WO2012132084A1 - Procédé pour la production d'un élastomère de poly(ester-amide), et élastomère de poly(ester-amide) obtenu par ledit procédé de production - Google Patents

Procédé pour la production d'un élastomère de poly(ester-amide), et élastomère de poly(ester-amide) obtenu par ledit procédé de production Download PDF

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WO2012132084A1
WO2012132084A1 PCT/JP2011/075215 JP2011075215W WO2012132084A1 WO 2012132084 A1 WO2012132084 A1 WO 2012132084A1 JP 2011075215 W JP2011075215 W JP 2011075215W WO 2012132084 A1 WO2012132084 A1 WO 2012132084A1
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component
acid
group
producing
polyetheramide elastomer
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Japanese (ja)
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孝治 中村
利雄 森山
佳史 赤川
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Ube Corp
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Ube Industries Ltd
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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
    • C08G69/44—Polyester-amides

Definitions

  • the present invention relates to a method for producing a polyetheramide elastomer and a polyetheramide elastomer obtained by the method.
  • Polyamide elastomers have excellent flexibility, low specific gravity, friction and wear characteristics, elasticity, bending fatigue resistance, low temperature characteristics, molding processability, and chemical resistance, so tubes, hoses, sporting goods, seals, Widely used as molded products such as packing and silencer gears.
  • Known polyamide elastomers include polyether ester amide elastomers and polyether amide elastomers, which use polyamide as a hard segment and polyether as a soft segment.
  • polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, and ⁇ , ⁇ -dihydroxy hydrocarbons are used as the soft segment.
  • polyoxybutylene glycol is mainly used.
  • the polyamide 12-based polyetheresteramide elastomer having polyoxybutylene glycol as a soft segment is not necessarily satisfactory in terms of elastic recovery and resistance to bending fatigue.
  • polyether ester amide elastomers have problems with water resistance, hydrolysis resistance, etc., for example, when durability is a problem when used in high temperature, high humidity environments, and applications are limited. There are many.
  • Patent Documents 1 and 2 disclose a polyether amide comprising a polyamide unit, a polyether unit in which polypropylene oxide (X) and polybutylene oxide (Y) are chemically bonded to form XYX, and a dicarboxylic acid unit. Elastomers are disclosed.
  • Patent Document 3 discloses a polyether amide elastomer composed of a polyamide unit, a polyether unit composed of polypropylene oxide (X) and a polybutylene oxide (Y) and a polyether unit composed of polypropylene oxide and a dicarboxylic acid unit. Has been.
  • phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are used as a catalyst as necessary to promote polymerization, and phosphorus phosphite is used for the effect of both the catalyst and the heat-resistant agent.
  • inorganic phosphorus atom-containing compounds such as acids, hypophosphorous acid, and alkali metal salts and alkaline earth metal salts thereof can be added.
  • inorganic phosphorous alkali metal salts and alkaline earth metal salt compounds such as sodium hypophosphite monohydrate generally used in the polymerization of polyamides are inexpensive and excellent for polyamides. It is a catalyst capable of polymerizing a polymer having a polymerization promoting effect, imparting a heat resistance effect, and excellent in color tone.
  • the present invention solves the above problems, Excellent melt moldability and moldability In addition to being excellent in toughness, bending fatigue resistance, rebound resilience, low temperature flexibility, sound deadening properties and rubber-like properties, Low specific gravity, and While maintaining the polymerization acceleration effect during the production of polyetheramide elastomer, It is an object of the present invention to provide a method for producing a polyetheramide elastomer which is excellent in color tone, heat discoloration, and transparency and has little change in transparency after wet heat treatment, and a polyetheramide elastomer obtained by the production method.
  • the present invention includes the following.
  • (1) Manufacture of a polyetheramide elastomer having a step of obtaining a polyetheramide elastomer by melt polycondensation of a diamine compound (component A), a polyamide-forming monomer (component B), and a dicarboxylic acid compound (component C)
  • a method A phosphorus atom-containing compound (component D) is added before, during, or after the step, When the component D is added before or during the step, the melt polycondensation is performed in the presence of the component D, When the component D is added after the step, the polymer obtained by melt polycondensation in the step is melt-kneaded in the presence of the component D,
  • the component A is represented by the following formula (1)
  • R 1 represents a linking group containing a hydrocarbon chain
  • component B1 aminocarboxylic acid compound
  • R 2 represents a linking group containing a hydrocarbon chain
  • component B2 represents a lactam compound
  • R 3 represents a linking group containing a hydrocarbon chain, m represents 0 or 1), and is a compound.
  • the component D is represented by the following formula (5)
  • R 4 to R 9 may be the same or different, and may be a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, X 1 to X 12 represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, excluding a metal element.
  • X 1 to X 12 represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, excluding a metal element.
  • And is at least one compound selected from the group consisting of: For 100 parts by mass of the polyetheramide elastomer, A method for producing a polyetheramide elastomer, wherein the phosphorus atom is 0.005 to 0.3 parts by mass. (2) A polyetheramide elastomer obtained by the production method described in (1) above.
  • the present invention is excellent in melt moldability and moldability, In addition to being excellent in toughness, bending fatigue resistance, rebound resilience, low temperature flexibility, sound deadening properties and rubber-like properties, Low specific gravity, and While maintaining the polymerization acceleration effect during the production of polyetheramide elastomer, It is possible to provide a method for producing a polyetheramide elastomer that is excellent in color tone, heat discoloration, and transparency, and has little change in transparency after wet heat treatment, and a polyetheramide elastomer obtained by the method.
