WO2012132084A1 - Method for producing polyester amide elastomer, and polyester amide elastomer obtained from said production method - Google Patents

Method for producing polyester amide elastomer, and polyester amide elastomer obtained from said production method 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
elastomer
diamine
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PCT/JP2011/075215
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French (fr)
Japanese (ja)
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孝治 中村
利雄 森山
佳史 赤川
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宇部興産株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44Polyester-amides

Abstract

Provided is a method for producing a polyester amide elastomer: which exhibits toughness, softness at low temperatures, excellent molten moldability, molding processability, resistance to bending fatigue, impact resilient, noise cancellation properties, rubber-like properties, little change in transparency after being hydrothermally treated, and color, transparency and resistance to thermal discoloration while maintaining the polymerization acceleration effects during the production of the polyester amide elastomer; and has a low specific gravity. Also provided is a polyester amide elastomer obtained from the aforementioned production method. A method for producing a polyester amide elastomer, the method involving a step for subjecting a specific diamine (A), a polyamide-forming monomer (B) and a dicarboxylic acid (C) to melt polycondensation, wherein, if a phosphorus atom-containing compound (D) is added before or during the aforementioned step, the aforementioned melt polycondensation will be performed in the presence of (D), and if (D) is added after the aforementioned step, the polymer obtained by performing melt polycondensation in the aforementioned step will be melt-kneaded in the presence of (D). The amount of phosphorus atoms is 0.05 to 0.3 parts by mass per 100 parts by mass of the polyester amide elastomer.

Description

Polyetheramide elastomer obtained by the production method and manufacturing method thereof polyetheramide elastomer

The present invention relates to a polyether amide elastomer obtained by the production method and manufacturing method thereof polyetheramide elastomer.

Polyamide elastomer, high flexibility, low specific gravity, abrasion-wear characteristics, elasticity, bending fatigue resistance, low-temperature characteristics, moldability and is superior in chemical resistance, tubes, hoses, sporting goods, seal packings are widely used as a molded article such as a silencer gears.
The polyamide elastomer, a polyamide as a hard segment, polyether ester amide elastomer or polyether amide elastomer of polyether as a soft segment is known.

In polyetheresteramide elastomers, the soft segment, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyalkylene glycols such as polyoxybutylene glycol, alpha, .omega. but dihydroxy hydrocarbon is used, among these heat resistance, water resistance, low temperature properties, elastic recovery property, from the viewpoint of mechanical strength, mainly, polyoxybutylene glycol is used. However, polyamide 12 system for a polyoxybutylene glycol as soft segment of the polyether ester amide elastomer, elastic recovery property, flex fatigue resistance are not necessarily satisfactory. Further, the polyether ester amide elastomer, water resistance, and a problem in hydrolysis resistance and the like, for example, high temperature, becomes durability problems when used in a high humid environment, if the application is limited there are many.

To solve the problem of these polyetheresteramide having,
Patent Document 1 and Patent Document 2, Polyamide, polypropylene oxide (X) and polybutylene oxide (Y) is a polyether units forming the XYX type chemically bound, and polyether amide comprising dicarboxylic acid units elastomers is disclosed.
Patent Document 3, Polyamide, polypropylene oxide (X) and polybutylene oxide (Y) is a polyether unit consisting of polyether and polypropylene oxide forming the XYX type, and polyether amide elastomer disclosed consisting of a dicarboxylic acid unit It is.
In the manufacture of such a polyether amide elastomer, in order to accelerate the polymerization, as a catalyst if necessary, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc., also aiming at the effects of both catalyst and heat stabilizers phosphorous acid, is disclosed hypophosphorous acid, and their alkali metal salts, and can be added inorganic phosphorus-containing compounds such as alkaline earth metal salts.
The polymerization sodium hypophosphite commonly used 1 including hydrate to inorganic phosphorus-based alkali metal salts, alkaline earth metal salt compound when the polyamide was superior to inexpensive, and polyamide has a polymerization promoting effect, a catalyst capable of polymerizing an excellent polymer can also be imparted tone heat effect.

JP 2004-161964 JP JP 2003-286341 JP JP 2004-346274 JP

However, as described in the Examples below, these inorganic phosphorus-based alkali metal salts, in case of applying the polyetheramide elastomer of the alkaline earth metal salt compound, compounds forming the polyether units and sodium hypophosphite 1 inorganic phosphorus-based alkali metal salt including hydrates, or the compatibility of the alkaline earth metal salt compound is poor, rather than the transparency of the polyetheramide elastomer molded article satisfactory level, after especially moist heat treatment transparency, inorganic phosphorus-based alkali metal salts, including sodium monohydrate hypophosphite, devitrification phenomenon seems to influence the moisture absorption of the alkaline earth metal salt compound is confirmed, is significantly impaired transparency it has been found.
Design of the polyetheramide elastomer molded article, when considering the decorative, it is of course that the initial transparency is excellent, even deterioration in its transparency when used under various environments can be prevented Rukoto is desired.

The present invention is to solve the above problems,
Melt moldability, excellent in moldability,
Toughness, flexural fatigue resistance, impact resilience, low temperature flexibility, with which good sound deadening properties and rubber-like properties such as,
A low specific gravity, further,
While maintaining the polymerization promoter effect during polyetheramide elastomer prepared,
Hue, heat discoloration resistance, excellent transparency, and an object to provide a manufacturing method and a polyetheramide elastomer obtained by the method for producing a wet transparency less polyetheramide elastomer change of after heat-treated.

The present invention is referred to as contents below.
(1) the diamine compound and (components A), a polyamide-forming monomer (component B), the production of polyether amide elastomer having a dicarboxylic acid compound (component C) and a melting polycondensation obtain polyetheramide elastomer step there is provided a method,
Before the step, during, or after the phosphorus atom-containing compound (component D) is added,
If the component D before or at medium of the process is added in the presence of the component D, the melt polycondensation is performed,
If the component D is added after the step, the polymer obtained by melt polycondensation in the step is in the presence of the component D, the melted and kneaded is made,
Wherein component A is a compound represented by the following formula (1)

Figure JPOXMLDOC01-appb-C000011

(In the formula (1), x is an integer of 1 to 20, y is an integer of 4 to 50, and z is an integer of 1-20, respectively.) Triblock polyether diamine compound represented by (component A1) It includes,
Wherein component B is a compound represented by the following formula (2)

Figure JPOXMLDOC01-appb-C000012

(Equation (2), R 1 represents. A linking group containing a hydrocarbon chain) amino acid compounds represented by (component B1) and / or the following formula (3)

Figure JPOXMLDOC01-appb-C000013

A (formula (3), R 2 represents a linking group containing a hydrocarbon chain.) Represented by a lactam compound (component B2),
Wherein component C is a compound represented by the following formula (4)

Figure JPOXMLDOC01-appb-C000014

(In the formula (4), R 3 represents a linking group containing a hydrocarbon chain, m represents. 0 or 1) is represented compounds,
Wherein component D is a compound represented by the following formula (5)

Figure JPOXMLDOC01-appb-C000015

A compound represented by the following formula (6)

Figure JPOXMLDOC01-appb-C000016

A compound represented by the following formula (7)

Figure JPOXMLDOC01-appb-C000017

A compound represented by the following formula (8)

Figure JPOXMLDOC01-appb-C000018

A compound represented by the following formula (9)

Figure JPOXMLDOC01-appb-C000019

A compound represented by, and the following formula (10)

Figure JPOXMLDOC01-appb-C000020

In in the compound represented by (formula (5) to (10) may be R 4 - R 9 are the same or different, a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, X 1 - X 12 is a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, at least one compound selected from the group consisting of metal elements are excluded.),
To the polyetheramide elastomer 100 parts by weight,
Method for producing a polyether amide elastomer, wherein the phosphorus atom 0.005 to 0.3 part by weight.
(2) wherein (1) polyetheramide elastomers obtained by the process according.

