WO2003062303A1 - Polyamide - Google Patents

Polyamide Download PDF

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Publication number
WO2003062303A1
WO2003062303A1 PCT/JP2002/013649 JP0213649W WO03062303A1 WO 2003062303 A1 WO2003062303 A1 WO 2003062303A1 JP 0213649 W JP0213649 W JP 0213649W WO 03062303 A1 WO03062303 A1 WO 03062303A1
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WO
WIPO (PCT)
Prior art keywords
acid
polyamide
molecular weight
present
branched
Prior art date
Application number
PCT/JP2002/013649
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English (en)
Japanese (ja)
Inventor
Harufumi Hagino
Suguru Ohara
Shigeru Murata
Original Assignee
Kyowa Hakko Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyowa Hakko Chemical Co., Ltd. filed Critical Kyowa Hakko Chemical Co., Ltd.
Priority to JP2003562177A priority Critical patent/JPWO2003062303A1/ja
Publication of WO2003062303A1 publication Critical patent/WO2003062303A1/fr

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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
    • C08G69/26—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

Definitions

  • the present invention relates to a polyamide useful for applications such as machine parts, bottles, electric parts, automobile parts, medical supplies, household goods, and the like.
  • An object of the present invention is to provide a polyamide which is excellent in solubility in an organic solvent such as a lower alcohol, heat stability and the like.
  • the present invention provides the following [1] to [3].
  • I 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and represent a hydrogen atom or lower alkyl, but RR 2 , R 3 , R 4 , R 5 and R 6 Wherein at least one of 6 is lower alkyl).
  • lower alkyl includes, for example, carbon Examples thereof include straight-chain or branched alkyl having the number of 1 to 6, and specific examples thereof include methyl, ethinole, propyl, isopropinole, butyl, isoptinole, s-petitinole, t-butyl, pentyl, isopentyl, neopentyl, Hexinole and the like, among which alkyl having 1 to 3 carbon atoms (methyl, ethyl, propyl, isopropyl) is preferable, and ethyl is more preferable.
  • a 1 1 Oyobishaku 3 are the same or different lower alkyl, Oh shall preferably at R 2, RR 5 and R 6 are hydrogen atoms, further More preferably, R 1 and R 3 are ethyl, and R 2 , RR 5 and R 6 are hydrogen atoms.
  • the polyamide of the present invention can be obtained by a polycondensation reaction of a dicarboxylic acid component containing branched dartaric acid and diamine.
  • the polycondensation reaction is carried out by a known method [Plastic Materials Course, Vol. 16, Polyamide Resin, page 27, 1970, Nikkan Kogyo Shimbun, Macromolecules, 33, 3511 (2000), J. Org . Chem., 61, 4 according to 1 96 (1 "6) or the like], in.
  • the polymer of the present invention can be obtained by synthesizing a polymer and further performing melt polymerization, solid phase polymerization or polymerization using a melt extruder.
  • the catalyst examples include substituted boric acids such as phenolic borate, 3,5-bis (trifluoromethyl) phenylboric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, and salts thereof (potassium salt, sodium salt) , Magnesium salts, vanadium salts, potassium salts, zinc salts, cobalt salts, manganese salts, tin salts, tungsten salts, germanium salts, titanium salts, antimony salts and other metal salts and ammonium salts, etc.) or their esters (Ethyl ester, isopropyl ester, butyl ester, hexyl ester, decyl ester, isodecyl ester, octadecinole ester, stearyl ester, phenyl ester, etc.).
  • the catalyst is used for the raw material of the polyamide of the present invention. It is preferably used in an amount of 0.001 to 5% by weight. Arbitr
  • the polyamide of the present invention can be prepared by a known method, It can also be obtained by previously synthesizing a product and interfacial polycondensation with diamine.
  • the acid chloride of branched dataric acid can be synthesized according to a known method [Experimental Chemistry Lecture 22, 4th edition, edited by The Chemical Society of Japan, Maruzen (1992), pp. 115-127, etc.]. .
  • it can be obtained by dropping branched dartaric acid dissolved in a solvent such as black form in ice-cooled thionyl chloride, and stirring under ice-cooling for an appropriate time and further at room temperature for an appropriate time.
  • a catalyst such as pyridine or hexamethylphosphoric triamide can be used.
  • the equivalent ratio of the branched glutaric acid to the thiol chloride is not particularly limited, but is preferably 1: 1.5 to 1: 3.
  • Interfacial polycondensation is performed by a known method [4th edition Experimental Chemistry Course 28, Chemical Society of Japan, Maruzen]
  • the obtained polyamide can be further purified by reprecipitation or the like.
  • the reprecipitation can be performed, for example, by dissolving the polyamide in formic acid and then adding the obtained solution to acetone.
  • the branched glutaric acid which is a raw material of the polyamide of the present invention means glutaric acid having one or more alkyl side chains, and preferable specific examples thereof include 2,4-dialkylglutaric acid, and 3-glutaric acid. Examples thereof include alkyl glutaric acid and 2,3-dialkyl glutaric acid. Among them, 2,4-dialkyl glutaric acid is preferable, and 2,4-dimethylethyl glutaric acid is more preferable.
  • the branched dataric acids described above are used alone or in combination of two or more.
  • the dicarboxylic acid component which is a raw material of the polyamide of the present invention, may contain a dicarboxylic acid other than branched dataric acid.
  • the amount of branched daltaric acid used is preferably at least 20 mol%, more preferably at least 30 mol ° / 0, based on the total amount of dicarboxylic acid used. Is more preferable.
  • the amount of the branched glutaric acid is at least 20 mol%, the solubility of the obtained polyamide in an organic solvent is further improved, which is preferable.
  • the dicarboxylic acid other than branched glutaric acid is not particularly limited, but is preferably a dicarboxylic acid having 3 to 22 carbon atoms. Preferred examples thereof include malonic acid, dimethylmalonic acid, and succinic acid. Acids, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 3,3-getyl succinic acid, azelaic acid, sebacic acid, suberic acid, and other aliphatic dicarboxylic acids; 1,3-cyclopentane Alicyclic dicarboxylic acids such as dicanolevonic acid, 1,4-six-mouth hexanedicanolonebonic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalene 1,6-diphenylenedioxydiacetic acid, 1,3-phenylenedioxydi
  • a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid may be used as a raw material of the polyamide of the present invention.
  • the polyvalent carboxylic acid is 0.1 to 10% by weight with respect to the branched dataric acid. / 0 is preferably used.