  • the method for producing the polyetheramide elastomer of the present invention (hereinafter also referred to as the production method of the present invention)
  • a method for producing a polyetheramide elastomer comprising a step of melt polycondensation of a diamine compound (component A), a polyamide-forming monomer (component B), and a dicarboxylic acid compound (component C),
  • the phosphorus atom-containing compound (component D) is added before or in the step (Aspect 1), or the component D is added after the step (Aspect 2),
  • the melt polycondensation is performed in the presence of the component D
  • the polymer obtained by melt polycondensation in the step is melt kneaded in the presence of the component D.
  • Aspect 2 further specifically includes: After melt-condensing components A, B and C to obtain a polymer, the polymer is melt-kneaded as it is, component D is added thereto, and the polymer is melted in the presence of component D. When kneading, After component A, B and C are melt-condensed, the polymer is formed into pellets, and component D is added at the stage of melting and kneading when the pellets are molded, etc. And the case where the polymer is melt-kneaded.
  • the production method of the present invention of aspect 1 is preferably selected from (A1) a diamine compound containing (A1) a triblock polyether diamine compound, (B1) an aminocarboxylic acid compound and (B2) a lactam compound (B).
  • the polyamide elastomer obtained by the production method of the present invention of aspect 1 is selected from (A1) a diamine compound containing a triblock polyether diamine compound, (B1) an aminocarboxylic acid compound and (B2) a lactam compound ( B) A component comprising a polyamide-forming monomer and (C) a dicarboxylic acid compound, (D1) a phosphoric acid compound, (D2) a phosphonic acid compound, (D3) a phosphinic acid compound, (D4) a phosphorous acid compound, ( It is a polyetheramide elastomer obtained by melt polycondensation in the presence of at least one (D) phosphorus atom-containing compound selected from the group consisting of D5) phosphonous acid compounds and (D6) phosphinic acid compounds.
  • One of the preferred embodiments of the polyamide elastomer obtained by the production method of the present invention of embodiment 1 is in addition to the XYX type triblock polyether diamine (A1) represented by the formula (1) and preferably the diamine (A1).
  • A a diamine compound comprising at least one (A2) diamine compound selected from a branched saturated diamine having 6 to 22 carbon atoms, a branched alicyclic diamine having 6 to 16 carbon atoms, and norbornane diamine;
  • B1 an aminocarboxylic acid compound represented by formula (4) and a (B2) lactam compound represented by formula (4)
  • C a dicarboxylic acid represented by formula (2) It is a polyetheramide elastomer obtained by polymerizing an acid compound.
  • Component A is represented by the following formula (1)
  • component A1 (In the formula (1), x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20, respectively) (component A1) including.
  • Component A1 represented by the formula (1) (hereinafter also referred to as XYX type triblock polyether diamine compound) is obtained by adding propylene oxide to both ends of poly (oxytetramethylene) glycol and the like to form polypropylene glycol.
  • the polyether diamine etc. which are manufactured by making ammonia etc. react with the terminal of this polypropylene glycol are mentioned.
  • x and z are usually 1 to 20, preferably 1 to 18, more preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.
  • y is usually from 4 to 50, preferably from 5 to 45, more preferably from 6 to 40, still more preferably from 7 to 35, and particularly preferably from 8 to 30.
  • XTJ-533 manufactured by HUNTSMAN USA (in formula (1), x is approximately 12, y is approximately 11, z is approximately 11), XTJ-536 (in formula (1), x is approximately 8.5, y is approximately 17, and z is approximately 7.5), XTJ-542 (in formula (1), x is about 3, y is about 9, and z is about 2), XTJ-559 (in formula (1), x is about 3, y is about 14, and z is about 2).
  • XYX type triblock polyether diamine compound XYX-1 (in formula (1), x is approximately 5, y is approximately 14, and z is approximately 2)
  • XYX-2 in formula (1), x is about 3, y is about 19, and z is about 2), etc. can also be used.
  • Component A includes a branched saturated diamine having 6 to 22 carbon atoms, carbon atoms in addition to Component A1 from the viewpoint of ensuring stable transparency of the polyetheramide elastomer composition obtained by the production method of the present invention. It is preferable to further contain at least one diamine compound (component A2) selected from the group consisting of 6 to 16 branched alicyclic diamines and norbornane diamines.
  • Examples of the branched saturated diamine having 6 to 22 carbon atoms of the (A2) diamine compound used in a preferred embodiment include 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4, and the like. -Trimethyl-1,6-diaminohexane, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane and the like. These can use 1 type (s) or 2 or more types.
  • branched alicyclic diamine having 6 to 16 carbon atoms of component A2 used in a preferred embodiment examples include 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine (also referred to as “isophoronediamine”), and the like. These diamines may be either cis- or trans-isomers or a mixture of these isomers. These can use 1 type (s) or 2 or more types.
  • component A2 used in a preferred embodiment, for example, 2,5-norbonane dimethylamine, 2,6-norbonane dimethylamine and the like can be mentioned. These can use 1 type (s) or 2 or more types.
  • diamine compound (component A) other diamine compounds (component A3) other than component A1 and component A2 may be included.