According to the present invention, excellent melt-moldability, the molding processability,
Toughness, flexural fatigue resistance, impact resilience, low temperature flexibility, with which good sound deadening properties and rubber-like properties such as,
A low specific gravity, further,
While maintaining the polymerization promoter effect during polyetheramide elastomer prepared,
Tone, it is possible to provide heat discoloration resistance, excellent transparency, and polyether amide elastomers obtained by the process and method for producing wet transparency less polyetheramide elastomer change of after heat-treated.

The method of producing the polyether amide elastomer of the present invention (hereinafter, also referred to as the production method of the present invention)
Diamine compound (components A), a polyamide-forming monomer (component B), a dicarboxylic acid compound A (component C) and a method for manufacturing a polyetheramide elastomer having a melt polycondensation to step,
Phosphorus atom-containing compound before or at the middle of the process (component D) is added (embodiment 1), or the component D is added after the step (aspect 2),
For embodiments 1 wherein component D before or at medium of the process is added in the presence of the component D, the melt polycondensation is performed,
If aspect 2 wherein the component D is added after the step, the polymer obtained by melt polycondensation in the step is melted and kneaded is effected in the presence of the component D.
Embodiment 2, further specifically,
Components A, B and C after obtaining the molten polycondensation to polymer, as the polymer is melted and kneaded, there were added the ingredients in the presence of D, component D, from melting the polymer If you want to kneading,
Components A, B and polymer after by melt condensation polymerization of C, and the pellet was added to component D in step the melted kneaded in such time of molding the pellets, the presence of component D in, like the case of melt kneading the polymers.

Production method of the present invention embodiment 1 are preferably selected from (A1) including a triblock polyether diamine compound (A) a diamine compound and, (B1) aminocarboxylic acid compound and (B2) a lactam compound (B) a polyamide-forming monomer, the component containing the (C) the dicarboxylic acid compound, (D1) phosphate compound, (D2) phosphonic acid compound, (D3) phosphinic acid compound, (D4) phosphite compound, (D5) phosphonous acid compounds, and (D6) is at least one (D) method for producing a polyamide elastomer which melt polycondensation in the presence of a phosphorus-containing compound selected from the group consisting of phosphinous acid compounds,

Polyamide elastomer obtained by the production method of the present invention embodiment 1 is selected from (A1) including a triblock polyether diamine compound (A) a diamine compound and, (B1) aminocarboxylic acid compound and (B2) a lactam compound ( B) a polyamide-forming monomer, the component containing the (C) the dicarboxylic acid compound, (D1) phosphate compound, (D2) phosphonic acid compound, (D3) phosphinic acid compound, (D4) phosphite compound, ( D5) phosphonous acid compounds, and (D6) is at least one (D) the polyether amide elastomer obtained by melt polycondensation in the presence of a phosphorus-containing compound selected from the group consisting of phosphinous acid compound.

One preferred embodiment of the obtained polyamide elastomer by the process of the present invention embodiment 1, the XYX type triblock polyether diamine (A1) represented by the formula (1), preferably in addition to the diamine (A1) branched saturated diamine having 6 to 22 carbon atoms, branched alicyclic diamine of 6 to 16 carbon atoms, selected from norbornane diamine containing at least one (A2) diamine compound (a) a diamine compound of formula (3 ) represented by (B1) aminocarboxylic acid compound and represented by the formula (4) (B2) selected from a lactam compound (B) polyamide-forming monomers, and represented by the formula (2) (C) a dicarboxylic it is a polyether amide elastomer obtained by polymerizing an acid compound.

[Component A]
Component A, the following formula (1)

Figure JPOXMLDOC01-appb-C000021

(In the formula (1), x is an integer of 1 to 20, y is an integer of 4 to 50, and z is an integer of 1-20, respectively.) Triblock polyether diamine compound represented by (component A1) including.

Equation (1) represented by component A1 (hereinafter, also referred to as XYX type triblock polyether diamine compound) After the polypropylene glycol by The adding propylene oxide to both terminals and poly (oxytetramethylene) glycol , polyether diamines, and the like which are prepared by reacting ammonia or the like to the end of the polypropylene glycol.

In XYX type triblock polyether diamine compound, to ensure stable properties of the polyether amide elastomers obtained by the process of the present invention, including rubber elasticity (also referred to as polyether amide elastomer), in the manufacturing method of the present invention in order to ensure a robust polyetheramide elastomer to improve the compatibility with the polyamide component,
x and z are usually 1 to 20, preferably from 1 to 18, more preferably 1 to 16, more preferably from 1 to 14, particularly preferably from 1 to 12 ,
y is usually 4 to 50, is preferably 5 to 45, more preferably 6 to 40, more preferably from 7-35, particularly preferably 8-30.

Specific examples of the XYX type triblock polyether diamine compound,
U.S. manufactured by HUNTSMAN XTJ-533 (formula (In 1), x is about 12, y is about 11, z is approximately 11),
XTJ-536 (in the formula (1), x is approximately 8.5, y is approximately 17, z is approximately 7.5),
XTJ-542 (in the formula (1), x is approximately 3, y is about 9, z is about 2),
XTJ-559 (in the formula (1), x is approximately 3, y is about 14, z is approximately 2), and the like.

Further, as the XYX type triblock polyether diamine compound,
XYX-1 (in formula (1), x is about 5, y is about 14, z is approximately 2),
(In the formula (1), x is approximately 3, y is about 19, z is approximately 2) XYX-2 can be used like.

Component A, from the viewpoint of ensuring a stable clarity polyetheramide elastomer composition obtained by the process of the present invention, in addition to the components A1, branched saturated diamine having 6 to 22 carbon atoms, carbon atoms more preferably contains 6-16 branched cycloaliphatic diamine and at least one diamine compound selected from the group consisting of norbornane diamine (component A2).

As the branched saturated diamine having 6 to 22 carbon atoms in the used in the preferred embodiment (A2) diamine compounds, for example, 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4 - trimethyl-1,6-diaminohexane, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diamino octane. These may be used alone or in combination.

The branched alicyclic diamine of 6 to 16 carbon atoms of component A2 used in the preferred embodiment,
For example, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, (also referred to as "isophorone diamine".) 5-amino-1,3,3-trimethylcyclohexane methylamine, and the like. Further, these diamines may be any of cis form and trans form, or may be a mixture of these isomers.
These may be used alone or in combination.

The norbornane diamine component A2 used in the preferred embodiment,
For example, 2,5-Bruno Rubo Nan dimethylamine, 2,6 Roh Rubo Nan dimethylamine, and the like.
These may be used alone or in combination.

As the diamine compound (components A), it may include other diamine compound other than the component A1 and component A2 (component A3).

As component A3,
1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino-heptane, 1,8-diamino-octane, 1 , 9-diaminononane, 1,10-diaminodecane, 1,11-di-aminoundecanoic, 1,12 diamino aliphatic diamines such as dodecane,
Bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 1,3 / 1 , 4-bis-aminomethyl cyclohexane, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, alicyclic diamines such as tricyclodecane dimethylamine, m-/ p-aromatic diamine is exemplified such as xylylenediamine It is.
These may be used alone or in combination.

[Component B]
Component B is represented by the following formula (2)

Figure JPOXMLDOC01-appb-C000022

(Equation (2), R 1 represents. A linking group containing a hydrocarbon chain) amino acid compounds represented by (component B1) and / or the following formula (3)

Figure JPOXMLDOC01-appb-C000023

It is (equation (3), R 2 represents a linking group containing a hydrocarbon chain.) Represented by a lactam compound (component B2).

In the component B1, from the viewpoint of ensuring stable strength polyetheramide elastomer composition obtained by the process of the present invention, the mechanical properties such as elastic modulus, R 1 is,
Aliphatic C 2-20 hydrocarbon group of alicyclic or aromatic preferably, more preferably an alkylene group having 2 to 20 carbon atoms,
Preferably the hydrocarbon group having 3 to 18 carbon atoms, more preferably an alkylene group having a carbon number of 3-18,
Preferably the hydrocarbon group having a carbon number of 4 to 15, more preferably an alkylene group having a carbon number of 4 to 15,
Preferably the hydrocarbon group having a carbon number of 10-15, and more preferably a carbon number 10-15 alkylene group.

