JPS6335625A - Production of polyether ester amide elastomer - Google Patents

Abstract

PURPOSE:To obtain a polyether ester amide elastomer at low cost by making it possible to perform transesterification in a molten state, by forcibly mixing nylon 66 having specified structures on both terminals with tetramethylene oxide and polycondensing them by transesterification. CONSTITUTION:A polyether ester amide elastomer wherein a hard segment comprises a nylon 66 chain and a soft segment comprises a tetramethylene oxide chain is obtained by mixing adipic acid with hexamethylenediamine and a compound of formula I, subjecting the mixture to amidation to form nylon 66 having groups of formula II on both terminals and forcibly mixing this nylon 66 with tetramethylene oxide glycol to polycondense them by transesterification.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a polyether ester amide, ie, a diaryamide elastomer, in which the hard segment is a polyamide chain and the soft segment is a polyether chain.

More specifically, the present invention relates to a method for producing polyester ether amide in which the polyamide chain is nylon 66 and the polyether chain is polytetramethyleneoxy P chain.

(Prior Art and Problems) Polyamide-based elastomers have good moldability, excellent abrasion resistance, and sound-dampening properties, so they have been widely studied as engineering resins and are being put into practical use.

There are some dangers when producing polyamide elastomers in which polyamide chains and polyether chains are linked by ester bonds.
First, a polyamide is formed from dicarginic acid and a diamine or a lactam, and its amino group terminals are reacted with dicarginic acid to produce a polyamide in which substantially both terminals are carboxyl groups.

Next, attempts have been made to add polyalkylene oxide glycol to this holamide and cause esterification under reduced pressure and in the presence of a catalyst to produce polyether ester amide. But with polyamide? Realkylene oxide glycols generally have poor compatibility, making it difficult for the above-mentioned esterification to proceed, making it difficult to obtain a satisfactory polymer. JP-A-59-213724 discloses that this tendency is remarkable in the case of nylon 66 and polytetramethylene oxide glycol, and that it is necessary to select a specific polyamide in order to obtain a satisfactory polymer. . U.S. Patent 3,044
, 987, adipic acid chloride was added to a benzene solution of polytetramethylene oxide glycol, and CA? CO(CHm)4cOo+c4HaO-)FIC
O(CHm)icOcl is produced, then a dioxane solution of adipic acid chloride is mixed into this solution, and a nooxa/solution of hexamethylene diamine is added.
The method used is to obtain a polyether ester amide by rapid mixing. In other words, by making incompatible reactants into a solution and making it easier to homogenize by mixing, at the same time, Cal cod? A polyether ester amide is obtained from nylon 66 and polytetramethylene oxide glycol by changing the terminal xyl group to an acid chloride group and increasing the activity of the condensation reaction with an amino group.

However, both the solution method and the acid chloride method are costly and significantly increase the cost of the polymer. Therefore, the method disclosed in US Pat. No. 3,044.987 is industrially extremely disadvantageous.

(Problems to be Solved by the Invention) In order to keep the cost of the polymer low, it is necessary to use adipic acid without converting it into acid chloride, and to conduct condensation polymerization in the presence of water or in a melt system. Ninth, it is necessary to improve the affinity between nylon 66 and polytetramethylene oxide glycol, and to allow condensation polymerization to proceed simply by stirring and mixing them in a molten state, even though they are poorly compatible. It is.

An object of the present invention is to provide a method for producing a polyetheresteramide elastomer by linking nylon 66 chains and polytetramethylene oxide chains through ester bonds in a molten state.

(Means for solving the problem) The present invention forms nylon 66 with carxyl groups substantially at both ends, and causes an esterification reaction with butanediol to form nylon 66 with carxyl groups at both ends. CH, CH,
C) The above-mentioned problems were solved by preparing nylon 66, which is I-OH, and forcibly mixing it with polytetramethylene oxide glycol, preferably in a molten state.

That is, the present invention provides a method for producing a polyether ester amide elastomer having a hard segment If Nylo 766 chain and a soft segment as a tetramethylene oxide chain, in which adipic acid bihebenzene methylenediamine and HOCH2CHz CHm CHz QCCHs CH
z CHz CHz COOH (hereinafter referred to as condensate B) to form nylon 66 having both ends (hereinafter referred to as polymer A) through an amidation reaction, and then the nylon 66 and tetramethylene oxide glycol This is a method for producing a polyether ester amide elastomer, which is characterized by forcibly mixing and condensation polymerization by an ester conversion reaction.

In the present invention, the polyether ester amide elastomer requires that the polyamide component be nylon 66 chains, ie polyhexamethylene adipamide chains. Nylon 66 has a high cohesive force of its crystals, which contributes to widening the elastic limit range of the elastomer.

In the present invention, the polyether component must be a polytetramethylene oxide chain. Polytetramethylene oxide chains are most advantageous in maintaining high resilience of the elastomer.

In the present invention, adipic acid, hexamethylene diamine, and condensate B must be mixed to cause an amidation reaction to form polymer A.

When equal amounts of adipic acid and hexamethylene diamine are charged and polycondensation is carried out, the amine groups and cal-2-xyl groups at both ends of nylon 66 usually remain in almost equal eclipse.

However, when a condensate of adipic acid and 1.4 pumendiol is mixed in addition to adipic acid and hexamethylene diamine, polymer A is formed by an amidation reaction. Also, by mixing this condensate with adipic acid and hexamethylene diamine in a ratio of 1=1, the amino group terminals of nylon 66 will be blocked, so depending on the charging ratio of the condensate and adipic acid and hexamethylene diamine, The degree of polymerization of nylon 66 in the elastomer can be controlled.

