JPS6037132B2 - Method for producing transparent polyester elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyester elastomer that is flexible, transparent, and has good hydrolytic stability.

Conventionally, plastic polyvinyl chloride, polyurethane, certain types of rubber, and the like have been widely used as transparent, elastic and/or flexible materials.

However, rubber or polyurethane is inherently susceptible to the effects of light or oxygen and tends to gradually lose its strength or elasticity, and plastic polyvinyl chloride does not have sufficient elasticity, making it difficult to manufacture extrusion-molded or injection-molded products. It was not always satisfactory as a material for use. Furthermore, since plasticized polyvinyl chloride generally contains a large amount of plasticizer, it has the disadvantage that the plasticizer leaches out during use, especially when used as a material for medical or food/drink equipment. This is problematic because many of them contain plasticizers whose toxicity to the human body has recently become a problem.

Furthermore, polyvinyl chloride has the problem of residual vinyl chloride monomer, and toxicity of vinyl chloride monomer to the human body has recently become a problem. Furthermore, when rubber and polyurethane are used for medical or food and beverage equipment, they are often heat sterilized or ethylene oxide gas sterilized before use. There is a high risk of deterioration.

The inventor of the present invention has conducted intensive studies to develop a new material that does not have the drawbacks of such conventional materials, has transparency, elasticity and/or flexibility, and can be melt-molded. We have arrived at the present invention.

That is, the present invention provides terephthalic acid and/or ester-forming derivatives thereof, 'B} tetramethylene glycol and/or ester-forming derivatives thereof, [C} above-mentioned compounds and [B]
}A compound having two ester-forming functional groups having a carbon number of 2 to 20 and a molecular weight of 400 or less and/or its ester-forming conductor, and wind average molecular weight (M
In producing a polyester elastomer by polymerizing a poly(oxyalkylene) glycol and/or its ester-forming derivative, in which s) is 500 to 5000 and the ratio of carbon atoms to oxygen atoms is 2 to 4.5. , the proportion of the components {K, legs, ni} and {D} in the total polymer is
壬；X・oo み5o…■ [However, W in the above formula
T is the total weight of the polymer, WD is the weight of the auxiliary component, A is the number of moles of the harmful component, D is the number of moles of the wind component, and C is the number of moles of the (2) component.

], and the melting point is 200 qo or more when a high-molecular-weight polymer having fiber-forming ability is formed from only the high-melting-point crystalline polyester segment constituents formed by the wind, legs, and Ni components. This is a method for producing a transparent polyester elastomer characterized by the following.

In the method of the present invention, a polyester elastomer is produced by polycondensing the above-mentioned components [B}, [C}, and supporting components. The resulting polyester elastomer is made by combining the terephthalic acid and/or its ester-forming active conductor as the wind component and the tetramethylene glycol and/or its ester-forming derivative as the component 'B' with the ester-forming functional group of the component {2}. The so-called hard segment is formed by the reaction of a part of the compound and/or its ester-forming derivative, and the carbon having an average molecular weight of 500 to 5,000 is the remainder of the harmful component, the remainder of the 'C} component, and the plate component. It consists of a so-called soft segment formed by the reaction of poly(oxyalkylene) glycol and/or its ester-forming derivative with a ratio of the number of atoms to the number of oxygen atoms of 2 to 4.5. . The proportion of soft segments in the polymer is 71 to 85% by weight, particularly preferably 71 to 8% by weight. The formula u represents the content (% by weight) of the soft segment in the polymer, and the formula {1} represents this.

If the proportion of soft segments is less than 71% by weight,
Sufficient flexibility is not achieved. Moreover, when the amount is more than 85% by weight, the moldability deteriorates, which is undesirable.
Those in the range of 5% by weight have sufficient flexibility, sufficient transparency, and extremely high hydrolytic stability.
Moreover, it is easy to manufacture.

