JPS58206627A - Preparation of polyether ester amide - Google Patents

Abstract

PURPOSE:To obtain the titled amide having transparency and improved elastomeric properties, by melt polymerizing a specific diamine with a dicarboxylic acid and a poly(alkylene oxide)glycol under a high vacuum. CONSTITUTION:(A) A diamine of the formula (R is 1-4C alkylene or alkylidene; R1 and R2 are H or CH3), e.g., 4,4'-diaminodicyclohexylmethane, is melt polymerized with (B) an equimolar amount of a 6-15C aliphatic or alicyclic dicarboxylic acid, e.g. dodecanedioic acid, (C) a poly(alkylene oxide)glycol having 300-2,000 number-average molecular weight and (D) a 4-20C dicarboxylic acid to give 5-90wt% polyamide units derived from the components (A) and (B) and 95-10wt% polyether ester units derived from the components (C) and (D) at 230-320 deg.C under a high vacuum.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for preparing block polyetheresteramides having transparency and improved elastomeric properties. .

Polymer-1: A poly-1-thyl ester amide having a polyamide repeating center, a polynythyl repeating position 11, and an ester bond in the chain is known, and polyether 1
Like stell or polyester ε1, it has been recently used as a new material in the field of L lastomers because it has excellent impact resistance and rubber elasticity.

In particular, polyether ester amide, which is made of nylon 12 and poly(teramethoxy, oxinodo) glycol, is lightweight, has excellent abrasion resistance, low-temperature impact resistance, and is less likely to cause flakes or sink marks during molding, so it is used in various types. Although it is promising for molding applications, there is still room for improvement in high-temperature properties and transparency.

The present inventors have conducted extensive studies on a method for producing polyether ester amide that has excellent high-temperature properties and transparency, and have arrived at the present invention. The present invention provides a diamine fa represented by the formula (+) (wherein R is alkyleno or alkylideno having 1 to 4 carbon atoms, and R1 and R2 represent I (or CH)); , substantially equimolar to ta+,
Aliphatic or cyclic dicarboxylic acid having 6 to 15 carbon atoms (
b) (However, (al component and (b) component may be in the form of a mixture or in the form of a salt), number, average molecular weight is 300 to 2.O
OO poly(alkylenookinodo') glycol (C)
, and a dicarboxylic acid having 4 to 20 carbon atoms (a)
component and fb) The polyamide unit holes derived from the component are 5
A block characterized by being melt-polymerized at 230 to 320°C under high vacuum so that it contains ~90% by weight and 95 to 10% by weight of polyether ester units FB+ derived from components (C1 component and id). A method for producing polyetheresteramide is provided.

The polyether ester amide of the present invention consists of an amorphous high Tg polyamide portion and a low Tg polyether portion,
Without this combination, the object of the present invention cannot be achieved. Especially the former is transparent! At the same time, it provides an elastomer with excellent high-temperature properties.

In the present invention, R in raremino (a) represented by formula (1) is alkylene or alkylideno having 1 to 4 carbon atoms, and typically represents methyleneno, inopropylidene, etc. Such diamines include trans and/or cis- 4,4'-Diamylnochlorohequinormethane can be cited as a representative example. Aliphatic or cyclic dicarboxylic acids having 6 to 15 carbon atoms (bl is aliphatic dicarboxylic acids such as adipinoic acid, azelaic acid, sebacic acid, dotecaronoic acid, and 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexane Although there are alicyclic dicarboxylic acids such as sanodicarboxylic acid and dinochlorohequinol-4,4'-dicarboxylic acid, azelaic acid, sebacic acid, and dodecanoic acid are preferably used from the viewpoint of polymerizability.

The number average molecular weight in the present invention is 300 to 2, OO, O
poly (alkylenooquinodo) glycol (cl as polyethylene glycol, poly (1,2- and 1,3-propylenooquinodo) glycol, poly (
Examples include tetramethylenookinodo) glycol, poly(hexamethyleneookinodo)glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofurano, etc. In particular, due to the excellent physical properties of polyether ester amide, such as heat resistance, water resistance, mechanical strength, and elastic recovery, the number average molecular weight is 5.
00-1. OOO poly(tetramethyleneokinodo)glycol is preferably used.

In the present invention, dicarboxylic acids having 4 to 20 carbon atoms (including terephthalic acid, inophthalic acid, phthalic acid, naphthalene-2,6-; carboxylic acid, naphthalene-2,7-',
Aromatic dicarboxylic acids such as carboxylic acid, diphenyl-4,4'-,, carbonic acid, diphenoxyethaldicarboxylic acid, sodium 5-sulfoisophthalate, 1.
Ring dicarboxylic acids such as 4-cyclohexanodicarboxylic acid, 1,2-cyclohexanodicarboxylic acid, and cinoclohexynol-4,4'-dicarboxylic acid, and such as succinic acid, acipinoic acid, sepadinoic acid, and dodecanonic acid (thecanodicarbonic acid). Mention may be made of aliphatic dicarboxylic acids. Although (d) can be used even if it is different from (d), it is preferable that they are the same from the physical properties of the resulting polyetheresteramide.