Adipic acid and hexamethylene diamine are usually used in the form of their salts (hereinafter referred to as flkAH salts), and the condensation polymerization of nylon 66 is carried out in an aqueous solution of the AH salts or in the presence of water.

Known conditions can be used for K to form polymer A. For example, condensation polymerization of AH salt and condensate B is carried out in the presence of water while maintaining the pressure at 17.5.

At this time, water is gradually drained out of the system. After water is removed, the temperature is raised to 270° C. or higher to further advance condensation polymerization.

As a result, the degree of polymerization is controlled and both ends are O0 HOCH,CH CH! OH Snow 0CCH Goose CH2CHx
A polyamide CH2CI(N-) is obtained.

In the present invention, after obtaining the polymer A, it is necessary to forcibly mix the polymer A and polytetramethylene oxide glycol and perform condensation polymerization by transesterification. Polymer A and polytetramethylene oxide glycerol will separate into two phases unless they are forcibly mixed.

However, since both ends of the polymer have a high affinity for polytetramethyleneoxy P, only the ends can be incorporated into the polytetramethylene oxide glycol phase 11CmD.

By forcibly mixing Polymer A and polytetramethylene oxide glycol, a state of microphase separation is created between the two phases, and the secondary transesterification reaction in which 1.4-butanediol is eliminated is facilitated. I can proceed. As a result, the nylon 66 chain and the polytetramethylene oxide chain are connected by an ester bond, and condensation polymerization proceeds to obtain a polyether ester amide F elastomer.

Condensation polymerization by transesterification proceeds as follows.

NHCO(CH2)4 C00(CH2)40H+HO
+C4HaO-)-nH-1→-NHCO(CH2)4
COO+C4H1IO÷H+HO(CH鵞), OH If forced mixing is not done, the two phases will separate and the condensation polymerization will not proceed.

Although the above transesterification reaction is possible without a catalyst, S
It is preferable to add a catalyst such as b20s*T t (OBu) 4 because the reaction rate increases.

Next, although this esterification reaction may be carried out under normal pressure, it is preferable to carry out it under reduced pressure because the reaction rate is high.

The charging ratio of Polymer A and polytetramethylene oxide glycol is preferably equal, and the reaction source (t is 270°C to 2
90°C is preferred.

Mayu, the degree of decompression is below IOIIIHg, and even more than 7rrm.
A value of 19 or less is preferable.

As 1.4-butanediol is distilled out as the condensation polymerization progresses, it is necessary to remove it from the system.

In the present invention, the degree of polymerization of the polyether ester amine P is preferably controlled by the reaction time. lη, = 1.6~
It is convenient to terminate the reaction at 2.0 when used as an elastomer.

The method for measuring η is as follows.

Solvent Orthochlorophenol polymer concentration 0.5 wt 4 Measuring temperature 35
°C Measurement method Follows the conventional method for measuring viscosity (effects of the present invention) By the present invention, a polyether ester amide elastomer, which has conventionally been difficult to obtain, is produced in which the t-hard segment is a nylon 66 chain and the soft segment is a polytetramethylene oxide chain. In doing so, it was possible to carry out the amidation reaction in the presence of water and the transesterification reaction in the molten state without using organic solvents, and there was no need to use raw materials or expensive acid chloride. .

As a result, it has become possible to keep manufacturing costs low.

Example 1 AH salt 26.29. Condensate B is 4.4,9. and water 4
．． 0g were mixed in a 200-autoclave and heated to 270°C.
Pour into an oil bath maintained at Internal pressure is 17.5p
Raise the temperature until it reaches /alG, then open the nonolube slightly so that the internal pressure becomes 17.5y/ajG! While adjusting the IC, raise the temperature to 270℃ until the internal temperature reaches 270℃.
Leave it for about 30 minutes after the temperature reaches ℃.

At that time, stir. The 1,4-butaneol that leaks out is trapped by a condenser.

Next, in an autoclave, add 34% of Bopp's tramethylene oxide glycol (molecular weight 1000). lit and 0.03g of 5b2o3, vacuum degree 0.5oaH
The mixture was reduced to a vacuum of 1.5 g and stirred forcefully at 270° C. for 2 hours.

Thereafter, the temperature is returned to room temperature to obtain a nidistomer.

After confirming the formation of polyether ester amide by infrared absorption spectrum, proceed as follows.

Comparative Example 1 Instead of adding Example 1 and condensate B, adipic acid was added to 2-
The same experiment was carried out except that 9 g was added. Even if 4-reather tetramethylene oxide glycol is added,
The reaction did not proceed, and the final product obtained was a clay-like substance with no elasticity, and infrared absorption spectroscopy confirmed that only a small amount of ester bonds were formed.

Claims (1)

[Claims] In a method for producing a polyether ester amide elastomer in which the hard segment is a nylon 66 chain and the soft segment is a tetramethylene oxide chain, there are adipic acid, hexamethylene diamine, and ▲mathematical formula, chemical formula, table, etc.▼ Nylon 66 whose both ends are ▲mathematical formula, chemical formula, table, etc.▼ by mixing and amidation reaction
A method for producing a polyether ester amide elastomer, which comprises forming nylon 66 and tetramethylene oxide glycol, and then forcibly mixing the nylon 66 and tetramethylene oxide glycol to perform condensation polymerization through a transesterification reaction.