  • the diamine which is a raw material of the polyamide of the present invention include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, and the like.
  • Diacis is preferably used in an amount of 0.5 to 3.0 equivalents (molar ratio), based on the total amount of all dicarboxylic acids or polyvalent carboxylic acids used, and 0.8 to 1.5 equivalents. (Molar ratio) More preferably used.
  • a reaction solvent may be used, if necessary.
  • aromatic hydrocarbons such as benzene, toluene, xylene, cresol, and mesitylene are preferable.
  • the amount used is preferably 0.5 to 100 times (weight) based on the total amount of the polyimide raw material.
  • the reaction solvents are used alone or in combination of two or more.
  • the weight average molecular weight of the polyamide of the present invention is not particularly limited, but is preferably from 100 to 100,000, and more preferably from 500 to 200,000. preferable.
  • weight average molecular weight is 100 or more, mechanical properties of a film or the like obtained from the polyamide of the present invention are improved, and when the weight average molecular weight is 100 or less, viscosity is low and processing is easy, which is preferable.
  • the polyamide of the present invention may contain a stabilizer, a coloring agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, a glass fiber, a plasticizer, a lubricant, etc.
  • the additive may be added in an amount of 0.001 to 5% by weight based on the amount of the polyamide of the present invention.
  • the polyamide of the present invention can be produced by, for example, injection molding, according to a known method (plastic material course 9, polyamide resin, page 138, Nikkan Kogyo Shimbun, published on April 15, 1953, etc.). It can be formed by blow molding, extrusion molding, compression molding, stretching, vacuum molding and the like.
  • the polyamide of the present invention can be used in an organic solvent (lower alcohol such as methanol, ethanol, propanol, isopropyl alcohol, etc., dimethinoles / rephoxide, N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, and chloroform).
  • the amide can be dissolved, the poly of the present invention
  • the amide can be dissolved in the above-mentioned organic solvent or the like and processed according to a known method (coating engineering, page 254, 1973, Asakura Shoten, etc.).
  • the polyamide of the present invention can be formed into various forms, for example, a sheet, a film, a fiber, or the like.
  • the polyamide of the present invention can be used for mechanical parts (gears, tunes, gears, etc.), bottles, electric parts (battery case, motor housing, switch case, etc.), automobile parts (gears, bearings, wipers, etc.), medical supplies (surgical) Brushes, chemical cups, etc.) and household goods (tableware, combs, fasteners, buttons, etc.).
  • the polyamide of the present invention has a low dielectric loss tangent value, it can be used for photosensitive drums and the like.
  • the generated hydrogen gas was measured with a gas meter, and the progress of the reaction was followed. The generation of gas was confirmed around 230 ° C, and the reaction was continued at 250 to 270 ° C. After reaching 250 ° C, 3.5 hours later, 8.9.4 L of hydrogen was generated. The reaction was continued for another 30 minutes, during which time 0.8 L of hydrogen gas was generated, the amount of generated hydrogen coincided with the theoretical amount, and the reaction rate was 100%. After the reaction, a reaction solution containing dipotassium 2,4-ethylglutarate was dissolved in water, and sulfuric acid was further added to obtain crude 2,4-ethylditartaric acid.
  • adipic acid 1,6-hexanediamine salt was 488 g in yield 93. /. Met.
  • 2,4-Getyldartaric acid ⁇ 1,6-Hexandiamine salt, 152 g, and 3,5-bis (trifinoleolomethinole) pheninoleboric acid, 6.5 g, were charged into a 3 L NAS flask.
  • Adipic acid ⁇ 1,6-hexanediamine salt 13 1 g and 3,5-bis (trifluoromethyl) phenylboric acid 6.5 g are charged into a 3 L eggplant-shaped flask, and m-cresol 10 m in 500 ml of mesitylene A mixed solution in which 1 was dissolved was added and dispersed in the mixed solution. Thereafter, the mixture was refluxed at 180 ° C. for 24 hours under a nitrogen stream. Product water was removed with a Dean Stark tube. After the reaction, the reaction solution was cooled to room temperature, and added to 5 L of methanol with stirring. The precipitated product was collected by filtration, washed three times with 20 Om 1 of boiling methanol, and dried in vacuo to obtain 106 g of the desired nylons 6,6.
  • 2,4-I-Jetinolegnoletanoleic acid 94.OO g was dissolved in a mixture of 200 ml of Closphoslem and 79.OO g of pyridine, and slowly added to 26.00 g of thionyl chloride in an ice bath. It was dropped. After completion of the dropwise addition, the mixture was stirred for 1 hour in an ice bath and further for 1.5 hours at room temperature. After the completion of the stirring, the mixture was filtered, and the filtrated form and excess thiol chloride contained in the filtrate were distilled off. Thereafter, vacuum distillation was performed at 95 ° C. and 1333 Pa to obtain 97.01 g of 2,4-getyl dartalic acid dichloride (yield: 86.3%).
  • the resulting polyamide was collected by filtration, poured into 400 ml of distilled water, and stirred. The polyamide was collected by filtration from the aqueous solution and dried under hot vacuum. Finally, in order to remove low molecular weight components, the obtained polyamide was dissolved in formic acid, and then reprecipitated using acetone. The resulting precipitate was collected by filtration, and further dried under hot vacuum at 40 ° C. and 400 Pa to obtain 10.88 g of DEGA-HMDA-based PA as the target polyamide. The number average molecular weight of this polyamide was 19,300 and the weight average molecular weight was 45,000.
  • Example 3 Synthesis of 2,4-detyldaltaric acid-meta-xylylenediamine-based polyamide (hereinafter sometimes referred to as DEGA-mXDA-based PA) by interfacial polycondensation 1, 6-Hexanediamine 9.29 g was replaced with m-xylylenediamine 10.9 1 g, and the same operation as in Example 2 was performed. 1 0.86 g was obtained.
  • the number average molecular weight of this polyamide was 14,500, and the weight average molecular weight was 32,400.
  • Example 2 The procedure of Example 2 was repeated, except that 9.29 g of 1,6-hexanediamine was replaced by 0.90 g of p-xylylenediamine to obtain 20.8 g of DEGA-p XDA PA.
  • the polyamide had a number average molecular weight of 10,400 and a weight average molecular weight of 26,800.
  • Thermal analysis was performed on the polyamides obtained in Examples 2 to 4 and Comparative Example 2 to compare heat stability. The results are shown in Table 1-2.
  • the heat-resistant temperature was a temperature at which a weight loss of 5% was exhibited.
  • the thermal analysis was performed in air at a heating rate of 10 ° CZ.

