO 2014104483 A1 WO2014104483 A1 WO 2014104483A1
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WIPO (PCT)
Prior art keywords
polyamide resin
dicarboxylic acid
acid
diamine
aliphatic dicarboxylic
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PCT/KR2013/002532
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English (en)
Korean (ko)
Inventor
이은주
권소영
김진규
방승엽
임상균
이기연
전석민
최성철
Original Assignee
제일모직 주식회사
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Publication of WO2014104483A1 publication Critical patent/WO2014104483A1/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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • 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
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a polyamide resin, a method for preparing the same, and a product including the same. More specifically, the present invention relates to a high heat-resistant polyamide resin having excellent heat resistance and processability and capable of reducing gas generation during molding, a method for preparing the same, and a molded article including the same.
  • Nylon 66 and nylon 6 are the best known polyamide resins, and aliphatic polyamide resins such as nylon 610, nylon 612, nylon 11 and nylon 12 have been continuously developed.
  • aliphatic polyamide resins such as nylon 610, nylon 612, nylon 11 and nylon 12 have been continuously developed.
  • high heat-resistant nylons such as nylon 6T, nylon 9T, nylon 10T, nylon 11T, and nylon 12T are underway to improve the poor thermal properties of aliphatic polyamide resins (nylons). It is becoming.
  • the heat resistance temperature is considerably higher than that of general nylon and can be used in various fields requiring high heat resistance properties.
  • the high heat-resistant polyamide resin since the melting temperature is very high and the decomposition temperature is lower than the processing temperature, it is difficult to use alone, and it is generally copolymerized to lower the processing temperature.
  • linear aliphatic dicarboxylic acids such as adipic acid are mainly used.
  • the melting temperature (Tm) is about 300 to about 320 ° C, and the moldability is improved.
  • Tm melting temperature
  • the moldability is improved.
  • gas is generated by the cyclization reaction as in Scheme 1.
  • An object of the present invention is to provide a high heat-resistant polyamide resin that is excellent in heat resistance and processability, and can reduce the amount of gas generated during molding.
  • Another object of the present invention is to provide a method for producing the polyamide resin.
  • Another object of the present invention is to provide a molded article formed of the polyamide resin.
  • the polyamide resin is a polymer of dicarboxylic acid and diamine, and the dicarboxylic acid contains a branched aliphatic dicarboxylic acid.
  • the branched aliphatic dicarboxylic acid may comprise one or more of branched aliphatic dicarboxylic acids having about 5 to about 12 carbon atoms.
  • the dicarboxylic acid can comprise about 1 to about 60 mole% of the branched aliphatic dicarboxylic acid and about 40 to about 99 mole% of aromatic dicarboxylic acid.
  • the aromatic dicarboxylic acid may include one or more of aromatic dicarboxylic acids having 8 to 20 carbon atoms.
  • the dicarboxylic acid can further comprise up to about 45 mole percent linear aliphatic dicarboxylic acid.
  • the linear aliphatic dicarboxylic acid may include at least one of linear aliphatic dicarboxylic acids having 4 to 12 carbon atoms.
  • the diamine may comprise one or more of aliphatic diamines having 4 to 20 carbon atoms.
  • the glass transition temperature (Tg) of the polyamide resin is about 90 ° C. or more, the crystallization temperature (Tc) is about 250 to about 280 ° C., and the melting temperature (Tm) may be about 290 to about 320 ° C. have.
  • the intrinsic viscosity of the polyamide resin may be 0.3 to 2.0 dL / g.
  • the polyamide resin may be about 10% or less of gas generation under inert gas conditions and temperature conditions of about 120 to about 350 °C.
  • Another aspect of the present invention relates to a method for producing the polyamide resin.
  • the preparation method is characterized in that it comprises a step of polymerizing the dicarboxylic acid, and the diamine containing a branched aliphatic dicarboxylic acid.
  • the polyamide resin production method comprises preparing a prepolymer by polymerizing the dicarboxylic acid and the diamine; And solid phase polymerizing the prepolymer; It may include a step.