The polymerization method of polyether ester amide is 230-3
There is no particular limitation except that the melt polymerization is carried out under high vacuum at a temperature of 20°C. For example, a diamino component molecule al shown in formula (1) is reacted with a recarphonoic acid component (bl, f) to create a polyamide prepolymer having carfoquinol groups at both ends, and this is reacted with poly(alkylene 7-oquindo) glycol (C1). How to make it work■, or
, tbl, (C), (The compounds of the mountain are simultaneously charged into the reaction tank, melted and mixed, and then polymerized all at once under high vacuum 1
1 method (?).・Alternatively, after preparing the salts of (a) and (bl), this salt can be added to (C1, (Method G3) in which polymerization is proceeded with dl), but this method yields high-quality polyether ester amide. ■ is especially recommended.

The polyether ester amide composition of the present invention contains an antioxidant at any time during polymerization or after polymerization and before molding.
Additives such as thermal decomposition stability, stabilizers such as light-resistant agents, colorants, flame retardants, reinforcing materials, fillers, various molding aids, and plasticizers can be optionally mixed and used.

The present invention will now be explained by way of examples. In the examples, all parts expressed as "parts" or 1%1 are expressed as weight ratios.

Example 1 82.5% water, 8.4% 4,4'-rea2nosyncroquinormethano, and 9.1% dotekaluonoic acid were mixed and stirred. The pH of this aqueous solution was 220, which was 8.4. After standing still for 16 hours, filter out the salt and dry. Kocy1.
27.3 parts of A15l, 174 parts of dotecanreonoic acid, and 60.4 parts of poly(tetramethylene ookinodo) glycol with a number average molecular weight of 800 were added to Irganox 109.
80.2 parts (antioxidant) and tetrabutyl titanium
1. Charge 0.05 part of catalyst and a cane into a reaction vessel equipped with a helical ribbon stirring blade, purge with Nl, heat and stir at 250°C for 30 minutes to make a homogeneous transparent solution, then follow the temperature increase and pressure reduction program for 30 minutes. At 280℃, <1*shoulder 11g
polymerization conditions. When the reaction was carried out under these conditions for 2 hours, a viscous, colorless and transparent molten polymer was obtained, and this polymer was discharged into water as a gut.

The obtained polyetheresteramide (A-1) contains 25% polyamide hard segments. The relative viscosity (ηr) measured at 25'C10.5% concentration in orthochlorophenol was 188, and the glass transition temperature (Tg) by TMA was 110"C. After pressing this polymer pellet with 10 nodules, The total transmittance and mechanical properties were measured after cooling to a thickness of 1 mm.The total transmittance was 92%. (In the following examples, ηr, Tgs total transmittance, mechanical properties were measured. Table 1 shows the mechanical properties at room temperature (based on the ji° method).

Furthermore, the temperature dependence of the tensile modulus was -40.

Table 1 Example 2 43.7 parts of the salt fs described in Example 1, 158 parts of dodecaloheptacid, and 46.7 parts of poly(tetramethyleneokinodo)glycol having a homogeneous molecular weight of f4680 were added to "Ilkanox'10980". Polyether ester 72 (A-2) was prepared using a method similar to that described in Example 1. The boria 2 hard segment was 40%.The relative viscosity (ηr) was 1.64, the glass transition humidity (Tg) was 1250, and the total transmittance was 95%.Mechanical properties at room temperature. are shown in Table 2.

Table 2 Ratio 1 Bite Example 1 27.3 parts of aminotic acid, 13.4 parts of terephthalic acid, and 64.5 parts of poly(tetramethyleneokinodo)glycol with a number average molecular weight of 800 were added to 1 part of ``Ilcanox''.
0980.2 parts (oxidation protection Δ) 1) and 005 parts and 11 of the tetrabutyl titanate catalyst were polymerized in the same manner as described in Example 1, and 25%
Poly 1-thyl esteramide (B-1) was obtained. 4
11 Viscosity versus viscosity (y) r ) is 1.81, according to DSC.
The crystal melting point was 112, and the total transmittance was 78%. Table 3 shows the mechanical properties at room temperature.

Table 3 Comparative Example 2 43.7 parts of aminododecanoic acid, 127 parts of terefucuric acid,
50.4 parts of poly(tetramethyleneokinodo)glycol with number average molecule @68o
80.2 parts (1 oxidant) and tetraphthyl
Polymerization was carried out using the same yj method as in Example 1 with 0.05 part of a catalyst to obtain a polyether ester amide (B-2) containing 40% nylon 12 hard segmenol. Relative viscosity (y+r) 1.76, D S'lc 71 Crystal melting point 1. t120(], and the total transmittance was 43%. Table 4 shows the mechanical properties at room temperature.

Table 4

[Brief explanation of the drawing]

Figure 1 shows polyetheresteramides A-1, A-2, B-
1 is a graph showing the relationship between the tensile elastic modulus and temperature of B-2. Patent applicant: Higashi Shi Co., Ltd. 1 Figure 1

Claims (1)

[Scope of Claims] Diaminofa) represented by formula (1) (wherein R represents alkyleno or alkylidene having 1 to 4 carbon atoms, R1 and R4 represent H or C1l), and equimolar to ta),
Lucid aliphatic or alicyclic nocarbonoic acids having 6 to 15 carbon atoms (
bl (fli L, fa) component (bl component may be in the form of a mixture or salt), number) V-uniform molecular weight 30
0-2. OOO poly(alkylenooquinodo)glycol (C) and recarphonoic acid F having 4 to 20 carbon atoms
d), the polyamide 131 derived from the ta+ component and tb+bl has a content of 5 to 90 tons, and the (C) component and (d)
The polyether derived from the ingredients f
Bl Ka95~10 Heavy jit % *Ma JL 71
A yf method for producing pronocubary ether ester amide, which is characterized by melt-polymerizing 230 to 320 C1 high purity ester amide.