  • Component B is represented by the following formula (2)
  • R 1 represents a linking group containing a hydrocarbon chain
  • component B1 aminocarboxylic acid compound
  • R 2 represents a linking group containing a hydrocarbon chain.
  • a lactam compound (component B2) represents a lactam compound (component B2).
  • R 1 is: An aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms is preferable, and an alkylene group having 2 to 20 carbon atoms is more preferable.
  • the hydrocarbon group having 3 to 18 carbon atoms is preferable, and an alkylene group having 3 to 18 carbon atoms is more preferable.
  • the hydrocarbon group having 4 to 15 carbon atoms is preferable, and an alkylene group having 4 to 15 carbon atoms is more preferable.
  • the hydrocarbon group having 10 to 15 carbon atoms is preferable, and an alkylene group having 10 to 15 carbon atoms is more preferable.
  • R 2 is: An aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 20 carbon atoms is preferable, and an alkylene group having 3 to 20 carbon atoms is preferable.
  • the hydrocarbon group having 3 to 18 carbon atoms is preferable, and an alkylene group having 3 to 18 carbon atoms is more preferable.
  • the hydrocarbon group having 4 to 15 carbon atoms is preferable, and an alkylene group having 4 to 15 carbon atoms is more preferable.
  • the hydrocarbon group having 10 to 15 carbon atoms is preferable, and an alkylene group having 10 to 15 carbon atoms is more preferable.
  • Component B1 includes aliphatic groups having 5 to 20 carbon atoms such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.
  • An aminocarboxylic acid etc. are mentioned. These can use 1 type (s) or 2 or more types.
  • Component B2 includes aliphatic lactams having 5 to 20 carbon atoms such as caprolactam, enantolactam, undecaractam, dodecaractam, and 2-pyrrolidone. These can use 1 type (s) or 2 or more types.
  • Component C is represented by the following formula (4)
  • R 3 represents a linking group containing a hydrocarbon chain, and m represents 0 or 1).
  • R 3 is: It is preferably an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms,
  • the above hydrocarbon group having 1 to 15 carbon atoms is preferred, more preferably an alkylene group having 1 to 15 carbon atoms,
  • the hydrocarbon group having 2 to 12 carbon atoms is preferable, and an alkylene group having 2 to 12 carbon atoms is more preferable.
  • the hydrocarbon group having 4 to 10 carbon atoms is preferable, and an alkylene group having 4 to 10 carbon atoms is more preferable.
  • M represents 0 or 1.
  • Component C includes at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof.
  • component C include straight chain having 2 to 25 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc.
  • Dimerized aliphatic dicarboxylic acid having 14 to 48 carbon atoms obtained by dimerizing unsaturated fatty acid obtained by fractionation of aliphatic dicarboxylic acid or triglyceride, and hydrogenated products thereof (hydrogenated dimer acid)
  • Aliphatic dicarboxylic acids such as 1,3- / 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid, and terephthalic acid, isophthalic acid
  • aromatic dicarboxylic acids such as 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid. These can use 1 type (s) or 2 or more types.
  • Component C is preferably the above aliphatic dicarboxylic acid or alicyclic dicarboxylic acid.
  • dimer acid and hydrogenated dimer acid may be trade names “Pripol 1004”, “Plipol 1006”, “Plipol 1009”, “Plipol 1013”, etc. manufactured by Unikema Corporation.
  • R 4 to R 9 may be the same or different, and may be a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, X 1 to X 12 represents a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, excluding a metal element.) And is at least one compound selected from the group consisting of:
  • [Phosphorus atom-containing compound] Components A, B and C are melt polycondensed in the presence of a phosphorus atom-containing compound (Aspect 1), or a polymer obtained after melt polymerization of components A, B and C is obtained in the presence of a phosphorus atom-containing compound.
  • the polyetheramide elastomer obtained by melt kneading (Aspect 2) is excellent in color tone, heat discoloration, and transparency, and has little change in transparency after wet heat treatment.
  • Examples of the alkyl group represented by R 4 to R 9 and X 1 to X 12 include C1-C24 linear or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl Group, n-pentyl group, isopentyl group, t-pentyl group, neopentyl group, hexyl group, sec-hexyl group, heptyl group, sec-heptyl group, octyl group, sec-octyl group, 2-ethylhexyl group, nonyl group, sec-nonyl, decyl, sec-decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, methyl group, ethy
  • Examples of the cycloalkyl group represented by R 4 to R 9 and X 1 to X 12 include A cycloalkyl group having 3 to 20 carbon atoms, such as cyclopentyl group, methylcyclopentyl group, cyclopentylmethyl group, 2-cyclopentylethyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cyclohexylmethyl group, 2-cyclohexyl Examples thereof include an ethyl group, an ethylcyclohexyl group, a propylcyclohexyl group, a cycloheptyl group, a methylcycloheptyl group, a cyclooctyl group, a cyclooctylmethyl group, and a 2-cyclooctylethyl group.