Examples of the components used in the method of the present invention include, in addition to terephthalic acid, alkyl esters (eg, methyl ester, ethyl ester, etc.) and aryl esters (eg, phenyl ester, etc.) of terephthalic acid. In addition, [C) component has a carbon number of 2 to 20 and a molecular weight of 40
Examples of compounds having two ester-forming functional groups of 0 or less include isophthalic acid, phthalic acid, methyl terephthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid. , diphenyl dicarboxylic acid, diphenoxychetane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, hexahydroterephthalic acid,
Dicarboxylic acids other than terephthalic acid such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, etc. and such as ethylene glycol, trimethylene glycol, propylene glycol, bentamethylene glycol, hexamethylene glycol, neobentyl glycol, diethylene glycol, cyclohexane Glycols other than tetramethylene glycol such as dimethanol, bishydroxyethoxybisphenol A, 4,4-bishydroxyethoxydiphenyl sulfone, xylylene glycol, and oxybenzoic acid, hydroxyethoxybenzoic acid, oxycaproic acid, etc. Examples include acids.

Examples of ester-forming derivatives of the above-mentioned compounds as a component include alkyl esters of dicarboxylic acids and oxycarboxylic acids (e.g., methyl ester, ethyl ester, etc.), aryl esters (e.g., phenyl ester, etc.), and lower carboxylic acid esters of glycols. (for example, ester acetate, etc.), alkylene oxides such as ethylene oxide, and the like.

These may be used alone or in combination of two or more. Preferred among these are a glycol component which forms a high melting point crystalline polyester with the terephthalic acid component, or a dicarboxylic component which forms a high melting point crystalline polyester with the tetramethylene glycol component.
Particularly preferred components include ethylene glycol component,
1,4-cyclohexanedimethanol component, 4,4'-
Examples include a diphenyl dicarboso brewing component, a 2,6-naphthalenedicarbone brewing component, and the like. When these high melting point crystalline components are used, the expression of transparency is particularly remarkable,
Furthermore, the obtained polyester elastomer is characterized by good heat resistance. In the method of the present invention,
(2) As a component, a poly(oxyalkylene) glycol with an average molecular weight of 500 to 5,000 and a ratio of carbon atoms to oxygen atoms of 2 to 4.5 and/or its ester-forming conductor is used. Specific examples thereof Examples include poly(oxytetramethylene) glycol, poly(oxytrimethylene) glycol, poly(oxyethylene) glycol, poly(oxyhexamethylene) glycol, and the like.

These poly(oxyalkylene) glycols can be used not only as a single component but also as a copolymer of two or more components. A typical example of the copolymerized polyoxyalkylene glycol is an ethylene oxide/trimethylene oxide copolymer. These can be used alone or in combination of two or more. Similarly to the above-mentioned poly(oxyalkylene) glycol, its ester-forming derivatives can also be used.

Examples of such ester-forming derivatives include monoesters and gesters with monocarboxylic acids. Among these poly(oxyalkylene) glycols, poly(oxytettomethylene) glycol and poly(oxyethylene) glycol are preferably used, and among these, poly(oxytetramethylene) glycol is particularly preferably used. In the present invention, 'C in the total polymer
} The molar amount of the component must be 50% or less of "the number of moles of wind - the number of moles of wind", and the high melting point crystal formed by the wind component, [B} component and 'C} component When a high molecular weight polymer having fiber-forming ability is formed from only the polyester segment constituent components, the melting point must be less than 200°C.

If the above-mentioned melting point is 200 qo or higher, transparency will not be sufficiently developed, which is undesirable, and if the amount of component (C) is greater than the specified amount, the molded product will develop stickiness after melt molding. Further, when the molded product is a tubular product, etc., when the tubular product is rolled up after melt molding, it tends to be set in a rolled shape, which is not preferable. Furthermore, if the amount of the 'C} component is greater than the specified amount, there is a significant drawback that devitrification occurs during high-temperature steam sterilization or ethylene oxide sterilization of molded products when used for medical or food applications. has.

