JPH0363573B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a process for making block polyetheresteramides, and more particularly to a process for making block polyetheresteramides having transparency and improved elastomeric properties. Polyether ester amide, which has polyamide repeating units, polyether repeating units, and ester bonds in the polymer main chain, is well known, and like polyether ester or polyester amide, it has excellent impact resistance and rubber elasticity, so it is a new product in the elastomer field. It has been attracting attention as a material in recent years. In particular, polyether ester amide, which is made of nylon 12 and poly(tetramethylene oxide) glycol, is lightweight, has excellent abrasion resistance, and low-temperature impact resistance, and is less likely to cause burrs or sink marks during molding, making it promising for various molding applications. However, 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. That is, the present invention has the following formula: (However, in the formula, R is alkylene or alkylidene having 1 to 4 carbon atoms, R ₁ and R ₂ are H or CH ₃ , and diamine a is substantially equimolar to a.
Aliphatic or alicyclic dicarboxylic acid b having 6 to 15 carbon atoms (however, components a and b may be in the form of a mixture or salt), poly(alkylene oxide) glycol c having a number average molecular weight of 300 to 2000 , and dicarboxylic acid d having 4 to 20 carbon atoms, 5 to 90% by weight of polyamide units A derived from components a and b, and 95 to 10% by weight of polyether ester units B derived from components c and d. Weight% included:
Provided is a method for producing a block polyether ester amide, which is characterized by carrying out melt polymerization at 230 to 320°C under high vacuum. The polyether esteramide of the present invention has amorphous high
It consists of a polyamide part with a high Tg and a polyether part with a low Tg, and the object of the present invention cannot be achieved without this combination. In particular, the former provides an elastomer that not only provides transparency but also has excellent high-temperature properties. Diamine a represented by formula () in the present invention
R is alkylene or alkylidene having 1 to 4 carbon atoms, typically methylene or isopropylidene, and representative examples of such diamine include trans and/or cis-4,4'-diaminodicyclohexylmethane. be able to. Examples of aliphatic or alicyclic dicarboxylic acids b having 6 to 15 carbon atoms include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid and 1,2- There are alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, but azelaic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability. In the present invention, the poly(alkylene oxide) glycol c having a number average molecular weight of 300 to 2000 includes polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol,
Poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc., among others, have excellent heat resistance, water resistance, Due to the excellent physical properties of polyetheresteramide, such as mechanical strength and elastic recovery, the number average molecular weight is 500~
1000 poly(tetramethylene oxide) glycol is preferably used. Dicarboxylic acid d having 4 to 20 carbon atoms in the present invention
Examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 5-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid alicyclic dicarboxylic acids such as acids, and succinic acid,
Mention may be made of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodecanedic acid (decanedicarboxylic acid). Although d may be different from b, it is preferable that they be the same from the viewpoint of the physical properties of the polyether ester amide obtained. The polymerization method of polyether ester amide is
There is no particular limitation except that the polymerization is carried out under high vacuum at a temperature of 230 to 320°C. For example, a method of reacting diamine component a represented by formula () with dicarboxylic acid components b and d to produce a polyamide prepolymer having carboxyl groups at both ends, and reacting this with poly(alkylene oxide) glycol c; , b, c, and d are simultaneously charged into a reaction tank, melt-mixed, and then polymerized all at once under high vacuum. Or a
Methods include preparing salts of and b and then proceeding with polymerization of the salts with c and d, but this method is particularly recommended since it yields high quality polyetheresteramide. The polyether ester amide composition of the present invention may contain stabilizers such as antioxidants, thermal decomposition stabilizers, and light stabilizers, colorants, flame retardants, reinforcing materials, and fillers at any time during polymerization or after polymerization and before molding. Additives such as molding agents, various molding aids, and plasticizers can be optionally mixed and used. The present invention will be explained below with reference to Examples. In the examples, all "parts" or "%" are expressed as weight ratios. Example 1 82.5% water, 8.4% 4,4'-diaminodicyclohexylmethane, and 9.1% dodecanedioic acid were mixed and stirred. The pH of this aqueous solution was 8.4 at 22°C.
After standing still for 16 hours, the salt was filtered off and dried. This salt S27.3
parts, 17.4 parts of dodecanedioic acid and number average molecular weight
60.4 parts of poly(tetramethylene oxide) glycol 800, 0.2 parts of "Irganox" 1098 (antioxidant) and 0.05 parts of tetrabutyl titanate catalyst
The mixture was charged into a reaction vessel equipped with a helical ribbon stirring blade, purged with _N2 , heated and stirred at 250°C for 30 minutes to obtain a homogeneous transparent solution, and then heated to 280°C and << Polymerization conditions were brought to 1 mmHg. 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 polyether ester amide (A-
1) is 25% polyamide hard segment.
The relative viscosity (ηr) measured in orthochlorophenol at 25°C at 0.5% concentration was 1.88, and the glass transition temperature (Tg) by TMA was 110°C. This polymer pellet was hot-pressed and allowed to cool to form a test piece with a thickness of 1 mm, and its total transmittance and mechanical properties were measured. The total transmittance was 92%. (In the following examples, ηr, Tg, total transmittance, and mechanical properties were determined using this method.) The mechanical properties at room temperature are shown in Table 1. In addition, the temperature dependence of the tensile modulus was determined from -40 to +120℃.
The results are shown in FIG. 1 together with Example 1 and Comparative Examples 1 and 2 below.