In the component B2, from the viewpoint of ensuring stable strength polyetheramide elastomer composition obtained by the process of the present invention, the mechanical properties such as elastic modulus, R 2 is
Aliphatic C3-20 hydrocarbon group alicyclic or aromatic preferably is preferably an alkylene group having 3 to 20 carbon atoms,
Preferably the hydrocarbon group having 3 to 18 carbon atoms, more preferably an alkylene group having a carbon number of 3-18,
Preferably the hydrocarbon group having a carbon number of 4 to 15, more preferably an alkylene group having a carbon number of 4 to 15,
Preferably the hydrocarbon group having a carbon number of 10-15, and more preferably an alkylene group having a carbon number of 10-15.

As component B1, 6- aminocaproic acid, 7-amino heptanoic acid, 8-amino octanoic acid, 10 Aminokapurin acid, 11-aminoundecanoic acid, aliphatic having 5 to 20 carbon atoms such as 12-aminododecanoic acid and amino acids.
These may be used alone or in combination.

As component B2, caprolactam, enantholactam, undecanolactam lactam, dodecalactam, and aliphatic lactams having 5 to 20 carbon atoms of 2-pyrrolidone, and the like.
These may be used alone or in combination.

[Component C]
Component C, the following formula (4)

Figure JPOXMLDOC01-appb-C000024
(In the formula (4), R 3 represents a linking group containing a hydrocarbon chain, m represents. 0 or 1) a dicarboxylic acid compound represented by the.

In the component from C, in view of ensuring a stable rubber elasticity and flexibility of the polyetheramide elastomer composition obtained by the process of the present invention, R 3 is
Aliphatic of 1 to 20 carbon atoms, preferably an alicyclic or aromatic hydrocarbon group or an alkylene group having 1 to 20 carbon atoms,
Preferably the hydrocarbon group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms,
Preferably the hydrocarbon group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 12 carbon atoms,
Preferably the hydrocarbon group having 4 to 10 carbon atoms, more preferably an alkylene group having 4 to 10 carbon atoms. Also, m is 0 or 1.

As component C, aliphatic, at least one dicarboxylic acid or derivatives thereof selected from cycloaliphatic and aromatic dicarboxylic acids.

Specific examples of the component C, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic diacid, linear C 2 -C 25 such as dodecanedioic acid aliphatic dicarboxylic acids, or, dimerized aliphatic dicarboxylic acid having a carbon atom number of 14 to 48 unsaturated fatty acids obtained were dimerization by fractional distillation of triglycerides (dimer acid) and hydrogenated products thereof (hydrogenated dimer acid) aliphatic dicarboxylic acids and the like, 1,3- / 1,4-cyclohexanedicarboxylic acid, di-cyclohexane-4,4'-dicarboxylic acid, alicyclic dicarboxylic acids such as norbornane carboxylic acid and terephthalic acid, isophthalic acid , an aromatic dicarboxylic acid such as 1,4 / 2,6 / 2,7-naphthalenedicarboxylic acid.
These may be used alone or in combination.

Component C is preferably the aliphatic dicarboxylic acid or alicyclic dicarboxylic acid.
As component C, dimer acid and hydrogenated dimer acid, Uniqema trade name "Pripol 1004", "Pripol 1006", "Pripol 1009", can be used to "Pripol 1013", and the like.

[Component D]
Wherein component D is a compound represented by the following formula (5)

Figure JPOXMLDOC01-appb-C000025

A compound represented by the following formula (6)

Figure JPOXMLDOC01-appb-C000026

A compound represented by the following formula (7)

Figure JPOXMLDOC01-appb-C000027

A compound represented by the following formula (8)

Figure JPOXMLDOC01-appb-C000028

A compound represented by the following formula (9)

Figure JPOXMLDOC01-appb-C000029

A compound represented by, and the following formula (10)

Figure JPOXMLDOC01-appb-C000030

In in the compound represented by (formula (5) to (10) may be R 4 - R 9 are the same or different, a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, X 1 - X 12 represents a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, at least one compound selected from the group consisting of metal elements are excluded.).

[Phosphorus-containing compound]
Components A, B and C by melt polycondensation in the presence of a phosphorus-containing compound (embodiment 1), or components A, B and polymer obtained after melt polymerization of C in the presence of a phosphorus-containing compound and melt kneaded (embodiment 2) resulting polyetheramide elastomers, color tone, heat discoloration resistance, excellent transparency, and transparency changes after wet heat treatment is small.

In the formula (5) to (10),
The alkyl group of R 4 ~ R 9 and X 1 ~ X 12,
An alkyl group having 1 to 24 carbon atoms linear or branched, such as methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, t- butyl group, n- pentyl group, isopentyl group, t-pentyl group, a neopentyl group, a hexyl group, sec- hexyl, heptyl, sec- heptyl group, octyl group, sec- octyl group, 2-ethylhexyl group, nonyl group, sec- nonyl group, decyl group, sec- decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, 2-butyl octyl group, 2-Buchirudeshiru group, 2-hexyl octyl , 2-hexyl decyl group, 2-octyl-decyl group, and 2-hexyl dodecyl group .

In the formula (5) to (10),
The cycloalkyl group of R 4 ~ R 9 and X 1 ~ X 12,
A cycloalkyl group having 3 to 20 carbon atoms, e.g., cyclopentyl, methylcyclopentyl group, cyclopentylmethyl group, 2-cyclopentylethyl group, a cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cyclohexylmethyl group, 2-cyclohexyl ethyl group, an ethyl cyclohexyl group, propyl cyclohexyl group, cycloheptyl group, methyl cycloheptyl, cyclooctyl, cyclooctyl methyl group, 2-cyclooctyl-ethyl group and the like.

In the formula (5) to (10),
The aryl group of R 4 ~ R 9 and X 1 ~ X 12,
An aryl group having 6 to 24 carbon atoms (including all isomers), for example, a phenyl group, toluyl group, xylyl group, cumenyl group, trimethylphenyl group (mesityl), ethylphenyl group, ethyl methyl phenyl group, diethylphenyl group, an ethyl dimethylphenyl group, triethylphenyl group, propylphenyl group, propylmethylphenyl, propyl ethylphenyl group, dipropylphenyl group, tripropyl phenyl group, butylphenyl group, dibutylphenyl group, tributylphenyl group , pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl, dodecylphenyl group, 1-naphthyl, 2-naphthyl, methylnaphthyl group, anthranyl group Benzyl phenyl group, cumylphenyl group, a biphenyl group, a 2,4,6-phenylphenyl group and the like.

In the formula (5) to (10),
The aralkyl group of R 4 ~ R 9 and X 1 ~ X 12,
An aralkyl group having 7 to 24 carbon atoms (including all isomers), for example, benzyl group, phenethyl group, benzhydryl group, trityl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group, methylbenzyl group , methylphenethyl group, methyl naphthyl methyl group, and a phenyl benzyl group.

Formula (8) Phosphorous Compounds represented, it is possible to tautomerize the general formula (6) phosphonic acid compounds represented by the influence of hydrogen ion concentration, also,
Phosphonic acid compounds represented by the general formula (6) may also be tautomerize phosphite compound represented by the general formula (8) due to the influence of temperature.
The phosphonous acid compounds represented by the general formula (9), may tautomerize to the general formula (7) phosphinic acid compound represented by the influence of hydrogen ion concentration, also,
Phosphinic acid compound represented by the general formula (7) may also be tautomerize the phosphonous acid compound represented by the general formula (9) due to the influence of temperature.