In the method of the present invention, a trifunctional or polyfunctional compound (eg, pentaerythritol, etc.) can be used as a crosslinking agent for various modification purposes.

The polyester elastomer of the present invention can be produced by a conventional vehicle processing method.

That is, the four components, ``■'', ``B}'', and the dish components, can be reacted in any manner. For example '1'
, A method of starting polycondensation after charging all four components, wind, (B}, {C), and D} into a reactor at the same time; A method of polycondensing to some extent and then adding a supporting component to copolymerize; '3}, a method of first adding the auxiliary and ① components and allowing some degree of polycondensation, and then adding the auxiliary and ① components to copolymerize. etc. can be mentioned. The polycondensation reaction temperature should preferably be in the range from the melting point of the resulting polymer to 2703C; if it is too high than 270°C, deterioration will become significant, so it is not preferred.

Suitable catalysts for use in the above reaction include tetrabutyl titanate, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, di-n
-butyl-tin-laurate, di-n-butyl-tin-oxide, dibutyl-tin-sebacinoate, zinc acetate and antimony oxide, magnesium acetate and antimony oxide, zinc acetate and germanium oxide, magnesium acetate and germanium oxide, lead monoxide, lead dioxide, oxide magnesium,
Examples include zinc oxide.

Among these, organic titanium compounds are preferred as catalysts.
'The amount of these catalysts is preferably in the range of 0.003 to 0.7 wt% based on the total weight of the produced polymer.

The polyester elastomer obtained by the method of the present invention can be melt-molded and has excellent curing properties.
As a transparent and flexible material with elasticity, it has excellent moldability.

Therefore, the polyester elastomer can be molded into various shapes by various melt molding methods and used to advantage. Examples of melt-molded products include extrusion-molded products such as tubes, films, and sheets; ■ blow-molded products such as bottles; and injection-molded products such as various containers and utensils. can be mentioned. Moreover, a molding method other than the melt molding method can be performed as necessary. Molded products made from the polymer obtained by the method of the present invention do not require the addition of plasticizers used in flexible polyvinyl chloride, so there is no need to add any plasticizers to the human body due to the subsequent generation of plasticizers. Since there is no need to worry, the molded product of the present invention is particularly preferably used for medical equipment or food/beverage equipment.

A molded article made from the polymer obtained by the method of the present invention, for example, a wall thickness of 0.5 to 1. The transparency of the tubular material is extremely high, and its transparency is comparable to that of plasticized polyvinyl chloride. In addition, molded products made from the polymer obtained by the method of the present invention, such as tubular products with a wall thickness of about 0.5 to 1.0, can be processed by high-temperature steaming when used for medical or food/beverage equipment applications. Sterilization treatment (steam lk9/negative G, 124qC, 40 minutes) or ethylene oxide sterilization [ethylene oxide gas (1 ol%, C○29
and ol%), lk9/KiG, 50-6000, song rs]
Even after such treatment, its transparency retention is outstanding and exceeds that of medical plasticized polyvinyl chloride tubes.

Furthermore, it has extremely excellent dimensional stability during sterilization, which far exceeds that of medical plasticized polyvinyl chloride tubes.

The polyester elastomer obtained by the method of the present invention has excellent color tone, very little coloring, and has, for example, a wall thickness of 0.
．． The tubular material of about 5 to 1.0 legs is colorless and transparent, and its transparency is exactly equivalent to that of a medical plasticized polyvinyl chloride tube.

Furthermore, the molded product made from the above-mentioned polyester elastomer may be subjected to a stretching operation and a heat treatment operation as necessary.

In the method of the present invention, additives such as antioxidants, light stabilizers, terminal stoppers, polymerization accelerators, fillers, brighteners, colorants, etc. may be used within the range that does not impair the purpose of the present invention. can.

EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited by these.

In addition, in the examples, "parts" mean parts by weight.