  • a cycloalkyl group having 3 to 20 carbon atoms such as cyclopent
  • Examples of the aryl group of R 4 to R 9 and X 1 to X 12 include An aryl group having 6 to 24 carbon atoms (including all substituted isomers), for example, phenyl group, toluyl group, xylyl group, cumenyl group, trimethylphenyl group (mesityl group), ethylphenyl group, ethylmethylphenyl Group, diethylphenyl group, ethyldimethylphenyl group, triethylphenyl group, propylphenyl group, propylmethylphenyl group, propylethylphenyl group, dipropylphenyl group, tripropylphenyl group, butylphenyl group, dibutylphenyl group, tributylphenyl group Pentylphenyl group, hexylphenyl group, heptylphenyl group, octylpheny
  • Aralkyl groups having 7 to 24 carbon atoms such as benzyl group, phenethyl group, benzhydryl group, trityl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group, methylbenzyl group Methylphenethyl group, methylnaphthylmethyl group, phenylbenzyl group and the like.
  • the phosphorous acid compound represented by the general formula (8) may be tautomerized to the phosphonic acid compound represented by the general formula (6) due to the influence of the hydrogen ion concentration, etc.
  • the phosphonic acid compound represented by the general formula (6) may also be tautomerized to the phosphorous acid compound represented by the general formula (8) due to the influence of temperature or the like.
  • the phosphonous acid compound represented by the general formula (9) may be tautomerized to the phosphinic acid compound represented by the general formula (7) due to the influence of the hydrogen ion concentration, etc.
  • the phosphinic acid compound represented by the general formula (7) may be tautomerized to the phosphonous acid compound represented by the general formula (9) due to the influence of temperature or the like.
  • the phosphorus atom-containing compound represented by the formula (5) is (D1) a phosphate compound
  • Examples thereof include phosphoric acid, phosphoric acid ester, and acidic phosphoric acid ester.
  • phosphate esters include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tri (2-ethylhexyl) phosphate, trinonyl phosphate, Tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, ethyl dibutyl phosphate, tricyclohexyl phosphate, tri Phenyl phosphate,
  • acidic phosphate ester examples include mono- or dimethyl acid phosphate, mono- or diethyl acid phosphate, mono- or di-n-propyl acid phosphate, mono- or diisopropyl acid phosphate, mono- or dibutyl acid phosphate, mono- or dipentyl acid phosphate, mono- or di- Dihexyl acid phosphate, mono or diheptyl acid phosphate, mono or dioctyl acid phosphate, mono or di (2-ethylhexyl) acid phosphate, mono or dinonyl acid phosphate, mono or didecyl acid phosphate, mono or diundecyl acid phosphate, mono Or didodecyl acid phosphate, mono or ditridecyl acid phosphate, mono or ditet Decyl acid phosphate, mono or dipentadecyl acid phosphate, mono or dihexadecyl acid phosphate, mono or dihepta
  • the phosphorus atom-containing compound represented by the formula (6) is (D2) a phosphonic acid compound, for example, Phosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, octylphosphonic acid, 2-ethylhexylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, octadecylphosphonic acid, oleyl Phosphonic acid, phenylphosphonic acid, tolylphosphonic acid, methyl methylphosphonate, ethyl methylphosphonate, methyl phosphonate dodecyl, methyl phosphonate, methyl phenylphosphonate, ethyl phenylphosphonate, phenyl phosphonate dodecyl, phenyl phenylphosphonate, dimethyl methylphosphonate
  • the phosphorus atom-containing compound represented by the formula (7) is (D3) phosphinic acid compound, for example, phosphinic acid (hypophosphorous acid), trimethylphosphinic acid, ethyl dimethylphosphinate, dimethylphosphinic acid propyl, dimethylphosphinic acid Butyl, pentyl dimethylphosphinate, hexyl dimethylphosphinate, heptyl dimethylphosphinate, octyl dimethylphosphinate, phenyl dimethylphosphinate, toluyl dimethylphosphinate, naphthyl dimethylphosphinate, methyl methylphenylphosphinate, ethyl methylphenylphosphinate, diethyl Methyl phosphinate, triethylphosphinic acid, propyl diethylphosphinate, butyl diethylphosphinate, pentyl diethylphos
  • the phosphorus atom-containing compound represented by the formula (8) is (D4) a phosphorous acid compound, Examples thereof include phosphorous acid, phosphorous acid ester, and acidic phosphorous acid mono- or diester.
  • phosphites include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, triisooctyl phosphite.