  • the prepolymer may have an intrinsic viscosity of about 0.05 kPa to about 0.40 dL / g.
  • the solid phase polymerization may be to heat the prepolymer to a temperature of about 170 to about 280 °C in the presence of an inert gas.
  • Another aspect of the present invention relates to a molded article formed from the polyamide resin.
  • the present invention has the effect of the invention to provide a high heat-resistant polyamide resin, a manufacturing method thereof, and a molded article including the same, which is excellent in heat resistance and workability and can reduce the amount of gas generated during molding.
  • the polyamide resin according to the present invention is a polymer of dicarboxylic acid and diamine, wherein the dicarboxylic acid includes a branched aliphatic dicarboxylic acid, and the dicarboxylic acid moiety and the diamine derived from the dicarboxylic acid.
  • the diamine moiety derived from has a repeating structure.
  • dicarboxylic acid or the like refers to dicarboxylic acid, alkyl esters thereof (lower alkyl esters having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester), and acids thereof. It is used in the sense including acid anhydride and the like, and reacts with diamine to form a dicarboxylic acid moiety.
  • the dicarboxylic acid moiety and the diamine moiety are residues remaining after the hydrogen atom, the hydroxy group or the alkoxy group is removed when the dicarboxylic acid and the diamine are polymerized. residue).
  • Dicarboxylic acids (components) used in the present invention include branched aliphatic dicarboxylic acids.
  • branched aliphatic dicarboxylic acid a compound containing at least one branched aliphatic dicarboxylic acid having 5 to 12 carbon atoms, which may or may not contain a hetero atom such as an oxygen atom (O), may be used.
  • O oxygen atom
  • 3- (tert-butyl) adipic acid (3- (tert-butyl) adipic acid), 3-methoxy-adipic acid, 2-methoxy-adipic acid (2-methoxy-adipic acid), 3-methyl adipic acid, 3- (3-methoxybenzoyl) -adipic acid, 3- (3-methoxy benzoyl) -adipic acid, Mixtures of these and the like can be used, but are not limited thereto.
  • aliphatic dicarboxylic acid in which the ⁇ -position, such as 3-methyl adipic acid, is branched can be used.
  • the content of the branched aliphatic dicarboxylic acid is about 1 to about 60 mole%, preferably about 20 to about 55 mole%, more preferably about 35 to about 55 mole% of the total dicarboxylic acid. It is excellent in heat resistance, processability, etc. of the polyamide resin in the above range, it is possible to prevent or reduce the generation of gas during molding.
  • the dicarboxylic acid includes aromatic dicarboxylic acid in addition to the branched aliphatic dicarboxylic acid.
  • aromatic dicarboxylic acid the compound containing 1 or more types of C8-C20 aromatic dicarboxylic acid can be used, For example, terephthalic acid, isophthalic acid, 2, 6- naphthalenedicarboxylic acid, 2 , 7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxyphenylene acid, 1,3-phenylenedioxydiacetic acid, defenic acid, 4,4'-oxybis ( Benzoic acid), benzylphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-diphenylcarboxylic acid, mixtures thereof, and the like.
  • terephthalic acid isophthalic acid, 2,
  • the content of the aromatic dicarboxylic acid is about 40 to about 99 mol%, preferably about 45 to about 80 mol%, more preferably about 45 to about 65 mol%, of the total dicarboxylic acids. It is excellent in heat resistance, workability, etc. of a polyamide resin in the said range.
  • the dicarboxylic acid used in the present invention may further include linear aliphatic dicarboxylic acid in order to improve processability and economical efficiency of the polyamide resin.
  • the linear aliphatic dicarboxylic acid may be a linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms, preferably adipic acid, but is not limited thereto.
  • the linear aliphatic dicarboxylic acid may further comprise about 45 mol% or less, preferably about 1 to about 40 mol%, of all dicarboxylic acids. In the above range, a copolymerized polyamide resin having more excellent processability and economical efficiency can be obtained.
  • one or more common aliphatic diamines for example, aliphatic diamines having 4 to 20 carbon atoms can be used.
  • Specific examples of the aliphatic diamine include 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,10-decanediamine (DDA), 1,12 Dodecanediamine (DDDA), 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine , 5-methyl-1,9-nonanediamine, 2,2-oxybis (ethylamine), bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether (EGBA), 1,7- One or more aliphatic linear diamines, such as diamino-3,5-dioxoheptane and mixtures thereof, may be