In addition, the reduced viscosity is a value determined from the solution viscosity measured at 35° C. by dissolving 1.2 liters of polymer in 100 ml of orthochlorophenol. Moreover, the softening point is a value measured with a Picat softening point measuring device.

Examples 1 to 4 and Comparative Example 1 The raw material composition shown in Table 1 below is charged into a reactor equipped with a Kashiyo machine, a distillation device, and a nitrogen introduction tube, and heated to 180 to 220°C to produce methanol. The theoretical amount of 80-90
%Crab came out.

After that, the reaction temperature was raised to 245°C, the reaction was carried out at normal pressure for IQ minutes, and then the reaction temperature was increased to 245°C for about 3 minutes. The reaction was carried out for 30 minutes in a weak vacuum of 0.1 to 0.3 Hga. Polymerization was carried out for 30 minutes under high vacuum. Next, after returning the pressure in the system to normal pressure with nitrogen, bis(8-hydroxyethyl>terephthalate (BHET) was added in the amount shown in Table 1 below, and further 0.1
~0.3 ribs Hga 戊. The reaction was carried out under high vacuum for 7 hours. The obtained polymer was discharged from the reactor and made into chips. Its physical properties are shown in Table 1. Table 1 (story) 2) Measure the chips with a Hunter type color meter 3) After drying the chips, melt them in a nitrogen atmosphere, form them into a 2-thick sheet, quickly cool them in ice water, and make a sheet. Created.

Transparency was measured using a Poitzk integrating sphere microcandometer SEP-TU manufactured by Nippon Precision Optics Co., Ltd.

4) Separately polymerize a polymer that does not contain poly(oxytetramethylene) glycol, and heat a small piece of the polymer at a rate of 5° C./metre under a polarizing microscope to determine the temperature t at which the crystals begin to thorn.
The average value T, (=t1 grass t2) of the temperature t2 at which the thorns end is determined.

Next, heat treatment at (T・-20)℃ for 30 minutes, and then 1
The melting point (mp) of the polymer is defined as the average value of the temperature at which the crystals begin to thorn and the temperature at which thorns end when the temperature is raised again at a temperature of .degree. 1 of the transparent polymer chips of Examples 1 to 4 above
After drying in a hot air dryer at 000°C for 2 hours, the tube was extruded using an extruder with an annular die at the cylinder temperature and die temperature shown in Table 2, cooled in a water bath, and heated to 20°C.
I rolled it up.

Table 2 shows the outer diameter, wall thickness, and characteristics of the obtained tube. Further, the tube was cut into a length of 20 skins and subjected to the following high temperature steam sterilization treatment to measure the stability of the tube. The results are also shown in Table 2. High temperature steam sterilization processing conditions Pressure: 40 minutes in steam at lk9/inhibitory temperature:
12r○ For comparison, Table 2 shows the characteristics of a commercially available plasticized polyvinyl chloride tube.

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'N Tsuyu Ikkou Go Ant L' Shigemi long hair Kaoruei Shibi S Go (mother's heart 0 eyes Saki usu cloudy and three togosunya Since the crystallization speed of the polymer is very high, even if the tube extruded from the extruder through the annular die into the water tank is immediately rolled up, it will not be set in a rolled shape.

Moreover, almost no crystallinity is observed. And the transparency is also excellent and comparable to that of plasticized polyvinyl chloride tubes. In each tube of this example, even if steam sterilization is performed, the decrease in transparency is slight and the dimensional stability is also good.

On the other hand, in Comparative Example 1, the transparency was significantly reduced by the steam sterilization treatment, and the shrinkage was large, causing problems in dimensional stability. From the above, it can be seen that the polymer obtained in this example has excellent properties and is extremely useful for applications such as medical equipment or food and drink equipment.