  • acid phosphite examples include mono- or dimethyl hydrogen phosphite, mono- or diethyl hydrogen phosphite, mono- or dipropyl hydrogen phosphite, mono- or dibutyl hydrogen phosphite, mono- or dipentyl hydrogen phosphite Mono or dihexyl hydrogen phosphite, mono or diheptyl hydrogen phosphite, mono or dioctyl hydrogen phosphite, mono or di-2-ethylhexyl hydrogen phosphite, mono or dinonyl hydrogen phosphite, mono or di Decyl hydrogen phosphite, mono or diundecyl hydrogen phosphite, mono or didodecyl hydrogen phosphite, mono or dihexadecyl hydro Phosphite, mono or dioctadecyl hydrogen phosphite, mono or dioleyl hydrogen phos
  • the phosphorus atom-containing compound represented by the formula (9) is (D5) a phosphonous acid compound, for example, phosphonous acid, methylphosphonous acid, ethylphosphonous acid, dodecylphosphonous acid, phenylphosphonous acid, methyl Phosphorous acid monomethyl, methylphosphonous acid monoethyl, methylphosphonous acid monododecyl, methylphosphonous acid monophenyl, ethylphosphonous acid monomethyl, ethylphosphonous acid monoethyl, ethylphosphonous acid monododecyl, ethylphosphonous acid monophenyl , Phenylphosphonous acid monomethyl, phenylphosphonous acid monoethyl, phenylphosphonous acid monododecyl, phenylphosphonous acid monophenyl, trimethylphosphonous acid, methylphosphonous acid methylethyl, methylphosphonous acid diethyl, methylphosphonous acid dipro Dibuty
  • the phosphorus atom-containing compound represented by the formula (10) is (D6) a phosphinic acid compound, for example, Phosphinous acid, methyl phosphinic acid, ethyl phosphinic acid, butyl phosphinic acid, phenyl phosphinic acid, methyl methyl phosphite, methyl methyl phosphite, butyl methyl phosphite, phenyl methyl phosphite, ethyl phosphite Methyl phosphinate, ethyl ethylphosphite, ethyl butylphosphite, phenyl ethylphosphite, methyl butylphosphite, ethyl butylphosphite, butylbutylphosphite, phenylbutylphosphite, phenylphosphinic acid Meth
  • component D because of its high catalytic activity and low colorability, From the group consisting of (D1) phosphoric acid compound represented by formula (5), (D3) phosphinic acid compound represented by formula (7), and (D4) phosphorous acid compound represented by formula (8). Preferably at least one selected, More preferably, it is at least one selected from the group consisting of phosphoric acid, phosphorous acid, and hypophosphorous acid.
  • Component D includes metal phosphates that are metal salts composed of phosphoric acid, phosphorous acid, or hypophosphorous acid and Group 1 metal of the periodic table, which are generally used as a polymerization catalyst for polyamide, Metal phosphates and metal hypophosphites are excluded.
  • the proportions of components A, B and C improve the crystallinity of the polyamide component of the resulting polyetheramide elastomer, and mechanical properties such as strength and elastic modulus of the resulting polyetheramide elastomer. From the viewpoint of ensuring the function and performance as an elastomer such as rubber elasticity and flexibility, For all components, i.e.
  • Component B is preferably 10 to 95% by mass, More preferably, it is 15 to 90% by mass, More preferably, it is 15 to 85% by mass, More preferably, it is 15 to 80% by mass,
  • the total of component A and component C is preferably 5 to 90% by mass, More preferably, it is 10 to 85% by mass, More preferably, it is 15 to 85% by mass, More preferably, it is 20 to 85% by mass.
  • Component A and Component C are preferably charged so that the amino group of Component A (including the amino group when other diamine compounds are included) and the carboxyl group of Component C are approximately equimolar,
  • the molar ratio of the amino group of component A (including other amino groups when it contains other diamine compounds) and the carboxyl group of component C is: It is preferably 45/55 to 55/45, More preferably, it is 47/53 to 53/47, More preferably, it is 49/51 to 51/49, More preferably, it is 50/50.
  • the terminal carboxylic acid or carboxyl group contained in components A, B and C that is, derived from components A, B and C, and the terminal amino group Therefore, it is preferable to charge at a ratio such that the carboxylic acid or carboxyl group of components A, B and C and the terminal amino group are approximately equimolar. .
  • the proportion of component A1 when melt-condensation polymerization is performed is performed. In 100% by mass of component A, 50 to 100% by mass is preferable, 80 to 100% by mass is more preferable, 90 to 100% by mass is further preferable.
  • the proportion is the sum of components A, B and C from the viewpoint of ensuring stable transparency of the polyetheramide elastomer composition obtained by the production method of the present invention.
  • the amount is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass with respect to 100 parts by mass.
  • the amount of component D added to the polycondensation system or kneading system of the polyetheramide elastomer in aspect 1, or the amount of component D added to the melt kneading system of the polyetheramide elastomer in aspect 2 is: Suppressing the coloring of the polyamide during polymerization or kneading, improving the polymerization promoting effect, stably ensuring the initial color tone and heat discoloration, Reduce the amount of additives, reduce manufacturing costs, Suppresses the gelation reaction of polyetheramide elastomer, Suppressing the mixing of fish eyes that are thought to be caused by component D into the molded product, Ensures a stable appearance of molded products that are polyetheramide elastomers, Suppressing the frequency of filter clogging during molding to ensure stable productivity, From the viewpoint of ensuring stable transparency of molded products and stable transparency after wet heat treatment, 0.005 to 0.3 parts by mass as phosphorus atoms with respect to a total of
  • the component D is based on 100 parts by mass of the total of components A, B and C, or 100 parts by mass of the polyetheramide elastomer.
  • 0.005 to 4.5 parts by mass More preferably, it is 0.01 to 3.0 parts by mass, More preferably, it is 0.03 to 1.5 parts by mass.
  • the production method of the present invention comprises (A1) a diamine compound containing a triblock polyether diamine compound, (B1) a polyamide-forming monomer selected from (B1) an aminocarboxylic acid compound and (B2) a lactam compound; (C) A component containing a dicarboxylic acid compound is converted into (D1) phosphoric acid compound, (D2) phosphonic acid compound, (D3) phosphinic acid compound, (D4) phosphorous acid compound, (D5) phosphonous acid compound, and ( D6) A method for producing a polyamide elastomer which is melt polycondensed in the presence of at least one (D) phosphorus atom-containing compound selected from the group consisting of phosphinic acid compounds.
  • Component D may be added to the reaction system (Aspect 1) or kneading system (Aspect 2) at any time before the start of the polycondensation reaction and during the reaction, or before the start of kneading and during the kneading.