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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

L'invention concerne un polyamide dont la molécule renferme une unité de structure représentée par la formule générale (I), dans laquelle R1, R2, R3, R4, R5 et R6 sont identiques ou différents et représentent chacun hydrogène ou alkyle inférieur, pour autant qu'au moins l'un des R1, R2, R3, R4, R5 et R6 soit un alkyle inférieur. Le polyamide est excellent notamment en termes de solubilité dans des solvants organiques comportant des alcools inférieurs, et de stabilité thermique.
PCT/JP2002/013649 2001-12-27 2002-12-26 Polyamide WO2003062303A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003562177A JPWO2003062303A1 (ja) 2001-12-27 2002-12-26 ポリアミド

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001-396801 2001-12-27
JP2001396801 2001-12-27
JP2002290798 2002-10-03
JP2002-290798 2002-10-03

Publications (1)

Publication Number Publication Date
WO2003062303A1 true WO2003062303A1 (fr) 2003-07-31

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JP (1) JPWO2003062303A1 (fr)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10506430A (ja) * 1994-09-28 1998-06-23 ユニオン キャンプ コーポレイション インクジェット印刷組成物
JP2000063665A (ja) * 1998-08-24 2000-02-29 Asahi Chem Ind Co Ltd ポリアミド樹脂組成物の製造方法
JP2001106749A (ja) * 1999-10-04 2001-04-17 Nof Corp 共重合体、その製造法、医療用材料及び眼科用材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10506430A (ja) * 1994-09-28 1998-06-23 ユニオン キャンプ コーポレイション インクジェット印刷組成物
JP2000063665A (ja) * 1998-08-24 2000-02-29 Asahi Chem Ind Co Ltd ポリアミド樹脂組成物の製造方法
JP2001106749A (ja) * 1999-10-04 2001-04-17 Nof Corp 共重合体、その製造法、医療用材料及び眼科用材料

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