Comparative Examples 2 to 4 The raw materials shown in Table 3 below are charged into a reactor equipped with a hawker, a distillation device, and a nitrogen introduction tube, and heated to 180 to 2200 C, so that the methanol produced is 80 to 90% of the theoretical amount. I was able to leave.

After that, the reaction temperature was raised to 245°C, and the reaction was carried out at normal pressure for 10 minutes. The reaction was carried out in a weak vacuum for 3 minutes, and then 0.1 to 0.3 hours of Hgabs. 5. Under high vacuum. The insect time was superimposed. The obtained polymer was discharged from the reactor and made into chips. Using the obtained chips, various properties were measured in the same manner as in Examples 1 to 4. The results are shown in Table 3. Further, tubes were formed using the chips in the same manner as in Examples 1 to 4 except for the conditions shown in Table 4, and the characteristics thereof were determined in the same manner as in Examples 1 to 4.

The results are shown in Table 4. Table 3 (word): 1), 2), 3), and 4) are the same as the notes for Table 1 above, and the following are old.

Table 4 Note) 5) and 6) are the same as above.The tubes of Comparative Examples 2 and 3 had good tube formability and no stickiness was observed, but the transparency was extremely insufficient, which is undesirable.

In addition, although the tube of Comparative Example 4 has sufficient transparency, the crystallization rate of the polymer is extremely slow, making it extremely difficult to form the tube. It will be set to .

The tube also has extremely high stickiness. Example
5,6 The raw materials shown in Table 5 below are charged into a reactor equipped with a fly frame machine, a distillation device, and a nitrogen inlet tube, and heated to 180 to 0 °C to reduce the theoretical amount of methanol to 80 to 90 °C. % was distilled out.

Thereafter, the reaction temperature was raised to 245 pm, the reaction was carried out for 10 minutes at normal pressure, and then the reaction temperature was raised to 245 pm. The reaction was carried out for 30 minutes in a weak vacuum of 0.1 to 0.3 Hgabs. 5. Under high vacuum. The period time was superimposed. The obtained polymer was discharged from the reactor and made into chips. Table 5 10,000 pieces of the transparent soft polymer chips obtained above
After drying in a hot air dryer for 2 hours, the tube was extruded using an extruder with an annular die at the cylinder temperature and die temperature shown in Table 6, cooled in a water bath, and wound into a roll.

Table 6 shows the outer diameter and wall thickness of the obtained tube. Table 6 The moldability of the tube is extremely good, and since the crystallization rate of the polymer is fast, even if the tube is extruded from the extruder through a circular die into a water tank and immediately rolled up, it will not be set in a rolled shape.

In addition, almost no tackiness was observed. In addition, the transparency is excellent and comparable to that of plasticized vinyl chloride tubes. Furthermore, the tube of this example has very little coloration and is almost colorless, making it extremely useful as a tube for medical equipment or food equipment.

Claims (1)

[Scope of Claims] 1 (A) terephthalic acid and/or its ester-forming derivative, (B) tetramethylene glycol and/or its ester-forming derivative, (C) the above (
A) and (B) components other than those having 2 to 20 carbon atoms and a molecular weight of 4
A compound having two ester-forming functional groups of 00 or less and/or an ester-forming derivative thereof, and (D)
A polyester elastomer is produced by polymerizing poly(oxyalkylene) glycol and/or its ester-forming derivative having an average molecular weight (M_S) of 500 to 5000 and a ratio of carbon atoms to oxygen atoms of 2 to 4.5. In this case, (A), (B), (
The ratio of components C) and (D) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and C/(A-D)×100≦50…(2) [However,
In the above formula, W_T is the total weight of the polymer, W_D is the weight of component (D), A is the number of moles of component (A), D is the number of moles of component (D), and C is the number of moles of component (C). . ] and has a melting point of 200 when a high melting point crystalline polyester segment component formed from components (A), (B) and (C) forms a high molecular weight polymer having fiber forming ability only. A method for producing a polyester elastomer having transparency, characterized in that the temperature is below ℃.