Phosphorus atom-containing compound represented by the formula (5) is (D1) phosphate compound,

Phosphoric acid, phosphoric acid esters, acidic phosphoric acid esters.
Examples of the phosphoric acid esters, for example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tri (2-ethylhexyl) phosphate, trinonyl phosphate, tridecyl phosphate, tri-undecyl phosphate, tri-dodecyl phosphate, tri-tetradecyl phosphate, tri pentadecyl phosphate, trihexadecyl phosphate, tri heptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, ethyl dibutyl phosphate, tricyclohexyl phosphate, tri phenyl phosphate, tricresyl phosphate, tri Silyl phosphate, tris (nonylphenyl) phosphate, ethyl dibutyl phosphate, benzyl diphenyl phosphate, ethyl diphenyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate, dicresyl phenyl phosphate, (ethylphenyl) diphenyl phosphate, di (ethylphenyl) phenyl phosphate, (propylphenyl) diphenyl phosphate, di (propylphenyl) phenyl phosphate, (butylphenyl) diphenyl phosphate, di (butylphenyl) phenyl phosphate, tri (ethylphenyl) phosphate, tri (propylphenyl) phosphate, tri (butylphenyl ) phosphate, and the like.
These may be used alone or in combination.

The acidic phosphoric acid esters, such as mono- or dimethyl acid phosphate, mono- or diethyl acid phosphate, mono- or di-n- propyl acid phosphate, mono- or diisopropyl acid phosphate, mono- or di-butyl acid phosphate, mono- or dipentyl acid phosphate, mono- or dihexyl acid phosphate, mono- or di-heptyl acid phosphate, mono- or dioctyl acid phosphate, mono- or di (2-ethylhexyl) acid phosphate, mono- or di-nonyl acid phosphate, mono- or di-decyl acid phosphate, mono- or diundecyl acid phosphate, mono or di-dodecyl acid phosphate, mono- or di-decyl acid phosphate, mono or Jiteto Decyl acid phosphate, mono- or di-pentadecyl acid phosphate, mono- or di-hexadecyl acid phosphate, mono- or di-heptadecyl acid phosphate, mono- or di-octadecyl acid phosphate, mono- or dioleyl acid phosphate, mono- or diphenyl acid phosphate, mono- or dicyclopentyl acid phosphate, mono- or dicyclohexyl acid phosphate, mono- or di-cyclooctyl acid phosphate, mono- or diphenyl acid phosphate, and the like.
These may be used alone or in combination.

Phosphorus atom-containing compound represented by the formula (6) is (D2) phosphonic acid compound, e.g.,
Phosphonic acid, methylphosphonic acid, ethylphosphonic acid, propyl phosphonic acid, butylphosphonic acid, octyl phosphonic acid, 2-ethylhexyl phosphonic acid, Noniruhosuhon acid, decylphosphonic acid, dodecyl phosphonic acid, tridecyl acid, octadecyl phosphonic acid, oleyl phosphonate, phenylphosphonic acid, Toriruhosuhon acid, methyl methylphosphonate, ethyl methylphosphonic acid, methylphosphonic acid dodecyl, phenyl methylphosphonic acid, methyl phenyl phosphonic acid, phenylphosphonic acid ethyl, phenyl phosphonic acid dodecyl, phenyl phosphonic acid, dimethyl methylphosphonate , methylphosphonic acid diphenyl, phenylphosphonic acid dimethyl, phenylphosphonic acid methyl phenyl, phenyl phosphonic acid diethyl, phenyl phosphonic acid Phenyl, dimethylbenzyl acid, benzyl phosphonic acid diethyl, and the like dipropyl benzyl phosphonic acid.
These may be used alone or in combination.

Phosphorus atom-containing compound represented by the formula (7) and (D3) phosphinic acid compound, e.g., phosphinic acid (hypophosphorous acid), trimethyl phosphinate, ethyl dimethylphosphinate, dimethyl phosphinic acid propyl, dimethyl phosphinic acid butyl, pentyl dimethyl phosphinic acid, hexyl dimethyl phosphinic acid, heptyl dimethyl phosphinic acid, octyl dimethyl phosphinic acid, phenyl dimethyl phosphinic acid, dimethyl phosphinic acid toluyl, naphthyl dimethyl phosphinic acid, methylphenyl phosphinic acid methyl, ethyl methyl phenyl phosphinate, diethyl methyl phosphinic acid, triethylphosphine acid, diethyl phosphinic acid propyl, butyl diethylphosphinate, diethyl phosphinic acid pentyl, diethyl phosphinic acid hexyl, Heptyl ethyl phosphinic acid, diethyl phosphinic acid octyl, phenyl diethylphosphinate, toluic diethylphosphinate, naphthyl diethyl phosphinate, ethyl methyl phosphinate methyl, ethyl methyl ethyl phosphinate, ethyl methyl phosphinate propyl, ethyl propyl phosphinic acid methyl, ethyl ethyl propyl phosphinic acid, ethyl propyl phosphinic acid propyl, ethyl phenyl phosphinate methyl, ethyl phenyl phosphinate ethyl, methyl dipropyl phosphinic acid, ethyl dipropyl phosphinic acid, tripropyl phosphinic acid, butyl dipropyl phosphinic acid, dipropyl phosphinic acid pentyl, hexyl dipropyl phosphinic acid, dipropyl phosphinic acid heptyl, dipropyl phosphinic acid octyl, di B pills phosphinic acid phenyl, dipropyl phosphinic acid toluyl, naphthyl dipropyl phosphinic acid, tributylphosphine acid, trioctylphosphine acid, triphenylphosphine, methyl diphenyl phosphinic acid, diphenyl phosphinic acid cyclohexyl, tris-tolyl phosphinic acid, tricyclohexylphosphine acid, phenyl dicyclohexyl phosphinic acid, tribenzylphosphine acid, dimethyl phosphinic acid, methyl phosphinic acid, ethyl methyl phosphinate, dodecyl methyl phosphinic acid, phenylmethyl phosphinic acid, diphenyl phosphinic acid, methylphenyl phosphinate, ethylphenyl phosphinate, phenyl phosphinic acid dodecyl, phenyl phosphinic acid, methyl phosphinic acid, ethyl phosphinic acid , Hexyl phosphinic acid, octyl phosphinic acid, dodecyl phosphinic acid, hexadecyl phosphinic acid, octadecyl phosphinic acid, cyclohexyl phosphinic acid, phenyl phosphinic acid, tolyl phosphinic acid, benzyl phosphinic acid, pheneticillin like chill phosphinic acid.
These may be used alone or in combination.

Phosphorus atom-containing compound represented by the formula (8) is (D4) phosphite compounds,
Phosphorous acid, phosphorous acid esters, acidic phosphite mono- or diesters, and the like.

The phosphorous acid ester, for example, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, tri-isooctyl phosphite phosphite, tri (2-ethylhexyl) phosphite, trinonyl phosphite, tridecyl phosphite, tri undecyl phosphite, tridodecyl phosphite, tritriacontanoic decyl phosphite, trihexadecyl phosphite, trioctadecyl phosphite, trioleyl phosphite, tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di -t- Butylphenyl) phosphite, tris (nonylphenyl) phosphite, isooctyl diphenyl phosphite, phenyl diisooctyl phosphite, 2-ethylhexyl diphenyl phosphite, phenyldi-2-ethylhexyl phosphite, phenyl didecyl phosphite, decyl diphenyl phosphite, decyl phenyl phosphite, phenyl didodecyl phosphite, dodecyl diphenyl phosphite, tridecyl diphenyl phosphite, decyl dioctyl phosphite, dodecyl dioctyl phosphite, di (2,4-di -t- butyl-phenyl) Dodeshiruhosu phosphite, di (2,4-di -t- butyl phenyl) octyl phosphite, (2,4-di -t- butyl-phenyl) diisooctyl phosphite, di (nonylphenyl Decyl phosphite, (2,4-di -t- butyl-phenyl) dicyclohexyl phosphite include diisodecyl nonylphenyl phosphite.
These may be used alone or in combination.