  • the content of the aliphatic diamine may be about 60 mol% or more, preferably about 70 to about 99 mol%, in the total diamines. In the above range may be excellent in heat resistance, processability and the like of the polyamide resin.
  • the diamine used in the present invention may further contain an aromatic diamine in order to increase the heat resistance, processability and the like of the polyamide resin.
  • aromatic diamine one or more kinds of aromatic diamines having 6 to 30 carbon atoms can be used.
  • phenylenediamine compounds such as m-phenylenediamine and p-phenylenediamine
  • xylenediamine compounds such as m-xylenediamine and p-xylenediamine
  • naphthalenediamine compound, etc. can be illustrated, This is not restrictive.
  • the content thereof may be about 40 mol% or less, preferably about 1 to about 30 mol%, of the total diamine. It is excellent in heat resistance, workability, etc. of a copolyamide resin in the said range.
  • the ratio of the dicarboxylic acid and the diamine may be, for example, about 0.85 to about 1.05, preferably about 0.90 to about 1.03. In the above range, it is possible to prevent a decrease in physical properties due to unreacted monomers.
  • the polyamide resin of the present invention may be one in which the end group is sealed with an end capping agent containing at least one aliphatic carboxylic acid and aromatic carboxylic acid.
  • an end capping agent containing at least one aliphatic carboxylic acid and aromatic carboxylic acid.
  • the end-sealing agent for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauryl acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyl acid , Benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, mixtures thereof and the like may be used, but is not limited thereto.
  • the terminal encapsulant may be included, for example, about 0.01 to about 5 moles, preferably about 0.1 to about 3 moles, based on 100 moles of the dicarboxylic acid and the diamine.
  • the copolymerized polyamide resin of the present invention may be prepared according to a conventional polyamide production method, for example, may be prepared by polymerizing the dicarboxylic acid and the diamine.
  • the copolymerization may be carried out according to a conventional copolymerization preparation method, for example, may be carried out using a melt polymerization method or the like, and the polymerization temperature is about 80 to about 300 ° C, preferably about 90 to about 280 ° C.
  • the polymerization pressure may be about 10 to about 40 kgf / cm 2 , but is not limited thereto.
  • the method for producing the polyamide resin may be prepared by polymerizing the dicarboxylic acid and the diamine to prepare a prepolymer, and by prepolymerizing the prepolymer.
  • the dicarboxylic acid, the diamine, the catalyst and water are charged to the reactor, stirred at about 80 to about 150 ° C. for about 0.5 to about 2 hours, and then at a temperature of about 200 to about 280 ° C.
  • the prepolymer has an intrinsic viscosity [ ⁇ ] of about 0.05 kPa to about 0.40 dL / g, preferably about 0.1 kPa to about 0.40 kDL / g, measured by a Ubbelodhde viscometer at 25 ° C. using 98% sulfuric acid solution.
  • ⁇ intrinsic viscosity
  • Copolymer polyamide having a desired weight average molecular weight in the above range can be obtained.
  • the solid phase polymerisation of the prepolymer to about 170 to about 280 ° C., preferably about 180 to about 250 ° C., more preferably about 200 to about 250 ° C. in the presence of an inert gas such as nitrogen, argon May be heated.
  • Copolymer polyamide having a weight average molecular weight of about 20,000 kPa to about 45,000 g / mol in the above range can be obtained.
  • a catalyst may be used in the copolymerization reaction.
  • a phosphorus-based catalyst may be used.
  • phosphoric acid, phosphorus acid, hypophosphorous acid or salts or derivatives thereof may be used.
  • phosphoric acid, phosphoric acid, hypophosphorous acid, sodium hypophosphate, sodium hypophosphinate and the like can be used.
  • the catalyst is for example about 0 to about 3 parts by weight, preferably about 0.001 to about 1 part by weight, more preferably about 0.01 to about 1 part by weight based on 100 parts by weight of the total monomers (dicarboxylic acid and diamine). 0.5 parts by weight may be used, but is not limited thereto.
  • the terminal blocker may be used as the content in the method for preparing the polyamide resin, and by adjusting the content of the terminal blocker, the viscosity of the copolymerized polyamide resin may be adjusted.