[Table] Example 2 43.7 parts of the salt S described in Example 1, dodecanedioic acid
15.8 parts and 46.7 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 680 were polymerized in the same manner as described in Example 1, together with 0.2 parts of "Irganox" 1098 (antioxidant) and 0.05 parts of tetrabutyl titanate catalyst. Polyetheresteramide (A-2) was obtained. The polyamide hard segment accounts for 40%. Relative viscosity (ηr) is 1.64,
Glass transition temperature (Tg) is 125℃, total transmittance is 95%
It was hot. Table 2 shows the mechanical properties at room temperature.

[Table] Comparative Example 1 27.3 parts of aminododecanoic acid, 13.4 parts of terephthalic acid, and 64.5 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 800 were added to "Irganox".
Polymerization was carried out in the same manner as described in Example 1 with 0.2 part of 1098 (antioxidant) and 0.05 part of tetrabutyl titanate catalyst to obtain polyether ester amide (B-1) having 25% of nylon 12 hard segments.
The relative viscosity (ηr) is 1.81, and the crystal melting point by DSC is
At 112°C, the total transmittance was 78%. Table 3 shows the mechanical properties at room temperature.

[Table] Comparative example 2 Aminododecanoic acid 43.7 parts, terephthalic acid 12.7 parts
50.4 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 680 as "Irganox"
Polymerization was carried out in the same manner as described in Example 1 with 0.2 part of 1098 (antioxidant) and 0.05 part of tetrabutyl titanate catalyst to obtain a polyether ester amide (B-2) containing 40% of nylon 12 hard segments.
The relative viscosity (ηr) is 1.76, and the crystal melting point by DSC is
At 120°C, the total transmittance was 43%. Table 4 shows the mechanical properties at room temperature.

【table】 [Brief explanation of drawings]

Figure 1 shows polyetheresteramides A-1 and A-1 obtained in Examples 1 and 2 of the present invention and Comparative Examples 1 and 2.
It is a graph showing the relationship between the tensile elastic modulus and temperature of -2, B-1, and B-2.

Claims (1)

[Claims] 1 Formula () (However, in the formula, R represents alkylene or alkylidene having 1 to 4 carbon atoms, and R ₁ and R ₂ represent H or CH _3. )
Diamine a represented by a and aliphatic or alicyclic dicarboxylic acid b having 6 to 15 carbon atoms, substantially equimolar to a (however, component a and component b may be in the form of a mixture or a salt) , poly(alkylene oxide) glycol c having a number average molecular weight of 300 to 2000, and dicarboxylic acid d having 4 to 20 carbon atoms, component a and b
Melt at 230 to 320°C under high vacuum so that polyamide units A derived from the components contain 5 to 90% by weight and polyether ester units B derived from components c and d contain 95 to 10% by weight. A method for producing a block polyether ester amide, which comprises polymerization.