The acid phosphite, for example, mono- or dimethyl hydrogen phosphite, mono- or diethyl hydrogen phosphite, mono- or dipropyl hydrogen phosphite, mono- or di-butyl hydrogen phosphite, mono- or dipentyl hydrogen phosphite , mono- or dihexyl hydrogen phosphite, mono- or di-heptyl hydrogen phosphite, mono- or dioctyl hydrogen phosphite, mono- or di-2-ethylhexyl hydrogen phosphite, mono- or di-nonyl hydrogen phosphite, mono- or di decyl hydrogen phosphite, mono or diundecyl hydrogen host file, mono- or di-dodecyl hydrogen phosphite, mono- or di-hexadecyl Hydro Enhosufaito, mono- or di-octadecyl hydrogen phosphite, mono- or dioleyl hydrogen phosphite, mono- or dicyclohexyl hydrogen phosphite, mono- or diphenyl hydrogen phosphite, mono- or di-cresyl hydrogen phosphite, mono- or di-toluyl hydrogen phosphite, mono- or dibenzyl hydrogen phosphite, mono- or di-phenethyl hydrogen phosphite, and the like.
These may be used alone or in combination.

Phosphorus atom-containing compound represented by the formula (9) and (D5) phosphonous acid compounds, for example, phosphonous acid, methyl phosphonous acid, ethyl phosphonous acid, dodecyl phosphonous acid, phenyl phosphonous acid, methyl phosphonous acid monomethyl, monoethyl methyl phosphonous acid, methyl phosphonous acid monododecyl, methyl phosphonous acid monophenyl, ethyl phosphonous acid monomethyl, ethyl phosphonous acid monoethyl ethyl phosphonous acid mono dodecyl, ethyl phosphonous acid monophenyl , phenyl phosphonous acid monomethyl, monoethyl phenyl phosphonous acid, phenyl phosphonous acid mono dodecyl, phenyl phosphonous acid monophenyl, trimethyl phosphonous acid, methyl phosphonous acid methyl ethyl, methyl phosphonous diethyl, methyl phosphonous dipropionate Le, methyl phosphonous acid dibutyl, methyl phosphonous acid diphenyl, ethyl phosphonous dimethyl, triethyl phosphonous acid, ethyl phosphonous acid dipropyl, ethyl phosphonous acid dibutyl, ethyl phosphonous acid diphenyl, propyl phosphonous acid dimethyl, propyl phosphonous acid diethyl, tripropylamine phosphonous acid, propyl phosphonous acid dibutyl, propyl phosphonous acid diphenyl, butyl phosphonous acid dimethyl, butyl phosphonous acid diethyl, butyl phosphonous acid dipropyl, tributyl phosphonous acid, butyl phosphonous diphenyl, phenyl phosphonous acid dimethyl, methyl ethyl phenyl phosphonous acid, phenyl phosphonous acid diethyl, phenyl phosphonous acid dipropyl phenyl phosphonous acid dibutyl, triphenyl phosphite Such as phosphate and the like.
These may be used alone or in combination.

Phosphorus atom-containing compound represented by the formula (10) is (D6) phosphinous acid compounds, for example,
Phosphinous, methyl phosphinous, ethyl phosphinous, butyl phosphinous, phenyl phosphinous, methyl phosphinous, ethyl methyl phosphinous, butyl methyl phosphinous, phenylmethyl phosphinous, ethyl nitrite methyl phosphinic acid, ethyl nitrite ethyl phosphinate, ethyl phosphinous butyl, ethyl phosphinous phenyl, butyl phosphinous methyl, butyl phosphinous ethyl, butyl phosphinous butyl, butyl phosphinous phenyl, phenyl phosphinous methyl, phenyl phosphinous ethyl, butyl phenyl phosphinous, phenyl phosphinous, dimethyl phosphinous, methyl ethyl phosphinous, diethyl phosphinous, dibutyl phosphinous , Diphenylphosphinites, trimethyl phosphinous, triethyl phosphinous, tributyl phosphinous, triphenyl phosphine, ethyl dimethyl phosphinous, butyl dimethyl phosphinous, phenyl dimethyl phosphinous, methyl diethyl phosphinous , butyl diethyl phosphinous, phenyl diethyl phosphinous, dibutyl phosphinous methyl, dibutyl phosphinous ethyl, phenyl dibutyl phosphinous, methyl Diphenylphosphinites, ethyl Diphenylphosphinites, butyl Diphenylphosphinites etc. and the like.
These may be used alone or in combination.

Among the component D, from for low color property high catalytic activity,
Formula (5) (D1) phosphate compound represented by the formula (7) (D3) phosphinic acid compound, and from the group consisting of the (D4) phosphite compound with the formula (8) is preferably at least one selected,
Phosphoric acid, phosphorous acid, and more preferably at least one selected from the group consisting of hypophosphorous acid.
Further, component D, polyamide polymerization catalyst as phosphoric acid commonly used, phosphoric acid metal salts are phosphorous acid or hypophosphorous acid with periodic table Group 1 metals consisting of metal salts, nitrous phosphoric acid metal salts, hypophosphorous acid metal salts are excluded.

[Component A, B, charged ratio of C and D]
In the production method of the present invention, component A, were charged proportions of B and C is to improve the crystallinity of the polyamide component of the polyetheramide elastomer obtained, the intensity of the polyetheramide elastomer obtained, the mechanical properties such as elastic modulus ensuring the function as an elastomer such as rubber elasticity and flexibility, from the viewpoint of stably express the performance,
All components, i.e., the total 100% by weight of the components A, B and C,
Preferably component B is 10 to 95% by weight,
More preferably 15 to 90 mass%,
More preferably from 15 to 85 wt%,
More preferably from 15 to 80 wt%,
Preferably the total of components A and C is 5 to 90 mass%,
More preferably 10 to 85% by weight,
More preferably from 15 to 85 wt%,
More preferably 20 to 85 mass%.
Component A and component C is preferably charged as a carboxyl group (that may include an amino group when contain other diamine compound) and component C amino groups of component A is approximately equimolar,
The molar ratio of the carboxyl groups of component amino groups of A (when containing other diamine compounds including its amino group) and component C,
Is preferably 45 / 55-55 / 45,
More preferably 47 / 53-53 / 47,
Still more preferably 49 / 51-51 / 49,
And more preferably 50/50.

In the production method of the present invention, the polyether amide elastomer obtained, component A, contained in the B and C, i.e., components A, with a carboxylic acid or carboxyl group at the end derived from B and C, the amino group at the end since it is preferable to but at a ratio such that approximately equimolar, it is preferred that charged in proportions such as carboxylic acid or carboxyl groups of components a, B and C, the amino group at the end is approximately equimolar .

The proportion of component A1 when melt polycondensation, functions as a stable rubber elasticity or elastomer flexibility such a polyetheramide elastomer composition obtained by the process of the present invention, in order to ensure the performance,
In component A100 wt%, preferably 50 to 100 wt%, more preferably 80 to 100 mass%, more preferably 90 to 100 wt%,
When the melt polycondensation, may further comprise a component A2, the ratio, in order to ensure a stable transparency polyetheramide elastomer composition obtained by the process of the present invention, the total of components A, B and C per 100 parts by weight, preferably 0.5 to 10 mass%, and more preferably 1 to 5 mass%.

The amount of the polycondensation system or component D is added to the kneading within system polyetheramide elastomers in embodiments 1, or, the amount of component D is added to the molten kneading system polyetheramide elastomers in embodiments 2,
Suppressing coloration of the polyamide during polymerization or during kneading, to improve the polymerization promoting effect, stably securing the initial color tone and heat discoloration resistance,
Suppressing the additive amount to suppress the manufacturing cost,
Suppressing gelation reaction of the polyether amide elastomer,
By suppressing incorporation into shaped articles in fisheyes attributed to component D, from
Securing a stable appearance of the molded article is a polyether amide elastomer,
By suppressing the frequency of filter clogging at the time of molding to ensure stable productivity, further,
From the viewpoint of securing a stable transparency after wet heat treatment and stable transparency of the molded product,
The component A, a total of 100 parts by weight of B and C, or, with respect polyetheramide elastomer 100 parts by mass, 0.005 to 0.3 part by weight as a phosphorus atom,
Preferably 0.01 to 0.2 part by weight,
And more preferably 0.03 to 0.15 mass parts.
From the same viewpoint, the total 100 parts by weight of components A, B and C, or, with respect polyetheramide elastomer 100 parts by weight, the component D, from
Preferably, 0.005 to 4.5 mass part,
More preferably, from 0.01 to 3.0 parts by mass,
More preferably, from 0.03 to 1.5 parts by mass.