  • the glass transition temperature (Tg) of the polyamide resin according to the present invention is about 90 ° C. or more, preferably about 90 ° C. to about 100 ° C.
  • the crystallization temperature (Tc) is about 250 to about 280 ° C., preferably about 260 ° C. It is about 280 ° C
  • the melting temperature (Tm) may be about 290 to about 320 ° C, preferably about 300 ° C to about 320 ° C.
  • the polyamide resin has an intrinsic viscosity [ ⁇ ] of about 0.3 kPa to about 2.0 kDL / g, preferably about 0.6 kPa to about 2.0 kDL / g, measured by a Ubbelodhde viscometer at 25 ° C. using 98% sulfuric acid solution. More preferably about 0.8 kPa to about 1.5 kPa dL / g.
  • the polyamide resin may have a weight average molecular weight of about 20,000 to about 45,000 ⁇ g / mol measured by GPC.
  • the polyamide resin may be about 10% or less, and preferably about 2% to about 8%, based on an inothermal TGA method, measured under inert gas conditions and temperature conditions of about 120 to about 350 ° C. Specifically, the gas generation amount is maintained for about 30 minutes at about 120 °C in the polymer specimen under a stream of nitrogen, to blow out moisture that may be present in the polymer, and then maintained at about 350 °C for about 30 minutes to the polyamide resin The weight loss rate was measured.
  • the molded article according to the invention is formed from the polyamide resin.
  • the molded article may be manufactured for use in a connector, which requires characteristics such as high heat resistance and low gas generation amount, but is not limited thereto.
  • the molded article can be easily formed by those skilled in the art to which the present invention pertains.
  • Example 1-3 and Comparative Example 1-3
  • dicarboxylic acid (Diacid)
  • terephthalic acid terephthalic acid (TPA)
  • 3-methyladipic acid 3-methyladipic acid
  • adipic acid adipic acid
  • diamine diamine
  • 1,6-hexamethylenediamine is used as the catalyst based on 1.65 mol parts of benzoic acid and 100 parts by weight of the dicarboxylic acid and diamine based on 100 mol parts of the dicarboxylic acid and diamine.
  • 0.1 parts by weight of hypophosphinate and about 97 parts by weight of water were placed in a 1 liter autoclave and filled with nitrogen. After stirring at 130 ° C.
  • the polyamide resins prepared in Examples and Comparative Examples were evaluated for melting temperature, crystallization temperature, glass transition temperature, intrinsic viscosity, and gas generation amount by the following method, and the results are shown in Table 2 below.
  • Tm Melting temperature
  • Tc crystallization temperature
  • Tg glass transition temperature
  • DSC Different Scanning Calorimeter
  • Gas generation amount (unit:%): It measured at inert gas conditions and # 120-350 degreeC using iso-thermal TGA. Specifically, under the nitrogen stream, the polymer specimen was maintained at 120 ° C. for 30 minutes to blow out moisture that may be present in the polymer, and then maintained at 350 ° C. for 30 minutes to measure the weight loss ratio.
  • the polyamide resins (Examples 1 to 3) according to the present invention have excellent heat resistance with a glass transition temperature of 90 ° C. or higher, and from the results of melting temperature, crystallization temperature and intrinsic viscosity, It can be seen that excellent.
  • the gas generation amount is 7.2% or less, and when used for the connector, blisters may not occur.
  • Comparative Example 1 which does not use the branched aliphatic dicarboxylic acid of the present invention, has a disadvantage that processing is difficult because the melting temperature is too high, and Comparative Examples 2 and 3 have blisters having a gas generation amount of 10% or more. There is a high possibility of occurrence.
  • the polyamide resins (Examples 1 to 3) according to the present invention are excellent in heat resistance at a glass transition temperature of 90 ° C. or higher and excellent in workability from the results of melting temperature, crystallization temperature, intrinsic viscosity, and the like.
  • the gas generation amount is 7.2% or less, and when used for the connector, blisters may not occur.
  • Comparative Example 1 which does not use the branched aliphatic dicarboxylic acid of the present invention, has a disadvantage that processing is difficult because the melting temperature is too high, and Comparative Examples 2 and 3 have blisters having a gas generation amount of 10% or more. There is a high possibility of occurrence.