  • the dispersion of the reaction system or kneading system is relatively less scattered, and the polymerization time or kneading time is relatively short.
  • the addition is preferably performed until 1.2 or until the relative viscosity of the kneaded melt reaches 1.2 immediately before the start of kneading.
  • Component D may be added to the reaction system or kneading system in the form of a slurry dispersed in a liquid such as water or a dissolved solution.
  • a method comprising a step of simultaneously subjecting the four components A, B, C and D to melt polymerization under pressure and / or normal pressure, and further melt polymerization under reduced pressure as necessary. It can. It is also possible to use a method in which the two components B and C are polymerized first, and then component A is polymerized together with component D.
  • the polymerization temperature is preferably 150 to 300 ° C. from the viewpoint of favorably progressing the polymerization reaction, suppressing thermal decomposition, and stably obtaining a polymer having good physical properties. It is more preferably ⁇ 280 ° C., and further preferably 180 ° -250 ° C.
  • aminocarboxylic acid When aminocarboxylic acid is used as component B, it can be produced by a method comprising steps of normal pressure melt polymerization or normal pressure melt polymerization followed by reduced pressure melt polymerization.
  • lactam when used as component B, it is produced by a method comprising coexisting an appropriate amount of water and usually comprising melt polymerization under a pressure of 0.1 to 5 MPa, followed by normal pressure melt polymerization and / or reduced pressure melt polymerization. can do.
  • the polymerization time is usually from 0.5 to 5 from the viewpoint of stably obtaining an increase in the molecular weight, and suppressing the coloring due to thermal decomposition and the like to stably obtain a polyetheramide elastomer having desired physical properties. It can be manufactured in 20 hours.
  • the production method of the present invention can be carried out batchwise or continuously, and batch-type reaction kettles, single-tank or multi-tank continuous reactors, tubular continuous reactors, etc., alone or in appropriate combination. Can be used.
  • the relative viscosity ( ⁇ r) (0.5 mass / volume% metacresol solution, 25 ° C.) of the polyetheramide elastomer obtained by the production method of the present invention is stable with that of the polyetheramide elastomer obtained by the production method of the present invention. From the viewpoint of securing a mechanical property and obtaining a polyetheramide elastomer without taking a long time in the production method of the present invention, it is preferably 1.2 to 3.5.
  • the polyetheramide elastomer obtained by the production method of the present invention is mixed with component D added in the production method of the present invention.
  • the polyetheramide elastomer obtained by the production method of the present invention refers to a state in which component D is mixed, and is also referred to as a polyetheramide elastomer mixture or a polyetheramide elastomer mixture obtained by the production method of the present invention.
  • the polyetheramide elastomer obtained by the production method of the present invention is: Polymers composed of units derived from component A, units derived from component B and units derived from component C are included, For a total of 100% by mass of the unit derived from component A, the unit derived from component B, and the unit derived from component C, the unit derived from component B is It is preferably 10 to 95% by mass, More preferably, it is 15 to 90% by mass, More preferably, it is 15 to 85% by mass, More preferably, it is 15 to 80% by mass, The sum of the unit derived from component A and the unit derived from component C is It is preferably 5 to 90% by mass, More preferably, it is 10 to 85% by mass, More preferably, it is 15 to 85% by mass, More preferably, it is 20 to 85% by mass, In the unit derived from component A and the unit derived from component C, the amino residue derived from component A (including the amino group when other diamine compounds are included) and the carboxyl residue derived from
  • component D mixed with the polyetheramide elastomer obtained by the production method of the present invention is composed of a unit derived from component A, a unit derived from component B, and a unit derived from component C in the polyetheramide elastomer.
  • component A a unit derived from component A
  • component B a unit derived from component B
  • component C a unit derived from component C in the polyetheramide elastomer.
  • 100 parts by weight of polymer It is preferably 0.005 to 0.3 parts by mass, More preferably from 0.01 to 0.2 parts by weight, The amount is more preferably 0.03 to 0.15 parts by mass.
  • the qualitative and quantitative determination of the unit derived from component A, the unit derived from component B, and the unit derived from component C in the polyetheramide elastomer is carried out by using a monomer by hydrolysis followed by liquid chromatography, gas chromatography IR, H 1 -NMR. It can be measured by a method generally used for polymer evaluation.
  • the qualitative and quantitative determination of the unit derived from component A, the unit derived from component B, and the unit derived from component C in the polyetheramide elastomer is carried out by using a monomer by hydrolysis followed by liquid chromatography, gas chromatography IR, H 1 -NMR. It can be measured by a method generally used for polymer evaluation.
  • An example of a composition analysis method by hydrolysis will be described.
  • the acid hydrobromic acid, hydrochloric acid or the like that can selectively hydrolyze the polyamide is used.
  • the amount of acid used is 50 to 100 ml with respect to 0.1 g of the polyetheramide elastomer mixture.
  • the polyetheramide elastomer mixture is pulverized, for example, by freeze pulverization and used in powder form.
  • the temperature during hydrolysis is 100 to 130 ° C.
  • the insoluble matter is separated from the acid solution by filtration or centrifugation.
  • HPLC high performance liquid chromatography analysis
  • GC / MS gas chromatography / mass spectrometry
  • the analytical instrument is a GCMS-QP5050A model manufactured by Shimadzu Corporation.