Other production conditions polyetheramide elastomer]
Production method of the present invention, the (A1) and triblock poly containing an ether diamine compound (A) a diamine compound, (B1) selected from an aminocarboxylic acid compound and (B2) a lactam compound (B) polyamide-forming monomers, the component (C) containing a dicarboxylic acid compound, (D1) phosphate compound, (D2) phosphonic acid compound, (D3) phosphinic acid compound, (D4) phosphite compound, (D5) phosphonous acid compounds, and ( D6) is at least one (D) method for producing a polyamide elastomer which melt polycondensation in the presence of a phosphorus-containing compound selected from the group consisting of phosphinous acid compound.

The timing of adding to the reaction system of the component D (embodiment 1) or kneading system (aspect 2), midway before and reaction of the condensation polymerization reaction, or may be any middle kneading before and kneading component D of the reaction system or scattering of the kneading system outside is relatively small that, and the polymerization time or kneading time is relatively short, the relative viscosity of the reaction product from the polycondensation reaction immediately before the polymerization reaction proceeds until reaching 1.2, or a relative viscosity of kneaded melt from kneading start immediately before it is preferably added until reaching 1.2. Component D may be added in the form of a solution or the like slurry and dissolved dispersed in a liquid such as water to the reaction system or kneading system.

By way of example, components A, B, and at the same time four components C and D, and melt polymerization under pressure and / or atmospheric pressure, it is possible to use a method comprising a step of melt polymerization in addition optionally under reduced pressure it can. Incidentally, by the polymerization of 2 of component B and component C above, then with component D, from available a method for polymerizing with component A.

In the production method of the present invention, the polymerization temperature is favorably proceeds polymerization reaction, thermal decomposition is suppressed, from the viewpoint of obtaining a polymer stably good physical properties, preferably from 0.99 ~ 300 ° C., 160 more preferably ~ is 280 ° C., more preferably from 180 - 250 ° C..

When using amino acids as component B, it is possible to manufacture by a method comprising the step of under reduced melt polymerization atmospheric melt polymerization or atmospheric melt polymerization and subsequent.
On the other hand, in the case of using a lactam as component B, the coexistence of a suitable amount of water, produced by the process consisting of melt polymerization and atmospheric melt polymerization and / or reduced pressure melt polymerization followed by under pressure of usually 0.1 ~ 5 MPa can do.

In the production method of the present invention, stably secure the increase of the molecular weight, by suppressing the coloration due to thermal decomposition stable from the viewpoint of obtaining a polyetheramide elastomer having desired physical properties, the polymerization time is usually 0.5 to it can be prepared in 20 hours.

In the production method of the present invention, even in a batch, can also be carried out continuously, also a batch reaction vessel, either alone or in appropriate combination one-pot type or Oso type continuous reaction apparatus, tubular continuous reaction apparatus and the like it can be used Te.

The relative viscosity (ηr) (0.5 weight / volume% m-cresol solution, 25 ° C.) of the polyetheramide elastomer obtained by the production method of the present invention, stable polyetheramide elastomers obtained by the production method of the present invention to ensure the mechanical properties, from the viewpoint of obtaining polyetheramide elastomer without requiring a long time in the production process of the present invention is preferably 1.2 to 3.5.

[Polyetheramide elastomers obtained by the process of the present invention]
Polyetheramide elastomer produced by the process of the invention is an added component D in the manufacturing method of the present invention are mixed. Hereinafter, the polyether amide elastomer obtained by the production method of the present invention refers to a state in which the component D is mixed, also referred to as production polyetheramide elastomer mixture obtainable by the process or polyetheramide elastomer mixtures of the present invention.

Furthermore, polyetheramide elastomers produced by the process of the present invention,
Units derived from the component A, include polymers composed of units and components C from the unit derived from the component B,
Units derived from the component A, the total 100 mass% of the units and components C from the unit derived from the component B, and a unit derived from the component B,
Preferably from 10 to 95% by weight,
More preferably 15 to 90 mass%,
More preferably from 15 to 85 wt%,
More preferably from 15 to 80 wt%,
Total units and units derived from the component C from component A,
Is preferably 5 to 90 mass%,
More preferably 10 to 85% by weight,
More preferably from 15 to 85 wt%,
More preferably from 20 to 85% by weight,
Units and units derived from the component C from component A is at approximately equimolar can (also includes the amino group when contain other diamine compound) carboxyl residues derived from the component C Amino acid residues derived from the component A it is preferable.

Further, component D being mixed polyetheramide elastomers produced by the process of the present invention, the unit derived from the component A in the polyether amide elastomer, composed of units and components C from the unit derived from the component B for the polymer to 100 parts by weight,
It is preferably 0.005 to 0.3 part by weight,
More preferably 0.01 to 0.2 part by weight,
More preferably 0.03 to 0.15 mass parts.

Units derived from the component A in the polyether amide elastomer, qualitative and quantitative units of units and derived components C from component B, after the monomer by hydrolysis, liquid chromatography or gas chromatography IR, H 1 -NMR equi generally can be measured by methods used in the evaluation of the polymer.
Units derived from the component A in the polyether amide elastomer, qualitative and quantitative units of units and derived components C from component B, after the monomer by hydrolysis, liquid chromatography or gas chromatography IR, H 1 -NMR equi generally can be measured by methods used in the evaluation of the polymer.
Illustrating an example of a method of composition analysis by hydrolysis.
As the acid, hydrobromic acid capable of selectively hydrolyzing the polyamide, hydrochloric acid or the like is used.
The amount of acid, relative to the polyetheramide elastomer mixture 0.1 g, which is 50 ~ 100 ml.
To promote faster hydrolysis, polyetheramide elastomer mixture is used in powder form for example, ground by cryogenic grinding.
Temperature during hydrolysis is 100 ~ 130 ° C..
After hydrolysis, separating the insolubles from the acid solution by filtration or centrifugation.
It can be used high performance liquid chromatographic analysis (HPLC) and gas chromatography / mass spectrometry (GC / MS) or the like as a method for evaluating the separated solution.
For example, in the case of a GC / MS, the analytical instrument manufactured by Shimadzu Corporation GCMS-QP5050A type,
The column Ultra ALLOY + -1 (MS / HT) (0.25φ × 15m, 0.15μm) used,
120-390 at a column temperature of ℃ (12 ℃ / min hold),
Inlet temperature 340 ° C., in the interface temperature 340 ° C. was introduced in a carrier gas He 2.0ml / min,
Ionization (EI method 70 eV), the measurement range 20-900, implantation Split Method 1: 8, can be measured by injection volume 1 [mu] l.

Polyetheramide elastomer obtained by the production method of the present invention, to the extent that its characteristics are not inhibited, heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, sealability improving agents, anti-fogging agents, releasing agents, plasticizers, pigments, dyes, perfumes, may be flame retardant, polyetheramide elastomer composition by adding a reinforcing material or the like.

Polyetheramide elastomer obtained by the production method of the present invention, the polyamide except polyetheramide elastomers, polyvinyl chloride, polyurethane resin, an acrylonitrile / butadiene / styrene copolymer (ABS) compatibility with the thermoplastic resin such as well, by blending with these thermoplastic resins, it can be molded of these resins, impact resistance, and polyether amide elastomer compositions with improved elasticity and flexibility, or the like.

Polyetheramide elastomer obtained by the production method of the present invention, while maintaining the properties inherent polyamide elastomer, color tone, heat discoloration resistance, excellent transparency, and transparency changes after wet heat treatment is small.
Further maintaining the polymerization promoting effect of polyetheramide elastomer during manufacture, it is possible to obtain polymers good productivity with a desired degree of polymerization.