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

Abstract

Une résine polyamide de la présente invention est un polymère d'un acide dicarboxylique et d'une diamine, et l'acide dicarboxylique comprend un acide dicarboxylique aliphatique ramifié. La résine polyamide présente une résistance à la chaleur et une aptitude au traitement remarquables, et peut réduire la génération de gaz pendant le moulage.
PCT/KR2013/002532 2012-12-28 2013-03-27 Résine polyamide, son procédé de préparation et produit moulé la comprenant WO2014104483A1 (fr)

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KR10-2012-0157680 2012-12-28
KR1020120157680A KR101557543B1 (ko) 2012-12-28 2012-12-28 폴리아미드 수지, 이의 제조방법 및 이를 포함하는 성형품

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170130001A1 (en) * 2015-11-10 2017-05-11 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine

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EP0982342A1 (fr) * 1998-08-27 2000-03-01 Ube Industries, Ltd. Polyamide présentant d'excellentes propriétés d'étirage
KR20070104246A (ko) * 2006-04-21 2007-10-25 이엠에스-케미에 아게 투명한 폴리아미드 몰딩 조성물
US20110135860A1 (en) * 2004-05-14 2011-06-09 Arkema France Blends of transparent amorphous polyamides based on diamines and on tetradecanedioic acid and semicrystalline polyamides
US20110189419A1 (en) * 2008-07-07 2011-08-04 Arkema France Polyamide, composition comprising such a polyamide and their uses
KR20120075348A (ko) * 2010-12-28 2012-07-06 제일모직주식회사 표면 반사율 및 내열성이 우수한 폴리아미드 조성물
KR101183393B1 (ko) * 2008-07-11 2012-09-14 상하이 킹파 사이언스 앤 테크놀로지 컴퍼니 리미티드 세미-방향족 폴리아미드 및 그 폐수 배출량을 낮추는 제조 방법

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JP4056194B2 (ja) 2000-03-27 2008-03-05 独立行政法人科学技術振興機構 カルボン酸とアミンを用いたアミド縮合物の製造方法

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Publication number Priority date Publication date Assignee Title
EP0982342A1 (fr) * 1998-08-27 2000-03-01 Ube Industries, Ltd. Polyamide présentant d'excellentes propriétés d'étirage
US20110135860A1 (en) * 2004-05-14 2011-06-09 Arkema France Blends of transparent amorphous polyamides based on diamines and on tetradecanedioic acid and semicrystalline polyamides
KR20070104246A (ko) * 2006-04-21 2007-10-25 이엠에스-케미에 아게 투명한 폴리아미드 몰딩 조성물
US20110189419A1 (en) * 2008-07-07 2011-08-04 Arkema France Polyamide, composition comprising such a polyamide and their uses
KR101183393B1 (ko) * 2008-07-11 2012-09-14 상하이 킹파 사이언스 앤 테크놀로지 컴퍼니 리미티드 세미-방향족 폴리아미드 및 그 폐수 배출량을 낮추는 제조 방법
KR20120075348A (ko) * 2010-12-28 2012-07-06 제일모직주식회사 표면 반사율 및 내열성이 우수한 폴리아미드 조성물

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170130001A1 (en) * 2015-11-10 2017-05-11 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US10793673B2 (en) * 2015-11-10 2020-10-06 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US11401377B2 (en) 2015-11-10 2022-08-02 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US11976169B2 (en) 2015-11-10 2024-05-07 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine

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