  • the column was Ultra ALLOY + -1 (MS / HT) (0.25 ⁇ ⁇ 15 m, 0.15 ⁇ m), At a column temperature of 120-390 ° C. (12 ° C./min hold), Introduced at a carrier gas He of 2.0 ml / min at an inlet temperature of 340 ° C. and an interface temperature of 340 ° C. It can be measured by ionization method (EI method 70 eV), measurement range 20-900, injection method split method 1: 8, injection amount 1 ⁇ l.
  • EI method 70 eV ionization method
  • the polyetheramide elastomer obtained by the production method of the present invention has a heat resistance agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, a crystal nucleating agent, as long as its properties are not hindered.
  • a polyether amide elastomer composition can be obtained by adding a tackifier, a seal improver, an antifogging agent, a release agent, a plasticizer, a pigment, a dye, a fragrance, a flame retardant, a reinforcing material and the like.
  • the polyetheramide elastomer obtained by the production method of the present invention is compatible with a thermoplastic resin such as polyamide, polyvinyl chloride, polyurethane resin, acrylonitrile / butadiene / styrene copolymer (ABS) excluding the polyetheramide elastomer.
  • a thermoplastic resin such as polyamide, polyvinyl chloride, polyurethane resin, acrylonitrile / butadiene / styrene copolymer (ABS) excluding the polyetheramide elastomer.
  • the polyetheramide elastomer obtained by the production method of the present invention is excellent in color tone, heat discoloration, and transparency while retaining the properties inherent to the polyamide elastomer, and has little change in transparency after wet heat treatment. Furthermore, it is possible to maintain the polymerization promoting effect during the production of the polyetheramide elastomer and obtain a polymer having a desired degree of polymerization with good productivity.
  • the polyetheramide elastomer obtained by the production method of the present invention can be molded by a known molding method such as injection molding, extrusion molding, blow molding, vacuum molding or pressure molding.
  • the obtained molded product is preferably used for, for example, automobile parts, electrical and electronic parts, industrial parts, sports equipment, medical equipment and the like.
  • Auto parts include constant velocity joint boots, rack and opinion boots, suspension boots, ball joint seals, safety belt parts, bumper fascias, emblems, moldings, instrument panels, center panels, center console boxes, door trims. , Pillars, assist grips, handles, airbag covers, etc., as electric and electronic components, such as wire coating materials, optical fiber coating materials, gears, rubber switches, membrane switches, tact switches, switch cases, watch bands, vacuum cleaner bumpers, remote controls Industrial parts such as switches, office automation (OA) key tops, silencers, etc.
  • OA office automation
  • hoses, coil tubes, seals, gears, cams, bearings, bearing packing gas Sports equipment, such as gaskets, packings, O-rings, conveyor belts, V-belts, rolls, anti-vibration damping materials, shock absorbers, couplings, diaphragms, fasteners, valves, joints, grips, caster rollers, clips, etc.
  • Golf shoes, baseball, soccer, athletics sports shoes bottoms, ski shoe ball ball, etc., sunglasses and glasses etc. as parts that require design and decoration, medical equipment such as medical tubes, blood transfusion packs, catheters Etc.
  • Other examples include elastic fibers, elastic sheets, tubes, hoses, pipes, rods, films, sheets, brushes, fish nets, nets, composite sheets, hot melt adhesives, and materials for alloying with other resins.
  • Terminal carboxyl group concentration 40 mL of benzyl alcohol was added to about 1 g of the polymer, dissolved by heating in a nitrogen gas atmosphere, phenolphthalein was added to the obtained sample solution as an indicator, and an N / 20 potassium hydroxide-ethanol solution. Titration with.
  • Terminal amino group concentration About 1 g of the polymer is dissolved in 40 mL of a phenol / methanol mixed solvent (volume ratio: 9/1), thymol blue is added as an indicator to the obtained sample solution, and titrated with N / 20 hydrochloric acid. did.
  • Haze cloudiness
  • HGM-2DP direct reading haze computer
  • Example 1 In a 70 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure adjusting device and polymer outlet, 9.000 kg of 12-aminododecanoic acid (manufactured by Ube Industries) Adipic acid (Asahi Kasei Co., Ltd.) 0.747 kg, XYX type triblock polyether diamine (manufactured by HUNTSMAN: XTJ-542, amine value: 1.96 meq / g) 3.564 kg, 0.274 kg of isophoronediamine (Evonik: VESTAMIN IPD), (D-1) 20.4 g of phosphorous acid and 40.8 g of a heat-resistant agent (manufactured by Yoshitomi Pharmaceutical Co., Ltd .: Tominox 917) were charged.
  • 12-aminododecanoic acid manufactured by Ube Industries
  • Adipic acid Adipic acid (Asahi Kasei
  • the temperature inside the container was raised from room temperature to 230 ° C. over 3.5 hours while the pressure inside the container was adjusted to 0.05 MPa while supplying nitrogen gas at 186 liters / hour. Polymerization was carried out at 230 ° C. while adjusting the internal pressure to 0.05 MPa. The amperage value of stirring power was recorded over time, and the polymerization end point was the time when the amperage value of stirring power reached 4.75A (ampere). After completion of the polymerization, stirring was stopped, and a colorless and transparent polymer in a molten state was drawn out from the polymer outlet in a string shape, cooled with water, and pelletized to obtain pellets.