Polyetheramide elastomer obtained by the production method of the present invention, injection molding, extrusion molding, blow molding, vacuum molding, it is possible to obtain a molded product by known molding methods pressure forming or the like. The resulting molded article, for example, automobile parts, electric and electronic parts, industrial parts, sports goods, are preferably used in medical articles or the like.

The automobile parts, constant velocity joint boots, rack-and-Opinio Yon boots, boots such as suspension boots, ball joint seal, safety belt parts, bumper fascia, emblem, mall, instrument panel, center panel, center console box, door trim , pillars, assist grips, handles, airbag covers, etc., as electrical and electronic parts, wire coating material, an optical fiber coating material, gears, rubber switches, membrane switches, tact switch, switch case, watch band, cleaner bumper, remote control switch, office automation (OA) equipment of the key top, mute gears, the industrial parts, hydraulic hose, a coil tube, sealing material, gear, cam, bearing, bearing packing, Gasquet Door, packing, O- ring, conveyor belts, V belts, roll, anti-vibration damping material, shock absorber, coupling, diaphragm, fasteners, valves, joint, grip, caster rollers, clips, etc., as sporting goods, golf, baseball, soccer, sports shoes bottom, such as athletics, ski shoes ball for a ball, etc., as parts requiring design properties and decorative properties, sunglasses, glasses, etc., as are medical supplies, medical tubes, blood transfusion pack, catheter or the like and the like. Also, other elastic fibers, elastic sheets, tubes, hoses, pipes, rods, films, sheets, brush acids, fishing nets, nets, composite sheet, hot-melt adhesives include alloys for materials such as with other resins.

The present invention will be described below by way of examples and comparative examples, the present invention is not limited to these examples.
[Measurement of Physical Properties, molding, Evaluation Method]
Measurements of physical properties, molding, evaluation was carried out in the following manner.

1) Relative viscosity (.eta.r)
The reagent special grade m- cresol as solvent, at a concentration of 5 g / dm 3, measured at 25 ° C. using an Ostwald viscometer.

2) a terminal carboxyl group concentration polymer about 1g was added benzyl alcohol 40 mL, heated and dissolved in a nitrogen gas atmosphere, adding phenolphthalein as an indicator to the sample solution obtained, N / 20 potassium hydroxide - ethanol solution in was titrated.

3) terminal amino group concentration polymer about 1g of 40mL phenol / methanol mixed solvent (volume ratio: dissolved in 9/1), and thymol blue was added as an indicator to the sample solution obtained, titration with N / 20 hydrochloric acid did.

4) Phosphorus atom concentration or decomposing dry ashing analysis sample in sodium carbonate the presence of, and wet digestion in sulfuric acid, nitric acid, and perchloric acid or sulfuric acid-hydrogen peroxide type, and phosphorus and orthophosphate. Then, 1 mol / L by reacting a molybdate salt in sulfuric acid solution, and phosphomolybdic acid, which an absorption photometer absorbance 830nm of heteropoly blue occurring is reduced with hydrazine sulfate (Hitachi, Ltd., Ltd., U and colorimetry was measured at -3000).

5) under the analytical sample sodium atom concentration of platinum crucible and ashed decomposed and evaporated to dryness by adding 6 mol / L hydrochloric acid. Was dissolved in 1.2 mol / L hydrochloric acid was quantified the solution with an atomic absorption spectrophotometer (manufactured by Shimadzu Corporation, AA-660).

Measurement of 6) shown below mechanical properties (1) to (3), a test piece below was molded by injection molding was performed using this.
(1) Tensile yield strength and tensile fracture strain: using a specimen having a thickness of 4 mm, conforming to ISO 527-1,2, was measured at 23 ° C..
(2) Bending test (bending strength and flexural modulus): using a specimen having a thickness of 4 mm, conforming to ISO 178, measured at 23 ° C..
(3) Charpy impact strength (notched): conforms to ISO 179-1EA using a specimen of notched thickness 4 mm (edgewise impact test) was measured at 23 ° C. and -40 ° C..

7) The haze (haze)
Using a sheet of molded 25 mm × 60 mm × thickness 2mm by injection molding, conforming to JIS K-7105, a direct-reading haze computer (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP) was used for the measurement.

8) a sheet of 25 mm × 60 mm × thickness 2mm were molded by transparent injection molding after the hot water treatment was immersed in hot water at 80 ° C., and held for 24 hours. Thereafter, the samples were removed at the 7) In a similar manner the haze (haze) was measured haze of the sample after hot water treatment, determine the change in value of the haze from the difference between the initial haze, after the hot water treatment It was evaluated transparency. When the change value of the haze is less than 12% was judged to be excellent in transparency after hot water treatment.

9) The color tone obtained pellets, a color computer (Suga Test Instruments Co., Ltd., using the SM-5-IS-2B), was measured yellowness YI.

10) Heat discoloration resistance resulting pellet was set at 100 ° C. oven and held for 24 hours. Thereafter, the pellets in the extraction above 9) colors and same method to measure the yellowness index YI of the heat treatment after the pellets, the yellowness index change value (.DELTA.YI) determined from the difference between the initial yellowness YI, resistance after heat treatment It was to evaluate the discoloration. If ΔYI is 10.0 or less, it was determined to be excellent in heat discoloration resistance after heat treatment.

[Raw materials used]
(Component D) phosphorus-containing compound (D-1) phosphite (Taihei Chemical Industrial Co., Ltd.)
(D-2) hypophosphorous acid (Taihei Chemical Industrial Co., Ltd.)
(D-3) phosphoric acid (Taihei Chemical Industrial Co., Ltd.)
(D-4) sodium hypophosphite (Taihei Chemical Industrial Co., Ltd.)
(D-5) Sodium phosphite (Taihei Chemical Industrial Co., Ltd.)

[Example 1]
Stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen gas inlet, a pressure vessel 70 liter with a pressure regulator and a polymer outlet,
12-aminododecanoic acid (manufactured by Ube Industries (Ltd.)) 9.000kg,
(Manufactured by Asahi Kasei Co., Ltd.) adipic acid 0.747kg,
XYX type triblock polyether diamine (HUNTSMAN Corp.: XTJ-542, amine value: 1.96meq / g) 3.564kg,
Isophorone diamine (Evonik Corporation: VESTAMIN IPD) 0.274kg,
(D-1) phosphorous acid 20.4g and heat stabilizers (Yoshitomi Pharmaceutical Co., Ltd.: Tominox 917) were charged 40.8 g.
After sufficiently purged with nitrogen in the vessel, while supplying nitrogen gas 186 l / h, the temperature was raised to 230 ° C. from room temperature over a period of 3.5 hours while the pressure was adjusted to 0.05MPa in the container, further container the pressure of the inner polymerization was carried out at adjustment while 230 ° C. to 0.05 MPa.
The amperage of the agitation power over time recording, the polymerization endpoint was when the amperage of the stirring power has reached 4.75A (amperes).
After completion of the polymerization, the stirring was stopped, extracted from the polymer outlet of a colorless transparent polymer in the molten state in a string-like, cooled with water to obtain pellets by pelletizing.

[Example 2]
In Example 1,
12-aminododecanoic acid (manufactured by Ube Industries (Ltd.)) 9.510kg,
(Manufactured by Asahi Kasei Co., Ltd.) adipic acid 0.511kg,
XYX type triblock polyether diamine (HUNTSMAN Corp.: XTJ-542, amine value: 1.96meq / g) converted to 3.565Kg,
Except for not using isophorone diamine, to obtain a polyetheramide elastomer in the same manner as in Example 1.

[Examples 3-4]
In Example 1, except that the amount of (D-1) was changed to the ratio shown in Table 1, to obtain a polyetheramide elastomer in the same manner as in Example 1.

[Example 5]
In Example 1, (D-1) was used as a (D-2), except for changing the proportions shown in Table 1, to obtain a polyetheramide elastomer in the same manner as in Example 1.

[Example 6]
In Example 1, (D-1) was used as a (D-3), except for changing the proportions shown in Table 1, to obtain a polyetheramide elastomer in the same manner as in Example 1.

[Comparative Example 1]
In Example 1, except that (D-1) is not used, to obtain a polyetheramide elastomer in the same manner as in Example 1.

[Comparative Examples 2 and 3]
In Example 1, except that the amount of (D-1) was changed to the ratio shown in Table 1, to obtain a polyetheramide elastomer in the same manner as in Example 1.

[Comparative Example 4]
In Example 1, except for changing (D-1) to (D-4) may obtain a polyetheramide elastomer in the same manner as in Example 1.

[Comparative Example 5]
In Example 1, except for changing (D-1) to (D-5) was obtained a polyetheramide elastomer in the same manner as in Example 1.

For polyetheramide elastomers obtained in Examples and Comparative Examples, the time taken for polycondensation reaction (polymerization time), the relative viscosity of the polymer, the terminal carboxyl group concentration, the terminal amino group concentration, phosphorus atom concentration, a sodium atom concentration results analysis and was subjected to the above evaluation are shown in Table 1.

Figure JPOXMLDOC01-appb-T000031

As is evident from Table 1,
Comparative Example 1 not using the component D takes a long time to completion of the polymerization, discoloration after the initial color tone and heat treatment is large, it was inferior in heat discoloration resistance.
Comparative Example 2 the amount of component D is less than the specified range takes a long time to completion of the polymerization, discoloration after the initial color tone and heat treatment is large, it was inferior in heat discoloration resistance.
In Comparative Example 3 in which the amount of component D is more than the specified range, since the balance of the end groups is lost, long polymerization time, was inferior in transparency after hot water treatment.
Comparative Examples 4 and 5 using component D other than the provisions of the present invention was inferior in transparency after hot water treatment.
On the other hand, polyetheramide elastomers as defined in the present invention from Example 1 6, while maintaining the properties inherent polyamide elastomer, color tone, heat discoloration resistance, excellent transparency, and moisture transparency after heat treatment much variation of, it is clear that the polymerization accelerator effect is sufficient.

Claims (16)

  1. Diamine compound (components A), a polyamide-forming monomer (component B), a dicarboxylic acid compound A (component C) and a method for manufacturing a polyetheramide elastomer having a melt polycondensation to step,
    Before the step, during, or after the phosphorus atom-containing compound (component D) is added,
    If the component D before or at medium of the process is added in the presence of the component D, the melt polycondensation is performed,
    If the component D is added after the step, the polymer obtained by melt polycondensation in the step is in the presence of the component D, the melted and kneaded is made,
    Wherein component A is a compound represented by the following formula (1)
    Figure JPOXMLDOC01-appb-C000001
    (In the formula (1), x is an integer of 1 to 20, y is an integer of 4 to 50, and z is an integer of 1-20, respectively.) Triblock polyether diamine compound represented by (component A1) It includes,
    Wherein component B is a compound represented by the following formula (2)
    Figure JPOXMLDOC01-appb-C000002
    (Equation (2), R 1 represents. A linking group containing a hydrocarbon chain) amino acid compounds represented by (component B1) and / or the following formula (3)
    Figure JPOXMLDOC01-appb-C000003
    A (formula (3), R 2 represents a linking group containing a hydrocarbon chain.) Represented by a lactam compound (component B2),
    Wherein component C is a compound represented by the following formula (4)
    Figure JPOXMLDOC01-appb-C000004
    (In the formula (4), R 3 represents a linking group containing a hydrocarbon chain, m represents. 0 or 1) a compound represented by,
    Wherein component D is a compound represented by the following formula (5)
    Figure JPOXMLDOC01-appb-C000005
    A compound represented by the following formula (6)
    Figure JPOXMLDOC01-appb-C000006
    A compound represented by the following formula (7)
    Figure JPOXMLDOC01-appb-C000007
    A compound represented by the following formula (8)
    Figure JPOXMLDOC01-appb-C000008
    A compound represented by the following formula (9)
    Figure JPOXMLDOC01-appb-C000009
    A compound represented by, and the following formula (10)
    Figure JPOXMLDOC01-appb-C000010
    In in the compound represented by (formula (5) to (10) may be R 4 - R 9 are the same or different, a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, X 1 - X 12 is a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, at least one compound selected from the group consisting of metal elements are excluded.),
    To the polyetheramide elastomer 100 parts by weight,
    Method for producing a polyether amide elastomer, wherein the phosphorus atom 0.005 to 0.3 part by weight.
  2. In the step 1, the component A, the total 100 mass% of B and C,
    Method for producing a polyether amide elastomer of claim 1 wherein the ratio is 10 to 95% by weight of the component B.
  3. In the step 1, the component A, the total 100 mass% of B and C,
    The proportion of the component B is 15 to 80 wt%,
    Wherein components A and C total production method of polyetheramide elastomer of claim 1 or 2 wherein the ratio is 20 to 85% by weight of.
  4. R 1 in the formula (2) The production method of the polyetheramide elastomer of any one of claims 1 to 3 containing an alkylene group having 2 to 20 carbon atoms.
  5. R 2 in the formula (3) The production method of the polyetheramide elastomer of any one of carbon atoms of claims 1 to 4, comprising an alkylene group having 2 to 20.
  6. Method for producing x is 2 ~ 6, y is 6-12 and polyetheramide elastomer according to any one of claims 1 to 5, z is from 1 to 5, wherein the formula (1).
  7. Method for producing x is 2-10, polyetheramide elastomer of y is 13-28 and z is according to any one of claims 1 to 5, which is a 1-9 in the formula (1).
  8. Wherein component A is branched saturated diamine having 6 to 22 carbon atoms, at least one diamine compound selected from the group consisting of branched cycloaliphatic diamine and norbornane diamine of 6 to 16 carbon atoms (component A2) further method for producing a polyether amide elastomer according to any one of claims 1 to 7 including.
  9. Said components A, relative to the total 100 mass% of B and C,
    Method for producing a polyether amide elastomer of claim 8 wherein the ratio is 0.5 to 10 mass% of the component A2.
  10. Branched saturated diamine of the carbon atoms of 6 to 22, 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, 2-methyl-1, 5-diaminopentane, 2-methyl-1,8-diamino-octane or manufacturing method of the polyetheramide elastomer of claim 8 or 9, wherein the diamine is selected from mixtures thereof.
  11. Branched alicyclic diamine of the 6 to 16 carbon atoms is 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexane methylamine, or their method for producing a polyether amide elastomer according to any one of claims 8 to 10, characterized in that a diamine selected from mixtures.
  12. The norbornane diamine, 2,5-norbornane dimethylamine, 2,6-norbornane dimethylamine or claims 8 to 11, characterized in that a diamine selected from mixtures thereof according to any one polyether amide elastomer Production method.
  13. Wherein component C, the production method of the polyetheramide elastomer according to any one of claims 1 to 12 is an aliphatic dicarboxylic acid or alicyclic dicarboxylic acid.
  14. In m is 1 in the formula (4), R 3 is a manufacturing method of a polyetheramide elastomer according to any one of claims 1 to 13, an alkylene group having 1 to 20 carbon atoms.
  15. Wherein component D is phosphoric acid, phosphorous acid, and at least one process for producing a polyether amide elastomer according to any one of claims 1 to 14 selected from the group consisting of hypophosphorous acid.
  16. Polyetheramide elastomers obtained by the process of the polyetheramide elastomer according to any one of claims 1 to 15.
PCT/JP2011/075215 2010-03-26 2011-11-01 Method for producing polyester amide elastomer, and polyester amide elastomer obtained from said production method WO2012132084A1 (en)

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WO2016182001A1 (en) * 2015-05-11 2016-11-17 株式会社カネカ Polyamide elastomer, medical device, and method for producing polyamide elastomer

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WO2016182002A1 (en) * 2015-05-11 2016-11-17 株式会社カネカ Polyamide elastomer, medical device, and method for producing polyamide elastomer
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