  • Example 2 In Example 1, 9.510 kg of 12-aminododecanoic acid (manufactured by Ube Industries) Adipic acid (Asahi Kasei Co., Ltd.) 0.511 kg, XYX type triblock polyether diamine (manufactured by HUNTSMAN: XTJ-542, amine value: 1.96 meq / g) was changed to 3.565 kg, A polyetheramide elastomer was obtained in the same manner as in Example 1 except that isophoronediamine was not used.
  • Examples 3 to 4 A polyetheramide elastomer was obtained in the same manner as in Example 1 except that the amount of (D-1) added was changed to the ratio shown in Table 1 in Example 1.
  • Example 5 A polyetheramide elastomer was obtained in the same manner as in Example 1, except that (D-1) was changed to (D-2) in Example 1 and the ratio was changed as shown in Table 1.
  • Example 6 A polyetheramide elastomer was obtained in the same manner as in Example 1, except that (D-1) was changed to (D-3) in Example 1 and the ratio was changed as shown in Table 1.
  • Example 1 A polyetheramide elastomer was obtained in the same manner as in Example 1 except that (D-1) was not used in Example 1.
  • Comparative Example 1 in which Component D was not used took a long time to complete the polymerization, had a large initial color tone and a high degree of discoloration after heat treatment, and was inferior in heat discoloration.
  • Comparative Example 2 in which the blending amount of Component D was less than the specified range required a great deal of time to complete the polymerization, had a large initial color tone and a high degree of discoloration after heat treatment, and was inferior in heat discoloration.
  • Comparative Examples 4 and 5 using Component D other than those defined in the present invention were inferior in transparency after the hot water treatment.
  • the polyetheramide elastomers defined in the present invention of Examples 1 to 6 are excellent in color tone, heat discoloration, and transparency while maintaining the properties inherent to the polyamide elastomer, and are transparent after wet heat treatment. It is clear that there is little change in the polymerization and the polymerization promoting effect is sufficient.

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Abstract

L'invention concerne un procédé pour la production d'un élastomère de poly(ester-amide) : qui montre une solidité, une souplesse aux basses températures, une excellente aptitude au moulage à l'état fondu, une excellente aptitude à la transformation par moulage, une excellente résistance à la fatigue au pliage, une excellente résilience aux chocs, d'excellentes propriétés d'insonorisation, d'excellentes propriétés de type caoutchouc, un faible changement de transparence après avoir été traité hydrothermiquement et une couleur, une transparence et une résistance à la décoloration thermique, tout en conservant les effets d'accélération de la polymérisation pendant la production de l'élastomère de poly(ester-amide) ; et qui présente une faible densité. Elle concerne également un élastomère de poly(ester-amide) obtenu par le procédé de production susmentionné. L'invention concerne un procédé pour la production d'un élastomère de poly(ester-amide), le procédé impliquant une étape de soumission d'une diamine spécifique (A), d'un monomère formant du polyamide (B) et d'un acide dicarboxylique (C) à une polycondensation en masse fondue. Si un composé (D) contenant un atome de phosphore est ajouté avant ou pendant l'étape susmentionnée, la polycondensation en masse fondue susmentionnée sera réalisée en présence de (D), et si (D) est ajouté après l'étape susmentionnée, le polymère obtenu par la réalisation de la polycondensation en masse fondue dans l'étape susmentionnée sera malaxé en masse fondue en présence de (D). La quantité d'atomes de phosphore est de 0,05 à 0,3 partie en masse par 100 parties en masse d'élastomère de poly(ester-amide).
PCT/JP2011/075215 2011-03-28 2011-11-01 Procédé pour la production d'un élastomère de poly(ester-amide), et élastomère de poly(ester-amide) obtenu par ledit procédé de production Ceased WO2012132084A1 (fr)

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US11421088B2 (en) * 2020-05-27 2022-08-23 Taiwan Textile Federation, R.O.C. Method of preparing polyester elastomer composite membrane with high bonding strength

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EP3421544A4 (fr) * 2016-02-23 2019-10-30 UBE Industries, Ltd. Composition d'élastomère de polyamide et fibre et objet moulé la comprenant

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WO2016181472A1 (fr) * 2015-05-11 2016-11-17 株式会社カネカ Élastomère de polyamide, dispositif médical, et procédé de production d'un élastomère de polyamide
WO2016182002A1 (fr) * 2015-05-11 2016-11-17 株式会社カネカ Élastomère de polyamide, dispositif médical, et procédé de production d'élastomère de polyamide
WO2016182001A1 (fr) * 2015-05-11 2016-11-17 株式会社カネカ Élastomère de polyamide, dispositif médical, et procédé de production d'un élastomère de polyamide
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JPWO2016182002A1 (ja) * 2015-05-11 2018-03-01 株式会社カネカ ポリアミドエラストマー、医療機器及びポリアミドエラストマーの製造方法
JPWO2016182001A1 (ja) * 2015-05-11 2018-03-01 株式会社カネカ ポリアミドエラストマー、医療機器及びポリアミドエラストマーの製造方法
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CN111019126A (zh) * 2019-12-06 2020-04-17 苏州大学 一种聚酯酰胺及其制备方法
US11421088B2 (en) * 2020-05-27 2022-08-23 Taiwan Textile Federation, R.O.C. Method of preparing polyester elastomer composite membrane with high bonding strength

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